JP2017222625A - Diol compound, and polycarbonate resin, polycarbonate polyol resin, polyester resin, polyester polyol resin and polyurethane resin produced from the diol compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a diol compound having excellent reactivity with another constitutional unit when used as a polymer constitutional unit, and a polycarbonate resin, a polycarbonate polyol resin and the like produced from the diol compound and having excellent heat resistance, transparency, light resistance, weather resistance, and mechanical strength.SOLUTION: A diol compound is illustrated by the following formula.SELECTED DRAWING: None

Description

  The present invention relates to a novel diol compound, a polycarbonate resin produced from the diol compound, a polycarbonate polyol resin, a polyester resin, a polyester polyol resin, and a polyurethane resin.

  In recent years, depletion of petroleum resources has become a major problem, and substitution of petroleum-derived raw materials with raw materials produced from plant-derived biomass resources leads to the protection of petroleum resources. In addition, raw materials derived from biomass resources contribute to the reduction of carbon dioxide emissions during disposal. For this reason, raw materials derived from biomass resources have attracted attention in recent years.

  Inositol is a cyclic polyhydric alcohol obtained from biomass resources, and is expected to form a polymer by linking with a compound that reacts with a hydroxy group (hereinafter sometimes referred to as “hydroxyl group”). Non-Patent Documents 2 to 3 report that heat resistance is improved in polyurethane synthesized from a derivative of inositol.

Polyurethane is obtained by reacting a polyhydric alcohol and diisocyanate under relatively mild conditions of 100 ° C. or less, and even a compound having a secondary hydroxyl group such as an inositol derivative reacts without problems. However, in general, an aliphatic diol compound having a secondary hydroxyl group has low polymerization reactivity due to its low acidity and steric hindrance, and it is known that it is difficult to obtain a high molecular weight product with a polycarbonate resin. (Non-patent Document 3).
Furthermore, in the case of polyurethane, not only a trifunctional structure is not a big problem, but also heat resistance can be improved by positively forming a network (Non-patent Document 4). On the other hand, in the thermoplastic resin represented by polycarbonate resin, when a trifunctional or more functional structure is connected, gelation proceeds, which causes insoluble matter and defects.

  As described above, inositol has the possibility of imparting favorable physical properties such as heat resistance to polymers, but there is a problem that it is difficult to use for the synthesis of polymers other than polyurethane. However, there has been a long-awaited appearance of an inositol derivative that can be applied without any problem.

Polymer 61 vol. April 204 (2012) Proceedings of the Society of Polymer Science 2013, 62, 396-398

  The object of the present invention is to provide a diol compound having excellent reactivity with other structural units when used as a structural unit of a polymer, heat resistance, transparency, light resistance, weather resistance, mechanical strength, etc. produced from the diol compound. An object of the present invention is to provide a polycarbonate resin, a polycarbonate polyol resin, a polyester resin, a polyester polyol resin, and a polyurethane resin that are excellent in the above-mentioned.

  By using a novel diol compound having a specific structure as a raw material monomer, the present inventors have good reactivity with other structural units, and excellent heat resistance, transparency, light resistance, weather resistance, mechanical properties The present inventors have found that a polycarbonate resin, a polycarbonate polyol resin, a polyester resin, a polyester polyol resin, and a polyurethane resin that have excellent mechanical strength can be obtained.

That is, the gist of the present invention is as follows.
[1] A diol compound represented by any one of the following general formulas (1) to (3).

[In Formulas (1) to (3), R ₁ and R ₂ each independently represent an alkylene group having 1 to 12 carbon atoms, an alkenylene group or an alkynylene group which may have a substituent. R < ₃ > -R < ₆ > shows the C1-C30 organic group which may have arbitrary substituents each independently. Further, any two or more of R _{3 to} R ₆ may be bonded to each other to form a ring. m and n are each independently an integer of 1 to 10. ]
[2] The diol compound according to [1], wherein R ₃ and R ₄ , R ₅ and R _{6 in the} above formulas (1) to (3) each form a ring with an acetal bond.
[3] The diol compound according to any one of [1] to [2], wherein R ₁ and R _{2 in the} above formulas (1) to (3) are ethylene groups.
[4] The diol compound according to [3], wherein m and n in the above formulas (1) to (3) are 1.
[5] The diol compound according to any one of [1] to [4], wherein the cyclohexane ring in the above formulas (1) to (3) is an inositol residue derived from myo-inositol.
[6] The diol compound according to [5], wherein R ₃ , R ₄ and R _{6 in the} above formula (2) form a ring with a methine group.
[7] A polycarbonate resin containing a structure represented by the following formula (4) in the molecule.

[X in the above formula (4) has a structure represented by any of the following formulas (5) to (7). In formulas (5) to (7), R ₁ and R ₂ each independently represent a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent. R ₃ to R ₆ each independently represent an organic group having 1 to 30 carbon atoms which may have an arbitrary substituent. Further, any two or more of R ₃ to R ₆ may be bonded to each other to form a ring. m and n are each independently an integer of 1 to 10. ]

[8] A polycarbonate polyol resin containing a structure represented by the following formula (13) in the molecule.

[X in the above formula (13) has a structure represented by any of the following formulas (5) to (7). In formulas (5) to (7), R ₁ and R ₂ each independently represent a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent. R ₃ to R ₆ each independently represent an organic group having 1 to 30 carbon atoms which may have an arbitrary substituent. Further, any two or more of R ₃ to R ₆ may be bonded to each other to form a ring. m and n are each independently an integer of 1 to 10. ]

[9] A polyester resin containing a structure represented by the following formula (14) in the molecule.

[X in the above formula (14) has a structure represented by any of the following formulas (5) to (7). In formulas (5) to (7), R ₁ and R ₂ each independently represent a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent. R ₃ to R ₆ each independently represent an organic group having 1 to 30 carbon atoms which may have an arbitrary substituent. Further, any two or more of R ₃ to R ₆ may be bonded to each other to form a ring. m and n are each independently an integer of 1 to 10. A in the above formula (9) is an optionally substituted alkylene group having 1 to 20 carbon atoms, an alkenylene group or an alkynylene group; an optionally substituted cyclohexane having 5 to 20 carbon atoms. An alkylene group, a cycloalkenylene group or a cycloalkynylene group: or an arylene group or heteroarylene group having 4 to 20 carbon atoms which may have a substituent. ]

[10] A polyester polyol resin containing a structure represented by the following formula (15) in the molecule.

[X in the above formula (15) has a structure represented by any of the following formulas (5) to (7). In formulas (5) to (7), R ₁ and R ₂ each independently represent a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent. R ₃ to R ₆ each independently represent an organic group having 1 to 30 carbon atoms which may have an arbitrary substituent. Further, any two or more of R ₃ to R ₆ may be bonded to each other to form a ring. m and n are each independently an integer of 1 to 10. A in the above formula (15) is an optionally substituted alkylene group, alkenylene group or alkynylene group having 1 to 20 carbon atoms; an optionally substituted cyclohexane having 5 to 20 carbon atoms. An alkylene group, a cycloalkenylene group or a cycloalkynylene group: or an arylene group or heteroarylene group having 4 to 20 carbon atoms which may have a substituent. ]


[11] A polyurethane resin containing a structure represented by the following formula (15) in the molecule.

[X in the above formula (16) has a structure represented by any of the following formulas (5) to (7). In formulas (5) to (7), R ₁ and R ₂ each independently represent a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent. R ₃ to R ₆ each independently represent an organic group having 1 to 30 carbon atoms which may have an arbitrary substituent. Further, any two or more of R ₃ to R ₆ may be bonded to each other to form a ring. m and n are each independently an integer of 1 to 10. A in the above formula (16) is an alkylene group having 1 to 20 carbon atoms, an alkenylene group or an alkynylene group which may have a substituent; a cyclohexane having 5 to 20 carbon atoms which may have a substituent. An alkylene group, a cycloalkenylene group or a cycloalkynylene group: or an arylene group or heteroarylene group having 4 to 20 carbon atoms which may have a substituent. ]

[12] The resin according to [7] to [10], wherein R ₃ and R ₄ , R ₅ and R _{6 in the} formulas (5) to (7) each form a ring with an acetal bond. .
[13] The resin according to any one of [7] to [11], wherein R ₁ and R _{2 in the} formulas (5) to (7) are ethylene groups. [14] The formulas (5) to (7 ), Wherein m and n are 1.
[15] The resin according to any one of [7] to [14], wherein the cyclohexane ring in the formulas (5) to (7) is an inositol residue derived from myo-inositol.
[16] The resin according to [15], wherein R ₃ , R ₄ and R ₆ in the formula (6) form a ring with a methine group.

  The novel diol compound of the present invention is excellent in reactivity with other structural units when used as a structural unit of a polymer. Also, a polycarbonate resin, a polycarbonate polyol resin produced using the diol compound as a raw material monomer, Polyester resin, polyester polyol resin and polyurethane resin are applied to molding materials in various molding fields such as injection molding field, extrusion molding field, compression molding field, etc., heat resistance, transparency, light resistance, weather resistance, mechanical strength It is possible to provide a molded article excellent in the above.

2 is a 1H-NMR spectrum of Example 4.

DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. It is not limited to the contents.
In the present invention, the carbon number of various substituents refers to the total carbon number including the carbon number of the substituent when the substituent further has a substituent.

[Diol compound]
The diol compound of the present invention is a diol compound represented by any one of the following general formulas (1) to (3).

[In Formulas (1) to (3), R ₁ and R ₂ each independently represent an alkylene group having 1 to 12 carbon atoms, an alkenylene group or an alkynylene group which may have a substituent. R < ₃ > -R < ₆ > shows the C1-C30 organic group which may have arbitrary substituents each independently. Further, any two or more of R _{3 to} R ₆ may be bonded to each other to form a ring. m and n are each independently an integer of 1 to 10. ]

In the above formulas (1) to (3), R ₁ and R ₂ are each independently a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent, preferably carbon. Number 2-8, More preferably, it is C2-C4, Most preferably, it is C2. When R ₁ and R ₂ have more than 12 carbon atoms, the mechanical strength of the polymer becomes too low when used as a polymer structural unit, such being undesirable. In the alkylene group, when the number of carbon atoms is 2, it becomes an ethylene group, which is particularly preferable from the viewpoint of easy synthesis of the diol compound.
Moreover, when these alkylene groups, alkenylene groups or alkynylene groups have a substituent, the diol compound of the present invention, and polycarbonate resins, polycarbonate polyol resins, polyester resins, and polyester polyols produced using the diol compounds as raw material monomers As long as the excellent physical properties of the resin and the polyurethane resin are not significantly impaired, the substituent is not particularly limited. In addition to the alkylene group having 1 to 12 carbon atoms, the alkenylene group and the alkynylene group, an alkoxy group Examples thereof include a hydroxy group, an amino group, a carboxyl group, an ester group, a halogen atom, a thiol group, a thioether group, and an organosilicon group. The alkylene group, alkenylene group or alkynylene group of R ₁ and R ₂ may have two or more of these substituents, and in this case, the two or more substituents may be the same or different. .

  In said formula (1)-(3), m and n are the integers of 1-10 each independently, Preferably it is 1-8, More preferably, it is 1-4, Most preferably, it is 2. If m and n exceed 10, the mechanical strength of the polymer becomes too low when used as a polymer structural unit, which is not preferable.

In the above formula _{(1) ~ (3),} R 3 ~R 6 is an organic group having 1 to 30 carbon atoms which may have a substituent. Examples of the organic group having 1 to 30 carbon atoms of R _{3 to} R ₆ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and Alkyl groups such as dodecyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; linear or branched chain alkenyl groups such as vinyl group, propenyl group and hexenyl group; cyclic alkenyl groups such as cyclopentenyl group and cyclohexenyl group : Alkynyl group such as ethynyl group, methylethynyl group and 1-propionyl group; aryl group such as phenyl group, naphthyl group and toluyl group; alkoxyphenyl group such as methoxyphenyl group: aralkyl group such as benzyl group and phenylethyl group: Examples include heterocyclic groups such as thienyl group, pyridyl group and furyl group. Among these, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group is preferable from the viewpoint of stability of the polymer itself, and an alkyl group or a cycloalkyl group is particularly preferable from the viewpoint of light resistance and weather resistance of the polymer itself.
In addition, when these organic groups have a substituent, the diol compound of the present invention and the polycarbonate resin, polycarbonate polyol resin, polyester resin, polyester polyol resin and polyurethane resin produced using the diol compound as a raw material monomer are excellent. The substituent is not particularly limited as long as it does not significantly impair the physical properties, but as the substituent, in addition to the organic group having 1 to 30 carbon atoms, an alkoxy group, a hydroxy group, an amino group, a carboxyl group, an ester group, A halogen atom, a thiol group, a thioether group, an organosilicon group and the like can be mentioned. The organic group of R _{1 to} R ₄ may have two or more of these substituents, and in this case, the two or more substituents may be the same or different.

In the above formulas (1) to (3), two or more, preferably two or three of R _{3 to} R ₆ may be bonded to each other to form a ring, and in particular, R ₃ and R _{3 5} , the diol compound of the present invention, and the polycarbonate resin, polycarbonate polyol resin, and polyester produced using the diol compound as a raw material monomer, that R ₄ and R ₆ each form a ring with an acetal bond. It is preferable from a viewpoint of the heat resistance improvement of resin, polyester polyol resin, and polyurethane resin.

Examples of the structure in which R ₃ and R ₅ , R ₄ and R ₆ form a ring by an acetal bond, preferably include those represented by the following structural formula, and among these, from the viewpoint of heat resistance Particularly preferred is a cyclohexylidene group.

In the above formula (2), when R ₃ , R ₄ and R ₆ form a ring with a methine group, the structure is similar to a thermodynamically stable adamantane. And from the viewpoint of improving the heat resistance of polycarbonate resins, polycarbonate polyol resins, polyester resins, polyester polyol resins and polyurethane resins produced using the diol compound as a raw material monomer.

  The cyclohexane ring in the above formulas (1) to (3) is preferably an inositol residue derived from inositol. Specific examples of the inositol include all-cis-inositol, epi-inositol, allo-inositol, muco-inositol, myo-inositol, neo-inositol, chiro-D-inositol, chiro-L-inositol, scyllo-inositol. However, from the viewpoint of easy availability of raw materials, myo-inositol is preferable, and the inositol residue is preferably an inositol residue derived from myo-inositol.

<Synthesis of diol compound>
The diol compound of the present invention can be synthesized using a secondary diol compound represented by the following formulas (1a) to (3a) as a raw material. In the following formulas, the structures of R _{3 to} R ₆ in (1a) to (3a), the mutual bonding relationship, and the cyclohexane ring are the same as those in the above formulas (1) to (3). Examples of the synthesis method include a method in which a raw material is reacted with an alkylene carbonate, alkenylene carbonate or alkynylene carbonate, alkylene oxide, alkenylene oxide or alkynylene oxide having 2 to 12 carbon atoms in the absence of a solvent or in the presence of a base catalyst. .

  The base catalyst is not particularly limited, but sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, sodium carbonate, carbonate Potassium, lithium carbonate, cesium carbonate, triethylamine, tributylamine, trioctylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylhexanediamine, tetramethylammonium hydroxy And potassium-t-butoxide, and one or more of them can be used in combination.

  The usage-amount of a catalyst is 0.01-5 equivalent normally with respect to the number-of-moles of a raw material, Preferably it is 0.01-0.5 equivalent. When the amount is less than 0.01 equivalent, the progress of the reaction may be slow, which is not preferable. When the amount is more than 5 equivalents, the production cost may increase, which is not preferable. Moreover, after completion | finish of reaction, a catalyst can be removed by neutralizing.

The alkylene carbonate having 2 to 12 carbon atoms is not particularly limited, and examples thereof include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, hexylene carbonate, heptylene carbonate, octylene carbonate, nonylene carbonate and decylene carbonate. Of these, one type or two or more types can be used in combination.
Examples of the alkenylene carbonate having 2 to 12 carbon atoms include, but are not limited to, ethenylene carbonate, propenylene carbonate, butenylene carbonate, pentenylene carbonate, hexenylene carbonate, heptenylene carbonate, octenylene carbonate, nonenylene carbonate, and desenylene carbonate. Of these, one type or two or more types can be used in combination.
Examples of the alkynylene carbonate having 2 to 12 carbon atoms include, but are not limited to, ethynylene carbonate, propynylene carbonate, butynylene carbonate, pentynylene carbonate, hexynylene carbonate, heptynylene carbonate, and octynylene carbonate, one of these Or two or more types can be used together.

The alkylene oxide having 2 to 12 carbon atoms is not particularly limited, but ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, heptylene oxide, octylene oxide, nonylene oxide, Silene oxide and the like can be mentioned, and one or more of these can be used in combination.
The alkenylene oxide having 2 to 12 carbon atoms is not particularly limited, but ethenylene oxide, propenylene oxide, butenylene oxide, pentenylene oxide, hexenylene oxide, heptenylene oxide, octenylene. Examples thereof include oxide, nonenylene oxide, and decenylene oxide, and one or more of these can be used in combination.
The alkynylene oxide having 2 to 12 carbon atoms is not particularly limited, but ethynylene oxide, propynylene oxide, butynylene oxide, pentynylene oxide, hexynylene oxide, heptynylene oxide, and octynylene oxide. Of these, one or more of these can be used in combination.

  The addition amount of alkylene carbonate, alkenylene carbonate, alkynylene carbonate, alkylene oxide, alkenylene oxide or alkynylene oxide is usually 2 to 10 equivalents, preferably 3 to 5 equivalents, relative to the number of moles of the raw material. When the amount is less than 2 equivalents, a compound in which m or n in the above formulas (1) to (3) is 0 may be generated, which is not preferable. When the amount is more than 10 equivalents, a compound in which m or n in the above formulas (1) to (3) exceeds 10 is not preferable. For alkylene carbonate, alkenylene carbonate or alkynylene carbonate or alkylene oxide, alkenylene oxide or alkynylene oxide, it is better to use alkylene carbonate, alkenylene carbonate or alkynylene carbonate from the viewpoint of material stability and safety during reaction. More preferred.

  The solvent is not particularly limited, but is preferably a raw material, alkylene carbonate, alkenylene carbonate, alkynylene carbonate, or alkylene oxide, alkenylene oxide, or alkynylene oxide having a high polarity from the viewpoint of solubility, water, methyl ethyl ketone, methyl Butyl ketone, acetone, cyclohexanone, tetrahydrofuran, methyl acetate, ethyl acetate, methanol, ethanol, butanol, isopropyl alcohol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, butanediol, acetonitrile, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl Glycol monobutyl ether, and diethylene glycol monomethyl ether. One or two or more of these can be used in combination. Further, when the above-mentioned alkylene carbonate, alkenylene carbonate or alkynylene carbonate or alkylene oxide, alkenylene oxide or alkynylene oxide has a melting point lower than the reaction temperature, they can be used as a solvent.

  The reaction temperature is usually 60 to 200 ° C, preferably 100 to 150 ° C. When the temperature is lower than 60 ° C., the reaction may not proceed, which is not preferable. When the temperature is higher than 200 ° C., a compound in which m or n in the above formulas (1) to (3) easily exceeds 10 is not preferable.

  The reaction time is usually 1 to 10 hours, preferably 2 to 5 hours. When the time is shorter than 1 hour, the reaction may not proceed sufficiently, which is not preferable. When the time is longer than 10 hours, a compound in which m or n in the above formulas (1) to (3) exceeds 10 is likely to be generated. .

The diol compound in which m and n in the diol compounds (1) to (3) of the present invention are 1 is synthesized by the following method using secondary diol compounds represented by the above formulas (1a) to (3a) as raw materials. be able to. The raw materials are deprotonated in a solvent and then reacted with a compound represented by the following formula (A) to synthesize the following formulas (1b) to (3b), and subsequently treat (1b) to (3b). Then, by removing Y, the diol compounds (1) to (3) can be obtained. In the following formulas, the structures of R ₁ and R ₂ in (1b) to (3b), the structures of R _{3 to} R ₆ and the mutual bond relationship, and the cyclohexane ring are the same as those in the above formulas (1) to (3). It is.

R ₈ in the compound represented by the above formula (A) is the same as R ₁ and R ₂ . Y is a protecting group for hydroxy group, and is not particularly limited. For example, methyl group, benzyl group, p-methoxybenzyl group, t-butyl group, methoxymethyl group, tetrahydropyranyl group, acetyl group, pivaloyl Group, benzoyl group, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group and the like. A is any one of a fluoro group, a chloro group, a bromo group, and an iodo group.

  The solvent is preferably an aprotic polar solvent and is not particularly limited, and examples thereof include methyl ether, ethyl ether, propyl ether, isopropyl ether, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide and the like.

  Although deprotonation is not particularly limited, it is preferable to use a proton abstracting agent such as sodium hydride, potassium hydride, or butyl lithium.

  As a method for removing Y, a known method for deprotecting a hydroxyl-protecting group can be used. In the methyl group, strong Lewis acid conditions such as boron tribromide are used, and in the benzyl group, palladium carbon is used. The p-methoxybenzyl group was subjected to hydrogenation reaction using palladium carbon and oxidation conditions by DDQ, and the t-butyl group was subjected to strong acidic conditions such as trifluoroacetic acid under methoxymethyl group and tetrahydropyrani group. The trimethylsilyl group, the triethylsilyl group and the t-silyl group are acidic under acidic conditions, acetyl group under potassium carbonate in methanol, pivaloyl machine under basic conditions stronger than acetyl group, and benzoyl group under strong base conditions. In the butyldimethylsilyl group, fluoride ions act It can be protected.

  The obtained diol compound can be purified by a known method, and the purification method is not particularly limited, and examples thereof include recrystallization, reprecipitation, column chromatography, and distillation. Two or more may be combined.

  The obtained diol compound can be identified by a known method, for example, by a gas chromatography method, an NMR method or the like.

[resin]
A polycarbonate resin, a polycarbonate polyol resin, a polyester resin, a polyester polyol resin, a polyurethane resin, and the like can be synthesized using the diol compound of the present invention as a raw material.
<Polycarbonate resin>
The polycarbonate resin of the present invention includes a structure represented by the following formula (4) in the molecule.

[X in the above formula (4) has a structure represented by any of the following formulas (5) to (7). In formulas (5) to (7), R ₁ and R ₂ each independently represent a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent. R ₃ to R ₆ each independently represent an organic group having 1 to 30 carbon atoms which may have an arbitrary substituent. Further, any two or more of R ₃ to R ₆ may be bonded to each other to form a ring. m and n are each independently an integer of 1 to 10. ]

  Hereinafter, the structure represented by formula (4) is referred to as “structure (4)”, and the structure represented by formula (4) in which X is a structure represented by formula (5) is referred to as “structure (4-5)”. The structure represented by Formula (4) in which X is a structure represented by Formula (6) is referred to as “Structure (4-6)”, and X is the structure represented by Formula (7) The structure represented by the formula (4) may be referred to as “structure (4-7)”.

The structure (4), preferably the structures (4-5) to (4-7), is itself introduced into the polycarbonate resin by a diol compound having excellent heat resistance as a raw material. By introducing into the polycarbonate resin, the heat resistance of the polycarbonate resin can be increased.
Further, the polycarbonate resin of the present invention can be excellent in light resistance and weather resistance as a structure not containing an aromatic ring structure as a main chain. Further, by introducing a ring having a specific aromaticity, unique optical properties can be imparted.

In the above formulas (5) to (7), R ₁ and R ₂ are each independently a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent, preferably carbon. Number 2-8, More preferably, it is C2-C4, Most preferably, it is C2. When R ₁ and R ₂ have more than 12 carbon atoms, the mechanical strength of the polymer becomes too low, which is not preferable.
Further, when these alkylene groups, alkenylene groups or alkynylene groups have a substituent, there is no particular limitation as long as the excellent physical properties of the polycarbonate resin of the present invention are not significantly impaired. In addition to the above alkylene groups 1 to 12, an alkoxy group, a hydroxy group, an amino group, a carboxyl group, an ester group, a halogen atom, a thiol group, a thioether group, an organosilicon group, and the like can be given. The alkylene group of R ₁ and R ₂ may have two or more of these substituents, and in this case, the two or more substituents may be the same or different.

  In the above formulas (5) to (7), m and n are each independently an integer of 1 to 10, preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. If m and n exceed 10, the mechanical strength of the polymer becomes too low, which is not preferable.

In said formula (5)-(7), R < ₃ > -R < ₆ > is a C1-C30 organic group which may have a substituent. Examples of the organic group having 1 to 30 carbon atoms of R _{3 to} R ₆ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and Alkyl groups such as dodecyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; linear or branched chain alkenyl groups such as vinyl group, propenyl group and hexenyl group; cyclic alkenyl groups such as cyclopentenyl group and cyclohexenyl group Alkynyl groups such as ethynyl group, methylethynyl group and 1-propionyl group; aryl groups such as phenyl group, naphthyl group and toluyl group; alkoxyphenyl groups such as methoxyphenyl group; aralkyl groups such as benzyl group and phenylethyl group; Examples include heterocyclic groups such as thienyl group, pyridyl group and furyl group. Among these, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group is preferable from the viewpoint of stability of the polymer itself, and an alkyl group or a cycloalkyl group is particularly preferable from the viewpoint of light resistance and weather resistance of the polymer itself.
Further, when these organic groups have a substituent, there is no particular limitation as long as the excellent physical properties of the polycarbonate resin of the present invention are not significantly impaired. In addition to the groups, alkoxy groups, hydroxy groups, amino groups, carboxyl groups, ester groups, halogen atoms, thiol groups, thioether groups, and organosilicon groups are exemplified. The organic group of R _{1 to} R ₄ may have two or more of these substituents, and in this case, the two or more substituents may be the same or different.

In the above formulas (5) to (7), R _{3 to} R ₆ may be two or more, preferably two or three of them may be bonded to each other to form a ring, and in particular, R ₃ and R _{3 5} , R ₄ and R ₆ are preferably acetal bonds with each other to form a ring from the viewpoint of improving the heat resistance of the polycarbonate resin.

Examples of the structure in which R ₃ and R ₅ , R ₄ and R ₆ form a ring by an acetal bond, preferably include those represented by the following structural formula, and among these, from the viewpoint of heat resistance Particularly preferred is a cyclohexylidene group.

In the above formula (6), when R ₃ , R _4, and R ₆ form a ring with a methine group, a structure similar to thermodynamically stable adamantane can be taken, so that the polycarbonate resin of the present invention It is preferable from the viewpoint of improving the heat resistance.

  The cyclohexane ring in the above formulas (5) to (7) is preferably an inositol residue derived from inositol. Specific examples of the inositol include all-cis-inositol, epi-inositol, allo-inositol, muco-inositol, myo-inositol, neo-inositol, chiro-D-inositol, chiro-L-inositol, scyllo-inositol. However, from the viewpoint of easy availability of raw materials, myo-inositol is preferable, and the inositol residue is preferably an inositol residue derived from myo-inositol.

  The polycarbonate resin of the present invention preferably contains 80 or less of the above structure (4), preferably the above structures (4-5) to (4-7) as repeating units when the total number of carbonate repeating units is 100. When this ratio is 80 or less, other repeating units can be introduced, and other characteristics such as optical characteristics can be introduced. From this viewpoint, the ratio of the structure (4), preferably the structures (4-5) to (4-7) is more preferably 70 or less, and preferably 60 or less. On the other hand, in order to effectively obtain the above-described effects by introducing the structure (4), the ratio of the structure (4), preferably the structures (4-5) to (4-7) is 1 or more. Preferably, it is 5 or more, more preferably 10 or more.

    The polycarbonate resin of the present invention may contain structural units derived from other diol compounds other than the structures (5) to (7) derived from the compounds (1) to (3).

  For example, the polycarbonate resin of the present invention may contain one or more structural units derived from an aliphatic diol compound and / or an alicyclic diol compound. This is preferable from the viewpoint that other characteristics such as optical characteristics can be introduced.

Examples of the aliphatic diol compound include a linear aliphatic diol compound and a branched aliphatic diol compound.
Examples of the linear aliphatic diol compound include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1 , 5-heptanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, and the like.
Examples of the branched aliphatic hydrocarbon diol compound include neopentyl glycol (hereinafter sometimes referred to as “NPG”) and hexylene glycol.

  Examples of the alicyclic diol compound include 1,2-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, and pentacyclopentadecane. Dimethanol, 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantane dimethanol And diol compounds derived from terpene compounds such as limonene.

  Among these diol compounds, an aliphatic diol compound having a primary hydroxyl group such as ethylene glycol, 1,3-propanediol, 1, from the viewpoint of imparting flexibility to the obtained polycarbonate resin and having excellent toughness. Alicyclic diol compounds having a primary hydroxyl group such as 4-butanediol, 1,6-hexanediol, 1,10-decanediol and 1,12-dodecanediol, such as 1,4-cyclohexanedimethanol and tricyclode Kandimethanol and the like are preferable.

  The polycarbonate resin of the present invention contains a structural unit derived from an aliphatic diol compound and / or an alicyclic diol compound, particularly a structural unit derived from an aliphatic diol compound having a primary hydroxyl group and / or an alicyclic diol compound. In this case, the content is preferably 0.1% by mass or more, more preferably 1% by mass or more from the viewpoint of imparting flexibility to the obtained polycarbonate resin and having excellent toughness. It is further preferably 3% by mass or more, preferably 20% by mass or less, more preferably 16% by mass or less, and further preferably 10% by mass or less.

  Further, the polycarbonate resin of the present invention may contain a structural unit derived from isosorbide. Isosorbide is abundant as a plant-derived resource, and is obtained by dehydrating condensation of sorbitol produced from various readily available starches. Ease of availability and production, weather resistance, optical properties, moldability From the viewpoint of heat resistance and carbon neutral, it is preferable as a structural unit of polycarbonate resin.

  When the polycarbonate resin of the present invention contains a structural unit derived from isosorbide, the content is preferably 5% by mass or more from the viewpoint of optical properties, mechanical properties, heat resistance, etc. More preferably, it is more preferably 20% by mass or more, more preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 65% by mass or less.

  The polycarbonate resin of the present invention also contains one or more structural units derived from a compound represented by the following formula (8) (hereinafter sometimes referred to as “diol compound (8)”). It is possible to provide excellent optical properties by including a structural unit derived from the diol compound (8).

(In the general formula (8), R ^{11 to} R ¹⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein Y ¹ and Y ² are each independently a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, or a substituted or unsubstituted carbon number. Represents a 6-20 cycloalkylene group or a substituted or unsubstituted arylene group having 6-20 carbon atoms, and m and n are each independently an integer of 0-5.)

  As said diol compound (8), the diol compound of Unexamined-Japanese-Patent No. 2012-214729 is mentioned.

  In the case where the polycarbonate resin of the present invention contains a structural unit derived from the diol compound (8), the content is a viewpoint that makes the wavelength dispersion characteristic preferable when the polycarbonate resin of the present invention is used as an optical film. Therefore, it is preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, particularly preferably 55% by mass or more, and particularly preferably 60% by mass or more. When the content ratio of the structural unit is excessively small, the wavelength dispersion characteristic when using the polycarbonate resin of the present invention as an optical film may not be preferable. Moreover, when the content ratio of the structural unit is excessively large, the ratio of the phase difference measured at a wavelength of 450 nm and the phase difference measured at a wavelength of 550 nm when the polycarbonate resin of the present invention is used as an optical film is excessively large. In some cases, the optical properties may not be preferable due to the increase in size. Therefore, it is preferably 95% by mass or less, particularly 90% by mass or less, particularly 85% by mass or less, and particularly preferably 80% by mass or less.

  The polycarbonate resin of the present invention also contains one or more structural units derived from a compound represented by the following formula (9) (hereinafter sometimes referred to as “diol compound (9)”). In addition, by containing a structural unit derived from the diol compound (9), the glass transition temperature is controlled within a suitable range, and there is a possibility of facilitating melt molding or film formation of the resulting polycarbonate resin. Instead, it is possible to obtain predetermined optical characteristics.

  As said diol compound (9), the diol compound of Unexamined-Japanese-Patent No. 2012-74107 is mentioned.

  When the polycarbonate resin of the present invention contains a structural unit derived from the diol compound (9), the content thereof controls the glass transition temperature within a suitable range, and melt molding and film formation of the resulting polycarbonate resin are easy. In addition to the possibility of obtaining predetermined optical characteristics, the structural unit derived from all diol compounds in the polycarbonate resin needs to be 50 mol% or more, preferably Is 55 mol% or more, more preferably 60 mol% or more, and particularly preferably 65 mol% or more. If the content of the structural unit derived from the diol compound (9) is small, the glass transition temperature becomes excessively high, and it becomes difficult to melt-mold and form a film of the obtained polycarbonate resin, or to filter later. In addition, there is a possibility that predetermined optical characteristics cannot be obtained. On the other hand, if the content of the structural unit derived from the diol compound (9) is too large, not only the predetermined optical characteristics may not be obtained but also heat resistance may be deteriorated. Is 80 mol% or less, more preferably 75 mol% or less.

  The polycarbonate resin of the present invention also has a structure represented by the following formula (10) (hereinafter sometimes referred to as “structure (10)”) and / or a structure represented by the following formula (11) (hereinafter “structure”). (11) "may be included. By containing these structures, reverse wavelength dispersion can be obtained. However, if the ratio including these structures (11) and (12) is excessively high, the photoelastic coefficient and reliability may be deteriorated, or high birefringence may not be obtained by stretching. In addition, if the proportion of these oligofluorene structural units in the resin becomes excessively high, the molecular design range becomes narrow, and it becomes difficult to improve when modification of the resin is required. On the other hand, even if the desired reverse wavelength dispersion is obtained with a very small amount of oligofluorene structural unit, in this case, the optical characteristics change sensitively according to slight variations in the content of oligofluorene. For this reason, it becomes difficult to manufacture the various characteristics within a certain range.

(In formulas (10) and (11), R ^{31 to} R ³³ are each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent, and R ^{34 to} R ^39. Each independently has a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, and a substituent. An optionally substituted acyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 4 to 10 carbon atoms, An amino group which may have a substituent, an alkenyl group having 2 to 10 carbon atoms which may have a substituent, an alkynyl group having 2 to 10 carbon atoms which may have a substituent, and a substituent; A sulfur atom having a substituent, a silicon atom having a substituent, a halogen atom, a nitro group, or An anode group. However, may form a ring adjacent the at least two groups are bonded to each other among the R ³⁴ to R ^39.)

  Examples of the diol compound and dicarboxylic acid compound, which are raw materials for introducing the structure (10) and the structure (11) into the polycarbonate resin, include those described in International Publication WO 2014/61677.

When the polycarbonate resin of the present invention contains the structure (10) and / or the structure (11), when the polycarbonate resin of the present invention is used for optical applications, the range of molecular design is expanded. From the viewpoint of increasing the degree of freedom in improving the characteristics, the content is preferably 1% by mass or more and 40% by mass or less, more preferably 10% by mass or more and 35% by mass or less, and more preferably 15% by mass or more and 32% by mass. % Or less is more preferable, and 20% by mass or more and 30% by mass or less is particularly preferable.
(Manufacture of polycarbonate resin)
The polycarbonate resin of the present invention can be produced by a generally used polymerization method, and the polymerization method may be either a solution polymerization method using phosgene or a melt polymerization method in which it reacts with a carbonic acid diester. In the presence of, a melt polymerization method in which a diol compound as a raw material is reacted with a carbonic diester having lower toxicity to the environment is preferable.

  Examples of the carbonic acid diester used in the melt polymerization method include those represented by the following formula (12).

(In Formula (12), A and A ′ are an optionally substituted aliphatic group having 1 to 18 carbon atoms or an optionally substituted aromatic group, and A and A 'May be the same or different.)

  Examples of the carbonic acid diester represented by the above formula (12) include diphenyl carbonate, substituted diphenyl carbonate typified by ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Includes diphenyl carbonate and substituted diphenyl carbonate. These carbonic acid diesters may be used alone or in combination of two or more.

  Moreover, said carbonic acid diester may substitute the quantity of the 50 mol% or less preferably 30 mol% or less with dicarboxylic acid or dicarboxylic acid ester preferably. Examples of typical dicarboxylic acid or dicarboxylic acid ester include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. Moreover, a dicarboxylic acid compound can also be used as a raw material for introducing the structure (12). When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate resin is obtained.

  The carbonic acid diester is preferably used in a molar ratio of 0.90 to 1.10, more preferably in a molar ratio of 0.96 to 1.04, with respect to all diol compounds used in the reaction. When this molar ratio is less than 0.90, the terminal OH group of the produced polycarbonate resin is increased, and the thermal stability of the polymer is deteriorated or a desired high molecular weight product cannot be obtained. Moreover, when the molar ratio is larger than 1.10, the rate of the transesterification reaction is decreased under the same conditions, and it is difficult to produce a polycarbonate resin having a desired molecular weight. The amount of residual carbonic acid diester increases, and this residual carbonic acid diester causes undesirable odor during molding or in the molded product.

  As a diol compound used as a raw material, a diol compound for introducing the above structure (1), an aliphatic diol compound, an alicyclic diol compound, isosorbide, a diol compound (8), a diol compound (9), a structure ( A diol compound such as a diol compound for introducing 10) is used so as to have a proportion as described above as a suitable proportion of the structural unit derived from each diol compound constituting the polycarbonate resin of the present invention.

  In addition, as a polymerization catalyst (transesterification catalyst) in melt polymerization, an alkali metal compound and / or an alkaline earth metal compound is used. A basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound can be used in combination with an alkali metal compound and / or an alkaline earth metal compound. It is particularly preferred to use only metal compounds and / or alkaline earth metal compounds.

  Examples of the alkali metal compound used as the polymerization catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate. , Lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, Cesium borohydride, sodium phenyl borohydride, potassium phenyl borohydride, lithium phenyl borohydride, cesium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, benzoic acid Cium, 2 sodium hydrogen phosphate, 2 potassium hydrogen phosphate, 2 lithium hydrogen phosphate, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium phenyl phosphate, Sodium, potassium, lithium, cesium alcoholate, phenolate, disodium salt of bisphenol A, 2 potassium salt, 2 lithium salt, 2 cesium salt and the like.

  Examples of the alkaline earth metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, Examples thereof include magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate.

  These alkali metal compounds and / or alkaline earth metal compounds may be used alone or in combination of two or more.

  Specific examples of basic boron compounds used in combination with alkali metal compounds and / or alkaline earth metal compounds include tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethyl Sodium salt such as phenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl boron, tributylphenyl boron, tetraphenyl boron, benzyltriphenyl boron, methyltriphenyl boron, butyltriphenyl boron, potassium salt, lithium Examples thereof include salts, calcium salts, barium salts, magnesium salts, and strontium salts.

  Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.

  Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide Sid and butyl triphenyl ammonium hydroxide, and the like.

  Examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline, etc. are mentioned.

  These basic compounds may also be used individually by 1 type, and may use 2 or more types together.

When using an alkali metal compound and / or an alkaline earth metal compound, the amount of the polymerization catalyst used is usually within a range of 0.1 to 100 μmol as a metal conversion amount with respect to 1 mol of all diol compounds used in the reaction. Used, preferably in the range of 0.5-50 μmol, more preferably in the range of 1-25 μmol. If the amount of the polymerization catalyst used is too small, the polymerization activity necessary to produce a polycarbonate resin having a desired molecular weight cannot be obtained. On the other hand, if the amount of the polymerization catalyst used is too large, the hue of the resulting polycarbonate resin deteriorates. However, by-products are generated and fluidity is lowered and gel is generated more frequently, making it difficult to produce a polycarbonate resin having a target quality.
The amount of catalyst remaining in the polycarbonate resin obtained after polymerization is not particularly limited, but is preferably 100 ppm or less, more preferably 50 ppm or less, still more preferably 30 ppm or less, particularly preferably 20 ppm or less, as the content in terms of catalyst metal. Most preferably, it is 10 ppm or less.

In the production of the polycarbonate resin of the present invention, various diol compounds used as raw materials may be supplied as solids, heated and supplied in a molten state, or as long as they are soluble in water. You may supply as aqueous solution.
When the diol compound is supplied in a molten state or in an aqueous solution, there is an advantage that it is easy to measure and transport in industrial production.

  In the present invention, the method of reacting a diol compound used as a raw material with a carbonic acid diester in the presence of a polymerization catalyst is usually carried out in a multistage process of two or more stages. Specifically, the first stage reaction is carried out at a temperature of 140 to 220 ° C., preferably 150 to 200 ° C. for 0.1 to 10 hours, preferably 0.5 to 3 hours. From the second stage onward, the reaction temperature is raised while gradually reducing the pressure of the reaction system from the pressure of the first stage, and at the same time, the phenol generated at the same time is removed from the reaction system. Is 200 Pa or less and a polycondensation reaction is performed under the temperature range of 210-280 degreeC.

  In the pressure reduction in this polycondensation reaction, it is important to control the balance between temperature and pressure in the reaction system. In particular, if either one of the temperature and the pressure is changed too quickly, unreacted monomers are distilled out, the molar ratio of the diol compound and the carbonic acid diester may be changed, and the degree of polymerization may be lowered. For example, in addition to myo-inositol as the diol compound, when isosorbide and 1,4-cyclohexanedimethanol are used, when the molar ratio of 1,4-cyclohexanedimethanol is 50 mol% or more with respect to the total diol compound, Since 1,4-cyclohexanedimethanol is easily distilled out as a monomer, the reaction is performed while the temperature in the reaction system is increased at a rate of temperature increase of 40 ° C. or less per hour under a reduced pressure of about 13 kPa. , Under a pressure up to about 6.67 kPa, the temperature is increased at a heating rate of 40 ° C. or less per hour, and finally a polycondensation reaction is performed at a pressure of 200 Pa or less and a temperature of 200 to 250 ° C., This is preferable because a polycarbonate resin having a sufficiently increased degree of polymerization can be obtained.

  In addition, when the molar ratio of 1,4-cyclohexanedimethanol is less than 50 mol% with respect to all diol compounds, particularly when the molar ratio is 30 mol% or less, the mol of 1,4-cyclohexanedimethanol Compared with the case where the ratio is 50 mol% or more, the viscosity rises rapidly. For example, until the pressure in the reaction system is about 13 kPa, the temperature is increased at a rate of temperature increase of 40 ° C. or less per hour. The reaction is further carried out at a pressure of up to about 6.67 kPa while the temperature is increased at a rate of temperature increase of 40 ° C. or more per hour, preferably 50 ° C. or more per hour. When a polycondensation reaction is performed at a temperature of 220 to 290 ° C. under a reduced pressure of 200 Pa or less, a polycarbonate resin having a sufficiently increased degree of polymerization can be obtained. Preferred.

  The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type.

  When the polycarbonate resin of the present invention is produced by a melt polymerization method, a phosphoric acid compound, a phosphorous acid compound or a metal salt thereof can be added during polymerization for the purpose of preventing coloring.

  As the phosphoric acid compound, one or more of trialkyl phosphates such as trimethyl phosphate and triethyl phosphate are preferably used. These are preferably added in an amount of 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less, based on all diol compounds used in the reaction. If the addition amount of the phosphorus compound is less than the above lower limit, the coloring prevention effect is small, and if it is more than the above upper limit, haze may be increased, or conversely, coloring may be promoted or heat resistance may be reduced. is there.

  When adding a phosphorous acid compound, the heat stabilizer shown below can be selected arbitrarily and used. In particular, trimethyl phosphite, triethyl phosphite, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) One or more of pentaerythritol diphosphites can be suitably used. These phosphorous acid compounds are preferably added in an amount of 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less, based on all diol compounds used in the reaction. Is preferred. If the amount of the phosphite compound is less than the above lower limit, the effect of preventing coloring is small, and if it is more than the above upper limit, it may cause haze to increase, or conversely promote coloring or reduce heat resistance. Sometimes.

  The phosphoric acid compound and the phosphorous acid compound or their metal salts can be added in combination. In this case, the addition amount is the total amount of the phosphoric acid compound and the phosphorous acid compound or their metal salts, as described above. Thus, it is preferably 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less, based on the total diol compound. If the amount added is less than the above lower limit, the effect of preventing coloring is small, and if it is more than the above upper limit, haze may be increased, or conversely, coloring may be promoted or heat resistance may be lowered.

In addition, as a metal salt of a phosphoric acid compound and a phosphite compound, these alkali metal salts and zinc salts are preferable, and zinc salts are particularly preferable. Among these zinc phosphate salts, long-chain alkyl zinc phosphate salts are preferable.
In the present invention, purification is carried out for the purpose of removing diol compounds, carbonate compounds, by-product low-boiling cyclic carbonates, alcohols by-produced from carbonate compounds, phenols and added catalysts in the polycarbonate resin product. May be.

(Physical properties of polycarbonate resin, etc.)
The glass transition temperature measured as the midpoint glass transition start temperature Tmg of the polycarbonate resin of the present invention is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, and preferably 110 ° C. or higher.
If the glass transition temperature is too low, the heat resistance is inferior, and therefore the reliability of various molded products may be inferior. On the other hand, if the glass transition temperature is high, the polycarbonate resin may deteriorate due to shear heat generation during extrusion, or the melt viscosity when filtering with a filter becomes too high, which may cause deterioration of the polycarbonate resin. The midpoint glass transition start temperature Tmg is preferably 230 ° C. or lower, more preferably 200 ° C. or lower, and particularly preferably 175 ° C. or lower.
In addition, the glass transition temperature of polycarbonate resin is measured by the method described in the item of the below-mentioned Example.

The number average molecular weight of the polycarbonate resin of the present invention is usually about 1 to 200,000. The number average molecular weight can be determined by nuclear magnetic resonance (NMR).
The weight average molecular weight / number average molecular weight (Mw / Mn) is not particularly limited, but the lower limit is preferably 1.5, more preferably 1.8. The upper limit is preferably 3.5, more preferably 3.0.
In addition, the polymerization degree (molecular weight) of polycarbonate resin can also be represented by reduced viscosity. The degree of polymerization (molecular weight) of the polycarbonate resin of the present invention is such that a mixed solvent of phenol and 1,1,2,2, -tetrachloroethane in a weight ratio of 1: 1 is used as the solvent, and the polycarbonate resin concentration is 1.00 g / dl. It can be measured as a reduced viscosity (hereinafter sometimes simply referred to as “reduced viscosity”) that is precisely adjusted and measured at a temperature of 30.0 ° C. ± 0.1 ° C. If the reduced viscosity of the resin is too low, the mechanical strength of the resulting molded product may be reduced. Therefore, the reduced viscosity is usually 0.20 dl / g or more, and preferably 0.30 dl / g or more. On the other hand, if the reduced viscosity of the resin is too high, the fluidity during molding tends to decrease, and the productivity and moldability tend to decrease, and the resulting molded product tends to become more distorted. Therefore, the reduced viscosity is usually 1.50 dl / g or less, preferably 1.20 dl / g or less, more preferably 1.01 dl / g or less, and 0.90 dl / g or less. Is more preferable.
More specifically, the reduced viscosity of the polycarbonate resin is measured by the method described in the Examples section below.

The 5% thermal weight loss temperature of the polycarbonate resin of the present invention is preferably 300 ° C. or higher, particularly preferably 320 ° C. or higher. The higher the 5% thermal weight loss temperature, the higher the thermal stability and withstand use at higher temperatures. In addition, the manufacturing temperature can be increased, and the control range at the time of manufacturing can be widened. On the other hand, the lower the 5% thermal weight loss temperature, the lower the thermal stability, making it difficult to use at high temperatures. Moreover, the control allowable width at the time of manufacture becomes narrow and it becomes difficult to manufacture. Although there is no restriction | limiting in particular in the upper limit of 5% thermogravimetric reduction temperature, Usually, it is 370 degrees C or less.
The 5% thermal weight loss temperature of the polycarbonate resin is measured by the method described in the Examples section below.

The Abbe number of the polycarbonate resin of the present invention is preferably 30 or more, particularly preferably 35 or more, when used as a convex lens for a single lens. As the Abbe number increases, the chromatic dispersion of the refractive index decreases. For example, chromatic aberration when used with a single lens decreases, and a clearer image can be easily obtained. As the Abbe number decreases, the chromatic dispersion of the refractive index increases, and when used with a single lens, chromatic aberration increases and the degree of image blur increases. The upper limit of the Abbe number is not particularly limited, but is usually 70 or less. On the other hand, when it is used for a concave lens and an achromatic lens, the Abbe number is preferably smaller, less than 30, preferably less than 28, particularly preferably less than 26.
In general, the polycarbonate resin of the present invention is preferably a polycarbonate resin with little coloring. The upper limit of the YI value of the polycarbonate resin of the present invention is usually preferably 20, more preferably 10, still more preferably 5, particularly preferably 3, while the lower limit is not particularly limited. Usually, it is preferably -20, more preferably -5, still more preferably -1.
A polycarbonate resin having a YI value of 20 or less has an advantage that the intended use of films and sheets is not limited. On the other hand, a polycarbonate resin having a YI value of −20 or more is economically advantageous because the manufacturing process for producing the polycarbonate resin does not become complicated, and an extremely expensive capital investment is not required.
(Polycarbonate resin composition)
The polycarbonate resin of the present invention can be blended with a heat stabilizer in order to prevent a decrease in molecular weight or a deterioration in hue during molding or the like.

  Examples of the heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2 , 4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl Phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-) tert- Tilphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, Trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), dimethylbenzenephosphonate, Examples include diethyl benzenephosphonate and dipropyl benzenephosphonate. Among them, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and dimethyl benzenephosphonate are preferably used.

  These heat stabilizers may be used alone or in combination of two or more.

  Such a heat stabilizer can be further added in addition to the addition amount added at the time of melt polymerization. That is, after blending an appropriate amount of a phosphorous acid compound and a phosphoric acid compound to obtain a polycarbonate resin, further blending a phosphorous acid compound by a blending method described later, an increase in haze during polymerization, coloring, In addition, more heat stabilizers can be blended while avoiding a decrease in heat resistance, and hue deterioration can be prevented.

  The blending amount of these heat stabilizers is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, and 0.001 to 0.2, based on 100 parts by weight of the polycarbonate resin. Part by mass is more preferable.

  In addition, the polycarbonate resin of the present invention can be blended with an antioxidant generally known for the purpose of antioxidant.

  Examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 3,5-trimethyl-2,4 -Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5 -Di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4'-biphenylenediphosphinic acid tetrakis (2,4 -Di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2, One type or two or more types such as 4,8,10-tetraoxaspiro (5,5) undecane may be mentioned.

  The blending amount of these antioxidants is preferably 0.0001 to 0.5 parts by mass when the polycarbonate is 100 parts by mass.

  In addition, a release agent can be blended with the polycarbonate resin of the present invention within a range that does not impair the object of the present invention in order to further improve the releasability from the mold during melt molding.

  Such release agents include higher fatty acid esters of monohydric or polyhydric alcohols, higher fatty acids, paraffin wax, beeswax, olefin waxes, olefin waxes containing carboxy groups and / or carboxylic anhydride groups, silicone oils, Examples include organopolysiloxane.

  The higher fatty acid ester is preferably a partial ester or a total ester of a monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Such partial esters or total esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbite, stearyl stearate, behenic acid monoglyceride, behenyl behenate, Pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate Sorbitan monostearate, 2-ethylhexyl stearate and the like.

  Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferably used.

  As the higher fatty acid, a saturated fatty acid having 10 to 30 carbon atoms is preferable. Such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like.

  One of these release agents may be used alone, or two or more thereof may be mixed and used.

  The amount of the release agent is preferably 0.01 to 5 parts by mass when polycarbonate is 100 parts by mass.

  In addition, a light stabilizer can be blended with the polycarbonate resin of the present invention as long as the object of the present invention is not impaired.

  Examples of such a light stabilizer include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole and 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzo. Triazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′- And methylenebis (4-cumyl-6-benzotriazolephenyl) and 2,2′-p-phenylenebis (1,3-benzoxazin-4-one).

  These light stabilizers may be used alone or in combination of two or more.

  The blending amount of the light stabilizer is preferably 0.01 to 2 parts by mass when the polycarbonate resin is 100 parts by mass.

  Further, the polycarbonate resin of the present invention can be blended with a bluing agent in order to counteract the yellowness of the lens based on the polymer or the ultraviolet absorber. Any bluing agent can be used without any problem as long as it is used for polycarbonate resins and polycarbonate resins. In general, anthraquinone dyes are preferred because they are readily available.

  Specific examples of the bluing agent include the general name Solvent Violet 13 [CA. No (color index No) 60725], generic name Solvent Violet 31 [CA. No 68210, generic name Solvent Violet 33 [CA. No 60725; generic name Solvent Blue 94 [CA. No 61500], generic name Solvent Violet 36 [CA. No. 68210], common name Solvent Blue 97 [manufactured by Bayer "Macrolex Violet RR"] and general name Solvent Blue 45 [CA. No. 61110] is given as a representative example.

  These bluing agents may be used individually by 1 type, and may use 2 or more types together.

These blueing agents are usually blended at a ratio of 0.1 × 10 ⁻⁴ to 2 × 10 ⁻⁴ parts by mass when the polycarbonate resin is taken as 100 parts by mass.

In addition, you may mix | blend additives, such as a nucleating agent, a flame retardant, a flame retardant adjuvant, an inorganic filler, an impact modifier, a hydrolysis inhibitor, a foaming agent, and a dye / pigment which are normally used for a resin composition.
Further, the polycarbonate resin of the present invention includes, for example, aromatic polycarbonate resin, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, ABS, AS, and other synthetic resins, polylactic acid, polybutylene succinate. It can also be used as a polymer alloy by kneading with one or more of biodegradable resins such as rubber and rubber.

  As a mixing method of the polycarbonate resin of the present invention and various additives as described above, for example, a method of mixing with a tumbler, V-type blender, super mixer, nauter mixer, Banbury mixer, kneading roll, extruder, etc., Alternatively, there is a solution blend method in which the above components are mixed in a common good solvent such as methylene chloride. However, this is not particularly limited, and any polymer blend method that is usually used can be used. Such a method may be used.

  The polycarbonate resin of the present invention thus obtained or a polycarbonate resin composition obtained by adding various additives to the polycarbonate resin as it is or after being once pelletized with a melt extruder, is then subjected to an injection molding method, an extrusion molding method or a compression molding method. The molded article can be formed by a generally known method such as a method.

  In order to increase the miscibility of the polycarbonate resin of the present invention and obtain stable release properties and physical properties, it is preferable to use a single screw extruder or a twin screw extruder in melt extrusion. A method using a single screw extruder or a twin screw extruder does not use a solvent or the like, has a small environmental load, and can be preferably used from the viewpoint of productivity.

  The melt kneading temperature of the extruder depends on the glass transition temperature of the polycarbonate resin of the present invention. When the glass transition temperature of the polycarbonate resin of the present invention is lower than 90 ° C, the melt kneading temperature of the extruder is usually 130 to 250. ° C, preferably 150-240 ° C. When the melt kneading temperature is lower than 130 ° C., the melt viscosity of the polycarbonate resin is high, the load on the extruder is increased, and the productivity is lowered. When it is higher than 250 ° C., the melt viscosity of the polycarbonate resin becomes low, it becomes difficult to obtain pellets, and the productivity is lowered.

  Moreover, when the glass transition temperature of the polycarbonate resin of this invention is 90 degreeC or more, the melt kneading | mixing temperature of an extruder is 200-300 degreeC normally, Preferably it is 220-260 degreeC. When the melt kneading temperature is lower than 200 ° C., the melt viscosity of the polycarbonate resin is high, the load on the extruder is increased, and the productivity is lowered. When the temperature is higher than 300 ° C., the polycarbonate resin is likely to be deteriorated, the color of the polycarbonate resin is yellowed, and the strength is deteriorated because the molecular weight is reduced.

  When an extruder is used, it is desirable to install a filter in order to prevent the polycarbonate resin from being burned and foreign matters from being mixed during extrusion. The size (aperture) of removing foreign matters from the filter depends on the required optical accuracy, but is preferably 100 μm or less. In particular, in the case of dislike mixing foreign substances, it is preferably 40 μm or less, more preferably 10 μm or less.

  The extrusion of the polycarbonate resin is desirably performed in a clean room in order to prevent foreign matter from being mixed after the extrusion.

  Moreover, when cooling the extruded polycarbonate resin into chips, it is preferable to use a cooling method such as air cooling or water cooling. As the air used for air cooling, it is desirable to use air from which foreign substances in the air have been removed in advance with a hepa filter or the like to prevent reattachment of foreign substances in the air. When water cooling is used, it is desirable to use water from which metal in water has been removed with an ion exchange resin or the like, and foreign matter in water has been removed with a filter. There are various filter sizes (openings), but a filter of 10 to 0.45 μm is preferable.

(Use of polycarbonate resin)
Since the polycarbonate resin of the present invention is excellent in heat resistance, transparency, light resistance, weather resistance, and mechanical strength, it is industrially useful as a molding material applied in various injection molding fields, extrusion molding fields, compression molding fields, etc. It is.

  Furthermore, the polycarbonate resin of the present invention can be used as a polyester elastomer. The polyester elastomer is a copolymer composed of a hard segment mainly composed of aromatic polyester and a soft segment mainly composed of aliphatic polyether, aliphatic polyester or aliphatic polycarbonate. In such a polyester elastomer, when the polycarbonate resin of the present invention is used as a constituent component of the soft segment, physical properties such as heat resistance and water resistance are excellent as compared with the case where an aliphatic polyether or aliphatic polyester is used. Compared to known polycarbonate resins, it is a polycarbonate ester elastomer with melt flowability, that is, a melt flow rate suitable for blow molding and extrusion molding, and excellent balance with mechanical strength and other physical properties. It can be suitably used for various molding materials including fibers, films and sheets, for example, molding materials such as elastic yarns and boots, gears, tubes and packings. Specifically, it can be effectively applied to applications such as joint boots such as automobiles and home appliance parts that require heat resistance and durability, and wire covering materials.

<Polycarbonate polyol resin>
The polycarbonate polyol resin of the present invention contains a structure represented by the following formula (13) in the molecule and has a number average molecular weight of 250 or more and less than 10,000, preferably 300 or more and 5500 or less. A polycarbonate diol resin is preferred as the polycarbonate polyol resin.
The polycarbonate polyol resin of the present invention is excellent in thermal stability by containing at least the structural units derived from the diol compounds of the above formulas (1) to (3), that is, the structures of the following formulas (5) to (7). A polycarbonate polyol resin can be obtained.

[X in the above formula (13) has a structure represented by any of the following formulas (5) to (7). In formulas (5) to (7), R ₁ and R ₂ each independently represent a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent. R ₃ to R ₆ each independently represent an organic group having 1 to 30 carbon atoms which may have an arbitrary substituent. Further, any two or more of R ₃ to R ₆ may be bonded to each other to form a ring. m and n are each independently an integer of 1 to 10. ]

  Hereinafter, the structure represented by the formula (13) is referred to as “structure (13)”, and the structure represented by the formula (13) in which X is a structure represented by the formula (5) is referred to as “structure (13-5)”. The structure represented by formula (13), wherein X is a structure represented by formula (6), is referred to as “structure (13-6)”, and X is represented by formula (7). The structure represented by the formula (13) may be referred to as “structure (13-7)”.

The structure (13), preferably the structures (13-5) to (13-7), is itself introduced into the polycarbonate polyol resin by a diol compound having excellent heat resistance used as a raw material. By introducing the structure into the polycarbonate polyol resin, the heat resistance of the polycarbonate polyol resin can be increased.
In addition, the polycarbonate polyol resin of the present invention can be excellent in light resistance and weather resistance as a structure not containing an aromatic ring structure as a main chain. Further, by introducing a ring having a specific aromaticity, unique optical properties can be imparted.

In the above formulas (5) to (7), R ₁ and R ₂ are each independently a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent, preferably carbon. Formula 2-8, More preferably, it is 2-4, Most preferably, it is 2. When R ₁ and R ₂ have more than 12 carbon atoms, the mechanical strength of the polymer becomes too low, which is not preferable.
Further, when these alkylene groups, alkenylene groups or alkynylene groups have a substituent, there is no particular limitation as long as the excellent physical properties of the polycarbonate polyol resin of the present invention are not significantly impaired. In addition to the alkylene group, alkenylene group or alkynylene group of formulas 1 to 12, an alkoxy group, a hydroxy group, an amino group, a carboxyl group, an ester group, a halogen atom, a thiol group, a thioether group, an organosilicon group, and the like can be given. The alkylene group, alkenylene group or alkynylene group of R ₁ and R ₂ may have two or more of these substituents, and in this case, the two or more substituents may be the same or different. .

  In the above formulas (5) to (7), m and n are each independently an integer of 1 to 10, preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. If m and n exceed 10, the mechanical strength of the polymer becomes too low, which is not preferable.

In said formula (5)-(7), R < ₃ > -R < ₆ > is a C1-C30 organic group which may have a substituent. Examples of the organic group having 1 to 30 carbon atoms of R _{3 to} R ₆ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and Alkyl groups such as dodecyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; linear or branched chain alkenyl groups such as vinyl group, propenyl group and hexenyl group; cyclic alkenyl groups such as cyclopentenyl group and cyclohexenyl group Alkynyl groups such as ethynyl group, methylethynyl group and 1-propionyl group; aryl groups such as phenyl group, naphthyl group and toluyl group; alkoxyphenyl groups such as methoxyphenyl group; aralkyl groups such as benzyl group and phenylethyl group; Examples include heterocyclic groups such as thienyl group, pyridyl group and furyl group. Among these, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group is preferable from the viewpoint of stability of the polymer itself, and an alkyl group or a cycloalkyl group is particularly preferable from the viewpoint of light resistance and weather resistance of the polymer itself.
Further, when these organic groups have a substituent, there is no particular limitation as long as the excellent physical properties of the polycarbonate resin of the present invention are not significantly impaired. In addition to the groups, alkoxy groups, hydroxy groups, amino groups, carboxyl groups, ester groups, halogen atoms, thiol groups, thioether groups, organosilicon groups, and the like can be given. The organic group of R ^{1 to} R ⁴ may have two or more of these substituents, and in this case, the two or more substituents may be the same or different.

In the above formulas (5) to (7), R _{3 to} R ₆ may be two or more, preferably two or three of them may be bonded to each other to form a ring, and in particular, R ₃ and R _{3 5} , R ₄ and R ₆ preferably form a ring with an acetal bond from the viewpoint of improving the heat resistance of the polycarbonate polyol resin.

Examples of the structure in which R ₃ and R ₅ , R ₄ and R ₆ form a ring by an acetal bond, preferably include those represented by the following structural formula, and among these, from the viewpoint of heat resistance Particularly preferred is a cyclohexylidene group.

In the above formula (6), when R ₃ , R ₄ and R ₆ form a ring with a methine group, a structure similar to a thermodynamically stable adamantane can be taken, so that the polycarbonate polyol of the present invention It is preferable from the viewpoint of improving the heat resistance of the resin.

  The cyclohexane ring in the above formulas (5) to (7) is preferably an inositol residue derived from inositol. Specific examples of the inositol include all-cis-inositol, epi-inositol, allo-inositol, muco-inositol, myo-inositol, neo-inositol, chiro-D-inositol, chiro-L-inositol, scyllo-inositol. However, from the viewpoint of easy availability of raw materials, myo-inositol is preferable, and the inositol residue is preferably an inositol residue derived from myo-inositol.

  The polycarbonate polyol resin of the present invention preferably contains 80 or less as a repeating unit of the structure (13), preferably the structures (13-5) to (13-7), when the total number of carbonate repeating units is 100. . When this ratio is 80 or less, other repeating units can be introduced, and other characteristics such as optical characteristics can be introduced. From this viewpoint, the ratio of the structure (13), preferably the structures (13-5) to (13-7) is more preferably 70 or less, and preferably 60 or less. On the other hand, in order to effectively obtain the above-described effects by introducing the structure (13), the ratio of the structure (13), preferably the structures (13-5) to (13-7) is 1 or more. Preferably, it is 5 or more, more preferably 10 or more.

  The polycarbonate polyol resin of the present invention may contain a structural unit derived from a diol compound other than the diol compounds of the above formulas (1) to (3) (hereinafter sometimes referred to as “other diol compounds”). As the other diol compounds, the aliphatic diol compounds and / or alicyclic diol compounds mentioned in the description of the polycarbonate resin can be used.

(Manufacture of polycarbonate polyol resin)
The polycarbonate polyol resin of the present invention can be produced in the same manner as the production method mentioned in the production of the above polycarbonate resin.
The amount of the carbonate compound such as carbonic acid diester described above is not particularly limited, but the lower limit is preferably 0.35, more preferably 0.50, and still more preferably 0.60 in terms of a molar ratio with respect to a total of 1 mol of diol compounds. And the upper limit is preferably 1.00, more preferably 0.98, and still more preferably 0.97. If the amount of carbonate compound used exceeds the above upper limit, the proportion of the polycarbonate polyol resin obtained in which the terminal group is not a hydroxy group may increase or the molecular weight may not fall within the predetermined range. May not progress.

In producing the polycarbonate polyol resin of the present invention, a transesterification catalyst (hereinafter sometimes referred to as a catalyst) is usually used.
If the catalyst is too small, the polycondensation reaction between the diol compound and the carbonate compound is difficult to proceed. Therefore, the amount of catalyst used is preferably 0.1 ppm or more, more preferably 0.5 ppm or more, as the content in terms of the catalyst metal. Preferably it is 1 ppm or more.

As the transesterification catalyst, any compound that is generally considered to have transesterification ability can be used without limitation, and those used in the production of the polycarbonate resin described above can be used.
The reaction temperature in the transesterification reaction can be arbitrarily adopted as long as a practical reaction rate can be obtained. Usually, the lower limit of the reaction temperature is preferably 70 ° C, more preferably 100 ° C, and further preferably 130 ° C. The upper limit of the reaction temperature is usually preferably 220 ° C, more preferably 200 ° C, and even more preferably 180 ° C. By setting the upper limit of the reaction temperature to the above value, it is possible to prevent quality problems such as coloring of the obtained polycarbonate polyol resin and formation of an ether structure.

Furthermore, the reaction temperature is preferably 180 ° C. or lower, more preferably 170 ° C. or lower, and even more preferably 160 ° C. or lower throughout the transesterification reaction for producing the polycarbonate polyol resin. By setting the reaction temperature to 180 ° C. or lower throughout all the steps, it is possible to prevent the color from being easily colored depending on conditions.
Although the reaction can be carried out at normal pressure, the transesterification reaction is an equilibrium reaction, and the reaction can be biased toward the production system by distilling off the light-boiling components produced out of the system. Therefore, usually, in the latter half of the reaction, it is preferable to carry out the reaction while distilling off the light-boiling components under reduced pressure conditions.

Or it is also possible to make it react, distilling off the light boiling component produced | generated by reducing pressure gradually from the middle of reaction. In particular, it is preferable to carry out the reaction by increasing the degree of vacuum at the end of the reaction, because by-produced monoalcohol, phenols, cyclic carbonate and the like can be distilled off.
In this case, the upper limit of the reaction pressure at the end of the reaction is preferably 10 kPa, more preferably 5 kPa, and further preferably 1 kPa. In order to effectively distill these light-boiling components, the reaction can also be performed while flowing an inert gas such as nitrogen, argon and helium through the reaction system.

When using a low-boiling diol compound or carbonate compound in the transesterification reaction, the reaction is initially performed near the boiling point of the diol compound or carbonate compound, and the temperature is gradually increased as the reaction proceeds. A method of allowing the reaction to proceed can also be employed. In this case, the unreacted carbonate compound can be prevented from being distilled off at the initial stage of the reaction, which is preferable.
Furthermore, in order to prevent the distillation of these raw materials, it is possible to carry out the reaction while refluxing the diol compound and the carbonate compound by attaching a reflux tube to the reactor. In this case, the amount of the reagent is not lost without losing the charged raw materials. This is preferable because the ratio can be accurately adjusted.
The polymerization reaction can be carried out batchwise or continuously. In the present invention, the polymerization reaction is preferably carried out continuously from the standpoint of product stability. The apparatus to be used may be any of a tank type, a tube type and a tower type, and a known polymerization tank equipped with various stirring blades can be used. The atmosphere during the temperature rise of the apparatus is not particularly limited, but from the viewpoint of product quality, it is preferably carried out in an inert gas such as nitrogen gas under normal pressure or reduced pressure.

  In the present invention, for the purpose of removing a diol compound, a carbonate compound, a light-boiling cyclic carbonate produced as a by-product, alcohols produced as a by-product from the carbonate compound, phenols, an added catalyst, etc. in the polycarbonate polyol product, for example, You may refine | purify by methods, such as vacuum distillation, steam distillation, and thin film distillation. Among them, thin film distillation is effective.

  Although there is no restriction | limiting in particular as thin film distillation conditions, As for the temperature at the time of thin film distillation, it is preferable that an upper limit is 250 degreeC, and it is preferable that it is 200 degreeC. Moreover, it is preferable that a minimum is 120 degreeC, and it is more preferable that it is 150 degreeC. By setting the lower limit of the temperature at the time of thin-film distillation to the above value, the effect of removing light boiling components becomes sufficient. Further, by setting the upper limit to 250 ° C., it is possible to prevent the polycarbonate polyol resin obtained after thin film distillation from being colored.

  The upper limit of the pressure during thin film distillation is preferably 500 Pa, more preferably 150 Pa, and even more preferably 50 Pa. By setting the pressure during thin film distillation to the upper limit value or less, a light boiling component removal effect can be sufficiently obtained. Further, the upper limit of the temperature of the polycarbonate polyol resin just before thin film distillation is preferably 250 ° C., more preferably 150 ° C. Moreover, it is preferable that a minimum is 80 degreeC, and it is more preferable that it is 120 degreeC.

By setting the temperature of the polycarbonate polyol resin just before the thin film distillation to the above lower limit or more, the fluidity of the polycarbonate polyol resin just before the thin film distillation can be prevented from being lowered. On the other hand, by setting it to the upper limit or less, the polycarbonate polyol resin obtained after thin film distillation can be prevented from being colored.
Further, in order to remove water-soluble impurities, it may be washed with water, alkaline water, acidic water, a chelating agent solution or the like. In that case, the compound to be dissolved in water can be arbitrarily selected.

(Physical properties of polycarbonate polyol resin)
The polycarbonate polyol resin of the present invention has a number average molecular weight of 250 or more and less than 10,000, preferably 300 or more and 5500 or less.
More preferably, the lower limit is 500, and more preferably 750. On the other hand, the upper limit is more preferably 4,500, still more preferably 3,500, and particularly preferably 3,000.
When the number average molecular weight of the polycarbonate polyol resin is less than the lower limit, there may be cases where sufficient flexibility cannot be obtained when polyurethane is used. On the other hand, if the upper limit is exceeded, the viscosity increases, and handling during polyurethane formation may be impaired.

The weight average molecular weight / number average molecular weight (Mw / Mn), which is the molecular weight distribution of the polycarbonate polyol resin of the present invention, is not particularly limited, but the lower limit is preferably 1.5, and more preferably 1.8. The upper limit is preferably 3.5, more preferably 3.0. When the molecular weight distribution exceeds the above range, the physical properties of the polyurethane produced using this polycarbonate polyol tend to become hard at low temperatures or decrease in elongation, and an attempt is made to produce a polycarbonate polyol having a molecular weight distribution less than the above range. Then, an advanced purification operation such as removing the oligomer may be necessary.
The weight average molecular weight is a polystyrene-equivalent weight average molecular weight, and the number-average molecular weight is a polystyrene-equivalent number average molecular weight, and can be usually determined by measurement of gel permeation chromatography (sometimes abbreviated as GPC).

  The molecular chain terminal of the polycarbonate polyol resin of the present invention is mainly a hydroxy group. However, in the case of a polycarbonate diol obtained by the reaction of a diol compound and a carbonate compound, there may be an impurity in which some molecular chain terminals are not hydroxy groups. As specific examples thereof, the molecular chain terminal is an alkyloxy group or an aryloxy group, and many have a structure derived from a carbonate compound.

For example, when diphenyl carbonate is used as the carbonate compound, phenoxy group (PhO-) is used as the aryloxy group, methoxy group (MeO-) is used as the alkyloxy group when dimethyl carbonate is used, and ethoxy group is used when diethyl carbonate is used. (EtO-), when using ethylene carbonate which may hydroxyethoxy group _(HOCH 2 _CH 2 O-) remains as a molecular chain terminal (here, Ph represents a phenyl group, Me represents a methyl group Et represents an ethyl group).

  The molecular chain terminal of the polycarbonate polyol resin of the present invention has a ratio of the total number of terminals derived from the diol compound to the total number of terminals, preferably 90 mol% or more, more preferably 95 mol% or more, Preferably it is 97 mol% or more, Most preferably, it is 99 mol% or more. By setting the amount within the above range, it becomes easy to obtain a desired molecular weight when polyurethane is used, and it becomes possible to become a polyurethane raw material having an excellent balance of physical properties.

The ratio of the number of terminal groups in which the molecular chain terminal of the polycarbonate polyol resin is derived from the carbonate compound is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 3 mol, based on the total number of terminals. % Or less, particularly preferably 1 mol% or less.
The lower limit of the hydroxyl value of the polycarbonate polyol resin of the present invention is preferably 20 mg-KOH / g, more preferably 25 mg-KOH / g, still more preferably 30 mg-KOH / g, and most preferably 35 mg-KOH / g. Moreover, an upper limit becomes like this. Preferably it is 450 mg-KOH / g, More preferably, it is 230 mg-KOH / g, More preferably, it is 150 mg-KOH / g. If the hydroxyl value is less than the above lower limit, the viscosity may be too high and handling during polyurethane formation may be difficult. If the upper limit is exceeded, physical properties such as flexibility and low-temperature characteristics may be insufficient when polyurethane is used.

  The turbidity of the polycarbonate polyol resin of the present invention was previously set in the apparatus by putting a 50% methylene chloride solution of the polycarbonate polyol resin in a 10 mm cell with an integrating sphere turbidimeter PT-200 manufactured by Mitsubishi Chemical Corporation. The value measured using a polystyrene calibration curve is preferably 2.0 ppm or less, more preferably 1.0 ppm or less, and particularly preferably 0.5 ppm or less. If the turbidity is higher than 2.0 ppm, the transparency of polyurethane obtained using polycarbonate polyol resin as a raw material may be deteriorated, thereby reducing the commercial value and mechanical properties. Turbidity is thought to be mainly caused by aggregation / precipitation of catalyst components, aggregation / precipitation of additives, and cyclic oligomers with low solubility. To reduce turbidity to 2.0 ppm or less, polycarbonate polyol resin production It is necessary to comprehensively control the catalyst at the time, the selection of the type and amount of the additive, the thermal history, the concentration of the monohydroxy compound during and after the polymerization and the concentration of the unreacted monomer. For example, if the solubility of the catalyst itself in the polycarbonate polyol resin is low, the catalyst is likely to be precipitated, and if the concentration is high, the precipitation is promoted. On the other hand, in order to suppress the formation of cyclic oligomers having poor solubility, selection and combination of diol compounds as monomers are also important. For example, in the case of a homopolymer, a cyclic oligomer tends to be generated, but by copolymerization, it becomes difficult to obtain a stable cyclic structure, and the turbidity tends to decrease. Further, if the temperature during the production of the polycarbonate polyol resin is high, a cyclic oligomer is likely to be generated thermodynamically, so it is effective to lower the polymerization temperature. However, it is not preferable to reduce the amount too much because productivity is hindered, excessive time is required, color tone is deteriorated, and turbidity is deteriorated.

The upper limit of the YI value of the polycarbonate polyol resin of the present invention is usually preferably 20, more preferably 10, still more preferably 5, particularly preferably 3, while the lower limit is not particularly limited. Is usually preferably -20, more preferably -5, still more preferably -1.
If the YI value exceeds 20, the color tone of polyurethane obtained using polycarbonate polyol as a raw material may be deteriorated, and the commercial value may be deteriorated or the thermal stability may be deteriorated. In order to make the YI value 20 or less, the catalyst at the time of polycarbonate polyol resin production, the selection of the type and amount of additives, the thermal history, the concentration of monohydroxy compound during polymerization and after completion of polymerization, and the concentration of unreacted monomer are set. It is necessary to control comprehensively. In addition, light shielding during and after polymerization is also effective. It is also important to set the molecular weight of the polycarbonate polyol and to select the diol compound species that is a monomer. In particular, a polycarbonate polyol resin made from an aliphatic diol compound having an alcoholic hydroxy group, when processed into polyurethane, exhibits various excellent performances such as flexibility, water resistance, and light resistance. The thermal history and coloration due to the catalyst tend to be remarkably higher than when using as a raw material.

(Polycarbonate polyol resin composition)
The polycarbonate polyol resin of the present invention includes, for example, aromatic polycarbonate resin, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, synthetic resin such as ABS and AS, polylactic acid and polybutylene succinate. It can also be used as a polymer alloy by kneading with one or more of biodegradable resins and rubbers.

  Further, the polycarbonate polyol resin of the present invention includes a nucleating agent, a flame retardant, a flame retardant aid, an inorganic filler, an impact modifier, a hydrolysis inhibitor, and a foaming agent that are usually used in a resin composition together with these other resin components. A polycarbonate polyol resin composition can be prepared by adding a dye or pigment.

  The above resin composition containing the polycarbonate polyol resin of the present invention can be formed into a molded product by a generally known method such as an injection molding method, an extrusion molding method, a compression molding method, etc., and has heat resistance, transparency, light resistance. A molded article having excellent properties, weather resistance, and mechanical strength can be obtained.

(Use of polycarbonate polyol resin)
The polycarbonate polyol resin of the present invention is also useful as a polyurethane raw material, and can produce a polyurethane excellent in heat resistance, weather resistance, abrasion resistance, mechanical strength, and chemical resistance. In this case, an aqueous polyurethane emulsion or urethane (meth) acrylate may be used.
Since the polyurethane using the polycarbonate polyol resin of the present invention is excellent in chemical resistance, low temperature characteristics, heat resistance, etc., artificial leather, synthetic leather, aqueous polyurethane, elastomer, adhesive, elastic fiber, medical material, flooring, It can be suitably used in all applications where polyols are usually used, such as raw materials for paints, coating agents, active energy ray-curable resin compositions, and the like.

<Polyester resin>
The polyester resin of the present invention includes a structure represented by the following formula (14) in the molecule.

[X in the above formula (14) has a structure represented by any of the following formulas (5) to (7). In formulas (5) to (7), R ₁ and R ₂ each independently represent a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent. R ₃ to R ₆ each independently represent an organic group having 1 to 30 carbon atoms which may have an arbitrary substituent. Further, any two or more of R ₃ to R ₆ may be bonded to each other to form a ring. m and n are each independently an integer of 1 to 10. A in the above formula (14) is an optionally substituted alkylene group having 1 to 20 carbon atoms, an alkenylene group or an alkynylene group; An alkylene group, a cycloalkenylene group or a cycloalkynylene group; or an arylene group or heteroarylene group having 4 to 20 carbon atoms which may have a substituent. ]

  Hereinafter, the structure represented by the formula (14) is referred to as “structure (14)”, and the structure represented by the formula (14) in which X is a structure represented by the formula (5) is referred to as “structure (14-5)”. The structure represented by formula (14), wherein X is a structure represented by formula (6), is referred to as “structure (14-6)”, and X is represented by formula (7). The structure represented by the formula (14) is sometimes referred to as “structure (14-7)”.

The structure (14), preferably the structures (14-5) to (14-7), is itself introduced into the polyester resin by a diol compound having excellent heat resistance as a raw material. By introducing into the polyester resin, the heat resistance of the polyester resin can be increased.
Moreover, the polyester resin of the present invention can be excellent in light resistance and weather resistance as a structure not including an aromatic ring structure as a main chain. Further, by introducing a ring having a specific aromaticity, unique optical properties can be imparted.

In the above formulas (5) to (7), R ₁ and R ₂ are each independently a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent, preferably carbon. Number 2-8, More preferably, it is C2-C4, Most preferably, it is C2. When R ₁ and R ₂ have more than 12 carbon atoms, the mechanical strength of the polymer becomes too low, which is not preferable.
Further, when these alkylene groups, alkenylene groups or alkynylene groups have a substituent, there is no particular limitation as long as the excellent physical properties of the polyester resin of the present invention are not significantly impaired. In addition to 1 to 12 of the alkylene group, alkenylene group or alkynylene group, an alkoxy group, a hydroxy group, an amino group, a carboxyl group, an ester group, a halogen atom, a thiol group, a thioether group, an organosilicon group, and the like can be given. The alkylene group, alkenylene group or alkynylene group of R ₁ and R ₂ may have two or more of these substituents, and in this case, the two or more substituents may be the same or different. .

  In the above formulas (5) to (7), m and n are each independently an integer of 1 to 10, preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. If m and n exceed 10, the mechanical strength of the polymer becomes too low, which is not preferable.

In said formula (5)-(7), R < ₃ > -R < ₆ > is a C1-C30 organic group which may have a substituent. Examples of the organic group having 1 to 30 carbon atoms of R _{3 to} R ₆ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and Alkyl groups such as dodecyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; linear or branched chain alkenyl groups such as vinyl group, propenyl group and hexenyl group; cyclic alkenyl groups such as cyclopentenyl group and cyclohexenyl group Alkynyl groups such as ethynyl group, methylethynyl group and 1-propionyl group; aryl groups such as phenyl group, naphthyl group and toluyl group; alkoxyphenyl groups such as methoxyphenyl group; aralkyl groups such as benzyl group and phenylethyl group; Examples include heterocyclic groups such as thienyl group, pyridyl group and furyl group. Among these, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group is preferable from the viewpoint of stability of the polymer itself, and an alkyl group or a cycloalkyl group is particularly preferable from the viewpoint of light resistance and weather resistance of the polymer itself.
Moreover, when these organic groups have a substituent, there is no particular limitation as long as the excellent physical properties of the polyester resin of the present invention are not significantly impaired. In addition to the groups, an alkoxy group, a hydroxy group, an amino group, a carboxyl group, an ester group, a halogen atom, a thiol group, a thioether group, an organosilicon group, and the like can be given. The organic group of R ^{1 to} R ⁴ may have two or more of these substituents, and in this case, the two or more substituents may be the same or different.

In the above formulas (5) to (7), R _{3 to} R ₆ may be two or more, preferably two or three of them may be bonded to each other to form a ring, and in particular, R ₃ and R _{3 5} , R ₄ and R ₆ preferably form a ring with an acetal bond from the viewpoint of improving the heat resistance of the polyester resin.

Examples of the structure in which R ₃ and R ₅ , R ₄ and R ₆ form a ring by an acetal bond, preferably include those represented by the following structural formula, and among these, from the viewpoint of heat resistance Particularly preferred is a cyclohexylidene group.

In the above formulas (5) to (7), when R ₃ and R ₅ , R ₄ and R ₆ each form a ring with an ethylene group, a thermodynamically stable six-membered ring is formed. Therefore, it is preferable from the viewpoint of improving the heat resistance of the polyester resin of the present invention.

In the above formula (6), when R ₃ , R ₄ and R ₆ form a ring with a methine group, a structure similar to a thermodynamically stable adamantane can be taken, so that the polyester resin of the present invention It is preferable from the viewpoint of improving the heat resistance.

  The cyclohexane ring in the above formulas (5) to (7) is preferably an inositol residue derived from inositol. Specific examples of the inositol include all-cis-inositol, epi-inositol, allo-inositol, muco-inositol, myo-inositol, neo-inositol, chiro-D-inositol, chiro-L-inositol, scyllo-inositol. However, from the viewpoint of easy availability of raw materials, myo-inositol is preferable, and the inositol residue is preferably an inositol residue derived from myo-inositol.

  The polyester resin of the present invention preferably contains 80 or less of the above structure (14), preferably the above structures (14-5) to (14-7) as repeating units, assuming that all ester repeating units are 100. When this ratio is 80 or less, other repeating units can be introduced, and other characteristics such as optical characteristics can be introduced. From this viewpoint, the ratio of the structure (14, preferably the structures (14-5) to (14-7) is more preferably 70 or less, and preferably 60 or less. On the other hand, the structure (14) In order to effectively obtain the above-described effects by introducing, the ratio of the structure (14), preferably the structures (14-5) to (14-7) is preferably 1 or more, and is preferably 5 or more. Is more preferable, and it is still more preferable that it is 10 or more.

(Manufacture of polyester resin)
The polyester resin of the present invention has a dicarboxylic acid unit and a diol unit.

  Examples of the dicarboxylic acid constituting the dicarboxylic acid unit include an aliphatic dicarboxylic acid or a mixture thereof, an aromatic dicarboxylic acid or a mixture thereof, and a mixture of an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid. Among these, those containing an aliphatic dicarboxylic acid as a main component are preferable. The main component referred to in the present invention is usually 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, and particularly preferably 90 mol% or more with respect to all dicarboxylic acid units.

  Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid 4,4′-diphenylsulfone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,5-furandicarboxylic acid and the like, and examples of the aromatic dicarboxylic acid derivative include lower alkyl esters of aromatic dicarboxylic acid, specifically Specifically, methyl ester, ethyl ester, propyl ester, butyl ester and the like can be mentioned. Among these, terephthalic acid is preferable as the aromatic dicarboxylic acid, and dimethyl terephthalate is preferable as the derivative of the aromatic dicarboxylic acid. Even when the aromatic dicarboxylic acid disclosed in the present specification is used, a desired aromatic polyester resin can be obtained by using any aromatic dicarboxylic acid such as polyester of dimethyl terephthalate and 1,4-butanediol. Can be manufactured.

  As the aliphatic dicarboxylic acid component, an alicyclic carboxylic acid, a chain aliphatic dicarboxylic acid or a derivative thereof is used. The cycloaliphatic carboxylic acid includes 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, cyclohexanedicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, 2,3-norbornene dicarboxylic acid, and chain aliphatic dicarboxylic acid. As malonic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, etc. The following chain or alicyclic dicarboxylic acids are mentioned. Examples of the aliphatic dicarboxylic acid derivative include lower alkyl esters such as methyl ester, ethyl ester, propyl ester, and butyl ester of the aliphatic dicarboxylic acid, and cyclic acid anhydrides of the aliphatic dicarboxylic acid such as succinic anhydride. Can be used. Among these, as the aliphatic dicarboxylic acid, adipic acid, succinic acid, dimer acid or a mixture thereof is preferable from the viewpoint of physical properties of the obtained polymer, and those having succinic acid as a main component are particularly preferable. As the derivative of the aliphatic dicarboxylic acid, methyl esters of adipic acid and succinic acid, or a mixture thereof are more preferable.

  The diol unit of the polyester resin of the present invention can be obtained by using any one of the above formulas (1) to (3) or a combination of two or more as the diol compound.

  The polyester resin of the present invention may contain diol units derived from other diol compounds other than the structures (1) to (3). As the other diol compound, a known diol compound such as an aromatic diol and / or an aliphatic diol can be used, but an aliphatic diol is preferably used.

  The aliphatic diol is not particularly limited as long as it is a chain or alicyclic compound having two OH groups, but the lower limit of the carbon number is 2 or more, and the upper limit is usually 10 or less, preferably 6 The following aliphatic diols are mentioned. Among these, an even number of diols or a mixture thereof is preferable because a polymer having a higher melting point can be obtained. Specific examples of the aliphatic diol include, for example, ethylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, decamethylene glycol, 1,4-butanediol, and 1,4- And cyclohexanedimethanol. These may be used alone or as a mixture of two or more.

  Among these, ethylene glycol, 1,4-butanediol, 1,3-propylene glycol and 1,4-cyclohexanedimethanol are preferable, and among them, ethylene glycol and 1,4-butanediol, and these In particular, a mixture mainly composed of 1,4-butanediol or 1,4-butanediol is particularly preferable. The main component here is usually 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, particularly preferably based on all diol compound units other than the structures (1) to (3). Represents 90 mol% or more.

  The aromatic diol is not particularly limited as long as it is an aromatic compound having two OH groups, and examples thereof include aromatic diols having a lower limit of 6 or more carbon atoms and an upper limit of usually 15 or less. . Specific examples of the aromatic diol include, for example, hydroquinone, 1,5-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl, bis (p-hydroxyphenyl) methane and bis (p-hydroxyphenyl) -2,2-propane. Etc. In the present invention, the content of the aromatic diol in the total amount of diol is usually 30 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less.

Further, both terminal hydroxy polyethers may be used by mixing with the above aliphatic diol. As both-end hydroxy polyether, the lower limit is usually 4 or more, preferably 10 or more, and the upper limit is usually 1000 or less, preferably 200 or less, more preferably 100 or less.
Specific examples of both terminal hydroxy polyethers include diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly 1,3-propanediol, and poly 1,6-hexamethylene glycol. . In addition, a copolymerized polyether of polyethylene glycol and polypropylene glycol can be used.

  When manufacturing the polyester resin of this invention, you may copolymerize other components other than the said dicarboxylic acid component and a diol component. Other copolymerization components that can be used in this case include lactic acid, glycolic acid, hydroxybutyric acid, hydroxycaproic acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2- Oxycarboxylic acids such as hydroxyisocaproic acid, malic acid, maleic acid, citric acid and fumaric acid; esters and lactones of the oxycarboxylic acid, oxycarboxylic acid polymers, etc .; propanetricarboxylic acid, pyromellitic acid, trimellitic acid, Trifunctional or higher polyvalent carboxylic acid such as benzophenone tetracarboxylic acid and anhydride thereof and anhydride thereof; erythritol and ester thereof such as dipentaerythritol and pentaerythritol monostearate, 2,3,4-pentanetriol, 3 -Methyl-1,3,5-pentanetrio 1,2,3-cyclohexanetriol, 1,2,3-hexanetriol, 1,2,3-heptanetriol, 3-hydroxyethyl-1,5-pentanediol, 2,4,6-heptanetriol and tri A trifunctional or higher polyhydric alcohol such as methylolethane can be used. By adding a small amount of trifunctional or higher functional oxycarboxylic acid, trifunctional or higher functional carboxylic acid, trifunctional or higher functional alcohol and the like, a highly viscous polyester resin can be easily obtained. Of these, oxycarboxylic acids such as malic acid, citric acid, and fumaric acid are preferable, and malic acid is particularly preferably used.

  When these other copolymerization components are used, the amount used is preferably 0.01 mol% or more, more preferably 0.05 mol%, preferably 1 mol, based on the dicarboxylic acid component used in the production of the polyester resin. % Or less, more preferably 0.5 mol% or less. By using other copolymer components, as described above, the viscosity of the resulting polyester resin can be increased, but if the amount used is too large, gelation tends to occur.

  As a method for producing a polyester resin in the present invention, the diol compound represented by the above formulas (1) to (3) at any stage of raw material charging, esterification reaction or polycondensation reaction before the polyester resin is produced. A known method can be used except for adding, for example, an esterification reaction and / or a transesterification reaction between the dicarboxylic acid component and the diol component described above, followed by a polycondensation reaction under reduced pressure. It can also be produced by a general method of melt polycondensation such as, or a known solution heating dehydration condensation method using an organic solvent, but from the viewpoint of economy and simplicity of the production process, the melting is carried out in the absence of a solvent. It is preferable to produce a polyester resin by a polycondensation method.

  Moreover, each reaction at the time of manufacturing a polyester resin in this invention can be performed by a batch method or a continuous method.

  As a method for producing a polyester resin by the melt polycondensation method, melt polycondensation is carried out in two stages of an esterification and / or transesterification step and a reduced pressure polycondensation step using the same or different reactors. Examples of the polycondensation reactor include a method using a stirred tank reactor equipped with a vacuum exhaust pipe connecting the vacuum pump and the reactor. In addition, a method is preferred in which a condenser is connected between the vacuum exhaust pipe connecting the vacuum pump and the reactor, and the volatile components and unreacted monomers generated during the polycondensation reaction are recovered by the condenser. Used.

  In the method for producing a polyester resin of the present invention, an esterification reaction between a carboxylic acid terminal and an alcohol terminal of a polyester resin is performed under reduced pressure after an esterification reaction and / or a transesterification reaction between a dicarboxylic acid component and a diol component. And / or a method of increasing the degree of polymerization of the polyester resin while distilling off water and diol produced by the ester exchange reaction between the alcohol ends, or dicarboxylic acid and / or acid anhydride thereof is distilled from the carboxylic acid end of the polyester resin. A method is used in which the degree of polymerization of the polyester resin is increased while leaving.

  Hereinafter, the production method of the aliphatic polyester resin by the batch method and the production method of the aromatic polyester resin by the batch method will be described in detail. However, the production method of the present invention is not limited to this unless it exceeds the gist of the present invention. It is not something.

(Manufacture of aliphatic polyester resin)
In the present invention, the reaction conditions for the esterification and / or transesterification step when producing the aliphatic polyester resin can be set as follows.
The lower limit of the reaction temperature is usually 150 ° C., preferably 180 ° C., more preferably 200 ° C., and the upper limit is usually 250 ° C., preferably 240 ° C., more preferably 230 ° C. If the reaction temperature is less than the lower limit, the esterification reaction rate is slow and the reaction time tends to be long. On the other hand, when the above upper limit is exceeded, there is a tendency that foreign matter generation due to an increase in scattered matter in the reaction tank and decomposition of the aliphatic diol component and the aliphatic dicarboxylic acid component increase. In addition, the aliphatic polyhydric alcohol compound becomes a branching base point and tends to cause gelation.

  The lower limit of the reaction pressure is usually 50 kPa, preferably 60 kPa, more preferably 70 kPa, and the upper limit is usually 200 kPa, preferably 130 kPa, more preferably 110 kPa. If the reaction pressure is less than the above lower limit, the amount of scattered matter in the reaction tank increases, the haze of the reaction product increases, and it is easy to cause an increase in foreign matter. It tends to cause a decrease in On the other hand, if the upper limit is exceeded, dehydration decomposition of the aliphatic diol component increases, and the polycondensation rate tends to decrease.

  The reaction time is usually 1 hour or longer, and the upper limit is usually 10 hours or shorter, preferably 4 hours or shorter.

The reaction conditions of the reduced pressure polycondensation reaction step when producing the aliphatic polyester resin in the present invention can be set as follows.
The lower limit of the reaction temperature is usually 180 ° C., preferably 200 ° C., more preferably 220 ° C., and the upper limit is usually 270 ° C., preferably 265 ° C., more preferably 260 ° C. If the reaction temperature is less than the lower limit, the polycondensation reaction rate tends to be slow and a long reaction time tends to be required. Also, the melt viscosity becomes too high, and it is not easy to extract the polymer. On the other hand, when the above upper limit is exceeded, there is a tendency that foreign matter generation due to an increase in scattered matter in the reaction tank and decomposition of the aliphatic diol component and the aliphatic dicarboxylic acid component increase. Further, the polyhydric alcohol compound becomes a branching base point and tends to cause gelation.

  The lower limit of the final ultimate pressure during the polycondensation reaction is usually 0.01 kPa, preferably 0.05 kPa, more preferably 0.1 kPa, and the upper limit is usually 1 kPa, preferably 0.8 kPa, more preferably 0.5 kPa. An attempt to make the reaction pressure below the lower limit requires an expensive vacuum device and is not economical. On the other hand, if the upper limit is exceeded, the polycondensation rate tends to decrease, and side reactions starting from the alcohol terminal proceed, and the terminal acid value tends to increase.

  The reaction time is usually 1 hour or longer, and the upper limit is usually 10 hours or shorter, preferably 4 hours or shorter.

  In the esterification and / or transesterification reaction step and the polycondensation reaction step, the reaction is promoted by using a reaction catalyst. However, in the esterification and / or transesterification reaction step, a sufficient reaction rate can be obtained without an esterification reaction catalyst, and water generated by the esterification reaction when an esterification reaction catalyst is present during the esterification reaction. As a result, the catalyst produces a precipitate insoluble in the reaction product, which may impair the transparency of the resulting aliphatic polyester resin (that is, haze increases) and may become a foreign substance. It is preferable that no additive is used.

In the polycondensation reaction step, the reaction is difficult to proceed without a catalyst, and a catalyst is preferably used.
As the polycondensation reaction catalyst, a metal compound containing at least one of the metal elements of Groups 1 to 14 of the periodic table is generally used. Specific examples of the metal element include scandium, yttrium, samarium, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, and calcium. , Strontium, sodium and potassium. Among them, scandium, yttrium, titanium, zirconium, vanadium, molybdenum, tungsten, zinc, iron, and germanium are preferable, and titanium, zirconium, tungsten, and germanium are particularly preferable.

  Furthermore, in order to reduce the terminal acid value that affects the thermal stability of the aliphatic polyester resin, among the above metal elements, metal elements of Group 3 to 6 of the periodic table showing Lewis acidity are preferable. Specifically, scandium, titanium, zirconium, vanadium, molybdenum, and tungsten are preferable, and titanium and zirconium are particularly preferable from the viewpoint of availability, and titanium is more preferable from the viewpoint of reaction activity.

  Examples of the catalyst include compounds containing organic groups such as carboxylates, alkoxy salts, organic sulfonates and β-diketonate salts containing these metal elements, and inorganic compounds such as metal oxides and halides described above. A mixture thereof is preferably used.

  The catalyst is preferably a compound that is liquid at the time of polycondensation or dissolved in an ester low polymer or a polyester resin because the polycondensation rate increases when it is in a melted or dissolved state during polycondensation.

  The polycondensation is preferably carried out without a solvent, but separately from this, a small amount of solvent may be used to dissolve the catalyst. Solvents for dissolving the catalyst include alcohols such as methanol, ethanol, isopropanol and butanol; diols such as ethylene glycol, butanediol and pentanediol; ethers such as diethyl ether and tetrahydrofuran; nitriles such as acetonitrile. Hydrocarbon compounds such as heptane and toluene; water and mixtures thereof, and the like. These solvents are used so that the catalyst concentration is usually 0.0001 wt% or more and 99 wt% or less.

  As a titanium compound used as a polycondensation catalyst, tetraalkyl titanate and its hydrolyzate are preferable, and specifically, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl. Examples include titanate, tetraphenyl titanate, tetracyclohexyl titanate, tetrabenzyl titanate and mixed titanates thereof and hydrolysates thereof. In addition, titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, titanium (diisoproxide) acetylacetonate, titanium bis (ammonium lactate) dihydroxide, titanium bis (ethylacetoacetate) diisopropoxide, titanium (triethanolaminate) ) Isopropoxide, polyhydroxytitanium stearate, titanium lactate, titanium triethanolamate and butyl titanate dimer are also preferably used. Moreover, the liquid substance obtained by mixing alcohol, an alkaline-earth metal compound, a phosphate ester compound, and a titanium compound is also used.

  Among these, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, titanium bis (ammonium lactate) dihydroxide, polyhydroxytitanium stearate Preferred are liquids obtained by mixing rate, titanium lactate and butyl titanate dimer, and alcohol, alkaline earth metal compound, phosphate ester compound and titanium compound. Tetra-n-butyl titanate, titanium (oxy) acetyl Acetonate, titanium tetraacetylacetonate, polyhydroxytitanium stearate, titanium lactate, butyl titanate dimer, alcohol, alkaline earth metal compound, phosphate ester A liquid obtained by mixing a compound and a titanium compound is more preferable, and in particular, tetra-n-butyl titanate, polyhydroxytitanium stearate, titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, alcohol, alkaline earth A liquid material obtained by mixing a metal compound, a phosphate ester compound and a titanium compound is preferred.

  Specific examples of the zirconium compound used as the polycondensation catalyst include zirconium tetraacetate, zirconium acetate hydroxide, zirconium tris (butoxy) stearate, zirconyl diacetate, zirconium oxalate, zirconyl oxalate, potassium potassium oxalate, Polyhydroxyzirconium stearate, zirconium ethoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide, zirconium tributoxyacetylacetonate and mixtures thereof. It is done. Among these, zirconyl diacetate, zirconium tris (butoxy) stearate, zirconium tetraacetate, zirconium acetate hydroxide, zirconium ammonium oxalate, potassium zirconium oxalate, polyhydroxyzirconium stearate, zirconium tetra-n-propoxide, Zirconium tetraisopropoxide, zirconium tetra-n-butoxide and zirconium tetra-t-butoxide are preferred, zirconyl diacetate, zirconium tetraacetate, zirconium acetate hydroxide, zirconium tris (butoxy) stearate, zirconium ammonium oxalate, zirconium tetra -N-propoxide and zirconium tetra-n-butoxide are more preferred , Preferred specific reason that zirconium tris (butoxy) stearate is readily obtained polyester resin having a high polymerization degree without coloring.

  Specific examples of the germanium compound used as the polycondensation catalyst include inorganic germanium compounds such as germanium oxide and germanium chloride, and organic germanium compounds such as tetraalkoxygermanium. From the viewpoint of price and availability, germanium oxide, tetraethoxygermanium, mu and tetrabutoxygermanium are preferable, and germanium oxide is particularly preferable.

  In the present invention, in addition to the polycondensation catalyst, a promoter such as an alkaline earth metal compound or an acidic phosphate compound can be used.

  Specific examples of the alkaline earth metal compound include various compounds of beryllium, magnesium, calcium, strontium, and barium, and magnesium and calcium compounds are preferable from the viewpoint of handling and availability, and catalytic effect. A magnesium compound having an excellent catalytic effect is preferred. Specific examples of the magnesium compound include magnesium acetate, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium alkoxide, and magnesium hydrogen phosphate. Among these, magnesium acetate is preferable. These alkaline earth metal compounds may be used alone or in combination of two or more.

  As the acidic phosphate compound, those having an ester structure of phosphoric acid having at least one hydroxy group represented by the following general formula (i) and / or (ii) are preferably used.

(In the above formula, R, R ′, and R ″ each independently represent an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, an aryl group, or a 2-hydroxyethyl group. In the formula (i), R and R ′ represent They may be the same or different.)

  Specific examples of such acidic phosphoric acid ester compounds include methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate and octyl acid phosphate. Among them, ethyl acid phosphate and butyl acid phosphate are preferable. These acidic phosphate ester compounds may be used alone or in combination of two or more.

  The acidic phosphate compound includes a diester form represented by the above general formula (i) and a monoester form represented by the above general formula (ii). From the reason that a catalyst exhibiting activity is obtained, it is preferable to use a monoester or a mixture of a monoester and a diester. 20-80: 80-20 are preferable, as for the mixing weight ratio (monoester body: diester body) of a monoester body and a diester body, More preferably, it is 30-70: 70-30, Most preferably, it is 40-60: 60-40.

  When these metal compounds are used as the polycondensation catalyst, the amount of catalyst added is usually 0.1 wtppm or more, preferably 0.5 wtppm or more, more preferably 1 wtppm or more, as the metal amount with respect to the aliphatic polyester resin to be produced. The upper limit is usually 10000 wtppm or less, preferably 1000 wtppm or less, more preferably 500 wtppm or less, still more preferably 200 wtppm or less, and particularly preferably 150 wtppm or less. If the amount of the catalyst used is too large, it is not only economically disadvantageous, but also increases the terminal acid value at the time of extracting the polymer, and tends to decrease the thermal stability and hydrolysis resistance of the polyester resin. On the other hand, when the amount is too small, the polycondensation activity is lowered, and thermal decomposition of the polyester resin is induced during production, and it tends to be difficult to obtain a polyester resin exhibiting practically useful physical properties.

  The timing of addition of the polycondensation catalyst to the reaction system is not particularly limited as long as it is before the polycondensation reaction step, and may be added when the raw materials are charged, but a large amount of unreacted dicarboxylic acid or water is present or generated. If the catalyst coexists under the present conditions, the catalyst may be deactivated and foreign matter may be precipitated, which may impair the quality of the product. Therefore, it is preferably added after the esterification reaction step.

(Physical properties of aliphatic polyester resin)
The value of reduced viscosity (ηsp / c) of the aliphatic polyester resin produced in the present invention can be controlled by polycondensation time, polycondensation temperature, polycondensation pressure or the like. The reduced viscosity has a lower limit of usually 1.6 dl / g or more, preferably 2.0 dl / g or more, more preferably 2.2 dl / g or more, particularly preferably because the practically sufficient mechanical properties of the polyester resin can be obtained. Is 2.3 dl / g or more. In addition, from the viewpoint of operability such as ease of extraction after polyester resin polycondensation reaction and ease of molding, the upper limit is usually 6.0 dl / g or less, preferably 5.0 dl / g or less, more preferably Is 4.0 dl / g or less.

  In addition, the aliphatic polyester resin of the present invention has a characteristic of good color tone. The YI value, which is an index of color tone, can be controlled by the polycondensation temperature, the amount of catalyst or the amount of triol component added, and is preferably −5.0 to 10.0, and the upper limit is more preferably 6 or less. It is. If the YI value exceeds the above upper limit, it may be unfavorable due to yellowishness when formed into a molded product.

(Aliphatic polyester resin composition)
The optional step of the production process of the aliphatic polyester resin of the present invention or the resulting aliphatic polyester resin, various additives such as heat stabilizers, antioxidants, crystal nucleating agents, as long as the properties are not impaired. In addition, flame retardants, antistatic agents, mold release agents, ultraviolet absorbers and the like may be added.
Further, when molding the aliphatic polyester resin, in addition to the above-mentioned various additives, reinforcing agents and extenders such as glass fiber, carbon fiber, titanium whisker, mica, talc, CaCO ₃ , TiO ₂ or silica are added. Can also be molded.

(Manufacture of aromatic polyester resin)
In the present invention, esterification reaction and / or transesterification reaction conditions and polycondensation reaction conditions in producing an aromatic polyester are arbitrary as long as the reaction can proceed, but a polyethylene terephthalate copolymer is taken as an example. Then you can set as follows.

  As for the reaction temperature of esterification reaction and / or transesterification, the lower limit is usually 150 ° C., preferably 180 ° C., more preferably 200 ° C., and the upper limit is usually 270 ° C., preferably 260 ° C., more preferably 250 ° C. It is. If the reaction temperature is less than the lower limit, the esterification reaction and / or transesterification reaction rate is slow and the reaction time tends to be long. On the other hand, when the above upper limit is exceeded, foreign matter is generated due to an increase in scattered matter in the reaction tank, and the amount of decomposition of ethylene glycol and terephthalic acid as raw materials tends to increase.

  The lower limit of the esterification reaction and / or transesterification reaction pressure is usually 50 kPa, preferably 60 kPa, more preferably 70 kPa, and the upper limit is usually 200 kPa, preferably 130 kPa, more preferably 110 kPa. If the reaction pressure is less than the above lower limit, the amount of scattered matter in the reaction vessel increases, the haze of the reaction product increases and it is easy to cause an increase in foreign matter, and the distillation of ethylene glycol to the outside of the reaction system increases and the reaction rate decreases. It tends to be easy. On the other hand, when the above upper limit is exceeded, the dehydration decomposition of ethylene glycol increases, and the polycondensation rate tends to decrease.

  The reaction time is usually 1 hour or longer, and the upper limit is usually 10 hours or shorter, preferably 4 hours or shorter.

  The lower limit of the reaction temperature in the reduced pressure polycondensation reaction step is usually 260 ° C., preferably 265 ° C., more preferably 270 ° C., and the upper limit is usually 290 ° C., preferably 285 ° C., more preferably 280 ° C. If the reaction temperature is less than the lower limit, the polycondensation reaction rate tends to be slow and a long reaction time tends to be required. Also, the melt viscosity tends to be too high and the polymer cannot be easily extracted. On the other hand, when the above upper limit is exceeded, there is a tendency that foreign matter generation due to an increase in scattered matter in the reaction tank and decomposition of ethylene glycol and terephthalic acid increase.

  The lower limit of the final ultimate pressure during the polycondensation reaction is usually 0.01 kPa, preferably 0.05 kPa, more preferably 0.1 kPa, and the upper limit is usually 1 kPa, preferably 0.8 kPa, more preferably 0.5 kPa. An attempt to make the reaction pressure below the lower limit requires an expensive vacuum device and is not economical. On the other hand, if the upper limit is exceeded, the polycondensation rate tends to decrease, and side reactions starting from the alcohol terminal proceed, and the terminal acid value tends to increase.

  The reaction time is usually 1 hour or longer, and the upper limit is usually 10 hours or shorter, preferably 4 hours or shorter.

  In the esterification and / or transesterification reaction step and the polycondensation reaction step, the reaction is promoted by using a catalyst. However, when an aromatic dicarboxylic acid such as terephthalic acid is used as a raw material, a sufficient reaction rate tends to be obtained even in the absence of an esterification reaction catalyst in esterification. On the other hand, when a dicarboxylic acid diester such as dimethyl terephthalate is used, it is preferable to use an alkaline earth metal such as Ca or Mg or a transition metal such as Mn or Zn as the transesterification catalyst.

  In the polycondensation reaction step, the reaction is difficult to proceed without a catalyst, and a catalyst is preferably used. As the polycondensation reaction catalyst, a metal compound containing at least one of the metal elements of Groups 1 to 14 of the periodic table is generally used. Specifically, as the metal element of the catalyst, scandium, yttrium, samarium, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, Examples include calcium, strontium, sodium and potassium. Among them, scandium, yttrium, titanium, zirconium, vanadium, molybdenum, tungsten, zinc, iron, and germanium are preferable, and titanium, antimony, zirconium, tungsten, and germanium are particularly preferable.

  In the present invention, in addition to the polycondensation catalyst, a promoter such as an alkaline earth metal compound and a phosphoric acid compound can be used.

  Specific examples of the alkaline earth metal compound include various compounds of beryllium, magnesium, calcium, strontium and barium, but lithium, sodium, potassium, magnesium and calcium are used from the viewpoint of handling and availability and catalytic effect. Of these, preferred is a magnesium or lithium compound having excellent catalytic effect, and particularly preferred is a magnesium compound. Specific examples of the magnesium compound include magnesium acetate, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium alkoxide, and magnesium hydrogen phosphate. Among these, magnesium acetate is preferable. These may be used alone or in combination of two or more.

  Specific examples of phosphorus compounds include orthophosphoric acid, polyphosphoric acid, trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (triethylene glycol) phosphate, methyl There are acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, monobutyl phosphate, dibutyl phosphate, dioctyl phosphate, triethylene glycol acid phosphate, etc. Among them, normal phosphoric acid is preferable.

  Specific examples of the polycondensation catalyst include metal compounds of the polycondensation catalyst exemplified in the description of the method for producing an aliphatic polyester resin.

  The amount of catalyst added when these metal compounds are used as the polycondensation catalyst, the lower limit is usually 1 wtppm or more, preferably 5 wtppm or more, and the upper limit is usually 1000 wtppm or less, preferably 500 wtppm or less More preferably, it is 300 wtppm or less, More preferably, it is 200 wtppm or less, Especially preferably, it is 150 wtppm or less. If the amount of catalyst used is too large, it is not only economically disadvantageous, but also increases the terminal acid value at the time of extracting the polymer, and tends to decrease the thermal stability and hydrolysis resistance of the polyethylene terephthalate copolymer. is there. On the other hand, when the amount is too small, the polycondensation activity is lowered, and the thermal decomposition of the polyethylene terephthalate copolymer is induced during the production, and it tends to be difficult to obtain a polyethylene terephthalate copolymer showing practically useful physical properties.

  The timing of addition of the catalyst to the reaction system is not particularly limited as long as it is before the polycondensation reaction step, and may be added when the raw materials are charged, but a large amount of unreacted terephthalic acid or water is present or generated. If the catalyst coexists under the present conditions, the catalyst may be deactivated and foreign matter may be precipitated, which may impair the quality of the product. Therefore, it is preferably added after the esterification reaction step.

  Taking a polybutylene terephthalate copolymer as an example, esterification reaction and / or transesterification reaction conditions and polycondensation reaction conditions can be set as follows.

  As for the reaction temperature of esterification reaction and / or transesterification, the lower limit is usually 180 ° C., preferably 200 ° C., more preferably 210 ° C., and the upper limit is usually 260 ° C., preferably 245 ° C., more preferably 235 ° C. It is. If the reaction temperature is less than the lower limit, the esterification reaction and / or transesterification reaction rate is slow and the reaction time tends to be long. On the other hand, when the above upper limit is exceeded, the amount of tetrahydrofuran generated by thermal decomposition of 1,4-butanediol, which is a raw material, increases, or foreign matter is generated and tends to increase due to an increase in scattered matter in the reaction tank.

  The lower limit of the esterification reaction and / or transesterification reaction pressure is usually 10 kPa, preferably 13 kPa, more preferably 50 kPa, particularly preferably 60 kPa, and the upper limit is usually 133 kPa, preferably 101 kPa, more preferably 90 kPa, Particularly preferred is 80 kPa.

  If the reaction pressure is less than the above lower limit, the amount of scattered matter in the reaction vessel increases, the haze of the reaction product tends to increase, and foreign matter tends to increase, and 1,4-butanediol is not distilled out of the reaction system. It tends to cause a decrease in the polycondensation reaction rate. On the other hand, when the above upper limit is exceeded, the amount of tetrahydrofuran generated by thermal decomposition of 1,4-butanediol increases, which tends to be economically disadvantageous.

  The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, and more preferably 2 to 6 hours.

  The lower limit of the reaction temperature in the reduced pressure polycondensation reaction step is usually 210 ° C, preferably 225 ° C, more preferably 230 ° C, and the upper limit is usually 280 ° C, preferably 265 ° C, more preferably 255 ° C. If the reaction temperature is less than the lower limit, the polycondensation reaction rate tends to be slow and a long reaction time tends to be required. Also, the melt viscosity may become too high, making it difficult to extract the polymer. On the other hand, when the above upper limit is exceeded, foreign matter generation due to an increase in the amount of scattered matter in the reaction tank increases, or side reaction due to resin coloring or Back-Biting reaction proceeds, which tends to increase the terminal acid value. Further, when a polyhydric alcohol compound other than 1,4-butanediol is added, depending on the type, it becomes a branching base point and tends to cause gelation.

  The lower limit of the final ultimate pressure during the polycondensation reaction is usually 0.01 kPa, preferably 0.05 kPa, more preferably 0.1 kPa, and the upper limit is usually 1 kPa, preferably 0.8 kPa, more preferably 0.5 kPa. If the reaction pressure is to be made lower than the above lower limit, an expensive vacuum device is required, which tends to be uneconomical. On the other hand, if the upper limit is exceeded, the polycondensation rate tends to decrease, and a side reaction due to the back-biting reaction proceeds, and the terminal acid value tends to increase.

  The reaction time is usually 1 hour or longer, and the upper limit is usually 10 hours or shorter, preferably 5 hours or shorter.

  In the esterification and / or transesterification reaction step and the polycondensation reaction step, the reaction is promoted by using a catalyst. As the catalyst, a titanium catalyst is preferably used.

  Specific examples of the titanium catalyst in the present invention include inorganic titanium compounds such as titanium oxide and titanium tetrachloride, titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate and tetrabutyl titanate, titanium phenolates such as tetraphenyl titanate and the like. Can be mentioned. Among these, tetraalkyl titanate is preferable, and among them, tetrabutyl titanate is preferable.

  A titanium compound having a chelate ligand can also be used. For example, titanium tetraacetylacetonate, titanium diisopropoxybis (acetylacetonate), titanium diisopropoxybis (ethylacetoacetate), titanium dibutoxybis (acetylacetonate), titanium lactate, titanium lactate ammonium salt, titanium di 2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide), titanium triisopropoxy (triethanolamate), titanium diisopropoxybis (triethanolaminate) and titanium tributoxy (triethanolamin) Nate) titanium dibutoxybis (triethanolaminate) and the like. Of these, titanium tetraacetylacetonate, titanium diisopropoxybis (acetylacetonate), titanium lactate and titanium diisopropoxybis (triethanolaminate) are particularly preferable.

  When the esterification reaction and / or transesterification reaction is performed in the presence of a titanium catalyst, a catalyst may be further added before or during the polycondensation reaction after the esterification reaction and / or transesterification reaction. Is possible.

  Even in such a case, the lower limit of the titanium content in the finally obtained polybutylene terephthalate copolymer is usually 10 wtppm or more, preferably 15 wtppm or more, more preferably 20 wtppm or more, particularly preferably 25 wtppm as a titanium atom equivalent amount. As described above, most preferably 30 wtppm or more, and the upper limit is usually 150 wtppm or less, preferably 100 wtppm or less, more preferably 80 wtppm or less, particularly preferably 60 wtppm or less, and most preferably 50 wtppm or less. When the titanium content exceeds the above upper limit, the color tone of the polybutylene terephthalate copolymer obtained, the hydrolysis resistance tends to deteriorate, and the foreign matter derived from the deactivated substance of the titanium catalyst tends to increase, When the amount is less than the lower limit, the reactivity tends to decrease, and the esterification reaction and / or transesterification reaction and the polycondensation time tend to be delayed.

In the production of the polybutylene terephthalate copolymer, in addition to the titanium catalyst, a catalyst known per se, such as a tin catalyst, may be used in combination. Examples of the tin catalyst include tin compounds, and specific examples thereof include dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, cyclohexahexylditin oxide, didodecyltin oxide, and triethyltin hydroxide. , Triphenyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, tributyltin chloride, dibutyltin sulfide, butylhydroxytin oxide, methylstannic acid, ethylstannic acid and butylstannic acid Is mentioned.
However, since tin deteriorates the color tone of the polybutylene terephthalate copolymer, the amount added is usually 200 wtppm or less, preferably 100 wtppm or less, more preferably 10 wtppm as the amount of tin atom in the resulting polybutylene terephthalate copolymer. Most preferably, it is not added.

In the present invention, in addition to the titanium catalyst, a compound of at least one metal selected from metals of Group 1 and 2 of the periodic table can be added as a metal atom.
In this case, the amount of the compound of at least one metal selected from Group 1 and Group 2 metals of the periodic table in the resulting polybutylene terephthalate copolymer is usually 0.1 wtppm or more as the metal atom equivalent amount. , Preferably 0.5 wtppm or more, more preferably 1 wtppm or more, and particularly preferably 3 wtppm or more. The upper limit is usually 100 wtppm or less, preferably 60 wtppm or less, more preferably 40 wtppm or less, and particularly preferably 30 wtppm or less. If the content of these metals exceeds the above upper limit, the polycondensation reaction rate tends to decrease as the polycondensation reaction proceeds, and the color tone and hydrolysis resistance of the resulting polybutylene terephthalate copolymer may deteriorate. On the other hand, if the amount is less than the above lower limit, the effect tends to be difficult to obtain. In addition, said value points out the total amount, when multiple metal seed | species is contained.

  Specific examples of the compound of Group 1 metal of the periodic table include various compounds of lithium, sodium, potassium, rubidium and cesium. Specific examples of the compounds of Group 2 metals in the periodic table include various compounds of beryllium, magnesium, calcium, strontium, and barium. Of these, lithium, sodium, potassium, magnesium or calcium compounds are preferred from the viewpoint of handling and availability, and catalytic effects, magnesium or lithium compounds having excellent catalytic effects are more preferred, and magnesium compounds are particularly preferred. Specific examples of the magnesium compound include magnesium acetate, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium alkoxide, and magnesium hydrogen phosphate. Of these, magnesium acetate is preferred.

  The addition time to the reaction system of at least one metal selected from Group 1 and 2 metals of the periodic table is not particularly limited as long as it is before the polycondensation reaction step, and may be added at the time of charging the raw materials. However, if the metal component coexists in the presence of a large amount of unreacted terephthalic acid, a precipitate is formed, which may cause foreign matters and impair the quality of the product. It is preferably added after the transesterification step.

(Physical properties of aromatic polyester resin, etc.)
The intrinsic viscosity (IV, Inherent Viscosity) (dl / g) of the aromatic polyester resin produced in the present invention can be controlled by the polycondensation time, polycondensation temperature, polycondensation pressure and the like. In addition, the intrinsic viscosity can be further increased by solid phase polymerization. The intrinsic viscosity of the aromatic polyester resin is such that the lower limit is usually 0.40 dl / g or more, preferably 0.45 dl / g or more in the case of a polyethylene terephthalate copolymer, because the practically sufficient mechanical properties of the polyester resin can be obtained. , More preferably 0.50 dl / g or more, particularly preferably 0.55 dl / g or more. From the viewpoint of ease of extraction after the polycondensation reaction of the polyester resin and operability such as ease of molding, the upper limit is usually 1.20 dl / g or less, preferably 1.00 dl / g or less, more Preferably it is 0.85 dl / g or less, Most preferably, it is 0.75 dl / g or less. On the other hand, in the case of a polybutylene terephthalate copolymer, the lower limit is usually 0.50 dl / g or more, preferably 0.55 dl / g or more, more preferably 0.60 dl / g or more, particularly preferably 0.65 dl / g or more. is there. From the viewpoint of ease of extraction after the polycondensation reaction of the polyester resin and operability such as ease of molding, the upper limit is usually 1.80 dl / g or less, preferably 1.50 dl / g or less, more Preferably it is 1.10 dl / g or less, Especially preferably, it is 0.90 dl / g or less.

Further, a polyethylene terephthalate copolymer obtained in the present invention is a melt volume rate ^{(MVR) (cm 3 / 10min} ) is optional unless significantly impairing the effects of the present invention, is preferably 30 cm ³ / 10min about . The melt volume rate can be controlled by the addition amount of the triol component, depending on the polymerization degree of the polyethylene terephthalate copolymer, the upper limit is usually at most 100 cm ³ / 10min, preferably not more than 80 cm ³ / 10min, more preferably 60cm ³ / 10min or less, particularly less preferably 50 cm ³ / 10min, the lower limit is usually 15cm ³ / 10min or more, preferably 20 cm ³ / 10min, more preferably 25 cm ³ / 10min, particularly preferably 30 cm ³ / 10min or more It is. If the melt volume rate is larger than the above upper limit, the viscosity of the molten resin may be greatly reduced, the melt tension at the time of molding is insufficient, and depending on molding conditions such as the molding method or molding temperature, a molded body can be obtained. May not be possible. On the other hand, if the melt volume rate is smaller than the above lower limit, the viscosity of the resin composition may become very high, the load tends to be excessively applied to the extruder during the molding process, and the resin is deteriorated by shearing heat generation. In some cases, a molded article cannot be stably obtained because of the occurrence.

  Further, the polybutylene terephthalate copolymer obtained in the present invention can control the melt viscosity at a shear rate of 6080 / sec by the addition amount of a triol component, etc., and the polybutylene terephthalate copolymer at a shear rate of 6080 / sec. The melt viscosity depends on the degree of polymerization of the polybutylene terephthalate copolymer, but the upper limit is usually 100 Pa / sec or less, preferably 80 Pa / sec or less, more preferably 60 Pa / sec or less, and particularly preferably 40 Pa / sec or less. The lower limit is usually 1 Pa / sec or more, preferably 3 Pa / sec or more, more preferably 5 Pa / sec or more, and particularly preferably 10 Pa / sec or more. If the melt viscosity at a shear rate of 6080 / sec is greater than the above upper limit, the viscosity of the resin composition may become very high, the extruder will be overloaded during the molding process, and the resin will be deteriorated by shearing heat generation. There is a possibility that a molded body cannot be stably obtained because of the occurrence. On the other hand, when the melt viscosity is smaller than the lower limit, the melt tension at the time of molding is insufficient, and depending on molding conditions such as the molding method and molding temperature, there is a possibility that a molded body cannot be obtained.

(Aromatic polyester resin composition)
Various additives such as heat stabilizers, antioxidants, crystal nucleating agents, flame retardants are included in the aromatic polyester resin in any stage of the production process of the aromatic polyester resin or in the range where the characteristics are not impaired. Further, an antistatic agent, a release agent, an ultraviolet absorber and the like may be added.
When molding aromatic polyester resins, in addition to the above-mentioned various additives, molding is performed by adding reinforcing agents and extenders such as glass fiber, carbon fiber, titanium whisker, mica, talc, CaCO3, TiO2 and silica. You can also

(Use of polyester resin)
The polyester resin of the present invention is excellent in heat resistance and color tone, is excellent in hydrolysis resistance and biodegradability, and can be produced at low cost, and is therefore suitable for various film applications and injection-molded product applications.

  Specific applications include injection molded products (for example, fresh food trays, fast food containers, outdoor leisure products, electrical and electronic parts, etc.), extruded products (films, sheets, fishing lines, fishing nets, vegetation nets, water retaining sheets). Etc.), hollow molded products (bottles, etc.), and agricultural films, coating materials, fertilizer coating materials, laminate films, plates, stretched sheets, monofilaments, multifilaments, non-woven fabrics, flat yarns, staples, wrinkles Shrinked fiber, striped tape, split yarn, composite fiber, blow bottle, foam, shopping bag, garbage bag, compost bag, cosmetic container, detergent container, bleach container, rope, binding material, surgical thread, sanitary cover stock Used for materials, cold box, cushion film, synthetic paper, paper laminate products, etc. It is a function.

<Polyester polyol resin>
The polyester polyol resin of the present invention contains a structure represented by the following formula (15) in the molecule and has a number average molecular weight of 250 or more and less than 10,000, preferably 500 or more and 5000 or less.

[X in the above formula (15) has a structure represented by any of the following formulas (5) to (7). In formulas (5) to (7), R ₁ and R ₂ each independently represent a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent. R ₃ to R ₆ each independently represent an organic group having 1 to 30 carbon atoms which may have an arbitrary substituent. Further, any two or more of R ₃ to R ₆ may be bonded to each other to form a ring. m and n are each independently an integer of 1 to 10. A in the above formula (15) is an optionally substituted alkylene group, alkenylene group or alkynylene group having 1 to 20 carbon atoms; an optionally substituted cyclohexane having 5 to 20 carbon atoms. An alkylene group, a cycloalkenylene group or a cycloalkynylene group; or an arylene group or a heteroarylene group having 4 to 20 carbon atoms which may have a substituent. ]

  Hereinafter, the structure represented by the formula (15) is referred to as “structure (15)”, and the structure represented by the formula (15) in which X is a structure represented by the formula (5) is referred to as “structure (15-5)”. The structure represented by formula (15), wherein X is a structure represented by formula (6), is referred to as “structure (15-6)”, and X is the structure represented by formula (7) The structure represented by the formula (15) is sometimes referred to as “structure (15-7)”.

The structure (15), preferably the structures (15-5) to (15-7), is itself introduced into the polyester polyol resin by a diol compound having excellent heat resistance as a raw material. By introducing the structure into the polyester polyol resin, the heat resistance of the polyester polyol resin can be increased.
In addition, the polyester polyol resin of the present invention can be excellent in light resistance and weather resistance as a structure not including an aromatic ring structure as a main chain. Further, by introducing a ring having a specific aromaticity, unique optical properties can be imparted.

In the above formulas (5) to (7), R ₁ and R ₂ are each independently a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent, preferably carbon. Number 2-8, More preferably, it is C2-C4, Most preferably, it is C2. When R ₁ and R ₂ have more than 12 carbon atoms, the mechanical strength of the polymer becomes too low, which is not preferable.
Further, when these alkylene groups, alkenylene groups or alkynylene groups have a substituent, there is no particular limitation as long as the excellent physical properties of the polyester polyol resin of the present invention are not significantly impaired. In addition to the alkylene group, alkenylene group or alkynylene group of formulas 1 to 12, an alkoxy group, a hydroxy group, an amino group, a carboxyl group, an ester group, a halogen atom, a thiol group, a thioether group, an organosilicon group, and the like can be given. The alkylene group, alkenylene group or alkynylene group of R ₁ and R ₂ may have two or more of these substituents, and in this case, the two or more substituents may be the same or different. .

  In the above formulas (5) to (7), m and n are each independently an integer of 1 to 10, preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. If m and n exceed 10, the mechanical strength of the polymer becomes too low, which is not preferable.

In said formula (5)-(7), R < ₃ > -R < ₆ > is a C1-C30 organic group which may have a substituent. Examples of the organic group having 1 to 30 carbon atoms of R _{3 to} R ₆ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, Alkyl groups such as dodecyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, linear or branched chain alkenyl groups such as vinyl group, propenyl group and hexenyl group, cyclic alkenyl groups such as cyclopentenyl group and cyclohexenyl group Alkynyl groups such as ethynyl group, methylethynyl group, 1-propionyl group, aryl groups such as phenyl group, naphthyl group, toluyl group, alkoxyphenyl groups such as methoxyphenyl group, aralkyl groups such as benzyl group, phenylethyl group, Heterocyclic groups such as thienyl group, pyridyl group, furyl group and the like can be mentioned. Among these, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like are preferable from the viewpoint of stability of the polymer itself, and an alkyl group and a cycloalkyl group are particularly preferable from the viewpoint of light resistance and weather resistance of the polymer itself.
In addition, when these organic groups have a substituent, there is no particular limitation as long as the excellent physical properties of the polyester polyol resin of the present invention are not significantly impaired, the substituent has 1 to 30 carbon atoms. In addition to the organic group, an alkoxy group, a hydroxy group, an amino group, a carboxyl group, an ester group, a halogen atom, a thiol group, a thioether group, an organic silicon group, and the like can be given. The organic group of R ^{1 to} R ⁴ may have two or more of these substituents, and in this case, the two or more substituents may be the same or different.

In the above formulas (5) to (7), R _{3 to} R ₆ may be two or more, preferably two or three of them may be bonded to each other to form a ring, and in particular, R ₃ and R _{3 5} , R ₄ and R ₆ are preferably acetal bonds with each other to form a ring from the viewpoint of improving the heat resistance of the polyester polyol resin.

Examples of the structure in which R ₃ and R ₅ , R ₄ and R ₆ form a ring by an acetal bond, preferably include those represented by the following structural formula, and among these, from the viewpoint of heat resistance Particularly preferred is a cyclohexylidene group.

In the above formulas (5) to (7), when R ₃ and R ₅ , R ₄ and R ₆ each form a ring with an ethylene group, a thermodynamically stable six-membered ring is formed. Therefore, it is preferable from the viewpoint of improving the heat resistance of the polyester polyol resin of the present invention.

In the above formula (6), when R ₃ , R ₄ and R ₆ form a ring with a methine group, a structure similar to a thermodynamically stable adamantane can be taken. It is preferable from the viewpoint of improving the heat resistance of the resin.

  The cyclohexane ring in the above formulas (5) to (7) is preferably an inositol residue derived from inositol. Specific examples of the inositol include all-cis-inositol, epi-inositol, allo-inositol, muco-inositol, myo-inositol, neo-inositol, chiro-D-inositol, chiro-L-inositol, scyllo-inositol. However, from the viewpoint of easy availability of raw materials, myo-inositol is preferable, and the inositol residue is preferably an inositol residue derived from myo-inositol.

The polyester polyol resin of the present invention preferably contains 80 or less of the structure (15), preferably the structures (15-5) to (15-7) as a repeating unit, when the total ester repeating unit is 100. . When this ratio is 80 or less, other repeating units can be introduced, and other characteristics such as optical characteristics can be introduced. In this respect, the ratio of the structure (15, preferably the structures (15-5) to (15-7) is more preferably 70 or less, and preferably 60 or less. On the other hand, the structure (15) In order to effectively obtain the above-described effects by introducing the structure, the ratio of the structure (15), preferably the structures (15-5) to (15-7) is preferably 1 or more, and is preferably 5 or more. Is more preferable, and it is still more preferable that it is 10 or more.
(Production of polyester polyol resin)
The polyester polyol resin of the present invention can be produced in the same manner as the production method mentioned in the production of the above-mentioned polyester resin, specifically, dicarboxylic acid and / or a derivative thereof (hereinafter referred to as “dicarboxylic acid component”). And a diol compound are esterified and / or transesterified.
In the method for producing a polyester polyol of the present invention, the diol compound of the above formulas (1) to (3) is used as the diol compound.

Examples of the dicarboxylic acid component used in the present invention include aliphatic dicarboxylic acids or mixtures thereof, aromatic dicarboxylic acids or mixtures thereof, and mixtures of aromatic dicarboxylic acids and aliphatic dicarboxylic acids. Among these, those containing an aliphatic dicarboxylic acid as a main component are preferable. The main component referred to in the present invention is usually 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, and particularly preferably 90 mol% or more with respect to all dicarboxylic acid units.
As aliphatic carboxylic acid and aromatic dicarboxylic acid, what was mentioned in description of the above-mentioned polyester resin can be used.

In general, the dicarboxylic acid component used in the present invention is preferably less colored. The upper limit of the yellowness (YI value) of the dicarboxylic acid component used in the present invention is usually preferably 50, more preferably 20, more preferably 10, still more preferably 6, particularly preferably 4. On the other hand, the lower limit thereof is not particularly limited, but is usually preferably −20, more preferably −10, still more preferably −5, particularly preferably −3, and most preferably −1.
By using a dicarboxylic acid component having a YI value of 50 or less, coloring of the resulting polyurethane resin can be suppressed. On the other hand, the use of a dicarboxylic acid component having a YI value of −20 or more is economically advantageous in that it does not require an extremely high capital investment for its production and does not require a great amount of production time. In addition, the YI value in this specification is a value measured by the method based on JIS-K7105 as mentioned above.

The diol compound used in the production of the polyester polyol resin of the present invention may be a mixture of the diol compounds of the above formulas (1) to (3) and other diol compounds. An aromatic diol compound and an aliphatic diol compound may be used, and one of these may be used alone, or two or more may be mixed and used.
Of these, the diol compound is preferably an aliphatic diol compound, i.e., a linear or branched chain or alicyclic diol compound, from the viewpoint of easy handling of the resulting polyester polyol resin and balance of physical properties. The lower limit of the carbon number is preferably 2, and the upper limit is preferably 10, and more preferably 6.

  As specific examples of the aliphatic diol compound, those mentioned in the description of the polyester resin can be used.

The aromatic diol compound is not particularly limited as long as it is an aromatic diol compound having two hydroxy groups, but the lower limit of the carbon number is preferably 6, and the upper limit is preferably 15. Compounds.
As specific examples of the aromatic diol compound, those mentioned in the description of the polyester resin can be used.
In the present invention, the content of the aromatic diol compound in all diol compounds used in the production of the polyester polyol resin is preferably preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol%. It is as follows.

  Moreover, as other diol compounds, both terminal hydroxy polyethers can also be used. The lower limit of the carbon number of both terminal hydroxy polyethers is usually preferably 4, more preferably 10, and the upper limit is usually preferably 1000, more preferably 200, still more preferably 100. As specific examples of both terminal hydroxy polyethers, those mentioned in the above description of the polyester resin can be used.

  The amount of these both terminal hydroxy polyethers used is usually preferably 90% by mass or less, more preferably 50% by mass, as the content of structural units derived from both terminal hydroxy polyethers in the resulting polyester polyol resin. Hereinafter, it is more preferably 30% by mass or less.

(Production of polyester polyol resin)
The polyester polyol resin of the present invention is produced by esterifying and / or transesterifying the dicarboxylic acid component and the diol compound.

  The amount of the diol compound used when producing the polyester polyol resin is substantially equimolar to the amount of the diol compound necessary to become a polyester polyol resin having a desired molecular weight, relative to the number of moles of the dicarboxylic acid component. Generally, since there is distillation of the diol compound during esterification and / or transesterification, it is preferably used in an excess of 0.1 to 20 mol%.

  The esterification and / or transesterification reaction is preferably performed in the presence of an esterification catalyst. The addition timing of the esterification catalyst is not particularly limited, and may be added at the time of charging the raw material, or after removing water to some extent or at the start of pressure reduction.

  When dicarboxylic acid is used as a raw material, the dicarboxylic acid itself exhibits a catalytic action. Therefore, the reaction is carried out without adding a catalyst in the initial stage of the reaction, and the raw material components are used when the reaction rate becomes insufficient in accordance with the production rate of the produced water. It is common to add a different esterification catalyst. At this time, when the esterification catalyst different from the raw material component is added, the final esterification reaction rate is preferably 1/3 or less, more preferably 1/5 or less with respect to the esterification reaction rate at the initial stage of the catalyst-free addition reaction. It is preferable that the reaction is easy to control.

  As an esterification catalyst, the compound containing the periodic table group 1-14 group metal element except a hydrogen atom and a carbon atom is mentioned, for example. Specifically, for example, at least one or more selected from the group consisting of titanium, zirconium, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, calcium, strontium, sodium and potassium Examples thereof include compounds containing organic groups such as metal-containing carboxylates, metal alkoxides, organic sulfonates, and β-diketonate salts, and inorganic compounds such as metal oxides and halides described above, and mixtures thereof.

  Among the above esterification catalysts, a metal compound containing titanium, zirconium, germanium, zinc, aluminum, magnesium or calcium or a mixture thereof is preferable, and among them, a titanium compound, a zirconium compound or a germanium compound is particularly preferable. In addition, the catalyst is preferably a compound that is liquid during the esterification reaction or that dissolves in the produced polyester polyol because the reaction rate increases when the catalyst is melted or dissolved during the esterification reaction.

As the titanium compound used as the esterification catalyst, for example, tetraalkyl titanate is preferable, and specifically, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, tetra Examples thereof include phenyl titanate, tetracyclohexyl titanate, tetrabenzyl titanate, and mixed titanates thereof.
Preferred titanium compounds include, for example, titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, titanium (diisopropoxide) acetylacetonate, titanium bis (ammonium lactate) dihydroxide, titanium bis (ethylacetoacetate). Examples also include diisopropoxide, titanium (triethanolaminate) isopropoxide, polyhydroxytitanium stearate, titanium lactate, titanium triethanolamate, and butyl titanate dimer.

  Furthermore, as a preferable titanium compound, for example, a composite oxide containing titanium oxide or titanium and silicon (for example, a titania / silica composite oxide) can also be used.

  Among these, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, titanium bis (ammonium lactate) dihydroxide, polyhydroxytitanium stearate Preferred are rate, titanium lactate, butyl titanate dimer, titanium oxide or titania / silica composite oxide, tetra-n-butyl titanate, titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, polyhydroxy titanium stearate, titanium lactate Butyl titanate dimer or titania / silica composite oxide is more preferable, especially tetra-n-butyl titanate, polyhydroxy titanium stearate, titanium (o Shi) acetylacetonate, titanium tetraacetyl acetonate or titania / silica composite oxide.

  Examples of the zirconium compound used as the esterification catalyst include zirconium tetraacetate, zirconium acetate hydroxide, zirconium tris (butoxy) stearate, zirconyl diacetate, zirconium oxalate, zirconyl oxalate, ammonium ammonium oxalate, and zirconium oxalate. Potassium, polyhydroxyzirconium stearate, zirconium ethoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide and zirconium tributoxyacetylacetonate and mixtures thereof Is mentioned.

  Further, as the zirconium compound, zirconium oxide or a composite oxide containing zirconium and silicon is also preferably used.

  Among these, zirconyl diacetate, zirconium tris (butoxy) stearate, zirconium tetraacetate, zirconium acetate hydroxide, zirconium ammonium oxalate, potassium zirconium oxalate, polyhydroxyzirconium stearate, zirconium tetra-n-propoxide, Zirconium tetraisopropoxide, zirconium tetra-n-butoxide and zirconium tetra-t-butoxide are preferred, zirconyl diacetate, zirconium tetraacetate, zirconium acetate hydroxide, zirconium tris (butoxy) stearate, zirconium ammonium oxalate, zirconium Tetra-n-propoxide or zirconium tetra-n-butoxide is more preferred Ku, in particular zirconium tris (butoxy) stearate is preferred.

  Specific examples of the germanium compound used as the esterification catalyst include inorganic germanium compounds such as germanium oxide and germanium chloride, and organic germanium compounds such as tetraalkoxygermanium. In view of price and availability, germanium oxide, tetraethoxygermanium, tetrabutoxygermanium, and the like are preferable, and germanium oxide is particularly preferable.

  The amount of catalyst used in the case of using these metal compounds as an esterification catalyst is preferably 1 ppm, more preferably 3 ppm, as a metal-converted mass concentration with respect to the produced polyester polyol. The upper limit is usually preferably 30000 ppm, more preferably 1000 ppm, still more preferably 250 ppm, particularly preferably 130 ppm. When the amount of the catalyst used is 30000 ppm or less, not only is it economically advantageous, but also the thermal stability of the resulting polyester polyol resin can be improved. Moreover, the polymerization activity at the time of polyester polyol manufacture reaction can be improved by setting it as 1 ppm or more.

  The reaction temperature of the esterification reaction and / or transesterification reaction between the dicarboxylic acid component and the diol compound is preferably 150 ° C at the lower limit, more preferably 180 ° C, and preferably 260 ° C at the upper limit. More preferably, it is 250 ° C. The reaction atmosphere is usually an inert gas atmosphere such as nitrogen and / or argon. The reaction pressure is usually preferably from normal pressure to 10 kPa, more preferably from normal pressure to 1 kPa. The lower limit of the reaction time is usually preferably 10 minutes, and the upper limit is usually preferably 10 hours, more preferably 5 hours.

  In addition, the esterification reaction and / or transesterification reaction is carried out at normal pressure or reduced pressure, but the reaction rate is matched, and the boiling point of the diol compound as a raw material, and when the azeotropic solvent coexists, the boiling point is matched. It is preferable to adjust the time and the degree of decompression. In order to perform a more stable operation, the reaction is carried out at normal pressure at the start of the esterification reaction and / or transesterification reaction, and the resulting esterification reaction and / or transesterification reaction rate becomes ½ or less of the initial rate. After that, it is preferable to start depressurization at a preferred time. The decompression start time may be any before or after the catalyst addition time.

  As a reaction apparatus used for producing the polyester polyol resin, a known vertical type or horizontal type stirring tank type reactor can be used. For example, a method using a stirred tank reactor equipped with a vacuum exhaust pipe connecting a vacuum pump and the reactor can be mentioned. Further, it is preferable that a condenser is connected between the vacuum exhaust pipe connecting the vacuum pump and the reactor, and the volatile component or unreacted raw material generated during the polycondensation reaction is recovered by the condenser.

  In the industrial production method, the reaction is judged exclusively by the outflow amount of the distillate component, and the end point of the reaction is determined. The appropriate outflow amount depends on the boiling point (ease of outflow) of the diol compound as a raw material. Generally, the reaction end point is determined by the acid value during the reaction. In some cases, a treatment for adjusting the polyester polyol resin to a desired molecular weight (recondensation or depolymerization by adding a diol compound as a raw material) is added. In general, the end point of the reaction is determined based on the outflow amount. After the reaction is completed, the acid value of the product is measured. If the acid value is outside the target specification, further esterification and / or transesterification is performed. The reaction is performed again, and the acid value of the resulting polyester polyol resin is adjusted to the desired acid value.

  The acid value of the polyester polyol resin used as the end point of the reaction is preferably 1.0 mgKOH / g or less, more preferably 0.5 mgKOH / g or less, and still more preferably 0.2 mgKOH / g or less. preferable. In addition, a preferable water content at the end of the reaction is preferably 200 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less. In order to adjust an appropriate acid value and water content at the end point, It is also possible to carry out the reaction by adding an azeotropic solvent that forms an azeotrope and forms two phases and has no active hydrogen. The azeotropic solvent is not particularly limited as long as it has such performance, but inexpensive aromatic compounds such as benzene and toluene are generally used.

  After the production reaction of such a polyester polyol resin, it can be supplied to the storage or urethanization reaction as it is, or can be supplied to the storage or urethanization reaction after the treatment for deactivating the added catalyst. Although there is no restriction | limiting in particular in the method of deactivating an addition catalyst, It is more preferable to use catalyst deactivation additives, such as a phosphorous acid triester, than the method with a possibility of destroying polyester polyol structures, such as water treatment.

(Physical properties of polyester polyol resin, etc.)
The number average molecular weight of the polyester polyol resin is preferably usually 500 to 5000 in terms of hydroxyl value, more preferably 700 to 4000, still more preferably 800 to 3000. When the polyester polyol resin has a number average molecular weight of 500 or more, when a polyurethane resin is produced using this polyester polyol resin, a material having satisfactory physical properties as a polyurethane resin is obtained. Further, when it is 5000 or less, the handleability is good without the viscosity of the polyester polyol resin being too high.

  Furthermore, the molecular weight distribution (Mw / Mn) by GPC (gel permeation chromatography) measurement of this polyester polyol resin is usually preferably from 1.2 to 4.0, more preferably from 1.5 to 3.5, Preferably it is 1.8-3.0. By making the molecular weight distribution 1.2 or more, the economics of polyester polyol resin production is improved. Moreover, the physical property of the polyurethane resin obtained using this polyester polyol resin improves by setting it as 4.0 or less.

Furthermore, these polyester polyol resins are preferably liquid at 40 ° C. when the polyurethane production reaction is carried out without solvent, and more preferably have a viscosity at 40 ° C. of 15000 mPa · s or less.
The polyester polyol of the present invention is not particularly limited whether it is solid at room temperature or liquid (liquid), but it is preferably liquid at room temperature for handling.

The polyester polyol resin of the present invention is usually preferably a polyester polyol resin with little coloring. The upper limit of the value represented by the color tone b value of the polyester polyol resin of the present invention is usually preferably 1.5, more preferably 1.1, still more preferably 0.8, and particularly preferably 0.65. On the other hand, the lower limit thereof is not particularly limited, but it is usually preferably -2, more preferably -1.5, still more preferably -0.8. A polyester polyol having a color tone b value of 1.5 or less has an advantage that, for example, use applications such as polyurethane films and sheets using the polyester polyol as a raw material are not limited. On the other hand, a polyester polyol having a color tone b value of −2 or more is economically advantageous because the production process for producing the polyester polyol is not complicated, and an extremely expensive equipment investment is unnecessary.
(Use of polyester polyol resin)
The polyester polyol resin of the present invention is also useful as a polyurethane raw material, and can produce a polyurethane excellent in heat resistance, weather resistance, abrasion resistance, mechanical strength, and chemical resistance. In this case, an aqueous polyurethane emulsion or urethane (meth) acrylate may be used.
Polyurethane using the polyester polyol resin of the present invention is excellent in chemical resistance, low temperature characteristics, heat resistance, etc. It can be suitably used in all applications where polyols are usually used, such as raw materials for paints, coating agents, active energy ray-curable resin compositions, and the like.
<Polyurethane resin>
<Structure>
The polyurethane resin of the present invention includes a structure represented by the following formula (16) in the molecule.

[X in the above formula (16) has a structure represented by any of the following formulas (5) to (7). In formulas (5) to (7), R ₁ and R ₂ each independently represent a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent. R ₃ to R ₆ each independently represent an organic group having 1 to 30 carbon atoms which may have an arbitrary substituent. Further, any two or more of R ₃ to R ₆ may be bonded to each other to form a ring. m and n are each independently an integer of 1 to 10. A in the above formula (16) is an alkylene group having 1 to 20 carbon atoms, an alkenylene group or an alkynylene group which may have a substituent; a cyclohexane having 5 to 20 carbon atoms which may have a substituent. An alkylene group, a cycloalkenylene group or a cycloalkynylene group: or an arylene group or heteroarylene group having 4 to 20 carbon atoms which may have a substituent. ]

  Hereinafter, the structure represented by the formula (16) is referred to as “structure (16)”, and the structure represented by the formula (16) in which X is a structure represented by the formula (5) is referred to as “structure (16-5)”. The structure represented by formula (16), wherein X is a structure represented by formula (6), is referred to as “structure (16-6)”, and X is represented by formula (7). The structure represented by the formula (16) may be referred to as “structure (16-7)”.

The structure (16), preferably the structures (16-5) to (16-7), is itself introduced into the polyurethane resin by a diol compound having excellent heat resistance as a raw material. By introducing into the polyurethane resin, the heat resistance of the polyurethane resin can be increased.
In addition, the polyurethane resin of the present invention can be excellent in light resistance and weather resistance as a structure not including an aromatic ring structure as a main chain. Further, by introducing a ring having a specific aromaticity, unique optical properties can be imparted.

In the above formulas (5) to (7), R ₁ and R ₂ are each independently a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent, preferably carbon. Formula 2-8, More preferably, it is 2-4, Most preferably, it is 2. When R ₁ and R ₂ have more than 12 carbon atoms, the mechanical strength of the polymer becomes too low, which is not preferable.
Further, when these alkylene group, alkenylene group or alkynylene group has a substituent, there is no particular limitation as long as it does not significantly impair the excellent physical properties of the polyurethane resin of the present invention. In addition to 1 to 12 of the alkylene group, alkenylene group and alkynylene group, an alkoxy group, a hydroxy group, an amino group, a carboxyl group, an ester group, a halogen atom, a thiol group, a thioether group, an organosilicon group, and the like can be given. The alkylene group, alkenylene group or alkynylene group of R ₁ and R ₂ may have two or more of these substituents, and in this case, the two or more substituents may be the same or different. .

  In the above formulas (5) to (7), m and n are each independently an integer of 1 to 10, preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. If m and n exceed 10, the mechanical strength of the polymer becomes too low, which is not preferable.

In said formula (5)-(7), R < ₃ > -R < ₆ > is a C1-C30 organic group which may have a substituent. Examples of the organic group having 1 to 30 carbon atoms of R _{3 to} R ₆ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and Alkyl groups such as dodecyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; linear or branched chain alkenyl groups such as vinyl group, propenyl group and hexenyl group; cyclic alkenyl groups such as cyclopentenyl group and cyclohexenyl group An alkynyl group such as an ethynyl group, a methylethynyl group and a 1-propionyl group; an aryl group such as a phenyl group, a naphthyl group and a toluyl group; an alkoxyphenyl group such as a methoxyphenyl group; an aralkyl group such as a benzyl group and a phenylethyl group; Examples include heterocyclic groups such as thienyl group, pyridyl group and furyl group. Among these, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group is preferable from the viewpoint of stability of the polymer itself, and an alkyl group or a cycloalkyl group is particularly preferable from the viewpoint of light resistance and weather resistance of the polymer itself.
Moreover, when these organic groups have a substituent, there is no particular limitation as long as the excellent physical properties of the polyurethane resin of the present invention are not significantly impaired. In addition to the groups, an alkoxy group, a hydroxy group, an amino group, a carboxyl group, an ester group, a halogen atom, a thiol group, a thioether group, an organosilicon group, and the like can be given. The organic group of R _{3 to} R ₆ may have two or more of these substituents, and in this case, the two or more substituents may be the same or different.

In the above formulas (5) to (7), R _{3 to} R ₆ may be two or more, preferably two or three of them may be bonded to each other to form a ring, and in particular, R ₃ and R _{3 5} , R ₄ and R ₆ preferably form a ring with an acetal bond with each other from the viewpoint of improving the heat resistance of the polyurethane resin.

Examples of the structure in which R ₃ and R ₅ , R ₄ and R ₆ form a ring by an acetal bond, preferably include those represented by the following structural formula, and among these, from the viewpoint of heat resistance Particularly preferred is a cyclohexylidene group.

In the above formula (6), when R ₃ , R ₄ and R ₆ form a ring with a methine group, a structure similar to a thermodynamically stable adamantane can be taken. It is preferable from the viewpoint of improving the heat resistance.

  The cyclohexane ring in the above formulas (5) to (7) is preferably an inositol residue derived from inositol. Specific examples of the inositol include all-cis-inositol, epi-inositol, allo-inositol, muco-inositol, myo-inositol, neo-inositol, chiro-D-inositol, chiro-L-inositol, scyllo-inositol. However, from the viewpoint of easy availability of raw materials, myo-inositol is preferable, and the inositol residue is preferably an inositol residue derived from myo-inositol.

  The polyurethane resin of the present invention preferably contains 80 or less of the above structure (15), preferably the above structures (15-5) to (15-7) as repeating units, assuming that all urethane repeating units are 100. When this ratio is 80 or less, other repeating units can be introduced, and other characteristics such as optical characteristics can be introduced. From this viewpoint, the ratio of the structure (15), preferably the structures (15-5) to (15-7) is more preferably 70 or less, and preferably 60 or less. On the other hand, in order to effectively obtain the above-described effects by introducing the structure (15), the ratio of the structure (15), preferably the structures (15-5) to (15-7) is 1 or more. Preferably, it is 5 or more, more preferably 10 or more.

(Manufacture of polyurethane resin)
In the present invention, in the production of the polyurethane resin, one or more of the above-described polyester polyol resin or polycarbonate polyol resin of the present invention may be used, and one or more known polyols may be further mixed and used.
A polyurethane can be produced using the above-described polyol and isocyanate compound and, if necessary, a chain extender, a chain terminator, a crosslinking agent and the like.

  Examples of the isocyanate compound used in the production of the polyurethane resin of the present invention include 2,4- or 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), paraphenylene diisocyanate, 1 Aromatic diisocyanates such as, 5-naphthalene diisocyanate or tolidine diisocyanate; aliphatic diisocyanates having an aromatic ring such as α, α, α ′, α′-tetramethylxylylene diisocyanate; methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, Chain aliphatic diisocyanates such as 2,4- or 2,4,4-trimethylhexamethylene diisocyanate or 1,6-hexamethylene diisocyanate; -Cyclohexane diisocyanate, methylcyclohexane diisocyanate (hydrogenated TDI), 1-isocyanate-3-isocyanate methyl-3,5,5-trimethylcyclohexane (IPDI), 4,4'-dicyclohexylmethane diisocyanate or isopropylidene dicyclohexyl-4,4 And alicyclic aliphatic diisocyanates such as' -diisocyanate. These may be used alone or in combination of two or more.

  In the present invention, a chain aliphatic diisocyanate and / or an alicyclic aliphatic diisocyanate is used in applications requiring weather resistance, such as synthetic / artificial leather and paint, in terms of less yellowing due to light. It is preferable. Among them, it is preferable to use 1,6-hexamethylene diisocyanate, 1-isocyanate-3-isocyanate methyl-3,5,5-trimethylcyclohexane or 4,4'-dicyclohexylmethane diisocyanate because it has good physical properties and is easily available. . On the other hand, it is preferable to use aromatic diisocyanates with high cohesive strength for applications that require strength, such as elastic fibers, and in particular, tolylene diisocyanate (TDI) or diphenylmethane diisocyanate in terms of good physical properties and easy availability. (Hereinafter sometimes referred to as MDI) is preferably used. Further, a part of the NCO group of the isocyanate compound may be modified to urethane, urea, burette, allophanate, carbodiimide, oxazolidone, amide, imide or the like, and the polynuclear substance contains isomers other than the above. Some are included.

The amount of these isocyanate compounds used is usually preferably 0.1 to 10 equivalents, more preferably 0.8 to 1 with respect to 1 equivalent of the hydroxyl group of the polyol and 1 equivalent of the hydroxy group and amino group of the chain extender. 0.5 equivalent, more preferably 0.9 to 1.05 equivalent.
By making the usage-amount of an isocyanate compound below the said upper limit, it is prevented that an unreacted isocyanate group raise | generates an unfavorable reaction and a desired physical property is easy to be obtained. Moreover, by making the usage-amount of an isocyanate compound more than the said minimum, the molecular weight of the polyurethane resin obtained becomes large enough, and desired performance can be expressed.

  Since the isocyanate compound reacts with moisture contained in the polyurethane raw material other than the isocyanate compound such as a polyol and a chain extender and partially disappears, the amount of the isocyanate compound may be added to a desired amount of the isocyanate compound used. Specifically, before mixing with the isocyanate compound during the reaction, the moisture content of the polyol or chain extender is measured, and an isocyanate compound having an isocyanate group equivalent to twice the moisture content is obtained. This is in addition to the predetermined usage amount.

  The mechanism by which the isocyanate group disappears by reacting with moisture is that the isocyanate group reacts with water molecules to become an amine compound, and the amine compound further reacts with the isocyanate group to form a urea bond. Two isocyanate groups disappear. Since the disappearance of the isocyanate compound required due to this disappearance may result in failure to obtain the desired physical properties, it is effective to add an isocyanate compound to compensate for the amount of water by the method described above. is there.

  In the present invention, a chain extender having two or more active hydrogens may be used as necessary. Chain extenders are mainly classified into compounds having two or more hydroxy groups or compounds having two or more amino groups. Of these, short-chain polyols, specifically compounds having two or more hydroxy groups, are preferred for polyurethane applications, and polyamine compounds, specifically compounds having two or more amino groups, are preferred for polyurethane urea applications. . In addition, it is more preferable in view of physical properties to use a compound having a molecular weight (number average molecular weight) of 500 or less as the chain extender because the rubber elasticity of the polyurethane resin is improved.

  Examples of the compound having two or more hydroxy groups include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,2-butanediol, 1, 3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2 -Propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl 1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-butyl-2-hexyl-1,3-propanediol, 1,8-octanediol, 2-methyl-1,8- Examples include chain aliphatic glycols such as octanediol and 1,9-nonanediol; alicyclic glycols such as bishydroxymethylcyclohexane; and glycols having an aromatic ring such as xylylene glycol and bishydroxyethoxybenzene.

  Examples of the compound having two or more amino groups include aromatic diamines such as 2,4- or 2,6-tolylenediamine, xylylenediamine, and 4,4'-diphenylmethanediamine; ethylenediamine, 1,2- Propylenediamine, 1,6-hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, 1,3-diaminopentane, 2,2,4- or 2, Chain aliphatic diamines such as 4,4-trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine and 1,10-decanediamine; 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 4,4'-dicyclohexylmethane Min (hydrogenated MDA), isopropylidene cyclohexyl-4,4'-diamine, alicyclic aliphatic diamines such as 1,4-diaminocyclohexane and 1,3-bis-aminomethyl cyclohexane.

  Among these, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3 are preferable in the present invention. -Propanediol, isophorone diamine, hexamethylene diamine, ethylene diamine, propylene diamine, 1,3-diaminopentane or 2-methyl-1,5-pentane diamine, especially the ease of handling and storage and the physical properties of the resulting polyurethane 1,4-butanediol is preferred in terms of excellent balance.

Although the usage-amount of these chain extenders is not specifically limited, It is preferable that they are 0.1 equivalent or more and 10 equivalent or less normally with respect to 1 equivalent of polyester polyols.
By setting the amount of the chain extender to be not more than the above upper limit, the obtained polyurethane (or polyurethane urea) is prevented from becoming too hard, desired properties are obtained, and it is easily soluble in a solvent and easy to process. Moreover, by setting it as the said minimum or more, sufficient intensity | strength, elastic recovery performance, or elastic retention performance is obtained without the polyurethane resin obtained being too soft, and a high temperature characteristic can be improved.

  In the present invention, when a diol compound is used as the chain extender, the content of the cyclic carbonyl compound having 5 or 6 carbon atoms is preferably used, and the number of carbon atoms in the diol compound used as the chain extender is 5 Or the upper limit of content of 6 cyclic carbonyl compounds is 100 ppm normally, Preferably it is 50 ppm, More preferably, it is 12 ppm, More preferably, it is 2 ppm. Further, the lower limit is usually 0.01 ppm, preferably 0.1 ppm, more preferably 0.2 ppm, and in particular, the lower limit is preferably 0.5 ppm from the viewpoint of economy of the purification process. When the content of the cyclic carbonyl compound having 5 or 6 carbon atoms in the diol compound derived from biomass resources, particularly 1,4-butanediol, is not more than the above upper limit, the color tone in polyurethane production tends to be preferable. . On the other hand, when it is at least the above lower limit, the purification process of the biomass resource-derived diol compound becomes simple and economically advantageous.

  In the present invention, a chain terminator having one active hydrogen group can also be used as necessary for the purpose of controlling the molecular weight of the resulting polyurethane resin. These chain terminators include compounds having a hydroxy group and compounds having an amino group. Specifically, “the compound having a hydroxy group includes aliphatic monohydroxy compounds such as methanol, ethanol, propanol, butanol and hexanol. The compounds having an amino group include morpholine, diethylamine, dibutylamine. And aliphatic monoamines such as monoethanolamine and diethanolamine, etc. These may be used alone or in combination of two or more.

  In the present invention, a crosslinking agent having three or more active hydrogen groups or isocyanate groups can be used as necessary for the purpose of increasing the heat resistance and strength of the resulting polyurethane resin. Examples of these crosslinking agents include trimethylolpropane, glycerin and its isocyanate-modified product, and polymeric MDI.

  In the present invention, the polyurethane resin may be produced by reacting in a bulk, that is, without solvent, or may be produced by reacting in a solvent excellent in solubility of the polyurethane resin such as an aprotic polar solvent.

Although an example of the manufacturing method of the polyurethane resin of this invention is shown below, the manufacturing method of the polyurethane resin of this invention is not limited to the following methods at all.
Examples of the method for producing polyurethane include a one-stage method and a two-stage method.

(One-step method)
The one-stage method is also called a one-shot method, and is a method in which a reaction is carried out by adding together a polyol, an isocyanate compound and a chain extender. The amount of each compound used may be the amount described above.
The one-shot method may or may not use a solvent. When a solvent is not used, the isocyanate compound and polyol may be reacted using a low-pressure foaming machine or a high-pressure foaming machine, or may be reacted by stirring and mixing using a high-speed rotary mixer.

When a solvent is used, examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers such as dioxane and tetrahydrofuran, hydrocarbons such as hexane and cyclohexane, and aromatics such as toluene and xylene. Hydrocarbons, esters such as ethyl acetate and butyl acetate, halogenated hydrocarbons such as chlorobenzene, trichlene and perchlene, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide and Examples include aprotic polar solvents such as N, N-dimethylacetamide and mixtures of two or more thereof.
Among these organic solvents, an aprotic polar solvent is preferable from the viewpoint of solubility. Preferable specific examples of the aprotic polar solvent include methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone and dimethyl sulfoxide, more preferably N, N-dimethylformamide and N, N-dimethylacetamide are mentioned.

In the one-shot method, the lower limit of the reaction equivalent ratio of NCO / active hydrogen group (polyester polyol and chain extender) is usually preferably 0.50, more preferably 0.8, and the upper limit is usually 1. 5 is preferable, and a range of 1.2 is more preferable.
By setting the reaction equivalent ratio to 1.5 or less, it is possible to prevent an excessive isocyanate group from causing a side reaction and undesirably affecting the physical properties of the polyurethane resin. Moreover, by setting it as 0.50 or more, it can prevent that the molecular weight of the obtained polyurethane resin rises sufficiently and a problem arises in an intensity | strength or heat stability.

  The reaction is preferably carried out at a temperature of 0 to 100 ° C., but this temperature is preferably adjusted according to the amount of the solvent, the reactivity of the raw materials used, the reaction equipment and the like. If the reaction temperature is too low, the progress of the reaction is too slow, or the solubility of the raw materials and the polymer is low, so that the productivity is poor, and if it is too high, side reactions and decomposition of the polyurethane resin occur. The reaction may be performed while degassing under reduced pressure.

Moreover, a catalyst, a stabilizer, etc. can also be added to a reaction system as needed.
Examples of the catalyst include triethylamine, tributylamine, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dineodecanate, stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid.
Examples of the stabilizer include 2,6-dibutyl-4-methylphenol, distearylthiodipropionate, di-β-naphthylphenylenediamine, and tri (dinonylphenyl) phosphite.

(Two-stage method)
The two-stage method is also called a prepolymer method, in which a prepolymer obtained by reacting an isocyanate compound and a polyol in advance at a reaction equivalent ratio of preferably 0.1 to 10.00 is prepared, and then the prepolymer is mixed with an isocyanate compound, In this method, an active hydrogen compound component that is a chain extender is added and reacted in two stages. In particular, after an isocyanate compound having an equivalent amount or more is reacted with a polyol to produce a prepolymer having both ends of an isocyanate group (hereinafter also referred to as “NCO group”) (hereinafter also referred to as “isocyanate group-terminated prepolymer”), Thus, a method of obtaining a polyurethane by reacting a short chain diol compound or a diamine compound which is a chain extender is useful.
A method of reacting a prepolymer with a chain extender after producing a prepolymer having isocyanate groups at both ends (hereinafter also referred to as “two-stage method of isocyanate group ends”) is a method in which a polyester polyol is previously added in an amount of 1 equivalent or more of an isocyanate compound. This is followed by a step of preparing an intermediate (prepolymer) corresponding to the soft segment of the polyurethane resin and having both ends sealed with an isocyanate compound. By reacting with the agent, the molecular weight of the soft segment portion can be easily adjusted, the phase separation of the soft segment and the hard segment can be easily performed, and the characteristics as an elastomer are easily obtained.
In particular, when the chain extender is a diamine compound, it is more preferable to carry out the polyurethane urea formation by the prepolymer method because the reaction rate of the hydroxyl group and the isocyanate group of the polyol is greatly different.

The two-stage method may or may not use a solvent. When a solvent is used, examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers such as dioxane and tetrahydrofuran, hydrocarbons such as hexane and cyclohexane, and aromatic carbonization such as toluene and xylene. Hydrogens, esters such as ethyl acetate and butyl acetate, halogenated hydrocarbons such as chlorobenzene, trichlene and perchlene, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide and N , N-dimethylacetamide and other aprotic polar solvents and mixtures of two or more thereof.
In the present invention, among these organic solvents, an aprotic polar solvent is preferable from the viewpoint of solubility. Preferred specific examples of the aprotic polar solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone and dimethylsulfoxide, and more preferably N, N-dimethylformamide. And N, N-dimethylacetamide.

  When synthesizing an isocyanate group-terminated prepolymer, (1) a prepolymer may be synthesized by directly reacting an isocyanate compound and a polyol without using a solvent, or may be used as it is (2) by the method of (1) A prepolymer may be synthesized and then dissolved in a solvent for use, or (3) a prepolymer may be synthesized by reacting an isocyanate compound and a polyol using a solvent.

In the case of (1), when the chain extender is allowed to act, the polyurethane resin coexists with the solvent by dissolving the chain extender in the solvent or simultaneously introducing the prepolymer and the chain extender into the solvent. It is preferable to obtain by.

  The reaction equivalent ratio of NCO / active hydrogen group (polyol) during prepolymer synthesis is preferably preferably 0.1 at the lower limit, more preferably 0.8, and preferably 10 at the upper limit. The range is more preferably 5, and still more preferably 3.

  The amount of chain extender used is not particularly limited, but the lower limit is usually preferably 0.8, more preferably 0.9, in terms of the equivalent ratio of NCO groups or OH groups contained in the prepolymer. The upper limit is usually preferably 2, more preferably 1.2. By setting this ratio to 2 or less, it is possible to prevent an excessive chain extender from causing a side reaction and adversely affecting the physical properties of the polyurethane. Moreover, by setting this ratio to 0.8 or more, it is possible to prevent the resulting polyurethane resin from having a sufficiently increased molecular weight and causing problems in strength and thermal stability.

  Moreover, you may coexist monofunctional organic amine and alcohol at the time of reaction.

  The reaction temperature is preferably 0 to 250 ° C., but this temperature is preferably adjusted by the amount of the solvent, the reactivity of the raw materials used, the reaction equipment, and the like. If the reaction temperature is too low, the progress of the reaction is too slow, or the solubility of the raw materials and the polymer is low, so that the productivity is poor, and if it is too high, side reactions and decomposition of the polyurethane resin occur. The reaction may be performed while degassing under reduced pressure.

Moreover, a catalyst, a stabilizer, etc. can also be added to a reaction system as needed.
Examples of the catalyst include triethylamine, tributylamine, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dineodecanate, stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid.
However, when the chain extender is highly reactive such as a short-chain aliphatic amine, it is preferable to carry out without adding a catalyst.
Examples of the stabilizer include 2,6-dibutyl-4-methylphenol, distearylthiodipropionate, di-β-naphthylphenylenediamine, and tri (dinonylphenyl) phosphite.

(Physical properties of polyurethane resin, etc.)
The physical properties of the polyurethane resin of the present invention can be explained by taking a polyurethane resin using a polyester polyol obtained from an aliphatic diol such as polybutylene succinate or polybutylene succinate adipate and an aliphatic dicarboxylic acid as an example. It is preferable to have very wide physical properties such as a tensile breaking stress of 5 to 150 MPa and a breaking elongation of 100 to 1500%.
Moreover, when targeting a specific use, it can be set as the polyurethane resin which has the characteristics of arbitrary wide ranges beyond the range of the above ranges. These characteristics can be arbitrarily adjusted by changing the raw materials of polyurethane resin, types of additives, polymerization conditions, molding conditions and the like according to the purpose of use.

  The range of the typical physical property value which the polyurethane resin of this invention has is shown below.

  The composition ratio of the polyurethane resin is preferably such that the molar ratio of the diol unit (constituent unit derived from the diol compound) and the dicarboxylic acid unit is substantially equal.

In general, the polyurethane resin of the present invention is preferably a polyurethane resin with little coloring. The upper limit of the YI value of the polyurethane resin of the present invention is usually preferably 20, more preferably 10, still more preferably 5, particularly preferably 3, while the lower limit is not particularly limited. Usually, it is preferably -20, more preferably -5, still more preferably -1.
A polyurethane resin having a YI value of 20 or less has an advantage that the intended use of films and sheets is not limited. On the other hand, a polyurethane resin having a YI value of −20 or more is economically advantageous because the manufacturing process for producing the polyurethane resin does not become complicated, and an extremely high capital investment is not required.

Although the weight average molecular weight of the polyurethane resin of the present invention as measured by gel permeation chromatography (GPC) varies depending on the use, it is usually preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000 as the polyurethane resin. More preferably, it is 100,000 to 400,000, and particularly preferably 100,000 to 300,000. As molecular weight distribution, Mw / Mn is preferably 1.5 to 3.5, more preferably 1.8 to 2.5, and still more preferably 1.9 to 2.3.
By setting the molecular weight to 1 million or less, the solution viscosity is prevented from becoming too high, and the handleability is improved. Moreover, by setting it as 10,000 or more, it can prevent that the physical property of the polyurethane resin obtained falls too much. When the molecular weight distribution is less than 1.5, it may be accompanied by advanced purification operations such as removal of oligomers, and in addition to the loss of economics of production, the elastic modulus of the resulting polyurethane resin also deteriorates. It is not preferable. Should be 1.5 or higher. Moreover, by making it 3.5 or less, it prevents that a solution viscosity becomes high too much, a handleability improves, and prevents the elasticity modulus of the polyurethane obtained too high, and an elastic recovery property improves.
A solution in which the polyurethane resin of the present invention is dissolved in an aprotic solvent (hereinafter also referred to as “polyurethane solution”) is less prone to gelation and has good storage stability such as a small change in viscosity over time. Since thixotropy is also small, it is convenient for processing into films and yarns.

The content of polyurethane in the polyurethane solution is usually preferably from 1 to 99% by mass, more preferably from 5 to 90% by mass, still more preferably from 10 to 70% by mass, particularly based on the total mass of the polyurethane solution. Preferably it is 15-50 mass%. By setting the content of polyurethane in the polyurethane solution to 1% by mass or more, it is not necessary to remove a large amount of solvent, and productivity can be improved. Moreover, by setting it as 99 mass% or less, the viscosity of a solution can be suppressed and operativity or workability can be improved.
The polyurethane solution is not particularly specified, but is preferably stored in an atmosphere of an inert gas such as nitrogen or argon when stored over a long period of time.

(Polyurethane resin composition)
You may add various additives to the polyurethane resin of this invention as needed. Examples of these additives include CYANOX 1790 (manufactured by Cyanamid Co., Ltd.), IRGANOX 245 and IRGANOX 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.) and 2 , 6-dibutyl-4-methylphenol (BHT), etc .; TINUVIN 622LD and TINUVIN 765 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), SANOL LS-2626, LS-765 (above, Sankyo Corp.) )), Etc .; UV absorbers such as TINUVIN 328 and TINUVIN 234 (above, manufactured by Ciba Specialty Chemicals); silicon compounds such as dimethylsiloxane polyoxyalkylene copolymer, red phosphorus, organic Compounds, phosphorus and halogen-containing organic compounds, bromine or chlorine-containing organic compounds, ammonium polyphosphate, aluminum hydroxide, antimony oxide, etc. and reactive flame retardants; pigments such as titanium dioxide; colorings such as dyes and carbon black Agents; hydrolysis inhibitors such as carbodiimide compounds; fillers such as short glass fibers, carbon fibers, alumina, talc, graphite, melamine and clay; lubricants, oil agents, surfactants, other inorganic extenders and organic solvents In addition, foaming agents such as water and alternative chlorofluorocarbons may be added, which is particularly useful for polyurethane foam for shoe soles.

(Use of polyurethane resin)
The polyurethane resin and the polyurethane resin solution of the present invention can express various characteristics, and are widely used in foams, elastomers, paints, fibers, adhesives, flooring materials, sealants, automotive parts materials, medical materials and artificial leathers. Can be used.

<Method for measuring physical properties of resin>
(Reduced viscosity (ηsp / c))
It was measured by the method described in the examples.

(Terminal acid value of resin (AV))
After pulverizing the pellet-shaped resin, the sample was dried at 60 ° C. for 30 minutes in a hot air dryer, cooled to room temperature in a desiccator, 0.1 g was accurately weighed and collected in a test tube, and 3 ml of benzyl alcohol was added. In addition, it was dissolved at 195 ° C. for 3 minutes while blowing dry nitrogen gas, and then 5 ml of chloroform was gradually added and cooled to room temperature. Add 1 to 2 drops of phenol red indicator to this solution, and titrate with 0.1 mol / l sodium benzyl alcohol solution of sodium hydroxide with stirring while blowing dry nitrogen gas. did. Moreover, the same operation was implemented as a blank, without adding a resin sample, and the terminal acid value (AV) was computed by the following formula | equation (I).
Terminal acid value (μ equivalent / g) = (ab) × 0.1 × f / w (I)
(Where a is the amount of benzyl alcohol solution of 0.1 mol / l sodium hydroxide required for titration (μl), b is the amount of 0.1 mol / l sodium hydroxide required for titration with a blank. The amount of benzyl alcohol solution (μl), w is the amount of resin sample (g), and f is the titer of benzyl alcohol solution of 0.1 mol / l sodium hydroxide.

In addition, the titer (f) of the benzyl alcohol solution of 0.1 mol / l sodium hydroxide was calculated | required with the following method.
Collect 5 ml of methanol in a test tube, add 1-2 drops of phenol red ethanol solution as an indicator, Titrate to a color change point with 0.4 ml of a 1 mol / l sodium hydroxide benzyl alcohol solution, then add 0.2 ml of a 0.1 mol / l aqueous hydrochloric acid solution with a known titer as a standard solution, and add 0. The solution was titrated with a 1 mol / l sodium hydroxide solution in benzyl alcohol to the discoloration point (the above operation was performed while blowing dry nitrogen gas), and the titer (f) was calculated by the following formula (II).
Titer (f) = fHCl × QHCl / QNaOH (II)
(Where fHCl is the titer of 0.1 mol / l hydrochloric acid aqueous solution, QHCl is the amount of collected 0.1 μl hydrochloric acid aqueous solution (μl), QNaOH is 0.1 mol / l sodium hydroxide benzyl alcohol Solution titration (μl).)
The lower the terminal acid value, the better the heat resistance and hydrolysis resistance of the resin.

(YI value)
The YI value is measured by filling a pellet-shaped resin into a cylindrical powder measurement cell having an inner diameter of 30 mm and a depth of 12 mm, and using a colorimetric color difference meter Color Meter ZE2000 (Nippon Denshoku Industries Co., Ltd.). It measured based on the method of K7105. The measurement cell was rotated by 90 degrees by the reflection method and obtained as a simple average value of values measured at four points.

(Intrinsic viscosity of resin (IV))
It calculated | required in the following way using the Ubbelohde type viscometer. That is, using a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1), the number of seconds of dropping only the resin solution having a concentration of 1.0 g / dl and the solvent was measured at 30 ° C., and the following formula (III) I asked more.
IV = ((1 + 4KHηsp) 0.5-1) / (2KHC) (III)
(Where ηsp = η / η0−1, η is the resin solution falling seconds, η0 is the solvent dropping seconds, C is the resin concentration (g / dl) of the resin solution, and KH is the Huggins constant. (KH is 0.33.)

(Melt Volume Rate (MVR))
Melt volume rate (MVR) is a numerical value that represents the fluidity of a thermoplastic resin when it melts. The resin melted in a cylinder has a specified diameter set at the bottom of the cylinder under constant temperature and load conditions. It is a value calculated by the following formula (IV) by measuring the amount of resin extruded from a die for 10 minutes, and is displayed in units of “cm3 / 10 min”. The resin sample was subjected to measurement after heat drying at 160 ° C. for 4 hours or more, or vacuum drying treatment at 60 ° C. for 24 hours or more.
The melt time was 6 minutes, the measurement temperature was 260 ° C., the load was 2.16 kg, and the die diameter was 2 mm.
^{MVR (cm 3 / 10min) =} (427 × L) / t ... (IV)
(Here, L is a predetermined piston moving distance (cm), t is an average value (sec) of measurement time, and “427” is an average cross-sectional area of the piston and cylinder 0.711 (cm 2) × reference time) (This is a value calculated in 600 seconds (second).)

(Metal content of resin)
The metal content of the resin was quantified by ICP (Inductively Coupled Plasma) -MS (Mass Spectrometer) method after recovering the metal in the polymer by wet ashing.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded.

[Raw materials]
In the following Examples and Comparative Examples, the materials used for the production of diol compounds and the respective resins are as follows.
<Production material of diol compound>
DL-2,3: 5,6-di-O-cyclohexylidene-myo-inositol (hereinafter referred to as “DCMI”): synthesized according to Reference Example 1

Ethylene carbonate: manufactured by Tokyo Chemical Industry Co., Ltd. Benzyl-2-bromoethyl ether: manufactured by Tokyo Chemical Industry Co., Ltd. Potassium carbonate: manufactured by Wako Pure Chemical Industries, Ltd. Sodium hydride: manufactured by Tokyo Chemical Industry Co., Ltd. Palladium carbon: manufactured by N.E. Chemcat Co., Ltd. Polycarbonate resin production material>
DCMI
1,4-dihydroxyethyl-DL-2,3: 5,6-di-O-cyclohexylidene-myo-inositol (hereinafter referred to as “DCMI-2EO”): synthesized in Example 1, 1,4- Cyclohexanedimethanol (hereinafter referred to as “CHDM”)
Diphenyl carbonate (hereinafter referred to as “DPC”)
Calcium acetate monohydrate Isosorbide (hereinafter referred to as “ISB”)

[Evaluation methods, etc.]
<Confirmation of diol compound>
Gas chromatograph (GC) analysis and NMR analysis were performed.

(Gas chromatograph (GC) analysis conditions)
Equipment: Shimadzu Corporation GC2014
Column: DB-1 (0.25 mm × 30 mm) manufactured by Agilent Technologies
Film thickness 0.25μm
Temperature rising condition: 100 ° C. to 320 ° C. at a rate of 10 ° C./min, held at 320 ° C. for 10 minutes.
Carrier gas: He

⁽¹ H-NMR Analysis Conditions)
¹ H-NMR was measured at a resonance frequency of 400 MHz, a flip angle of 45 °, and a measurement temperature of 25 ° C. using “AVANCE” manufactured by Bruker BioSpin, using heavy DMSO as a solvent.

<Evaluation of resin>
The polycarbonate resin obtained in each production example was evaluated by the method described in the following evaluation items.

(1) Glass transition temperature (Tig · Tmg)
Using a differential scanning calorimeter (“EXSTAR 6220” manufactured by SII Nano Technology Co., Ltd.), about 10 mg of the sample is heated at a heating rate of 10 ° C./min, and the temperature of the sample is measured. In accordance with JISK7121 (1987). The extrapolated glass transition, which is the temperature at the intersection of the straight line obtained by extending the base line on the low temperature side to the high temperature side and the broken line drawn with a line that maximizes the slope of the step change portion of the glass transition The temperature Tig was determined. Further, the intermediate point glass transition start temperature Tmg was determined from the temperature at which the straight line equidistant in the vertical axis direction from the straight line extended from each base line and the curve of the stepwise change portion of the glass transition intersect.

(2) Reduced viscosity Using a Ubbelohde type with a DT-504 automatic viscometer manufactured by Chuo Rika Co., Ltd., and using a 1: 1 mixed solvent (mass ratio) of phenol and 1,1,2,2-tetrachloroethane as a solvent, The temperature was measured at 30.0 ° C. ± 0.1 ° C. The concentration was precisely adjusted to be 1.00 g / dl. The sample was dissolved in 30 minutes while stirring at 110 ° C., and used for measurement after cooling. From the passage time t _{0 of the} solvent and the passage time t of the solution, the relative viscosity ηrel is obtained from the following formula,
ηrel = t / t ₀ (g · cm ⁻¹ · sec ⁻¹ )
From the relative viscosity ηrel, the specific viscosity ηsp was determined from the following formula.
ηsp = (η−η ₀ ) / η ₀ = ηrel−1
The reduced viscosity (converted viscosity) ηred was determined by dividing the specific viscosity ηsp by the concentration c (g / dl).
ηred = ηsp / c
The higher this number, the greater the molecular weight.

(3) 5% thermal weight loss temperature (Td)
In Examples 3 and 4 and Comparative Examples 1 and 2, “TG-DTA” (2000SA) manufactured by Netch Japan Co., Ltd. was used, and about 10 mg of a sample was placed on a platinum container, and the temperature was increased in a nitrogen atmosphere (nitrogen flow rate 50 ml / min). The mass of the sample was measured from 30 ° C. to 500 ° C. at a temperature rate of 10 ° C./min, and the temperature (Td) when the 5% weight decreased was obtained. The higher this temperature is, the harder it is to decompose.

(4) NMR
In Example 4, about 30 mg of a sample was placed in an NMR sample tube having an outer diameter of 5 mm and dissolved in 0.7 ml of deuterated chloroform (containing 0.03 v / v% tetramethylsilane). A ¹ H-NMR spectrum, a COSY spectrum, a 1H-13C HSQC spectrum, and a 1H-13C HMBC spectrum were obtained using a Bruker "AVANCE III 950" at a resonance frequency of 950.3 MHz, a flip angle of 30 °, and a measurement temperature of 25 ° C. It was measured.

(5) Press film production test About 2 g of resin pellets vacuum-dried at 60 ° C. for 5 hours or more, aluminum having an outer width of 10 cm × width of 10 cm, an inner width of 8 cm × width of 8 cm, and a thickness of 0.2 mm Using a spacer made of SUS, spread a 10 cm x 10 cm x 1 mm mirror-finished SUS plate sprayed on the top and bottom of the sample using a silicon aerosol 200 spray manufactured by Toray Dow Corning Silicone for several seconds, and preheat at a temperature of 200-230 ° C for 3 minutes. After pressurizing for 5 minutes under the condition of a pressure of 40 MPa, the entire spacer was taken out and cooled to produce a film. When this film was peeled off and removed, whether or not a press film could be produced was determined based on whether or not the film was peeled off without being broken.

Reference Example 1 Synthesis of DCMI A 500 ml reaction vessel equipped with a Dimroth was purged with nitrogen, and then 30 ml (167 mmol) of myo-inositol, 200 ml of N, N-dimethylformamide (hereinafter referred to as “DMF”), p- 863 mg of toluenesulfonic acid monohydrate and 75 mL of dimethoxycyclohexane were added and stirred at 100 ° C. for 3 hours. After cooling to 40 ° C., 2.5 mL of triethylamine was added, and DMF as a reaction solvent was distilled off under reduced pressure. Thereafter, 250 mL of ethyl acetate was added, and liquid separation was performed with 300 mL of a 5% aqueous sodium carbonate solution, followed by washing once with 300 mL of ion-exchanged water. The obtained organic phase was distilled off under reduced pressure, crystallization was carried out with 50 mL of ethyl acetate / 70 mL of n-hexane, and the resulting white precipitate was filtered. Thereafter, crystallization was performed again with 50 mL of ethyl acetate / 70 mL of n-hexane. The obtained solid was vacuum-dried at 60 ° C. for 5 hours to obtain 9.8 g (yield: 17.2%) of DCMI as the target compound. ¹ H-NMR analysis of this compound was conducted, and it was confirmed that the compound was the target compound and that the purity was 99.0 area% by gas chromatographic analysis.

Example 1
<Production of diol compound>

In a 300 mL four-necked flask equipped with a thermometer, a Dimroth condenser, a ball plug, and a stirrer bar, DCMI 30.2 g (88.1 mmol), ethylene carbonate 31.9 g (361 mmol), potassium carbonate 0.305 g (2.20 mmol) Was added. A three-way cock was attached to the tip of the Dimroth condenser, one connected to a nitrogen flow line and the other connected to a bubbler. The nitrogen flow was continued for 5 minutes, and the inside of the container was purged with nitrogen. The temperature was raised to 150 ° C. in an oil bath, and the mixture was stirred as it was for 3 hours. After cooling to room temperature, the reaction mixture was dissolved in about 1700 mL of ethyl acetate with an ultrasonic cleaner. The ethyl acetate solution was washed 3 times with demineralized water. The ethyl acetate layer was dried over anhydrous sodium sulfate. Sodium sulfate was removed by filtration, and the filtrate was concentrated to dryness to give a pale yellow oil. Yield 42.5 g (93% yield). When this pale yellow oil was analyzed by proton NMR, the proton signal of the secondary alcohol derived from DCMI disappeared, and the proton signal of the ethylene chain of the adduct and the proton signal of the primary alcohol appeared. This revealed that the addition reaction of ethylene carbonate proceeded. Furthermore, when this pale yellow oily substance was analyzed by GC, it was found that the following compounds 1, 2, 3, 4 and 5 were contained in the same order at a ratio of 1: 42: 36: 17: 4. .
In the compounds 1 to 5, a structure in which ethylene oxide (hereinafter referred to as “EO”) is added to two hydroxyl groups of DCMI is referred to as DCMI-2EO. From the notation DCMI-2EO, a structure in which n EOs are added to DCMI is indicated as DCMI-nEO. Moreover, the said yield was made into the ratio with respect to the theoretical yield when all the ethylene carbonate 4 equivalents reacted with DCMI and became DCMI-4EO.

Example 2
<Production of diol compound>

(Production of Compound 6 as a Precursor of Compound 2)
After nitrogen flow in the container, under nitrogen, 8.41 g (210 mmol) of sodium hydride (oil) and 80 ml of dry tetrahydrofuran were added to a 1000 ml four-necked flask, and 344.00 g of DCMI was cooled in an ice-water bath. A solution in which (100 mmol) was dissolved in 350 ml of tetrahydrofuran was added dropwise. Immediately after the dropwise addition of the DCMI solution in tetrahydrofuran, bubbling thought to be H ₂ was observed. After foaming subsided, the temperature was raised to room temperature and stirred for 1 hour. Thereafter, a solution prepared by dissolving 50.01 g (233 mmol) of benzyl-2-bromoethyl ether in 50 ml of dry THF was dropped while the flask was cooled again with an ice-water bath. After the dropwise addition, the ice-water bath was removed, and the mixture was stirred at room temperature for 30 minutes, then warmed to 60 to 70 ° C. and stirred for 18 hours. In the middle, the change with time was observed by TLC, and when the amount of benzyl-2-bromoethyl ether became very small and was almost consumed, the heating was stopped.
As a post-treatment, the flask was ice-cooled with stirring under nitrogen, 150 ml of ethyl acetate was added to the flask, 100 ml of water was slowly added dropwise, the aqueous phase was separated and the organic phase was washed with 100 ml of water. And washed twice. The organic phase was concentrated with an evaporator to obtain 68.10 g of a yellowish viscous liquid. Then, silica gel column purification was performed using a mixed solvent of hexane and ethyl acetate (hexane / ethyl acetate = 10/1 to 1/1 (volume ratio)), and the solvent was distilled off under reduced pressure, thereby clearing the following compound 6: As a viscous liquid, 46.36 g (76.2 mmol: yield 76.2%) was obtained.
The NMR measurement results of the obtained compound 6 are as follows.
¹ H-NMR (400 MHz, CDCl ₃ ) δ1.35-1.79 (20H, m), 3.32 (1H, dd, J = 10.6, 1.3 Hz), 3.62 (1H, dd, J = 10.6, 4.0 Hz), 3.66-3.75 (4H, m), 3.81 (1H, dd), 3.88-4.01 (5H, m), 4.07 ( dd, J = 5.1, 1.5 Hz), 4.49 (1H, dd, J = 4.1, 1.0 Hz). 4.59 (4H, bs), 7.23-7.40 (10H, m)

(Production of Compound 2)
In a 500 ml-3 necked flask, 21.95 g (36.05 mmol) of DCMI-2EO-Bn (Compound 6) and 220 ml of tetrohydrofuran were charged under nitrogen, and the mixture was stirred and completely dissolved, and then the vessel was cooled with ice-water. Then, 10% -palladium carbon (manufactured by N.E. Chemcat, PE-Type: 55.25% water content) was charged, and the inside of the container was replaced with hydrogen using a hydrogen-containing balloon. Then, hydrogenation was performed. After 2 hours, disappearance of the raw material was confirmed by thin layer chromatography (hereinafter referred to as “TLC”). Palladium carbon was removed by filtration, and washing was performed by sprinkling twice with 5 ml of tetrahydrofuran. The obtained filtrate was evaporated under reduced pressure to obtain 15.30 g of a white solid. This white solid was dissolved in about 23 ml of THF, stirred in an ice-water bath while cooling, and about 200 ml of hexane was added dropwise to precipitate crystals. Further, cooling with an ice-water bath was continued, and the mixture was stirred for 1 hour, filtered under reduced pressure, and washed with 3 ml of ice-cooled THF / hexane (= 1/10) solution. Then, it dried until it became constant weight at 80 degreeC using the vacuum dryer, and obtained 15.21g (33.3mmol, yield 92.4%) of the compound 2 as a white crystal.
The NMR measurement result of the obtained compound 2 is as follows. ¹ H-NMR (400 MHz, DMSO-d6) δ 1.35 (4H, b), 1.45-1.72 (16H, m), 3.35-3.55 (10H, m), 3.56- 3.70 (4H, m), 3.72-3.86 (2H, m), 4.01 (1H, dd, J = 5.2, 1.0 Hz), 4.46 (1H, dd, J = 4.9, 0.7 Hz), 4.54 (1 H, t, J = 5.5 Hz), 4.60 (1 H, t, J = 5.4 Hz)

Example 3
<Manufacture of polycarbonate resin>
DCMI-2EO 7.55 g (0.0176 mol), CHDM 5.93 g (0.0411 mol), DPC 13.08 g (0.0611 mol), and calcium acetate monohydrate 3.10 × 10 ⁻³ g (Catalyst) 1.76 × 10 ⁻⁵ mol) is charged into a reaction vessel, and the heating bath temperature is heated to 150 ° C. under a nitrogen atmosphere, stirring is performed as necessary, and the pressure is increased to 220 ° C. in 60 minutes at normal pressure. The raw material was dissolved by heating.
As the first step of the reaction, after maintaining at 220 ° C. for 30 minutes, the pressure is reduced from normal pressure to 13.3 kPa in 40 minutes and then held at 13.3 kPa for 60 minutes, and the generated phenol is stored in the reaction vessel. I pulled out. As the second step, the phenol generated was withdrawn out of the reaction vessel while controlling the heating bath temperature to 240 ° C. in 20 minutes and controlling the pressure to 0.200 kPa or less in 30 minutes. . After reaching a predetermined stirring torque, the reaction was terminated, and the produced reaction product was taken out from the reaction vessel to obtain a polycarbonate resin.
The polycarbonate resin obtained had a reduced viscosity of 0.944 dl / g, a glass transition temperature Tig of 67 ° C., and a Tmg of 70 ° C. The 5% thermal weight loss temperature (Td) under a nitrogen atmosphere was 348 ° C.
Moreover, the press film was able to be created.
The production conditions and evaluation results of the obtained polycarbonate resin are shown in Table 1.

Example 4
<Manufacture of polycarbonate resin>
DCMI-2EO 4.50 g (0.0105 mol), ISB 7.16 g (0.0490 mol), CHDM 1.51 g (0.0105 mol), DPC 15.15 g (0.0707 mol), and acetic acid as catalyst Calcium monohydrate 3.70 × 10 ⁻³ g (2.10 × 10 ⁻⁵ mol) was charged into the reaction vessel, and the heating bath temperature was heated to 150 ° C. in a nitrogen atmosphere. Stirring was performed, and the temperature was raised to 220 ° C. in 60 minutes at normal pressure to dissolve the raw materials.
As the first step of the reaction, after maintaining at 220 ° C. for 30 minutes, the pressure is reduced from normal pressure to 13.3 kPa in 40 minutes and then held at 13.3 kPa for 60 minutes, and the generated phenol is stored in the reaction vessel. I pulled out. As the second step, the phenol generated was withdrawn out of the reaction vessel while controlling the heating bath temperature to 240 ° C. in 20 minutes and controlling the pressure to 0.200 kPa or less in 30 minutes. . After reaching a predetermined stirring torque, the reaction was terminated, and the produced reaction product was taken out from the reaction vessel to obtain a polycarbonate resin.
The polycarbonate resin obtained had a reduced viscosity of 0.767 dl / g, a glass transition temperature Tig of 123 ° C., and a Tmg of 127 ° C. The 5% thermal weight loss temperature (Td) under a nitrogen atmosphere was 341 ° C.
Moreover, the press film was able to be created.
The production conditions and evaluation results of the obtained polycarbonate resin are shown in Table 1.
The NMR chart of this polycarbonate resin is shown in FIG. 1, and the calculation results of the composition are shown in Table 2.

[Comparative Example 1]
DCMI 6.69 g (0.0197 mol), CHDM 6.61 g (0.0458 mol), DPC 14.59 g (0.0681 mol), and calcium acetate monohydrate 3.46 × 10 ⁻³ g (1. 97 × 10 ⁻⁵ mol) was used and the reaction was carried out in the same manner as in Example 3.
The polycarbonate resin obtained had a reduced viscosity of 0.369 dl / g, a glass transition temperature Tig of 96 ° C., and a Tmg of 106 ° C. The 5% thermal weight loss temperature (Td) under a nitrogen atmosphere was 341 ° C.
Moreover, when the press film preparation test was done, since the film was brittle and it was cracked when it was peeled off from the SUS plate, the film could not be prepared.
The production conditions and evaluation results of Comparative Example 1 are shown in Table 1.

[Comparative Example 2]
3.81 g DCMI (0.0112 mol), 7.64 g (0.0523 mol) ISB, 1.61 g (0.0112 mol) CHDM, 16.63 g (0.0776 mol) DPC, and acetic acid as catalyst The reaction was carried out in the same manner as in Example 1 using 3.95 × 10 ⁻³ g (2.24 × 10 ⁻⁵ mol) of calcium monohydrate.
The polycarbonate copolymer obtained had a reduced viscosity of 0.469 dl / g, a glass transition temperature Tig of 151 ° C., and a Tmg of 155 ° C. The 5% thermal weight loss temperature (Td) in a nitrogen atmosphere was 338 ° C.
Moreover, when the press film preparation test was done, since the film was brittle and it was cracked when it was peeled off from the SUS plate, the film could not be prepared.
Table 1 shows the production conditions and evaluation results of Comparative Example 2.

  The diol compound of the present invention is excellent in reactivity when used as a structural unit of a polymer. Polycarbonate resin, polycarbonate polyol resin, polyester resin, polyester polyol resin and polyurethane resin produced from the diol compound are heat resistant. Since it is excellent in transparency, light resistance, weather resistance and mechanical strength, it is industrially useful as a molding material applied in various injection molding fields, extrusion molding fields, compression molding fields and the like.

Claims (16)

A diol compound represented by any one of the following general formulas (1) to (3).

[In Formulas (1) to (3), R ₁ and R ₂ each independently represent an alkylene group having 1 to 12 carbon atoms, an alkenylene group or an alkynylene group which may have a substituent. R < ₃ > -R < ₆ > shows the C1-C30 organic group which may have arbitrary substituents each independently. Further, any two or more of R _{3 to} R ₆ may be bonded to each other to form a ring. m and n are each independently an integer of 1 to 10. ] The diol compound according to claim 1, wherein R ₃ and R ₄ , R ₅ and R _{6 in the} above formulas (1) to (3) each form a ring with an acetal bond. The diol compound according to claim _1, wherein R ₁ and R _{2 in the} above formulas (1) to (3) are ethylene groups.   The diol compound according to claim 3, wherein m and n in the formulas (1) to (3) are 1.   The diol compound according to any one of claims 1 to 4, wherein the cyclohexane ring in the above formulas (1) to (3) is an inositol residue derived from myo-inositol. The diol compound according to claim 5, wherein R ₃ , R ₄ and R ₆ in the formula (2) form a ring with a methine group. A polycarbonate resin containing a structure represented by the following formula (4) in the molecule.

[X in the above formula (4) has a structure represented by any of the following formulas (5) to (7). In formulas (5) to (7), R ₁ and R ₂ each independently represent a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent. R ₃ to R ₆ each independently represent an organic group having 1 to 30 carbon atoms which may have an arbitrary substituent. Further, any two or more of R ₃ to R ₆ may be bonded to each other to form a ring. m and n are each independently an integer of 1 to 10. ]
A polycarbonate polyol resin containing a structure represented by the following formula (13) in the molecule.

[X in the above formula (13) has a structure represented by any of the following formulas (5) to (7). In formulas (5) to (7), R ₁ and R ₂ each independently represent a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent. R ₃ to R ₆ each independently represent an organic group having 1 to 30 carbon atoms which may have an arbitrary substituent. Further, any two or more of R ₃ to R ₆ may be bonded to each other to form a ring. m and n are each independently an integer of 1 to 10. ]
A polyester resin containing a structure represented by the following formula (14) in the molecule.

[X in the above formula (14) has a structure represented by any of the following formulas (5) to (7). In formulas (5) to (7), R ₁ and R ₂ each independently represent a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent. R ₃ to R ₆ each independently represent an organic group having 1 to 30 carbon atoms which may have an arbitrary substituent. Further, any two or more of R ₃ to R ₆ may be bonded to each other to form a ring. m and n are each independently an integer of 1 to 10. A in the above formula (9) is an optionally substituted alkylene group having 1 to 20 carbon atoms, an alkenylene group or an alkynylene group; an optionally substituted cyclohexane having 5 to 20 carbon atoms. An alkylene group, a cycloalkenylene group or a cycloalkynylene group: or an arylene group or heteroarylene group having 4 to 20 carbon atoms which may have a substituent. ]
A polyester polyol resin containing a structure represented by the following formula (15) in the molecule.

[X in the above formula (15) has a structure represented by any of the following formulas (5) to (7). In formulas (5) to (7), R ₁ and R ₂ each independently represent a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent. R ₃ to R ₆ each independently represent an organic group having 1 to 30 carbon atoms which may have an arbitrary substituent. Further, any two or more of R ₃ to R ₆ may be bonded to each other to form a ring. m and n are each independently an integer of 1 to 10. A in the above formula (15) is an optionally substituted alkylene group, alkenylene group or alkynylene group having 1 to 20 carbon atoms; an optionally substituted cyclohexane having 5 to 20 carbon atoms. An alkylene group, a cycloalkenylene group or a cycloalkynylene group: or an arylene group or heteroarylene group having 4 to 20 carbon atoms which may have a substituent. ]
A polyurethane resin containing a structure represented by the following formula (15) in the molecule.

[X in the above formula (16) has a structure represented by any of the following formulas (5) to (7). In formulas (5) to (7), R ₁ and R ₂ each independently represent a C 1-12 alkylene group, alkenylene group or alkynylene group which may have a substituent. R ₃ to R ₆ each independently represent an organic group having 1 to 30 carbon atoms which may have an arbitrary substituent. Further, any two or more of R ₃ to R ₆ may be bonded to each other to form a ring. m and n are each independently an integer of 1 to 10. A in the above formula (16) is an alkylene group having 1 to 20 carbon atoms, an alkenylene group or an alkynylene group which may have a substituent; a cyclohexane having 5 to 20 carbon atoms which may have a substituent. An alkylene group, a cycloalkenylene group or a cycloalkynylene group: or an arylene group or heteroarylene group having 4 to 20 carbon atoms which may have a substituent. ]
The resin according to claim 7 to 10, wherein R ₃ and R ₄ , R ₅ and R _{6 in the} formulas (5) to (7) each form a ring with an acetal bond. The resin according to any one of claims 7 to 11, wherein R ₁ and R _{2 in the} formulas (5) to (7) are ethylene groups.   The resin according to claim 13, wherein m and n in the formulas (5) to (7) are 1.   The resin according to any one of claims 7 to 14, wherein the cyclohexane ring in the formulas (5) to (7) is an inositol residue derived from myo-inositol. The resin according to claim 15, wherein R ₃ , R ₄ and R ₆ in the formula (6) form a ring with a methine group.