JP2020186304A - Triazine ring-containing polymer, and thermoplastic resin and optical component containing the same - Google Patents

Abstract

To provide a triazine ring-containing polymer that achieves both of high refractive index and high glass transition temperature.SOLUTION: A triazine ring-containing polymer has a repeating unit of formula (1): -[A-B]-.SELECTED DRAWING: None

Description

The present invention relates to triazine ring-containing polymers, and thermoplastic resins and optical components containing the same.

In recent years, research on optical materials has been actively conducted. Examples of the optical material include various cameras such as cameras, video cameras, and in-vehicle cameras, and materials for optical lenses used in optical systems such as smartphone lenses. As a material for an optical lens, a material having a high refractive index and Abbe number, and also having excellent heat resistance, light transmission (transparency), and easy moldability is required. Compared to glass lenses, resin lenses are lighter and harder to break, have lower material costs, and have the advantages of being able to be processed into various shapes by heat pressing or injection molding. However, in recent years, in order to meet the needs for thinner products and higher pixel counts of cameras, it is required to increase the refractive index of the material itself.

Attempts have been made to introduce aromatic rings, halogen atoms, and sulfur atoms as a method for increasing the refractive index of a polymer, which is a resin material. Among them, the episulfide resin and the thiourethane resin into which a sulfur atom is introduced have a refractive index of 1.7 or more, but have no plasticity, so that the practical range is limited.

Many polymers having a triazine ring have been studied as a highly refracting resin having plasticity. For example, Patent Documents 1 and 2 disclose a triazine ring-containing polymer containing a repeating unit having a triazine ring and having a refractive index of 1.7 or more.

Japanese Unexamined Patent Publication No. 2014-162829 Japanese Unexamined Patent Publication No. 2014-162830

However, the triazine ring-containing polymers described in Patent Documents 1 and 2 have a high refractive index and a high glass transition temperature (Tg), and high thermal stability can be expected. However, especially in optical lens applications such as in-vehicle cameras, further high heat resistance is required.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a material having both a high glass transition temperature and a refractive index.

Another object of the present invention is to provide a thermoplastic molded product containing the above triazine ring-containing polymer.

Another object of the present invention is to provide an optical component including the above-mentioned thermoplastic molded product.

As a result of diligent studies, the present inventors have found that the above problems can be solved by a linear polymer containing a repeating unit in which a triazine structure and an aromatic hydrocarbon group are linked by a thioether bond, and complete the present invention. I let you.

That is, the triazine ring-containing polymer according to the present invention has a repeating unit represented by the following formula (1).

In the above formula (1), A is independently represented by the following formula (2); and B is independently represented by the following formula (3).

In the above formula (2), L represents a single bond or a linking group, and R ₁ is composed of a group consisting of an oxygen atom (O), a sulfur atom (S), a nitrogen atom (N) and a selenium atom (Se). Represents a group with at least one atom selected,

In the above formula (3), R ₂ is a divalent aromatic hydrocarbon group or two or more aromatic hydrocarbon groups having an alkylene group, an oxygen atom (O), a sulfur atom (S) or a selenium atom (Se). Represents a divalent aromatic hydrocarbon linking group that is linked.

According to the present invention, it is possible to provide a triazine ring-containing polymer having both a high glass transition temperature and a high refractive index. In addition, the triazine ring-containing polymer of the present invention has thermoplasticity and is suitable for molding processes such as hot pressing and injection molding.

Hereinafter, embodiments of the present invention will be described, but the technical scope of the present invention should be determined based on the description of the scope of claims, and is not limited to the following embodiments. Unless otherwise specified, in the present specification, operations and physical properties are measured under the conditions of room temperature (20 ° C. or higher and 25 ° C. or lower) / relative humidity of 40% RH or more and 50% RH or less.

In the present specification, the "triazine ring-containing polymer" is also simply referred to as a "polymer", and the "thermoplastic molded product" is also simply referred to as a "molded product". Further, in the present specification, "a divalent aromatic hydrocarbon group or two or more aromatic hydrocarbon groups are linked by an alkylene group, an oxygen atom (O), a sulfur atom (S) or a selenium atom (Se). The divalent aromatic hydrocarbon linking group is also simply referred to as "divalent aromatic hydrocarbon group or the like" or "aromatic hydrocarbon group or the like".

The triazine ring-containing polymer according to one embodiment of the present invention contains a repeating unit represented by the following formula (1). In the present specification, the structural unit represented by the following formula (2) is also referred to as “constituent unit A”. Similarly, the structural unit represented by the following formula (3) is also referred to as “constituent unit B”.

In the above formula (1), A is independently represented by the following formula (2). Further, B is independently represented by the following equation (3).

In the above formula (2), L represents a single bond or a linking group, and R ₁ is composed of a group consisting of an oxygen atom (O), a sulfur atom (S), a nitrogen atom (N) and a selenium atom (Se). Represents a group having at least one atom selected.

In the above formula (3), R ₂ is a divalent aromatic hydrocarbon group or two or more aromatic hydrocarbon groups having an alkylene group, an oxygen atom (O), a sulfur atom (S) or a selenium atom (Se). Represents a divalent aromatic hydrocarbon linking group that is linked.

In the triazine ring-containing polymer according to the present invention, the triazine structure in the structural unit A and the structural unit B (divalent aromatic hydrocarbon group, etc.) are linked via a thioether bond (-S-) to form a main chain. Configure. A polymer having a triazine structure in the main chain has a high refractive index, but it is considered that the refractive index of the polymer can be further improved by further introducing a divalent aromatic hydrocarbon group or the like into the main chain. Further, it is considered that the Tg of the polymer can be increased by introducing a divalent aromatic hydrocarbon group or the like into the main chain. Therefore, the triazine ring-containing polymer according to the present invention can achieve both a high refractive index and a high Tg. The above effect is a divalent aromatic hydrocarbon linking group in which two or more aromatic hydrocarbon groups (such as a divalent aromatic hydrocarbon group) are linked via a sulfur atom (S). Notable in some cases. It is particularly remarkable when it has a thianthrene structure or a diphenylsulfide structure as described below. Further, the triazine ring-containing polymer according to the present invention is rigid and has a high glass transition temperature, and therefore has high environmental reliability. Further, the triazine ring-containing polymer according to the present invention has high plasticity when the weight average molecular weight is 1 million or less, and is suitable for molding steps such as heat pressing and injection molding.

Therefore, the triazine ring-containing polymer of the present invention has a high refractive index, a high glass transition temperature (Tg), exhibits thermoplasticity, and can be used in molding steps such as hot pressing and injection molding. Therefore, the triazine ring-containing polymer of the present invention can be suitably used as a material for various cameras such as cameras and video cameras, and optical lenses used in optical systems such as smartphone lenses. The triazine ring-containing polymer of the present invention can be used as an optical component for an in-vehicle camera or the like, which requires particularly high heat resistance.

The triazine ring-containing polymer according to one embodiment of the present invention has a structural unit A represented by the following formula (2).

In the above formula (2), L represents a single bond or a linking group. Here, L is the a single bond, it means that the substituents R ₁ and triazine structure are linked directly. Further, the linking group when L is a linking group is not particularly limited as long as it does not inhibit the effect of the present invention. Specifically, one or more 6 or less carbon atoms in the alkylene group (e.g., methylene group, ethylene group, trimethylene group, a propylene group, an isopropylidene group _{[-C (CH 3) 2 -} ], tetramethylene group, 2- Methyltrimethylene group, 1-methyltrimethylene group, 1-ethylethylene group, 1,2-dimethylethylene group, 1,1-dimethylethylene group, etc.), and the following structures and the like can be mentioned.

Of these, from the viewpoint of further improving the refractive index and further improving Tg, L is preferably a single bond, phenylene, biphenylene, or naphthylene, and more preferably a single bond.

In the above formula (2), R ₁ represents a group having at least one atom selected from the group consisting of an oxygen atom (O), a sulfur atom (S), a nitrogen atom (N) and a selenium atom (Se). .. Here, as a specific example of R ₁ , there is no particular limitation as long as it does not inhibit the effect of the present invention. Specifically, the following structure can be mentioned.

Of these, R ₁ preferably has the following structure from the viewpoint of further improving the refractive index and Tg (thermal stability). That is, in a preferred embodiment of the present invention, R ₁ is represented by the following group:

Is selected from. In the above structure, m is an integer of 1 or more and 6 or less. From the viewpoint of further improving the refractive index and Tg (thermal stability), m is preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2. n is an integer of 1 or more and 6 or less. From the viewpoint of further improving the refractive index and Tg (heat stability), n is preferably an integer of 1 or more and 3 or less, and more preferably 1. o is an integer of 1 or more and 5 or less. From the viewpoint of further improving the refractive index and Tg (heat stability), o is preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2.

Further, R ₁ is more preferably selected from the following group.

Even more preferably, R ₁ is selected from the following groups.

Particularly preferably, R ₁ is selected from the following group.

The triazine ring-containing polymer according to one embodiment of the present invention has a structural unit B represented by the following formula (3).

In the above formula (3), R ₂ is a divalent aromatic hydrocarbon group or two or more aromatic hydrocarbon groups having an alkylene group, an oxygen atom (O), a sulfur atom (S) or a selenium atom (Se). Represents a divalent aromatic hydrocarbon linking group that is linked. Here, the divalent aromatic hydrocarbon group is not particularly limited as long as it does not inhibit the effect of the present invention. The aromatic hydrocarbon constituting the divalent aromatic hydrocarbon group may be a non-condensed ring or a condensed ring. Specifically, benzene, pentalene, inden, naphthalene, anthracene, azulene, heptalene, acenaphthalene, phenalene, fluorene, anthracene, phenanthrene, biphenyl, terphenyl, quarterphenyl, kinkphenyl, sexiphenyl, triphenylene, pyrene, chrysene, picene. , Perylene, pentaphene, pentacene, tetraphene, hexaphene, hexacene, rubicene, trinaphthylene, heptaphene, pyranthrene and the like. Of these, benzene, naphthalene, biphenyl and triphenylene are preferable, and benzene and biphenyl are more preferable, from the viewpoint of further improving the refractive index and Tg (heat stability).

Further, it is a divalent aromatic hydrocarbon linking group in which aromatic hydrocarbon groups having R ₂ or more are linked by an alkylene group, an oxygen atom (O), a sulfur atom (S) or a selenium atom (Se). In this case, the aromatic hydrocarbon group is not particularly limited as long as it does not interfere with the effects of the present invention. A specific example thereof is the same as the example in the case where R ₂ is a divalent aromatic hydrocarbon group, and thus the description thereof will be omitted here. Of these, a divalent group derived from benzene or naphthalene is preferable, and a divalent group derived from benzene (phenylene group) is more preferable, from the viewpoint of further improving the refractive index and Tg (thermal stability). Further, in the above embodiment, the number of linked aromatic hydrocarbon groups is not particularly limited as long as it does not interfere with the effect of the present invention. From the viewpoint of further improving the refractive index and Tg (heat stability), the number of linked aromatic hydrocarbon groups is preferably 2 or more and 5 or less. The number of linked aromatic hydrocarbon groups is more preferably 2 or 3, and particularly preferably 2. In the above form, the atom connecting the aromatic hydrocarbon group is also not particularly limited as long as it does not inhibit the effect of the present invention. When R ₂ is a divalent aromatic hydrocarbon linking group in which two or more aromatic hydrocarbon groups are linked by an alkylene group, the alkylene group is also not particularly limited. For example, a methylene group, an ethylene group, a trimethylene group, a propylene group, an isopropylidene group _{[-C (CH 3) 2 -} ], tetramethylene group, 2-methyltrimethylene group, 1-methyltrimethylene group, 1-ethyl ethylene Examples thereof include linear or branched alkylene groups having 1 or more and 6 or less carbon atoms such as groups, 1,2-dimethylethylene groups and 1,1-dimethylethylene groups. Among these, from the viewpoint of further improving the refractive index and Tg (thermal stability), the group or atom connecting the aromatic hydrocarbon group is preferably an alkylene group having 2 or more and 4 or less carbon atoms, an oxygen atom, and the like. It is a sulfur atom. The group or atom linking the aromatic hydrocarbon group is more preferably an isopropylidene group, an oxygen atom or a sulfur atom, and particularly preferably a sulfur atom. In particular, when R ₂ is formed by linking aromatic hydrocarbon groups via sulfur atoms, the effect of improving the refractive index and Tg of the polymer can be further promoted.

When R ₂ is a divalent aromatic hydrocarbon group or the like, the positions of the two bonds are not particularly limited. However, the positions of the two bonds are preferably located at the most distant positions. That is, for example, in the case of a phenylene group, it is preferable that two sulfur atoms constituting the main chain are bonded to the para position of the phenylene group.

That is, in a preferred embodiment of the present invention, the structural unit B (R ₂ in the formula (3)) is independently divided into the following groups:

Is selected from.

In a more preferred embodiment of the present invention, the structural unit B (R ₂ in the formula (3)) is independently divided into the following groups:

Is selected from.

In an even more preferred embodiment of the present invention, the structural unit B (R ₂ in the formula (3)) is independently divided into the following groups:

Is selected from.

In a more preferred embodiment of the present invention, the structural unit B (R ₂ in the formula (3)) is independently divided into the following groups:

Is selected from.

In a particularly preferred embodiment of the present invention, the structural unit B (R ₂ in the formula (3)) has the following structure. According to this form, it exhibits thermoplasticity, and molding such as hot pressing and injection molding can be facilitated.

The structural unit B (R ₂ in the equation (3)) has the following structure:

If R ₁ in the formula (1) has the following structure (tertiary amino group):

It is preferable to have. By adopting this structure, the refractive index and Tg (thermal stability) can be further improved.

The triazine ring-containing polymer according to one embodiment of the present invention may have one type of constitutional unit A alone, or may have two or more types of constitutional unit A. From the viewpoint of further improving the refractive index, the triazine ring-containing polymer preferably has 2 or more and 5 or less constituent units A, and more preferably has two constituent units A. Similarly, the triazine ring-containing polymer according to one embodiment of the present invention may have one type of constitutional unit B alone, or may have two or more types of constitutional unit B. From the viewpoint of the refractive index and the controllability of Tg, the triazine ring-containing polymer preferably has one type of single structural unit B or two or more types of structural unit B, and one type of single structural unit B. It is more preferable to have or have two kinds of structural units B, and it is particularly preferable to have one kind of single structural unit B.

That is, in a preferred embodiment of the present invention, the triazine ring-containing polymer has a repeating unit represented by the following formula (1-1) and a repeating unit represented by the following formula (1-2):

In the above formulas (1-1) and (1-2), A'and A'have the same definitions as A in the above formula (1), but A'and A'are different. (Although the structure of A'is different from the structure of A', both are included in the structural unit A.) Further, B has the same definition as B in the above formula (1), and at this time, B in formulas (1-1) and (1-2) is the same (B in formulas (1-1) and (1-2) has the same structure).

Further, it is essential that the triazine ring-containing polymer according to the invention contains a repeating unit composed of at least one structural unit A and at least one structural unit B as described above. However, from the viewpoint of improving the solubility in a solvent, it is preferable that it contains 2 or more and 5 or less structural units A and / or 2 or more and 5 or less structural units B. More preferably, it contains two types of structural units A and / or two types of structural units B.

That is, in another preferred embodiment of the present invention, the triazine ring-containing polymer has a repeating unit represented by the following formula (1-3) and a repeating unit represented by the following formula (1-4):

In the above formulas (1-3) and (1-4), A has the same definition as A in the above formula (1), and at this time, in the above formulas (1-3) and (1-4). A is the same (A in formulas (1-3) and (1-4) has the same structure). Further, B'and B'are independently defined in the same manner as B in the above formula (1), but B'and B'are different (the structure of B'is different from the structure of B'. However, both are included in the structural unit B).

Further, in still more preferred embodiments of the present invention, the triazine ring-containing polymer has a repeating unit represented by the following formula (1-5), a repeating unit represented by the following formula (1-6), and the following formula (1-6). It has a repeating unit represented by 1-7) and a repeating unit represented by the following formula (1-8):

In the above formulas (1-5), (1-6), (1-7) and (1-8), A'and A "are independently the same as A in the above formula (1). By definition, A'and A'are different (the structure of A'is different from the structure of A', but both are included in the building block A), and B'and B'are independent of each other. The definition is the same as that of B in the above equation (1), but B'and B "are different (the structure of B'is different from the structure of B", but both are included in the structural unit B. ).

In the above formulas (1-1) to (1-8), "-A'-" and "-A"-"are defined in the above formula (2) except that A'and A" have different structures. Since it is the same as the above, the description thereof is omitted here. Similarly, in the above equations (1-1) to (1-8), "-B'-" and "-B"-" are referred to as B'. Since it is the same as the definition in the above equation (3) except that B ”has a different structure, the description thereof will be omitted here.

In the present specification, the structural unit of the above "-A'-" is also simply referred to as "constituent unit A'". The structural unit of "-A"-" is also simply referred to as" structural unit A "". Similarly, the structural unit of "-B'-" is also simply referred to as "constituent unit B'". The structural unit of "-B"-" is also simply referred to as" structural unit B "".

As described above, the polymer containing 2 or more and 5 or less structural units A and / or 2 or more and 5 or less structural units B has excellent solubility in a solvent. Therefore, for example, it is advantageous when purifying by reprecipitation.

Further, in the embodiment including two or more and five or less structural units A, it is preferable that at least one of the two or more structural units A is selected from the above preferable forms. By selecting at least one of the two or more and five or less constituent units A from these forms, the effect of further improving the refractive index can be exhibited.

When the triazine ring-containing polymer has two kinds of structural units A (constituent unit A'and structural unit A "), the combination of the structural units A'and A" is particularly suitable as long as it does not inhibit the effect of the present invention. Not limited. From the viewpoint of further improving the refractive index and Tg (thermal stability), R ₁ is

The structural unit A'and R ₁ are

The combination with the structural unit A ”is preferable.

Also, R ₁

The structural unit A'and R ₁ are

The combination with the structural unit A ”is more preferable.

Further, L is a single bond and R ₁ is

The structural unit A'is, L is a single bond, and R ₁ is.

The combination with the structural unit A ”is particularly preferable.

Further, in the above preferred embodiment, the abundance ratio of the constituent unit A'and the constituent unit A'is not particularly limited as long as it does not interfere with the effect of the present invention. Further improving the refractive index and Tg (thermal stability) and the like. From the viewpoint, the abundance ratio (molar ratio) of the constituent unit A'and the constituent unit A'is preferably 10 to 50:90 to 50, more preferably 25 to 50:75 to 50. In the above definition of "abundance ratio", the total of the constituent unit A'and the constituent unit A'is 100 mol. In the constituent unit A', R ₁ is -N (phenyl group) (hydrogen atom or It is represented by the formulas (1-1), (1-5) and (1-7) which are alkyl groups). In the structural unit A ", R ₁ is -S (alkyl group) or -S-alkylene group-phenyl. It is represented by the underlying formulas (1-2), (1-6) and (1-8).

Further, in the embodiment including two or more and five or less structural units B, it is preferable that at least one of the two or more structural units B is selected from the above preferable forms. By selecting at least one of the two or more and five or less structural units B from these forms, the effect of further improving the refractive index can be exhibited.

When the triazine ring-containing polymer has two types of structural units B (constituent unit B'and B'), the combination of the structural units B'and B'is particularly limited as long as it does not interfere with the effects of the present invention. Not limited. From the viewpoint of further improving the refractive index, solubility, etc., R ₂ is preferable.

The structural unit B'and R ₂ are

The combination of the structural unit B "is preferable.

In the above preferred embodiment, the abundance ratio of the constituent unit B'and the constituent unit B'is not particularly limited as long as it does not interfere with the effect of the present invention. From the viewpoint of further improving the refractive index, solubility, etc. The abundance ratio of B'and the constituent unit B'is preferably 20 to 60:80 to 40, more preferably 30 to 50:70, when the total number of the constituent unit B'and the constituent unit B'is 100. In addition, in the above-mentioned definition of "abundance ratio", the total of the constituent unit B'and the constituent unit B "is 100 mol. In addition, the constituent unit B'is an expression in which R ₂ is a phenylene group. It is represented by (1-3), (1-5) and (1-6). The structural unit B "is represented by the formulas (1-4), (1-7) and (1-4) in which R ₂ is a p-biphenylene group. It is shown by 1-8).

Further, the triazine ring-containing polymer may contain a repeating unit other than the structural unit A and the structural unit B (hereinafter, also referred to as “another repeating unit”). However, from the viewpoint of satisfactorily exerting the effect of the present invention, it is preferable not to include other repeating units. That is, the triazine ring-containing polymer is preferably composed of only the repeating unit of the formula (1). Even when other repeating units are included, the ratio of the number of other repeating units to the total number of repeating units is preferably 10% or less. The ratio of the number of other repeating units is more preferably 5% or less, further preferably 3% or less, and particularly preferably 1% or less (lower limit: more than 0%). When the ratio of the other repeating units is within the above range, it is possible to prevent a decrease in the refractive index and difficulty in a molding process such as hot pressing and injection molding.

When the triazine ring-containing polymer contains two or more repeating units, that is, when it is a copolymer, the arrangement form of the repeating units is not particularly limited. The arrangement form of the repeating unit may be block-like (block copolymer), random (random copolymer), or alternately arranged (alternate copolymer).

The triazine ring-containing polymer of the present invention has both a high refractive index and a high Tg. The refractive index _{n d} of the triazine ring-containing polymer is preferably 1.70 or more, more preferably 1.74 or more. Within the above range, a molded product having a high refractive index suitable for optical components can be obtained. The glass transition temperature Tg of the triazine ring-containing polymer is preferably 100 ° C. or higher, more preferably 130 ° C. or higher. Within the above range, a molded product having high thermal stability can be obtained. In this specification, the refractive index n _d adopts a value measured by a method described in Examples set forth below.

That is, in a preferred embodiment of the present invention, the triazine ring-containing polymer has a refractive index ( _nd ) of 1.70 or higher and a glass transition temperature (Tg) of 100 ° C. or higher. In a more preferred embodiment of the present invention, a triazine ring-containing polymer has a 1.74 refractive index greater than _{(n d)} and glass transition temperature above 110 ℃ (Tg).

The weight average molecular weight (Mw) of the triazine ring-containing polymer is preferably more than 10,000 and 1,000,000 or less, more preferably 13,000 or more and 500,000 or less, and further preferably. It is 15,000 or more and 150,000 or less. When the weight average molecular weight is within the above numerical range, the transmittance (transparency) and heat resistance of the molded product are particularly excellent, and the mechanical strength of the obtained molded product is excellent. The method for controlling the weight average molecular weight within the above numerical range is not particularly limited, and examples thereof include a method for controlling the polymerization reaction time. In addition, in this specification, the value measured by the method described in the Examples described later is adopted as the weight average molecular weight.

The triazine ring-containing polymer has a glass transition temperature (Tg). That is, an inflection point is observed in the differential calorimetry curve obtained by the differential scanning calorimetry. As described above, the resin having the glass transition temperature has thermoplasticity and can be processed by hot pressing or injection molding. The glass transition temperature of the triazine ring-containing polymer is preferably 100 ° C. or higher, more preferably 110 ° C. or higher and 190 ° C. or lower, and particularly preferably 130 ° C. or higher and 160 ° C. or lower. The glass transition temperature can be adjusted by controlling the structure of the repeating unit represented by the equation (1). For example, the glass transition temperature can be increased by introducing a bulky structure or a rigid structure into R ₁ in the equation (1). In this specification, the glass transition temperature (Tg) adopts the value measured by the method described in Examples described later.

The viscosity of the triazine ring-containing polymer in the molten state is preferably 100 Pa · s or more and less than 100,000 Pa · s, more preferably 1,000 Pa · s or more and 50,000 Pa · s or less, and further preferably 6,000 Pa · s. -S or more and 30,000 Pa · s or less. When the viscosity in the molten state is within the above numerical range, the molding processability such as hot pressing and injection molding is excellent. In this specification, the viscosity of the polymer in a molten state adopts a value measured by the method described in Examples described later.

The triazine ring-containing polymer can be produced, for example, by reacting a dihalogenated (for example, dichloroylated) triazine compound with a dimercapto aromatic compound in the presence of a phase transfer catalyst.

The dihalogenated triazine compound is not particularly limited and can be appropriately selected in consideration of the structure of the structural unit A. Specifically, 2-anilino-4,6-dichlorotriazine [2-anilino-4,6-dichloro-1,3,5-triazine], 2- (N-methylanilino) -4,6-dichlorotriazine [ 2- (N-methylanilino) -4,6-dichloro-1,3,5-triazine], 2- (N-ethylanilino) -4,6-dichlorotriazine [2- (N-ethylanilino) -4,6- Dichloro-1,3,5-triazine], 2,4-dichloro-6-phenylsulfanyl-1,3,5-triazine, 2-benzylsulfanyl-4,6-dichloro-1,3,5-triazine, 2 Examples thereof include -methylthio-4,6-dichloro-1,3,5-triazine and 2-ethylthio-4,6-dichloro-1,3,5-triazine.

The dimercapto aromatic compound is not particularly limited and can be appropriately selected in consideration of the structure of the structural unit B. Specifically, 2,6-thians range thiol, 2,7-thians range thiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 4,4'-biphenyldithiol, 4,4'-thiobisbenzenethiol, 2,6-naphthalenedithiol, 4,4'-oxybisbenzenethiol and the like can be used. These can be used alone or in combination of two or more.

As the phase transfer catalyst used for the reaction between the dihalogenated triazine compound and the dimercapto aromatic compound, long-chain alkyl quaternary ammonium salts and crown ethers that can be used for interfacial polycondensation are preferable, and for example, hexa bromide More preferably, decyltrimethylammonium or the like can be used. The mixing ratio of the dihalogenated triazine compound to the dimercapto aromatic compound is usually a ratio that is stoichiometrically approximately equimolar.

As the reaction system, a two-phase system of water and an organic solvent can be used, and a two-phase system of water and an organic solvent such as chloroform, dichloromethane, benzonitrile or nitrobenzene is preferable. The reaction is preferably carried out at a temperature of −10 ° C. or higher and 100 ° C. or lower for 2 hours or longer and 120 hours or lower by adding a base such as sodium hydroxide or potassium hydroxide. The above operation may be performed under stirring.

The triazine ring-containing polymer obtained as described above may be purified by a general purification method such as a reprecipitation method, a dialysis method, an ultrafiltration method, or an extraction method.

Another embodiment of the present invention relates to a thermoplastic molded article containing the above-mentioned triazine ring-containing polymer. Yet another embodiment of the present invention relates to an optical component comprising the above triazine ring-containing polymer.

The shape of the molded product is not particularly limited, and may be in any form such as a lens shape (spherical lens, aspherical lens, Fresnel lens, etc.), a film shape, a sheet shape, a plate shape, a rod shape, a fibrous shape, a prism shape, or the like. It may be there. In the production of molded products, for example, injection molding method, compression molding method, extrusion molding method, transfer molding method, blow molding method, pressure molding method, coating method (spin coating method, roll coating method, curtain coating method, dip). A known molding method such as a coating method, a casting molding method, etc. can be used. Above all, the composition according to the present invention is particularly suitable for hot pressing and injection molding. Prior to molding, the raw materials may be mixed using a kneader such as a Henschel mixer, a kneader, a Banbury mixer, or an extruder. When molding is performed by injection molding, for example, the cylinder temperature is 150 ° C. or higher and 300 ° C. or lower, and the mold temperature is 50 ° C. or higher and 100 ° C. or lower.

The above optical components include displays (for example, smartphone displays, liquid crystal displays and plasma displays, etc.), photographing devices (for example, cameras and videos), optical pickups, projectors, optical fiber communication devices (for example, optical amplifiers, etc.), and automobiles. It can be suitably used as an optical component (passive optical component) that transmits light in a head lamp or the like. Examples of such passive optical components include lenses, films, optical waveguides, prisms, prism sheets, panels, optical disks, LED encapsulants, and the like. Such optical components may have various functional layers such as an antireflection layer, a light absorption layer, a hard coat layer, and an antiglare layer, if necessary.

Hereinafter, the present invention will be described in detail with reference to Examples, but these are not intended to limit the present invention. In the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

<Measurement method of physical property value>
(Number average molecular weight (Mn) and weight average molecular weight (Mw))
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer were measured by the following methods.

The polymer was dissolved in tetrahydrofuran (THF) so as to have a concentration of 0.1% by mass, and filtered through a membrane filter made of polytetrafluoroethylene having a pore size of 0.2 μm to prepare a measurement sample. With respect to the measurement sample prepared above, the number average molecular weight and the weight average molecular weight of the polymer were measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase and a differential refraction meter as a detector. Monodisperse polystyrene was used as the standard substance of molecular weight.

(Glass transition temperature (Tg))
The glass transition temperature (Tg) of the polymer was measured by the following method.

Using a differential scanning calorimeter (DSC), a sample (polymer) that has been heated to 300 ° C. at a heating rate of 10 ° C./min and held for 10 minutes is cooled to 25 ° C. at a temperature lowering rate of 10 ° C./min. Hold for minutes. Then, the temperature was raised again to 300 ° C. at a heating rate of 10 ° C./min, and the glass transition temperature (Tg) was measured. After the measurement was completed, the mixture was cooled to room temperature (25 ° C.) at 10 ° C./min.

(Refractive index _nd and Abbe number ν _d )
The refractive index _nd and Abbe number ν _d of the polymer were measured by the following methods.

After the polymerization reaction, the reaction solution was added dropwise to a large excess of isopropyl alcohol and reprecipitated to purify the polymer, and this sample (solid) was dried under vacuum at 100 ° C. for 48 hours before use. 2 g of this sample was compression molded at 200 ° C. and 3 MPa for 5 minutes to prepare a molded plate (plate-shaped molded product) having a length of 3 cm, a width of 3 cm, and a thickness of 0.5 mm. Using the obtained molded plate, the refractive index at wavelengths of 473 nm, 594 nm, and 657 nm was measured with a prism coupler (Model 2010, manufactured by Metricon). From the measured values, the refractive indexes of the C line (656.3 nm), the d line (587.6 nm), and the F line (486.1 nm) were calculated by calculation. Among these, the refractive index of the refractive index at the d-line (587.6nm) _{(n d).} Further, using the values of the refractive indexes at the above three wavelengths, the Abbe number (ν _d ) (= (nd-1) / (nF-nC); nd is the refractive index for the d line, and nF is for the F line. It is the refractive index, and nC is the refractive index with respect to the C line).

(Measurement of viscosity of polymer in molten state)
The viscosity (rheology) of the polymer in the molten state was measured using a rheometer (MCR302, manufactured by Anton Pearl Co., Ltd.) under a nitrogen atmosphere at 250 ° C. and a shear rate of 0.1 (1 / s).

<Synthesis of triazine ring-containing polymer>
[Synthesis Example 1] Synthesis of 2-anilino-4,6-dichloro-1,3,5-triazine (1) In a 2 L three-necked flask equipped with a 500 mL dropping funnel, 200 g (1.08 mol) of cyanuric chloride and 1 L of tetrahydrofuran. Was put in and cooled to 0 ° C. in an ice bath. A solution of 116.23 g (1.08 mol) of aniline in 300 mL of tetrahydrofuran was added dropwise from a dropping funnel over 120 minutes. After completion of the dropping, 300 mL of an aqueous solution in which 115 g of sodium carbonate was dissolved was added, and the mixture was stirred for 30 minutes. The upper tetrahydrofuran layer was taken out and the solvent was distilled off under reduced pressure to obtain 242 g (yield 93%) of 2-anilino-4,6-dichloro-1,3,5-triazine (1) having the following structure. ..

<Synthesis Example 2> Synthesis of 2,7-dibenzylthiothianthrene (2) 4.85 g (43 mmol) of potassium tert-butoxide and 15 mL of dimethylformamide were placed in a 30 mL flask under nitrogen. After cooling to 0 ° C., 5.1 mL (42 mmol) of benzyl mercaptan and 3.98 g (15.8 mmol) of 2,7-difluorothiansrene (DFT) were added, the temperature was raised to 60 ° C., and the temperature was raised to 60 ° C. for 24 hours. , Stirred. Water is added to the reaction product, the precipitate is collected by filtration, and dried in vacuum to obtain 4.65 g (yield 64%) of 2,7-dibenzylthiothianlensene (DBTT) (2) having the following structure. It was.

<Synthesis Example 3> Synthesis of 2,7-thyansrangethiol (3) 1.38 g (3.0 mmol) of DBTT (2) synthesized in Synthesis Example 2 above at 0 ° C. in a 50 mL flask under a nitrogen atmosphere. After charging 0.078 g (0.31 mmol) of titanosendichloride (Cp ₂ TiCl ₂ ) and diglyme (10 mL), add 1 M din-butylmagnesium heptane solution (50 mL) little by little, and then stir at 0 ° C. for 3 hours. I let you. Aqueous sodium carbonate solution (20 mL) was slowly added at 0 ° C. to stop the reaction. Dichloromethane and pure water were added to the reaction product, and then the aqueous layer was separated. After adding hydrochloric acid to the aqueous layer, the mixture was stirred for 1 hour. The precipitate was collected by filtration and dried in vacuum to obtain 0.51 g (yield 60%) of 2,7-thiane rangethiol (3) having the following structure.

<Example 1> Synthesis of triazine ring-containing polymer (4) 2.23 g (8.46 mmol) of 2,7-thianthrangethiol (3) synthesized in Synthesis Example 3 is placed in a 100 mL flask, and pure water is added. After adding 14 mL, 1.69 mL of a 10 M NaOH aqueous solution was added and heated to 70 ° C. to obtain an aqueous solution. After dissolving 2.00 g (8.46 mmol) of 2-anilino-4,6-dichloro-1,3,5-triazine (1) synthesized in Synthesis Example 1 in 15 mL of nitrobenzene, this was added to the aqueous solution. To the resulting mixture was added 123 mg of hexadecyltrimethylammonium bromide and stirred vigorously at 70 ° C. for 24 hours. The reaction solution was added dropwise to methanol and reprecipitated to obtain a white triazine ring-containing polymer (4) having the following structure. The obtained triazine ring-containing polymer (4) had a number average molecular weight (Mn): 20000, a weight average molecular weight (Mw): 125000, and a glass transition temperature (Tg): 187 ° C. The viscosity of the triazine ring-containing polymer (4) in the molten state was less than 100,000 Pa · s.

<Example 2> Synthesis of triazine ring-containing polymer (5) In Example 1, 4.23 mmol instead of 8.46 mmol of 2-anilino-4,6-dichloro-1,3,5-triazine (1). Performed except with the use of 2-anilino-4,6-dichloro-1,3,5-triazine (1) and 4.23 mmol of 2-methylthio-4,6-dichloro-1,3,5-triazine. A white triazine ring-containing polymer (5) having the following structure was obtained in the same manner as in Example 1. The obtained triazine ring-containing polymer (5) had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 70,000, and a glass transition temperature (Tg) of 188 ° C.

<Synthesis Example 4> Synthesis of 2- (N-methylanilino) -4,6-dichloro-1,3,5-triazine (6) 200 g (1.08 mol) of cyanuric chloride in a 2 L three-necked flask equipped with a 500 mL dropping funnel. ), 1 L of tetrahydrofuran was added, and the mixture was cooled to 0 ° C. in an ice bath. A solution prepared by dissolving 116.23 g (1.08 mol) of N-methylaniline in 300 mL of tetrahydrofuran was added dropwise from a dropping funnel over 120 minutes. After completion of the dropping, 300 mL of an aqueous solution in which 115 g of sodium carbonate was dissolved was added, and the mixture was stirred for 30 minutes. By taking out the upper tetrahydrofuran layer and distilling off the solvent under reduced pressure, 263 g of 2- (N-methylanilino) -4,6-dichloro-1,3,5-triazine (6) having the following structure (yield 95%) was obtained. ) Was obtained.

<Example 3> Synthesis of triazine ring-containing polymer (7) 1.20 g (8.46 mmol) of 1,4-benzenedithiol was placed in a 100 mL flask, 10 mL of pure water was added, and 1.69 mL of a 10 M NaOH aqueous solution was added. It was added and heated at 70 ° C. to obtain an aqueous solution. 2.16 g (8.46 mmol) of 2- (N-methylanilino) -4,6-dichloro-1,3,5-triazine (6) synthesized in Synthesis Example 4 is dissolved in 14 mL of nitrobenzene and then added to the aqueous solution. did. To the resulting mixture was added 123 mg of hexadecyltrimethylammonium bromide and stirred vigorously at 70 ° C. for 24 hours. The reaction solution was added dropwise to methanol and reprecipitated to obtain a white triazine ring-containing polymer (6) having the following structure. The obtained triazine ring-containing polymer (7) had a number average molecular weight (Mn): 13000, a weight average molecular weight (Mw): 43000, and a glass transition temperature (Tg): 139 ° C.

<Example 4> Synthesis of triazine ring-containing polymer (8) 1.84 g (8.45 mmol) of 4,4'-biphenyldithiol was placed in a 100 mL flask, 14 mL of pure water was added, and then 1.69 mL of a 10 M NaOH aqueous solution was added. Was added and heated at 70 ° C. to obtain an aqueous solution. 2.16 g (8.46 mmol) of 2- (N-methylanilino) -4,6-dichloro-1,3,5-triazine (6) synthesized in Synthesis Example 4 is dissolved in 15 mL of nitrobenzene and then added to the aqueous solution. did. To the resulting mixture was added 123 mg of hexadecyltrimethylammonium bromide and stirred vigorously at 70 ° C. for 24 hours. The reaction solution was added dropwise to methanol and reprecipitated to obtain a white triazine ring-containing polymer (8) having the following structure. The obtained triazine ring-containing polymer (8) had a number average molecular weight (Mn) of 11,000, a weight average molecular weight (Mw) of 38,000, and a glass transition temperature (Tg) of 148 ° C.

<Example 5> Synthesis of triazine ring-containing polymer (9) In a 100 mL flask, 2.23 g (8.46 mmol) of 2,7-thianthrangethiol (3) synthesized in Synthesis Example 3 was placed, and pure water was added. After adding 14 mL, 1.69 mL of a 10 M NaOH aqueous solution was added and heated at 70 ° C. to obtain an aqueous solution. 2.16 g (8.46 mmol) of 2- (N-methylanilino) -4,6-dichloro-1,3,5-triazine (6) synthesized in Synthesis Example 4 is dissolved in 15 mL of nitrobenzene and then added to the aqueous solution. did. To the resulting mixture was added 123 mg of hexadecyltrimethylammonium bromide and stirred vigorously at 70 ° C. for 24 hours. The reaction solution was added dropwise to methanol and reprecipitated to obtain a white triazine ring-containing polymer (9) having the following structure. The obtained triazine ring-containing polymer (9) had a number average molecular weight (Mn): 20000, a weight average molecular weight (Mw): 125000, and a glass transition temperature (Tg): 175 ° C. The viscosity of the triazine ring-containing polymer (9) in the molten state was less than 100,000 Pa · s.

<Example 6> Synthesis of triazine ring-containing polymer (10) In Example 5, instead of 8.46 mmol of 2- (N-methylanilino) -4,6-dichloro-1,3,5-triazine (6) 4.23 mmol of 2- (N-methylanilino) -4,6-dichloro-1,3,5-triazine (6) and 4.23 mmol of 2-methylthio-4,6-dichloro-1,3,5- A white triazine ring-containing polymer (10) having the following structure was obtained in the same manner as in Example 4 except that triazine was used. The obtained triazine ring-containing polymer (10) had a number average molecular weight (Mn): 18,000, a weight average molecular weight (Mw): 65,000, and a glass transition temperature (Tg): 182 ° C.

<Example 7> Synthesis of triazine ring-containing polymer (11) 2.12 g (8.47 mmol) of 4,4'-thiobisbenzenethiol is placed in a 100 mL flask, 14 mL of pure water is added, and then a 10 M NaOH aqueous solution 1 .69 mL was added and heated at 70 ° C. to obtain an aqueous solution. 2.16 g (8.46 mmol) of 2- (N-methylanilino) -4,6-dichloro-1,3,5-triazine (6) synthesized in Synthesis Example 4 is dissolved in 15 mL of nitrobenzene and then added to the aqueous solution. did. To the resulting mixture was added 123 mg of hexadecyltrimethylammonium bromide and stirred vigorously at 70 ° C. for 24 hours. The reaction solution was added dropwise to methanol and reprecipitated to obtain a white triazine ring-containing polymer (11) having the following structure. The obtained triazine ring-containing polymer (11) had a number average molecular weight (Mn): 24,000, a weight average molecular weight (Mw): 85,000, and a glass transition temperature (Tg): 160 ° C.

<Comparative Example 1> Synthesis of Triazine Ring-Containing Polymer (12) In Example 1, 1.03 g (8.46 mmol) of 1,4-butanedithiol was used instead of 2,7-thians rangethiol (3). A white triazine ring-containing polymer (12) having the following structure was obtained in the same manner as in Example 1 except for the above. The obtained triazine ring-containing polymer (12) had a number average molecular weight (Mn) of 20,000, a weight average molecular weight (Mw) of 52,000, and a glass transition temperature (Tg) of 78 ° C.

<Evaluation 1>
A plate-shaped molded product having a thickness of 0.5 mm was prepared by compressing 2 g of the triazine ring-containing polymer obtained in Examples 1 to 5 and Comparative Example 1 at 200 ° C. and 10 MPa for 5 minutes using a compression molding machine. did. The refractive index _nd and the Abbe number ν _d were measured for the obtained plate-shaped molded product. The results are shown in Table 1 below.

From the results in Table 1 above, all of the triazine ring-containing polymers (4) to (11) according to the present invention have a refractive index of 1.7 or more. The refractive index of the triazine ring-containing polymer (12) of Comparative Example 1 is 1.6 or more and less than 1.7, and a higher refractive index contributes to miniaturization and weight reduction of the lens or the like after molding. Further, the triazine ring-containing polymers (5) and (10) further having the methylthiotriazine monomer have a refractive index of 0, respectively, as compared with the triazine ring-containing polymers (4) and (9) having no methylthiotriazine monomer. It is higher than 01. Therefore, it is suggested that the triazine ring-containing polymer containing two types of triazine-derived structural unit A and one type of structural unit B can have a higher refractive index. A triazine ring-containing polymer containing two types of triazine-derived structural units A is expected to contribute to further miniaturization and weight reduction of lenses and the like.

On the other hand, in order to use it as an in-vehicle optical component that requires high weather resistance, particularly heat resistance, a high glass transition temperature (Tg) of 100 ° C. or higher is required. The Tg of all the triazine ring-containing polymers (4) to (11) of the present invention is as high as 130 ° C. or higher, and an optical lens having excellent thermal stability can be obtained. However, the Tg of the triazine ring-containing polymer (12) of Comparative Example 1 is as low as 78 ° C., which is not suitable for such an application.

Therefore, the triazine ring-containing polymer according to the present invention has a high refractive index and glass transition temperature, exhibits thermoplasticity, and is suitable for applications such as in-vehicle optical lenses.

Claims (11)

A triazine ring-containing polymer having a repeating unit represented by the following formula (1):

In the above formula (1), A is independently represented by the following formula (2); and B is independently represented by the following formula (3).

In the above formula (2), L represents a single bond or a linking group, and R ₁ is composed of a group consisting of an oxygen atom (O), a sulfur atom (S), a nitrogen atom (N) and a selenium atom (Se). Represents a group with at least one atom selected,

In the above formula (3), R ₂ is a divalent aromatic hydrocarbon group or two or more aromatic hydrocarbon groups having an alkylene group, an oxygen atom (O), a sulfur atom (S) or a selenium atom (Se). Represents a divalent aromatic hydrocarbon linking group that is linked. In the above formula (3), R ₂ is independently divided into the following groups:

The triazine ring-containing polymer according to claim 1, which is selected from. The triazine ring-containing polymer according to claim 1 or 2, wherein L represents a single bond in the formula (2). In the above formula (2), R ₁ is the following group:

In the above structure, m is an integer of 1 or more and 6 or less.
n is an integer of 1 or more and 6 or less, and o is an integer of 1 or more and 6 or less.
The triazine ring-containing polymer according to any one of claims 1 to 3, which is selected from. The triazine ring-containing polymer according to any one of claims 1 to 4, which has a repeating unit represented by the following formula (1-1) and a repeating unit represented by the following formula (1-2):

In the above formulas (1-1) and (1-2), A'and A "have the same definitions as A in the above formula (1), respectively, and in this case, A'and A'". Is different
B has the same definition as B in the above formula (1), and at this time, B in the formulas (1-1) and (1-2) is the same. The triazine ring-containing polymer according to any one of claims 1 to 4, which has a repeating unit represented by the following formula (1-3) and a repeating unit represented by the following formula (1-4);

In the above formulas (1-3) and (1-4), A has the same definition as A in the above formula (1), and at this time, in the above formulas (1-3) and (1-4). A is the same,
B'and B'are independent of each other and have the same definition as B in the above formula (1), and B'and B'are different at this time. The repeating unit represented by the following formula (1-5), the repeating unit represented by the following formula (1-6), the repeating unit represented by the following formula (1-7), and the following formula (1-8). The triazine ring-containing polymer according to any one of claims 1 to 4, having a repeating unit represented;

In the formulas (1-5), (1-6), (1-7) and (1-8), A'and A "are independently the same as A in the formula (1). It is a definition, and in this case, A'and A'are different.
B'and B'are independent of each other and have the same definition as B in the above formula (1), and B'and B'are different at this time. The triazine ring-containing polymer according to any one of claims 1 to 7, which has a glass transition temperature (Tg) of 100 ° C. or higher. The triazine ring-containing polymer according to any one of claims 1 to 8, which has a refractive index of 1.70 or more. A thermoplastic molded product containing the triazine ring-containing polymer according to any one of claims 1 to 9. An optical component comprising the triazine ring-containing polymer according to any one of claims 1 to 10.