JP2931377B2 - Polyurethane - Google Patents

Description

The present invention relates to a novel polyurethane. More specifically, the present invention relates to a polyurethane containing a specific polyester diol component and a polylactone diol component as essential components.

The leather-like composite sheet comprising the polyurethane of the present invention and a fiber substrate has an excellent feeling such as a unique sliminess, and is excellent in durability. It is useful as a resin material for producing synthetic leather or artificial leather which is extremely useful as a material for bags, bags, clothing, and the like.

[Conventional technology]

Conventionally, as a leather-like composite sheet made of a fiber base and a polyurethane-based resin, various synthetic leathers and artificial leathers having a so-called silver or suede tone are known. It has been proposed to use a polymethylvalerolactone-based polyurethane resin as the polyurethane-based resin. That is, JP-A-60-26019 describes that a poly (β-methyl-δ-valerolactone) polyurethane resin is excellent in hydrolysis resistance and the like and can be used for artificial leather. JP-A-63-315676 discloses a polyurethane obtained by reacting polymethyl valerolactone polyol or a mixed polymer polyol thereof with polybutylene adipate polyol or polyethylene butylene adipate polyol with an organic diisocyanate and 1,4-butanediol. It describes that a synthetic leather obtained by forming a resin layer on a base material has excellent hydrolysis resistance and light resistance. Also, JP-A-1-132885
Japanese Patent Application Laid-Open Publication No. H11-163873 discloses a poly (β-methyl-δ-valerolactone) as one of soft segments which can constitute a polyurethane capable of producing a leather-like composite sheet by impregnating or coating a fiber substrate. ).

On the other hand, it is also possible to use a polyester-based polyurethane obtained by reacting a polyester polyol containing 2-methyl-1,8-octanediol unit with an organic polyisocyanate as a polyurethane-based resin used for a leather-like composite sheet. Proposed. That is,
JP-A-62-22817 describes that the polyester-based polyurethane is excellent in hydrolysis resistance and that it can be used for synthetic leather and artificial leather.

[Problems to be solved by the invention]

In recent years, there has been a remarkable trend toward higher quality in consumer life and the emphasis on sensibility and emphasis on fashion, and there has been a strict demand for properties that have not been required in the past even in leather-like composite sheet materials such as synthetic leather and artificial leather. I'm getting better.

The inventors of the present invention examined the slimy feeling of the leather-like composite sheet-like material, and found that the above JP-A-60-26019, JP-A-63-315676 and JP-A-1-132885. From the polyurethane obtained by reacting polymethyl valerolactone diol with an organic diisocyanate as described, it was found that a leather-like composite sheet having a firm and slimy feeling could not be obtained. did. Furthermore, a mixed polymer diol of polymethyl valerolactone diol such as poly (β-methyl-δ-valerolactone) diol and polybutylene adipate diol can be prepared according to the description in JP-A-63-315676 by using organic diisocyanate and chain elongation. The leather-like composite sheet produced using the polyurethane obtained by reacting with the agent may have a good slimy feeling, but on the other hand,
It has been found that various properties such as a feeling of sliminess significantly deteriorate with time due to a decrease in hydrolysis resistance. In addition, the method disclosed in Japanese Patent Application Laid-Open No. Sho.
From the polyurethane obtained by reacting a polyester polyol containing a methyl-1,8-octanediol unit with an organic polyisocyanate, it was found that a leather-like composite sheet having a good slimy feeling could not be obtained. .

Thus, an object of the present invention is to provide a polyurethane for producing a leather-like composite sheet having extremely good slickness and excellent in durability without accompanying deterioration of the good slickness over time. An object of the present invention is to provide a novel polyurethane useful as a system resin.

[Means for solving the problem]

According to the invention, the above object is achieved by the formula An alkanediol unit containing at least 10 mol% of a 2-methyl-1,8-octanediol unit represented by the formula: (Wherein m represents an integer of 4 to 8) From a polyester diol having a number average molecular weight of 500 to 10,000 substantially consisting of a dicarboxylic acid unit represented by the following formula, two of two alcoholic hydroxyl groups at both ends of the molecule are used. Polymer diol unit (A-1) excluding a hydrogen atom, formula as a constitutional repeating unit A lactone unit containing at least 60 mol% of a β-methyl-δ-valerolactone unit represented by the formula (1) and a divalent unit derived from a polymerization initiator.
A polymer diol unit (A-2) in which two hydrogen atoms in two alcoholic hydroxyl groups at both ends of the molecule are removed from 0000 polylactone diols and a general formula (Wherein, R represents a divalent organic group) mainly comprising an organic diisocyanate unit (B) represented by the following formula: wherein the weight ratio of the polymer diol unit (A-1) to the polymer diol unit (A-2) is 90. By providing a polyurethane characterized in that the viscosity of the solution in a dimethylformamide solvent at a concentration of 25% by weight, measured at 30 ° C., is from 5 to 2000 poise, in the range of from 10 to 10 to 90. Achieved.

The polyester diol which gives a polymer diol unit (A-1) which is one of the essential constitutional units of the polyurethane of the present invention [hereinafter, such polyester diol is referred to as polyester diol (a-1)] is the above-mentioned specific diol. It has an alkanediol unit and a dicarboxylic acid unit as essential constituent units, and has an average of two alcoholic hydroxyl groups at the molecular chain terminals.

The specific alkanediol unit, which is one of the essential structural units of the polyesterdiol (a-1), includes at least the 2-methyl-1,8-octanediol unit (hereinafter, referred to as a MOD unit). Contains 10 mol%. MO in alkanediol unit in polyesterdiol
When the content of the D unit is less than 10 mol%, a polyurethane which gives a leather-like composite sheet having sufficiently excellent sliminess and durability can not always be obtained.
90 mol% or less of the alkanediol unit in the polyester diol (a-1) may be an alkanediol unit other than the MOD unit. Examples of the alkanediol unit other than the MOD unit include ethylene glycol, propylene glycol and 1 Alkanediols having 2 to 10 carbon atoms such as 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol and neopentyl glycol, in which two hydrogen atoms contained in two hydroxyl groups have been removed And at least one kind of units such as In terms of obtaining a polyurethane which gives a leather-like composite sheet having particularly excellent sliminess and durability, the alkanediol unit in the polyester diol (a-1) generally has a MOD unit content of the polyester diol. (A-
1) at least 20 mol% with respect to all alkanediol units contained in polyesterdiol (a-1)
A relationship such that the sum of the product of the mole fraction of each alkanediol unit contained in each alkanediol unit and the number of carbon atoms of each alkanediol unit is 7.0 or more, that is, the equation (In the formula, k represents the number of types of alkanediol units contained in the polyesterdiol, Xi represents the number of carbon atoms of the alkanediol unit of the i-th type, and Mi represents the total alkane contained in the polyesterdiol. (Representing the mole fraction of the i-th alkanediol unit with respect to the diol). In particular, the alkanediol unit may be a MOD unit alone or a MOD unit and a compound of the formula -O- (CH ₂ ) 1,9-nonanediol unit represented by _9- O- (hereinafter referred to as ND
), And 20 to 100 mol%, particularly 20 to 80 mol%, of the alkanediol unit is M.
It is preferably an OD unit.

Specific examples of the dicarboxylic acid unit represented by the general formula (I) constituting the polyester diol (a-1) include two of the two carboxyl groups from adipic acid, pimelic acid, suberic acid, azelaic acid or sebacic acid. And at least one unit excluding the hydroxyl group.

The polyester diol (a-1) is as described above.
It is substantially composed of at least one alkanediol unit containing a MOD unit and at least one dicarboxylic acid unit represented by the general formula (I), but a small amount within a range that does not impair the action and effect of the present invention. If so, other units may be included. Such optionally included units include saturated alicyclic diols such as 1,4-cyclohexanediol; divalent aromatic alcohols such as xylylene glycol; or glycerin, pentaerythritol,
A divalent or trivalent unit in which a hydrogen atom in a hydroxyl group is removed from a trivalent or higher polyhydric alcohol such as trimethylolpropane; and two carboxyl groups from an aromatic dicarboxylic acid such as isophthalic acid and terephthalic acid. And a divalent unit excluding two hydroxyl groups.

The number average molecular weight of the polyester diol (a-1) is
From the viewpoint of the slimy feeling and the durability of the leather-like composite sheet produced from the obtained polyurethane, from 500 to 100
It is essential to be within the range of 00, and preferably within the range of 800 to 5000.

The method for producing the polyester diol (a-1) is not particularly limited, and known polyester production means can be applied. For example, polyester diol (a-1) is an alkanediol having a structure corresponding to a desired alkanediol unit and a dicarboxylic acid having a structure corresponding to a desired dicarboxylic acid unit or an ester-forming agent such as a methyl ester or an ethyl ester thereof. The derivative is esterified or transesterified at 150-250 ° C in the presence of an esterification catalyst and / or a transesterification catalyst using a desired ratio, and the resulting reaction product is then reduced under reduced pressure to 200-200C. It can be produced by condensation polymerization at 300 ° C.

The polylactone diol (hereinafter referred to as polylactone diol (a-2)) which gives a polymer diol unit (A-2) which is one of the essential constitutional units of the polyurethane of the present invention is a molecule The chain contains one divalent unit derived from a polymerization initiator and the above-mentioned specific lactone unit as a constitutional repeating unit, and has two alcoholic hydroxyl groups on the molecular chain terminal on average. .

At least 60 mol% of the lactone units in the polylactone diol (a-2) comprise at least one of the ring-opened form of β-methyl-δ-valerolactone of the formula Is a β-methyl-δ-valerolactone unit (hereinafter referred to as an MVL unit). The content of MVL units in lactone units in polylactone diol is 60
When the amount is less than mol%, a leather-like composite sheet having sufficiently excellent sliminess and durability can not always be obtained. Less than 40 mol% of the lactone units in the polylactone diol (a-2) may be lactone units other than the MVL unit, and examples of the lactone unit other than the MVL unit include δ-valerolactone and ε-caprolactone. Α-methyl-δ-valerolactone, γ-methyl-δ
Valerolactone, δ-methyl-δ-valerolactone,
β such as β, β, δ-trimethyl-ε-caprolactone
At least one unit such as a ring-opened lactone having a side chain other than -methyl-δ-valerolactone is exemplified. It is preferable that substantially all of the lactone units are MVL units, from the viewpoint of obtaining a polyurethane that gives a leather-like composite sheet having particularly excellent sliminess and durability.

The polymerization initiator that gives one divalent unit contained in the molecular chain of the polylactone diol (a-2) is a compound containing two active hydrogen atoms in the molecule. , Ethylene glycol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-
1,8-octanediol, 1,9-nonanediol, 1,10
-Dihydric alcohols having 2 to 22 carbon atoms such as decanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, naphthalene diol, diethylene glycol and tetraethylene glycol; average molecular weight 200 to 200
Polyoxyalkylene glycols having 2 to 12 carbon atoms oxyalkylene groups or 4 to 10 carbon atoms oxycycloalkylene groups such as 0 polyoxyethylene glycol and polyoxypropylene glycol as repeating constitutional units; ethylenediamine, 1,4 -Butanediamine, 1,6
Diamines having 2 to 12 carbon atoms, such as -hexanediamine, p-phenylenediamine, and piperazine; The divalent units derived from these polymerization initiators are units obtained by removing two active hydrogen atoms from the molecules of the polymerization initiator.

The number average molecular weight of the polylactone diol (a-2) is
From the viewpoint of the slimy feeling and the durability of the leather-like composite sheet produced from the obtained polyurethane, from 500 to 100
It is essential to be within the range of 00, and preferably within the range of 500 to 5000.

The method for producing the polylactone diol (a-2) is not particularly limited, and a known polylactone production means can be applied. For example, polylactone diol (a-2) is a compound containing two active hydrogen atoms as a polymerization initiator, a lactone having a structure corresponding to a desired lactone unit, and lithium, sodium, n-butyllithium, and sulfuric acid. 10 to 200 in the presence of a polymerization catalyst such as
It can be produced by ring-opening polymerization at ℃.

In the polyurethane of the present invention, the polymer diol unit (A-1) and the polymer diol unit (A-2)
It is essential that they be included in a weight ratio in the range of 90:10 to 10:90. When the weight ratio of the polymer diol unit (A-1) to the polymer diol unit (A-2) in the polyurethane is out of the above range, a leather-like composite sheet having a slimy feeling and sufficiently excellent durability can be obtained. I can't get anything. The weight ratio of the polymer diol unit (A-1) to the polymer diol unit (A-2) is 80:20 from the viewpoint that a polyurethane which gives a leather-like composite sheet having particularly excellent sliminess and durability can be obtained. Preferably it is in the range of 2020 to 80.

The polyurethane of the present invention may contain, as the polymer diol unit, a polymer diol unit other than the essential polymer diol unit such as the polymer diol unit (A-1) and the polymer diol unit (A-2). Examples of the polymer diol that provides the polymer diol unit that may be optionally contained include polyester diols other than the polyester diol (a-1); and polylactone diols (a-2) such as poly (ε-caprolactone) diol. ); Polyether diols such as poly (oxypropylene) diol and poly (oxytetramethylene) diol; and polycarbonate diols. Examples of the polyester diol other than the polyester diol (a-1) include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, xylylene glycol, Condensation polymer of at least one diol such as pentyl glycol and at least two aliphatic or aromatic dicarboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, etc. Can be mentioned.
The content of the polymer diol unit which may be arbitrarily contained is not particularly limited as long as the action and effect of the present invention are not impaired, but is not more than 50% by weight based on the total amount of the polymer diol unit. This is generally preferred because the leather-like composite sheet produced from the obtained polyurethane often has particularly good performance such as sliminess and durability.

The organic diisocyanate unit (B), which is one of the essential constitutional units of the polyurethane of the present invention, has a general formula O = C = N-RN-C = O (III) (where R is as defined above) Is a unit derived from an organic diisocyanate represented by Examples of the divalent organic group represented by R in formulas (II) and (III) include a divalent saturated aliphatic hydrocarbon group such as a hexamethylene group; an isophoronediyl group, and dicyclohexylmethane-4,4 '. -Diyl group, methylcyclohexanediyl group, dimethylcyclohexane-α, α'-
Divalent saturated alicyclic hydrocarbon group such as diyl group; divalent aromatic hydrocarbon group such as diphenylmethane-4,4'-diyl group, phenylene group, methylphenylene group, xylene-α, α'-diyl group And the like. General formula (III)
As the organic diisocyanate represented by, for example, 4,
Aromatic diisocyanates such as 4'-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, xylylene diisocyanate;
Examples thereof include aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated xylylene diisocyanate. Among these organic diisocyanates, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and the like are particularly advantageous for industrial use because of their high versatility. It is.

As described above, the polyurethane of the present invention comprises a polymer diol unit (A-1) and a polymer diol unit (A-
It is mainly composed of 2) and the organic diisocyanate unit (B), and may contain a small amount of a structural unit derived from a chain extender as described below in addition to these structural units. The content of the structural unit derived from such a chain extender is usually 30% by weight or less based on the polyurethane. For the purpose of obtaining a polyurethane which is particularly suitable as a material of the leather-like composite sheet, the polyurethane has a structural unit derived from a chain extender containing two active hydrogen atoms capable of reacting with isocyanate in a molecule, relative to the polyurethane. Is desirably contained in an amount of 1 to 20% by weight.

The structural unit derived from a chain extender is a conventional chain extender as used for the production of ordinary polyurethane, that is, having two or more active hydrogen atoms capable of reacting with isocyanate in water separation. It is a divalent or higher-valent structural unit in which two or more active hydrogen atoms are removed from a low-molecular compound having a molecular weight of 400 or less. Representative examples of the low molecular weight compound include ethylene glycol, propylene glycol, 1,4
-Butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2
Aliphatic diols such as -methyl-1,8-octadiol;
Alicyclic diols such as 1,4-cyclohexanediol;
Divalent aromatic alcohols such as xylylene glycol;
Polyalkylene glycols such as diethylene glycol, dipropylene glycol, dibutylene glycol, triethylene glycol and tripropylene glycol; diols such as carboxylic acid-containing diols such as dimethylolpropionic acid; ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, Aliphatic, alicyclic or aromatic diamines such as nitrylenediamine and tolylenediamine; heterocyclic compounds containing two imino groups in a cyclic structure such as piperazine; dihydrazides such as adipic dihydrazide and isophthalic dihydrazide Hydrazine; trihydric or higher alcohols such as trimethylolpropane, pentaerythritol and glycerin. Examples of the chain extender include at least one of the above-mentioned diols, diamines, heterocyclic compounds having two imino groups in a cyclic structure, low-molecular compounds having two active hydrogen atoms in the molecule, such as dihydrazide and hydrazine. It is preferable to use one kind alone or in combination with at least one kind of the above trihydric or higher alcohols.

In the polyurethane of the present invention, the viscosity of a 25% by weight solution in dimethylformamide solvent measured at 30 ° C is in the range of 5 to 2000 poise. From the viewpoint of obtaining a polyurethane which gives a leather-like composite sheet having particularly excellent sliminess and durability, the viscosity of the solution is 50%.
It is preferably within the range of ~ 900 poise.

For a specific operation method for producing the polyurethane of the present invention, a known technique of a urethane reaction is used. For example, the polyester diol (a-
1) A polymer diol such as polylactone diol (a-2) and, if necessary, a chain extender are mixed, and about 40 to 100
After preheating to ℃, add organic diisocyanate,
After reacting at 140 ° C for several hours, if necessary, mix the same or different chain extenders with those already used,
For several hours to obtain the polyurethane of the present invention. In the urethanization reaction, a normal urethanization reaction catalyst, for example, an organic tin compound, an organic titanium compound, a tertiary amine, or the like may be used, if desired. Also,
The above reaction may be performed in the presence of an organic solvent inert to the organic diisocyanate. As the organic solvent,
Aromatic hydrocarbons such as toluene; esters such as ethyl acetate; amides such as dimethylformamide; ketones such as methyl ethyl ketone, methyl isobutyl ketone and acetone; cyclic ethers such as tetrahydrofuran;
Halogenated hydrocarbons such as trichloroethylene are used alone or in any mixture. These exemplified organic solvents may be used by mixing with alcohols such as isopropanol, ethanol, and methanol. When the reaction is carried out in the presence of an organic solvent, the amount of the organic solvent used is generally adjusted so that the solid content at the end of the reaction is 5 to 90% by weight, especially 10 to 60% by weight. is there.

The polyurethane of the present invention is used alone or in a mixture with another polyurethane elastomer as a polyurethane-based resin constituting a leather-like composite sheet with a fiber substrate. As such a polyurethane elastomer which can be optionally used in combination with the polyurethane of the present invention, a normal polyurethane elastomer used for composing ordinary artificial leather or synthetic leather with a fiber substrate can be used. Representative examples of such polyurethane elastomers that may optionally be used include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, xylylene glycol, neopentyl glycol, and the like. Is a condensation polymer of at least one of low molecular diols with at least one of aliphatic or aromatic dicarboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, isophthalic acid, and terephthalic acid. Polyol polyols such as poly (oxypropylene) polyol and poly (oxytetramethylene) polyol; polylactone polyols such as poly (ε-caprolactone) polyol; polymer polyols such as polycarbonate polyol And the like polyurethane elastomer was collected using cowpea to urethane by a conventional method using a chain and extender, if necessary with Le and an organic diisocyanate. The amount of the polyurethane elastomer that may optionally be used is 50% by weight or less based on the total amount of the polyurethane-based resin constituting the leather-like composite sheet-like material as the fiber substrate and the seed. It is generally preferred that both the slickness and the durability of the composite sheet are particularly good in many cases.

The fiber substrate used in producing a leather-like composite sheet using the polyurethane of the present invention is, for example, a woven fabric, a knitted fabric, or a nonwoven fabric, which is used for producing ordinary synthetic leather and artificial leather. Is a two-dimensional fiber aggregate or a three-dimensional fiber aggregate. Examples of the fibers constituting the fiber base include natural fibers such as cotton, silk, hemp, wool, and asbestos; regenerated fibers such as viscose rayon fibers and copper ammonia rayon fibers; semi-synthetic fibers such as acetate fibers; polyamide fibers (nylon 6 Fiber, nylon 66 fiber, aromatic nylon fiber, etc.), polypinyl alcohol fiber, polyvinylidene chloride fiber, polyester fiber, polyacrylonitrile fiber, polyurethane fiber, synthetic fiber such as poly (alkylene paraoxybenzoate) fiber or the like, or 2
More than one kind can be used, and among them, cotton, polyamide fiber (nylon 6 fiber, nylon 66 fiber, aromatic nylon fiber, etc.), polyvinyl alcohol fiber, polyester fiber, polyurethane fiber and the like are preferably used. These fibers may be ordinary fibers or specially-shaped fibers such as fine fibers and porous fibers. The fiber substrate may be one obtained by impregnating the above-mentioned fiber aggregate with an elastic polymer such as a polyurethane elastomer.

The leather-like composite sheet produced using the polyurethane of the present invention has a so-called silver-attached or polymer suede-like form in which a layer made of a polyurethane resin is coated on a fiber base, and Any of so-called fibrous suede-like forms in which a polyurethane resin is impregnated. In a leather-like composite sheet having a form in which a layer made of a polyurethane-based resin is coated in the form of a fiber base, an adhesive layer and / or an adhesive layer and / or a polyurethane-based resin-containing layer of the present invention are provided between the layer and the fiber base. Alternatively, a mesothelial layer may be interposed. As the resin constituting the adhesive layer or the intermediate layer, for example, polyurethane is preferably employed. Various additives such as those used in ordinary synthetic leather or artificial leather can be blended with the polyurethane resin containing the polyurethane of the present invention, depending on the purpose of use of the leather-like composite sheet. . As such additives, for example, pigments, coloring agents such as dyes, inorganic fillers, hiding agents, softeners, antioxidants, ultraviolet absorbers, surfactants,
Coagulation regulators, lubricants and the like.

The leather-like composite sheet using the polyurethane of the present invention can be produced by a known method, such as a wet method or a dry method, which is employed for producing ordinary synthetic leather and artificial leather. It can be manufactured according to it.

As a method for producing a leather-like composite sheet by a dry method, for example, the following transfer method can be adopted.
First, a solution of a polyurethane resin containing the polyurethane of the present invention was applied on release paper with a doctor knife, and 90 to 90
By drying with hot air at 110 ° C. for 2 to 3 minutes, a resin layer for skin is formed on release paper. A solution of a resin for an adhesive such as polyurethane is applied onto the resin layer on the release paper, and a fiber substrate is further laminated thereon using a laminating roll, and dried with hot air at 90 to 110 ° C. for 2 to 3 minutes. I do. Next, after the obtained laminate was aged at 40 to 60 ° C. for 2 to 3 days, the release paper was peeled off, and the surface was finished several times with a gravure roll, if necessary.
A leather-like composite sheet is obtained. The application of the solution of the polyurethane resin containing the polyurethane of the present invention to release paper is not always uniform according to the intended use of the obtained leather-like composite sheet, but is usually used for the skin to be formed. The solution concentration and the application amount are selected so that the thickness of the resin layer becomes 10 to 100 μm. In addition, as the resin solution for the adhesive, a solution having a resin concentration of 30 to 50% by weight is used.
When applied on the resin layer for skin with an application amount of 60 to 150 g / m ³ , an adhesive layer having a thickness of several tens of μm is formed after drying. Further, a resin film having releasability may be used in place of the above release paper, and as a method of forming a resin layer for a skin on the release paper or on the resin film, polyurethane resin may be used instead of hot air drying. A method of solidifying the polyurethane resin by immersing the release paper or the resin film coated with the system resin solution in the non-solvent of the polyurethane resin can also be adopted.

As a method for producing a leather-like composite sheet by a wet method, for example, a fiber substrate is impregnated and / or coated with a solution of a polyurethane resin, and then immersed in a non-solvent of the polyurethane resin. A method including forming a layer made of a polyurethane resin can be adopted.

The leather-like composite sheet using the polyurethane of the present invention may be subjected to various post-treatments as required for ordinary synthetic leather and artificial leather as necessary. Such post-processing includes, for example, embossing;
Kneading; wrinkling; softener treatment; top coat for improving the feeling, coloring, and surface properties.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

In the examples, the compounds may be indicated by the following abbreviations.

BD: 1,4-butanediol DMF: N, N-dimethylformamide EG: Ethylene glycol MDI; 4,4'-diphenylmethane diisocyanate MOD; 2-methyl-1,8-octanediol ND: 1,9-nonane Diol PMVL: β using ethylene glycol as a polymerization initiator
-(Β-methyl-δ-valerolactone) obtained by ring-opening polymerization of -methyl-δ-valerolactone
Diol PCL: ε using ethylene glycol as polymerization initiator
-Poly (ε-caprolactone) diol obtained by ring-opening polymerization of caprolactone Example 1 Obtained by condensation polymerization of a mixture of ND and MOD (molar ratio: 30/70) with adipic acid. Number average molecular weight 20
MDI, a polymer diol consisting of a 50:50 weight ratio mixture of a polyester diol of 00 and PMVL having a number average molecular weight of 2,000
And EG (polymer diol, MDI and EG molar ratio is 1: 3.
2: 2.2; the amount of nitrogen derived from isocyanate groups is 3.2% by weight) in a DMF solvent at 85 ° C. for about 8 hours according to a conventional method to obtain a 25% by weight polyurethane solution in DMF. Was. The viscosity of the solution at 30 ° C. was 400 poise.

The polyurethane solution thus obtained was diluted with methyl ethyl ketone to obtain a polyurethane solution for a skin layer having a solid content of 20% by weight.

A number average molecular weight of 10 obtained by condensation polymerization of a mixture of ND and MOD (molar ratio: 30/70) and adipic acid.
The polyester diol and tolylene diisocyanate of Example 00 were subjected to a urethanization reaction in a toluene solvent under reflux of the solvent, and then diluted with a mixed solvent of DMF and ethyl acetate to give a solid content of 45% by weight and a viscosity of 700 poise ( 30 ° C.) to obtain a solution-based polyurethane main agent for an adhesive. Then the main ingredient
To 100 parts by weight, 5.5 parts by weight of a tolylene diisocyanate adduct of trimethylolpropane as a curing agent and D
The desired amount of MF was added to obtain an adhesive polyurethane solution having a viscosity of 50 poise (30 ° C.).

Using a knife coater, apply a polyurethane solution for the skin layer (solid content: 20% by weight) on a release paper to a dry thickness of 25 μm.
Then, the resultant was applied in such an amount as to obtain the following, and dried by heating at 100 ° C. for 3 minutes to form a polyurethane film for a skin layer. Next, a polyurethane solution for an adhesive is applied on the above-mentioned film.
Applied using a knife coater in an amount such that the weight per unit area of 120 g / m ^3, immediately thereon, a polyester yarn as the warp, and napped obtained Te cowpea to union with rayon yarn as weft Were bonded together, and then pressed by a laminating roll. 10
After drying at 0 ° C for 2 minutes and curing at 50 ° C for 3 days, the release paper was peeled off to obtain a leather-like composite sheet.

A part of the obtained leather-like composite sheet was subjected to a relative humidity of 95% and a temperature of 70 ° C. for 6 hours using a jangle tester.
We processed for a week (1000 hours).

Each of the leather-like composite sheets not subjected to the jangle test and the leather-like composite sheets subjected to the jangle test was tactilely (touched) and visually (visually) to 10 adult panelists. Based on the evaluation, the sliminess and the surface smoothness of the epidermis were evaluated. Regarding the feeling of sliminess, each panelist should have "a very good slimy feeling", "have a good sliminess", and "have a slight sliminess". "I feel" and "I have no slimy feeling" at four levels, and the numerical value corresponding to each evaluation (3, 2, 1 respectively)
And sliminess was scored in 0). The surface smoothness was evaluated by each panel on a four-point scale: "very smooth,""almostsmooth,""slightlysmooth," and "no smoothness was felt." Then, the surface smoothness was scored by numerical values (3, 2, 1, and 0, respectively) corresponding to each evaluation. Table 1 shows the average score of each paneler for the sliminess and surface smoothness.

It is clear from Table 1 that the leather-like composite sheet having the obtained polyurethane as a skin layer has a very good surface smoothness and a strong slimy feeling. It is. In addition, since the leather-like composite sheet has extremely good surface smoothness and retains a slimy feeling even after being subjected to the jangle test, it has excellent durability and excellent hydrolysis resistance. It is a sheet.

Comparative Example 1 PMVL, MDI and EG having a number average molecular weight of 2000 (the molar ratio thereof is 1: 3.4: 2.4; the amount of nitrogen derived from isocyanate groups is
(3.2% by weight) in a DMF solvent at 85 ° C. for about 13 hours to obtain a 25% by weight solution of polyurethane in DMF. The viscosity of the solution at 30 ° C. was 400 poise.

The polyurethane solution thus obtained was diluted with methyl ethyl ketone to obtain a polyurethane solution for a skin layer having a solid content of 20% by weight. A leather-like composite sheet was obtained in the same manner as in Example 1, except that the thus obtained polyurethane solution for a skin layer was used.

For each of the sample of the leather-like composite sheet obtained in this way and the sample obtained by subjecting it to the jangle test, the same sliminess and surface smoothness as in Example 1 were evaluated. I got it. Table 2 shows the average score of each panelist.

As is clear from Table 2, the leather-like composite sheet having the obtained polyurethane as a skin layer has good surface smoothness, but hardly gives a slimy feeling. It is a seat lacking in luxury.

Comparative Example 2 A 25% by weight polyurethane DMF was prepared in the same manner as in Example 1 except that a polyester diol having a number average molecular weight of 2000 obtained by subjecting BD to adipic acid by condensation polymerization was used as the polyester diol. A solution in was obtained. The viscosity of the solution at 30 degrees was 400 poise.

The polyurethane solution thus obtained was diluted with methyl ethyl ketone to obtain a polyurethane solution for a skin layer having a solid content of 20% by weight. A leather-like composite sheet was obtained in the same manner as in Example 1, except that the thus obtained polyurethane solution for a skin layer was used.

For each of the sample of the leather-like composite sheet obtained in this way and the sample obtained by subjecting it to the jangle test, the same sliminess and surface smoothness as in Example 1 were evaluated. I got it. Table 3 shows the average score of each panelist.

As is clear from Table 3, the leather-like composite sheet using the obtained polyurethane as a skin layer has a good surface smoothness, but it is hard to say that the slimy feeling is sufficiently excellent. Further, they have poor hydrolysis resistance, and markedly deteriorate surface smoothness and slimy feeling after the jangle test.

Comparative Example 3 Poly (α-methyl-δ-valerolactone) diol having a number average molecular weight of 2,000 obtained by ring-opening polymerization of α-methyl-δ-valerolactone using ethylene glycol as a polymerization initiator was number-averaged. Polymer diol, MDI and EG were reacted in the same manner as in Example 1 except that PMVL having a molecular weight of 2000 was used instead of PMVL having a molecular weight of 2000, thereby obtaining a 25% by weight DMF of a polyurethane for a skin layer having a concentration of 25% by weight.
A solution in was obtained. The viscosity of the solution at 30 ° C. was 420 poise. The solution was diluted with methyl ethyl ketone to obtain a polyurethane solution for a skin layer having a solid content of 20% by weight. A leather-like composite sheet was obtained in the same manner as in Example 1, except that the thus obtained polyurethane solution for a skin layer was used.

For each of the sample of the leather-like composite sheet obtained in this way and the sample obtained by subjecting it to the jangle test, the same sliminess and surface smoothness as in Example 1 were evaluated. I got it. According to the average evaluation based on the score of each panelist, the obtained leather-like composite sheet material has a good surface smoothness and a slimy feeling, but it is inferior in hydrolysis resistance and Later, it was found that the surface smoothness and the slimy feeling were reduced, and in particular, the slickness was significantly reduced.

Comparative Example 4 Poly (γ-methyl-δ-valerolactone) diol having a number average molecular weight of 2,000 obtained by ring-opening polymerization of γ-methyl-δ-valerolactone using ethylene glycol as a polymerization initiator was number-averaged. Polymer diol, MDI and EG were reacted in the same manner as in Example 1 except that PMVL having a molecular weight of 2000 was used instead of PMVL having a molecular weight of 2000, thereby obtaining a 25% by weight DMF of a polyurethane for a skin layer having a concentration of 25% by weight.
A solution in was obtained. The viscosity at 30 ° C. of the solution was 430 poise. The solution was diluted with methyl ethyl ketone to obtain a polyurethane solution for a skin layer having a solid content of 20% by weight. A leather-like composite sheet was obtained in the same manner as in Example 1, except that the thus obtained polyurethane solution for a skin layer was used.

For each of the sample of the leather-like composite sheet obtained in this way and the sample obtained by subjecting it to the jangle test, the same sliminess and surface smoothness as in Example 1 were evaluated. I got it. According to the average evaluation based on the score of each panelist, the obtained leather-like composite sheet material has a good surface smoothness and a slimy feeling, but is inferior in hydrolysis resistance and after the Yangle test. It turned out that the surface smoothness and the slimy feeling were reduced, and especially the slickness was significantly reduced.

Examples 2-4 ND used to make polyester diol and
The molar ratio with MOD, the number average molecular weight and mixing ratio of the polyester diol and PMVL used to produce the polyurethane, and the polymer diol, MDI and E
A 25 wt% solution of polyurethane in DMF was obtained in the same manner as in Example 1 except that the conditions shown in Table 4 were employed as the molar ratio of G. The viscosity of the solution at 30 ° C. is about 4
It was 00 poise.

The polyurethane solution thus obtained was diluted with methyl ethyl ketone to obtain a polyurethane solution for a skin layer having a solid content of 20% by weight.

A leather-like composite sheet was obtained in the same manner as in Example 1, except that the thus obtained polyurethane solution for a skin layer was used.

Each of the sample of the leather-like composite sheet thus obtained and the sample obtained by subjecting it to the jangle test was evaluated for the slimy feeling and the surface smoothness as in Example 1. . Table 4 shows the average evaluation based on the scores of each panelist.

As is evident from Table 4, the leather-like composite sheet having the obtained polyurethane as a skin layer is extremely excellent in sliminess and durability, and also excellent in surface smoothness and durability. .

Example 5 Condensation of a mixture of ND, MOD and BD (molar ratio: 8: 8: 9; product of the mole fraction of each diol and the number of carbon atoms of the diol is 7.2) with adipic acid as a polyester diol A 25% by weight polyurethane solution in DMF was obtained in the same manner as in Example 1 except that a polyester diol having a number average molecular weight of 2,000 obtained by polymerization was used. The viscosity of the solution at 30 ° C. was 400 poise.

The polyurethane solution thus obtained was diluted with methyl ethyl ketone to obtain a polyurethane solution for a skin layer having a solid content of 20% by weight. A leather-like composite sheet was obtained in the same manner as in Example 1, except that the thus obtained polyurethane solution for a skin layer was used.

For each of the sample of the leather-like composite sheet obtained in this way and the sample obtained by subjecting it to the jangle test, the same sliminess and surface smoothness as in Example 1 were evaluated. I got it. According to the average evaluation based on the score of each panelist, the leather-like composite sheet having the obtained polyurethane as a skin layer has extremely good surface smoothness and slimy feeling, and after the jangling test. , The good surface smoothness and slimy feeling were maintained.

Example 6 Condensation of a mixture of ND, MOD and BD (molar ratio: 8: 8: 18; product of the mole fraction of each diol and the number of carbon atoms of the diol is 6.4) with adipic acid as a polyester diol A 25% by weight polyurethane solution in DMF was obtained in the same manner as in Example 1 except that a polyester diol having a number average molecular weight of 2,000 obtained by polymerization was used. The viscosity of the solution at 30 ° C. was 00 poise.

The polyurethane solution thus obtained was diluted with methyl ethyl ketone to obtain a polyurethane solution for a skin layer having a solid content of 20% by weight. A leather-like composite sheet was obtained in the same manner as in Example 1, except that the thus obtained polyurethane solution for a skin layer was used.

For each of the sample of the leather-like composite sheet obtained in this way and the sample obtained by subjecting it to the jangle test, the same sliminess and surface smoothness as in Example 1 were evaluated. I got it. According to the average evaluation based on the score of each panelist, the leather-like composite sheet having the obtained polyurethane as a skin layer has good surface smoothness and slimy feeling, and after the jangling test, Although the surface smoothness and slimy feeling were slightly lowered, they were still good.

Example 7 A number average molecular weight of 20 obtained by condensation polymerization of a mixture of ND and MOD (molar ratio: 50/50) and adipic acid.
MDI, a polymer diol consisting of a 50:50 weight ratio mixture of a polyester diol of 00 and PMVL having a number average molecular weight of 2,000
And BD (polymer diol: MDI: BD molar ratio is 1: 6:
5; The amount of nitrogen derived from isocyanate groups was 4.3% by weight) in a DMF solvent at 85 ° C. for about 8.2 hours according to a conventional method to obtain a 25% by weight polyurethane solution in DMF. The viscosity at 30 ° C. of the solution was 400 poise.

The polyurethane solution thus obtained was diluted with DMF so that the solid content concentration became 13% by weight, and the weight ratio of alcohol-modified silicone oil and polyoxyethylene / polyoxypropylene block copolymer as an additive was further reduced. 20% by weight of 0.5: 1 mixture to polyurethane
And a carbon black as a coloring agent was added in an amount of 1% by weight to the polyurethane to prepare a polyurethane composition liquid.

This polyurethane composition solution was applied on a polyethylene sheet by a casting method so that the composition amount was 500 g / m ² (polyurethane amount: 62 g / m ² ), and then dimethylformamide 25% by weight was applied.
It was immersed in a coagulation solution at a temperature of 40 ° C. consisting of an aqueous solution. The solidified polyurethane sheet was peeled off from the polyethylene sheet, the solvent was removed and washed in hot water at 80 ° C., and dried to obtain a porous polyurethane sheet. Such a porous polyurethane sheet has a basis weight of 70 g / m ² , a thickness of 0.33 mm, and an apparent density of 0.23 g / cm ³ , and has a sponge structure having long pores extending in a direction substantially perpendicular to the surface and extremely smooth. It was a flexible one with a smooth surface.

After bonding the surface of the porous polyurethane sheet that was in contact with the polyethylene sheet to the nylon tricot with a cross-linkable polyurethane adhesive, the surface of the porous polyurethane sheet is sandpaper-coated until the thickness becomes about 0.04 to 0.05 mm. When the internal pores were exposed by polishing, a suede-like leather-like composite sheet having a beautiful appearance and formed by uniform pores was obtained. This leather-like composite sheet was a luxurious black sheet that had a slimy, slimy feel and was rich in flexibility and drape, and was suitable as a material for clothing. In addition, the leather-like composite sheet maintained a good texture such as a slimy feeling even after the jangle test.

Comparative Example 5 A number average molecular weight of 20 obtained by condensation polymerization of a mixture of ND and MOD (molar ratio: 50/50) with adipic acid.
00 polyester diol, MDI and BD (molar ratio 1:
6: 5; the amount of nitrogen derived from isocyanate groups is 4.3% by weight)
Was reacted in a DMF solvent at 85 ° C. for about 8 hours according to a conventional method to obtain a 25% by weight polyurethane solution in DMF. The viscosity of the solution at 30 ° C. was 400 poise.

Preparation of a polyurethane composition solution, production of a porous polyurethane sheet, and production of a leather-like composite sheet were performed in the same manner as in Example 7 except that the polyurethane solution thus obtained was used.

The obtained porous polyurethane sheet has a basis weight of 69 g / m ² ,
It had a thickness of 0.31 mm, an apparent density of 0.25 g / cm ³ , and had a sponge structure with irregular pores and a surface with many irregularities. Further, the suede-like leather-like composite sheet obtained by using it did not have a slimy, slimy feeling and was not of a high quality.

Example 8 A number average molecular weight of 20 obtained by condensation polymerization of a mixture of ND and MOD (molar ratio: 40/60) and adipic acid.
MDI, a polymer diol consisting of a mixture of polyester diol of 00 and PMVL having a number average molecular weight of 2000 in a weight ratio of 30:70
And BD (the molar ratio of polymer diol to MDI and BD is (1:
7.9: 6.9; the amount of nitrogen derived from isocyanate groups is 4.8% by weight) in a DMF solvent at 85 ° C. for about 9 hours according to a conventional method to obtain a 25% by weight polyurethane solution in DMF. Was. The viscosity at 30 ° C. of the solution was 370 poise.

The polyurethane solution thus obtained was diluted with DMF so that the solid content concentration became 13% by weight, and the weight ratio of alcohol-modified silicone oil and polyoxyethylene / polyoxypropylene block copolymer as an additive was further reduced. 20% by weight of 0.5: 1 mixture to polyurethane
To prepare a polyurethane composition liquid.

This polyurethane composition solution was applied onto a polyethylene sheet so as to have a liquid amount of 600 g / m ^2, and then immersed in a coagulation solution composed of a 25% by weight aqueous solution of dimethylformamide at a temperature of 40 ° C. The coagulated polyurethane sheet was peeled off from the polyethylene sheet, the solvent was removed in hot water, washed, and dried to obtain a porous polyurethane sheet having extremely good surface smoothness.

This porous polyurethane sheet is adhered to a 1.2 mm-thick fiber base material obtained by incorporating a polyester-based polyurethane in a nylon-6 ultrafine fiber bundle fiber-entangled nonwoven fabric with a polyurethane-based adhesive, and embossed. By doing so, a grain-finished leather-like composite sheet was obtained.

The obtained leather-like composite sheet-like article had a good embossed pattern, and the sheet-like article had a large number of thin and long creases. And a luxurious leather-like sheet having Further, this leather-like composite sheet-like material retained the above-mentioned various favorable characteristics even after the jangle test.

Example 9 A number average molecular weight of 20 obtained by subjecting a mixture of ND and MOD (molar ratio: 40/60) to condensation polymerization with adipic acid.
A polymer diol having a concentration of 25% by weight was prepared in the same manner as in Example 8 except that a polymer diol consisting of a polyester diol of No. 00, PMVL having a number average molecular weight of 2000, and PCL having a number average molecular weight of 2000 was used in a weight ratio of 40:36:24. A solution of the polyurethane in DMF was obtained. The viscosity at 30 ° C. of the solution was 370 poise.

A silver-finished leather-like composite sheet was obtained in the same manner as in Example 8, except that the polyurethane solution thus obtained was used.

Although the obtained leather-like composite sheet was slightly inferior to that obtained in Example 8, it was a slimy and slimy sheet, and the slimy feeling was sufficient even after the jangle test. Was held in.

Example 10 A number average molecular weight of 20 obtained by condensation polymerization of a mixture of ND and MOD (molar ratio: 40/60) with adipic acid.
MDI, a polymer diol consisting of a mixture of polyester diol of 00 and PMVL having a number average molecular weight of 2000 in a weight ratio of 30:70
And BD (molar ratio of polymer diol, MDI and BD is 1: 7.
9: 6.9; the amount of nitrogen derived from isocyanate groups is 4.8% by weight) in a DMF solvent at 85 ° C. for about 9 hours according to a conventional method to obtain a polyurethane having a concentration of 25% by weight [hereinafter, referred to as “polyurethane”.
Polyurethane (X)] in DMF.
The viscosity of the solution at 30 ° C. was 380 poise.

Polybutylene adipate having a number average molecular weight of 2,000, MDI and BD (molar ratio 1: 7.9: 6.9; nitrogen content derived from isocyanate group is 4.8% by weight) was dissolved in a DMF solvent at 85 ° C. by a conventional method.
For about 7 hours to obtain 25% by weight of polyurethane (hereinafter referred to as polyurethane (Y)) in DMF.
A solution in was obtained. The viscosity at 30 ° C. of the solution was 360 poise.

The two types of polyurethanes (X) and polyurethane (Y) thus obtained were mixed so that the weight ratio became 75:25, and diluted with DMF so that the solid concentration became 13% by weight. Further, a polyurethane composition liquid was prepared by adding a mixture of an alcohol-modified silicone oil and a polyoxyethylene / polyoxypropylene block copolymer at a weight ratio of 0.5: 1 as an additive in an amount of 20% by weight based on the polyurethane. .

This polyurethane composition solution was applied onto a polyethylene sheet so as to have a liquid amount of 600 g / m ^2, and then immersed in a coagulation solution of a 25% by weight aqueous solution of dimethylformamide at a temperature of 40 ° C. The coagulated polyurethane sheet was peeled off from the polyethylene sheet, the solvent was removed in hot water, washed, and dried to obtain a porous polyurethane sheet having extremely good surface smoothness.

This porous polyurethane sheet is adhered to a 1.2 mm-thick fiber base material obtained by incorporating a polyester-based polyurethane in a nylon-6 ultrafine fiber bundle fiber-entangled nonwoven fabric with a polyurethane-based adhesive, and embossed. By doing so, a grain-finished leather-like composite sheet was obtained.

The obtained leather-like composite sheet is a high-quality leather-like sheet having a slimy, slimy feeling and an apparent weight feeling, and retains these good features even after the jangle test. Was.

Comparative Example 6 PMVL, MDI and BD having a number average molecular weight of 2000 (the molar ratio is 1:
7.9: 6.9; the amount of nitrogen derived from isocyanate groups is 4.8% by weight) in a DMF solvent at 85 ° C. for about 13 hours according to a conventional method to obtain a 25% by weight polyurethane DMF.
A solution was obtained. The viscosity at 30 ° C. of the solution was 390 poise.

A DMF solution of polyurethane (Y) was prepared in the same manner as in Example 10 except that the DMF solution of polyurethane having a concentration of 25% by weight thus obtained was used instead of the DMF solution of polyurethane (X) having the same concentration. Then, preparation of a polyurethane composition solution, production of a porous polyurethane sheet, and production of a grain-finished leather-like composite sheet were performed.

Although the obtained porous polyurethane sheet had a substantially good surface smoothness, the resulting leather-like composite sheet with silver did not give a slimy, slimy feeling and a After the test, the surface was insufficient in durability such as cracks on the silver surface.

〔The invention's effect〕

As is clear from the above examples, according to the present invention,
Polyurethane that gives a leather-like composite sheet with excellent durability that can hold a good feeling of slimming and that can maintain the good feeling of sliming for a long time even under high temperature and high humidity. Provided. The leather-like composite sheet having a tone of silver produced using the polyurethane provided by the present invention has an extremely good surface smoothness on the silver surface, and further, if the surface is subjected to surface processing, it will be broken. It has a good appearance in the form of wrinkles, embossed fixing properties, and the like. The suede-like leather-like composite sheet produced using the polyurethane provided by the present invention has a good suede feeling. Furthermore, the leather-like composite sheet produced using the polyurethane provided by the present invention is also excellent in secondary workability, for example, cutting workability, sewing workability, plowing, embossability, and the like. .

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-60-26019 (JP, A) JP-A-62-22817 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 18/42

Claims (1)

(57) [Claims] (1) Expression An alkanediol unit containing at least 10 mol% of a 2-methyl-1,8-octanediol unit represented by the formula: (Wherein m represents an integer of 4 to 8) From a polyester diol having a number average molecular weight of 500 to 10,000 substantially consisting of a dicarboxylic acid unit represented by the following formula, two of two alcoholic hydroxyl groups at both ends of the molecule are used. Polymer diol unit (A-1) excluding a hydrogen atom, formula as a constitutional repeating unit A lactone unit containing at least 60 mol% of a β-methyl-δ-valerolactone unit represented by the formula (1) and a divalent unit derived from a polymerization initiator.
A polymer diol unit (A-2) in which two hydrogen atoms in two alcoholic hydroxyl groups at both ends of the molecule are removed from 0000 polylactone diols and a general formula (Wherein, R represents a divalent organic group) mainly comprising an organic diisocyanate unit (B) represented by the following formula: wherein the weight ratio of the polymer diol unit (A-1) to the polymer diol unit (A-2) is 90. Polyurethane characterized in that the viscosity of a 25% strength by weight solution in dimethylformamide solvent measured at 30 ° C. is in the range of 10 to 10 to 90 to 5 to 2000 poise.