KR20140002060A - Elastic strength improver used in polyurethane resin for synthetic leather, and polyol composition and polyurethane resin using same - Google Patents

Abstract

[식 중, X¹ 은 m 가의 활성 수소 함유 화합물로부터 c 개의 활성 수소를 제거한 잔기, c 는 1≤c≤m 을 만족시키는 정수 (m 은 1 ∼ 20 의 정수), X² 는 활성 수소 함유 화합물로부터 1 개의 활성 수소를 제거한 잔기, Y 는 3 가 이상의 방향족 폴리카르복실산으로부터 모든 카르복실기를 제거한 잔기 (Y 의 방향 고리는 탄소 원자로 구성되고, 그 탄소 원자에는 카르복실기 이외의 치환기 및/또는 할로겐 원자가 결합되어 있어도 되지만, 적어도 1 개의 탄소 원자는 치환기가 결합되어 있지 않다), a 는 1 이상의 정수, b 는 0 이상의 정수, 또한 2≤a＋b≤d-2 를 만족시킨다 (d 는 상기 방향족 폴리카르복실산의 카르복실기를 포함하는 모든 치환기를 수소 원자로 치환한 경우의 방향 고리를 구성하는 탄소 원자에 결합된 수소 원자의 수, 즉 방향 고리 상에서 치환 가능한 부위의 수)]This invention relates to the elongation improver used for the polyurethane resin for synthetic leather shown by General formula (1).

[Wherein X ¹ is a residue obtained by removing c active hydrogens from an m-valent active hydrogen-containing compound, c is an integer satisfying 1 ≦ c ≦ m (m is an integer of 1 to 20), and X ² is an active hydrogen-containing compound Residues obtained by removing one active hydrogen from the residues, Y residues obtained by removing all carboxyl groups from trivalent or more aromatic polycarboxylic acids (the aromatic ring of Y is composed of carbon atoms, and substituents other than carboxyl groups and / or halogen atoms are bonded to the carbon atoms) Although at least one carbon atom is not bonded to a substituent, a is an integer of 1 or more, b is an integer of 0 or more, and satisfies 2 ≦ a + b ≦ d-2 (d is the aromatic polycarboxylic acid. Number of hydrogen atoms bonded to the carbon atoms constituting the aromatic ring in the case where all substituents including the carboxyl group of Above)

Description

Elongation enhancers used in polyurethane resins for synthetic leather, and polyol compositions and polyurethane resins using the same. {ELASTIC STRENGTH IMPROVER USED IN POLYURETHANE RESIN FOR SYNTHETIC LEATHER, AND POLYOL COMPOSITION AND POLYURETHANE RESIN USING SAME}

The present invention relates to an elongation enhancer used in a polyurethane resin for synthetic leather and a polyol composition and a polyurethane resin using the same.

Polyurethane resins are resins having a urethane bond using a polyol component and an organic polyisocyanate component as raw materials, and are generally elastic resins rich in elasticity, and are used in the production of bags and shoes. As a physical property item which shows the characteristic of a polyurethane resin, there exists a breaking elongation which shows the elongation at the time of elongation at the time of elongation to break, and the breaking strength which shows the stress at the time of breaking, It is a tough resin that is easy to stretch and does not break easily. The breaking elongation and the breaking strength are adjusted by changing the molecular weight and the number of functional groups of the polyol which is the raw material, but the breaking elongation and the breaking strength are generally contrary items (see Non-Patent Document 1, for example). Specifically, in the increase in the urethane bond concentration due to the decrease in the molecular weight of the polyol, which is an improvement in the breaking strength, or in the increase in the crosslinking density due to the increase in the number of functional groups of the polyol, the resin obtained is stiffened and the elongation at break decreases, resulting in the texture of the final product. It is damaged. If the breaking elongation can be improved while improving the breaking strength of the resin, a resin having excellent texture and durability of the final product can be obtained, thereby expanding the scope of application, and thus a polyurethane resin capable of achieving both high breaking strength and high breaking elongation. Is being requested.

Collection of Latest Polyurethane Design and Modifications and Highly Functionalized Technology, First Edition, Technical Information Society, March 2007, p.

An object of the present invention is to provide a polyurethane resin for synthetic leather having high mechanical properties (strength: breaking strength and breaking elongation) and an elongation improving agent that enables the production thereof.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the present inventors discovered that the polyurethane resin which has a high mechanical property (breaking strength and elongation at break) is obtained by using the elongation improving agent which has a specific structure, and reached | attained this invention. . That is, this invention is an elongation improving agent (S) used for the polyurethane resin for synthetic leather represented by General formula (1); The said elongation improving agent (S) and a hydroxyl value are 20-2000 mgKOH / g, and molar average functional group Polyol composition (A) used for the polyurethane resin for synthetic leather containing polyol (a1) other than the said elongation improving agent (S) whose number is 2-8; Active hydrogen component (H) containing the said polyol composition (A) Synthetic leather which is a polyurethane resin obtained by reacting an organic polyisocyanate component (I) with the elongation improving agent (S) represented by the said General formula (1) in the said polyol composition being an elongation improving agent (S1) which has at least 1 active hydrogen. Polyurethane resin for; The polyurethane resin composition for synthetic leather containing the said elongation improving agent (S) and a polyurethane resin;

[Formula 1]

[In General Formula (1), X <^1> represents the residue remove | excluding c active hydrogen from m-valent active hydrogen containing compound; c represents the integer (1) which satisfy | fills 1 <c <= m; m is 1-20 X ² represents a residue obtained by removing one active hydrogen from an active hydrogen-containing compound, and a plurality of X ^{2 's} may be the same as or different from each other, and X ² And X ¹ may be the same as or different from each other; Y represents a residue obtained by removing all carboxyl groups from a trivalent or more aromatic polycarboxylic acid, and the aromatic ring of Y is composed of carbon atoms, and substituents other than carboxyl groups include Or a halogen atom may be bonded, but at least one carbon atom is not bonded to a substituent; a represents an integer of 1 or more, b represents an integer of 0 or more, and satisfies 2≤a + b≤d-2 D represents the number of hydrogen atoms bonded to the carbon atom constituting the aromatic ring when all substituents including the carboxyl group of the aromatic polycarboxylic acid are substituted with a hydrogen atom, that is, the number of sites that can be substituted on the aromatic ring;

By introducing the elongation improving agent (S) represented by General formula (1) to a polyurethane resin frame | skeleton, the polyurethane resin for synthetic leather excellent in mechanical properties, such as breaking elongation and breaking strength, can be obtained.

Moreover, the polyurethane resin composition for synthetic leather excellent in mechanical properties, such as breaking elongation and breaking strength, can be obtained by adding the elongation improving agent (S) represented by General formula (1) to a polyurethane resin.

The elongation improving agent (S) of this invention is represented by General formula (1), and consists of an elongation improving agent (S1) which has at least 1 active hydrogen, and an elongation improving agent (S2) which does not have active hydrogen.

The polyol composition (A) used for the polyurethane resin for synthetic leather of this invention contains the polyol (a1) other than the elongation improving agent (S) and (S) represented by General formula (1), and this polyol composition The polyurethane resin for synthetic leathers of this invention is obtained by making active hydrogen component (H) containing (A) and organic polyisocyanate component (I) react.

When an elongation enhancer (S1) is used for a polyol composition (A), the said predetermined effect is exhibited by inserting an elongation enhancer (S1) into the molecular skeleton of the polyurethane resin using (A). In addition, when using an elongation enhancer (S2) for (A), if a polyurethane resin is manufactured using (A), (S2) will not be inserted in the molecular skeleton of a polyurethane resin, and a polyurethane resin and an elongation enhancer (S2) Polyurethane resin composition of this invention containing is obtained.

The polyurethane resin composition for synthetic leather of the present invention contains a polyurethane resin and an elongation enhancer (S) represented by General Formula (1). Elongation enhancer (S1) even if an elongation enhancer (S) represented by the general formula (1) is added to a polyurethane resin represented by the general formula (1) and to which the elongation enhancer (S1) having at least one active hydrogen is not inserted. The same effect as the polyurethane resin which inserted this is shown. In the polyurethane resin composition for synthetic leather of the present invention, both an elongation enhancer (S1) and an elongation enhancer (S2) can be used. Elongation enhancer (S1) and (S2) may be used individually by 1 type, and may use 2 or more types together.

Hereinafter, although the elongation improving agent (S) represented by General formula (1) is demonstrated, the composition, numerical value, etc. which are described as a preferable range as an elongation improving agent (S) have at least 1 active hydrogen inserted into a polyurethane resin. Also in the case of an elongation enhancer (S1), also in the case of the elongation enhancer (S) used for a polyurethane resin composition, it is the same unless it specifies in particular.

Elongation improving agent (S) is represented by General formula (1). Elongation enhancer (S) may be used individually by 1 type, and may use 2 or more types together.

(2)

X <^1> in General formula (1) represents the residue which removed c active hydrogen from m-valent active hydrogen containing compound.

As an active hydrogen containing compound, a hydroxyl group containing compound, ammonia, an amino group containing compound, a thiol group containing compound, etc. are mentioned. An active hydrogen containing compound may be used individually by 1 type, and may use 2 or more types together.

As a hydroxyl group containing compound, C1-C20 monohydric alcohol, C2-C20 polyhydric alcohol, and phenols; These alkylene oxide (hereinafter abbreviated as AO) addition product; Ammonia, an amino-group containing compound, and a thiol-group containing compound AO adduct of these; etc. are mentioned.

As a C1-C20 monohydric alcohol, C1-C20 alkanol (methanol, ethanol, butanol, octanol, decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.), C2 And alkenols (such as oleyl alcohol and linolyl alcohol) and aromatic aliphatic alcohols having 7 to 20 carbon atoms (such as benzyl alcohol and naphthyl ethanol).

As a C2-C20 polyhydric alcohol, C2-C20 dihydric alcohol [aliphatic diol (ethylene glycol, propylene glycol, 1, 3- or 1, 4- butanediol, 1, 6- hexanediol, neopentyl glycol, and 1,10-decanediol and the like), alicyclic diols (such as cyclohexanediol and cyclohexanedimethanol) and aromatic aliphatic diols {1,4-bis (hydroxyethyl) benzene and the like}], and 3 to 20 carbon atoms Polyhydric alcohols [aliphatic triols (such as glycerin and trimethylolpropane)] and 4-8 carbon atoms having 5 to 20 carbon atoms [aliphatic polyols (pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc.); ) And sugars (sucrose, glucose, mannose, fructose, methylglucoside and derivatives thereof).

Examples of the phenols include monohydric phenols (such as phenol, 1-hydroxynaphthalene, anthrol and 1-hydroxypyrene), and polyhydric phenols [fluoroglucin, pyrogallol, catechol, hydroquinone, bisphenol A, Bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, 1,4,5,8-tetrahydroxyanthracene, condensates of phenol and formaldehyde (novolac) and US Pat. And polyphenols described in the above.

As an amino-group containing compound, C1-C20 monohydrocarbylamine [alkylamine (such as butylamine), benzylamine, aniline, etc.], C2-C20 aliphatic polyamine (ethylenediamine, hexamethylenediamine, and diethylenetri) Amines), alicyclic polyamines having 6 to 20 carbon atoms (such as diaminocyclohexane, dicyclohexylmethanediamine and isophoronediamine), aromatic polyamines having 2 to 20 carbon atoms (phenylenediamine, tolylenediamine and diphenylmethanediamine) Etc.), heterocyclic polyamines having 2 to 20 carbon atoms (such as piperazine and N-aminoethylpiperazine), alkanolamines (such as monoethanolamine, diethanolamine and triethanolamine), condensation of dicarboxylic acid with excess polyamine Polyamide polyamine, polyetherpolyamine, hydrazine (such as hydrazine and monoalkylhydrazine), dihydrazide (succinic acid dihydra) obtained by Zide and terephthalic acid dihydrazide, etc.), guanidine (such as butylguanidine and 1-cyanoguanidine), and dicyandiamide, and the like.

Examples of the thiol group-containing compound include monovalent thiol compounds having 1 to 20 carbon atoms (alkyl thiols such as ethyl thiol, phenylthiol and benzyl thiol), and polyvalent thiol compounds (such as ethylenedithiol and 1,6-hexanedithiol). Can be mentioned.

Examples of AO used in the hydroxyl group-containing compound include AO having 2 to 4 carbon atoms, for example, ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propylene oxide And 1,2-, 1,3- or 2,3-butylene oxide and tetrahydrofuran (hereinafter abbreviated as THF) and the like. Among them, EO, PO and THF are preferable from the viewpoint of breaking strength. AO may be used individually by 1 type, or may use 2 or more types together, As an addition method in the case of using 2 or more types of AO, block addition may be sufficient, random addition may be sufficient, these may be used together.

As for the added mole number of AO, 8-100 are preferable from a viewpoint of breaking strength, More preferably, it is 10-80. Moreover, it is preferable that the hydroxyl value of AO adduct is 18-360 mgKOH / g. In this invention, a hydroxyl value is measured based on JISK1557-1.

Moreover, as an active hydrogen containing compound, the compound which has 2 or more types of active hydrogen containing functional groups (hydroxyl group, amino group, thiol group etc.) in a molecule | numerator can also be used.

As the active hydrogen-containing compound for introducing X ¹ into the elongation enhancer (S), preferred are hydroxyl group-containing compounds, amino group-containing compounds, and AO adducts thereof in view of the breaking strength and the elongation at break of the polyurethane resin, and more The polyether polyol which added AO to the C2-C20 polyhydric alcohol, the C2-C20 polyhydric alcohol, and the C2-C20 aliphatic polyamine, Especially preferably, the C2-C20 polyhydric alcohol and C2-C20 Polyether polyol which added AO to polyhydric alcohol, Most preferably, polyether polyol which added AO to C2-C20 polyhydric alcohol.

The valence m of the active hydrogen-containing compound is usually 1 to 20, preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2 from the viewpoint of the breaking strength and the breaking elongation of the polyurethane resin. .

C in General formula (1) represents the integer which is 1-20 and satisfy | fills 1 <= c <= m, From a viewpoint of breaking strength and breaking elongation of a polyurethane resin, Preferably it is 1-8, Furthermore, Preferably it is 1-4, Especially preferably, it is 2.

General formula (1) X ² is, represents the residue obtained by removing one active hydrogen atom from a 1 to 20-valent active hydrogen-containing compound, a plurality of X ² in the May be the same or different, respectively.

Examples of the active hydrogen-containing compound used for constituting X ² include the same ones as those of the active hydrogen-containing compound represented by X ¹ described above, and X ² and X ¹ may be the same as or different from each other. In view of the breaking strength and the elongation at break, X ¹ and at least one X ² are preferably different groups.

In addition, the valence of X ² is usually 1 to 20, preferably 1 to 8, more preferably 1 to 4, particularly preferably 1 to 2, from the viewpoint of the breaking strength and the elongation at break of the polyurethane resin. Most preferably 2.

In addition, X ¹ and X ² can be introduced into the elongation enhancer (S) by reacting the active hydrogen-containing compound with a trivalent or higher polycarboxylic acid used to constitute Y described later. When it is a C2-C4 diol or a C2-C4 polyether polyol of a repeating unit, an equivalent compound can also be obtained by adding the said C2-C4 AO to the carboxyl group of a polycarboxylic acid. For example, when an active hydrogen containing compound is ethylene glycol, the residue remove | excluding one active hydrogen from ethylene glycol can be introduce | transduced by making 1 mol of EO react with the carboxyl group of a polycarboxylic acid.

Y in General formula (1) represents the residue remove | excluding all the carboxyl groups from trivalent or more aromatic polycarboxylic acid. The aromatic ring of Y is composed of carbon atoms, and substituents other than carboxyl groups and / or halogen atoms may be bonded to the carbon atoms, but at least one carbon atom needs to be bonded to a hydrogen atom without having a substituent bonded thereto.

Examples of the substituent other than the carboxyl group include alkyl groups, vinyl groups, allyl groups, cycloalkyl groups, amino groups, hydroxyl groups, hydroxyamino groups, nitro groups, thiol groups, aryl groups, and cyano groups.

As a trivalent or more aromatic polycarboxylic acid used in order to comprise Y, C9-30 aromatic polycarboxylic acid, for example, trimellitic acid, 1,2,3-benzenetricarboxylic acid, trimes Tricarboxylic acids such as acid, hemimeltic acid, 1,2,4-, 1,3,6- or 2,3,6-naphthalenetricarboxylic acid and 2,3,6-anthracenic carboxylic acid; Pyromellitic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, 2,2', 3,3'-benzophenonetetracarboxylic acid, 2,3,3 ', 4'-benzophenone Tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic acid, 2,3,3 ', 4'-ratio Phenyltetracarboxylic acid, 4,4'-oxybisphthalic acid, diphenylmethanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid , Tetracarboxylic acids such as 2,3,6,7-naphthalenetetracarboxylic acid and 4,4 '-(hexafluoroisopropylidene) bisphthalic acid And the like. An aromatic polycarboxylic acid may be used individually by 1 type, and may use 2 or more types together.

In the preparation of the elongation enhancer (S), these ester-forming derivatives [acid anhydrides, lower alkyl (C 1-4) esters (methyl esters, ethyl esters and isopropyl esters, etc.) and acid halides (acid chlorides) Etc.) may be used.

Among these aromatic polycarboxylic acids, from the viewpoint of the breaking strength and the elongation at break of the polyurethane resin, preferred are two carboxyl groups forming an aromatic ring, adjacent to a carbon atom to which no substituent is bonded, and forming an aromatic ring. It is preferable to have the structure couple | bonded with two carbon atoms, respectively, More preferably, it has a structure which further couple | bonded 1 carboxyl group to at least one of the carbon atoms adjacent to the carbon atom which the said carboxyl group couple | bonded.

In view of the breaking strength and the elongation at break of the polyurethane resin, particularly preferred as the aromatic polycarboxylic acid used to constitute Y are monocyclic compounds, and most preferred are trimellitic acid and pyromellitic acid.

A in General formula (1) represents an integer greater than or equal to 1, b represents an integer greater than or equal to 0, satisfy | fills 2 <= a + b <= d-2, and d contains all the carboxyl groups of the said aromatic polycarboxylic acid. The number of hydrogen atoms bonded to the carbon atoms constituting the aromatic ring when the substituent is substituted with a hydrogen atom, that is, the number of sites that can be substituted on the aromatic ring is shown. For example, when the aromatic ring is a benzene ring composed of 6 carbon atoms, d is 6, and a + b may have a value of 2 to 4, and when the aromatic ring is a naphthalene ring composed of 10 carbon atoms, d Is 8 and a + b can take the value of 2-6. When an aromatic ring is a monocyclic aromatic ring, 2 + 3 is preferable from a viewpoint of breaking strength and breaking elongation of a polyurethane resin. Moreover, from a viewpoint of breaking strength and breaking elongation of a polyurethane resin, it is preferable that b is 1/2 or less of a, and 0 is especially preferable.

The hydroxyl value of the elongation enhancer (S) in the present invention is preferably 0 or 70 to 500 mgKOH / g, (S) having a hydroxyl group in view of the breaking strength and the elongation at break of the polyurethane resin. More preferably, it is 75-350 mgKOH / g. When (S) has a hydroxyl group, when the hydroxyl value is less than 70 mgKOH / g, the breaking strength of the polyurethane resin tends to decrease, and when it exceeds 500 mgKOH / g, the breaking elongation of the polyurethane resin decreases. There is a tendency.

In addition, the hydroxyl value of elongation improving agent (S) is 0 means that X <^1> , X <^2> and Y in General formula (1) do not have a hydroxyl group at all.

The concentration of Y in the elongation enhancer (S) means the number of moles of residue Y in 1 g of the elongation enhancer (S), and is preferably 1.0 to 3.5 from the point of breaking strength and elongation at break of the polyurethane resin. mmol / g, more preferably 1.1 to 3.4 mmol / g, particularly preferably 1.2 to 3.3 mmol / g. If the concentration of Y is less than 1.0 mmol / g, the breaking strength of the polyurethane resin tends to decrease, while if it exceeds 3.5 mmol / g, the breaking elongation of the polyurethane resin tends to decrease.

The carbonyl group concentration of the elongation enhancer (S) is preferably 3.0 to 10.0 mmol / g, more preferably 3.0 to 9.7 mmol / g, particularly preferably 3.0 from the viewpoint of the breaking strength and the elongation at break of the polyurethane resin. 9.5 mmol / g. If the carbonyl group concentration is less than 3.0 mmol / g, the breaking strength of the polyurethane resin tends to decrease, and when the carbonyl group concentration exceeds 10.0 mmol / g, the breaking elongation tends to decrease. The carbonyl group in the carbonyl group concentration in the present invention refers to a carbonyl group bonded to Y in General Formula (1), that is, a carboxyl group of a trivalent or higher aromatic polycarboxylic acid used to introduce Y and derived from the same. Carbonyl groups in functional groups, such as an ester group, a thioester group, and an amide group, are meant.

2-8 are preferable from a viewpoint of the mechanical strength of a polyurethane resin, and, as for the molar average functional group number of an elongation improving agent (S), More preferably, it is 2-6, Especially preferably, it is 2-4.

The molar average number of functional groups in the present invention is a value obtained by dividing the total of the number of functional groups having active hydrogen of each component in the composition by the number of moles of each component divided by the total number of moles of each component, and the number of moles of each component is It is the value obtained by dividing the weight of each component by the molecular weight of each component. As a molecular weight used for calculation, like a low molecular weight compound, when there is no distribution in molecular weight, a chemical formula is used, and when there is a distribution in molecular weight, a number average molecular weight (hereinafter, abbreviated as Mn) is used. The elongation improving agent (S) and Mn of a polyol in this invention are measured by gel permeation chromatography using polyoxypropylene glycol as a reference material, using THF as a solvent. The sample concentration is 0.25% by weight, and the column fixed phase is one in which one TSKgel Super H2000, one TSKgel Super H3000, or one TSKgel Super H4000 (all manufactured by Tosoh Corporation) is connected, and the column temperature may be 40 ° C.

The elongation enhancer (S1) having at least one active hydrogen is a compound in which at least one of X ¹ , X ² and Y in General Formula (1) has active hydrogen. More specifically, at least the valence m and c of X ¹ satisfy m> c, Y is substituted by a substituent having active hydrogen such as an amino group, a hydroxyl group, a hydroxyamino group and a thiol group, or X ^When the active hydrogen containing compound which comprises 2 is bivalent or more, or b is 1 or more, the elongation enhancer (S1) has at least 1 active hydrogen.

The polyol composition (A) of the present invention contains an elongation enhancer (S) and a polyol (a1) other than the above (S) having a hydroxyl value of 20 to 2000 mgKOH / g and a molar average functional group number of 2 to 8, Used in polyurethane resins for synthetic leather.

As a polyol (a1) which a polyol composition (A) contains, a hydroxyl value is 20-2000 mgKOH / g, the said C2-C20 polyhydric alcohol whose molar average functional group is 2-8, and the C2-C20 polyhydric acid The polyether polyol which added the said C2-C4 AO to alcohol, polyester polyols other than (S), another polyol, etc. are mentioned. Polyol (a1) may be used individually by 1 type, and may use 2 or more types together.

Among the polyether polyols as the polyol (a1), preferred from the viewpoint of breaking strength is that AO is EO, PO, 1,2-butylene oxide and / or THF.

As a polyester polyol, the said C2-C20 polyhydric alcohol and / or the said polyether polyol, a di- tetravalent aromatic polycarboxylic acid and / or aliphatic polycarboxylic acid, and these anhydrides or lower alkyl (carbon number of an alkyl group) 1-4) Condensation reaction products of ester-forming derivatives, such as ester, What is other than the said elongation enhancer (S); These AO adducts; Polylactone polyol [For example, the said C2-C20 polyhydric alcohol What is obtained by ring-opening-polymerizing lactone ((epsilon) -caprolactone etc.) as an initiator]; And polycarbonate polyol (For example, the reactant of the said C2-C20 polyhydric alcohol and alkylene carbonate); These etc. are mentioned.

As a bivalent tetravalent aromatic polycarboxylic acid, terephthalic acid, isophthalic acid, a phthalic acid, 2, 3- naphthalenedicarboxylic acid, 2, 6- naphthalenedicarboxylic acid, 1, 4- naphthalenedicarboxylic acid, 1 , 8-naphthalenedicarboxylic acid, anthracenedicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid Aromatic dicarboxyl having 8 to 30 carbon atoms, such as 3,3'-biphenyl ether dicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid, and 4,4'-binafyldicarboxylic acid Acids and the said trivalent or tetravalent aromatic polycarboxylic acid etc. are mentioned.

Examples of the divalent aliphatic polycarboxylic acid include oxalic acid, succinic acid, malonic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, itaconic acid, C2-C30 aliphatic polycarboxylic acids, such as a tricarvalic acid and hexane tricarboxylic acid, etc. are mentioned.

Other polyols include polyols and silicones in which 1 mole of AO is added per hydroxyl group to hydroxyl groups of monocyclic polyhydric phenols (such as pyrogallol, hydroquinone and phloroglucin) or bisphenols (such as bisphenol A, bisphenol F and bisphenol S). Polyols, polymer polyols, polydiene polyols (polybutadiene polyols, etc.), hydrogenated products of polydiene polyols, acrylic polyols, natural oil-based polyols (such as castor oil), and modified products of natural oil-based polyols.

The hydroxyl value of a polyol (a1) is 20-2000 mgKOH / g normally from a viewpoint of breaking strength and breaking elongation of a polyurethane resin, Preferably it is 25-1900 mgKOH / g. If the hydroxyl value is less than 20 mgKOH / g, the breaking strength of the polyurethane resin is lowered. If it exceeds 2000 mgKOH / g, the breaking elongation of the polyurethane resin is deteriorated.

As for the mole average functional group number of a polyol (a1), 2-8 are preferable from a viewpoint of the breaking elongation of a polyurethane resin, More preferably, it is 2-6, Especially preferably, it is 2-4, Most preferably, it is 2. .

The content of the elongation enhancer (S) is preferably 0.01 to 10% by weight, more preferably 0.015 to 8 from the viewpoint of the breaking strength and the elongation at break of the polyurethane resin based on the weight of the polyol composition (A). Weight%, Especially preferably, it is 0.02-6 weight%, Especially preferably, it is 0.025-3 weight%, Most preferably, it is 0.03-1.5 weight%.

As for content of a polyol (a1), 90-99.99 weight% is preferable from a viewpoint of the breaking elongation of a polyurethane resin based on the weight of a polyol composition (A), More preferably, it is 92-99.985 weight%, Especially Preferably it is 94-99.98 weight%.

The polyurethane resin for synthetic leather of the present invention is obtained by reacting an active hydrogen component (H) containing the polyol composition (A) with an organic polyisocyanate component (I), and is represented by General Formula (1) in (A). When the elongation enhancer (S) shown is an elongation enhancer (S1) having at least one active hydrogen, the elongation enhancer (S1) is inserted into the molecular skeleton of the polyurethane resin.

The active hydrogen component (H) may contain, in addition to the polyol composition (A), a chain extender, a reaction terminator, and the like.

Examples of the chain extender include water, diamines having 2 to 10 carbon atoms (for example, ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, toluenediamine and piperazine), and polyalkylenepolyamines (for example, Diethylenetriamine and triethylenetetramine), hydrazine or derivatives thereof (e.g. dibasic acid dihydrazide such as adipic dihydrazide) and amino alcohols having 2 to 10 carbon atoms (e.g. ethanol Amine, diethanolamine, 2-amino-2-methylpropanol, triethanolamine, etc.) etc. are mentioned. A chain extender may be used individually by 1 type, and may use 2 or more types together.

Moreover, the C2-C20 polyhydric alcohol in the said polyol (a1), etc. also function as a chain extender.

Examples of the reaction terminator include monoalcohols having 1 to 8 carbon atoms (methanol, ethanol, isopropanol, cellosolves and carbitols, etc.) and monoamines having 1 to 10 carbon atoms (monomethylamine, monoethylamine, monobutylamine, Mono or dialkylamines such as dibutylamine and monooctylamine; mono or dialkanolamines such as monoethanolamine, diethanolamine, diisopropanolamine, and the like). A reaction terminator may be used individually by 1 type, and may use 2 or more types together.

As the organic polyisocyanate component (I), generally all of the organic polyisocyanates used in the production of the polyurethane resin can be used, for example, aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates and these And modified substances (urethane group, carbodiimide group, allophanate group, urea group, biuret group, isocyanurate group, oxazolidone group-containing modified substance, etc.) and the like. An organic polyisocyanate component (I) may be used individually by 1 type, and may use 2 or more types together.

As an aromatic polyisocyanate, C6-C16 aromatic diisocyanate, C6-C20 aromatic triisocyanate, and preparations of these isocyanates are carbon atoms (except carbon in an NCO group). ), And the like. As a specific example, 1, 3- or 1, 4- phenylene diisocyanate, 2, 4- or 2, 6- tolylene diisocyanate (TDI), a crude TDI, 2, 4'- or 4, 4'- diphenyl Methane diisocyanate (MDI), polymethylene polyphenylene polyisocyanate (prepared MDI), naphthylene-1,5- diisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate, etc. are mentioned.

Examples of the aliphatic polyisocyanate include aliphatic diisocyanates having 1 to 6 carbon atoms (1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and lysine diisocyanate).

As alicyclic polyisocyanate, C6-C16 alicyclic diisocyanate (isophorone diisocyanate, 4,4'- dicyclohexyl methane diisocyanate, 1, 4- cyclohexane diisocyanate, norbornane diisocyanate, etc.) etc. are mentioned. Can be mentioned.

As aromatic aliphatic isocyanate, C8-C12 aromatic aliphatic diisocyanate (xylylene diisocyanate and (alpha), (alpha), (alpha) ', (alpha)' tetramethyl xylylene diisocyanate) etc. are mentioned.

Specific examples of the modified polyisocyanate include carbodiimide-modified MDI.

Among them, from the viewpoint of breaking strength, preferred are aromatic polyisocyanates, more preferred are modified products of TDI, prepared TDI, MDI, prepared MDI and these isocyanates, and particularly preferred are the total content of MDI, prepared MDI and modified products thereof. It is 10 weight% or more (especially 15-80 weight%), and content of TDI, prepared TDI, and these modified substances (especially TDI) is 90 weight% or less (especially 20-85 weight%). As for isocyanate group content (NCO%) as an isocyanate component (I) whole, 25-45 weight% is preferable.

The polyurethane resin for synthetic leather of this invention can be used, melt | dissolving in an organic solvent as needed, and can also add and use an additive.

As an organic solvent, the solvent which does not contain an active hydrogen group is mentioned. Specific examples include amide solvents (N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like), sulfoxide solvents (dimethyl sulfoxide and the like), ketone solvents (methyl Ethyl ketone and methyl isobutyl ketone and the like), ether solvents (such as dioxane and THF), ester solvents (such as methyl acetate, ethyl acetate and butyl acetate), aromatic solvents (such as toluene and xylene), and the like. have. An organic solvent may be used individually by 1 type, and may use 2 or more types together.

Additives include plasticizers (such as phthalic acid esters and adipic acid esters), fillers (such as calcium carbonate), colorants (dyes and pigments), flame retardants (such as phosphate esters and halogenated phosphate esters), anti-aging agents (such as triazoles and benzophenones) And known auxiliary components such as antioxidants (hindered phenol and hindered amine, etc.).

Isocyanate index (index) [(equivalent of NCO group / equivalent to active hydrogen atom-containing group) × 100] at the time of production of the polyurethane resin for synthetic leather of the present invention is the breaking strength and the elongation at break of the polyurethane resin. 70-135 are preferable from a viewpoint of more preferable, More preferably, it is 75-130, Especially preferably, it is 80-125.

As for content of the polyol composition (A) as a structural unit in the polyurethane resin for synthetic leather of this invention, content of an elongation improving agent (S1) is based on the weight of a polyurethane resin from a viewpoint of breaking strength and breaking elongation. The amount is preferably 0.005 to 7% by weight, more preferably 0.007 to 5.5% by weight, and particularly preferably 0.01 to 4% by weight.

The manufacturing method of the polyurethane resin for synthetic leathers of this invention is not specifically limited, It can manufacture by a well-known method etc .. For example, an active hydrogen component (H), an organic polyisocyanate component (I), an organic solvent, and additives may be injected collectively as needed, and may be made to react, and an active hydrogen component (H) and an organic polyisocyanate component (I) may be made to react. After reacting and obtaining the prepolymer of an isocyanate group terminal, you may perform an extension reaction with a chain extender. In addition, by using a kneader or the like as the reaction apparatus, the reaction can also be carried out under a solvent-free.

The polyurethane resin composition for synthetic leather of the present invention contains a polyurethane resin and an elongation enhancer (S) represented by General Formula (1). The polyurethane resin used for the polyurethane resin composition of this invention is not specifically limited, It may or may not have an elongation enhancer (S1) as a structural component of the molecule | numerator, for example, the said polyol (a1) and a necessity. Thus, it is obtained by reacting the active hydrogen component (H2) containing the chain extender, the reaction terminator and the elongation enhancer (S1) with the organic polyisocyanate component (I).

When using an elongation improving agent (S) in addition to a polyurethane resin, the addition amount is based on the weight of a polyurethane resin from a viewpoint of breaking strength and elongation at break, Preferably it is 0.005-7 weight%, More preferably, Is 0.007 to 5.5% by weight, particularly preferably 0.01 to 4% by weight.

The addition time of an elongation enhancer (S) with respect to a polyurethane resin at the time of manufacturing a polyurethane resin composition is not specifically limited, After manufacturing a polyurethane resin, you may mix with an elongation enhancer (S), and an elongation enhancer (S) When is an elongation enhancer (S2) which does not have active hydrogen, you may manufacture a polyurethane resin in presence of (S2). In the case where the elongation enhancer (S) in the polyol composition (A) of the present invention is (S2), producing a polyurethane resin using this polyol composition (A) requires a polyurethane resin in the presence of (S2). It means to manufacture.

The polyurethane resin composition of this invention can contain the said organic solvent and the said additive further.

Example

Hereinafter, although an Example further demonstrates this invention, this invention is not limited to these. In addition, below, a part shows a weight part.

Example 1 [Production of Strength Enhancer (S1-1)]

PO / EO block adduct of propylene glycol (Sanyo Chemical Co., Ltd. product "SANIX PL-910"; Mn 900, hydroxyl value 124.7) 900.0 parts, trimelli anhydride in a stainless steel autoclave with a stirring device and a temperature control device 384.0 parts of tric acid and 2.0 parts of an alkali catalyst (N-ethyl morpholine) were injected and reacted for 5 hours at 0.20 MPa and 130 ± 10 ° C under a nitrogen atmosphere to effect half-esterification of the acid anhydride group, thereby producing PO of propylene glycol. The ester compound by which 2 mol of trimellitic anhydride reacted with 1 mol of / EO block addition products was obtained. Subsequently, 198.0 parts of EO was dripped over 5 hours, controlling so that a pressure might be 0.50 Mpa or less at 100 +/- 10 degreeC, and it aged for 1 hour at 100 +/- 10 degreeC, and the stiffness improver which added EO to the carboxyl group of the said ester compound. (S1-1) was obtained.

Example 2 [Production of Strength Enhancer (S1-2)]

Except for changing 900.0 parts of propylene glycol PO / EO block adducts to 1000.0 parts of polytetramethylene ether glycol ("PTMG1000" manufactured by Mitsubishi Chemical Co., Ltd .; Mn 1000, hydroxyl value 112.2), the same as in Example 1, an elongation enhancer (S1- 2) was obtained.

Example 3 [Production of Strength Enhancer (S1-3)]

900.0 parts of PO / EO block adducts of propylene glycol were added to polyoxypropylene triol (Sanyo Kasei Kogyo Co., Ltd. "SANIX GP-1500"; Mn 1500, hydroxyl value 112.2) 1500.0 parts, and the injection amount of trimellitic anhydride was 576.0 parts, Except having changed the injection amount of EO into 297.0 parts, it carried out similarly to Example 1, and obtained the elongation improving agent (S1-3).

Example 4 [Preparation of Elongation Enhancer (S1-4)]

900.0 parts of PO / EO block adducts of propylene glycol were carried out except that polypropylene glycol (Sanyo Chemical Co., Ltd. product "SANIX PP-1000"; Mn 1000, hydroxyl value 112.2) was 1000.0 parts, and the amount of EO injected was changed to 101.2 parts. In the same manner as in Example 1, a ductility enhancer (S1-4) was obtained.

Example 5 [Production of Strength Enhancer (S1-5)]

324.0 parts of diethylene glycol monobutyl ether, 218.0 parts of pyromellitic anhydride, 542.0 parts of dimethylformamide as a solvent and 2.0 parts of an alkali catalyst (N-ethylmorpholine) were injected into a stainless autoclave with a stirring device and a temperature control device. The reaction mixture was then reacted at 0.20 MPa at 25 ± 10 ° C. for 5 hours in a nitrogen atmosphere to effect half esterification of an acid anhydride group, and 2 moles of diethylene glycol monobutyl ether reacted with 1 mole of pyromellitic anhydride. Got. Subsequently, 198.0 parts of EO were dripped over 5 hours, controlling so that the pressure might be 0.50 Mpa or less at 50 +/- 10 degreeC, and aged at 50 +/- 10 degreeC for 1 hour, and a dimethylformamide was heated at 100 degreeC +/- 10 degreeC It removed over 5 hours, controlling so that it might become -0.1 Mpa, and obtained the stiffness improving agent (S1-5) which added EO to the carboxyl group of the said ester compound.

Example 6 [Production of Strength Enhancer (S1-6)]

Into a stainless steel autoclave with a stirring device and a temperature control device, 60.0 parts of ethylenediamine, 384.0 parts of trimellitic anhydride, 1.0 part of alkali catalyst (N-ethylmorpholine) and 219 parts of THF as a solvent were injected, and under nitrogen atmosphere, It was made to react at 80 +/- 10 degreeC for 2 hours, and half amidation of the acid anhydride group part was obtained, and the amide compound which 2 mol of trimellitic anhydride reacted with 1 mol of ethylenediamine was obtained. Subsequently, EO 198.0 parts were added dropwise over 5 hours while controlling the pressure to be 0.50 MPa or less at 80 ± 10 ° C, and then aged at 80 ± 10 ° C for 1 hour, and the solvent was distilled at 80 ± 10 ° C and 10 kPa. By removing, the elongation improver (S1-6) which added EO to the carboxyl group of the said amide compound was obtained.

Example 7 [Production of Strength Enhancer (S2-1)]

PO / EO block adduct of propylene glycol (Sanyo Chemical Co., Ltd. product "SANIX PL-910"; Mn 900, hydroxyl value 124.7) 900.0 parts, trimelli anhydride in a stainless steel autoclave with a stirring device and a temperature control device 384.0 parts of triacid, 1.0 part of alkali catalyst (N-ethylmorpholine) and 460 parts of toluene were charged, and reacted at 0.20 MPa and 130 ± 10 ° C for 5 hours under nitrogen atmosphere to effect half esterification of the acid anhydride group. An ester compound obtained by reacting 2 mol of trimellitic anhydride with 1 mol of PO / EO block adduct of propylene glycol was obtained. Subsequently, 432.0 parts of benzyl alcohol was added, it controlled to be 95 +/- 5 degreeC, 0.06 Mpa or less, condensed volatilized toluene and water with a cooler, and it reacted for 6 hours continuously returning toluene separated by the trap to the reaction container. I was. The elongation improver (S2-1) which made the carboxyl group of the said ester compound the benzyloxycarbonyl group by distilling a solvent off at 80 +/- 10 degreeC and 10 Pa after reaction was obtained.

Example 8 [Production of Strength Enhancer (S2-2)]

The elongation improving agent (S2-2) was obtained like Example 7 except having changed 432.0 parts of benzyl alcohol into 428.0 parts of benzylamine.

Example 9 [Production of Strength Enhancer (S2-3)]

The elongation improving agent (S2-3) was obtained like Example 7 except having changed 432.0 parts of benzyl alcohol into 496.0 parts of benzyl thiol.

Example 10 [Production of Strength Enhancer (S2-4)]

60.0 parts of ethylenediamine, 384 parts of trimellitic anhydride, 1.0 part of alkali catalysts (N-ethylmorpholine) and 460 parts of toluene as a solvent were injected into a stainless autoclave with a stirring device and a temperature control device, It was made to react at 80 +/- 10 degreeC for 2 hours, and half amidation of the acid anhydride group part was obtained, and the amide compound in which 2 mol of trimellitic anhydride reacted with 1 mol of ethylenediamine was obtained. Subsequently, 432.0 parts of benzyl alcohol was added, it controlled to be 95 +/- 5 degreeC, 0.06 Mpa or less, condensed volatilized toluene and water with a cooler, and it reacted for 6 hours continuously returning toluene separated by the trap to the reaction container. I was. The elongation improver (S2-4) which made the carboxyl group of the said amide compound benzyloxycarbonyl group by distilling a solvent off at 80 +/- 10 degreeC and 10 Pa after reaction was obtained.

Comparative Example 1 [Preparation of Comparative Strength Enhancer (S1′-1)]

900.0 parts of propylene glycol PO / EO block adducts were made into polyoxypropylene triol (Sanyo Chemical Co., Ltd. "Sannix GP-3000"; Mn 3200, hydroxyl value 52.6) 3200.0 parts, trimellitic anhydride 384.0 parts to 444 parts of phthalic anhydride And the comparative elongation improving agent (S1'-2) was obtained like Example 1 except having changed the injection amount of and EO into 149.0 parts.

Comparative Example 2 [Preparation of Comparative Strength Enhancer (S1′-2)]

A comparative elongation improver (S1'-2) was obtained in the same manner as in Example 1 except that 384.0 parts of trimellitic anhydride were changed to 296 parts of phthalic anhydride and the amount of EO injected was 99.0 parts.

Table 1 shows the analysis results of the compounds obtained in Examples 1 to 10 and Comparative Examples 1 and 2.

[Table 1]

<Examples 11-26 and Comparative Examples 3-7>

According to the formulation shown in Table 2-1 and Table 2-2, an elongation enhancer (S) and a polyol (a1) were injected into a container, and it stirred at 60 degreeC for 15 minutes, The polyol composition (A-1)-(of this invention) A-16) and the comparative polyol composition (A'-1)-(A'-5) were obtained. The analysis values of the elongation enhancer (S) and the polyol (a1) are shown in Tables 2-1 and 2-2.

In addition, the composition of PP-2000, PTMG2000, and P-2010 in Table 2-1 and Table 2-2 is as follows.

PP-2000: polyoxypropylene polyol having a molar average number of functional groups of 2.0 and a hydroxyl group of 56.1 obtained by adding PO to propylene glycol ("Sannix PP-2000" manufactured by Sanyo Chemical Industries, Ltd.)

PTMG2000: polytetramethylene ether glycol, molar average number of functional groups 2.0, hydroxyl value 56.1 ("PTMG2000" manufactured by Mitsubishi Chemical Corporation)

ㆍ P-2010: Polyester polyol, molar average number of functional groups 2.0, hydroxyl value 56.1 (Kurare Co., Ltd. "Kurare polyol P-2010")

TABLE 2-1

Table 2-2

<Examples 27-42 and Comparative Examples 8-12>

Into the reaction vessel provided with a stirrer and a thermometer, a polyol composition (A), an organic polyisocyanate component (I) and an organic solvent in the incidental active hydrogen component (H) shown in Tables 3-1 and 3-2 are injected, The solution of the polyurethane resins (P-1) to (P-11) of the present invention and the polyurethane resin by injecting a reaction terminator and performing a terminal stop reaction for 1 hour after reaction at 70 ° C. for 12 hours in a dry nitrogen atmosphere. Solutions of compositions (W-1) to (W-5) and comparative polyurethane resins (P'-1) to (P'-5) were obtained.

Table 3-1

Table 3-2

<Examples 43-44 and Comparative Example 13>

A polyol (a1), a chain extender, an organic polyisocyanate component (I) and an organic solvent in the incidental active hydrogen component (H2) shown in Table 4 are injected into a reaction vessel equipped with a stirrer and a thermometer, and under a dry nitrogen atmosphere. The reaction terminator was injected | thrown-in after 10 hours of reaction at 70 degreeC, and terminal stop reaction was performed for 1 hour. Then, the elongation improver (S) as an additive shown in Table 4 was added, and the polyurethane resin composition (W-6)-(W-7) and the comparative polyurethane resin composition (W'-1) were obtained.

[Table 4]

The solution of the polyurethane resin and the polyurethane resin composition obtained above were casted on a glass plate so that the film thickness after drying might be set to 200 micrometers, and the pure air dried at 60 degreeC for 3 hours, and also 60 degreeC and a gauge pressure After drying under reduced pressure at about -0.1 MPa for 3 hours, the mixture was stopped for one day in a constant temperature and humidity chamber at 25 ° C and a humidity of 50%, and the breaking strength and the breaking elongation of the resin were measured in accordance with JIS K 7311. The ratio of the weight of the elongation enhancer (S) to the content of the elongation enhancer (S) in the polyol composition (A) and the weight of the polyurethane resin (excluding the weight of the comparative elongation enhancer (S ')) (weight %) Is shown in Table 3-1, Table 3-2 and Table 4.

Industrial availability

The polyurethane resin and polyurethane resin composition using the elongation improving agent (S) of this invention are excellent in elongation (breaking strength and elongation at break) compared with the conventional thing. Therefore, it is especially useful as a synthetic leather used for manufacture of a bag or shoes.

Claims (14)

Elongation improving agent (S) used for the polyurethane resin for synthetic leather represented by General formula (1).
[Chemical Formula 1]

[In General Formula (1), X <^1> shows the residue which removed c active hydrogen from m-valent active hydrogen containing compound; c represents the integer which satisfy | fills 1 <= c <= m; m represents the integer of 1-20. X ² represents a residue obtained by removing one active hydrogen from an active hydrogen-containing compound, and a plurality of X ² may be the same as or different from each other, and X ² And X ¹ may be the same as or different from each other; Y represents a residue obtained by removing all carboxyl groups from a trivalent or more aromatic polycarboxylic acid, and the aromatic ring of Y is composed of carbon atoms, and substituents other than carboxyl groups include Or a halogen atom may be bonded, but at least one carbon atom is not bonded to a substituent; a represents an integer of 1 or more, b represents an integer of 0 or more, and satisfies 2≤a + b≤d-2 D represents the number of hydrogen atoms bonded to the carbon atom constituting the aromatic ring when all substituents including the carboxyl group of the aromatic polycarboxylic acid are substituted with a hydrogen atom, that is, the number of sites that can be substituted on the aromatic ring; The method of claim 1,
An elongation enhancer, wherein the trivalent or higher aromatic polycarboxylic acid constitutes the aromatic ring and has a structure in which a carboxyl group is bonded to two carbon atoms adjacent to a carbon atom to which a substituent is not bonded. 3. The method of claim 2,
An elongation enhancer having a structure in which a carboxyl group is further bonded to at least one of carbon atoms adjacent to a carbon atom bonded to the carboxyl group. The method of claim 1,
An elongation enhancer, wherein the trivalent or higher aromatic polycarboxylic acid is trimellitic acid and / or pyromellitic acid. The method according to any one of claims 1 to 4,
Elongation improver whose c in the said General formula (1) is 2. 6. The method according to any one of claims 1 to 5,
An elongation enhancer having a hydroxyl value of 0 or 70 to 500 mgKOH / g. 7. The method according to any one of claims 1 to 6,
Elongation enhancer whose density | concentration of Y in the said elongation enhancer (S) is 1.0-3.5 mmol / g. The method according to any one of claims 1 to 7,
The elongation improver whose carbonyl group concentration of the said elongation improver (S) is 2.0-10.0 mmol / g. Polyols other than the said elongation improving agent (S) in any one of Claims 1-8, and the said elongation improving agent (S) whose hydroxyl value is 20-2000 mgKOH / g, and whose molar average functional groups are 2-8 ( Polyol composition (A) used for the polyurethane resin for synthetic leather characterized by containing a1). The method of claim 9,
The polyol composition whose content of the said elongation improving agent (S) is 0.01 to 10 weight% based on the weight of the said polyol composition (A). 11. The method according to claim 9 or 10,
The polyol (a1) is a polyol, a polyether polyol, a polyester polyol, or a silicone in which 1 mol of an alkylene oxide having 2 to 4 carbon atoms is added per hydroxyl group to a hydroxyl group of a C 2-20 polyhydric alcohol, a monocyclic polyphenol, or a bisphenol. A polyol composition comprising at least one polyol selected from the group consisting of polyols, polymer polyols, polydiene polyols, hydrogenated products of polydiene polyols, acrylic polyols, natural oil-based polyols and modified products of natural oil-based polyols. 12. The method according to any one of claims 9 to 11,
The polyol composition whose mole average functional group number of the said polyol (a1) is 2. The polyurethane resin obtained by making the active hydrogen component (H) containing the polyol composition as described in any one of Claims 9-12, and the organic polyisocyanate component (I) react, The said General formula (1) in the said polyol composition Polyurethane resin for synthetic leathers which is an elongation enhancer (S) represented by) is an elongation enhancer (S1) which has at least 1 active hydrogen. The polyurethane resin composition for synthetic leather containing the elongation improver (S) and polyurethane resin as described in any one of Claims 1-8.