JPH1160936A - Crosslinkable polyurethane resin composition and artificial leather and synthetic leather using the same - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To be particularly excellent in solvent resistance, chemical resistance, etc., and, in particular, excellent in stability of a liquid mixture, especially, storage stability. Even if it is gelled during the process, it is also excellent in washing and removing properties of its film, etc., and a highly practical crosslinkable polyurethane resin composition, together with the polyurethane resin composition To provide artificial leather and synthetic leather using a material. SOLUTION: A polyurethane resin composition composed of a polyurethane resin containing a hydrolyzable silyl group and a polyurethane resin containing no hydrolyzable group and, if necessary, a latent catalyst is used. As a result, for the first time, the inventor found that the above-mentioned various performances were exhibited, and was able to achieve the purpose brilliantly.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful crosslinkable polyurethane resin composition and artificial leather and synthetic leather produced using the same. More specifically, the present invention comprises a specific polyurethane resin having a hydrolyzable silyl group, a polyurethane resin having no hydrolyzable silyl group, and an organic solvent,
Alternatively, the hydrolyzable silyl group-containing polyurethane resin, and the hydrolyzable silyl group-free polyurethane resin,
The present invention relates to a polyurethane resin composition comprising an organic solvent and a catalyst for hydrolysis / condensation of the hydrolyzable silyl group, and artificial leather and synthetic leather produced using the composition.

[0002]

2. Description of the Related Art Polyurethane resin solutions have been widely used and applied for artificial leather and synthetic leather.

[0003] Such artificial leather or synthetic leather is
In a broad sense, it refers to a sheet-like material in which a polyurethane resin composition and a nonwoven fabric, a woven fabric, a knitted fabric, or the like are combined, but generally, it is classified as follows. It is.

[0004] First, artificial leather refers to a sheet-like material obtained by filling or laminating a so-called polyurethane resin composition in a non-woven fabric. A non-woven fabric is impregnated with or coated with a dimethylformamide (hereinafter abbreviated as DMF) solution of the composition, and then the non-woven fabric is coagulated in a water coagulation bath or a DMF-water mixed solution. Among them, a so-called wet process in which a polyurethane resin is coagulated into a porous shape, and then subjected to a washing step and a drying step is employed.

[0005] Further, if necessary, the surface of the sheet-like material thus obtained can be made to have a smooth tone by laminating or coating.
Alternatively, a method of buffing the surface of the sheet-like material to give it a nubuck tone or a suede tone is also employed.

Next, synthetic leather is generally classified into wet synthetic leather and dry synthetic leather, and is a sheet in which a polyurethane resin composition is laminated on a woven or knitted fabric. The wet synthetic leather is generally prepared by impregnating or coating a woven or knitted fabric with a DMF solution of the polyurethane resin composition, and then impregnating the woven or knitted fabric. ,
In a water coagulation bath or a coagulation bath composed of a mixed solution of DMF and water, wet processing is performed in which a polyurethane resin is coagulated into a porous form, and then subjected to a washing step and a drying step. .

Further, if necessary, the surface of the sheet-like material thus obtained can be made smooth or smooth by laminating or coating it.
Alternatively, a method of buffing the surface of the sheet-like material to give it a nubuck tone or a suede tone is also employed.

[0008] As another method for preparing dry synthetic leather in synthetic leather, generally, a polyurethane resin composition is cast on release paper, and then heated to evaporate a solvent to form a film. At the very least, if necessary, using an adhesive, laminating on a woven or knitted fabric, or the so-called lamination method, or on a woven or knitted fabric, directly coating the polyurethane resin composition For example, a so-called direct coating method of drying by heating.

[0009] Of these, artificial leather has recently been required to have a very supple feel with deer skin tone.

On the other hand, synthetic leather is required to have durability against sweat and sebum, etc., and that there is a strong demand for durability for hair styling products and toiletry products.

For the former, so-called supple artificial leather, a method is employed in which the fibers of the nonwoven fabric, which is the base cloth, are made extremely fine, that is, a method of making fine denier.

As a method for making the fibers of the nonwoven fabric ultrafine, a nonwoven fabric made of sea-island fibers (fibers having a sea-island structure) is impregnated or coated with a polyurethane resin, wet coagulated, and then subjected to a solvent or alkaline aqueous solution. Thus, a process of dissolving and eluting the sea component or the island component of the sea-island fiber or decomposing and eluting the same is employed.

According to such a method, it is possible to impart flexibility to artificial leather. Usually, for the sea component of the nonwoven fabric, as a material that is easily eluted with a solvent or the like, for example, polystyrene or polyethylene is used, while the island component is a material that is hardly eluted with a solvent, for example, A common method is to use polyester or nylon to elute sea components with a solvent such as heated toluene to leave island components.

In some cases, a polyester is used for the sea component or the island component to decompose and elute the polyester with a hot alkaline aqueous solution.

When a processing method of elution with a solvent is employed,
Generally, it is necessary to perform a treatment for leaching the sea component of the nonwoven fabric fiber by immersing it in toluene heated to 90 to 100 ° C. for about 1 hour.

Therefore, the polyurethane resin used in such a method is required to have a high solvent resistance such that it is not eluted by a solvent such as heated toluene and does not swell.

Generally, a general-purpose polyurethane resin prepared using a so-called aromatic diisocyanate compound such as diphenylmethane diisocyanate (hereinafter abbreviated as MDI) as an isocyanate compound is used for the above-mentioned sea-island fiber. When used in the preparation of artificial leather made of ultrafine fiber nonwoven fabric (hereinafter also referred to as ultrafine fiber artificial leather) using a nonwoven fabric composed of a nonwoven fabric, a method of increasing the number of hard segments of a polyurethane resin to make it harder, The solvent resistance is improved by increasing the group diisocyanate content.

However, as long as such a method is followed,
As the polyurethane resin becomes harder, the solvent resistance becomes better, but it is a place where the suppleness is impaired, which is also the aim of ultrafine fiber artificial leather.

As described above, a very practical ultrafine fiber artificial leather using a polyurethane resin based on an aromatic diisocyanate, which is soft, supple and excellent in solvent resistance, is still being developed. The fact is that there is no such thing.

In addition, in the case of a so-called non-yellowing type polyurethane resin prepared using an aliphatic or alicyclic diisocyanate compound, the type of raw materials, the ratio of use thereof, and the molecular weight are not limited. Attempts have been made to improve the solvent resistance by means such as changing, but after all, a significant improvement in solvent resistance has not been achieved at all. Indeed, it has been almost impossible to prepare microfiber artificial leather with non-yellowing polyurethane resins based on aliphatic or cycloaliphatic diisocyanate compounds. .

On the other hand, one of the synthetic leathers has already been used and applied as an automobile seat or furniture, such as a sofa, and is particularly resistant to sweat, sebum, a hairdressing product, or a toiletry product. Development of synthetic leather with high practicality, which has been improved, is still strongly desired.

[0022]

The object of the present invention is mainly for artificial leather and synthetic leather using a general-purpose polyurethane resin based on an aromatic diisocyanate compound such as MDI. Even in the case of artificial leather and synthetic leather in the form of a soft type in which the usage ratio of an aromatic diisocyanate compound is low, or in the form of a non-yellowing type polyurethane resin using an aliphatic or alicyclic diisosonate compound To provide an artificial leather and a synthetic leather having good solvent resistance, and can be used as an ultrafine fiber artificial leather, and also excellent in chemical resistance and the like. It is in.

Accordingly, the present inventors have conducted intensive studies with an eye on the problems to be solved by the invention as described above, and as a result, have found that a hydrolyzable silyl group may be added to the side chain and / or the terminal of the molecule. By wet or dry film formation of an organic solvent solution of a polyurethane resin having a, a polyurethane resin film having a network structure is obtained by a hydrolysis reaction of a hydrolyzable silyl group and crosslinking by a condensation reaction. And that the solvent resistance and chemical resistance are remarkably improved.
45 Japanese Patent Application Nos. 8-215605 and 8-235
No. 057 has already been filed for a patent.

However, as described in the above-mentioned application patent, a solution of a polyurethane resin having a hydrolyzable silyl group in a side chain and / or a terminal of a molecule in an organic solvent,
In some cases, when a synthetic liquid containing a curing catalyst is used to produce artificial leather or synthetic leather, the stability of such a mixed liquid is insufficient, so that the mixed liquid is produced during the manufacturing process, or It may thicken in the piping line, or it may gel and harden.

Further, even if the gelled film is to be washed and removed with a solvent such as DMF, it cannot be washed or removed because it does not dissolve in DMF at all. There was a problem in on-site operation, such as cost.

[0026]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies with the aim of solving the problems to be solved by the invention as described above. When a blend of the polyurethane resin (A) having a hydrolyzable silyl group at the side chain and / or the terminal and the polyurethane resin (B) not having the hydrolyzable silyl group is used, particularly, the resistance to the use of the polyurethane resin is high. It has excellent solvent resistance and chemical resistance, as well as excellent stability of the liquid mixture.
Further, the present inventors have found that the gelled film is excellent in washing and removing properties, and have now completed the present invention.

That is, the present invention basically comprises a polyurethane resin (A) having a hydrolyzable silyl group at a side chain and / or a terminal of a molecule and a polyurethane resin (B) having no hydrolyzable silyl group. And a cross-linkable polyurethane resin composition comprising an organic solvent (C) and a catalyst (D) for hydrolyzing or condensing a hydrolyzable silyl group with the composition. The present invention also provides an artificial leather or a synthetic leather in a form in which both of these compositions are impregnated or coated on a woven or nonwoven fabric, or are laminated with each other. is there.

In the present invention, a polyurethane resin (A) having a hydrolyzable silyl group at a side chain and / or a terminal of a molecule [hereinafter, also referred to as a polyurethane resin containing a hydrolyzable silyl group (A)]. ] And a polyurethane resin (B) having no hydrolyzable silyl group [hereinafter, also referred to as a polyurethane resin (B) containing no hydrolyzable silyl group]. Is appropriate in the range of 1/9 to 9/1 by weight ratio of (A) / (B).
/ 8 to 8/2 are particularly preferred.

When the ratio of the hydrolyzable silyl group-containing polyurethane resin (A) is less than (A) / (B) = 1/9, the stability of the blended liquid and the cleaning Although the removability is good, the effect of crosslinking is likely to be reduced and the solvent resistance of hot toluene and the like is deteriorated. On the other hand, the use ratio of the above-mentioned polyurethane resin (B) containing no hydrolyzable silyl group is used. Is (A) / (B) = 9 /
In the case of less than 1, the cross-linking effect is inevitably large, and therefore, although the solvent resistance of hot toluene and the like is excellent, on the other hand, the stability of the compounded liquid and the cleaning and removability are likely to deteriorate. In either case, it is not preferable.

Here, in the artificial leather and the synthetic leather according to the present invention, a polyurethane resin (A) having a hydrolyzable silyl group at a side chain and / or a terminal of a molecule as a base resin component; Polyurethane resin (B) containing no reactive silyl group is used. As such polyurethane resin (A) and (B), a polyurethane resin having a urethane bond may be used,
Further, it is needless to say that a so-called polyurethane polyurea resin having both a urethane bond and a urea bond may be used.

The hydrolyzable silyl group contained in the polyurethane resin (A) is, for example, a compound represented by the following general formula [I]:

[0032]

Embedded image

(Wherein R ¹ represents a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group, and R ² represents a hydrogen atom or a halogen atom or an alkoxyl group, a substituted alkoxy group, Group, acyloxy group, substituted acyloxy group, phenoxy group, iminooxy group or alkenyloxy group, and a is an integer of 0, 1 or 2.)

Each of the groups is easily hydrolyzed, such as a hydrosilyl group, a halosilyl group, an alkoxysilyl group, an acyloxysilyl group, a phenoxysilyl group, an iminooxysilyl group or an alkenyloxysilyl group. It refers to various reactive groups having a bonded silicon atom.

In preparing the polyurethane resin (A), (i) a class having both a functional group capable of reacting with various isocyanate groups, such as an amino group and a hydroxyl group, and a hydrolyzable silyl group. It is a method of using the compound of the as an essential raw material component,

(Ii) a previously prepared polyurethane resin having various active hydrogen-containing groups (active hydrogen-containing groups) such as hydroxyl groups on the side chains and / or terminals of the molecule;
A method of reacting a functional group capable of reacting with an active hydrogen-containing group, such as an isocyanate group, with a class of compounds having a hydrolyzable silyl group,

(Iii) A previously prepared polyurethane resin having a double bond in a side chain and / or a terminal of a molecule, and various hydrosilane compounds such as trimethoxysilane, triethoxysilane or trichlorosilane,
Various known and commonly used methods such as a method of performing an addition reaction by a hydrosilylation reaction can be applied,
Among them, the method (i) is the simplest.

The method for preparing the hydrolyzable silyl group-containing polyurethane resin (A) by the above-mentioned method (i) can be carried out by adding (iv) a polyurethane resin having an isocyanate group at a terminal to an isocyanate group, respectively. A method in which one of the functional groups capable of reacting with a group is reacted with a compound having a hydrolyzable silyl group to introduce the hydrolyzable silyl group into the molecular terminal,

(V) By using a compound having two functional groups capable of reacting with an isocyanate group and a hydrolyzable silyl group, the inside of the main chain of the polyurethane molecule, that is, It is a method to introduce this hydrolyzable silyl group into the side chain part of

(Vi) In a previously prepared polyurethane resin having an isocyanate group at the molecular terminal and having a hydrolyzable silyl group at a side chain of the molecule, one of the functional groups reactive with the isocyanate group is added to the polyurethane resin. Various methods such as a method of introducing a hydrolyzable silyl group into both a side chain portion and a molecular terminal of a molecule by reacting a compound having a hydrolyzable silyl group are applied. I can do it.

A compound having both a functional group capable of reacting with an isocyanate group and a hydrolyzable silyl group, which is used when preparing the polyurethane resin (A) by these various methods [hereinafter referred to as (a) -1), compound (a)
-1). In, the only functional group capable of reacting with the isocyanate group is an amino group or a hydroxyl group, if only a typical one is exemplified.
Among these, both groups are preferred.

The compound (a-1) having both a functional group and a hydrolyzable silyl group capable of reacting with the isocyanate group
Among them, 2 of the functional groups capable of reacting with the isocyanate group
And a compound having both a hydrolyzable silyl group and a particularly typical compound only.

Γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-hydroxylethyl)
Aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2
-Hydroxylethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-hydroxylethyl) aminopropylmethyl Dimethoxysilane, γ
-(2-hydroxylethyl) aminopropylmethyldiethoxysilane or γ- (bis-2-hydroxylethyl) aminopropyltriethoxysilane.

Further, among such compounds (a-1),
As a compound having one of the functional groups capable of reacting with an isocyanate group and a hydrolyzable silyl group, only typical compounds are exemplified, and γ-aminopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane, γ-aminopropylmethyldimethoxysilane, γ
-Aminopropylmethyldiethoxysilane or γ-
(N-phenyl) aminopropyltrimethoxysilane and the like.

The polyurethane resin (A) can be prepared by various methods as described above using the various compounds (a-1) as described above. In particular, when only typical formulations are exemplified, such a compound (a-1) and a long-chain diol compound [hereinafter also referred to as (a-2). ]
And a diisocyanate compound [hereinafter referred to as (a-3)
Also called. Is used as an essential raw material component, and a method of reacting each of these raw material components,

Alternatively, each of the compounds (a-
1), a long-chain diol compound (a-2), a diisocyanate compound (a-3) and, if necessary, a so-called chain extender [hereinafter also referred to as (a-4). ]
And the like.

In order to prepare one hydrolyzable silyl group-free polyurethane resin (B), the use of the hydrolyzable silyl group was carried out except that the use of (a-1) was changed to be completely absent. It can be carried out in the same manner as in the method for preparing the group-containing polyurethane resin (A).

The long-chain diol compound (a-2) used for preparing the resin (A) and the resin (B) is not particularly limited. Among them, polyester diols, polycarbonate diols, polyether diols, and the like, as well as mixtures or copolymers thereof, may be mentioned only as typical examples.

Among these long-chain diol compounds (a-2), first, polyester-based diols are known and commonly used various diol compounds, known and commonly used various dicarboxylic acids, and various types thereof. It is prepared by reacting a reactive derivative with various known and commonly used methods, that is, according to a conventional method.

Here, only particularly typical examples of the diol compound are ethylene glycol, 1,3- or 1,2-propylene glycol, 1,4- or 1,3- or 2,3-
Butylene glycol, 1,6-hexanediol, 1,
8-octanediol, neopentyl glycol, 1,
4-bis- (hydroxymethyl) -cyclohexane, 2
-Methyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol,

2,4,8,10-tetraoxaspiro [5,5] undecane-3,9-diethanol, β,
β'-dimethyl-2,4,8,10-tetraoxaspiro [5,5] undecane-3,9-diethanol, 3,
9-bis (1,1-dimethyl-2-hydroxyethyl)
-2,4,8,10-tetraoxaspiro [5,5] undecane,

Examples include diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, dibutylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol.

As the dicarboxylic acids, any of aliphatic-, alicyclic-, aromatic- and heterocyclic compounds can of course be used. By way of example only, it may itself be a so-called unsaturated compound or, for example, a compound substituted with a halogen atom.

As carboxylic acids or reactive derivatives thereof, only typical ones are given as typical examples. Succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid Acid, isophthalic acid, terephthalic acid, trimetic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endmethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride, maleic acid, fumaric acid,
Such as dimer fatty acid or dimethyl terephthalate.

Further, as the polyester diol, ε
A ring-opening polymer such as -caprolactone, or a polycondensate of ε-hydroxycaproic acid.

Further, if only typical polycarbonate diols are exemplified, only 1,2
3-propanediol, 1,4-butanediol, 1,
Diols represented by 6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol- or polytetramethylene glycol and the like, and dialkyl carbonates represented by dimethyl carbonate and the like or ethylene carbonate and the like. Reaction products with various cyclic carbonates.

Further, only typical examples of polyether-based diols are exemplified, and compounds having an active hydrogen atom (reactive hydrogen atom), ethylene oxide, propylene oxide, butylene oxide, and styrene oxide may be used. ,
Reaction products with various alkylene oxides such as tetrahydrofuran or epichlorohydrin and the like, and further, reaction products with these mixtures and the like.

Compounds having a reactive hydrogen atom used in preparing the polyether diol include:
Examples of the water, bisphenol A and polyester-based diols used in preparing the diol compounds include various diol compounds known and used as described above.

The diisocyanate compound (a-3) used for preparing the polyurethane resin (A) and the polyurethane resin (B) is represented by the general formula

[0060]

Embedded image R (NCO) ₂

(However, R in the formula represents an arbitrary divalent organic group.)

The diisocyanate compound is not particularly limited, but among these diisocyanate compounds, only typical ones are exemplified. 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- or 1,4-diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5 , 5-trimethylcyclohexane (also called isophorone diisocyanate), bis-
(4-isocyanatocyclohexyl) methane (alias:
Also called hydrogenated MDI. ),

2- or 4-isocyanatocyclohexyl-2'-isocyanatocyclohexylmethane,
3- or 1,4-bis- (isocyanatomethyl)-
Cyclohexane, bis- (4-isocyanato-3-methylcyclohexyl) methane, 1,3- or 1,4-
α, α, α ′, α′-tetramethylxylylene diisocyanate, 2,4- or 2,6-diisocyanatotoluene, 2,2′-, 2,4′- or 4,4′-diisocyanate Diphenylmethane (ie, MDI),
1,5-naphthalenediisocyanate, p- or m
-Phenylene diisocyanate, xylylene diisocyanate or diphenyl-4,4'-diisocyanate.

Of these, use of an aromatic diisocyanate compound is desirable from the viewpoint of mechanical strength and the like, and aliphatic- or alicyclic is preferable from the viewpoints of durability and light resistance. The use of diisocyanate compounds is preferred.

As typical examples of the chain extender (a-4), only typical ones may be used, and various known and commonly used short-chain diol compounds may be used. And so on.

Among these, as the short-chain diol compound, those used in preparing the above-mentioned polyester-based diol compound, among the various diol compounds already exemplified, are relatively short. Low molecular weight diols are exemplified.

Among the chain extenders (a-4), only typical examples of the diamine compounds are given below. For example, 1,2-diaminoethane, 1,2- or 1,3- Diaminopropane, 1,2- or 1,3-
Or 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, piperazine, N,
N'-bis- (2-aminoethyl) piperazine, 1-amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane (= isophoronediamine), bis- (4-
Aminocyclohexyl) methane, bis- (4-amino-
3-butylcyclohexyl) methane, 1,2-, 1,3
-Or 1,4-diaminocyclohexane and the like, and hydrazine or adipic dihydrazide can also be used.

The polyurethane resin (A) and the polyurethane resin (B) are prepared by using the raw materials described above and described above in various known and conventional manners by using the respective raw material components. do it.

That is, for example, the reaction may be carried out in the range of 0 to about 250 ° C., preferably in the range of 20 to 100 ° C., without using a solvent or in an organic solvent.

When the reaction is carried out in an organic solvent, ethyl acetate, n-butyl acetate, methyl ethyl ketone, toluene, tetrahydrofuran, isopropanol, cyclohexanone, dimethylformamide (DMF), ethylene glycol monoethyl ether or ethylene glycol monoethyl ether acetate Various known organic solvents can be added at any stage of the reaction, such as at the start of the reaction, during the reaction, or at the end of the reaction. .

The ratio of each of the raw materials used in the reaction of the various raw materials described above is not particularly limited, but may be used when preparing the silyl group-containing polyurethane resin (A). The compound (a-
1) That is, a compound having both a functional group capable of reacting with an isocyanate group and a hydrolyzable silyl group is contained in an amount of preferably 0.1 to about 30% by weight, based on the total weight of the various raw material components. Is suitably used in such a ratio as to be in the range of 0.5 to 20% by weight, more preferably in the range of 1 to 10% by weight.

When the amount of the compound (a-1) used is less than 0.1% by weight, the cross-linking property is inevitably deteriorated. When the cured product becomes too easy to obtain, on the other hand, if it exceeds about 30% and becomes too large, the crosslink density tends to be too high and the artificial leather is inferior in flexibility. In both cases, synthetic leather can be obtained.

In preparing the polyurethane resin (A), the amount of the diisocyanate compound (a-3) used is usually those (a-1), (a-2) and (a-4). When the total amount of active hydrogen contained in each raw material component is 1 equivalent, the isocyanate group content is about 0.1 equivalent.
What is necessary is just to set so that it may become the ratio of 9 to about 1.1 equivalent.

On the other hand, when the polyurethane resin (B) is prepared, the amount of the diisocyanate compound (a-3) to be used is usually those (a-2) and (a-4)
When the total amount of active hydrogen contained in each raw material component is 1 equivalent, the isocyanate group is about 0.9 to about 1.1.
What is necessary is just to set so that it may become an equivalent ratio.

In preparing the polyurethane resins (A) and (B) used in the present invention, if necessary, monoalcohol, trifunctional or higher functional alcohol, organic monoamine, trifunctional or higher functional amine, organic monoisocyanate and A polyisocyanate having three or more functions may be used.

In preparing the polyurethane resins (A) and (B), if necessary, a urethanizing catalyst or a stabilizer may be used. These catalysts and stabilizers can be added at any stage of the reaction.

As the urethanization catalyst, only typical ones are exemplified, and triethylamine,
Various nitrogen-containing compounds represented by triethylenediamine or N-methylmorpholine; various metal salts represented by potassium acetate, zinc stearate or tin octylate; and represented by dibutyltin dilaurate and the like. And various organometallic compounds.

Further, only typical representative examples of the above-mentioned stabilizers include various stabilizers against ultraviolet rays, such as substituted benzotriazoles, and the like. There are various stabilizers against thermal oxidation, such as phenol derivatives, and these stabilizers can be appropriately selected and added according to the purpose.

The number average molecular weight of the polyurethane resin (A) and the polyurethane resin (B) thus prepared is from about 5,000 to about 500, especially from the viewpoint of fluidity and processability. A range of 000 is suitable, preferably a range of 5,000 to 100,000.

The above-mentioned organic solvent (C) used for preparing the polyurethane resin composition according to the present invention.
Any compound can be used as long as it can dissolve the polyurethane resin (A) and the polyurethane resin (B) as described above.

As such an organic solvent (C), there can be used various compounds as already listed as those used in preparing the polyurethane resin (A) and the polyurethane resin (B).

The polyurethane resin (A)
And when the reaction is carried out in an organic solvent when preparing the polyurethane resin (B), the organic solvent used for the reaction is directly used without adding the organic solvent (C). (C) What can be considered as a component is
Needless to say.

The amount of the organic solvent (C) used is as follows.
The amount is preferably in the range of about 40 to about 5,000 parts with respect to 100 parts by weight of the solid content of the components (A) and (B),
It is particularly preferably in the range of 100 to 2,000 parts.
A range of from 00 to 900 parts is appropriate.

The polyurethane resin (A) in the present invention
In the manufacturing process of artificial leather and synthetic leather, hydrolysis and condensation, respectively, also occur due to heat and moisture (humidity), etc., respectively, and a condensation occurs to form a crosslinked structure.
It does not necessarily require the addition of a curing catalyst.

However, when it is necessary to surely hydrolyze and condense the hydrolyzable silyl group in a short time, the following catalyst for hydrolysis or condensation of the hydrolyzable silyl group is used. It is effective to add (D).

As the catalyst (D) for hydrolysis or condensation of a hydrolyzable silyl group, only typical ones are exemplified. Malic acid, citric acid, pivalic acid, succinic acid, maleic acid Acetic acid, lactic acid, salicylic acid, phthalic acid, benzoic acid, tetrachlorophthalic acid, tetrahydrophthalic acid, dodecylbenzenesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid or mono Various acidic compounds, such as alkyl phosphites;

Lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, triethylamine,
Various basic compounds such as tri-n-butylamine, dimethyllaurylamine or triethylenediamine; tetraisopropyl titanate, tetra-n-butyl titanate, aluminum tris (ethyl acetate), aluminum tris (acetylacetonate),
Tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, zinc naphthenate, cobalt naphthenate, di-n-butyltin diacetate, di-n-butyltin dioctoate, di-n-butyl Various metal-containing compounds, such as tin dilaurate, di-n-butyltin oxide, dioctyltin oxide or di-n-butyltin maleate;

Alternatively, a copolymer of maleic anhydride, itaconic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, alkenyl succinic anhydride, or maleic anhydride with styrene, Including maleic anhydride and copolymers of α-olefins,

Further, copolymers of various carboxylic anhydride-containing vinyl monomers as described above and monomers having copolymerizability with the monomers, or benzoic anhydride, Compounds having various carboxylic anhydride groups, such as mixed anhydrides of methacrylic acid or benzoic acid and acetic acid; benzenesulfonic acid, p-toluenesulfonic anhydride, dodecylbenzenesulfonic acid or benzenesulfonic acid; Various sulfonic anhydrides such as mixed anhydrides with methanesulfonic acid; mixed anhydrides of acetic acid or benzoic acid with benzenesulfonic acid, mixed anhydrides of benzoic acid and methanesulfonic acid , A mixed acid anhydride of various carboxylic acids and sulfonic acids, and the like,

Further, salts of various amines or ammonia such as trimethylamine, triethylamine, tri-n-butylamine or 2-dimethylaminoethanol with various acids as described above;

4-Methylbenzyl-4-cyanopyridinium-hexafluoroantimonate and 4-chlorobenzyl-2-methylpyridinium-hexaline described in JP-A-2-232253 or JP-A-4-23807. Fluoroantimonate, 4-methoxybenzyl-3-chloropyridinium-tetrafluoroborate or N- (α-methylbenzyl) -N, N-
Various pyridinium salts or ammonium salts which generate an acid upon heating, such as dimethyl-N-phenylammonium hexafluoroantimonate;

[0092] Prenyl-tetramethylenesulfonium-hexafluoroantimonate, crotyl-tetramethylenesulfonium-hexafluoroarsenate or benzyl-4-ether described in JP-A-58-198532 or JP-A-4-11626. Sulfonium salts which generate an acid upon heating, such as hydroxyphenyl-methylsulfonium hexafluoroantimonate;

Various 2-sulfonic acid esters of organic sulfonic acids and esters of various organic sulfonic acids with secondary alcohols described in JP-A-4-108861, and the like. Including compounds that release sulfonic acid, etc.
JP-A-80242, a compound having a ketal ester group or an acetal ester group, which can be obtained by subjecting various compounds having a protonic acid group to an addition reaction with vinyl ethers, Those which produce a compound having a free acid group.

Although any of such catalysts can be effectively used, the polyurethane resin composition in the form of the component (A), the component (B), the component (C) and the curing catalyst (D) is useful. When it is necessary to maintain the storage stability for a longer period of time, as a curing catalyst (D),
Various compounds listed above as those that generate an acid upon heating, a compound that functions as a so-called heat latent catalyst, or a compound having an acid anhydride group, or a salt of an amine or ammonia with an acid May be used as such a catalyst.

That is, when a compound containing a so-called acid anhydride group such as a carboxylic acid anhydride group, a sulfonic acid anhydride group, or a carboxylic acid-sulfonic acid mixed acid anhydride group is used as the catalyst, the composition itself may be used. Although it shows good stability, in wet film formation, it is hydrolyzed by water in a coagulation bath or a washing bath, while in dry film formation, it is hydrolyzed by moisture in the air during heating film formation. As a result, a compound that generates a so-called free acid such as carboxylic acid or sulfonic acid and exhibits a catalytic effect may be used as such a catalyst.

Also, when a salt of an amine or ammonia and an acid is used as such a catalyst,
The composition of the present invention itself containing such a catalyst exhibits good stability, and furthermore, is heated by a drying process after the wet film formation in a wet film formation or is heated by a dry film formation. A compound which exerts a catalytic effect by generating a so-called free acid such as carboxylic acid, phosphoric acid or sulfonic acid by causing a deammonification reaction or a deamination reaction by the heat at the time of the film formation using such a catalyst. This means that it can be used as

That is, when these catalysts are used, the catalytic effect is not exhibited until the wet film formation or the dry film formation is performed, and the stability of the blended liquid can be maintained.

Therefore, such a compound having an acid anhydride group or a compound such as a salt of an amine or ammonia with an acid functions as a so-called latent catalyst.

The amount of the curing catalyst (D) varies depending on the effect of each catalyst, for example, acidity or basicity, or the content of the active ingredient. , Total amount of solid content of polyurethane resin (A) and polyurethane resin (B) 1
In the range of about 0.05 to about 10 parts by weight, preferably in the range of 0.2 to 7.0 parts by weight,
Most preferably, the range of 0.5 to 5.0 parts is appropriate.

In this way, (A),
A polyurethane resin composition comprising (B) and (C),
Alternatively, a polyurethane resin composition comprising (A), (B), (C) and (D) is obtained, and these various compositions may further contain, if necessary, a film-forming aid and a surfactant. Or a dye-controlling agent, or a resin for blending, such as a hydrolyzable silyl group-containing compound, and various known additives and pigments, and further, fillers and the like Can also be blended.

Among these additives, the dye-controlling agent is a hydrophilic polymer having a polyethylene glycol chain or a quaternary base of an amine, and specific examples thereof include a polyurethane polymer made of polyethylene glycol and diisocyanate. Resin, a poly (meth) acrylic resin obtained by copolymerizing a monomer having a quaternary ammonium salt structure obtained by reacting dimethylaminoethyl methacrylate with methyl chloride or benzyl chloride, N-methyl-N-di- Polyurethane resins in the form of β-hydroxyethyl-N-benzyl ammonium chloride copolymerized, and the like,

As the resin for blending, poly (meth)
Acrylic resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl propionate copolymer, polyvinyl butyral resin, cellulose resin, polyester resin,
An epoxy resin, a phenoxy resin, a polyamide resin, or the like can be given.

Further, only typical examples of the above-mentioned hydrolyzable silyl group-containing compounds are given below, and tetraethyl silicate or a partially hydrolyzed condensate thereof; partial hydrolysis of tetramethyl silicate Condensate;
Alternatively, various alkyl silicates or partial hydrolyzed condensates thereof, such as tetraisopropyl silicate or partial hydrolyzed condensates thereof, and further,
In general, various compounds such as those described below in the class referred to as silane coupling, and various compounds already exemplified as those used in preparing the polyurethane resin (A) (A-1).

That is, if only typical silane couplings are exemplified, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4 Epoxycyclohexyl) ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane or γ-chloropropyltrimethoxysilane.

The method for producing the artificial leather and the synthetic leather per se according to the present invention is not limited at all, but is generally produced and applied by the following method. That is.

That is, the method for producing the artificial leather and the synthetic leather of the present invention by the wet processing method will be described.
First, a base fabric such as a nonwoven fabric, a woven fabric, or a knitted fabric is impregnated with or coated with a polyurethane resin composition having a nonvolatile content adjusted to about 5 to 25%.

Then, coagulation is carried out by immersing in water at about 5 to 50 ° C. or in a DMF-water mixture containing about 5 to 50% DMF for about 3 to 30 minutes.

Further, after passing through a so-called washing step of washing in water at about 20 to 95 ° C. or in hot or hot water, drying at a temperature of about 60 to 130 ° C. makes it possible to produce the artificial ink of the present invention. Leather or synthetic leather can be obtained.

During the above-mentioned processing steps, the hydrolyzable silyl group-containing polyurethane resin (A), which is the base resin component of the polyurethane resin composition, undergoes hydrolysis and condensation to be crosslinked and non-crosslinked. An artificial leather and a synthetic leather having a polyurethane resin film containing the polyurethane resin (B) can be obtained. Both of these leathers have a high degree of solvent resistance, chemical resistance and the like.

Here, when a non-woven fabric is used as the base fabric, artificial leather is obtained, and when a woven or knitted fabric is used as the base fabric, a synthetic leather is obtained. Leather will be obtained.

In the production of the artificial leather described above, a nonwoven fabric made of sea-island fibers is used as the base material, and at least one component of the nonwoven fabric fibers is removed by dissolution or elution to make the nonwoven fabric ultrafine. By making it porous, an artificial leather having flexibility can be obtained.

For example, in the case of dissolution and elution, first, after a washing step in the above-mentioned wet processing method and, if necessary, a drying step, the mixture is placed in heated toluene at about 70 to about 90 ° C. for 15 to 90 minutes. Let soak for a while.

Further, the artificial leather according to the present invention is produced by washing with water at about 20 to 95 ° C. or with hot or hot water and then drying at a temperature of about 60 to 130 ° C. It is.

In this step, for example, polystyrene or polyethylene is used as one component of the sea-island fiber, and these components are dissolved and eluted, thereby achieving a process of achieving ultrafineness.

In the artificial leather according to the present invention, since the polyurethane coating itself has a high degree of solvent resistance and the like, the polyurethane resin coating itself is heated in toluene in the above-mentioned ultra-fine process. It is possible to obtain an extremely practical artificial leather which is not eluted by an elution solvent such as the above, and is particularly excellent in flexibility and the like.

Further, the viscosity stability of the blended liquid is good, and even if the blended liquid is gelled during the manufacturing process and solidified in a pipe or the like, the gelled product is converted into DMF. This makes it easier to wash and remove.

In the case of decomposition and elution, after the washing step in the above-mentioned wet processing method, if necessary, drying and heating to about 70 to 90 ° C., about 3 to about 15%
By immersing for about 15 to 90 minutes in an aqueous solution of sodium hydroxide at a concentration,

Next, the artificial leather according to the present invention can be produced by washing with water at about 20 to 95 ° C. or with hot or hot water and then drying at a temperature of about 60 to 130 ° C. I can do it.

In such a series of steps, for example, polyester is used as one component of the sea-island fiber, and this component is decomposed and eluted, thereby achieving ultrafineness.

Further, in the preparation of artificial leather, split fibers composed of one component or multiple components may be used as the material of the nonwoven fabric. However, in the artificial leather according to the present invention, the type of nonwoven fabric used or the processing Is not limited at all, and the use and shape of the artificial leather according to the present invention are not limited at all.

The artificial leather and the synthetic leather according to the present invention obtained by the wet processing method as described above are:
Furthermore, in addition to such wet processing, the artificial leather according to the present invention, which is obtained by performing the above-described treatment for making the nonwoven fabric fibers extremely fine, is laminated by various known and common methods. Alternatively, surface shaping or buffing by coating may be performed, but these various processing methods are not limited at all.

Next, the method for producing the synthetic leather according to the present invention according to the dry method will also be described. In the production by this method, the processing conditions are not limited at all, but generally, it can be performed under the following processing conditions.

That is, in the case of laminating, the polyurethane resin composition according to the present invention, in which the nonvolatile content is adjusted to about 10 to 30%, is placed on release paper so that the film thickness after drying is about 5 to about 50%. The desired method of preparing a polyurethane film can be adopted by casting the film to a micrometer (μm) and drying it at a temperature of about 50 to 150 ° C.

Next, the polyurethane thus obtained
By laminating a film and a base fabric such as a nonwoven fabric, a woven fabric or a knitted fabric using various known and commonly used adhesives, performing an appropriate heat treatment, and then separating the film from the release paper, the present invention Is obtained.

In the case of direct coating, the polyurethane resin composition of the present invention, in which the nonvolatile content is adjusted to about 10 to 50%, is applied onto a base fabric such as a nonwoven fabric, a woven fabric or a knitted fabric. Apply directly, 50-150
A method of forming a target polyurethane film by drying at a temperature of about ° C. can be adopted, and thus the synthetic leather according to the present invention can be obtained.

Also, if necessary, often, similarly,
The coating process may be repeated a plurality of times.

The synthetic leather obtained by the above-mentioned dry method also has a high durability and the like, in particular, excellent in solvent resistance and chemical resistance, since it has a polyurethane coating. It is doing.

In preparing the synthetic leather and artificial leather according to the present invention, a polyurethane resin composition containing no catalyst (D) for hydrolysis / condensation of a hydrolyzable silyl group is used. Even if
In such a composition, water is added, a wet coagulation bath or a washing bath is made acidic or alkaline, and further, in various drying steps, a known and commonly used compound such as an amine compound is used. It is possible to promote the hydrolysis or condensation of the hydrolyzable silyl group contained in the polyurethane resin (A) by various prescriptions such as heating in the vapor atmosphere of various catalysts.

[0129]

Next, the present invention will be described more specifically with reference to examples and comparative examples.
It is by no means limited to only these illustrative examples. In the following, all parts and percentages are by weight unless otherwise specified.

REFERENCE EXAMPLE 1 Adipic acid / 1,4-, having a number average molecular weight of 2,000
Butanediol polyester diol (PE-200
0) and 30 of polytetramethylene glycol (PTMG-2000) having a number average molecular weight of 2,000.
Parts, 10 parts of ethylene glycol, 394 parts of dimethylformamide (DMF), and 3 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane.
The mixture was placed in a liter four-necked flask and uniformly dissolved.

Next, while vigorously stirring this solution,
Here, diphenylmethane diisocyanate (MDI)
And reacting at 70 ° C. for 10 hours to obtain a nonvolatile content of 30.0% and a Brookfield viscosity at 25 ° C. (hereinafter the same) of 950 poise (ps). Thus, a solution of a polyurethane resin having a hydrolyzable silyl group in the side chain of the molecule was obtained.
Hereinafter, this is abbreviated as polyurethane resin solution (A-1).

Reference Example 2 The reaction was carried out in the same manner as in Reference Example 1, except that 1.0 part of ethylene glycol was used instead of γ- (2-aminoethyl) aminopropyltrimethoxysilane. As a result, a polyurethane resin solution having a non-volatile content of 30.0% and a viscosity of 950 ps and containing no hydrolyzable silyl groups was obtained. Less than,
This polyurethane resin solution is abbreviated as (B-1).

Example 1 50 parts of (A-1) and 50 parts of (B-1) were mixed together, and “Additive No. 10” was used as a film-forming aid.
1.0 parts of [Dai Nippon Ink Chemical Industry Co., Ltd. product]
2 parts of “Assister SD-8i” (manufactured by the same company) were added, and DM was added so that the nonvolatile content was 20%.
F was added.

Next, 0.15 parts of dibutyltin dilaurate (DBTL) as a catalyst for hydrolysis / condensation of a hydrolyzable silyl group was added to such a mixture, followed by mixing, whereby a polyurethane resin composition was obtained. Prepared. The polyurethane resin composition thus obtained had good viscosity stability of the solution, and the viscosity of the solution hardly changed even after 3 months.

Next, the composition thus obtained was cast on a polyethylene terephthalate (PET) sheet so as to have a thickness of about 1 mm.

Thereafter, the PET sheet coated with the polyurethane resin composition was immersed in a DMF aqueous solution having a DMF concentration of 10% at 25 ° C. for 20 minutes to be coagulated.

Then, the sheet was thoroughly washed in warm water of 40 ° C., and dried in a hot air drier heated to 100 ° C. for 30 minutes to obtain a crosslinked polyurethane resin porous layer sheet. .

Subsequently, the sheet was immersed in toluene heated to 90 ° C. for 1 hour,
The plate was washed with hot water of 0 ° C. for 1 hour and dried at 80 ° C. for 30 minutes.

The sheet thus obtained had good surface smoothness and apparent specific gravity of 0.472. When the cross section of the sheet was observed, it was uniformly dispersed. Had fine pores.

Further, the weight loss rate expressed by the weight loss rate after immersion in heated toluene to the weight before immersion in heated toluene was 0.8%, and the sheet before immersion in heated toluene was 0.8%. The area retention, expressed by the area retention of the sheet after immersion in heated toluene, was 98.5% of the area.

Next, when this sheet was immersed in DMF at 50 ° C., its shape gradually collapsed and became a dispersed state in DMF, and it was possible to wash and remove it with DMF.

The polyurethane resin composition was prepared by mixing the sea component with polyethylene so that the thickness became about 1 mm.
In addition, it was coated on a sea-island fiber non-woven fabric having a polyester island component.

Subsequently, this was coagulated by immersing it in a DMF aqueous solution having a DMF concentration of 10% at 25 ° C. for 20 minutes. Subsequently, after thoroughly washing in warm water of 40 ° C.,
The resultant was dried in a hot-air dryer heated for 30 minutes to obtain artificial leather having a polyurethane porous layer sheet.

Next, this artificial leather was immersed in toluene heated to 90 ° C. for one hour, and then washed with hot water at 90 ° C. for one hour.
Dry at 30 ° C. for 30 minutes.

The surface of the artificial leather thus obtained was excellent in smoothness, and the cross-section thereof was observed to have uniformly dispersed fine pores. The feel of this artificial leather was very soft and supple.

Comparative Example 1 Example 1 was repeated except that 100 parts of (A-1) were used instead of 50 parts of (A-1) and 50 parts of (B-1). In the same manner as in the above, a polyurethane resin composition for control was prepared. In the polyurethane resin composition thus obtained, the viscosity stability of the solution was not good, and the entire solution solidified as soon as about 5 days or less.

Subsequently, using this polyurethane solution, a sheet was produced in the same manner as in Example 1.

The surface of the sheet obtained here was excellent in smoothness and apparent specific gravity was 0.472. Observation of the cross section of the sheet revealed that the sheet had fine pores dispersed uniformly. Was.

Further, the weight reduction rate expressed by the weight reduction rate after heating toluene immersion with respect to the weight after drying and before heating toluene immersion is 0.8%. The area retention, expressed by the area retention of the sheet after immersion in heated toluene, was 98.5% of the area.

However, even if this sheet is immersed in DMF at 50 ° C., it does not lose its shape at all, does not dissolve in DMF or becomes dispersed, and is washed and removed with DMF. Proved impossible.

Comparative Example 2 A change was made so that 100 parts of (B-1) were used instead of 50 parts of (A-1) and 50 parts of (B-1). A control polyurethane resin composition was prepared in the same manner as in Example 1 except that the composition was not added.

Next, a sheet was prepared from this polyurethane solution in the same manner as in Example 1, and the apparent specific gravity was 0.4
A porous layer sheet having a good surface smoothness of 75 was obtained.

In the same manner as in Example 1, immersion in heated toluene, washing with hot water and drying were performed.
As a result, the weight loss of the sheet was 5.5%, the area retention was 96.5%, and the surface condition was poor. It was not something that could be offered. In addition, the sheet was soluble in DMF.

Reference Example 3 First, 70 parts of PE-2000, 30 parts of PTMG-2000 and 366 parts of DMF were placed in a one-liter four-necked flask and uniformly dissolved.

Next, while vigorously stirring this solution,
To this, 44 parts of MDI was charged and reacted at 70 ° C. for 3 hours to obtain a solution of a urethane prepolymer having an isocyanate group at the terminal of the molecule.

Further, this solution was stirred at 40 ° C. with vigorous stirring while 10 parts of 1,4-butanediol and γ
After charging 3 parts of-(2-aminoethyl) aminopropylmethyldimethoxysilane, the temperature was raised to 70 ° C., and the reaction was carried out at the same temperature for 5 hours to obtain a nonvolatile content of 30.0%. Moreover, the viscosity becomes 930 ps,
A solution of a polyurethane resin having a hydrolyzable silyl group on the side chain of the molecule was obtained. Hereinafter, this polyurethane resin solution is abbreviated as (A-2).

Reference Example 4 Reference Example 3 was repeated except that 1.0 part of 1,4-butadiol was used in place of 3 parts of γ- (2-aminoethyl) aminopropylmethyldimethoxysilane. Similarly, by carrying out the reaction, the non-hydrolyzable silyl group-free, non-volatile content is 30.0%, and the viscosity is 9%.
A solution of polyurethane resin of 50 ps was obtained. Less than,
This polyurethane resin solution is abbreviated as (B-2).

Example 2 Each of (A-1) was replaced with the same amount of (A-2)
Was changed to use the same amount of (B-2) in place of (B-1) in the same manner as in Example 1 except that the film-forming auxiliary was mixed with DMF and DBTL. Thereby, the polyurethane resin composition of the present invention was prepared.

The polyurethane resin composition thus obtained had good viscosity stability of the solution, and the viscosity of the solution hardly changed even after 3 months.

Thereafter, except that the composition was changed to use, a porous layer sheet was obtained by performing wet film formation, washing and drying in the same manner as in Example 1.

The sheet obtained had good surface smoothness and an apparent specific gravity of 0.470. Observation of the cross section of the sheet revealed that fine pores were uniformly dispersed. Turned out to be.

Further, the film-formed porous layer sheet was immersed in toluene at 90 ° C. for one hour,
It was washed with hot water for a time and dried at 80 ° C. for 30 minutes.

The sheet thus obtained had a smooth surface condition, a reduced weight loss of 0.9% after drying, and an area retention of 98.8%.

Further, when this sheet was immersed in DMF at 50 ° C., the shape gradually collapsed, and the sheet became dispersed in DMF, and it was possible to wash and remove the sheet with DMF.

Subsequently, the polyurethane resin composition was coated on a sea-island fiber nonwoven fabric in the same manner as in Example 1.
After being subjected to ing and wet film formation, elution with heated toluene, washing with hot water and drying were performed to obtain the intended artificial leather having a polyurethane porous layer sheet.

The artificial leather thus obtained also had good surface smoothness, and the cross section thereof was observed to have uniformly dispersed fine pores. The hand was very soft and supple.

Comparative Example 3 Example 2 was repeated except that 100 parts of (A-2) were used instead of 50 parts of (A-2) and 50 parts of (B-2). In the same manner as in the above, a polyurethane resin composition for control was prepared.

The control polyurethane resin composition was as follows:
The viscosity stability of the solution was not good and the entire solution solidified in about 5 days.

Using this polyurethane solution, a sheet was prepared in the same manner as in Example 1. The sheet thus obtained had good surface smoothness and an apparent specific gravity of 0.472. Observation of the cross section of the sheet revealed that the sheet had uniformly dispersed fine pores. .

Further, the weight reduction rate expressed by the weight reduction rate after heating toluene immersion with respect to the weight after drying and before heating toluene immersion was 0.8%. The area retention, expressed by the area retention of the sheet after immersion in heated toluene, was 98.5% of the area.

However, even if this sheet is immersed in DMF at 50 ° C., it does not lose its shape at all, does not dissolve in DMF or becomes dispersed, and can be washed and removed with DMF. It was impossible.

COMPARATIVE EXAMPLE 4 Instead of 50 parts of (A-2) and 50 parts of (B-2), 100 parts of (B-2) were changed to be used, and the DBTL of the catalyst was changed. A control polyurethane resin composition was prepared in the same manner as in Example 2 except that no was added.

Next, this composition was subjected to wet film formation in the same manner as in Example 2 to obtain a porous layer sheet having an apparent specific gravity of 0.475 and excellent surface smoothness. Further, the heat-resistant toluene test was carried out on this control film-formed porous layer sheet in the same manner as in Example 2. As a result, the weight loss was as large as 5.5%, and the area retention was 96. 5%.

In addition, the surface condition of this sheet was deteriorated, and therefore, it was not practically usable for ultrafine fiber artificial leather. In addition, the sheet was soluble in DMF.

Reference Example 5 60 parts of adipic acid / ethylene glycol (EG) polyesterdiol having a number average molecular weight of 2,000, 40 parts of polytetramethylene glycol having a molecular weight of 1,300, and 5 parts of EG And 410 parts of DMF were placed in a 1-liter four-necked flask and uniformly dissolved.

Next, while vigorously stirring this solution,
By charging 35 parts of MDI and performing a reaction at 70 ° C. for 10 hours, a solution of a polyurethane resin having a hydroxyl group at a molecular terminal was obtained.

Subsequently, the solution was kept at 40 ° C. and stirred vigorously while 5 parts of EG and 5 parts of γ- (2-aminoethyl) aminopropylmethyldimethoxysilane were added.
And 26 parts of MDI were charged sequentially.

Thereafter, the temperature was raised to 70 ° C. and the reaction was carried out at the same temperature for 5 hours, so that the non-volatile content was 3
A target solution of a polyurethane resin having a hydrolyzable silyl group in the side chain of the molecule, which was 0.0% and had a viscosity of 1,010 ps, was obtained. Hereinafter, this polyurethane resin solution is abbreviated as (A-3).

Reference Example 6 The procedure of Reference Example 5 was repeated except that 1.0 part of EG was used instead of 5 parts of γ- (2-aminoethyl) aminopropylmethyldimethoxysilane. ,
By performing the reaction, the nonvolatile content is 30.0%,
A solution of a polyurethane resin having a viscosity of 950 ps and containing no hydrolyzable silyl groups was obtained. Hereinafter, this polyurethane resin solution is abbreviated as (B-3).

Example 3 Except that 30 parts of (A-3) and 70 parts of (B-3) were changed to be used in a mixed form.
In the same manner as in Example 1, a film forming aid, DMF and DB
By mixing with TL, a polyurethane resin composition of the present invention was prepared.

The polyurethane resin composition thus obtained had good viscosity stability of the solution, and almost no increase in viscosity was observed even after one month.

Thereafter, in the same manner as in Example 1 except that this composition was changed to use, a wet film was formed, followed by extraction with heated toluene and washing with hot water and drying. Thus, a porous layer sheet was obtained.

The sheet thus obtained had good smoothness and an apparent specific gravity of 0.474. Observation of the sheet cross section revealed that the sheet had uniformly dispersed fine pores. I was

The surface state of this sheet was smooth, the weight loss after drying was as small as 0.9%, and the area retention was 98.8%. Also, this sheet is
When immersed in DMF at ℃, the shape gradually collapsed,
It became dispersed in DMF and could be washed and removed with DMF.

Comparative Example 5 30 parts of (A-3) of Example 3 and 70 parts of (B-3)
A control polyurethane resin composition was prepared in the same manner as in Example 3, except that 100 parts of (A-3) was used instead of 100 parts.

In the polyurethane resin composition, the viscosity stability of the solution was not so good, and the entire solution solidified in about 5 days.

Next, this polyurethane solution was cast on a PET sheet so as to have a thickness of about 1 mm.

Thereafter, the PET sheet coated with the polyurethane resin composition was immersed in a DMF aqueous solution having a DMF concentration of 10% at 25 ° C. for 20 minutes to be coagulated.

Then, after being sufficiently washed in warm water of 40 ° C., it was heated in a hot air drier heated to 100 ° C. for 30 minutes.
By drying for a period of minutes, a crosslinked polyurethane resin porous layer sheet was obtained.

Subsequently, the sheet was immersed in toluene heated to 90 ° C. for one hour, and then washed with hot water at 90 ° C. for one hour.
Dry at 80 ° C. for 30 minutes.

The sheet thus obtained had good surface smoothness and an apparent specific gravity of 0.472, and the cross section of the sheet was observed. Had.

Further, the weight loss rate expressed by the weight loss rate after immersion in heated toluene with respect to the weight before immersion in heated toluene was 0.8%, and the sheet before immersion in heated toluene was 0.8%. The area retention, expressed by the area retention of the sheet after immersion in heated toluene, was 98.5% of the area.

However, even if this sheet is immersed in DMF at 50 ° C., it does not lose its shape at all and does not dissolve or disperse in DMF, making it impossible to wash and remove it with DMF. understood.

Comparative Example 6 A urethane resin solution containing no hydrolyzable silyl group (B
In the same manner as in Example 3 except that 100 parts of -3) was used, a control containing no hydrolyzable silyl group was obtained by adding a film-forming aid and DMF. , A non-crosslinked polyurethane resin composition was prepared.

By subjecting the composition thus obtained to wet film formation in the same manner as in Example 3, a porous layer sheet having an apparent specific gravity of 0.475 and excellent surface smoothness was obtained. Obtained.

Further, the heat-resistant toluene test was carried out on the film-formed porous layer sheet in the same manner as in Example 3. As a result, the weight loss was as large as 5.5% and the area retention was 9%.
6.5%. The surface condition of this sheet has deteriorated, and therefore, it has never been practically usable for ultrafine fiber artificial leather.

Reference Example 7 100 parts of PTMG-2000, 10 parts of EG, D
394 parts of MF and 3 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane were placed in a 1-liter four-necked flask and uniformly dissolved.

Next, while vigorously stirring this solution,
By charging 56 parts of MDI and performing the reaction at 70 ° C. for 10 hours, the nonvolatile content was 30.0%.
% And a solution of a polyurethane resin having a viscosity of 890 ps and having a hydrolyzable silyl group in the side chain of the molecule. Hereinafter, this polyurethane resin solution is abbreviated as (A-4).

Reference Example 8 The procedure of Example 4 was repeated, except that 1.0 part of EG was used instead of 3 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane. By performing synthesis, the resin concentration is 30.0%
A solution of a polyurethane resin having a viscosity of 910 ps and containing no hydrolyzable silyl group was obtained. Hereinafter, this polyurethane resin solution is abbreviated as (B-4).

Example 4 (A-4) was changed to 30 parts, and (B-4) was changed to 70 parts.
Part, and add DMF to reduce non-volatile content to 15%
Further, the same procedure as in Example 1 was performed except that 0.15 part of phthalic anhydride was further added and mixed as a catalyst for hydrolysis and condensation of the hydrolyzable silyl group. Thus, a polyurethane resin composition of the present invention was prepared.

Then, when the composition thus obtained was stored at room temperature for 3 months, the increase in viscosity was as follows:
No stability was observed, thus confirming that the stability of the composition was very good.

Subsequently, this composition was impregnated into a non-woven fabric consisting of sea-island fibers in which the sea component was polyethylene and the island component was polyester.

Next, the non-woven fabric thus impregnated was
In a DMF aqueous solution having a DMF concentration of 10% at 5 ° C,
The polyurethane resin was solidified by immersion for 0 minutes.

Then, after thoroughly washed in warm water of 40 ° C., dried in a hot air drier of 100 ° C. for 30 minutes, and then put in toluene heated to 90 ° C. for 1 hour. During this time, the polyethylene portion of the sea-island fiber was eluted.

Thereafter, artificial leather was obtained by washing with hot water of 90 ° C. for 1 hour and drying at 80 ° C. for 30 minutes.

The thickness of the artificial leather after the extraction treatment with heated toluene was 89% of the thickness before the extraction, that is, the thickness retention was 89%. When the cross section of the artificial leather was observed with a microscope, it was confirmed that the polyethylene which had formed the sea-island fibers was eluted, while the polyurethane resin remained mostly. The texture was very soft and had the desired deer skin texture.

Subsequently, the procedure of Example 1 was repeated, except that the composition was changed to use this composition. Then, after performing wet film formation, extraction with heated toluene, and washing and drying were performed. When a porous layer sheet was obtained and immersed in DMF at 50 ° C., the shape gradually collapsed and became a dispersed state in DMF, which could be washed and removed with DMF.

Comparative Example 7 Hydrolyzable silyl group-containing polyurethane resin solution (A-
A polyurethane resin composition was prepared in the same manner as in Example 4 except that 100 parts of 4) were used, and thereafter, the same sea-island fiber nonwoven fabric as that used in Example 7 was impregnated. After that, treatment was performed in the same manner as in Example 7 to prepare a control artificial leather.

The artificial leather for control thus obtained had an extremely high thickness retention of 91% after toluene treatment. In addition, when the cross section of this artificial leather was observed with a microscope, it was found that the polyethylene that had formed the sea-island fibers was eluted, but the polyurethane resin was hardly eluted, and most of it remained. found. Moreover, the artificial leather thus prepared was very soft and had a very good feeling.

[0210] In the same manner as in Example 4 except that this composition was changed to use, a wet film was formed, followed by extraction with heated toluene and washing with hot water and drying. Even if the porous sheet is immersed in DMF at 50 ° C., it does not dissolve or lose its shape.
It became dispersed in F and could be washed and removed with DMF.

Comparative Example 8 Urethane resin solution containing no hydrolyzable silyl group (B-4)
Use 100 parts of so that the non-volatile content becomes 15%,
A control, non-crosslinked polyurethane resin composition was prepared in the same manner as in Example 7, except that it was diluted with DMF.

Subsequently, the composition thus obtained was
An impregnated sea-island fiber nonwoven fabric similar to that used in Example 7 was impregnated, and then treated in the same manner as in Example 4 to prepare a control artificial leather.

The artificial leather for control thus obtained had an extremely low thickness retention of 35% after the toluene treatment. Also, when the cross section of this artificial leather was observed with a microscope, it was found that the polystyrene that had formed the sea-island fibers was eluted, and that the polyurethane resin was also almost eluted, and that only a very small amount remained. found.

[0214] The artificial leather for control thus prepared was very hard and extremely inferior in feel.

Reference Example 9 100 parts of polytetramethylene glycol having a number average molecular weight of 1,400, 10 parts of 1,4-butanediol, 383 parts of DMF, and γ- (2-aminoethyl) aminopropyl Four parts of methyldimethoxysilane were placed in a one-liter four-necked flask and uniformly dissolved.

Next, while vigorously stirring this solution,
By charging 50 parts of MDI and conducting the reaction at 70 ° C. for 10 hours, the resin concentration was 30.0%.
%, And a solution of a polyurethane resin having a hydrolyzable silyl group in the side chain of the molecule, having a viscosity of 1,100 ps at 25 ° C. was obtained. Hereinafter, this polyurethane resin solution is abbreviated as (A-5).

Reference Example 10 Reference Example 9 was repeated except that 2 parts of 1,4-butanediol was used in place of 4 parts of γ- (2-aminoethyl) aminopropylmethyldimethoxysilane.
By performing the synthesis reaction in the same manner as
A polyurethane resin solution having a nonvolatile content of 30.0% and a viscosity of 980 ps and containing no hydrolyzable silyl group was obtained. Hereinafter, this polyurethane resin solution is abbreviated as (B-5).

Example 5 In 35 parts of (A-5) and 65 parts of (B-5), citric acid 3 as a catalyst for hydrolysis and condensation of a hydrolyzable silyl group was used.
A polyurethane resin composition was prepared by mixing with 0.3 parts of ammonium.

Next, the composition thus obtained was cast on a release paper so that the thickness after the solvent was volatilized was 30 μm, and heated at 140 ° C. for 3 minutes to obtain a film. Was prepared.

Subsequently, this film was heated at room temperature.
After letting it stand for 3 days, the film was peeled off, and in oleic acid, a component of sweat, in isopropanol, a component of hairdressing agent, and toluene and acetic acid as substitutes for toiletry products, respectively. When immersed in ethyl and methanol at room temperature for 1 hour, the appearance of the film did not change at all.

When this film was immersed in DMF at 50 ° C., the shape gradually collapsed, and the film became dispersed in DMF, and could be removed by washing with DMF.

Next, the synthetic leather produced by laminating this film on a woven fabric was excellent especially in sweat resistance and hair styling resistance.

Further, it was confirmed that the polyurethane resin composition used here did not show an increase in viscosity even after being stored at room temperature for 3 months, and was therefore excellent in stability. Was done.

Comparative Example 9 A film was formed on release paper in the same manner as in Example 5, except that 100 parts of (A-5) was used.

Subsequently, the control film thus obtained was allowed to stand at room temperature for 3 days, and then the film was peeled off. The film was separated into oleic acid, a component of sweat, and a hairdressing agent. In the component isopropanol, and as a substitute for toiletries, toluene,
It was immersed in ethyl acetate and methanol at room temperature for 1 hour.

The appearance of this control film was not changed at all, and was excellent in chemical resistance and solvent resistance. However, when this control film was immersed in DMF at 50 ° C., it did not dissolve at all,
The shape did not collapse, and it was impossible to remove by washing with DMF.

Comparative Example 10 A film was formed on release paper in the same manner as in Example 5, except that 100 parts of (B-5) was used.

Subsequently, the control film thus obtained was allowed to stand at room temperature for 3 days, and then the film was peeled off. The film was separated into oleic acid, a component of sweat, and a hairdressing agent. In the component isopropanol, and as a substitute for toiletries, toluene,
It was immersed in ethyl acetate and methanol at room temperature for 1 hour.

The control film was completely dissolved,
Alternatively, the shape of the control film was lost, so that the control film was inferior in chemical resistance and solvent resistance, among others.

Reference Example 11 100 parts of a 1,6-hexanediol-based polycarbonate diol (PC-2000) having a number average molecular weight of 2,000 and 66 parts of DMF were placed in a 1-liter four-necked flask. And dissolve under stirring.

Next, 22 parts of hydrogenated MDI and 0.005 parts of DBTL as a urethanization catalyst were added to this mixture so that the NCO / OH equivalent ratio was 1.7 / 1.0. At 85 ° C. for 3 hours.
When the CO equivalent was measured, it was confirmed that the NCO equivalent reached the theoretical value.

Subsequently, by charging 300 parts of DMF, the non-volatile content was adjusted to 25%, and then the mixture was maintained at 35 ° C. and stirred while γ- (2-aminoethyl) aminopropyl tripropyl was added. Four parts of methoxysilane and two parts of isophoronediamine (IPDA) are sequentially charged.

After stirring for 15 minutes, DMF was added.
And 15 parts of methanol and 10 parts of methanol are added and further stirred for one hour to dissolve, so that the nonvolatile content is 20% and the viscosity is 70 p.
s, a solution of a polyurethane resin having a hydrolyzable silyl group in the side chain of the molecule was obtained. Hereinafter, this polyurethane resin solution is abbreviated as (A-6).

Reference Example 12 A synthesis reaction was carried out in the same manner as in Reference Example 11, except that 3 parts of IPDA were used instead of 4 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane. Is performed, the resin concentration becomes 20.0%.
% And a solution of polyurethane having a viscosity of 68 ps and containing no hydrolyzable silyl group. Hereinafter, this polyurethane resin solution is abbreviated as (B-6).

Example 6 To 40 parts of (A-6), 60 parts of (B-6) were mixed, and DMF was added to make the non-volatile content 15%. A polyurethane resin composition of the present invention was prepared by adding and mixing 0.1 part of succinic anhydride as a catalyst for hydrolysis and condensation.

Subsequently, this composition was treated at room temperature for 3 hours.
When stored for a period of months, only a slight increase in viscosity was observed, confirming that the product was extremely excellent in storage stability.

Further, this composition was impregnated in the same sea-island fiber nonwoven fabric as used in Example 4, and then impregnated.
An artificial leather was prepared by performing the treatment in the same manner as in Example 4.

Next, the artificial leather thus obtained was very good, with the thickness retention after the toluene treatment being 90%. In addition, when the cross section of the artificial leather was observed with a microscope, it was confirmed that the polyethylene forming the sea-island fibers was eluted, while the polyurethane resin remained almost completely. .

The artificial leather thus obtained was very soft and had the desired deer skin texture.

Comparative Example 11 A solution of a hydrolyzable silyl group-containing polyurethane resin (A-
6), except that it was changed to use 100 parts, so that the sea-island fiber nonwoven fabric was impregnated in the same manner as in Example 6 and then treated in the same manner as in Example 6. A control polyurethane resin composition was obtained, and a control artificial leather was prepared.

The thus obtained artificial leather had a high thickness retention of 90% after the toluene treatment. Also,
When the cross section of the artificial leather for comparison was observed with a microscope, it was confirmed that the polyethylene which constituted the sea-island fiber was eluted, but the polyurethane resin was not eluted and most of the polyurethane resin remained. .

In addition, the artificial leather for control obtained in this manner was very soft and had a desired deer skin texture.

However, when this control composition was stored at room temperature for one month, a considerable increase in viscosity was observed, and therefore the storage stability of the viscosity was poor. It was confirmed that.

Comparative Example 12 A solution of a polyurethane resin containing no hydrolyzable silyl group (B
-6), except that it was changed to use 100 parts, so that the sea-island fiber nonwoven fabric was impregnated in the same manner as in Example 6, and then treated in the same manner as in Example 6. An artificial leather for control was prepared.

The artificial leather for control thus obtained had a low thickness retention of 45% after the toluene treatment. Further, when the cross section of the artificial leather for comparison was observed with a microscope, it was found that the polyethylene which constituted the sea-island fiber was eluted, and the polyurethane resin was also almost eluted, and only a small amount remained. It was confirmed that.

Further, the texture was very hard, and it was not practically usable.

Reference Example 13 100 parts of PC-2000, 13 parts of 1,4-butanediol, and 89 parts of toluene were placed in a two-liter four-necked flask and dissolved with stirring.

Next, 5 parts of hydrogenated MDI was added to the mixture so that the NCO / OH equivalent ratio was 2.0 / 1.0.
1 part and 44 parts of isophorone diisocyanate (IPDI) were added, and 0.007 part of DBTL as a urethanization catalyst was also added. Then, the temperature was raised to 85 ° C., and the temperature was increased for 5 hours. During this time, the reaction was continued and the NCO equivalent was measured to confirm that the theoretical value had been reached.

Thereafter, 375 parts of DMF and 160 parts of toluene were added to adjust the nonvolatile content to 25%.

Further, the urethane prepolymer solution was kept at 35 ° C., and while stirring, 6.5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane was added.
And 28 parts of IPDA.

After stirring for 15 minutes, DMF was added.
And 394 parts of methanol and 12 parts of methanol were charged and stirred for one hour to dissolve,
A solution of a polyurethane resin having a nonvolatile content of 20% and a viscosity of 80 ps and having a hydrolyzable silyl group in a side chain of the molecule was obtained. Hereinafter, this polyurethane resin solution is referred to as (A-
7).

Reference Example 14 The same procedure as in Reference Example 13 was carried out except that 5 parts of IPDA was used instead of 6.5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane. By performing the synthesis reaction, the resin concentration is 20.0% and the viscosity is 85 ps.
A solution of a polyurethane resin containing no hydrolyzable silyl group was obtained. Hereinafter, this polyurethane resin solution is referred to as (B-
7).

Example 7 70 parts of (A-7) was blended with 30 parts of (B-7), and then triammonium citrate was used as a catalyst for hydrolysis / condensation of a hydrolyzable silyl group. By adding and mixing 0.2 parts, a polyurethane resin composition of the present invention was prepared.

Subsequently, a film was formed on release paper in the same manner as in Example 5, except that this composition was changed to use.

Next, the film thus obtained was allowed to stand at room temperature for 3 days, after which the film was peeled off. Then, oleic acid, which is a component of sweat, and a component of a hairdressing agent, respectively. When the film was immersed in isopropanol as described above and in toluene, ethyl acetate and methanol as substitutes for toiletries, almost no change was observed in the appearance of the film. When this film was immersed in DMF at 50 ° C., the shape gradually collapsed, and the film became dispersed in DMF.
F was able to wash and remove.

Synthetic leather produced by laminating this film on a woven fabric is particularly excellent in sweat resistance and hair styling resistance, and is particularly suitable for use in automobile seats. Was confirmed.

The polyurethane resin composition used in this example hardly shows an increase in viscosity even when it is stored at room temperature for 3 months, and therefore has extremely excellent storage stability. Was confirmed.

Comparative Example 13 A solution of a hydrolyzable silyl group-containing polyurethane resin (A-
A film was formed on release paper in the same manner as in Example 7, except that 100 parts of 7) were changed to be used.

Then, after leaving this film at room temperature for 3 days, the film was peeled off, and the film was removed in oleic acid, a component of sweat, and in isopropanol, a component of a hairdressing agent. And, as a substitute for toiletries, the film was immersed in toluene, ethyl acetate, and methanol.
Almost no change was observed. In addition, this film
When immersed in DMF at 0 ° C., the shape gradually collapsed and became a dispersed state in DMF, which could be washed and removed with DMF.

Synthetic leather produced by laminating this film on a woven fabric is particularly excellent in sweat resistance and hair styling resistance, and is particularly suitable for use in automobile seats. Was confirmed.

However, the control polyurethane resin composition used was stored at room temperature for one month, but its viscosity increased and it was not possible to remove it from the container. Was inferior in storage stability.

Comparative Example 14 A solution of a polyurethane resin containing no hydrolyzable silyl group (B
A film for comparison was produced on release paper in the same manner as in Example 7, except that 100 parts of -7) were changed to be used.

After leaving the film at room temperature for 3 days, the film was peeled off. In oleic acid, which is a component of sweat, in isopropanol, which is a component of a hairdressing agent, and a substitute for toiletries. At room temperature in toluene, ethyl acetate and methanol.
Let it soak for a while. The film was either completely dissolved or lost its shape, and thus was especially poor in chemical resistance and solvent resistance.

Reference Example 15 100 parts of PC-2000 and a number average molecular weight of 1,000
50 parts of 1,6-hexanediol-based polycarbonate diol (PC-1000) and 8 parts of toluene
3 parts were placed in a 2 liter four-necked flask and dissolved under stirring.

Next, 44 parts of IPDI were added to this mixture so that the NCO / OH equivalent ratio became 2.0 / 1.0, and 0.007 parts of DBTL as a urethanization catalyst was further added. After the introduction, the temperature was raised to 85 ° C., and the reaction was continued at the same temperature for 6 hours. The NCO equivalent was measured to confirm that the NCO equivalent had reached the theoretical value.

Thereafter, 499 parts of DMF was added to adjust the non-volatile content to 25%. Subsequently, while keeping the urethane prepolymer solution at 35 ° C. and stirring, 6 parts of γ-aminopropyltriethoxysilane and 6 parts of hydrogenated MDA (dicyclohexylmethanediamine) were successively added. , Was put.

Next, the mixture was stirred for 15 minutes, and then 193 parts of DMF and 10 parts of methanol were added, and the mixture was stirred for 1 hour to dissolve. , Non-volatile content is 20
%, And a solution of a polyurethane resin having a viscosity of 50 ps and having a hydrolyzable silyl group at the terminal of the molecule was obtained. Hereinafter, this polyurethane resin solution is abbreviated as (A-8).

Reference Example 16 The synthesis reaction was carried out in the same manner as in Reference Example 15 except that 3 parts of di-n-butylamine was used instead of 6 parts of γ-aminopropyltriethoxysilane. As a result, a polyurethane resin solution having a nonvolatile content of 20% and a viscosity of 55 ps and containing no hydrolyzable silyl groups was obtained. Less than,
This polyurethane resin solution is abbreviated as (B-8).

Example 8 50 parts of (B-8) were mixed with 50 parts of (A-8).
Furthermore, a polyurethane resin composition was prepared by adding and mixing 0.2 parts of ammonium phthalate as a catalyst for hydrolysis and condensation of a hydrolyzable silyl group.

Next, a film was formed on release paper in the same manner as in Example 5, except that this composition was changed to use.

After leaving at room temperature for 3 days, oleic acid as a component of sweat, isopropanol as a component of a hairdressing agent, and a substitute for toiletries were placed on the surface of this film. , Toluene, ethyl acetate and methanol were placed thereon, and several drops were allowed to stand at room temperature for one hour. Then, the state of the film surface was observed.

As a result, no change was observed on the surface of the film. Also, this film,
When it was immersed in DMF at 50 ° C., the shape gradually collapsed, and it became dispersed in DMF, and it was possible to wash and remove with DMF.

Next, the synthetic leather produced by laminating this film on a woven fabric is particularly excellent in sweat resistance and hair styling resistance, and is particularly suitable for automobile seats. It was that.

Further, the composition used in this example hardly shows an increase in viscosity even after storage at room temperature for 3 months, and therefore has a very excellent storage stability. It was confirmed that it came out.

Comparative Example 15 A control film was formed on release paper in the same manner as in Example 8, except that 100 parts of the polyurethane resin solution (A-8) was used. .

[0276] Then, after leaving at room temperature for 3 days, oleic acid as a component of sweat, isopropanol as a component of hairdressing agent, and a substitute for toiletries were placed on the surface of this film. , A few drops of toluene, ethyl acetate and methanol were placed, and allowed to stand at room temperature for 1 hour, and the surface condition was observed.

As a result, although no change was observed on the surface of the control film, the shape of the control film was lost even when the control film was immersed in DMF at 50 ° C. , And it was found that washing and removal with DMF was impossible.

Comparative Example 16 Separation was carried out in the same manner as in Example 8 except that 100 parts of a solution (B-8) of a polyurethane resin having no hydrolyzable silyl group was used. A control film was prepared on the pattern paper.

[0279] Then, after leaving it to stand at room temperature for 3 days, oleic acid which is a component of sweat, isopropanol which is a component of a hairdressing agent, and After placing a few drops of toluene, ethyl acetate and methanol as substitutes, leaving them to stand at room temperature for 1 hour, the surface condition was observed.

As a result, the surface of this control film was shrunk or whitened.
It turned out to be very poor in terms of chemical resistance and solvent resistance.

Reference Example 17 50 parts of 1,6-hexanediol-based polycarbonate diol (PC-1000) having a number average molecular weight of 1,000, 50 parts of PC-2000, and 70 parts of DMF were combined with 1 part. Dispense into a four liter four-necked flask with stirring.

Next, the mixture was mixed with hydrogenated MDI to obtain an NCO / OH equivalent ratio of 1.5 / 1.0.
5 parts, and DBT as a urethanization catalyst
0.005 parts of L was also charged, and the reaction was carried out at 85 ° C. for 3 hours. The NCO equivalent was measured to confirm that the theoretical value had been reached.

Subsequently, 320 parts of DMF was added to adjust the non-volatile content to 25%. Then, while stirring at 35 ° C., γ- (2-aminoethyl) aminopropyltrimethoxysilane was added. 4 parts and 2 parts of IPDA were sequentially charged.

After stirring for 15 minutes, DMF was added.
150 parts of methanol and 10 parts of methanol are added, and further stirred for 1 hour to dissolve, so that the non-volatile content is 20% and the viscosity is 40 ps. A solution of a polyurethane resin having a hydrophilic silyl group was obtained. Hereinafter, this polyurethane resin solution is abbreviated as (A-9).

Reference Example 18 Synthesis was performed in the same manner as in Reference Example 17 except that 3 parts of IPDA was used instead of 4 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane. By performing the reaction, the resin concentration is 20%
Thus, a polyurethane solution having a Brookfield viscosity of 41 ps at 25 ° C. and containing no hydrolyzable silyl groups was obtained. Hereinafter, this polyurethane resin solution is abbreviated as (B-9).

Example 9 In 60 parts of (A-9), 40 parts of (B-9) and DMF
In this example, in particular, a catalyst for hydrolysis / condensation of a hydrolyzable silyl group is not added at all. A crosslinkable polyurethane resin composition was prepared.

Subsequently, this composition was impregnated in the same sea-island fiber nonwoven fabric as that used in Example 4, and then dried after wet film formation in a hot air drier at 100 ° C. for 2 hours. The intended artificial leather was prepared by carrying out the treatment in the same manner as in Example 4, except that the drying was carried out under the condition of drying.

The artificial leather thus obtained had a very good thickness retention of 88% after the toluene treatment, and was very good. In addition, when the cross section of this artificial leather was observed with a microscope, the polyethylene that formed the sea-island fibers was eluted, while the polyurethane resin was almost completely left. It was confirmed that.

The artificial leather thus obtained was very soft and had the desired deer skin texture.

Also, except that the composition was changed to use, a porous film was formed by performing wet film formation, extracting with heated toluene, washing and drying in the same manner as in Example 4. When a sheet was obtained and then immersed in DMF at 50 ° C., the shape gradually collapsed and became a dispersed state in DMF, and washing with DMF was possible.

Comparative Example 17 A sea-island fiber nonwoven fabric was impregnated with a polyurethane resin solution (A-9) in the same manner as in Example 4, and thereafter the treatment was performed in the same manner as in Example 9. A control polyurethane resin composition and artificial leather were prepared.

The artificial leather for control obtained in this manner had a very high thickness retention of 90% after the toluene treatment. In addition, when the cross section of the artificial leather for comparison was observed with a microscope, it was confirmed that the polyethylene which constituted the sea-island fiber was eluted, but the polyurethane resin was completely left.

In addition, except that this control composition was changed to the above, a wet film was formed, followed by extraction with heated toluene, washing and drying in the same manner as in Example 4. Then, a control porous layer sheet was obtained. Thereafter, the sheet was immersed in DMF at 50 ° C., but the shape did not collapse, and washing with DMF was impossible.

Comparative Example 18 A sea-island fiber nonwoven fabric was impregnated with a solution (B-9) of a polyurethane resin containing no hydrolyzable silyl group at all in the same manner as in Example 4. By performing the treatment in the same manner as in the above, a control polyurethane resin composition and an artificial leather were prepared.

The artificial leather for control thus obtained had a low thickness retention of 45% after toluene treatment. In addition, when the cross section of the artificial leather for comparison was observed with a microscope, the polyethylene which constituted the sea-island fiber was eluted, and almost all of the polyurethane resin was also eluted, and only a small amount remained. Not confirmed.

Further, the texture was very hard, and it was not something that could be practically used at all.

[0297]

The polyurethane resin composition according to the present invention comprises a mixture of a polyurethane resin which can be crosslinked by moisture and a polyurethane resin which is not crosslinked by moisture, to form a resin composition comprising only a polyurethane resin which can be crosslinked. It is superior in viscosity stability to a compounded liquid containing a catalyst, and can withstand a solvent having a relatively low solubility such as toluene.
The non-crosslinked urethane resin dissolves in a highly soluble solvent such as that described above, causing the shape to collapse. And it is easy to wash and remove.

In the artificial leather according to the present invention, particularly the microfiber artificial leather, using the resin composition of the present invention having such characteristics, particularly in the toluene extraction treatment step for ultrafineness, The polyurethane resin is less liable to be eluted, is extremely supple, and has an excellent appearance. Synthetic leather is particularly excellent in solvent resistance and chemical resistance.

The artificial leather and synthetic leather according to the present invention are extremely practical for clothing, sports shoes, automobile seats, and furniture.

In addition, since a resin composition having excellent storage stability can be provided, conventionally, there was a production trouble that the polyurethane resin composition gelled before use. The present invention is to prevent such troubles.

Claims (8)

[Claims] 1. A polyurethane resin (A) having a hydrolyzable silyl group at a side chain and / or a terminal of a molecule, and a polyurethane resin (B) not having a hydrolyzable silyl group.
A polyurethane resin composition comprising an organic solvent (C) as an essential component. 2. A polyurethane resin having a hydrolyzable silyl group at a side chain and / or a terminal of a molecule (A), and a polyurethane resin having no hydrolyzable silyl group (B),
A polyurethane resin composition comprising, as essential components, an organic solvent (C) and a catalyst (D) for hydrolyzing or condensing a hydrolyzable silyl group. 3. The composition according to claim 2, wherein the catalyst (D) is a compound having an acid anhydride group. 4. The composition according to claim 2, wherein the catalyst (D) is a salt of an acid and an amine or ammonia. 5. A polyurethane resin having a hydrolyzable silyl group at a side chain and / or a terminal of a molecule (A), and a polyurethane resin having no hydrolyzable silyl group (B).
An artificial leather and a synthetic leather, which are filled or laminated with a polyurethane resin composition containing an organic solvent (C) as an essential component. 6. A polyurethane resin (A) having a hydrolyzable silyl group at a side chain and / or a terminal of a molecule, and a polyurethane resin (B) having no hydrolyzable silyl group,
Artificial leather, characterized by being filled or laminated with a polyurethane resin composition containing an organic solvent (C) and a catalyst (D) for hydrolyzing or condensing a hydrolyzable silyl group as essential components. And synthetic leather. 7. The leather according to claim 6, wherein the catalyst (D) is a compound having an acid anhydride group. 8. The leather according to claim 6, wherein the catalyst (D) is a salt of an acid and an amine or ammonia.