JPH1081826A - Crosslinkable polyurethane resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a crosslinkable polyurethane resin which can be stably stored and is suitable for various applications such as artificial leathers by incorporating a compd., which develops catalytic activity upon hydrolysis, such as an acid anhydride, into a hydrolyzable silyl-contg. polyurethane resin. SOLUTION: This crosslinkable polyurethane resin compsn. comprises: a polyurethane resin (A) having a hydrolyzable silyl group; and a latent catalyst (B) for hydrolysis/condensation of the hydrolyzable silyl group. The component (B) is a salt of a compd. having an acid anhydride group, such as maleic anhydride, a copolymer thereof, or an acid compd. with an amine compd. or ammonia. The component (A) is prepd. by a method using a compd. having both an isocyanate group and a hydrolyzable silyl group as a starting compd., by reacting a polyurethane resin having active hydrogen with a compd. having a hydrolyzable silyl group. In this compsn. the component (B) may be selected depending upon applications. The compsn. can be widely used in artificial leathers by wet film formation, an adhesive which produces a cured product upon contact with moisture in air, and a sealing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel and useful crosslinkable polyurethane resin composition. More specifically, the present invention mainly comprises an artificial polyurethane resin comprising a specific polyurethane resin having a hydrolyzable silyl group in a molecule and a latent catalyst for hydrolysis or condensation of the hydrolyzable silyl group. The present invention relates to a crosslinkable polyurethane resin composition having excellent storage stability, which can be used for leather, synthetic leather, paints, coatings, adhesives, sealing agents, pressure-sensitive adhesives, films or sheets, and the like.

[0002]

2. Description of the Related Art Up to now, polyurethane resin solutions have been widely used for artificial leather, synthetic leather, paints, coatings, adhesives, sealing agents, adhesives, films or sheets. However, in these applications, at the time of use, by crosslinking reaction, the strength of the polyurethane resin,
Attempts have been made to improve the adhesive strength, heat resistance, solvent resistance, etc., and various crosslinking methods have been proposed.

As one of them, a polyurethane resin in which a hydrolyzable silyl group is introduced into a molecular side chain and / or a molecular terminal has been proposed. Polyurethane resin of this form forms a strong network structure by hydrolysis reaction of hydrolyzable silyl groups and subsequent crosslinking by condensation reaction, and the urethane resin has remarkable strength, adhesive strength, heat resistance and solvent resistance etc. It is to provide an improved crosslinked product (cured product).

[0004] A catalyst for hydrolysis or condensation of a hydrolyzable silyl group (hereinafter also referred to as a curing catalyst) is used for the purpose of efficiently and efficiently proceeding such crosslinking of a polyurethane resin in a short time. Is

For example, various acidic compounds such as malic acid, citric acid, succinic acid, maleic acid, phthalic acid, p-toluenesulfonic acid or dialkyl phosphoric acid; various acidic compounds such as sodium hydroxide, sodium methylate or triethylamine. Basic compounds: Various metal-containing compounds such as tetraisopropyl titanate, tin octylate, di-n-butyltin dilaurate or di-n-butyltin oxide are used.

However, when such curing catalysts are added, the stability of the composition containing such curing catalyst is poor, and the viscosity becomes too high within a short period of time.
There is a problem that the fluidity is reduced or gelled, that is, there is a problem that the pot life is short, and therefore, the workability in various processing steps such as coating, impregnation or casting is reduced. There was a disadvantage.

[0007] For this reason, when the above-mentioned curing catalysts are added, the curing catalysts are mixed only immediately before processing, which is an extremely limited use. Had to be used up, or if the mixture remained, it had to be discarded.

Therefore, when a conventional curing catalyst is blended, generally, only a predetermined amount is blended immediately before the use (processing) of the curing catalyst, and the curing catalyst is used up within a certain pot life (pot life). That is, it must be used in a so-called two-pack type.

In such a two-pack type, each time it is used,
It is necessary to repeat the work of weighing and mixing, and in order to eliminate the complexity of such work processes, the emergence of a stable one-pack type composition in which a curing catalyst has been blended in advance However, although desperately desired, nothing has yet been obtained to satisfy these requirements.
That is the current situation.

[0010]

[Problems to be solved by the invention]

In view of the above-mentioned various drawbacks or defects in the conventional technology, the present inventors have started intensive research to meet the demands of the industry.

Accordingly, the object of the present invention is mainly to provide a polyurethane resin having a hydrolyzable silyl group at a side chain and / or a terminal with a latent catalyst for hydrolysis or condensation of the hydrolyzable silyl group. It consists of compounding, of course, it is excellent in stability, it is also excellent in workability, and in addition, it forms a cured product with excellent chemical resistance and solvent resistance, among others,

[0013] Solution-type or solvent-free crosslinkable polyurethane resin suitable for various uses such as artificial leather, synthetic leather, paints, coatings, adhesives, adhesives, sealing agents, and films or sheets. It is to provide a composition.

[0014]

[Means for solving the problem]

The inventors of the present invention have conducted intensive studies with an eye on the problems to be solved by the invention as described above, and as a result, it has been found that a compound having no catalytic effect as it is, A so-called latent catalyst that, when heated, comes into contact with water, moisture, etc., causes a thermal decomposition reaction, hydrolysis reaction, etc., transforms into a compound that has a catalytic effect, and exhibits catalytic activity. A compound that functions as

[0016] A solution type or solvent-free type cross-linking which has excellent storage stability and good workability by being compounded as a curing catalyst with a polyurethane resin having a hydrolyzable silyl group at a side chain and / or a terminal. Here, the present invention has been completed by finding that a water-soluble polyurethane resin composition can be obtained.

The present invention basically comprises a polyurethane resin (A) having a hydrolyzable silyl group at a side chain and / or a terminal, respectively, and a latent catalyst for hydrolysis or condensation of the hydrolyzable silyl group. And (B) to provide a highly practical crosslinkable polyurethane resin composition.

Specifically, the latent catalyst (B) described above
Are, respectively, a specific compound having an acid anhydride group, or an acid and a specific compound such as a salt of an amine or ammonia, a highly practical crosslinkable polyurethane resin composition. Is also to offer.

[0019]

DETAILED DESCRIPTION OF THE INVENTION Thus, the present application provides, in part,
A crosslinkable polyurethane comprising a polyurethane resin (A) having a hydrolyzable silyl group at a side chain and / or a terminal and a latent catalyst (B) for hydrolysis or condensation of the hydrolyzable silyl group. Claims a resin composition,

Two, the latent catalyst (B) described above is
It is said that a cross-linkable polyurethane resin composition, such as a compound having an acid anhydride group, is also claimed,

Third, the latent catalyst (B) described above comprises:
It also claims a crosslinkable polyurethane resin composition that is a salt of an acid with an amine or ammonia.

Hereinafter, the present invention will be described in more detail.

Here, the base resin of the polyurethane resin composition according to the present invention is a resin having side chains of molecules and / or
Alternatively, a polyurethane resin (A) having a hydrolyzable silyl group at a terminal [hereinafter, this is also referred to as a hydrolyzable silyl group-containing polyurethane resin (A). ] May simply be a polyurethane resin having a urethane bond, or may be a so-called polyurethane polyurea resin having both a urethane bond and a urea bond.

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

[0025]

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 or a substituted alkoxy group. , An acyloxy group, a substituted acyloxy group, a phenoxy group, an iminooxy group or an 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. A method of preparing a polyurethane resin by using a compound of as an essential raw material component,

(Ii) a polyurethane resin prepared in advance 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 this active hydrogen-containing group, such as an isocyanate group, with a compound having a hydrolyzable silyl group,

(Iii) Hydrosilylation of a previously prepared polyurethane resin having a double bond in the side chain and / or terminal of the molecule with 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 reaction can be applied, and among these, 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 also be carried out by adding (iv) a polyurethane resin having an isocyanate group at a terminal to an isocyanate group. 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 a hydrolyzable silyl group into a molecular terminal,

(V) By using a compound having two functional groups capable of reacting with an isocyanate group and a hydrolyzable silyl group, the compound is located inside the main chain of the polyurethane molecule, that is, preferably, in the molecule. It is a method of introducing a hydrolyzable silyl group into the side chain of

(Vi) One of the functional groups reactive with the isocyanate group is added to the previously prepared polyurethane resin having an isocyanate group at the molecular terminal and having a hydrolyzable silyl group at the side chain of the molecule. And by reacting a compound having a hydrolyzable silyl group together with a compound having a hydrolyzable silyl group, to introduce a hydrolyzable silyl group into both the side chain portion and the molecular end of the molecule. Can be adopted and applied.

By these various methods, 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) [hereinafter referred to as ( Also referred to as a-1). ], Amino groups or hydroxyl groups, etc., which are particularly typical as functional groups capable of reacting with the isocyanate group, are preferred, and both of these groups are suitable.

The functional group capable of reacting with the isocyanate group and the compound having a hydrolyzable silyl group (a-1)
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- (N, N-di-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, if only a typical formulation is exemplified, the compound (a-1) and a long-chain diol compound [hereinafter also referred to as (a-2). 〕When,
Diisocyanate compound [hereinafter also referred to as (a-3). Is used as an essential raw material component to react,

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.

Here, the long-chain diol compound (a-2) used in preparing the resin (A) is not particularly limited. If just to illustrate, polyester-based diol, polycarbonate-based diol or polyether-based diol and the like, and further,
Such a mixture or a copolymer is used.

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.

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-hexane glycol,
1,8-octanediol, neopentyl glycol,
1,4-bis- (hydroxymethyl) -cyclohexane, 2-methyl-1,3-propanediol, 2,2,2
4-trimethyl-1,3-pentanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, dibutylene glycol, polyethylene glycol, polypropylene glycol or polytetramethylene glycol.

As one of the dicarboxylic acids, aliphatic-,
Any of alicyclic, aromatic and / or heterocyclic compounds can be used. Among them, succinic acid, succinic anhydride, adipic acid and the like may be used. , Suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimetic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endmethylene tetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride Acid, maleic acid, fumaric acid, dimer fatty acid or dimethyl terephthalate.

In preparing the polyester diol compound, 4- (2-hydroxy) ethoxybenzoic acid,
Methyl 4- (2-hydroxy) ethoxybenzoate, ε-
A hydroxycarboxylic acid or a reactive derivative thereof such as hydroxycaproic acid or ε-caprolactone can be used as a raw material component.

As the polyester diol, a ring-opening polymer such as ε-caprolactone, a polycondensate of ε-hydroxycaproic acid, and the like can also be used.

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

Further, if only typical representative examples of polyether diols are given, the presence of a compound having an active hydrogen atom (reactive hydrogen atom)
It can be obtained by ring-opening polymerization of various three- or four-membered ring ether compounds, such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran or epichlorohydrin, alone or in a mixture of two or more. It is a polymer.

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

If only specific examples of the polyether-based diol are given, there are polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.

The diisocyanate compound (a-3) used when preparing the polyurethane resin (A) is represented by the following general formula:

[0051]

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, only typical ones are exemplified.

1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,1
2-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 (also called hydrogenated MDI),

2- or 4-isocyanatocyclohexyl-2'-isocyanatocyclohexylmethane, 1,
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, the use of an aromatic diisocyanate compound is desirable in terms of mechanical strength and the like, and the use of an aliphatic or alicyclic compound is particularly desirable in terms of durability and light resistance. The use of diisocyanate compounds is preferred.

Further, only typical examples of the chain extender (a-4) include short-chain diol compounds, and further include diamine compounds.

Of these, the short-chain diol compounds used for preparing the above-mentioned polyester diols are relatively low diol compounds among the various diol compounds already exemplified. And diols having a molecular weight.

First, among the chain extenders (a-4), only typical examples of the diamine compounds will be given below. For example, 1,2-diaminoethane and 1,2-diaminoethane may be used.
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 or 1,3-diaminopropane, and hydrazine or adipic dihydrazide can also be used.

As described above and described above, respectively, (a
-1), (a-2) and (a-3), and, if necessary, (a)
-4) In order to prepare the polyurethane resin (A) from the component, the polyurethane resin (A) may be reacted by various known and commonly used methods.

That is, for example, it is appropriate to carry out the reaction 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 and commonly used organic solvents such as, for example, 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 raw material component used in the reaction of the various raw material components as described above is not particularly limited, but may be used in preparing the polyurethane resin (A). First, 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 about 0.1 to about 30% by weight based on the total weight of the various raw material components. Preferably, it is used in such a ratio that it is in the range of 0.5 to 10% by weight, more preferably in the range of 1 to 5% by weight.

When the amount of the compound (a-1) used is less than about 0.1% by weight, the cured product obtained from the composition of the present invention, in particular, has an inferior cross-linking property. If the solvent resistance and chemical resistance tend to be insufficient, on the other hand, if it exceeds about 30% and is too large, the crosslinked density of the cured product tends to be too high. In particular, it is easy to obtain a cured product having inferior flexibility.

In preparing the polyurethane resin (A), the amount of the diisocyanate compound (a-3) to be used is usually (a-1), (a-2) or (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.

In preparing the polyurethane resin (A) used in the present invention, if necessary, monoalcohol, trifunctional or higher functional alcohol, organic monoamine,
Trifunctional or higher amines, organic monoisocyanates and / or
Alternatively, a tri- or higher functional polyisocyanate may be used.

In preparing the polyurethane resin (A), 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 only the typical urethanization catalysts mentioned above, 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.

On the other hand, only typical representative examples of the above-mentioned stabilizers include stabilizers against ultraviolet rays such as substituted benzotriazoles and the like, and further, such as phenol derivatives. These are stabilizers against thermal oxidation, and each of these stabilizers is
It can be appropriately selected and added according to the purpose.

The number average molecular weight of the polyurethane resin (A) thus prepared is in the range of about 500 to about 500,000, preferably 1 to 5, from the viewpoint of fluidity and processability. A range between 000 and 100,000 is suitable.

The crosslinkable polyurethane resin composition according to the present invention does not necessarily require an organic solvent. When an organic solvent is used, the organic solvent may be, for example, the above-mentioned polyurethane resin (A Any compound can be used as long as it is capable of dissolving ()).

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

When the reaction is carried out in an organic solvent when preparing the polyurethane resin (A), the organic solvent used for the reaction can be used without any special addition of the organic solvent. It goes without saying that it can be regarded as the component.

When a crosslinkable polyurethane resin composition containing an organic solvent is used, the amount of the organic solvent to be used is about 40 to about 5 to 100 parts by weight of the solid content of the component (A). 2,000 parts, preferably 100 parts
In the range of 2,000 to 2,000 parts, particularly preferably 100 to
A range of 900 parts is appropriate.

As the latent catalyst (B) for hydrolysis or condensation of the hydrolyzable silyl group used in the present invention, only those which are particularly representative are exemplified.
Compounds having various cyclic carboxylic anhydride groups, such as maleic anhydride, itaconic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride or alkenyl succinic anhydride; maleic anhydride Various carboxylic acid anhydride group-containing vinyl monomers as described above, such as a copolymer of styrene and styrene or a copolymer of maleic anhydride and α-olefins, and copolymerized with the monomer. Copolymers with monomeric compounds; or compounds having various linear carboxylic anhydride groups, such as benzoic anhydride, methacrylic anhydride or a mixed acid anhydride of benzoic acid and acetic acid;

Various sulfonic anhydrides, such as benzenesulfonic anhydride, p-toluenesulfonic anhydride, dodecylbenzenesulfonic anhydride or a mixed acid anhydride of benzenesulfonic acid and methanesulfonic acid;

Various mixed acid anhydrides of carboxylic acid and sulfonic acid, such as mixed acid anhydride of acetic acid or benzoic acid and benzenesulfonic acid or mixed acid anhydride of benzoic acid and methanesulfonic acid, etc. And also salts of various amines or ammonia, such as trimethylamine, triethylamine, tri-n-butylamine or 2-dimethylaminoethanol, with various acids as listed above;

As described in JP-A-2-232253 or JP-A-4-23807, 4-methylbenzyl-4-cyanopyridinium-hexafluoroantimonate and 4-chlorobenzyl-2-, respectively. Various types such as methylpyridinium-hexafluoroantimonate, 4-methoxybenzyl-3-chloropyridinium-tetrafluoroborate or N- (α-methylbenzyl) -N, N-dimethyl-N-phenylammonium hexafluoroantimonate A pyridinium salt or a quaternary ammonium salt which generates an acid upon heating;

As described in JP-A-58-198532 or JP-A-4-11626,
Various sulfoniums which generate an acid upon heating, such as prenyl-tetramethylenesulfonium-hexafluoroantimonate, crotyl-tetramethylenesulfonium-hexafluoroarsenate or benzyl-4-hydroxyphenyl-methylsulfonium hexafluoroantimonate, respectively salts;

There are various 2-hydroxyalkyl esters of organic sulfonic acids and esters of various organic sulfonic acids with secondary alcohols as described in JP-A-4-108861, Compounds that release sulfonic acid upon heating;
No. 242, a compound having a ketal ester group or an acetal ester group obtained by subjecting various compounds having a protonic acid group to an addition reaction of vinyl ethers, One that produces a compound having an acid group.

Among these latent catalysts, compounds having 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 are used as the latent catalyst (B). When used, the composition itself shows good stability, but is a wet process that uses water, such as is applied when manufacturing artificial leather in the process of forming a cured product. In the film forming method, water such as a coagulation bath and a cleaning bath is used.

On the other hand, a dry film-forming method applied in the production of artificial leather or synthetic leather, or a water-free film-forming method for paints, coatings, adhesives, adhesives, films, sheets or sealing materials, etc. Or, in the curing method, at the time of room temperature curing or heat curing, such compounds are hydrolyzed by moisture in the air to generate a so-called free acid such as a carboxylic acid or a sulfonic acid, so that a catalytic effect is expressed. Will be.

Among the above-mentioned latent catalysts, even when salts of amines or ammonia and acids are used as such catalysts, the composition of the present invention comprising such catalysts can be used. The material itself exhibits good stability, and is heated by a heat in a drying process after the wet film formation in a wet film formation or a heating method in a film formation method or a curing method using no water such as a dry film formation. The heat at the time of film formation causes a deammonification reaction or a deamination reaction, such as carboxylic acid, phosphoric acid or sulfonic acid.
That is, a so-called free acid is generated to exhibit a catalytic effect.

Compounds having an acid anhydride group; or the above-mentioned latent catalysts other than amines or salts of ammonia and acids, such as pyridinium salts, quaternary ammonium salts, sulfonium salts, and organic sulfonic acid 2-
Even when a hydroxyalkyl ester, an ester of an organic sulfonic acid and a secondary alcohol, or a compound having a ketal ester group or an acetal ester group is used as the latent catalyst (B), such a catalyst is used. The composition of the present invention itself, which contains, exhibits good stability, and furthermore, water in a drying step after the wet film formation in the wet film formation, or water such as a dry film formation. These compounds are thermally decomposed by heat during film formation by heating in a film forming method or a curing method that is not used, thereby generating various organic acids, thereby exhibiting a catalytic effect.

In other words, when these various catalysts are used, until a wet film forming process or a film forming process or a hardening process that does not use water, such as a dry film forming process, is performed.
This is where the stability of the blended liquid can be maintained without exhibiting a so-called catalytic effect.

Accordingly, such an acid anhydride group-containing compound; or a salt of an amine or ammonia with an acid; or other than these, various compounds as described above function as a so-called latent catalyst. Things.

The type of the latent catalyst (B) used in preparing the crosslinkable polyurethane resin composition according to the present invention depends on the use of the polyurethane resin composition, the processing method, the curing conditions, and the like. Then, it may be appropriately selected.

In particular, when the composition of the present invention is used as an artificial leather to which a wet film forming method using water is applied, and particularly for an ultrafine fiber artificial leather as described later, alkenyl is used. Succinic anhydride is wet-solidified in a non-bonded state between the fiber and the polyurethane resin due to the adhesion inhibitory effect of the alkenyl group, and a space is formed between the fiber and the polyurethane resin, and the artificial leather is further softened. In addition, since it has flexibility, it can be used as a particularly suitable latent catalyst.

The amount of the latent catalyst (B) to be added may be, for example, the acidity of an acidic substance produced by a reaction such as thermal decomposition or hydrolysis, or the basic substance as an effect of each catalyst. It depends on the degree of basicity, etc., or the content of the active ingredient, etc.
With respect to 100 parts by weight of the solid content of the polyurethane resin (A), the range of about 0.05 to about 10 parts by weight, preferably the range of 0.2 to 7.0 parts, and most preferably,
A range of 0.5 to 5.0 parts is appropriate.

As described above, the crosslinkable polyurethane according to the present invention in the form of the component (A) and the component (B) or in the form of the component (A) and the component (B) and the organic solvent is used. A resin composition is obtained, and these various compositions may further include, if necessary, various known and commonly used additives such as a film-forming aid, a surfactant or a compound containing a hydrolyzable silyl group. Or a pigment or the like, or a filler or the like.

Of these various additives, only the above-mentioned typical examples of the hydrolyzable silyl group-containing compound are tetraethyl silicate or a partially hydrolyzed condensate thereof; tetramethyl silicate; A partially hydrolyzed condensate of silicate; or tetraisopropyl silicate or its partially hydrolyzed condensate,
Examples thereof include various alkyl silicates and partial hydrolysis condensates thereof, and various compounds generally referred to as silane coupling, such as the following examples, and polyurethane resins (A )), Various compounds (a-1) and the like which have already been exemplified.

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 crosslinkable urethane resin composition according to the present invention is mainly used for various uses such as artificial leather, synthetic leather, adhesives, sealing agents, adhesives, paints, coating agents, films or sheets. And can be applied.

Here, the above-mentioned artificial leather refers to a polyurethane resin composition and a nonwoven fabric, while synthetic leather refers to a combination of a polyurethane resin composition and a woven or knitted fabric. , Refers to a so-called leather-like sheet, the composition of the present invention, artificial leather, in particular,
Among them, it is suitable for the use of a class of artificial leather called ultrafine nonwoven fabric artificial leather.

That is, the above-mentioned ultrafine fiber non-woven artificial leather is an artificial leather having a deer skin tone and a very supple touch, and a method of making the non-woven fabric which is the base cloth ultra-fine, that is, from sea-island fiber. The nonwoven fabric is impregnated or coated with a polyurethane resin, wet coagulated, and then dissolved with a solvent such as toluene to dissolve and elute the sea component or the island component of the sea-island fiber.

In the nonwoven fabric used for producing such an ultrafine nonwoven fabric artificial leather, the sea component usually contains, for example, a material which is easily eluted with a solvent.
Use polystyrene or polyethylene, etc., as the island component, as a material that is difficult to elute with a solvent, for example, by using polyester or nylon, elute the sea component with a solvent such as heated toluene , Leaving island components
General.

Accordingly, the polyurethane resin used in the artificial leather of the microfiber nonwoven fabric produced by such a method has a high solvent resistance such that it is not eluted by a solvent such as heated toluene and does not swell. However, the cured product obtained from the crosslinkable polyurethane resin composition according to the present invention has a high degree of solvent resistance and satisfies such requirements.

[0098] Synthetic leather is mainly used for automobile seats and various furniture such as sofas and the like, and especially has a durability against sweat, sebum, hair styling or toiletry products. Drastically,
The use of the crosslinkable polyurethane resin composition according to the present invention makes it possible, for the first time, to produce an improved, highly practical synthetic leather.

Further, in polyurethane resin paints and coating agents, improvement in solvent resistance and heat deformation resistance is required, and the composition of the present invention satisfies these requirements. It can be used and applied effectively in the field.

In applications such as adhesives, sealing agents and pressure-sensitive adhesives, it is a standard method to improve strength, adhesion, adhesion, durability, solvent resistance, etc. by cross-linking. Cross-linking methods utilizing groups are common.

For example, an ordinary polyurethane resin having no hydrolyzable silyl group, which is obtained by an ordinary method, is
A two-part type, in which a cross-linking reaction is caused by using a polyisocyanate compound as a cross-linking agent to obtain a cured product, and a urethane prepolymer having an isocyanate group at the terminal is cured by moisture in the air. One-component moisture-curing types, which are used, are widely used.

The conventional system using a polyurethane resin has a drawback that the initial adhesiveness and tackiness cannot be rapidly developed because of the low initial crosslinking rate. Should replace it,
It is also excellent in the initial curing property, a system such as fast expression of the initial adhesiveness and tackiness was required, but the composition of the present invention, these requirements, very, to be used as a match That you can do it.

[0103] Films and sheets are used for:
For example, it is suitable for applications such as marking films, which are said to be pasted paints, and various protective films or protective sheets. Properties, heat resistance, weather resistance, etc. are required, and by using the composition of the present invention, the production of films and sheets in a form that can satisfy these various required properties,
For the first time, it becomes possible.

The crosslinkable polyurethane resin composition according to the present invention is used mainly for various applications such as artificial leather, synthetic leather, adhesives, sealing agents, adhesives, paints, coating agents, films or sheets, etc. In order to obtain a crosslinked product (cured product) of, for example, in the case of artificial leather or synthetic leather using a wet film forming method, a nonwoven fabric,
A so-called base fabric, such as a woven fabric or a knitted fabric, is impregnated or coated with the crosslinkable polyurethane resin composition according to the present invention, and then immersed in water at about 5 to 50 ° C. Alternatively, it is immersed in a DMF-water mixture containing about 5 to 50% DMF for about 3 to 30 minutes, and further washed in water at about 20 to 95 ° C., or in hot or hot water. By performing drying at a temperature of about 60 to 130 ° C. after a so-called washing step, the crosslinking (curing) is completed.

In the case of synthetic leather, paint, coating agent or film or sheet, respectively, according to the dry film-forming method, the crosslinkable polyurethane resin composition according to the present invention may be used with release paper, base cloth, plastic or metal. It is applied on a board or the like, and is heated at a temperature of about 50 to 250 ° C. for several seconds to several hours, thereby comprising a desired cross-linked (cured) polyurethane resin, synthetic leather, paint, and coating, respectively. This is where the agent, film or sheet is obtained.

On the other hand, with respect to adhesives, sealing agents or pressure-sensitive adhesives, the crosslinkable polyurethane resin composition of the present invention is applied to a substrate to be adhered, pressed and subjected to an appropriate heat treatment. Alternatively, curing is performed for an appropriate period of time without performing heat treatment, whereby a method such as crosslinking (curing) is performed.

[0107]

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

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

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

Subsequently, 100 parts of this (A-1) and 0.3 part of triammonium citrate (CAA) as a catalyst for hydrolysis / condensation of a hydrolyzable silyl group were mixed, whereby A desired crosslinkable polyurethane resin composition was prepared.

Next, the composition thus obtained was cast on a release paper so that the thickness of the solvent after volatilization was 30 μm (μm).
A film was prepared by heating for 3 minutes.

Subsequently, the film was heated at room temperature
After leaving it for 3 days, this film was peeled off, and in oleic acid, a component of sweat, in isopropanol, a component of hairdressing agent, and toluene and ethyl acetate as substitutes for toiletry products. When the film was immersed in methanol for 1 hour at room temperature, the appearance of the film did not change at all,
Moreover, no dissolution in solvents was observed at all.

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

Further, the above-mentioned crosslinkable polyurethane resin composition used here does not show an increase in viscosity even after storage for one month at room temperature, and is therefore excellent in stability. It was confirmed that.

Comparative Example 1 0.3 parts of citric acid was replaced with 0.3 parts of CAA.
A control crosslinkable polyurethane resin composition was prepared in the same manner as in Example 1 except that the mixture was changed to (A-1).

Thereafter, a film was prepared on release paper in the same manner as in Example 1, and the thus obtained film was evaluated and evaluated for solvent resistance, sweat resistance and hair styling resistance. As in the case of Example 1, it was excellent.

However, the above-mentioned crosslinkable polyurethane resin composition used here increases in viscosity after storage for one month at room temperature, and becomes a semi-gel state having almost no fluidity. It was confirmed that the storage stability was poor.

Comparative Example 2 Same as Example 1 except that 2 parts of 1,4-butanediol were used instead of 4 parts of γ- (2-aminoethyl) aminopropylmethyldimethoxysilane. By carrying out the synthesis reaction, a non-hydrolyzable silyl group-free polyurethane resin having a non-volatile content of 30.0% and a Brookfield viscosity at 25 ° C. of 980 ps was obtained. A solution was obtained. Hereinafter, this polyurethane resin solution is referred to as (P-1)
Abbreviated.

Next, except that this (P-1) was changed to use, the same procedure as in Example 1 was carried out on release paper.
A film was prepared.

Subsequently, the film was heated at room temperature
After letting it stand for 3 days, peel off the film,
Each was immersed in oleic acid, a component of sweat, in isopropanol, a component of a hairdressing agent, and in toluene, ethyl acetate, and methanol as substitutes for toiletries, for 1 hour at room temperature. . As a result, the film was completely dissolved or the shape was lost, and the film was inferior in chemical resistance and solvent resistance, among others.

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

Next, 22 parts of hydrogenated MDI and 0.005 parts of dibutyltin dilaurate (DBTDL) as a urethanization catalyst were added to the mixture so that the NCO / OH equivalent ratio was 1.7 / 1.0. And at 85 ° C,
The reaction was carried out for 3 hours, and the NCO equivalent was measured. As a result, it was confirmed that the NCO equivalent reached the theoretical value.

Subsequently, by charging 300 parts of DMF, the nonvolatile content was adjusted to 25%.
While maintaining the temperature at 35 ° C., 4 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane and 2 parts of isophoronediamine (IPDA) were sequentially charged with stirring.

After stirring for 15 minutes, DMF was added.
And 151 parts of methanol and 10 parts of methanol, and then stirred for one hour to dissolve, thereby obtaining a non-volatile content of 20% and a Brookfield viscosity at 25 ° C. of 70 ps. A solution of a polyurethane resin having a hydrolyzable silyl group in a side chain was obtained. Hereinafter, this polyurethane resin solution is referred to as (A-2)
Abbreviated.

Next, in 100 parts of (A-2), D
By adding MF, the non-volatile content is reduced to 15%,
Furthermore, 0.3 parts of an alkenyl succinic anhydride having 16 to 18 carbon atoms of an alkenyl group as a catalyst for hydrolysis / condensation of a hydrolyzable silyl group is added, and the mixture is mixed. A crosslinkable polyurethane resin composition was prepared.

Subsequently, the composition was allowed to stand at room temperature for 1 hour.
After storage for a period of months, only a slight increase in viscosity was observed, confirming that the storage stability was extremely excellent.

Thereafter, this composition was impregnated into a non-woven fabric consisting of sea-island fibers in which the sea component was polystyrene 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.

Thereafter, the plate was thoroughly washed in warm water of 40 ° C., dried in a hot air drier at 100 ° C. for 30 minutes, and immersed in toluene heated to 90 ° C. for 1 hour. As a result, the polystyrene portion of the sea-island fiber was eluted.

Subsequently, the resultant was washed with hot water at 90 ° C. for 1 hour and dried at 80 ° C. for 30 minutes to obtain an ultrafine fiber non-woven artificial leather.

The artificial leather thus obtained had very good solvent resistance and the like such that the thickness retention after the toluene treatment was 90%. When the cross section of the artificial leather was observed with a microscope, the polystyrene forming the islands-in-the-sea fibers was eluted, and on the other hand, it was recognized that the polyurethane resin remained almost completely. .

Further, a space is formed between the polyurethane resin and the fiber, and the artificial leather obtained here has a very soft, supple, and intended texture of deer skin. Was.

Comparative Example 3 In place of 0.3 part of the alkenyl succinic anhydride having 16 to 18 carbon atoms of the alkenyl group, 0.3 part of the alkenyl succinic acid having 16 to 18 carbon atoms of the alkenyl group was replaced by ( A
Example 2 except that the mixture was changed to -2).
In the same manner as in the above, a control crosslinkable polyurethane resin composition was prepared.

Next, a sea-island fiber nonwoven fabric was impregnated in the same manner as in Example 2 except that the crosslinkable polyurethane resin composition was changed to use, and then the treatment was performed in the same manner as in Example 2. Thus, artificial leather was prepared.

Subsequently, the artificial leather thus obtained had extremely good solvent resistance such that the thickness retention after the toluene treatment was 90%. In addition, when the cross section of the artificial leather was observed with a microscope, it was confirmed that the polystyrene that had formed the sea-island fibers was eluted, while the polyurethane resin was almost completely left. .

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

However, after storage for one month at room temperature, the above-mentioned crosslinkable polyurethane resin composition used here increased in viscosity and became a semi-gel state having almost no fluidity. It was confirmed that the storage stability was poor.

Comparative Example 4 The synthesis reaction was carried out in the same manner as in Example 2 except that 3 parts of IPDA was used instead of 4 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane. , The non-volatile content is 20.0
% And a control polyurethane solution having no hydrolyzable silyl groups and a Brookfield viscosity at 25 ° C. of 68 ps. Hereinafter, this polyurethane resin solution is abbreviated as (P-2).

Then, an ultrafine fiber non-woven fabric artificial leather was prepared in the same manner as in Example 2 except that (P-2) was used.

The artificial leather for control obtained in this manner had a low thickness retention of 45% after toluene treatment and was inferior in solvent resistance. Also, when the cross section of the artificial leather for comparison was observed with a microscope, the polystyrene that constituted the sea-island fiber was eluted,
It was confirmed that the polyurethane resin was also almost eluted, and only a small amount remained.

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

Example 3 75 parts of PC-2000, 10 parts of 1,4-butanediol, and 78 parts of toluene were placed in a 1-liter four-necked flask and dissolved with stirring.

Then, 51 parts of hydrogenated MDI and 22 parts of isophorone diisocyanate (IPDI) were added to the mixture so that the NCO / OH equivalent ratio was 2.0 / 1.0.
Of DBTL as a urethanization catalyst.
After 006 parts were also charged, the temperature was raised to 85 ° C., the reaction was continued at the same temperature for 5 hours, and the NCO equivalent was measured to confirm that the theoretical value had been reached.

Thereafter, 327 parts of DMF and 140 parts of toluene were added to adjust the nonvolatile content to 25%. Further, while maintaining the urethane prepolymer solution at 35 ° C. and stirring, 5.4 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane and IPD
19 parts of A were sequentially charged.

After stirring for 15 minutes,
By adding 140 parts of DMF and 10 parts of methanol, stirring and dissolving for 1 hour, the non-volatile content is 20%, and the Brookfield viscosity at 25 ° C. is 80 ps. A solution of a polyurethane resin having a hydrolyzable silyl group in the chain was obtained.
Hereinafter, this polyurethane resin solution is abbreviated as (A-3).

Next, one of the thus obtained (A-3)
To 00 parts, 0.2 part of ammonium phthalate as a catalyst for hydrolysis / condensation of a hydrolyzable silyl group was added and mixed to prepare a target crosslinkable polyurethane resin composition.

Subsequently, the same procedure as in Example 1 was carried out except that the composition was changed to use this composition.
A film was produced.

Thereafter, this film was heated at room temperature.
After leaving for 3 days, the film was peeled off and immersed in gasoline, isopropanol, toluene, ethyl acetate and methanol for 1 hour at room temperature, respectively, the appearance of this film changed completely. Was not observed, and no dissolution in solvents was observed at all.

The crosslinkable polyurethane resin composition used in this example hardly shows an increase in viscosity even when stored at room temperature for one month. It was confirmed that it was excellent.

Comparative Example 5 In the same manner as in Example 3 except that 0.2 parts of phthalic acid was changed to (A-3) instead of 0.2 parts of ammonium phthalate. A control crosslinkable polyurethane resin composition was prepared. Next, in the same manner as in Example 1, a film was formed on release paper.

Subsequently, this film was heated at room temperature for 3 hours.
After leaving for a day, the film was peeled off and immersed in gasoline, isopropanol, toluene, ethyl acetate and methanol for 1 hour at room temperature, respectively, the appearance of this film changed completely. Was not observed, and no dissolution in solvents was observed at all.

However, after storage for one month at room temperature, the above-mentioned crosslinkable polyurethane resin composition used here increased in viscosity and became a semi-gel state having almost no fluidity. It was confirmed that the storage stability was poor.

Comparative Example 6 The procedure of Example 3 was repeated, except that 5 parts of IPDA was used instead of 6.5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane. By performing the synthesis reaction, the non-volatile content becomes 20.0%.
%, And a solution of a control polyurethane resin having a Brookfield viscosity at 25 ° C. of 85 ps and having no hydrolyzable silyl group was obtained. Hereinafter, this polyurethane resin solution is abbreviated as (P-3).

Next, a film was prepared in the same manner as in Example 3 except that (P-3) was used, and the solvent resistance was evaluated and determined in the same manner as in Example 3.
The film was completely dissolved or lost its shape, resulting in poor solvent resistance.

Example 4 250 parts of PC-2000, 12 parts of 1,4-butanediol and 162 parts of toluene were put in a 1-liter four-necked flask and dissolved with stirring.

Next, 116 parts of IPDI and 0.015 part of DBTDL as a urethanization catalyst were added to the mixture so that the NCO / OH equivalent ratio became 2.0 / 1.0, and 95% of the mixture was added. At 8 ° C. for 8 hours.
When the NCO equivalent was measured, it was confirmed that the NCO equivalent reached the theoretical value.

Subsequently, 127 parts of n-butyl acetate and 124 parts of isopropanol (IPA) were introduced,
While maintaining the temperature at 35 ° C. and stirring, 13 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane,
21 parts of IPDA were sequentially charged.

After stirring for 15 minutes, acetic acid n-
By injecting 60 parts of butyl and 50 parts of IPA and further stirring and dissolving for 1 hour, the non-volatile content is 45% and the Brookfield viscosity at 25 ° C. is 62 ps. A solution of a polyurethane resin having a hydrolyzable silyl group in the chain was obtained. Hereinafter, this polyurethane resin solution is abbreviated as (A-4).

Subsequently, 100 parts of this (A-4) was mixed with 0.3 part of ammonium malate as a catalyst for hydrolysis / condensation of a hydrolyzable silyl group, thereby achieving the object. A crosslinkable polyurethane resin composition was prepared.

The composition was applied on a chromate-treated aluminum plate using a bar coater so that the dry film thickness was about 40 μm.
After baking for minutes, the desired cured coating film was obtained. After leaving this coating film at room temperature for 3 days, it is evaluated that various properties are evaluated and judged to have excellent mechanical strength and solvent resistance as described below. confirmed.

Erichsen value 7 mm or more Impact resistance 50 cm or more (1/2 inch / 500 g) Xylene rubbing No abnormality after 30 cycles (load: 1.1 kg)

The crosslinkable polyurethane resin composition used here does not show an increase in viscosity even after storage at room temperature for two months, and therefore has excellent stability. Was confirmed.

Comparative Example 7 A control was carried out in the same manner as in Example 4 except that the same amount of malic acid was mixed with (A-4) in place of 0.3 part of ammonium malate. A crosslinkable polyurethane resin composition for use was prepared.

Thereafter, a cured coating film was prepared and evaluated in the same manner as in Example 4. When the film was evaluated and evaluated, the mechanical strength and solvent resistance were the same as in the cured film obtained in Example 4. It was something that was excellent.

However, the above-mentioned crosslinkable polyurethane resin composition used here increased in viscosity after storage for 2 months at room temperature, and became a semi-gel state having almost no fluidity. It was confirmed that the storage stability was poor.

Example 5 100 parts of sebacic acid / isophthalic acid / ethylene glycol / neopentyl glycol polyesterdiol having a number average molecular weight of 2,000 and 3 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane And M
49 parts of DI, 0.05 parts of stannous octoate, and 110 parts of toluene were mixed and reacted at 70 ° C. for 2 hours.

Subsequently, 263 of methyl ethyl ketone was added.
And 8 parts of ethylene glycol were added and the reaction was allowed to continue at 70 ° C. for 12 hours.
By adding 3 parts of methanol and performing the reaction at 60 ° C. for 1 hour, the nonvolatile content becomes 30%.
%, And a solution of a polyurethane resin having a hydrolyzable silyl group in the side chain of the molecule and having a Brookfield viscosity at 25 ° C. of 70 ps was obtained. Hereinafter, this polyurethane resin solution is abbreviated as (A-5).

Next, one of the thus obtained (A-5)
To 00 parts, 0.2 part of maleic anhydride as a catalyst for hydrolysis / condensation of a hydrolyzable silyl group was added and mixed to prepare a desired crosslinkable polyurethane resin composition.

On a steel plate degreased with acetone, the polyurethane resin composition was coated with a bar coater at an application amount of 6 g / g.
It was applied as a m ^2. The sheet was heated in a drier at 195 ° C. for 1 minute, and then immediately passed through a hot roll at 120 ° C. to laminate a polyvinyl chloride (PVC) sheet.

After leaving at room temperature for 24 hours,
The peel strength of the PVC sheet was examined. As a result, the peel strength was as high as 7.5 kg / inch (inch), and it was found that the adhesive strength was extremely excellent.

The crosslinkable polyurethane resin composition used in this example hardly increases in viscosity even when it is stored at room temperature for one month. It was confirmed that the composition had excellent stability.

Comparative Example 8 The procedure of Example 5 was repeated, except that 0.2 parts of maleic anhydride was used instead of 0.2 parts of maleic anhydride and (A-5) was mixed. A control crosslinkable polyurethane resin composition was prepared.

Next, the adhesion of the steel sheet was examined in the same manner as in Example 5. As a result, the peel strength was as large as 7.3 kg / inch, and it was found that the steel sheet had extremely excellent adhesion to steel sheets.

However, after storage for one month at room temperature, the above-mentioned crosslinkable polyurethane resin composition used here increased in viscosity and became a semi-gel state having almost no fluidity. It was confirmed that the storage stability was poor.

Example 6 A 2-liter four-necked flask was charged with a number average molecular weight of 3,0.
397 parts of a polypropylene diol having a number average molecular weight of 2,000 (1,6
-Hexanediol / neopentylglycol / adipic acid) and 147 parts of dimethylolheptane and 269 parts of ethyl acetate were added and uniformly dissolved.

Next, stannous octylate was added at a concentration of 50%.
ppm, then add 216 parts of tolylene diisocyanate (TDI) in portions at 40 ° C. until the concentration of isocyanate groups becomes constant.
The reaction was performed at 5 ° C. After that, 43 of ethyl acetate
By adding 8 parts and 53 parts of toluene, Resin 1 having a terminal isocyanate group and having a non-volatile content of 54.4% was obtained.

In a two-liter four-necked flask, 431 of polypropylenediol having a number average molecular weight of 3,000 were added.
And 154 parts of a polyesterdiol (1,6-hexanediol-neopentyl glycol-adipic acid) having a number average molecular weight of 2,000, 154 parts of dimethylol heptane and 246 parts of toluene Was added to dissolve uniformly.

Next, DBTDL was added at a concentration of 50 ppm.
And then at 40 ° C., T
The reaction was carried out at 75 ° C. until 299 parts of DI was added in portions until the concentration of isocyanate groups became constant. Thereafter, 198 parts of toluene was added to obtain Resin 2 having a non-volatile content of 70.0% and having a terminal isocyanate group.

Thereafter, 132 parts of resin 1 and resin 2
And further stirred vigorously at 30 to 40 ° C., and gradually added 24 parts of γ-aminopropyltrimethoxysilane. After the addition, the mixture was stirred for 30 minutes. . Non-volatile content is 63% and 25 ° C
A solution of a polyurethane resin having a Brookfield viscosity of 25 ps and having a hydrolyzable silyl group at the terminal of the molecule was obtained. The solution of this polyurethane resin is referred to as (A-
Abbreviated as 6).

Subsequently, 100 parts of this (A-6) was added with a styrene / maleic anhydride copolymer (styrene / maleic anhydride = 1/1) as a catalyst for hydrolysis / condensation of a hydrolyzable silyl group. And the inorganic filler has a particle diameter of 15 μm, respectively.
m and less than about 96%, 62 parts of a clay mineral having a particle diameter of 15 μm or less and about 65%, and 12 parts of acetone. Was added and mixed to obtain a polyurethane resin composition having a non-volatile content of 73% and a Brookfield viscosity at 25 ° C. of 140 ps and having a hydrolyzable silyl group at the terminal of the molecule.

Next, this polyurethane resin composition was applied to a slatted plate using a comb iron, and was heated at a temperature of 23 ° C. and a relative humidity of 65%.
After standing for a minute, the PVC sheet was clamped using a hand roll.

The processed product thus obtained was subjected to an evaluation judgment test according to the following procedure, and various adhesive strengths were measured.

<Test Method and Evaluation Criteria>

Peel strength: After pressing, the temperature was 23 ° C.
After curing for a predetermined period of time under the condition of a relative humidity of 65%, the PVC sheet is cut into a size of 1 inch (width) × 10 cm (length), thereby forming a test piece. Did it.

However, the peel test was carried out using Tensilon at an angle of 180 ° in an atmosphere at a temperature of 23 ° C. and a relative humidity of 65%.

Initial adhesive strength: measured after 20 minutes of curing time. Adhesion under normal conditions: Measured 72 hours after curing time.

The result of the evaluation was that the initial adhesive strength was 1.0K.
g / inch and an adhesive force in a normal state of 2.4 kg.
/ Inch, which proved to be a processed product having extremely excellent initial and normal adhesion.

The crosslinkable polyurethane resin composition used in this example hardly increases in viscosity even when it is stored at room temperature for one month. It was confirmed that the composition had excellent stability.

Comparative Example 9 A styrene / maleic anhydride copolymer (styrene / maleic anhydride = 1/1 parts by weight) was replaced with 1.2 parts of a styrene / maleic anhydride copolymer (styrene / maleic anhydride). 1.2 parts by weight of maleic acid = 1/1)
A control crosslinkable polyurethane resin composition was prepared in the same manner as in Example 6, except that the mixture was changed to (A-6). Next, the initial and normal adhesion were examined in the same manner as in Example 6.

As a result, the initial adhesive strength was 0.9 kg / in.
ch, the normal state adhesive strength was 2.3 kg / inch, and it was found that the processed product had extremely excellent initial and normal state adhesiveness.

However, the above-mentioned crosslinkable polyurethane resin composition used here increased in viscosity after storage for one month at room temperature, and became a semi-gel state having almost no fluidity. It was confirmed that the storage stability was poor.

[0192]

The crosslinkable polyurethane resin composition according to the present invention is such that the crosslinking reaction proceeds easily by moisture or moisture, and a strong crosslinked cured product is formed.

The composition is also excellent in storage stability. Conventionally, the viscosity of the composition is greatly increased or gelled during the period from compounding to use. There was a problem of poor stability,
The present invention is able to solve these problems brilliantly.

Further, the composition of the present invention has an extremely good cross-linking curability and, in addition, the cured product is excellent, in particular, in strength, adhesive strength, durability, solvent resistance and chemical resistance. From where it is, mainly artificial leather, synthetic leather, adhesives, adhesives, sealing agents, paints,
It is extremely practical for applications such as coating agents or films or sheets.

Claims (3)

[Claims] 1. A polyurethane resin (A) having a hydrolyzable silyl group at a side chain and / or a terminal, and a latent catalyst (B) for hydrolysis or condensation of the hydrolyzable silyl group.
And a crosslinkable polyurethane resin composition. 2. The composition according to claim 1, wherein the latent catalyst (B) is a compound having an acid anhydride group. 3. The method according to claim 1, wherein the latent catalyst (B) comprises an acid,
The composition according to claim 1, which is a salt with an amine or ammonia.