JPS61276812A - Curable composition - Google Patents

Abstract

PURPOSE:To provide the titled composition composed of a water-soluble polymer containing active hydrogen, a mixture of a specific unsaturated isocyanate and a silane-coupling agent and a peroxide and having long pot life and excellent workability, adhesive strength, water-resistance and stability. CONSTITUTION:The objective composition is composed of (A) a water-soluble polymer containing active hydrogen (preferably PVA) and/or aqueous emulsion, (B) a mixture of (b1) an unsaturated isocyanate containing <=1 equivalent of NCO group and >=1 equivalent of (meth)acryloyl group in a molecule (e.g. a reaction product of 2-hydroxyethyl methacrylate and 2,4-tolylene diisocyanate, etc.) and (b2) a silane-coupling agent (preferably vinyltriethoxysilane) and (C) a peroxide (e.g. methyl ethyl ketone peroxide). The composition may be further incorporated with (D) a monomer copolymerizable with the above unsaturated isocyanate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a curable composition having a long pot life, excellent workability, improved adhesive strength, water resistance and stability. It is particularly suitable as an adhesive.

[Conventional technology]

Currently, methods for forming a film from a water-soluble polymer and/or aqueous emulsion containing active hydrogen and curing it include adding a polyvalent isocyanate compound to the water-soluble polymer and/or aqueous emulsion containing active hydrogen; , a method of adding a polyvalent aziridine compound, etc. are known. However, the method of adding a polyvalent isocyanate compound to a water-soluble polymer having active hydrogen and/or an aqueous emulsion has the disadvantage that the pot life of the curable composition is short. As a way to improve this shortcoming,
It has been proposed to use a polyvalent isocyanate compound dissolved in a hydrophobic solvent. This method certainly improves the stability and water resistance of the adhesive composition, but on the other hand, the added solvent remains in the adhesive layer.
Acts as a plasticizer and has a negative effect on adhesive strength.

Furthermore, systems containing polyvalent aziridine compounds have the drawback of being relatively expensive.

[Problem that the invention seeks to solve]

The ability to cure adhesives made of water-soluble polymers containing active hydrogen and/or water-based emulsions at room temperature, and to improve their physical properties without significantly increasing costs, will help expand the use of water-based emulsions. This is extremely useful.

The present inventors have conducted intensive studies in view of the above-mentioned circumstances, and have found that a water-soluble polymer having active hydrogen and/or an aqueous emulsion contains an isocyanate group of 1 equivalent or less and an acryloyl group of 1 equivalent or more in one molecule. A composition containing a mixture of an unsaturated isocyanate containing a group or a methacryloyl group and a silane coupling agent dissolved in a radically polymerizable monomer and a peroxide can cure a film containing active hydrogen at room temperature. ,
Moreover, no low-molecular compounds that act as plasticizers and degrade the physical properties of the film remain in the cured film. Furthermore, they found that it is low in cost, has excellent workability, and has improved pore drive and adhesive strength, leading to the completion of the present invention.

[Means for solving problems]

That is, the present invention provides 1) (1) a water-soluble polymer having active hydrogen and/or
or an aqueous emulsion.

(2) A mixture of an unsaturated isocyanate and a silane coupling agent containing 1 equivalent or less of isocyanate group and 1 equivalent or more of acryloyl group or methacryloyl group in one molecule (3) Curable composition consisting of peroxide and 2) (1) a water-soluble polymer having active hydrogen and/or
or an aqueous emulsion.

(2) A mixture of an unsaturated isocyanate and a silane coupling agent containing 1 equivalent or less of isocyanate group and 1 equivalent or more of acryloyl group or methacryloyl group in one molecule (3) Together with the above unsaturated isocyanate This invention relates to a curable composition comprising polymerizable monomers (4) peroxide.

[Effect]

In the curable composition of the present invention, an unsaturated isocyanate reacts with a polymer or a silane coupling agent constituting a water-soluble polymer aqueous solution and/or an aqueous emulsion with an isocyanate group in the unsaturated isocyanate, and a silane coupling agent. The ring agent reacts with the inorganic filler with its alkoxy group, and then the (
meth) Acryloyl groups polymerize together, or copolymerize with monomers, so that j? It is presumed that the IJ polymer is cured by crosslinking.

The configuration of the present invention will be explained in detail below.

The water-soluble polymer having active hydrogen used in the present invention is selected from PVA (polyvinyl alcohol) or its modified products and derivatives, CMC (cargomethylcellulose) polyacrylate, alginate, lignin sulfonate, etc. One or more of these can be used as desired. However, in the present invention, P is used as a water-soluble polymer.
Preferably, VA or a modified product or derivative thereof is used.

The aqueous emulsion used in the present invention refers to a commonly known aqueous dispersion of a polymer, and the monomers constituting the polymer component are not particularly limited, such as ethylene, vinyl acetate, vinyl propionate, Methacrylic esters such as methyl methacrylate, acrylic esters such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylonitrile, styrene, chlorostyrene, vinyltoluene, vinyl chloride, vinylidene chloride, acrylamide, methylolacrylamide, 2- Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2
-Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, butadiene, chloroglene, isogrene, imbutylene, and the like.

Among the aqueous emulsions containing the above monomers as polymer components, in the present invention, functional groups reactive with the isocyanate groups of unsaturated isocyanates, or functional groups reactive with silane coupling agents, such as hydroxyl groups, carboxylic It is preferable to use an emulsion of a polymer having a functional group such as a group or an acid amide group, or an emulsion using polyvinyl alcohol, water-soluble cellulose esters, or the like as a protective colloid.

The unsaturated isocyanate used in the present invention is 1
It contains 1 equivalent or less of incyanate group and 1 equivalent or more of acryloyl group or methacryloyl group [hereinafter abbreviated as (meth)acryloyl group] in the molecule, and one example is the one shown by the following formula. be able to.

O In the present invention, the unsaturated isocyanate has the role of increasing the adhesive strength of the composition and improving the water resistance and heat resistance of the film.

When using an unsaturated isocyanate containing more than 1 equivalent of isocyanate group in one molecule, or when using an unsaturated isocyanate group containing less than 1 equivalent of (meth)acryloyl group in one molecule. is undesirable because it has a tendency to become rubbery in a short time after mixing.

Various types of unsaturated isocyanates are known, but from a practical standpoint, those synthesized by an addition reaction between an unsaturated monoalcohol containing a (meth)acryloyl group and a polyvalent isocyanate compound are used. It is preferable.

Examples of the unsaturated monoalcohol containing a (meth)acryloyl group include 2-hydroxyethyl acrylate, 2
-Hydroxypropyl acrylate, trimethylol gulo gun diacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, trimethylol gulo gun dimethacrylate, and the like.

As the polyvalent isocyanate compound, for example, 2.4-
tolylene diisocyanate, 2.6-tolylene diisocyanate, 2,4-tolylene diisocyanate and 2.
6-) Mixture with lylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, noclaphenylene diisocyanate, xylylene diisocyanate, inphorone diisocyanate, 1,6-hexamethylene Examples include diisocyanate, hydrogenated xylylene diisocyanate, oligomers having isocyanate groups at both ends (reaction product of 1 mole of oligomers having hydroxyl groups at both ends and 2 moles of polyvalent isocyanate, etc.).

The unsaturated isocyanate used in the present invention contains 1 to 1.8 mol, preferably 1 to 1.4 mol, of an unsaturated monoalcohol containing a (meth)acryloyl group per 1 mol of the polyvalent isocyanate compound. It is produced by reacting within the range of

Synthesis of unsaturated isocyanates includes acrylic esters,
In monomers such as methacrylic acid esters, styrene, aromatic vinyl compounds such as vinyltoluene, ethyl acetate,
An unsaturated monoalcohol containing a (meth)acryloyl group is added dropwise to a polyvalent isocyanate compound in a solvent such as methyl ethyl ketone or toluene, or in a plasticizer such as dibutyl phthalate, dioctyl phthalate, or diethyl acrylate phthalate, to cause an addition reaction. The method is advantageous because it can be used as it is as a monomer solution, solvent solution or plasticizer solution, but it can be used without using monomers, solvents or plasticizers. A monoalcohol may also be reacted. At this time, it is preferable to use a urethanization catalyst such as a tertiary amine or an organic compound of tin.

In the unsaturated isocyanate used in the present invention, the isocyanate group and the (meth)acryloyl group do not necessarily have to be equimolar. For example, polyvalent isocyanate 1
1 to 1.8 moles of an unsaturated monoalcohol having a (meth)acryloyl group.
Any material containing a meth)acryloyl group may be used. For example, if we use 2-hydroxyethyl methacrylate as an unsaturated monoalcohol having a (meth)acryloyl group and 2,4-tolylene diisocyanate as a polyvalent isocyanate compound, the reaction will be A mixture of monomethacrylate and dimethacrylate is formed, and this mixture may be used in the present invention.

(a) Monomethacrylate O (b) Dimethacrylate N-C-0-CI (2-CH2-0-C-C-CH2O) The unsaturated isocyanate containing dimethacrylate as described above is water-soluble and has active hydrogen. It not only has the advantage of improving the polar specific velocity of films formed from aqueous emulsions containing polymers, and also improves physical properties such as the hardness and adhesive strength (especially water-resistant adhesive strength) of cured films, but also improves the physical properties of cured films such as hardness and adhesive strength (especially water-resistant adhesive strength). It has the advantage of protecting the isocyanate groups and increasing the reaction between the isocyanate groups and the polymer constituting the aqueous emulsion containing the water-soluble polymer having active hydrogen.

Examples of the silane coupling agent used in the present invention include vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-glycidoxypropylmethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Typical examples include chloropropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-ureidoglopyltriethoxysilane.

Among these, sulfinyltriethoxysilane and vinyltris (β
-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, and the like are particularly preferred.

Furthermore, in the present invention, the silane coupling agent and the unsaturated isocyanate may be used as they are or mixed in any proportion in the presence of monomers copolymerizable with the unsaturated isocyanate; The ratio of NAT and silane coupling agent is preferably 5:95 to 95:5.

The amount of the mixture of unsaturated isocyanate and silane coupling agent to be added varies depending on the purpose of use of the curable composition, so it cannot be determined unconditionally, but it is generally used for water-soluble polymers having active hydrogen and/or solids of aqueous emulsions. Minutes (
Resin content) The appropriate amount is 3 to 200 parts by weight, preferably 5 to 150 parts by weight, based on 100 parts by weight. That is,
If the amount of unsaturated isocyanate and silane coupling agent is less than 3 parts by weight, the effect of addition will be small, and
When the amount is more than 1 part by weight, the effect of increasing the amount is no longer observed.

In the present invention, a mixture of an unsaturated isocyanate and a silane coupling agent is combined with a hydrophobic radically polymerizable monomer (that is, a mixture of an unsaturated isocyanate and a silane coupling agent that exhibits almost no mutual solubility with water). can be blended by being dissolved in a mutually soluble monomer) (hereinafter, this monomer will simply be referred to as a "monomer").

By using this "monomer", the mixture of unsaturated isocyanate and silane coupling agent can be uniformly dispersed in the water-soluble polymer having active hydrogen and/or the aqueous emulsion, and furthermore, the mixture of unsaturated isocyanate and silane coupling agent can be dispersed uniformly in the water-soluble polymer having active hydrogen and/or the aqueous emulsion. It is also possible to protect the isocyanate groups from water by reducing contact with water by emulsification. Further, by using a mixture of an unsaturated isocyanate and a silane coupling agent dissolved in the above-mentioned "monomer", an adhesive solution which is stable and has excellent water resistance can be obtained. The term "monomer" that dissolves the mixture of unsaturated isocyanate and 7-run coupling agent means a substance that is normally liquid, undergoes radical polymerization with peroxides, and has low solubility in water.

Typical monomers include methyl methacrylate, ethyl methacrylate, isobutyl methacrylate,
n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate), 2-1-tylhexyl methacrylate, nonyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, phenoxyethyl acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate), 1,6-hexanesiol dimethacrylate, trimethylolgulonotrimethacrylate, Examples include (meth)acrylic acid esters such as trimethylolpropane triacrylate, aromatic vinyl compounds such as styrene, vinyltoluene, and the like. Two or more of these "monomers" may be used in combination.

The combination of "monomers" not only increases the storage stability of the unsaturated isocyanate, but also polymerizes with peroxide when the curable composition cures, creating a low-molecular compound that acts as a plasticizer in the adhesive layer. Since no residue remains, it has the advantage of improving physical properties such as adhesive strength.

The amount of "monomers" is unsaturated isocyanate: 100%
0 to 150 parts by weight, preferably 0 to 100 parts by weight
within the range of parts by weight, and the ratio of the compound having an isocyanate group to the "monomer" is 10:90 to 95:5
It is preferable that The amount of “monomers” is 15
If the amount is more than 0 parts by weight, the effect of compounding the isocyanate group-containing compound is diminished, and it tends to be difficult to improve the physical properties of the cured product, such as the adhesion.

In addition to hydrogen peroxide, the peroxides used in the present invention include ketone peroxides such as methyl ethyl ketone mother oxide, cyclohexano/peroxide, methyl isobutyl ketone peroxide, and methyl isobutyl ketone peroxide. -oxide, hydrogen oxides such as t-butyl hydrogen and monooxide, and t-butyl peroxide-2-ethylhexoate. Examples include organic peroxides such as acyl oxyesters such as benzoyl oxide, lauroyl 4-oxide, and 2,5-dichlorobenzoyl oxide.

These peroxides exhibit sufficient curing action even when used alone, and in order to further accelerate curing, it is preferable to use an organic peroxide and a curing accelerator in combination. For example, when using an organic peroxide, especially a hydroperoxide (keymenhypyrono-9-oxide) as the organic peroxide, curing is accelerated when this is used in combination with a curing accelerator of cobalt naphthenate. In addition, it has a long pot life and is convenient to use.

The amount of peroxide added is 0.1 parts by weight per 100 parts by weight of the solid content (resin content) of the water-soluble polymer having active hydrogen and/or the aqueous emulsion, and the total weight of "Nanatsuma".
A suitable range is 10 parts by weight, preferably 0.5 to 5 parts by weight. If the amount of peroxide is less than 0.1 parts by weight, curing properties at room temperature will be insufficient, while if the amount of peroxide is more than 10 parts by weight, no effect will be observed by increasing the amount. However, it has the drawbacks of high cost and deterioration of the physical properties of the cured product.

When a curing accelerator is used in combination with a peroxide, the amount of curing accelerator used depends on the solid content (resin content) and "monomer" of the water-soluble polymer having active hydrogen and/or the aqueous emulsion.
It is preferable that the amount is 0.01 to 10 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the total weight of the above.

The curable composition of the present invention is prepared by uniformly mixing a water-soluble polymer and/or an aqueous emulsion, an unsaturated isocyanate, a silane coupling agent, "monomers", and a peroxide. There is no particular restriction on the order of addition. When using peroxide with a curing accelerator,
A curing accelerator may be blended with the unsaturated isocyanate in advance.The composition of the present invention hardly progresses in curing while moisture is present, and only after the moisture is removed by dehydration or evaporation. Because it hardens, it has a long pot life and good workability. It also increases the hardness of the film formed from water-soluble polymers and/or water-based emulsions containing active hydrogen, and improves solvent resistance and creep resistance. It is useful as paints and adhesives because it improves properties and has extremely good adhesion to substrates.

The composition of the present invention is a (meth)acryloyl group produced by grafting an unsaturated isocyanate onto a water-soluble polymer having active hydrogen and/or a polymer constituting an aqueous emulsion using an isocyanate group in the unsaturated isocyanate. They polymerize together, or copolymerize with a silane curing agent or "monomer" having a vinyl group, thereby crosslinking the polymers and curing them.

Furthermore, the graft copolymerized silane coupling agent not only contributes to crosslinking between polymers, but also promotes the bonding between the inorganic filler and the polymer, thereby improving the strength of the cured composition.

Furthermore, in the present invention, if necessary, a formalin-based condensation resin can be blended. Here, formalin-based condensation resin refers to urea-formalin-based condensation resin, urea-melamine-based condensation resin,
These include formalin-based condensed resins, phenol-formalin-based condensed resins, etc., and among these, amine-based condensed resins are particularly preferred. The amount of formalin-based condensation resin to be added is determined at will.

Furthermore, by incorporating a surfactant in the present invention, water resistance is improved, and changes in water resistance over time are reduced.
Furthermore, the viscosity becomes stable, and the hardening agent solution becomes an emulsion. Therefore, the usage time of the curable composition of the present invention can be significantly extended.

As the surfactant to be used, nonionic and anionic surfactants are effective, with anionic surfactants being particularly effective. Any type of anionic surfactant used here is effective, regardless of its structural components, but examples include caldate salts (fatty acid salt soaps, etc.), sulfuric ester salts (higher alcohol sulfuric acid salts, etc.). ester salts, sulfated oils, sulfated fatty acid esters, sulfated olefins, etc.], sulfonates (alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates,
Pont-T, aerosol OT, lignin sulfonate, etc.), phosphate ester salts (higher alcohol phosphate ester salts, etc.).

The blending amount of the surfactant is 0.1 based on the solid content of the water-soluble polymer having active hydrogen and/or the aqueous emulsion.
-10 weight equivalent, particularly preferably 0.1-4
It is a weight board. If it is too small, it will be ineffective,
If the amount is too large, phenomena such as agglomeration of the emulsion may occur. Regarding the reason why stability is improved when an anionic surfactant is added to the cured composition of the present invention,
Although the details are unknown, these surfactants are adsorbed on the surface of the emulsion particles of unsaturated isocyanate and prevent direct contact between unsaturated isocyanate and water. This is thought to slow down the reaction and stabilize the emulsion.

Furthermore, an extender can be added to the cured composition of the present invention, if necessary. As the bulking agent, wheat flour,
Starch, defatted soybean flour, etc. can be used, but among these, wheat flour and starches are more preferable because they are imparted with hydrophobicity by unsaturated isocyanates, and do not gelatinize in cold water, but become gelatinized and viscous by heating during adhesion. .

Further, fillers can also be blended into the curable composition of the present invention. In addition to inorganic fillers such as clay, kaori, talc, and calcium carbonate, organic fillers such as wood flour and walnut shell powder can also be used.

The blending ratio of these extenders and/or fillers varies depending on the purpose of use of the curable composition, but if the water-soluble polymer having active hydrogen and/or the aqueous emulsion is
0 to 200 parts by weight, preferably 0 to 200 parts by weight
150 parts by weight is suitable. Further, these extenders and fillers may be used alone or in combination.

Furthermore, compounds of polyvalent metals can be used in the curable composition of the present invention. What are these polyvalent metal compounds?
It is a salt of metal cation oxides, hydroxides, and inorganic salts of the Group, and causes an ionic or chelate reaction with a polar group contained in a water-soluble polymer having active hydrogen and/or an aqueous emulsion, resulting in curable properties. It has the effect of improving the water resistance of the composition.

When a large amount of a water-soluble compound among these polyvalent metal compounds is added to a curable composition, the water-soluble polymer having active hydrogen and/or the polymer in the aqueous emulsion is salted out, and the active hydrogen is removed. The water-soluble polymer and/or aqueous emulsion that it has is easily fragile. Therefore, the amount added must be kept small. On the other hand, substances with low solubility in water can be added in large amounts to water-soluble polymers containing active hydrogen and/or aqueous emulsions, and can not only be expected to improve the water resistance of curable compositions, but also be effective as fillers. Therefore, it is desirable to use it. The water-insoluble polyvalent metal compound is the polymer 10 constituting the curable composition.
0 parts by weight, 1 to 400 parts by weight, preferably 5 to 2 parts by weight
00 parts by weight are added.

Furthermore, acids can be added to the curable composition of the present invention. As the acids, in addition to ordinary acids such as organic acids and inorganic acids, various acids such as salts that exhibit acidity when dissolved in water and which lower the - of the system are preferable, but among them, oxycaldic acid is the most preferable.

By blending acids into the curable composition of the present invention, the water resistance is improved, the change in water resistance over time is reduced, the viscosity is stabilized, and deltation is less likely to occur. Therefore, the usage time of the cured composition of the present invention can be extended. These can be used alone or in combination of two or more.

Even a small amount of acids can produce certain effects, but the most significant effect is when the - of the curable composition is between 2.0 and 2.0.
It can be obtained in an amount of about 5.

Furthermore, the curable composition of the present invention may contain hygroscopic compounds such as deliquescent inorganic salts, polyhydric alcohols, calcinols, etc. /
Acid salts and the like can be added.

Among these, deliquescent inorganic salts and polyhydric alcohols are particularly suitable as hygroscopic compounds, and the amount added thereof is 0.1 to 10% by weight in the curable composition including water. The range is 0.5 to 5 weight plates.

By adding a hygroscopic compound to the curable composition in this way, when the curable composition of the present invention is used as an adhesive, the drying of the adhesive solution after applying the adhesive to an adherend can be delayed. This not only eliminates adhesion defects caused by delayed adhesion during on-site work, but also provides useful countermeasures for adhesion work, such as reducing the amount of adhesive applied, enabling high-temperature adhesion work, and increasing adhesive concentration. It is possible to do so.

Furthermore, the curable composition of the present invention may contain other additives such as polymers, coloring agents, antifoaming agents, and fungicides, if necessary.

The curable composition of the present invention can be applied by lining the substrate, spraying, coating with a roll, etc., but in actual use, it is preferable to apply the coating with a lining of the substrate.

Naturally, a peroxide is added to a water-soluble polymer having active hydrogen and/or an aqueous emulsion, and an unsaturated isocyanate is dissolved in a hydrophobic "monomer", and if necessary, a curing accelerator is added. may be added, and each of these components may be applied using a double-headed spray gun.

〔Example〕

The present invention will be explained in more detail with reference to examples below. Example 1 Synthesis of unsaturated isocyanate (5) Eleven separable flasks equipped with a stirrer, a thermometer with a gas introduction tube, a dropping funnel, and a reflux condenser 2.4-
) 174 g of lylene diisocyanate (1 mol) and 153 g of methyl methacrylate were prepared, and 2
-Hydroxyglobil methacrylate) 173! i(1,
2 mol of diptyltin dilaure-1-0,31 (containing 0.07 g of lapenzoquinone) was added dropwise.The temperature rose as the dropwise addition was carried out, so once it reached 60°C, it was cooled and the temperature was maintained thereafter. After the addition of O 2 was completed, the reaction was carried out at 60° C. for 3 hours, and as a result of infrared analysis, it was determined that the free hydroxyl groups had disappeared.

Light yellowish brown, unsaturated isocyanate with a viscosity of 1.4 poise■
(Methyl methacrylate) 30.6 weight plate solution) was obtained. The obtained unsaturated isocyanate (4) contained 0.8 equivalents of isocyanate groups and 1.2 equivalents of methacryloyl groups @ previnyl acetate emulsion containing polyvinyl alcohol (Showa Kobunshi Co., Ltd.) 2 parts by weight of benzoyl peroxide (50% DOP paste) was added uniformly to 100 parts by weight of Polysol" 1200 manufactured by Polysol" 1200. Viscosity 200 poise, PH 4.0, MFT 10°C, solid content 52 weight 4).
Stir and mix uniformly to make polyvinyl acetate emulsion (a)
I got it.

Unsaturated incyaner) (A) 30 parts by weight and KBM503
(manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent) mixed with 5 parts by weight of polyvinyl acetate emulsion (a)
200 parts by weight were added and mixed by stirring.

When the obtained composition was applied to birch wood and an adhesion test was performed, the normal compressive shear force was 223 kg f 7 cm2,
Wood breakage rate is 65 degrees, compression shear force after water resistance test is 165 kg
f'/cm'', the wood breakage rate was 60cm, the compressive shear force after the hot water resistance test was 121+?f/crn2, and the wood breakage rate was 65cm.

Example 2 Synthesis of unsaturated isocyanate (B) In 11 separable flasks equipped with a stirrer, a thermometer with a gas introduction tube, a dropping funnel, and a reflux condenser, 222 g (1 mol) of unsaturated isocyanate (inphorone diincyanate) was added to an unsaturated isocyanate. (B) 10 parts by weight, 5 parts by weight of KBE1003 (manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent) and 0.02 parts by weight of accelerator D (manufactured by Showa Kobunshi Co., Ltd., main component dimethylaniline). After stirring and mixing, 100 parts by weight of modified styrene-butadiene latex (b) was added, and the mixture was stirred and mixed for 5 minutes.

When the obtained adhesive composition was applied to birch wood and an adhesion test was conducted, the normal compressive shear force was 225 kgf 7 cm2
, wood breakage rate is 70%, compressive shear force after water resistance test is 167k
g f 7cm", wood breakage rate 65 inches, compressive shear force after hot water test is 119 kg f7cm", wood breakage rate 60
Ll) was shown.

Example 3 Synthesis of unsaturated isocyanate (125 g (0.5 mol) of diphenylmethane diisocyanate was placed in an 11-set, 4-rubber flask equipped with a stirrer, a thermometer with a gas inlet tube, a dropping funnel, and a reflux condenser).
, 88g of butyl methacrylate was prepared in dry air,
87 g of 2-hydroxypropyl methacrylate (0,6
0.2.9 mol of dibutyltin dilaurate and 0.04 g of t4 rapenzoquinone] was added dropwise.

After the dropwise addition, the mixture was kept at 60° C. for 3 hours, and as a result of infrared analysis, it was determined that the free hydroxyl groups had disappeared.

Light reddish brown, unsaturated isocyanate with a viscosity of 2.9 poise (
0 (29.3 weight engagement of butyl methacrylate) was obtained.

The obtained unsaturated isocyanate (C) contained 0.8 equivalents of isocyanate groups and 1.2 equivalents of methacryloyl groups.

ffA 217016 weight board 50 parts by weight, 20 parts by weight of calcium carbonate, Perex C8 (Kako Soap Co., Ltd.)
0.3 parts by weight of anionic surfactant (manufactured by Co., Ltd.) and 0.3 parts by weight of sodium hexametaphosphate were added, and the mixture was stirred and mixed to uniformly disperse calcium carbonate. Next, modified acrylonitrile-butadiene latex (Nippon Zeon Co., Ltd., N
1pol 1571, viscosity 12 centipoise, PH8,
0.0, average particle size 0.12 μm, solid content 40%) and 1 part by weight of benzoyl oxide were added and mixed uniformly with stirring to obtain a modified acrylonitrile-butadiene latex (c).

(C) 15 parts by weight of A-17
4 (manufactured by Nippon Unicar Co., Ltd., 7-run coupling agent)
After stirring and mixing 3 parts by weight and 0.02 parts by weight of accelerator D, modified acrylonitrile-butadiene latex (c) 10
0 parts by weight and stirred and mixed for 5 minutes.

When the obtained adhesive composition was applied to birch wood and an adhesion test was performed, the normal compressive shear force was 217 to 9 f/α2, the wood breakage ratio was 55, and the compressive shear force after the water resistance test was 153 kl.
The il f was 7 cm2, the water wave rate was 40%, the compression shear force after the hot water test was 107 kgf/α2, and the water wave rate was 45 cm.

〔Effect of the invention〕

In the present invention, a curable composition prepared by blending a mixture of an unsaturated isocyanate and a silane coupling agent with an active hydrogen-containing water-soluble polymer and/or an aqueous emulsion has excellent water resistance. At the same time, there is less foaming, the viscosity is stable, and dulling is less likely to occur, and the water-resistant adhesive strength is less likely to deteriorate due to standing, and as a result, the pot life of the curable composition can be greatly extended.

Claims (1)

[Claims] 1) (1) Water-soluble polymer and/or aqueous emulsion having active hydrogen (2) Containing 1 equivalent or less of isocyanate group and 1 equivalent or more of acryloyl group or methacryloyl group in one molecule A curable composition comprising a mixture of an unsaturated isocyanate and a silane coupling agent (3) peroxide. 2) (1) Water-soluble polymer and/or aqueous emulsion having active hydrogen (2) Unsaturated isocyanate and silane containing 1 equivalent or less of isocyanate group and 1 equivalent or more of acryloyl group or methacryloyl group in one molecule A curable composition comprising a mixture of coupling agents (3) monomers copolymerizable with the unsaturated isocyanate and (4) a peroxide.