JPH0711154A - Curable polymer composition - Google Patents

Abstract

PURPOSE:To obtain a curablepolymer compsn. which is a long-stable one- component system, has an excellent curability, and gives a coating film with excellent properties by incorporating a specific nonaq. dispersion of a vinyl polymer and a specific compd. into the compsn. CONSTITUTION:This polymer compsn. contains a nonaq. dispersion of a vinyl polymer and at least one compd. selected from the group consisting of an aryldiazonium salt, a diaryliodinium salt, a triarylsulfonium salt, a triarylselenonium salt, a phenacylsulfonium salt, a 4-hydroxyphenylsulfonium salt, and a sulfonic ester (e.g. diphenyliodinium hexafluorophosphonate). The dispersion contains a dispersion-stabilizing resin and dispersed resin particles, each of them being a vinyl polymer and at least one of them having hydrolyzable silyl groups of the formula (wherein R1 is alkyl, aryl, or aralkyl; X is halogen, alkoxy, acyloxy, or hydroxyl; and (k) is 1-3) (e.g. a polymer produced by using gamma-methacryloxypropyltrimethoxysilane).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable polymer composition used as a paint, an adhesive, a sealing material and the like.

[0002]

2. Description of the Related Art Conventionally, a vinyl polymer having a hydrolyzable silyl group has a good adhesion to an inorganic material and is a cured coating film excellent in durability when cross-linked at room temperature by moisture in the air ( It is known to form a cured product). However, a vinyl-based polymer having a hydrolyzable silyl group has a slow crosslinking rate unless a curing catalyst is used, and the cured coating film obtained with a short curing period is not sufficient. Therefore, Japanese Patent Publication No. 63-443 and Japanese Patent Laid-Open No.
As shown in Japanese Patent Laid-Open No. 95116, generally, a vinyl polymer having a hydrolyzable silyl group is mixed with a curing catalyst for use.

[0003]

When a curing catalyst is blended, the curing catalyst is blended in a predetermined amount immediately before use, and is used in a so-called two-pack type, which can be used up within a certain pot life. is doing. With the two-pack type, it is necessary to repeat the work of weighing and mixing each time it is used, so in order to eliminate the complexity of the working process, a one-pack type in which a curing catalyst is preliminarily blended is desired, but it is sufficient. No such thing has been obtained.

[0004]

In the present invention, both (A) dispersion stabilizer resin (a) and dispersion resin particles (b) are vinyl polymers, and at least one of them is represented by the general formula (I).

[Chemical 2] (Wherein R ₁ is an alkyl group, an aryl group or an aralkyl group, X is a halogen atom, an alkoxy group, an acyloxy group or a hydroxyl group, and k is an integer of 1 to 3). A non-aqueous dispersion of a vinyl polymer, which has, and (B) an aryldiazonium salt, a diaryliodonium salt, a triarylsulfonium salt, a triarylselenonium salt, a phenacylsulfonium salt, a 4-hydroxyphenylsulfonium salt, and a sulfonic acid. The present invention relates to a curable polymer composition containing one or more compounds selected from esters.

First, the non-aqueous dispersion of the vinyl polymer as the component (A) will be described. Examples of the method for producing the dispersion stabilizer resin (a), which is a vinyl polymer having a hydrolyzable silyl group represented by the general formula (I), include: 1) hydrolysis by the general formula (I) Of copolymerizing a compound having a reactive silyl group and a vinyl group with a vinyl monomer, 2) reacting a vinyl polymer having a reactive functional group with a silane compound having a functional group capable of reacting with the functional group There is a way to do it.

Examples of the compound having a silyl group and a vinyl group represented by the general formula (I) used in the former case include:
There is a compound represented by the general formula (II).

[Chemical 3] (In the formula, R ₂ is a hydrogen atom or a methyl group, and R ₃ , R ₄
Alternatively, R ₅ is each independently a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, R ₆ is a divalent organic group, A is —COO— or a phenylene group, and X is a halogen atom, an alkoxy group. A group, an acyloxy group or a hydroxyl group, a is an integer of 0 to 20, and k is 1 to 3.
Is an integer)

As the compound represented by the general formula (II),
For example, γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane, γ -(Meth) acryloxypropyltrichlorosilane, γ- (meth) acryloxypropylmethyldichlorosilane, γ- (meth) acryloxypropyldimethylchlorosilane, γ-
(Meth) acryloxypropyltripropoxysilane, γ- (meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxypropyltributoxysilane, γ- (meth) acryloxybutyltrimethoxysilane, γ -(Meth) acryloxypentyltrimethoxysilane, γ- (meth) acryloxyhexyltrimethoxysilane, γ- (meth) acryloxyhexyltriethoxysilane, γ- (meth) acryloxyoctyltrimethoxysilane, γ- ( (Meth) acryloxydecyltrimethoxysilane, γ- (meth) acryloxydodecyltrimethoxysilane, γ- (meth) acryloxyoctadecyltrimethoxysilane, 1- (meth) acryloxypropyl-1,1,3,3- Tetramethyl-3-methoxydisiloxane, 1- (Meth) acryloxypropyl-1,1,3,3,5,5-hexamethyl-5-methoxytrisiloxane, 1- (meth) acryloxypropyl-1,1-dimethyl-3,3,3-methoxydisiloxane Etc. Here, (meth) acryloxy means methacryloxy or acryloxy. In addition to the compound represented by the general formula (II), for example, trimethoxyvinylsilane, triethoxyvinylsilane,
Examples thereof include vinylsilane compounds such as tris (ethylmethylketoxime) vinylsilane and triacetoxyvinylsilane, and allylsilane compounds such as allyltrimethoxysilane, allyltriethoxysilane and allyltrichlorosilane. These compounds may be used either individually or in combination of two or more.

The above-mentioned compound having a hydrolyzable silyl group and a vinyl group is copolymerized with a vinyl monomer such as (meth) acrylic acid ester to give a vinyl polymer having a hydrolyzable silyl group. It is said that Examples of the vinyl-based monomer used here include n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl (meth).
Carbon number of alkyl group such as acrylate, lauryl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate is 4 or more. (Meta)
Acrylic ester is mentioned as a preferable thing, and it is preferable to copolymerize these 1 type (s) or 2 or more types as a main component. In addition, as the vinyl-based monomer, for example, a methyl (meth) acrylate, an ethyl (meth) acrylate, an n-propyl (meth) acrylate, an isopropyl (meth) acrylate or the like having an alkyl group having 3 or less carbon atoms (meth). Acrylic acid ester, 2-hydroxyethyl (meth) acrylate, hydroxyl group-containing (meth) acrylic acid ester such as 2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl Amino group-containing (meth) acrylic acid esters such as (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate can be copolymerized. Further, as vinyl-based monomers, styrene, vinyltoluene, substituted styrenes such as α-methylstyrene, vinyl chloride, vinylidene chloride,
Acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, etc. can also be used together. In addition, (meth) acrylic acid means acrylic acid or methacrylic acid, and (meth) acrylate means methacrylate or acrylate.

The ratio of the compound having a silyl group and a vinyl group to the other vinyl monomer is preferably 1 to 50% by weight for the former, 50 to 99% by weight for the latter, and 3 to 3 for the former.
0% by weight, and the latter is more preferably 70 to 97% by weight. When the compound having a silyl group and a vinyl group is less than 1% by weight,
Crosslinking tends to decrease and the durability of the coating film tends to deteriorate, and when it exceeds 50% by weight, the polymer tends to thicken and gel during synthesis.

A known polymerization initiator is used in the polymerization of the compound having a silyl group and a vinyl group and other vinyl monomers. Examples of the polymerization initiator used in the present invention include t-butylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, methylethylketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide,
3,3,5-Trimethylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, dicumyl peroxide, α, α-bis (t-butyl) Peroxy-m-
Isopropyl) benzene, 2,5-dimethyl-2,5-
Di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-
3,1,1, -bis (t-butylperoxy) -3,
3,5-trimethylcyclohexane, 1,1-bis (t
-Butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-
Hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy)
Cyclododecane, 2-bis (4,4-di-t-butylperoxycyclohexane) propane, t-butyl hydroperoxide, cumene hydroperoxide, di-isopropylbenzene hydroperoxide, cumene hydroperoxide, 2,5 -Dimethylhexane 2,5-dihydroperoxide, t-hexyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,2'-azobis (isobutyronitrile), dimethylazodiisobutyi Rate, 2,2 '
-Azobis (2,4-dimethylvaleronitrile), 2,
2'-azobis (2-methylbutyronitrile) and the like can be mentioned. These polymerization initiators may be used either individually or in combination of two or more. The amount of these used is determined according to the target molecular weight, and is preferably 0.1 to 20.0 parts by weight based on 100 parts by weight of the total vinyl monomers used for the polymerization.

The vinyl polymer used as the dispersion stabilizer resin (a) of the present invention is obtained by polymerizing the vinyl monomer by a known polymerization method such as solution polymerization, suspension polymerization, emulsion polymerization and bulk polymerization. It is possible to obtain it. Solution polymerization is preferable when the dispersion resin particles (b) are directly subjected to the synthesis step. The reaction temperature during the polymerization is preferably 60 to 160 ° C, more preferably 80 to 140 ° C. Examples of the organic solvent used for the polymerization include pentane, hexane,
Examples thereof include linear aliphatic hydrocarbons such as heptane, octane and decane, cyclic aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, ethylcyclohexane and cycloheptane, and aromatic hydrocarbons such as benzene, toluene and xylene. Further, examples thereof include esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and alcohols such as methanol, ethanol, propanol and butanol. These may be used alone or in combination of two or more. In addition, a mixed solvent such as mineral spirit, mineral thinner, petroleum spirit, white spirit, and mineral terpene can be used.

Next, another method for obtaining the dispersion stabilizer resin (a)
A vinyl polymer having a reactive functional group, which has a functional group capable of reacting with the functional group and is represented by the general formula (I)
The method of reacting the compound having a hydrolyzable silyl group represented by In this method, a vinyl polymer having a functional group such as a carboxyl group, a hydroxyl group, an amide group and an epoxy group is produced, and then this polymer is prepared by using the general formula (III)

[Chemical 4] (In the formula, R ₇ is an alkyl group, an aryl group or an aralkyl group, X is a halogen atom, an alkoxy group, an acyloxy group or a hydroxyl group, Z is a carboxyl group,
It is a functional group that reacts with a functional group such as a hydroxyl group, an amide group or an epoxy group, and k is an integer of 1 to 3).

The starting material of a vinyl polymer having a functional group such as a carboxyl group, a hydroxyl group, an amide group and an epoxy group is a vinyl group having a functional group such as a carboxyl group, a hydroxyl group, an amide group and an epoxy group in one molecule and a vinyl group. It is a compound having a group, and a vinyl polymer having a reactive functional group is obtained by copolymerizing this with another vinyl monomer. By reacting this polymer with a compound represented by the general formula (III), a vinyl polymer having a hydrolyzable silyl group represented by the general formula (I) is obtained.

Examples of compounds having these functional groups and vinyl groups include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylamide, and glycidyl (meth). ) Acrylate and the like. The ratio of copolymerizing a compound having a vinyl group with a functional group such as a carboxyl group, a hydroxyl group, an amide group, an epoxy group (the former) and another vinyl-based monomer (the latter) is 5
-60% by weight and the latter 40-95% by weight are preferred. If the former is less than 5% by weight, general formula (I)
Since the amount of the hydrolyzable silyl group is small, it is difficult to obtain a cured product having good durability. On the other hand, when the former content exceeds 40% by weight, the viscosity tends to increase during the synthesis.

Examples of the compound represented by the general formula (III) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, β- (3,4-epoxycyclohexyl)
Examples thereof include ethyltrimethoxysilane and γ-mercaptopropyltrimethoxysilane. As a method of reacting, for example, there is a method of dissolving the vinyl polymer having a functional group described above in a solvent, then adding the compound represented by the general formula (III), and heating and stirring at 80 ° C. or higher. The ratio of the compound represented by the general formula (III) and the vinyl polymer having a functional group is 0.5 / 1.0 to 1.0 / 1. In terms of the former functional group / the latter functional group equivalent ratio. 0 is preferred. 0.
When it is less than 5 / 1.0, the amount of the hydrolyzable silyl group represented by the general formula (I) to be added is small, and thus a hardened product having good durability is difficult to obtain. When it exceeds 1.0 / 1.0, the unreacted silane compound remains in the resin, so that the storage stability of the coating tends to be poor.

In the present invention, the vinyl polymer obtained above is used as a dispersion stabilizer resin (a), and a vinyl monomer is polymerized in an organic solvent in which the vinyl polymer is dissolved.
A non-aqueous dispersion containing vinyl polymer particles (dispersion resin particles (b)) insoluble in the organic solvent is obtained. The vinyl-based monomer used in the dispersed resin particles (b) is not particularly limited, and the above-mentioned compound having a silyl group and a vinyl group and other vinyl-based monomers can be used. However, the use of an alkyl (meth) acrylate having an alkyl group having a smaller number of carbon atoms than the vinyl monomer used for the dispersion stabilizer resin (a) as a main component may reduce vinyl polymer particles unnecessary for an organic solvent. It is preferable because it is easy to form. Examples of such vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, and n-.
Propyl (meth) acrylate, isopropyl (meth)
Alkyl group of acrylate (meth) acrylic acid ester having 3 or less carbon atoms, or 2-hydroxyethyl (meth)
Hydroxyl group-containing (meth) acrylic acid ester such as acrylate, 2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) arylate, N, N-dimethyl Examples thereof include amino group-containing (meth) acrylic acid esters such as aminopropyl (meth) acrylate. Further, within a range in which the resulting vinyl-based polymer particles are insoluble in an organic solvent, for example, n-butyl (meth)
Acrylate, isobutyl (meth) acrylate, t-
Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate and the like (meth )
Acrylic ester, styrene, vinyltoluene, α-
Substituted styrenes such as methylstyrene, perfluorocyclohexyl (meth) acrylate, fluorine-containing compounds such as perfluorocyclohexyl ethylene, vinyl chloride,
It is also possible to use vinylidene chloride, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, etc. in combination. When a compound having a silyl group and a vinyl group is used, it is preferably used in the same proportion as the dispersion stabilizer resin (a).

In the present invention, the above-mentioned polymerization initiator is similarly used in the polymerization of the dispersed resin particles (b).
These can use 1 type (s) or 2 or more types. The amount used is determined by the intended molecular weight of the vinyl polymer particles, and the vinyl monomer 10 to be used for the polymerization is used.
0.1 to 10.0 parts by weight is preferable per 0 part by weight.
In the present invention, either the dispersion stabilizer resin (a) or the dispersion resin particles (b) may not have the silyl group represented by the general formula (I), but either vinyl-based resin may be used. The polymer must have a silyl group represented by the general formula (I).

The use ratio of the dispersion stabilizer resin (a) and the dispersion resin particles (b) thus obtained is (a) 10.
It is preferable to use 50 to 900 parts by weight of (b) with respect to 0 parts by weight. If the amount of (b) is less than 50 parts by weight, the sagging property tends to be poor, and if the amount of (b) exceeds 900 parts by weight, the dispersion stability tends to decrease. Upon polymerization, additives such as dispersion stabilizer and rheology control agent may be used in combination.

The average particle size of the vinyl polymer particles (dispersed resin particles (b)) in the non-aqueous dispersion thus obtained is usually in the range of about 100 nm to 2000 nm. If the average particle diameter is less than 100 nm, the viscosity of the varnish becomes high, and if the average particle diameter exceeds 2000 nm, the particles swell or aggregate during storage, which is not preferable. In the present invention,
The storage stability and the like can be further improved by chemically bonding the dispersion stabilizer resin (a) and the dispersion resin particles (b). As a method of binding, for example, in the presence of the dispersion stabilizer resin (a) having a vinyl group,
It can be carried out by polymerizing a vinyl-based monomer to obtain dispersed resin particles (b). Dispersion stabilizer resin (a)
The introduction of a vinyl group into, for example, a carboxyl group-containing vinyl monomer is used as a copolymer component of a vinyl polymer, and an epoxy group such as glycidyl (meth) acrylate or allyl glycidyl ether and a vinyl group are used for the carboxyl group. Can be carried out by reacting a compound containing Of course, an epoxy group may be contained in the polymer, and a carboxyl group-containing polymerizable unsaturated compound may be reacted with the epoxy group.

The curable polymer composition of the present invention comprises a vinyl polymer (A) having a hydrolyzable silyl group represented by the general formula (I) obtained by the above-mentioned method, and an aryl diazonium salt or diaryl iodonium salt. By blending one or more compounds (B) selected from salts, triarylsulfonium salts, triarylselenonium salts, dialkylphenacylsulfonium salts, dialkyl-4-hydroxyphenylsulfonium salts and sulfonates. can get. The aryl diazonium salt, diaryliodonium salt, triaryl sulfonium salt, triaryl selenonium salt, phenacyl sulfonium salt, 4-hydroxyphenyl sulfonium salt and sulfonic acid ester used in the present invention are Lewis acid, Bronsted acid, etc. upon light irradiation. It is a so-called photocationic polymerization initiator that generates

The aryldiazonium salt has the general formula (IV)

[Chemical 5] (In the formula, Ar ₁ is one or two selected from an alkyl group, a nitro group, an alkoxy group, a morpholino group and chlorine.
Is 1-3-substituted phenyl group or an unsubstituted phenyl group having a seed or more substituents, (X ₁₎ ^- is (PF ₆₎ ^-, (As
^{_{F 6) -, (SbF 6}} ) -, (SbCl 6) -, (BF 4) - , or (F
eCl ₄ ) ^- ), and a Lewis acid is generated by light irradiation. Specific examples of the aryldiazonium salt include 4-morpholino-2,5-dibutyroxybenzenediazonium borofluoride salt, phenyldiazonium hexafluorophosphonium salt, phenyldiazonium borofluoride salt, and phenyldiazonium hexafluoroantimonate salt. Can be mentioned.

The diaryliodonium salt has the general formula (V)

[Chemical 6] (In the formula, Ar ₂ is one or two selected from an alkyl group, a nitro group, an alkoxy group, a morpholino group and chlorine.
Is 1-3-substituted phenyl group or an unsubstituted phenyl group having a seed or more substituents, (X ₂₎ ^- is (PF ₆₎ ^-, (As
F ₆ ) ^- , (BF ₄ ) ^- , (ClO ₄ ) ^- , (CF ₃ SO ₃ ) ^- , (FS
O ₃₎ ^- or (F ₂ PO ₂₎ ^- is a compound represented by a is). Specific examples of the diaryl iodonium salt include diphenyl iodonium hexafluorophosphonium salt and diphenyl iodo hexafluoroantimonate salt.

The triarylsulfonium salt has the general formula (VI)

[Chemical 7] (In the formula, Ar ₃ is one or two selected from an alkyl group, a nitro group, an alkoxy group, a morpholino group and chlorine.
Is 1-3-substituted phenyl group or an unsubstituted phenyl group having a seed or more substituents, (X ₃₎ ^- is (PF ₆₎ ^-, (As
F ₆ ) ^- , (SbF ₆ ) ^- , (BF ₄ ) ^- , (ClO ₄ ) ^- , (CF ₃ SO
₃ ) ^- , (FSO ₃ ) ^-, or (F ₂ PO ₂ ) ^- ). Specific compounds of the triarylsulfonium salt include, for example, triphenylsulfonium hexafluorophosphonium salt, triphenylsulfonium hexafluoroantimonate salt, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate salt, diphenyl-4-thiophenoxyphenyl. Examples thereof include sulfonium pentafluorohydroxyantimonate salt and the like.

The triarylselenonium salt has the general formula (VII)

[Chemical 8] (In the formula, Ar ₄ is one or two selected from an alkyl group, a nitro group, an alkoxy group, a morpholino group and chlorine.
Is 1-3-substituted phenyl group or an unsubstituted phenyl group having a seed or more substituents, (X ₄₎ ^- is (PF ₆₎ ^-, (As
F ₆ ) ^- , (SbF ₆ ) ^- , (BF ₄ ) ^- , (ClO ₄ ) ^- , (CF ₃ S
^{_{O 3) -, (FSO 3}} ) - is a compound represented by a is) ^- or (F ₂ PO _2). Specific examples of the triarylselenonium salt include triphenylselenonium hexafluorophosphonium salt, triphenylselenonium borofluoride salt, triphenylselenonium hexafluoroantimonate salt and the like.

The phenacylsulfonium salt has the general formula (VI
II)

[Chemical 9] (In the formula, Ar ₅ is one or two selected from an alkyl group, a nitro group, an alkoxy group, a morpholino group and chlorine.
Is 1-3-substituted phenyl group or an unsubstituted phenyl group having a seed or more substituents, R ₈ and R ₉ is an alkyl group or a benzyl group, (X ₅₎ ^- is (AsF ₆₎ ^-, (SbF ₆ ) ^-
Or (PF ₆ ) ^- ). Examples of the phenacylsulfonium salt include dimethylphenacylsulfonium hexafluoroantimonate salt and diethylphenacylsulfonium hexafluoroantimonate salt.

The 4-hydroxyphenylsulfonium salt has the general formula (IX)

[Chemical 10] (In the formula, Ar ₆ is one or two selected from an alkyl group, a nitro group, an alkoxy group, a morpholino group and chlorine.
A phenylene group or an unsubstituted phenylene group having 1 to 3 species or more substituents, R ₁₀ and R ₁₁ is an alkyl group or a benzyl group, (X ₆₎ ^- is (AsF ₆₎ ^-, (Sb
F ₆₎ ^- or (PF ₆₎ ^- is a compound represented by a is).
Examples of the 4-hydroxyphenylsulfonium salt include 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate salt and 4-hydroxyphenylbenzylmethylsulfonium hexafluoroantimonate salt.

Examples of the sulfonic acid ester include α-hydroxymethylbenzoin sulfonic acid ester represented by the general formula (X), N-hydroxyimide sulfonate represented by the general formula (XI), and α-represented by the general formula (XII).
Sulfonyloxyketone, β-represented by the general formula (XIII)
Examples include sulfonyloxyketone.

[Chemical 11] (In the formula, R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ ,
R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ are alkyl groups or aryl groups)

The curable polymer composition of the present invention is cured with a photocationic polymerization initiator. The curing mechanism is not the generally known ring-opening reaction of epoxy group,
It is a condensation reaction of a hydrolyzable silyl group.

The photocationic polymerization initiator used in the present invention can be used in combination with a photosensitizer to further promote curability. Examples of the photosensitizer include erythrosine, eosin, perylene, anthracene, phenothiazine, pyrene, coronene, 1,2-benzanthracene,
Examples thereof include benzophenone, thioxanthone, 2-chlorothioxanthone, 9-fluorenone and anthraquinone.

The curable polymer composition of the present invention is prepared by adding a pigment such as titanium white, carbon black or phthalocyanine blue, an extender pigment such as calcium carbonate or barium sulfate, and a solvent to a non-aqueous dispersion type enamel paint by a conventional method. Can also be As a method for producing an enamel coating, for example, a known method such as a roll mill, a sand mill, a disperser can be used. Also, an enamel paint can be prepared by using a seed pen having good compatibility with the curable polymer composition of the present invention. Further, in order to improve performance as a paint, it is possible to add a pigment dispersant, a leveling agent, etc. at the time of making the paint or after making the paint. The curable polymer composition of the present invention is also useful as an adhesive, a sealing material and the like.

[0031]

EXAMPLES Examples of the present invention will be described below. Synthesis Example 1 (1) Synthesis of dispersion stabilizer resin (a-1) 300 g of mineral terpenes and 100 g of xylene were charged in a flask equipped with a stirrer, a reflux condenser and a thermometer. After the temperature was raised to 95 ° C., the polymerizable unsaturated compound of Table 1 was added dropwise over 2 hours.

[Table 1] After completion of dropping, the mixture was kept warm for 1 hour, and a solution of 2 g of t-butylperoxy-2-ethylhexanoate dissolved in 20 g of mineral terpene was added dropwise over 30 minutes. After the completion of the dropping, the temperature was raised to 100 ° C. and the temperature was kept for 1 hour to complete the polymerization reaction. After cooling, mineral terpen was further added to adjust the heating residue to 50%.

(2) Synthesis of non-aqueous dispersion liquid (N-1) The resin (a) synthesized in (1) was placed in the same flask as in (1).
-1) 400 g was collected, and 100 g of mineral terpenes and 50 g of xylene were added. After the temperature was raised to 100 ° C., the polymerizable unsaturated compound shown in Table 2 was added dropwise over 2 hours.

[Table 2] The liquid that was transparent before the dropping became cloudy as the polymerization proceeded, and became a non-aqueous dispersion liquid. After dripping, keep warm for 1 hour,
Further, a solution prepared by dissolving 2 g of t-butylperoxy-2-ethylhexanoate in 50 g of mineral terpene was additionally dropped, and the temperature was kept at 100 ° C. for 2 hours to complete the polymerization reaction. After cooling, add mineral turpentine and heat to a residue of 5
It was adjusted to be 0%. A milky white non-aqueous dispersion having a resin viscosity of 5400 centipoise, an average particle size of 830 nm and an acid value of 1 or less was obtained. This was named "N-1".

Preparation and Evaluation of Curable Polymeric Composition The non-aqueous dispersion prepared in Synthesis Example 1 was mixed with a curing catalyst in the proportions shown in Table 3 and the pot life and gel fraction were measured. <Pot life> The initial viscosity of the obtained curable polymer composition and the viscosity after storage for 3 months were measured, and the viscosity change (thickness increase rate) was determined by the following formula.

[Equation 1] <Gel Fraction> The obtained curable polymer composition was applied onto a treated steel plate with a bar coater (film thickness after drying: 25 to 35 μm).
m) After leaving it in the curing room for 2 weeks, it was subjected to Soxhlet extraction to determine the gel fraction.

[0034]

[Table 3]

(3) Evaluation of coating film characteristics Non-aqueous dispersion type paints were prepared with the formulations shown in Table 4 and the coating film characteristics were evaluated.

[0036]

[Table 4]

[0037]

The curable polymer composition of the present invention is stable as a one-pack type for a long period of time and exhibits sufficient curability when used. Also, when used as a paint, it exhibits excellent coating film properties.

Claims (1)

[Claims] 1. The dispersion stabilizer resin (a) (A) and the dispersion resin particles (b) are both vinyl polymers, and at least one of them is represented by the general formula (I): (Wherein R ₁ is an alkyl group, an aryl group or an aralkyl group, X is a halogen atom, an alkoxy group, an acyloxy group or a hydroxyl group, and k is an integer of 1 to 3) Non-aqueous dispersion of vinyl polymer having silyl group of (B) aryldiazonium salt, diaryliodonium salt, triarylsulfonium salt, triarylselenonium salt, phenacylsulfonium salt, 4-hydroxyphenylsulfonium salt A curable polymer composition containing one or more compounds selected from salts and sulfonates.