JP2001181498A - Cationically polymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition having no problem caused by a hydroxide group, e.g. the problem of the increase of the viscosity, capable of being formed into the one having higher solid content, good in compatibility, wettability to a substrate, preservation stability or the like, and capable of being cured by the combination of the irradiation of active energy rays with heating. SOLUTION: This cationically polymerizable composition comprises [A] a polyortho ester obtained by reacting (a) an ortho ester such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate and ethyl orthoacetate, (b) at least one kind of glycol compound selected from α-glycol and β-glycol, and (c) a hydroxy group-containing compound having at least two hydroxy groups in one molecule except the component (b), [B] an epoxy group-containing compound and [C] a photoacid generator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention can be cured by both active energy ray irradiation and heating.
The present invention also relates to a cationically polymerizable composition capable of lowering the viscosity and enabling high solid differentiation, and a method for forming a cured coating film using the composition.

[0002]

2. Description of the Related Art Orthoesters are conventionally used as a dehydrating agent, a raw material for synthesizing various compounds, and the like. The orthoester is also known as a protecting group for a hydroxyl group, and protects the hydroxyl group by reacting in the presence of an acid catalyst and under mild conditions such as room temperature, for example, as shown in the following formula (i).

[0003]

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The protected hydroxyl group is stable under basic conditions, but under acidic conditions, the following formula (ii) or (ii)
As shown in i), the protecting group is easily eliminated by hydrolysis.

[0005]

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[0006] Also, orthoesters generally readily hydrolyze to form two molecules of alcohol and one molecule of ester.

Embedded image Several techniques relating to polyorthoesters that industrially utilize such properties of orthoesters have been proposed. For example, Japanese Patent Publication No. Sho 63-20325 discloses a polyorthoester for photoresists,
Japanese Patent Publication No. 02465 describes a polyorthoester for drug delivery.

The polyorthoesters described in these publications are:
A compound having a specific repeating unit obtained by condensing a triol and an orthoester, for example, a repeating unit represented by the following formula (v). However, in the production of this compound, a specific compound as a hydroxyl group-containing compound is used. Only triols can be used, and there is only a degree of freedom to change the molecular weight depending on the blending ratio of triol and orthoester, and there is a problem that the degree of freedom in molecular design is low.

[0008]

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JP-A-57-42724 describes a polymer having a spiro-orthoester structure, and it has been shown that this polymer is a cross-linkable polymer with small volume shrinkage. Since it is essential to use caprolactone as a raw material, the degree of freedom in molecular design is low. Further, JP-A-60-233114 describes a polymer having a bicycloorthoester structure, which indicates that the polymer is a crosslinkable polymer having an excellent balance between elastic modulus and toughness. However, since it is essential to use trimethylolpropane or trimethylolethane as a raw material, there is a problem that the degree of freedom in molecular design is low.

As described above, the alkoxy group of the orthoester is known to undergo an alcohol exchange reaction with a hydroxyl group in the presence of an acidic catalyst. If a hydroxyl group-containing compound in which two hydroxyl groups are close to each other is used, it becomes 5%. A 6-membered ring, a 6-membered ring or a bicyclo ring can be formed. Utilizing this property, orthoester is mainly used as a protecting group for a nearby hydroxyl group in the field of biochemistry.

All three alkoxy groups of the orthoester can undergo an alcohol exchange reaction, and can be converted to a polyorthoester by combining with a polyhydric alcohol. At this time, simply exchange reaction between orthoester and polyhydric alcohol (condensation reaction by dealcoholization)
Is performed, the gel is formed by three-dimensionalization.

A photocurable composition comprising a combination of a compound or resin containing a polyvalent hydroxyl group, a compound having two or more epoxy groups in one molecule, and a photoacid generator has been known. The curable composition has a high viscosity, a low compatibility, a high polarity when applied to a base material, a poor wettability to the base material, and a hydroxyl group and an epoxy group at the time of light irradiation. There is a problem that a chain transfer reaction occurs with cation and inhibits cationic polymerization.

An object of the present invention is to provide a photocurable composition comprising a combination of a polyorthoester, an epoxy group-containing compound and a photoacid generator, which has a high degree of freedom in molecular design, low viscosity and easy control of molecular weight, No problems caused by hydroxyl groups, for example, no problem of increasing the viscosity of the photocurable composition, high solid differentiation is possible, compatibility, wettability to the substrate, storage stability, etc. are good at the time of light irradiation It is an object of the present invention to provide a cationically polymerizable composition which hardly inhibits the cationic polymerization of the above and has good reactivity between a hydroxyl group generated from a polyorthoester and an epoxy group by heating, and is cured by light irradiation and heating.

[0014]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, this time, a poly (glycol) obtained by reacting a specific glycol compound, an orthoester and a polyvalent hydroxyl group-containing compound has been obtained. The inventors have found that the above-mentioned problems can be solved by combining an orthoester, an epoxy group-containing compound, and a photoacid generator, and have completed the present invention.

That is, the present invention provides: [A] (a)

[0016]

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In the formula, R ¹ is a hydrogen atom or a group having 1 carbon atom.
Orthoesters represented by (b) α-glycol and β, wherein three R ² are the same or different and each represent an alkyl group having 1 to 4 carbon atoms.
A polyorthoester obtained by reacting at least one glycol compound selected from glycols, and (c) a hydroxyl group-containing compound other than the above (b) having at least two hydroxyl groups in one molecule, [B] epoxy An object of the present invention is to provide a cationically polymerizable composition comprising a group-containing compound and [C] a photoacid generator.

Further, the present invention provides a cured coating film comprising applying the above-mentioned cationically polymerizable composition to the surface of an object to be coated, and irradiating the applied coating film with active energy rays and heating to cure the coating. Is provided.

Hereinafter, the present invention will be described in detail.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The cationically polymerizable composition of the present invention contains the following polyorthoester [A], an epoxy group-containing compound [B], and a photoacid generator [C].

Polyorthoester [A] Polyorthoester [A] is obtained by reacting the following orthoester (a), glycol compound (b), and hydroxyl group-containing compound (c).

Orthoester (a): The orthoester (a) is represented by the following formula (1)

[0023]

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Where R¹ Is a hydrogen atom or a carbon atom having 1 to 1
4 represents an alkyl group, and three R ^Two Are the same or different
And each represents an alkyl group having 1 to 4 carbon atoms.
It is a compound shown.

In the above formula (1), the alkyl group having 1 to 4 carbon atoms represented by R ¹ or R ² is linear or branched, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-
A butyl group and the like can be mentioned.

Specific examples of the orthoester (a) include:
For example, methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, methyl orthoacetate,
Examples thereof include ethyl orthoacetate, methyl orthopropionate, ethyl orthopropionate, methyl orthobutyrate, and ethyl orthobutyrate. Of these, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate are preferred. . These can be used alone or in combination of two or more.

Glycol compound (b): The glycol compound as the component (b) is at least one glycol compound selected from α-glycol and β-glycol having two hydroxyl groups in one molecule.

As the α-glycol, particularly, the following formula (2)

[0029]

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In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and are each a hydrogen atom or a carbon atom having 1 to 24 carbon atoms.
An alkyl group, an aralkyl group having 7 to 24 carbon atoms or a phenyl group, or a group in which a part of these groups is substituted with an oxygen atom, and represented by R ³ , R ⁴ , R ⁵ and R ⁶ . The total number of carbon atoms of the group to be formed is in the range of 0 to 24, preferably 0 to 10, and R ⁴ and R ⁵ together with the carbon atom to which they are directly bonded form a cyclic structure. The compound represented by may be suitably used.

In the above formula (2), R ³ , R ⁴ , R ⁵
Or an alkyl group having 1 to 24 carbon atoms which can be represented by R ⁶ is linear, branched or cyclic, and methyl,
Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, n-octyl, 2-ethylhexyl, decyl, dodecyl, octadecyl, cyclohexyl, methylcyclohexyl, cyclohexylmethyl, cyclohexylethyl and the like be able to.

In the above formula (2), R ³ , R ⁴ , R ⁵
Alternatively, as the aralkyl group having 7 to 24 carbon atoms that can be represented by R ⁶ , a phenyl-substituted alkyl group is preferable, and specific examples include a benzyl and phenethyl group.

In the above formula (2), R ³ , R ⁴ , R ⁵
Or a group in which part of an alkyl group, an aralkyl group or a phenyl group represented by R ⁶ is substituted with an oxygen atom, includes an alkoxyalkyl group such as methoxymethyl, ethoxymethyl, propoxymethyl and butoxymethyl; And alkanoyloxyalkyl groups such as acetoxyethyl; phenoxymethyl and phenoxyethyl groups. Equation (2) above
In the above, R ³ , R ⁴ , R ⁵ or R ⁶ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Thus, typical examples of the α-glycol include, for example, ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 2,3
-Butylene glycol, 1,2-hexanediol,
Hydrolysis products of 1,2-dihydroxycyclohexane, pinacol, and long-chain alkyl monoepoxide; fatty acid monoglycerides (α-form) such as glycerin monoacetate (α-form) and glycerin monostearate (α-form); 3-ethoxypropane-1 , 2-diol, 3-phenoxypropane-1,2-diol, and the like.
Of these, ethylene glycol, 1,2
-Propylene glycol, 1,2-hexanediol are preferred.

On the other hand, as β-glycol, among others, the following formula (3)

[0036]

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In the formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different and are each a hydrogen atom or an alkyl group having 1 to 24 carbon atoms, or an alkyl group having 7 to 24 carbon atoms. An aralkyl group or a phenyl group, or a group in which a part of these groups is substituted with an oxygen atom, and R ⁷ , R ⁸ , R
^9, R ^10, a total of the number of carbon atoms of the groups represented by R ¹¹ and R ¹² in the range of 0-24, also R ⁷ and R ^9, or R ^7, R ⁹ and R ^11, these Which may form a cyclic structure together with the carbon atom directly bonded thereto, can be suitably used.

In the above formula (3), R ⁷ , R ⁸ , R ⁹
As the alkyl group having 1 to 24 carbon atoms represented by R ¹⁰ , R ¹⁰ , R ¹¹ or R ¹² , an alkyl group represented by R ³ , R ⁴ , R ⁵ or R ⁶ in the formula (2) can be used. Can be similarly mentioned.

In the above formula (3), R ⁷ , R ⁸ , R ⁹
The aralkyl group having 1 to 24 carbon atoms which can be represented by R ¹⁰ , R ¹¹ or R ¹² is preferably a phenyl-substituted alkyl group, and specifically includes, for example, benzyl, phenethyl and the like. Can be.

In the above formula (3), R ⁷ , R ⁸ , R ⁹
Examples of the group in which a part of the alkyl group, aralkyl group or phenyl group represented by R ¹⁰ , R ¹¹ or R ¹² is substituted with an oxygen atom include, for example, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl Alkoxyalkyl groups such as acetoxymethyl and acetoxyethyl; and phenoxymethyl and phenoxyethyl groups. In the above formula (3), R ⁷ and R ⁹ , or
Examples of the cyclic structure that R ⁷ , R ⁹ and R ¹¹ or R ¹² can form together with the carbon atom to which they are directly bonded include a cyclohexyl group and a cyclopentyl group. R ⁷ and R in the above formula (3)
^{8, R 9, R 1 0} , R 11 or R ¹² include, among others, is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Thus, typical examples of β-glycol include, for example, neopentyl glycol, 2-methyl-
1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol,
2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl-1,3 -Propanediol, 2-phenoxypropane-1,3-diol, 2-methyl-2-phenylpropane-1,3-diol, 1,3-propylene glycol, 1,3-butylene glycol, dimethylolpropionic acid, Methylolbutanoic acid, 2-ethyl-1,3
-Octanediol, 1,3-dihydroxycyclohexane; and fatty acid monoglycerides (β-form) such as glycerin monoacetate (β-form) and glycerin monostearate (β-form). Among these, neopentyl glycol, 2-methyl-1,3
-Propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-
1,3-propanediol, 2,2,4-trimethyl-
1,3-pentanediol, 2-butyl-2-ethyl-
1,3-propanediol is preferred.

(C) Hydroxyl-containing compound: The hydroxyl-containing compound as the component (c) is a compound other than the glycol compound (b) having two or more hydroxyl groups in one molecule.

Examples of the hydroxyl group-containing compound (c) include compounds having two hydroxyl groups other than α-glycol and β-glycol, or compounds having three or more hydroxyl groups in one molecule.

Compounds having two hydroxyl groups other than α-glycol and β-glycol include, for example, 1,4
-Butanediol, 1,4-dihydroxycyclohexane, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 3-methyl-1,5
-Pentanediol, 1,4-dimethylolcyclohexane, tricyclodecanedimethanol, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-
Hydroxypropionate [this corresponds to the ester of hydroxypivalic acid and neopentyl glycol], bisphenol A, bisphenol F, bis (4
-Hydroxyhexyl) -2,2-propane, bis (4
-Hydroxyhexyl) methane, 3,9-bis (1,1
-Dimethyl-2-hydroxyethyl) -2,4,8,1
0-tetraoxaspiro [5,5] undecane, diethylene glycol, triethylene glycol, polyethylene glycol of tetra or higher, dipropylene glycol,
Tripropylene glycol, tetra- or more polypropylene glycol, copolymers having hydroxyl groups at both ends obtained by copolymerizing ethylene oxide and propylene oxide, linear polyesters having hydroxyl groups at both ends such as polycaprolactone diol, polycarbonate diol And a carboxylic acid adduct of diepoxide.

Examples of the compound having three or more hydroxyl groups include glycerin, diglycerin, triglycerin, pentaerythritol, dipentaerythritol, sorbitol, mannitol, trimethylolethane, trimethylolpropane, and ditrimethylolpropane. , Tris (2-hydroxyethyl) isocyanurate, gluconic acid, polymers containing three or more hydroxyl groups (polyesters containing three or more hydroxyl groups, polyethers, acrylic polymers, ketone resins, phenolic resins, epoxy resins, urethanes Resins, polyvinyl alcohol which is a saponified product of polyvinyl acetate, natural saccharides such as glucose, etc.).

The hydroxyl group-containing compound (c) has a molecular weight in the range of 90 to 100,000, particularly 90 to 5,000, and has a hydroxyl value of 20 to 1850 mgKOH / g,
In particular, those in the range of 40 to 1650 mgKOH / g can be suitably used.

Production of polyorthoester: In producing the polyorthoester as the component [A] in the composition of the present invention, the mixing ratio of the orthoester (a), the glycol compound (b) and the hydroxyl group-containing compound (c). Is not particularly limited, but the amount of the orthoester (a) is 0.01 to 10 mol, preferably 0.05 to 5 mol, relative to 1 equivalent of the hydroxyl group in the hydroxyl group-containing compound (c). More preferably, it is in the range of 0.1 to 2 mol, and the amount of the glycol compound (B) is 0.01 to 10 mol, preferably 0.05 to 5 mol, more preferably 0.1 to 2 mol.
It is appropriate to use the compound in a molar ratio within a range from the viewpoint of easy control of the molecular weight.

The polyorthoester [A] can be obtained by subjecting the three components (a), (b) and (c) to a condensation reaction. For example, the above three components are optionally subjected to a condensation reaction in the presence of an organic solvent and an acid catalyst, usually at room temperature to 250 ° C, preferably at a temperature in the range of 70 to 200 ° C for about 1 to 20 hours. Thereby, it can be suitably manufactured.

In the present invention, the alkoxy group of the orthoester (a) undergoes an exchange reaction with the alcohol part of the glycol compound (b) and the hydroxyl group-containing compound (c).
At that time, the orthoester (a) usually reacts preferentially with α-glycol or β-glycol, which is a glycol compound (b) having an adjacent hydroxyl group, to form a cyclic structure. That is, the glycol compound (b) is preferentially reacted with the two functional groups (alkoxyl groups) of the trifunctional orthoester (a) to cyclize. The remaining one alkoxy group of the orthoester (a) can react with the hydroxyl group-containing compound (c). Thus, since the polyorthoester [A] does not involve a bridge between molecules in the production thereof, the molecular weight and the viscosity can be suppressed. On the other hand, the orthoester (a) and the hydroxyl group-containing compound (c) are used without the presence of the glycol compound (b).
Is directly reacted with each other, a cross-linking reaction occurs between molecules, and the molecular weight and viscosity of the product increase steadily. The polyorthoester [A] in the composition of the present invention is obtained by adding the glycol compound (b) to the orthoester (a) and the hydroxyl group-containing compound (c) and reacting them, thereby suppressing an increase in molecular weight or viscosity. It is.

The polyorthoester [A] produced as described above may be, for example, an orthoester of the formula (1), an α-glycol of the formula (2) and two hydroxyl groups in one molecule. When the compound having the above formula is used as a raw material,

[0051]

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In the formula, Y ¹ represents a residue obtained by removing two hydroxyl groups from a compound having two hydroxyl groups in one molecule;
¹ , R ³ , R ⁴ , R ⁵ and R ⁶ are as defined above,
In addition, when the orthoester of the formula (1), the β-glycol of the formula (3) and a compound having four hydroxyl groups in one molecule are used as a raw material, The following equation (5)

[0053]

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In the formula, Y ² represents a residue obtained by removing the four hydroxyl groups from a compound having four hydroxyl groups in one molecule;
¹ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² can have a structure as defined above.

Epoxy Group-Containing Compound [B] The epoxy group-containing compound, which is the component [B] in the composition of the present invention, contains 1,2-epoxy groups (adjacent 2
Is a compound having at least one, and preferably two or more, carbon atoms and oxygen atoms forming a three-membered ring, which can be cationically polymerized by an acid generated from a photoacid generator by light irradiation, The polyorthoester [A] can be cured by reacting with a hydroxyl group generated by hydrolysis of the orthoester group by heating. Representative examples of the epoxy group-containing compound [B] include, for example, allyl glycidyl ether, phenyl glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol Diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether,
1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, diglycerin tetraglycidyl ether, trimethylolpropane triglycidyl ether, 2,6-diglycidylphenyl ether,
Sorbitol triglycidyl ether, triglycidyl isocyanurate, diglycidylamine, diglycidylbenzylamine, diglycidyl phthalate, bisphenol A diglycidyl ether, butadiene dioxide, dicyclopentadiene dioxide, 3,4-
Diester of epoxycyclohexene carboxylic acid and ethylene glycol, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexane Carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene epoxide glycidyl ether, dipentenedionoxide,
Adduct of bisphenol A type epoxy resin and ethylene oxide, Eporide GT300 (manufactured by Daicel Chemical Industries, Ltd., trifunctional alicyclic epoxy compound), Eporide GT400 (manufactured by Daicel Chemical Industries, Ltd., tetrafunctional alicyclic epoxy) Compound); Epolide GT301, GT30
2, GT303 (all of which are manufactured by Daicel Chemical Industries, Ltd., and trifunctional alicyclic epoxy compounds containing a ring-opened ε-caprolactone chain); Eporide GT401, GT40
2, GT403 (all of which are manufactured by Daicel Chemical Industries, Ltd., tetrafunctional alicyclic epoxy compounds having a ring-opened ε-caprolactone chain); Epicoat 828, 834, and 1
001, (all of which are Yuka Shell Epoxy Co., Ltd.)
Bisphenol A type epoxy resin); Epicoat 1
54 (Cresol novolak type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.), celloxides 2081, 2082, and 2083 represented by the following formula (6) (all of which are manufactured by Daicel Chemical Industries, Ltd .; In (6), n = 1 is celoxide 2081, n = 2 is celoxide 2082, and n = 3 is celoxide 2083); Denacol EX represented by the following formula (7):
-411 (manufactured by Nagase Kasei Co., Ltd.) and the like.

[0056]

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In the formula (6), n represents an integer of 1 to 3, and the epoxy group-containing compound includes glycidyl (meth) acrylate, allyl glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate And the like. Copolymers of an epoxy group-containing polymerizable unsaturated monomer such as above and other polymerizable unsaturated monomers can also be mentioned. Examples of the other polymerizable unsaturated monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. ) acrylate, tert- butyl (meth) acrylate, 2-ethylhexyl acrylate, n- octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) C _{1 ~ 24} alkyl acrylates such as (meth ) Acrylates; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol Monoesters of polyhydric alcohols with acrylic acid or methacrylic acid, such as no (meth) acrylate; compounds obtained by ring-opening polymerization of ε-caprolactone with monoesters of polyhydric alcohols with acrylic acid or methacrylic acid; vinyl Trimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyl Oxypropylmethyldiethoxysilane, γ- (meth)
Acryloyloxypropyltriethoxysilane, β-
Alkoxysilyl group-containing polymerizable unsaturated compounds such as (meth) acryloyloxyethyltrimethoxysilane and γ- (meth) acryloyloxybutylphenyldimethoxysilane; vinyl aromatic compounds such as styrene, vinyltoluene and α-methylstyrene; acrylonitrile ,
Examples include methacrylonitrile, tricyclodecanyl (meth) acrylate, isobornyl (meth) acrylate, vinyl acetate, and veova monomers (manufactured by Shell Chemical Co., Ltd.).

The epoxy group-containing compound may be used alone or
More than one species can be used in combination. The epoxy group content of the epoxy group-containing compound is not particularly limited, but usually, the epoxy equivalent is 100 to 3,000.
Suitably, it is in the range of 0, preferably 100 to 1,500.

Photoacid Generator [C] The photoacid generator [C] is a compound that generates an acid upon irradiation with active energy rays. The generated acid causes a cationic polymerization reaction of an epoxy group and a removal of an orthoester group. It is a catalyst for accelerating the reaction of regenerating hydroxyl groups by blocking. Examples of the photoacid generator include an ionic photoacid generator (for example, a photoacid generator that generates protons) and a nonionic photoacid generator (for example, a photoacid generator that generates sulfonic acid). Can be.

The ionic photoacid generator includes, for example, Ar2I + .X- (where Ar represents an aryl group, for example, a phenyl group;
X- represents BF ₄ ⁻ , PF ₆ ⁻ , SbF ₅ (OH) ⁻ , SbF ₆ ⁻ ,
AsF ₆ ^- or the following formula

[0061]

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Ar ₃ S + .X− (wherein, Ar and X− have the same meanings as above),

[0063]

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(In the formula, R ¹³ represents an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms, n represents an integer of 0 to 3, and X- has the same meaning as described above.) ,

[0065]

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(Where Y− is PF ₆ ⁻ , SbF ₆ ⁻ , A
sF ₆ ^- or SbF ₅ (OH) ^- ),

[0067]

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(Wherein X- has the same meaning as described above),

[0069]

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(Wherein, X- has the same meaning as described above);

[0071]

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(Wherein, X- has the same meaning as described above),

[0073]

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[0074] (wherein, R ¹⁴ is an aralkyl group or an alkenyl group having a carbon number of 3 to 9 carbon atoms 7 to 15, R ¹⁵
Represents a hydrocarbon group having 1 to 7 carbon atoms or a hydroxyphenyl group, R ¹⁶ represents an alkyl group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, and X- has the same meaning as described above. Having)

[0075]

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(Wherein, R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms, and X- has the same meaning as described above.) Has),

[0077]

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Wherein R ²⁰ and R ²¹ are each independently
And a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms, and X- has the same meaning as described above.

Specific examples of the ionic acid generator include, for example, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, and 4-acetoxyphenylbenzylmethylsulfonium hexafluoro Antimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-
2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, benzyl-3-methyl-4-hydroxy-5-tert-butylphenylmethylsulfonium Hexafluoroantimonate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium Hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate Nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dinitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, β-naphthylmethyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate And the like.

Commercially available ionic acid generators include:
For example, Sun-Aid SI-L85, SI-L110,
SI-L145, SI-L160, SI-H1
5, same SI-H20, same SI-H25, same SI-H4
0, same SI-H50, same SI-60L, same SI-80
L, SI-100L, SI-110L, SI-1
80L, SI-80, SI-100 (all of which are manufactured by Sanshin Chemical Industry Co., Ltd., trade name); Cyracure UV
I-6970, UVI-6974, UVI-699
0 (all manufactured by Union Carbide, USA), Irgacure 261 and 264 (all manufactured by Ciba Specialty Chemicals), DAICA
T11 (product name, manufactured by Daicel Chemical Industries, Ltd.), CIT
-1682 (manufactured by Nippon Soda Co., Ltd.), BBI-102 (manufactured by Midori Kagaku), Adeka Optomer SP-150, S
P-170 (all of these are manufactured by Asahi Denka Co., Ltd.) and the like.

The nonionic photoacid generator usable as the photoacid generator [C] includes, for example,

[0082]

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(Wherein, R ²² and R ²³ each independently represent an alkyl group having 1 to 12 carbon atoms or 1 to 12 carbon atoms)
Represents an alkoxyl group)),

[0084]

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[0085]

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And the like.

Specific examples of the nonionic photoacid generator include:
Benzoin ester of toluenesulfonic acid, o- or p-nitrobenzyl ester of toluenesulfonic acid, 2,6-dinitrobenzyl ester of toluenesulfonic acid;
N-hydroxyamides and N-hydroxysulfonates described in U.S. Pat. No. 4,371,605; arylnaphthoquinonediazide-4-sulfonates and the like can be mentioned. Commercially available nonionic photoacid generators include, for example, “NAI-105”, “SI-10”
0 "," NDI-105 "," PI-105 "(above,
All of them are manufactured by Midori Kagaku Co., Ltd.).

These photoacid generators can be used alone or in combination of two or more. In the composition of the present invention, the curability can be further improved by using a combination of an ionic photoacid generator and a nonionic photoacid generator as the photoacid generator [C].

The cationically polymerizable composition of the present invention comprises the above-mentioned polyorthoester [A], the epoxy group-containing compound [B] and the photoacid generator [C] as essential components. Contained as The mixing ratio of the above components (A), (B) and (C) is not particularly limited, but from the viewpoints of curability, storage stability, processability of the cured product and finished appearance, it is usually (A) ] And [B] are suitably within the following ranges based on 100 parts by weight of the total amount of the components. [A] component: 5 to 95 parts by weight, preferably 10 to 70 parts by weight, [B] component: 5 to 95 parts by weight, preferably 30 to 90 parts by weight, [C] component: 0.01 to 20 parts by weight , Preferably 0.0
5 to 15 parts by weight.

The cationically polymerizable composition of the present invention may further comprise, if necessary, a cationically polymerizable compound such as an oxetane compound or a vinyl ether compound, in addition to the essential components [A], [B] and [C]. Organic solvent, curing catalyst,
A pigment, an ultraviolet absorber, a fluidity adjuster (including organic resin fine particles), a coating surface adjuster, an antioxidant, a wax and the like can be appropriately contained.

The composition of the present invention is usually a solvent-free or organic solvent-type composition. When the organic solvent-type composition is used, the organic solvent can dissolve or disperse each component of the composition of the present invention. And hydrocarbon solvents such as heptane, toluene, xylene, octane and mineral spirits; ester solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like. A ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and cyclohexanone; an alcohol solvent such as methanol, ethanol, isopropanol, n-butanol, sec-butanol, isobutanol; n-butyl ether, dioxa , Ethylene glycol monomethyl ether, ethers such as ethylene glycol monoethyl ether; Swasol 310, Swasol 100
And aromatic petroleum-based solvents such as SWOLSOL 1500 (all manufactured by Cosmo Oil) and SHELLSOL A (Shellsol A, manufactured by Shell Chemical). These organic solvents can be used alone or in combination of two or more.

Examples of the pigments to be added to the composition of the present invention as needed include inorganic coloring pigments such as titanium white, carbon black, red iron, titanium yellow and the like; quinacridone red, azo red, phthalocyanine blue, phthalocyanine green, organic yellow. Organic coloring pigments such as pigments; coloring pigments such as glittering pigments such as aluminum powder, glittering mica powder, and glittering graphite; extender pigments such as silica powder, calcium carbonate, barium sulfate, mica, clay, and talc; calcium ion exchange Examples include rust preventive pigments such as silica, phosphate rust preventive pigments and chromate pigments. The amount of the pigment can be used within a range that does not inhibit the curing reaction based on the photoradical reaction by light irradiation in the composition of the present invention. The amount of the pigment
Based on 100 parts by weight of the total amount of the components (A) and (B),
Usually, it is suitable to be within the range of 200 parts by weight or less, especially 100 parts by weight or less.

As the fluidity modifier, any fluidity modifier known per se in the field of paints can be used. For example, silica-based fine powder, bentonite-based regulator,
Examples include polyamide-based regulators, diurea-based regulators, organic resin fine particles produced by aqueous emulsion polymerization or non-aqueous dispersion polymerization, and the like. Each of the organic resin fine particles may be crosslinked.

The curable composition of the present invention can be suitably used as a coating composition, an adhesive, an ink and the like, and especially as a coating composition.

[0095] will be described below a method of forming a cured coating film by using the cationically polymerizable composition of the forming method of the present invention a cured coating film. Examples of the coating object that can form a coating film by applying the curable composition of the present invention include iron, zinc, aluminum, copper, tin-free steel, tinplate, galvanized steel sheet, and alloy plating of zinc and other metals. Metal plates such as steel plates; chemical conversion-treated metal plates obtained by subjecting these metals to phosphate treatment or chromate treatment; polyester resins such as polyethylene terephthalate, and polyolefin resins such as polyethylene and polypropylene , Polyamide resin, epoxy resin, resin film laminated metal plate laminated with resin film such as polyvinyl chloride; automobile body, can, etc. formed by processing these metal plate, chemical conversion treated metal plate or resin film laminated metal plate Moldings of wood, plastics,
Concrete; a coated base material having a coating film formed on the surface of these various base materials.

The composition of the present invention can be applied by a method such as roll coating, spray coating, brush coating, bar coating, roller coating, and silk screen printing. The dry coating thickness when applying the composition of the present invention may be appropriately selected within a range in which a good coating appearance, curability and the like can be obtained, but is usually about 2 to 80 μm as a dry coating thickness. When used for can coating, it is usually preferable to be within a range of about 2 to 20 μm, and when used for coating an automobile body, usually within a range of about 20 to 80 μm.

The composition of the present invention can be cured by using both irradiation of active energy rays such as ultraviolet rays and heating. Active energy ray irradiation and curing by heating may be performed simultaneously or may be performed sequentially, and the order in that case is not particularly limited, but after applying the composition of the present invention, the coating film is formed. When a solvent is contained, after the solvent is removed by air blowing, heating, or the like, curing can be performed by irradiating with active energy rays and, if necessary, heating. When the coating film does not contain a solvent, the step of removing the solvent can be omitted. Further, when heating with active energy rays is sufficiently performed at the time of irradiation with active energy rays, separate heating can be omitted. Further, when the composition of the present invention is spray-coated by spray coating or the like, the coating particles in flight, the coating film immediately after the application is irradiated with active energy rays to increase the viscosity of the applied coating film. It can also prevent sagging.

The irradiation condition of the active energy ray may be appropriately selected according to the kind and the film thickness of the applied cationically polymerizable composition, and the wavelength of the active energy ray to be irradiated is usually 200 to 450 nm. Within the range is appropriate,
An irradiation source having a wavelength with high sensitivity can be appropriately selected and used according to the type and thickness of the photoacid generator. Examples of the active energy ray irradiation source include a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, and sunlight.
When irradiating a coating film, the irradiation condition is usually a dose of 1
00 to 3000 mJ / cm ² , especially 150 to 2000 m
A range of J / cm ² is suitable.

As a heating device for curing the composition of the present invention, for example, a hot air drier, an infrared drier or the like can be suitably used. The heating condition is not particularly limited, but is usually 50 to 180 ° C., preferably 1 to 180 ° C.
Suitably, it is in the range of 00-160 ° C.

When the cationically polymerizable composition of the present invention is used as a coating, it can be used for any of a primer coating, an intermediate coating, a top coating coloring coating, and a top clear coating.
Among them, it is preferable to use it as a top clear paint.

When the composition of the present invention is used as an overcoat clear paint, a base coat or an ink layer is usually formed on a material for forming an overcoat film, and the overcoat clear paint is formed thereon. The above clear paint for top coat usually does not contain a coloring pigment, but if necessary, a coloring pigment can be blended to such an extent that the coloring base coat is not concealed.

As a material for forming the top coat, a primer is formed on a metal plate, for example, a chemically treated steel plate (including a plated steel plate) by, for example, electrodeposition coating, roll coating or spray coating. Materials coated with intermediate paint as needed, various plastic materials (surface treatment, primer coating, intermediate paint applied, etc., as required), metal plates laminated with polyester film, these materials are combined Composite members and the like.

In order to form an overcoat film on an automobile body, for example, a colored base coat / clear top coat may be applied to a top coat system or a material known in the automobile industry by a two-coat one-bake system or a two-coat two-bake system. Forming method: a method of forming a colored base coat / clear top coat / clear top coat by a three-coat one-bake method or a three-coat two-bake method can be applied. When the composition of the present invention is used as a clear top coat in the above-described two-coat one-bake method, a paint for a colored base coat is applied on the material by a conventional method such as spray coating.

As the paint for a colored base coat, the above-mentioned curable composition of the present invention containing a color pigment may be used, or a known base coat for a colored base coat conventionally used for forming an overcoat film may be used. Paint may be used. Known coating materials for a colored base coat include, for example, acrylic resin / amino resin (such as melamine resin, the same applies hereinafter), alkyd resin / amino resin, polyester resin amino resin, acrylic resin / polyisocyanate, alkyd resin / Polyisocyanate type, polyester resin / polyisocyanate type, etc. as a cured resin component, and a paint obtained by blending the above with the coloring pigment. The form of these per se known colored base coat paints is not particularly limited, and any form of organic solvent, non-aqueous dispersion type, aqueous solution type, aqueous dispersion type, high solid content type, powder type, etc. Things can be used.

Examples of the coating machine used for spray coating the paint for the colored base coat include ordinary air spray guns, airless spray guns, air spray electrostatic coating machines, airless spray electrostatic coating machines, and rotary atomizing static coating machines. An electric coating machine or the like can be used. The thickness of the colored base coat paint is preferably in the range of about 10 to 30 μm (after curing). After the colored base coat paint is applied, the paint is left at room temperature for several minutes or is forcedly dried at a temperature in the range of about 50 to 80 ° C. for several minutes, and then the curable composition of the present invention is a clear top coat paint. To paint. As a method of applying the clear top coat paint and a coating machine, the same paints as those for the colored base coat paint can be used. The thickness of the clear top coat paint is about 20-80μ
The range of m (after curing) is preferred.

Next, both the colored base coat coated film and the clear top coat coated film are heated and then cured by irradiation with active energy rays. In this case, the heating conditions are usually about 100 to 180 ° C. and 10 ° C.
About 60 minutes is preferable. The irradiation condition of the active energy ray is preferably in the range of the irradiation condition described above.

[0107]

The present invention will be described more specifically below with reference to examples and comparative examples. In the following, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.

Synthesis Example 1 of Polyester Solution Synthesis Example 1 A reactor equipped with a stirrer, a cooler, a temperature controller, a water separator, a rectification tower, a nitrogen inlet tube and a solvent recovery device was charged with 1,6
161 parts of hexanediol, 351 parts of 1,4-dimethylolcyclohexane, 146 parts of trimethylolpropane
, 114 parts of adipic acid, 300 parts of hexahydrophthalic anhydride and 243 parts of isophthalic acid, and the atmosphere in the reaction vessel was replaced with nitrogen.
The temperature was raised to 0 ° C. over 3 hours at a constant rate while removing condensed water, and then maintained at 230 ° C. for 1 hour. Thereafter, 50 parts of xylene was added, the reaction was further continued for 3 hours while removing condensed water by a water separator while maintaining the temperature at 230 ° C., and then cooled. A polyester solution (PE-1) having Gardner viscosity (20 ° C.) X was obtained. The obtained resin (solid content) has a resin acid value of about 6.5 mgKOH / g and a hydroxyl value of about 120 mg.
KOH / g, number average molecular weight was 1,00, and weight average molecular weight was 5,200.

Synthesis Example 2 983 parts of xylene and 240 parts of 3-methoxybutyl acetate were charged into a reactor equipped with a stirrer, a cooler, a temperature controller, a nitrogen inlet tube and a dropping funnel, and nitrogen in the reactor was replaced. And heated and maintained at 135 ° C. In this, styrene 600 parts, isobutyl methacrylate 63
6 parts, 552 parts of 2-ethylhexyl acrylate, 2-
A mixture consisting of 612 parts of hydroxyethyl methacrylate and 192 parts of azobisisobutyronitrile was added dropwise over 4 hours. After completion of the dropwise addition, the mixture was aged at 135 ° C. for 30 minutes, and then a mixed solution consisting of 168 parts of xylene and 12 parts of azobisisobutyronitrile was added dropwise over 1 hour. About 63%, Gardner viscosity (20 ° C) U ⁺ acrylic resin solution (AR
-1) was obtained. The obtained resin (solid content) has a hydroxyl value of 1
It was 10 mgKOH / g, number average molecular weight was 1,900, and weight average molecular weight was 4,300.

[0110] Preparation Example polyorthoesters 1 stirrer, condenser, reactor having a temperature control device and a solvent recovery apparatus, 424 parts of methyl orthoformate, 2-butyl-2-ethyl-1,3-propane 640 parts of a diol, 136 parts of pentaerythritol and 4 parts of a 90% formic acid aqueous solution were charged, and the mixture was maintained at about 85 ° C. for 1 hour while distilling off methanol produced by the alcohol exchange reaction. afterwards,
The temperature was raised to 190 ° C. over 2 hours to recover 365 parts of methanol to obtain a colorless, transparent and liquid polyorthoester (A-1) having a solid content of 100%. The resulting polyorthoester (A-1) had a Gardner viscosity X ⁺ and a weight average molecular weight of about 1540.

Production Examples 2 to 12 Reactions were carried out in the same manner as in Production Example 1 except that the raw material compositions to be blended were as shown in Table 1 below, and polyorthoesters were obtained. In Production Examples 6 and 7,
An organic solvent (xylene) contained in the raw material was partially distilled off in addition to the alcohol generated by the alcohol exchange. The polyorthoester solution obtained in Production Example 6 had a solid content of about 74%, and the polyorthoester solution obtained in Example 7 had a solid content of about 68%.

The polyorthoesters obtained in Production Examples 1 to 5 and 8 to 12 were all colorless, transparent and liquid polyorthoesters, and substantially had a solid content of about 100%. In Production Example 6, an acid catalyst was not blended, but a carboxyl group in the resin in the polyester solution (PE-1) served as a catalyst.

(Note) in Table 1 has the following meaning. (Note 1) Praxel 305: Daicel Chemical Industries, Ltd.
Manufactured by Polycaprolactone Polyol.

[0114]

[Table 1]

The weight average molecular weight, hydroxyl value and viscosity of the polyorthoester obtained in Production Examples 1 and 11 and PLACCEL 303 are compared as shown in Table 2 below.

(Note) in Table 2 has the following meaning. (Note 2) Praxel 303: Daicel Chemical Industries, Ltd.
Manufactured by Polycaprolactone Polyol.

[0117]

[Table 2]

Production Examples 2 to 5 and Production Examples 8 to 10 and 12
It is clear from Table 1 that all of the polyorthoesters obtained in the above have a Gardner viscosity lower than that of the polyorthoester obtained in Production Example 1.

The polyorthoester obtained in Production Example 6 had a solid content of about 74%, and had a Gardner viscosity of V when xylene was added to give a solid content of 69%. The viscosity was lower than the viscosity X of the 69% solids polyester solution (PE-1) used. The polyorthoester solution obtained in Production Example 7 had a solid content of about 6%.
8%, and xylene was added to this to give a solid content of 63%
The Gardner viscosity at the time of preparation was O, and the 63% solid content acrylic resin solution (A
The viscosity was lower than the viscosity U ⁺ of R-1).

Production Example 13 of Epoxy Group-Containing Compound A reactor equipped with a stirrer, a cooler, a temperature controller, a nitrogen inlet tube and a dropping funnel was charged with 983 parts of xylene and 240 parts of 3-methoxybutyl acetate. The atmosphere in the vessel was replaced with nitrogen, and the vessel was heated and maintained at 135 ° C. A mixture of 720 parts of styrene, 720 parts of 2-ethylhexyl acrylate, 960 parts of glycidyl methacrylate, and 192 parts of azobisisobutyronitrile was added to 4 parts of the mixture.
It was dropped over time. After completion of the dropwise addition, the mixture was aged at 135 ° C. for 30 minutes, and then a mixed solution composed of 168 parts of xylene and 12 parts of azobisisobutyronitrile was added dropwise over 1 hour.
Thereafter, the temperature is maintained at 135 ° C. for 30 minutes, and the non-volatile
%, A Gardner viscosity (20 ° C.) S 2 epoxy-containing acrylic resin solution (B-1) was obtained. The obtained resin (solid content) had an epoxy equivalent of about 370 and a number average molecular weight of about 2.1.
00, had a weight average molecular weight of about 4,900.

Production Example 14 A reactor equipped with a stirrer, a cooler, a temperature controller, a nitrogen inlet tube and a dropping funnel was charged with 983 parts of xylene and 240 parts of 3-methoxybutyl acetate. And heated and maintained at 135 ° C. A mixture of 720 parts of styrene, 720 parts of 2-ethylhexyl acrylate, 960 parts of 3,4-epoxycyclohexylmethyl acrylate, and 192 parts of azobisisobutyronitrile was added dropwise thereto over 4 hours. After completion of the dropwise addition, the mixture was aged at 135 ° C. for 30 minutes.
A mixture of 8 parts and 12 parts of azobisisobutyronitrile was added dropwise over 1 hour. Thereafter, the mixture was maintained at 135 ° C. for 30 minutes to obtain about 63% non-volatile content and Gardner viscosity (20%).
C) Epoxy group-containing acrylic resin solution of S (B-2)
I got The obtained resin (solid content) has an epoxy equivalent of about 4
75, a number average molecular weight of about 2,100 and a weight average molecular weight of about 4,900.

Preparation of Cationic Polymerizable Composition Example 1 100 parts of the polyorthoester (A-1) obtained in Production Example 1 was mixed with an epoxy group-containing acrylic resin solution (about 63% in nonvolatile content obtained in Production Example 13) B-1) 300 parts and "DAIC
AT11 "(Sulfonium salt ionic photoacid generator, manufactured by Daicel Chemical Industries, Ltd.) (15 parts) was mixed and stirred to obtain a cationically polymerizable composition.

Examples 2 to 12 and Comparative Examples 1 to 3 Each cationic polymerizable composition was obtained in the same manner as in Example 1, except that the composition was changed as shown in Table 3 below.

(Note) in Table 3 has the following meanings. (* 1) Celloxide 2021: 3,4-epoxycyclohexylmethyl-, manufactured by Daicel Chemical Industries, Ltd.
3,4-epoxycyclohexanecarboxylate. (* 2) Epicoat 828: Yuka Shell Epoxy Co., Ltd.
Bisphenol A type epoxy resin. (* 3) Epold GT300: a trifunctional alicyclic epoxy compound manufactured by Daicel Chemical Industries, Ltd. (* 4) HOX: Abbreviation of 3-ethyl-3-hexyloxymethyloxetane.

Forming Method of Cured Coated Film Forming Example 1 Using Cationic Polymerizable Composition of Example 1 The cationic polymerizable composition of Example 1 was applied to a tin plate with a bar coater so that the cured film thickness became 20 μm. And dried at 80 ° C. for 10 minutes as preheating to remove the solvent.
The coating was tacky and uncured. Then, using a 120 W / cm high pressure mercury lamp, 300 mJ
/ Cm ² dose. At this time, the tackiness of the coating film surface was lost, but it was not sufficiently cured. Immediately thereafter, it was dried in a hot air dryer at 140 ° C. for 3 minutes as post-heating to obtain a cured coating.

Example 2 using the cationically polymerizable composition of Example 2 The cationically polymerizable composition of Example 2 was coated on a tin plate with a bar coater so that the thickness of a cured coating film became 20 μm, and preheating was performed. Without using a high-pressure mercury lamp of 120 W / cm
A dose of 00 mJ / cm ² was applied. At this time, the coating film surface had no tackiness but was not sufficiently cured. Immediately afterwards, in a hot air drier at 140 ° C.
After drying for a minute, a cured coating film was obtained.

Example 3 using the cationically polymerizable composition of Example 2 The cationically polymerizable composition of Example 2 was coated on a tin plate with a bar coater so that the thickness of the cured coating film became 20 μm. Without using a 120 W / cm high pressure mercury lamp
Irradiated with a dose of 500 mJ / cm ² , a cured coating film was obtained without post-heating. At this time, the temperature of the tin plate had reached 130 ° C.

Forming Examples 4 to 16 In the above-mentioned forming example 1, the type of the cationically polymerizable composition,
A cured coating film was obtained in the same manner as in Formation Example 1, except that the preheating conditions, irradiation conditions with a high-pressure mercury lamp, and postheating conditions were as shown in Table 3 below. The forming examples 14 to 16 are forming examples for comparison.

The compatibility of each of the cationically polymerizable compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 3, and the solvent resistance and gel fraction of each cured coating film obtained in each formation example The test was performed based on the following test method. The results of these tests are shown in Table 3 below.

Test Method Compatibility: Each cationically polymerizable composition was placed in a test tube, and its appearance was visually observed and evaluated according to the following criteria. ：: transparent without clouding and good compatibility, Δ: cloudy and poor compatibility, ×: phase separation and remarkably poor compatibility.

Solvent resistance: The surface of each cured coating film on a tin plate was applied with a load of about 1 kg / cm ² to the coated surface with a three-layered gauze impregnated with xylene for a length of about 5 cm. The coating surface condition after 20 reciprocations between was evaluated according to the following criteria. ：: no damage or gloss on the coating film, good Δ: slight damage or gloss on the coating film, slightly poor ×: dissolution of the coating film or significant damage to the coating film

Gel fraction: The cured coating film was separated from the tin plate with a razor blade to obtain a free coating film. The free coating film was extracted in acetone for 6 hours under reflux, and the gel fraction (%) was determined from the weight of the coating film before and after extraction according to the following formula. Gel fraction (%) = (coating weight after extraction / coating weight before extraction) × 100

[0133]

[Table 3]

[0134]

[Table 4]

[0135]

The composition of the present invention is a cationically polymerizable composition containing a hydroxyl group-blocked polyorthoester, an epoxy group-containing compound, and a photoacid generator. There is no problem of increasing the viscosity of the photocurable composition, high solid differentiation is possible, good compatibility, good wettability to the substrate, storage stability, etc., causing the inhibition of cationic polymerization during light irradiation A cationically polymerizable composition which is difficult to cure and has good reactivity between a hydroxyl group generated from a polyorthoester by heating and an epoxy group, and is cured by light irradiation and heating.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J002 CD011 CD021 CD051 CD061 CD101 CD131 CD181 CD191 CF271 CH051 EL106 EU187 EV247 EV297 GH01 GP03 4J038 CE022 CF032 CG002 DA062 DB001 DB002 DD002 DF012 DG002 GA03 JA20 JA21 JA57 JB16 JB17 J38 JC33 PB04 PB07 PC02 PC04 PC06 PC08

Claims (9)

[Claims] [A] (a) (a) The following formula (1) In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and three R ^{2 s} are the same or different and each represent an alkyl group having 1 to 4 carbon atoms. An ester, (b) at least one glycol compound selected from α-glycol and β-glycol, and (c) a hydroxyl group-containing compound other than (b) having at least two hydroxyl groups in one molecule. A cationically polymerizable composition, comprising: a polyorthoester, [B] an epoxy group-containing compound, and [C] a photoacid generator. 2. The cationically polymerizable composition according to claim 1, wherein the photoacid generator [C] is a combination of an ionic acid generator and a nonionic acid generator. 3. The cation according to claim 1, wherein the orthoester (a) is at least one compound selected from methyl orthoformate, ethyl orthoformate, methyl orthoacetate and ethyl orthoacetate. Polymerizable composition. 4. The glycol compound (b) is represented by the following formula (2): Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different,
Represents a hydrogen atom or an alkyl group having 1 to 24 carbon atoms, an aralkyl group or a phenyl group having 7 to 24 carbon atoms, or represents a group in which a part of these groups is substituted with an oxygen atom, and The total number of carbon atoms of the groups represented by R ³ , R ⁴ , R ⁵ and R ⁶ is in the range of 0 to 24, and R ⁴ and R ⁵ are taken together with the carbon atom to which they are directly bonded. Α-glycol represented by the following formula (3), which may form a cyclic structure by In the formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different and each represent a hydrogen atom or a carbon atom having 1 to 24 carbon atoms.
Represents an alkyl group, an aralkyl group having 7 to 24 carbon atoms or a phenyl group, or represents a group in which a part of these groups is substituted by an oxygen atom, and R ⁷ , R ⁸ , R ⁹ ,
The total number of carbon atoms of the groups represented by R ¹⁰ , R ¹¹ and R ¹² is in the range of 0 to 24, and R ⁷ and R ⁹ or R
⁷ , R ⁹ and R ¹¹ are at least one kind of glycol compound selected from β-glycols represented by the following formulas, which may form a cyclic structure together with the carbon atom to which they are directly bonded. The cationically polymerizable composition according to any one of claims 1 to 3, which is characterized in that: 5. The glycol compound (b) is ethylene glycol, 1,2-propylene glycol, 1,2-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2, 4-pentanediol, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexanediol, 2,2-
Diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2
The cationically polymerizable composition according to any one of claims 1 to 4, which is at least one compound selected from -ethyl-1,3-propanediol. 6. The compound (c) having a hydroxyl group content of 90 to 10
6. A polymer having a molecular weight in the range of 000 and a hydroxyl value in the range of 20 to 1,850.
The cationically polymerizable composition according to any one of the above. 7. The method according to claim 1, wherein the hydroxyl group in the hydroxyl group-containing compound (c) is
The cation according to any one of claims 1 to 6, wherein the cation is blocked by a 5- or 6-membered orthoester composed of an orthoester (a) and a glycol compound (b). Polymerizable composition. 8. The compounding ratio of the polyorthoester [A] and the epoxy group-containing compound [B] is 5 to 95% based on 100 parts by weight of the total amount of the components [A] and [B].
The cationically polymerizable composition according to any one of claims 1 to 7, wherein the component (B) is in a range of 5 to 95 parts by weight. 9. The cationically polymerizable composition according to any one of claims 1 to 8, which is applied to the surface of an object to be coated, and the applied coating film is cured by irradiating active energy rays and heating. A method for forming a cured coating film, comprising: