JP2000086970A - Colored composition having cationic polymerizability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cationically polymerizable colored composition containing a coloring pigment in high dispersibility, exhibiting excellent fluidity, color- developing property and curability and giving a coating film free from defect when applied to a substrate. SOLUTION: The objective composition contains (A) a cationically polymerizable binder component containing a cationically polymerizable acrylic resin comprising a copolymer of (a) a (meth)acrylic acid ester monomer having a 6-31C aliphatic hydrocarbon group, (b) a polymerizable unsaturated monomer having cationic polymerizability and containing a polymerizable unsaturated group and a cationically polymerizable site selected from epoxy group and oxetane ring and, as necessary, (c) other polymerizable unsaturated monomer, (B) a cationic polymerization initiator to start the polymerization with light irradiation or heating and (C) a coloring pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cationically polymerizable coloring composition having good dispersibility of a coloring pigment, excellent fluidity, coloring and curability.

[0002]

2. Description of the Related Art
As the cationically polymerizable coloring composition, those using an epoxy compound as a binder component are known.In general, the epoxy compound has high polarity, and the wettability of the color pigment, particularly the wettability of the organic color pigment, is extremely poor. There were problems that the dispersibility of the color pigment was poor, the fluidity of the obtained color composition and the color development of the color pigment in the color composition were poor, and that repelling was liable to occur when applied to a substrate.

In order to improve the dispersibility of the color pigment, it is conceivable to disperse the pigment by using a pigment dispersing resin having no cationically polymerizable group such as an epoxy group. Has no cationic polymerizability, and thus has a problem that the curability of the obtained colored composition is poor.

An object of the present invention is to provide a pigment having good dispersibility,
An object of the present invention is to provide a cationically polymerizable coloring composition which is excellent in fluidity, coloring property and curability and does not cause defects such as cissing when applied to a substrate.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a cationically polymerizable acrylic resin having a long-chain aliphatic hydrocarbon group and a cationically polymerizable site as a cationically polymerizable binder component. The present inventors have found that the above object can be achieved by a cationically polymerizable coloring composition containing the present invention, and have completed the present invention.

That is, the present invention provides (A) (a) a (meth) acrylate monomer having an aliphatic hydrocarbon group having 6 to 31 carbon atoms, (b) a polymerizable unsaturated group, an epoxy group, and oxetane. A cationically polymerizable unsaturated monomer having a cationically polymerizable site selected from rings, and, if necessary, (c) a cationically polymerizable acrylic resin which is a copolymer of another polymerizable unsaturated monomer A cationically polymerizable colored composition comprising (A-1) a cationically polymerizable binder component, (B) a cationically polymerizable initiator for initiating polymerization by light irradiation or heating, and (C) a color pigment. Is provided.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The cationically polymerizable coating composition of the present invention is a coating composition which can be cured by causing cationic polymerization by irradiation with light such as ultraviolet rays or heating. Hereinafter, each component of the composition of the present invention will be described.

Cationically polymerizable binder component (A) The cationically polymerizable binder component, which is the component (A) of the coating composition of the present invention, is a binder component capable of undergoing cationic polymerization by irradiation with light such as ultraviolet rays or heating to be cured. Wherein the following cationically polymerizable acrylic resin (A-
1) is contained as an essential component.

The cationically polymerizable acrylic resin (A-
1) (a) a (meth) acrylate monomer having an aliphatic hydrocarbon group having 6 to 31 carbon atoms, (b)
It is a copolymer of a polymerizable unsaturated monomer containing a polymerizable unsaturated group and a cationically polymerizable site selected from an epoxy group and an oxetane ring, and if necessary, (c) a copolymer of another polymerizable unsaturated monomer. .

The (meth) acrylate monomer (a) having an aliphatic hydrocarbon group having 6 to 31 carbon atoms (hereinafter sometimes abbreviated as "monomer (a)") has a carbon atom in the molecule. It is a monomer having an aliphatic hydrocarbon group of the number 6 to 31, preferably 8 to 18, and as a specific example,
2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, n-stearyl (meth) acrylate, iso Stearyl (meth) acrylate and the like can be mentioned. In the present invention, “(meth) acrylate” means acrylate or methacrylate.

A polymerizable unsaturated monomer (b) containing a polymerizable unsaturated group and a cationically polymerizable site selected from an epoxy group and an oxetane ring (hereinafter sometimes abbreviated as “monomer (b)”) As a monomer having a polymerizable unsaturated group and an epoxy group (b-
1) (hereinafter sometimes abbreviated as “epoxy monomer (b-1)”) and monomer (b-2) having a polymerizable unsaturated group and an oxetane ring (hereinafter referred to as “oxetane monomer (b-2) ) ").

Specific examples of the epoxy monomer (b-1) include (methyl) glycidyl group-containing polymerizable unsaturated monomers such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate and allyl glycidyl ether; -Alicyclic epoxy group-containing polymerizable unsaturated monomers such as epoxycyclohexylmethyl (meth) acrylate.

As the oxetane monomer (b-2), for example, the following general formula (1)

[0014]

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(In the above formula (1), R ¹ is an alkyl group having 1 to 6 carbon atoms and R ² is a hydrogen atom or a methyl group); a hydroxyl-containing oxetane (for example, 3 -Ethyl-3-hydroxymethyloxetane), a functional group that reacts with the hydroxyl group and does not substantially react with the oxetane ring (for example, isocyanate group,
(E.g., a methyl ester group) and an unsaturated monomer containing an ethylenically unsaturated group (an acryloyl group, a methacryloyl group, a vinyl group, etc.) (for example, 2-isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-
Dimethylbenzyl isocyanate, methyl (meth) acrylate, etc.).

The oxetane monomer (b-2) includes
Among them, the compound represented by the above formula (1) is preferable,
Specific examples thereof include 3- (acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, and 3- (methacryloyloxymethyl) 3 -Ethyloxetane, 3- (acryloyloxymethyl) 3-butyloxetane, 3-
(Methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane and 3- (methacryloyloxymethyl) 3-
Hexyl oxetane and the like can be mentioned.

The other polymerizable unsaturated monomer (c)
(Hereinafter, “may be abbreviated as monomer (c)”) includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl. (meth) acrylate, isobutyl (meth) acrylate, tert- butyl (meth) acrylate, C _{1 to 5} equal
Alkyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, etc. Mono-esters of polyhydric alcohols with acrylic acid or methacrylic acid; hydroxyl-containing monomers such as compounds obtained by ring-opening polymerization of ε-caprolactone with mono-esters of polyhydric alcohols with acrylic acid or methacrylic acid; acrylic acid Carboxyl group-containing polymerizable unsaturated monomers such as methacrylic acid, maleic acid and maleic anhydride; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethyl Aminoalkyl (meth) acrylates such as aminopropyl (meth) acrylate; acrylamide, methacrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (Meth) acrylamide such as (meth) acrylamide, N-methylolacrylamide, N-methylolacrylamide methyl ether, N-methylolacrylamide butyl ether and derivatives thereof;
Examples include styrene, acrylonitrile, methacrylonitrile, and vinyl acetate. These compounds can be used alone or in combination of two or more. In the present invention, “(meth) acrylamide” means acrylamide or methacrylamide.

Cationically polymerizable acrylic resin (A-1)
Is produced by subjecting a mixture of the monomers (a), (b) and (c) to radical polymerization in, for example, an organic solvent or another cationically polymerizable compound in the presence of a radical polymerization initiator. be able to.

As the organic solvent, any inert organic solvent which does not substantially react with the monomers (a), (b) or (c) can be used without any particular limitation. Aromatic solvents such as toluene and xylene; acetate solvents such as amyl acetate, propyl acetate, butyl acetate, ethyl acetoacetate, 2-ethoxyethyl acetate and diethylene glycol monomethyl ether acetate; ethers such as dioxane and ethylene glycol diethyl ether Solvent: Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

The other cationically polymerizable compounds which can be used in the radical polymerization of the monomer mixture do not themselves cause a radical polymerization reaction as in the case of the above-mentioned organic solvent, and the polymerization system used when polymerizing the monomer is used. Is blended in order to lower the viscosity and promote the polymerization smoothly. Therefore, other cationically polymerizable compounds that can be blended at the time of the above radical polymerization have a low viscosity and do not have radical polymerization reactivity. The polymerizable binder component is preferably selected from binder components other than the cationically polymerizable acrylic resin (A-1), and usually contains a low-viscosity epoxy group having a viscosity at 70 ° C. of 500 centipoise (cps) or less. Compounds and low-viscosity oxetane ring-containing compounds can be suitably used.

As the radical polymerization initiator that can be used in producing the cationically polymerizable acrylic resin (A-1), a radical polymerization initiator known per se can be used without any particular limitation. Benzoyl, di-te
rt-butyl hydroperoxide, tert-butyl hydroperoxide, cumyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, tert-butylperoxybenzoate, lauryl peroxide, acetyl peroxide, tert-butyl-2- Ethyl hexanoate, tert-
Amyl peroxy-2-ethylhexanoate, 1,
Peroxides such as 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate; 2,2'-azobisisobutyronitrile, 2,2'-azobisisobutyronitrile, azo Examples include azo compounds such as bisdimethylvaleronitrile and azobiscyclohexanecarbonitrile. These can be used alone or in combination of two or more.

The conditions for the above radical polymerization reaction are not particularly limited, but are usually about 50 to 200 ° C., preferably about 70 to 150 ° C. for about 1 to 24 hours, preferably about 5 to 10 hours. Time ranges are preferred.

Cationically polymerizable acrylic resin (A-1)
Has a number average molecular weight of 300 to 200,000, preferably 500 to 100,000, more preferably 2,000.
It is suitable from the viewpoints of curability, coating workability and the like within the range of 0 to 50,000, and has one or more epoxy groups and / or oxetane rings per molecule, preferably epoxy group and oxetane ring. 2-100 on average
And more preferably 2 to 50 on average. In addition, a cationically polymerizable acrylic resin (A-
When 1) has only an epoxy group as the cationically polymerizable site, the epoxy group equivalent is 130 to 15,000.
0, preferably in the range of 140 to 7,000, and when having only an oxetane ring, the oxetane ring equivalent is 130 to 15,000, preferably 140 to 15,000.
In the case of having both an epoxy group and an oxetane ring as the cationically polymerizable site, the equivalent weight of the group when both of them are regarded as one group is 7,000. It is suitably in the range of 130 to 15,000, preferably 140 to 7,000 from the viewpoint of curability, suppression of volume shrinkage during curing, surface appearance of the cured product, and the like.

The proportions of the monomers (a), (b) and (c) constituting the cationically polymerizable acrylic resin (A-1) should be within the following ranges, because of their curability, pigment dispersibility and coating work. It is suitable from the viewpoint of properties and the like.

Monomer (a): 5 to 95% by weight, preferably 10 to 70% by weight, Monomer (b): 5 to 95% by weight, preferably 20 to 7%
0% by weight, monomer (c): 0 to 90% by weight, preferably 10 to 5%
0% by weight.

In the composition of the present invention, the above-mentioned cationically polymerizable acrylic resin (A-1) is used as an essential component as the cationically polymerizable binder component (A). Other cationically polymerizable compounds (A-2) can be used in combination. Examples of the other cationically polymerizable compound (A-2) include the following compounds (a), (b), (c), (d), and (e).

(A) Epoxy compound: a compound having one or more epoxy groups in one molecule, and having an epoxy equivalent of 70
To 5,000, preferably 80 to 3,000 can be suitably used. Representative examples thereof include, for example, dicyclopentadienedioxide, (3,4-epoxycyclohexyl) methyl-3,4-epoxy Cyclohexanecarboxylate, bis (2,3-epoxycyclopentyl) ether, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6)
-Methylcyclohexylmethyl) adipate, (3,4
-Epoxy-6-methylcyclohexyl) methyl-3,
4-epoxy-6-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl)
Acetal, bis (3,4-epoxycyclohexyl) ether of ethylene glycol, 3,4-epoxycyclohexanecarboxylic acid diester of ethylene glycol, (3,4-epoxycyclohexyl) methyl alcohol, (3,4-epoxycyclohexyl) ethyltriethyl Methoxysilane, 3-ethyl-3- (3,4-epoxycyclohexylmethyl) oxymethyloxetane, Epold GT300 (trade name, manufactured by Daicel Chemical Industries, Ltd., trifunctional alicyclic epoxy resin), Epold GT40
0 (manufactured by Daicel Chemical Industries, Ltd., trade name, 4-functional alicyclic epoxy resin), EHPE (Daicel Chemical Industries, Ltd.)
Made, trade name, polyfunctional alicyclic epoxy resin), the following formula

[0028]

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[0029]

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[0030]

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The compound represented by the formula (II), an alicyclic epoxy group-containing ethylenically unsaturated monomer such as 3,4-epoxycyclohexylmethyl (meth) acrylate and, if necessary, other polymerizable unsaturated monomers are A) an epoxy compound containing an alicyclic epoxy group such as an alicyclic epoxy group-containing (co) polymer obtained by polymerization; for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 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, spiroglycol diglycidyl ether, 2,6-diglycidylphenyl ether, sorbitol polyglycidyl ether, triglycidyl isocyanurate, bisphenol A diglycidyl ether, butadiene Dioxide, diglycidyl phthalate, 3-ethyl-3-glycidyloxymethyloxetane, bisphenol type epoxy resin, ε-caprolactone modified bisphenol type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, glycidyl (meth) Glycidyl group-containing ethylenically unsaturated monomer such as acrylate and, if necessary,
Epoxy compounds containing an aliphatic epoxy group, such as a glycidyl group-containing (co) polymer obtained by (co) polymerizing another polymerizable unsaturated monomer; for example, vinylcyclohexene dioxide, limonene dioxide, 3,4 -An alicyclic epoxy group-containing ethylenically unsaturated monomer such as epoxycyclohexylmethyl (meth) acrylate and a glycidyl group-containing ethylenically unsaturated monomer such as glycidyl (meth) acrylate, and if necessary, other polymerizable unsaturated monomers. An epoxy compound containing an alicyclic epoxy group and an aliphatic epoxy group, such as a (co) polymer containing an alicyclic epoxy group and a glycidyl group obtained by (co) polymerizing Compounds having two or more epoxy groups in the molecule have 6 to 33 carbon atoms.
And a fatty acid-modified epoxy compound having an epoxy group and a fatty acid ester group in one molecule obtained by reacting a fatty acid (e.g., lauric acid, oleic acid, linseed oil fatty acid, etc.) with a part of an epoxy group. it can.

(B) Vinyl compound: a compound having a vinyl group, for example, styrene, α-methylstyrene,
aromatic vinyl compounds such as p-chloromethylstyrene and vinyltoluene; substituted or unsubstituted alkyl vinyl ethers such as n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether and hydroxybutyl vinyl ether; allyl vinyl ether, ethenyl vinyl ether, 1-methyl Alkenyl vinyl ethers such as -2-propenyl vinyl ether; aryl vinyl ethers such as phenyl vinyl ether and p-methoxyphenyl vinyl ether; alkyl divinyl ethers such as butanediol divinyl ether, triethylene glycol divinyl ether and cyclohexanediol divinyl ether; -Benzene dimethanol divinyl ether, Nm-chlorophenyldiethanolamine Vinyl ether, m- phenylene bis (ethylene glycol) aralkyl divinyl ethers such as divinyl ether; hydroquinone divinyl ether, aryl divinyl ethers such as resorcinol divinyl ether; N- vinylcarbazole, N-
Cationic polymerizable nitrogen-containing compounds such as vinylpyrrolidone can be exemplified.

(C) Bicyclo orthoester compounds: For example, 1-phenyl-4-ethyl-2,6,7-trioxabicyclo- [2,2,2] -octane, 1-ethyl-4-hydroxymethyl- 2,6,7-trioxabicyclo- [2,2,2] -octane and the like can be mentioned.

(D) Spiro orthocarbonate compound:
For example, 1,5,7,11-tetraoxaspiro-
[5,5] -undecane, 3,9-dibenzyl-1,
5,7,11-tetraoxaspiro- [5,5] -undecane, 1,4,6-trioxaspiro- [4,4]-
Nonane, 2-methyl-1,4,6-trioxaspiro-
[4,4] -nonane, 1,4,6-trioxaspiro-
[4,5] -decane and the like can be mentioned.

(E) Oxetane compound:

[0036]

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A compound containing at least one oxetane ring represented by the following formula in the molecule, for example, a compound represented by the above general formula (1) and a compound represented by the following general formula (2) or (3) And the like.

[0038]

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(In the above formula, R ¹ has the same meaning as described above, and R ³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
Alkylene group, hydroxyalkyl group, having 2 to 2 carbon atoms
An alkoxyalkyl group optionally substituted with 10 hydroxyl groups, an aryl group optionally substituted with a hydroxyl group having 7 to 12 carbon atoms, an aralkyl group, an aryloxyalkyl group),

[0040]

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(In the above formula, two R ^{1 s} are the same or different and have the same meanings as described above, and R ⁴ is an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group, a phenylene group, a xylylene group, Represents a polyalkyleneoxy group having 4 to 30 atoms).

Representative examples of the oxetane compound represented by the general formula (1) include 3- (acryloyloxymethyl) 3-ethyloxetane and 3- (methacryloyloxymethyl) 3-ethyloxetane. .

Representative examples of the oxetane compound represented by the general formula (2) include 3-ethyl-3-methoxymethyloxetane, 3-ethyl-3-ethoxymethyloxetane, and 3-ethyl-3-butoxymethyloxetane. , 3
-Ethyl-3-hexyloxymethyloxetane, 3-
Methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-
Allyloxymethyl oxetane, 3-ethyl-3- (2
'-Hydroxyethyl) oxymethyloxetane, 3-
Ethyl-3- (2'-hydroxy-3'-phenoxypropyl) oxymethyloxetane, 3-ethyl-3-
(2′-hydroxy-3′-butoxypropyl) oxymethyloxetane, 3-ethyl-3- [2 ′-(2 ″)
-Ethoxyethyl) oxymethyl] oxetane, 3-ethyl-3- (2'-butoxyethyl) oxymethyloxetane, 3-ethyl-3-benzyloxymethyloxetane, 3-ethyl-3- (p-tert-butylbenzyl) (Oxymethyl) oxetane and the like.

As a typical example of the oxetane compound represented by the above formula (3), in the above formula (3), both R ¹ are each an ethyl group, and R ⁴ is methylene, ethylene, propylene, butylene. And cyclohexylene, phenylene, xylylene, poly (ethyleneoxy), and poly (propyleneoxy) groups.

As the oxetane compound (e), besides the compound represented by the above general formula (1), (2) or (3), for example, bis (3-ethyloxetanyl-3-methyl) oxide; A compound having a polymerizable unsaturated group represented by the formula (1) and an oxetane ring [for example, 3-
Ethyl-3- (acryloyloxymethyl) oxetane] as one monomer component, and a copolymer having an oxetane ring obtained by copolymerization with another polymerizable unsaturated monomer. The other polymerizable unsaturated monomer used in the copolymerization is used to produce the cationically polymerizable acrylic resin (A-1),
The same ones as the other polymerizable unsaturated monomers (c) can be used.

The other cationically polymerizable compounds (A-
As 2), an epoxy compound (a) and an oxetane compound (e) are particularly preferable from the viewpoint of the physical properties and curability of the cured product.

In the composition of the present invention, the cationically polymerizable binder component (A) may consist solely of the cationically polymerizable acrylic resin (A-1), but usually, other cationically polymerizable compounds (A- It is preferable to use 2) in combination. The mixing ratio of the cationically polymerizable acrylic resin (A-1) and the other cationically polymerizable compound (A-2) in the cationically polymerizable binder component (A) is as follows:
It is suitable that the former is in the range of 10 to 90% by weight, preferably 20 to 80% by weight, and the latter is in the range of 10 to 90% by weight, preferably 20 to 80% by weight based on the total amount of both.

Cation polymerization initiator (B) The cationic polymerization initiator (B) is prepared by irradiating light such as ultraviolet rays or the like or heating to the binder component (A) in the composition of the present invention.
It is compounded to promote cationic polymerization of a cationically polymerizable group such as an epoxy group or an oxetane ring therein, and to promote curing smoothly. Examples of the cationic polymerization initiator (B) include a cationic polymerization initiator that generates a substance that initiates cationic polymerization such as an acid by light such as ultraviolet light or heating.

The cationic polymerization initiator includes, for example, compounds represented by the following formulas.

Ar ₂ I ⁺ · X ⁻ (where Ar represents an aryl group, for example, a phenyl group;
X ^- is ^{_{BF 4 -, PF 6 -,}} SbF 5 (OH) -, Sb
F ₆ ^-, AsF ₆ ^- or the following formula

[0051]

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[0052] a group represented _{^{by) Ar 3 S + · X -}} (4) ( wherein, Ar and X ^- is the same as defined above)

[0053]

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(Wherein, R ⁵ represents an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms;
Represents an integer of 3 to 3, and X ^- has the same meaning as described above)

[0055]

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(Wherein, Y ⁻ represents PF ₆ ⁻ , SbF ₆ ⁻ or AsF ₆ ⁻ or SbF ₅ (OH) ⁻ )

[0057]

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

[0059]

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

[0061]

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

[0063]

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[0064] (wherein, R ⁶ is an alkenyl group having an aralkyl group, or -C 3-9 of 7 to 15 carbon atoms, R ⁷ is a hydrocarbon group or a hydroxyphenyl group having 1 to 7 carbon atoms, R ⁸ 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)

[0065]

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(Wherein R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 12 carbon atoms or 1 to 12 carbon atoms)
Represents an alkoxy group)

[0067]

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(Wherein R ⁹ and R ¹⁰ have the same meaning as described above)

[0069]

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[0070]

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(Wherein, R ⁹ , R ¹⁰ and R ¹¹ 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.) Have)

[0072]

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(Wherein R ¹² and R ¹³ are each independently
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.) A mixture of Ar ₃ Si—OOH and an aluminum chelate (wherein , Ar has the same meaning as described above) Examples of the cationic polymerization initiator include, in addition to the above, boron trifluoride, tetraethylammonium bromide, and the like. The cationic polymerization initiator can be used singly or as a mixture of two or more, and a thermal cationic polymerization initiator and a photocationic polymerization initiator can be used in combination.

Among the above cationic polymerization initiators, the aromatic sulfonium salt represented by the above formula (4), (5) or (6) is preferable as the thermal cationic polymerization initiator.
The aromatic sulfonium salt imparts excellent low-temperature curability to the composition of the present invention, and can cure a coating film from the composition of the present invention by heating at about 80 ° C. or more. Since it does not show a catalytic action, it does not deteriorate storage stability.

Specific examples of the above aromatic sulfonium salts 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 hexa Fluorophosphate, 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 aromatic sulfonium salts include, for example, San-Aid SI-L85 and SI-L11
0, same SI-L145, same SI-L160, same SI-H
15, 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, and SI-100 (all of which are manufactured by Sanshin Chemical Industry Co., Ltd., trade names).

Commercially available photocationic polymerization initiators include, for example, Cyracure UVI-6970 and UVC
I-6974 and UVI-6990 (both manufactured by Union Carbide Co., USA), Irgacure 26
1, 264 (all of which are Ciba Specialty
Chemicals), CIT-1682 (Nippon Soda Co., Ltd.)
), BBI-102 (manufactured by Midori Kagaku), Adeka Optomer SP-150, and SP-170 (all manufactured by Asahi Denka Co., Ltd.).

Some of the cationic polymerization initiators have a function of both a photocationic polymerization initiator and a thermal cationic polymerization initiator, and have a function of initiating cationic polymerization by light and by heating.

The amount of the cationic polymerization initiator to be mixed is curable,
From the viewpoint of storage stability, processability of the cured product, finished appearance, and the like, it is usually 0.01 to 20 parts by weight, preferably 0.0 to 20 parts by weight, based on 100 parts by weight of the cationically polymerizable binder component (A).
The range is preferably 5 to 15 parts by weight, more preferably 0.1 to 10 parts by weight.

Color pigment (C) The color pigment (C) to be incorporated in the composition of the present invention includes:
Color pigments commonly used in the field of paints and printing, for example, white pigments such as titanium white and zinc white; blue pigments such as cyanine blue and induslen blue; green pigments such as cyanine green and patina; azo-based and quinacridone-based Organic red pigments such as bengara; inorganic red pigments such as benzimidazoline, isoindolinone, isoindoline and quinophthalone; inorganic yellow pigments such as titanium yellow and graphite; carbon black, graphite, and pine smoke Black pigments such as aluminum powder, copper powder, nickel powder,
Glitter pigments such as titanium oxide-coated mica powder, iron oxide-coated mica powder, and glittering graphite are exemplified.

The color pigment (C) is preferably a neutral or acidic color pigment because it does not inhibit cationic polymerization, and a pigment whose pigment surface is neutralized or acidic is also preferable. Can be used.

The amount of the coloring pigment (C) in the composition of the present invention is 1 to 500 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the cationically polymerizable binder component (A).
Suitably, it is in the range of 0 parts by weight.

The cationically polymerizable coloring composition of the present invention contains a cationically polymerizable binder component (A), a cationic polymerization initiator (B) and a coloring pigment (C) as essential components. Lubrication of non-cationically polymerizable binder components, polymerization accelerators, fillers, pigment dispersants, flow control agents, leveling agents, defoamers, light stabilizers, antioxidants, thermal polymerization inhibitors, waxes, etc. A property imparting agent or the like can be contained.

Examples of the binder component having no cationic polymerizability include acrylic resins, polyester resins, rosin-modified phenol resins, and the like for the purpose of improving the viscosity of the composition and the properties and adhesion of the obtained cured product. Rosin-modified alkyd resins, ketone resins, and the like can also be blended. The compounding amount of the binder component having no cationic polymerizability is preferably within a range of 20 parts by weight or less based on 100 parts by weight of the cationically polymerizable binder component (A) in terms of curability and the like.

Examples of the polymerization accelerator that can be added to the composition of the present invention as required include alkylphosphine compounds such as triphenylphosphine and thioethers such as β-thiodiglycol. These can be used alone or in combination of two or more.

In the composition of the present invention, the color pigment (C)
Is required to be uniformly dispersed in the composition in order to sufficiently exhibit coloring power. The dispersion of the color pigment (C) is performed by dispersing the cationic polymerizable acrylic resin (A-1), the color pigment (C) and other components as necessary, for example, an organic solvent and other cationic polymerizable compounds (A-2). And a binder component having no cationic polymerizability by using a disperser such as a three-roll mill, a ball mill, a sand mill, and an attritor to disperse the pigment. By mixing the obtained pigment dispersion with the remaining components, if necessary, the cationically polymerizable colored composition of the present invention can be obtained.

The cationically polymerizable coloring composition of the present invention obtained as described above can be suitably used as a paint, ink, adhesive, resist material and the like.

The composition of the present invention can be applied to paper, plastic, metal, glass, wood, and a substrate combining these. For example, the coating amount of the composition of the present invention on the surface of these substrates is 1 to 50 μm, preferably 2
The coating can be performed so as to be within the range of ３０30 μm, and then cured by light irradiation or heating.

As the application means, it is possible to apply by a coating or printing method such as roll coater coating, spray coating, brush coating, bar coater coating, roller coating, screen printing, flat pressure printing, rotary printing and the like.

When the composition of the present invention contains a cationic photopolymerization initiator as a cationic polymerization initiator, it can be cured by irradiation with light. Can be cured.

When the applied composition of the present invention is cured by irradiation with light, if the composition of the present invention contains a solvent, the solvent may be removed by heating or the like, followed by irradiation with light such as ultraviolet rays. preferable. Light irradiation conditions are
The wavelength of light to be applied can be changed as appropriate depending on the type and thickness of the coated composition.
The range of 00 to 450 nm is appropriate, and an irradiation source having a wavelength with high sensitivity can be appropriately selected and used according to the type of the cationic photopolymerization initiator.

As a light irradiation source such as ultraviolet light, for example,
Examples include a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, and sunlight. The dose at the time of light irradiation is usually 10 to 200
0 mJ / cm ² , preferably 50 to 1000 mJ / cm
^A range of ² is suitable. After the light irradiation, heating may be performed. In some cases, the curing may be further advanced by heating, or the stress distortion of the cured product may be reduced, and the hardness and adhesion of the coating film may be improved. The heating is usually 150 to
It can be carried out at an atmosphere temperature of 400 ° C. for 5 seconds to 30 minutes.

When the applied composition of the present invention is cured not by light irradiation but by heating, it is usually from 80 to 200.
It is preferable to heat at an ambient temperature of 30 ° C. for 30 seconds to 5 hours.

[0094]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. . Hereinafter, both “parts” and “%” are based on weight.

Production Examples 1 to 6 of Cationic Polymerizable Acrylic Resin 50 parts of toluene was charged into a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, and a dropping device, and heated to 110 ° C. while blowing nitrogen gas. Warmed. Next, a mixed solution of a monomer shown in Table 1 below and 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator was dropped into the mixture over about 3 hours. After completion of the dropwise addition, the reaction was aged at 110 ° C. for 2 hours to complete the reaction. Then, using a vacuum pump, the pressure in the reaction vessel was reduced to remove the toluene solvent, and the cationically polymerizable acrylic resins (d) to (g) were removed.
I got The following table shows the glass transition temperature of the obtained resin by differential scanning calorimetry (DSC) measurement, the number average molecular weight by GPC (gel permeation chromatography) measurement, and the average number of epoxy groups and oxetane rings contained in one resin molecule. 1 is shown. Production Examples 5 and 6 are for comparison.

[0096]

[Table 1]

Examples 1 to 6 and Comparative Examples 1 to 3 Pigments and the cationically polymerizable acrylic resin obtained in each of the production examples were charged into a stirring and defoaming machine with the formulations shown in Table 2 below and kneaded for 10 minutes. The pigment was dispersed in this roll mill to obtain a pigment-dispersed paste.

To the obtained pigment dispersion paste, other cationically polymerizable binder components and a cationic polymerization initiator were charged into a stirring and defoaming machine at the ratios shown in Table 2 and kneaded for 3 minutes to prepare each of the cationically polymerizable coloring compositions. I got Table 2 shows the degree of pigment dispersion and the storage stability of each of the pigment dispersion pastes obtained in Examples 1 to 6 and Comparative Examples 1 to 3.

Preparation Method of Cured Coating (1) Each of the cationically polymerizable coloring compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 was applied to the surface of a 100 μm-thick polyethylene terephthalate film by a roll coater. ,
After coating to a thickness of 5 μm, ultraviolet rays were irradiated using a metal halide lamp so that the dose became 150 mJ / cm ² to obtain a cured coating film.

(2) Each of the cationically polymerizable coloring compositions obtained in Examples 5 to 6 and Comparative Example 3 was coated on a surface of an aluminum plate having a thickness of 500 μm by a bar coater so as to have a thickness of 8 μm. Thereafter, the coating was heated at 180 ° C. for 30 minutes to obtain a cured coating film.

The cured coating films obtained by the methods (1) and (2) were tested for appearance, pencil hardness, and surface curability of the cured coating film according to the following test methods. The test results are shown in Table 2 below.

Test Method Pigment dispersion degree of pigment dispersion paste: JIS K-5400
4.7.1 (1990) The distribution was determined based on the degree of dispersion. Observe the distribution density of the grains using a tub gauge,
The scale where the dense grains began to appear was read.

Storage stability of pigment-dispersed paste: The viscosity (initial viscosity) of the pigment-dispersed paste immediately after dispersion and the viscosity after storage at 40 ° C. for 1 week (viscosity after storage) were examined and evaluated according to the following criteria. The viscosity was measured with a rotary type dynamic viscoelasticity measuring device (manufactured by UBM) using a cone and plate at a shear rate of 20 s ^-1.
After breaking the structure for 3 minutes, the viscosity at a shear rate of 100 s ^-1 was measured.

：: Change in viscosity after storage is less than 10% based on initial viscosity Δ: Change in viscosity after storage is 10% or more based on initial viscosity 30
%: Change in viscosity after storage is 30% or more based on the initial viscosity.

Appearance of coating film: The smoothness, cracking and glossiness of the coating film were visually observed and evaluated according to the following criteria.

：: There is no abnormality in the coating film, and good. Δ: Slightly poor smoothness or gloss, but no crack is observed. ×: Crack is observed, or the smoothness or gloss is extremely poor.

Pencil hardness: JIS K-5400
A pencil scratch test specified in 4.2 (1990) was performed, and an evaluation based on scratches was performed.

Surface curability: The surface of the cured coating film was rubbed back and forth with a gauze impregnated with methyl ethyl ketone under a pressure of about 1 kg / cm ² , and the glossiness of the coating film surface was evaluated according to the following criteria.

◎: Little change in glossiness of the painted surface was observed even after 5 reciprocations. ○: Significant change in glossiness of the painted surface was recognized after 5 reciprocations, but almost no change in gloss after 2 reciprocations. Not observed, x: A considerable change in glossiness of the coated surface is observed after reciprocation.

[0110]

[Table 2]

(Note) in Table 2 has the following meanings.

(* 1) Alicyclic compound-1: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate. (* 2) Aliphatic compound-2: ethylene glycol diglycidyl ether.

(* 3) Eporide GT300: a product of Daicel Chemical Industries, Ltd., trade name, trifunctional alicyclic epoxy resin. (* 4) Oxetane compound-3: 3-ethyl 3-hydroxymethyloxetane.

(* 5) UVI-6990: a cationic photopolymerization initiator manufactured by Union Carbide Co., USA, trade name "Siracure UVI-6990". (* 6) BBI-102: manufactured by Midori Kagaku Co., Ltd., trade name, diallyliodonium salt-based photocationic polymerization initiator. (* 7) SI-180L: manufactured by Sanshin Chemical Industry Co., Ltd., thermal cationic polymerization initiator, trade name “Sun-Aid SI-180”
L ".

[0115]

The cationically polymerizable coloring composition of the present invention comprises:
As a binder component, since it contains a cationically polymerizable acrylic resin having a long-chain aliphatic hydrocarbon group in the side chain, the dispersion stability of the pigment is good, and it is cured by light irradiation or heating, and has excellent performance. A remarkable effect such as formation of a coating can be exhibited.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Michichi Kato 4-171-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Inside Kansai Paint Co., Ltd. (72) Inventor Ken Matsuda 4-1-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa F-term in Kansai Paint Co., Ltd. NA17 PA17 PC02 PC03 PC06 PC08 PC10 4J100 AB02R AE18P AG04R AJ02R AJ09R AK32R AL03R AL04Q AL05Q AL08P AL08R AL09R AL10P AM02R AM15R AM19R AM21R BA03R BA08R BA15P BA15R BA31R BA38P JA03 CA07 JA04

Claims (5)

[Claims] 1. (A) (a) a (meth) acrylate monomer having an aliphatic hydrocarbon group having 6 to 31 carbon atoms, (b) a polymerizable unsaturated group, an epoxy group and an oxetane ring A cationically polymerizable unsaturated monomer containing a cationically polymerizable site and, if necessary, (c) a cationically polymerizable acrylic resin (A-1) which is a copolymer of another polymerizable unsaturated monomer. (C) a cationically polymerizable binder component comprising: (B) a cationic polymerization initiator for initiating polymerization by light irradiation or heating; and (C) a color pigment. 2. The method according to claim 1, wherein the cationically polymerizable binder component (A) comprises:
10 to 90% by weight of a cationically polymerizable acrylic resin (A-1) and another cationically polymerizable binder component (A-2)
The coloring composition according to claim 1, comprising 10 to 90% by weight. 3. The colored composition according to claim 2, wherein the other cationically polymerizable binder component (A-2) is at least one binder component selected from an epoxy group-containing compound and an oxetane compound. 4. A cationically polymerizable binder component (A) 10.
0 parts by weight, based on the cationic polymerization initiator (B) 0.1 to
The coloring composition according to any one of claims 1 to 3, comprising 20 parts by weight. 5. The coloring pigment (C) is a neutral coloring pigment or an acidic coloring pigment, and is based on 100 parts by weight of the cationically polymerizable binder component (A).
5. The composition according to claim 1, wherein the content is 500 weight parts.
The coloring composition according to any one of the above.