JPH11106413A - Photocurable comosition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which can be photocured even in the inside of the composition even if a pigment having high masking property, a coloring dye, and the like are contained at high concentrations by including a compound having an ethylene-type unsaturated bond, a specific cationic coloring matter, and a specific sensitizer. SOLUTION: The compositions is obtained by including (A) 100 parts wt. of a compound having at least one redical-polymerizable ethylene-type unsaturated bond in its molecule [e.g. methyl (meth)acylate], (B) preferaby, 0.01-2 parts wt. of a cationic coloring matter shown by the formula; D1 +.A1 [D1 <+> is formula I (R1 and R2 are each an alkyl) and the like; A1 is an arbitrary anion], and (C) preferably, 0.05-5 part(s) wt. of a quaternary organic boron salt-based sensitizer shown by formula II (R11 -R14 are each are each an alkyl and the like; Z<+> is an arbitrary cation). It is preferable to add a polymerization promotor (e.g. sulfonium salt) and a UV radical polymerization initiator (e.g. benzoin isobutyl ether) to the composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a pigment and/or coloring dye having a high hiding property at a high concentration, a large thickness, or a material having a poor light transmission property. The present invention relates to a photocurable composition that can be photocured to the inside of the composition.

[0002]

2. Description of the Related Art Conventionally, photopolymerization is used in various fields such as curing and printing of coating film, resin relief and printed circuit board production, curing of photoresist or photomask, production of black and white or color transfer coloring sheet. In particular, recently, from the viewpoint of labor saving in response to global environmental problems, energy saving, and labor cost increase, attention has been paid to the fact that photopolymerization is possible even at room temperature, that it can be dried immediately, and that it can be solvent-free.
It is being actively developed.

In the development of printing inks, ultraviolet light curing inks have been studied for the purpose of solventlessness, improvement of productivity by rapid curing, or improvement of physical properties of cured films (for example, JP-A 1-229084, JP-A-2-22370
issue). Japanese Patent Laid-Open No. 22370/1990 discloses an ultraviolet light curable ink which is characterized by containing a poly(meth)acrylic acid ester and an ultraviolet light photopolymerization initiator and is excellent in curing speed and film hardness.

As for the development of coating materials, rapid drying and curing of colored coating films are being actively studied (for example,
JP-A-52-135341, JP-A-52-15243
6, JP-A-2-296875 and JP-A-3-626.
No. 5), curing by ultraviolet light is a method in which a polymerizable monomer is rapidly cured by cation polymerization or radical polymerization by irradiating with ultraviolet light of 200 to 400 nm, and a colored coating containing a pigment or a dye having a high hiding property. Ultraviolet light transmission becomes a problem in the film.

For example, when a pigment and/or a coloring dye having an excellent hiding power is added in order to obtain a colored coating film having excellent hiding property as described above, light is absorbed or reflected by the pigment or the coloring dye. As a result, the transmittance of light deteriorates, and the surface of the coating film is cured, but the interior of the coating film is not sufficiently cured. Even in a transparent system containing no pigment, coloring dye, etc., when the thickness of the composition is increased or the composition contains a material having poor ultraviolet light transmittance, the inside of the composition is not sufficiently cured. Had problems.

In order to solve this problem, Japanese Patent Laid-Open No. 4-80
No. 204 and JP-A-5-59110, a photopolymerization initiator comprising a visible light absorbing dye and a quaternary organic boron salt sensitizer is disclosed in JP-A-3-179003 and 4-39367.
JP-A-5-194619 proposes a near-infrared light radical polymerization initiator comprising a near-infrared light absorbing cationic dye and a quaternary organic boron salt sensitizer. Since these photopolymerization initiators have high sensitivity, they are said to be able to cure the inside of the composition even if they contain dyes and pigments and fillers having high hiding properties. However, the cationic dyes shown in these publications and
The sensitivity to light is still insufficient with the combination of high-grade organic boron salt-based sensitizers, so a composition containing a high concentration of dyes and pigments and fillers with high concealing properties such as enamel paints and inks at a sufficient depth It cannot be cured in the direction. Therefore, in order to increase the curability in the depth direction, there has been a demand for a more sensitive photopolymerization initiator that generates radicals even with weak light.

[0007]

SUMMARY OF THE INVENTION The present invention provides a pigment and/or
Alternatively, since it contains a coloring agent having a concealing property such as a coloring dye at a high concentration or contains a material having a poor light transmission property, it is possible to use a conventionally known cationic dye/organic quaternary boron salt sensitizer. A combination of a cationic dye and an organic quaternary boron salt sensitizer, which has a higher sensitivity than conventional initiator systems, can cure the interior of a composition that cannot be sufficiently photocured in combination in the depth direction in a short time. It is intended to provide a photocurable composition containing the composition.

[0008]

In order to solve this problem, the present inventors have developed a cationic dye having absorption in the visible light region,
Further, as a result of diligent studies of a photocurable composition in which a quaternary organic boron salt-based sensitizer is used as the sensitizer, even a composition containing a concealing pigment, a coloring dye or the like in a high concentration , A new combination of cationic dye/quaternary organic boron salt sensitizer capable of sufficiently curing the inside of the composition in the depth direction as compared with the cationic dye/quaternary organic boron salt sensitizers disclosed so far. Heading out, the present invention has been completed.

[0009]

[Wherein D ₁ ⁺ the general formula (2) shows the structure of the general formula (3), the general formula (4) or general formula (5), A ₁ ^- represents any anion. ]

General formula (2);

[Chemical 18] (R ₁ and R ₂ represent an alkyl group.) General formula (3);

[Chemical 19] (R ₃ and R ₄ represent an alkyl group.) General formula (4);

[Chemical 20] (R ₅ , R ₆ and R ₇ represent an alkyl group.) General formula (5);

[Chemical 21] (R ₈ , R ₉ and R ₁₀ represent an alkyl group) and a quaternary organic boron salt sensitizer represented by the general formula (6), the general formula (6);

[Chemical formula 22] (Wherein R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group or a halogen atom, and Z ⁺ is Any cation is shown) and mixed in a compound having a radical-polymerizable ethylenically unsaturated bond and irradiated with light having a wavelength at which a cationic dye is exposed, a composition containing a material having a hiding property. Even if it is a substance, the inside of the composition can be sufficiently photocured in the depth direction as compared with the conventional combination of cationic dye/quaternary organic boron salt sensitizer.

When the cation dye of the general formula (1) and the quaternary organic boron salt sensitizer of the general formula (6), which constitute the present invention, are used in combination, the cation dye is decomposed by light in the wavelength region where the cation dye is exposed. Occurs, and radical polymerization is started. At that time, the dye is generally decolored, the irradiation light is not blocked by the dye, and the photopolymerization reaction proceeds smoothly. If the quaternary organic boron salt-based sensitizer does not coexist, the decolorization reaction of the cationic dye does not proceed sufficiently or the polymerization reaction hardly occurs. The decolorization reaction of the dye efficiently proceeds, and the polymerization reaction proceeds.

The cationic dye D ₁ ⁺ used here is
The cationic dyes having the chemical structures of general formula (2), general formula (3), general formula (4) and general formula (5) are applicable. Here, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R
₈ , R ₉ and R _{10 each} represent an alkyl group, which may be linear or branched, and the number of carbon atoms is not particularly limited, but if the number of carbons is too large, the polymerization initiation efficiency may decrease. Alkyl groups having about 1 to 20 carbon atoms are usually preferable because problems may occur. More preferably, it is a C1-C10 alkyl group. Particularly, from the viewpoint of availability and the like, an alkyl group having 1, 2, 3 or 4 carbon atoms is most preferable. These alkyl groups may have a substituent, and specific examples of such a substituent include phenyl group, tolyl group, anisyl group, benzyl group, methoxy group,
Ethoxy group, n-propoxy group, isopropoxy group, n
-Butoxy group, sec-butoxy group, tert-butoxy group, phenoxy group, benzyloxy group, acetoxy group, benzoyloxy group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, benzoyl group, acetyl group, propionyl group, hydroxyl group, Examples thereof include a dimethylamino group, a diethylamino group, a cyano group, a sulfonic acid group, a fluoro group, a chloro group, and a bromo group, but the present invention is not limited to these examples.

Here, as particularly preferable D ₁ ⁺ , the structural formula (1) in the case of the general formula (2), the structural formula (2) in the case of the general formula (3), and the structural formula (3 in the case of the general formula (4). ) Or structural formula (4) and general formula (5) include structural formula (5). Structural formula (1);

[Chemical formula 23] Structural formula (2);

[Chemical formula 24] Structural formula (3);

[Chemical 25] Structural formula (4);

[Chemical formula 26] Structural formula (5);

[Chemical 27]

[0014] Here, the general formula of (1) of the cationic dye A ₁ ^-
Is any anion, and specific examples thereof include halogen anions such as chlorine, bromine, and iodine anions, benzenesulfonate anion, p-toluenesulfonate anion, 1-naphthalenesulfonate anion, and methanesulfonate anion. Borate anions such as acid anion, tetraphenylborate, tetraanisylborate, n-butyltriphenylborate, n-butyltri(4-tert-butylphenyl)borate, tetrabenzylborate, tetrafluoroborate, Cl
Examples include various anions such as O ₄ ⁻ , PF ₆ ⁻ , and SbF ₆ ⁻ . However, the present invention is not limited to these examples. Further, two or more kinds of the cationic dye of the general formula (1) may be used in an arbitrary ratio, if necessary.

The quaternary organic boron salt sensitizer used in the present invention is composed of a quaternary organic boron anion and an arbitrary cation (Z ⁺ ) as shown by the general formula (6). General formula (6);

[Chemical 28] (Wherein R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group or a halogen atom, and Z ⁺ is Indicates any cation.)

Here, R ₁₁ , R ₁₂ , and R ₁₃ of the general formula (6) are used.
And R ₁₄ represents an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group or a heterocyclic group, which may be linear or branched and the number of carbon atoms is not particularly limited. However, when the carbon number is too large, problems such as solubility and polymerization initiation efficiency may be deteriorated, and therefore, those having a carbon number of about 1 to 20 are usually preferable. More preferably, an alkyl group having 1 to 10 carbon atoms,
An aralkyl group, an alkenyl group, an aryl group having 6 to 20 carbon atoms, and a heterocyclic group.

R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ may have any substituents, and specific examples of such substituents include:
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group,
tert-butyl group, n-octyl group, n-dodecyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group, xylyl group, anisyl group, biphenyl group, naphthyl group, benzyl group, phenethyl group, diphenylmethyl group, methoxy Group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, methylenedioxy group,
Ethylenedioxy group, phenoxy group, naphthoxy group, benzyloxy group, methylthio group, phenylthio group, 2-
A furyl group, a 2-thienyl group, a 2-pyridyl group, a fluoro group and the like can be mentioned, but the present invention is not limited to these examples.

Specific examples of the quaternary organic boron anion which is the anion part of the quaternary organic boron salt sensitizer represented by the general formula (6) include methyltriphenylborate, ethyltriphenylborate and n-butyltriphenylborate. , N-
Octyl triphenyl borate, n-dodecyl triphenyl borate, sec-butyl triphenyl borate,
tert-butyltriphenylborate, benzyltriphenylborate, n-butyltrianisylborate,
n-octyl trianisyl borate, n-dodecyl trianisyl borate, n-butyltri(4-tolyl)borate, n-butyltri(2-tolyl)borate, n-butyltri(4-tert-butylphenyl)borate,
n-butyl tri(4-fluoro-2-methylphenyl)
Borate, n-butyltri(4-fluorophenyl)borate, n-butyltrinaphthylborate, n-butyltri(4-methylnaphthyl)borate, n-butyltri(4-methoxynaphthyl)borate, n-butyltri(6-methoxynaphthyl) ) Borate, triphenylsilyltriphenylborate, diphenylmethylsilyltriphenylborate, dimethylphenylsilyltriphenylborate, trimethylsilyltriphenylborate,
Examples thereof include tetra-n-butyl borate, di-n-butyl diphenyl borate and tetrabenzyl borate. Those having a structure in which R ₁₁ is an alkyl group and R ₁₂ , R ₁₃ and R ₁₄ are aryl groups have a polymerization initiation ability. The balance of stability is preferable. Further, it is particularly preferable that R ₁₁ is an alkyl group having 1 to 8 carbon atoms, and R ₁₂ , R ₁₃ and R ₁₄ are aryl groups having 6 to 15 carbon atoms.

The cation moiety Z ⁺ of the quaternary organic boron salt sensitizer of the general formula (6) is an arbitrary cation, but is preferably a quaternary ammonium cation, a quaternary pyridinium cation, or a quaternary chiral cation. Norinium cation, imidazolium cation, tetrazolium cation, oxazolium cation, isoxazolium cation, thiazolium cation, pyrylium cation, oxonium cation, phosphonium cation, sulfonium cation,
It is an oxosulfonium cation, an iodonium cation or a metal cation.

As specific examples, tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetraisopropylammonium, tetra-n-butylammonium, tetra-n-hexylammonium, tetraoctylammonium, N-methylpyridinium, N -Ethylpyridinium, N-methylquinolinium, N-ethylquinolinium, N-methylimidazolium, N-ethylimidazolium, N-ethyl-
5-phenylimidazolium, 2,3,5-triphenyltetrazolium, 2,3-bis(4-methoxyphenyl)-5-phenyltetrazolium, 2-chloro-3-
Ethylbenzoxazolium, 3-ethyl-2-methylbenzoxazolium, N-ethylisoxazolium, N-tert-butyl-5-methylisoxazolium, 3-methylbenzothiazolium, 3- Ethyl-2
-Methylbenzothiazolium, 2,4,6-triphenylpyrylium, 2,6-tert-butyl-4-methylpyrylium, triethyloxonium, tri-n-butyloxonium, tetramethylphosphonium, tetra-
Examples thereof include n-butylphosphonium, tetraphenylphosphonium, trimethylsulfonium, triphenylsulfonium, trimethylsulfoxonium, diphenyliodonium, di(4-tert-butylphenyl)iodonium, lithium cation and sodium cation, but the carbon atom is 2 Ammonium cations having ~8 alkyl groups are particularly suitable for increasing the solubility of quaternary organoboron sensitizers in compounds having ethylenically unsaturated bonds.

These quaternary organic boron anions and cation moieties Z ⁺ can be used in the present invention in any combination. Moreover, the present invention is not limited to these examples. Further, the quaternary organic boron salt sensitizer may be used in combination of two or more kinds.

Further, the sulfonium salt represented by the general formula (7), the diaryliodonium salt represented by the general formula (8), the N-alkoxypyridinium salt represented by the general formula (9), and the halogen represented by the general formula (10). A radical by adding at least one polymerization accelerator selected from a sulfonated sulfone compound, an organic peroxide represented by the general formula (11), and a triazine compound having a trihalomethyl group represented by the general formula (12). The polymerization initiation reaction proceeds more efficiently. These polymerization accelerators are compounds that generate electrons by accepting electrons from the dye radicals generated upon irradiation with light, and can further improve the internal curability of the composition.

General formula (7);

[Chemical 29] (In the formula, R ₁₅ and R ₁₆ represent an aryl group, R ₁₇ represents an alkyl group, an alkenyl group, an alicyclic group, an aryl group or an aralkyl group, and A ₂ ⁻ represents an arbitrary anion.)

General formula (8);

[Chemical 30] (In the formula, R ₁₈ and R ₁₉ each independently represent an aryl group, and A ₃ ⁻ represents any anion.)

General formula (9);

[Chemical 31] (In the formula, R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group,
It represents an alkoxy group, an aryl group or a heterocyclic group represented by the general formula (9), R ₂₅ represents an alkyl group, and A ₄ ⁻ represents an arbitrary anion. )

General formula (10);

[Chemical 32] (In the formula, R ₂₆ represents an aryl group, and R ₂₇ represents a halogen atom.)

General formula (11);

[Chemical 33] (In the formula, R ₂₈ represents an aryl group, and R ₂₉ represents an alkyl group, an aryl group or a benzoyl group.)

General formula (12);

[Chemical 34] (In the formula, R ₃₀ , R ₃₁ and R ₃₂ each independently represent a trihalomethyl group, an alkyl group, an alkenyl group or an aryl group, but at least one is a trihalomethyl group.)

The sulfonium salt represented by the general formula (7) is composed of a sulfonium cation and an arbitrary anion (A ₂ ^- ). Here, R ₁₅ and R ₁₆ are aryl groups, and R ₁₇
Represents an alkyl group, an alkenyl group, an alicyclic group, an aryl group or an aralkyl group, but may have a substituent. Specific examples of the substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a methoxy group, an ethoxy group, and an n-propoxy group. , Isopropoxy group, n-butoxy group, sec-butoxy group, tert-
Butoxy group, methylenedioxy group, benzyl group, phenethyl group, phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methylthio group, phenylthio group, cyano group, nitro group, diphenylsulfoniumyl group, fluoro group, Examples thereof include chloro group and bromo group, but the present invention is not limited to these examples.

Specific examples of the sulfonium cation include:
Triphenylsulfonium, diphenylanisylsulfonium, diphenyl(4-tolyl)sulfonium, diphenylmesitylsulfonium, diphenyl-tert-
Butylphenylsulfonium, trianisylsulfonium, tri(4-tolyl)sulfonium, tri(4-te)
rt-Butylphenyl)sulfonium, diphenylnaphthylsulfonium, diphenyl[4-(methylthio)phenyl]sulfonium, diphenyl[4-(phenylthio)phenyl]sulfonium, diphenyl[4-(diphenylsulfoniumyl)phenyl]sulfonium, diphenylbenzylsulfonium , Diphenyl(4-chlorobenzyl)sulfonium, diphenyl(4-bromobenzyl)sulfonium, di(4-tert-butylphenyl)benzylsulfonium, diphenylallylsulfonium, etc. are exemplified, and R ₁₅ , R ₁₆ and R ₁₇ Particularly preferred are sulfonium cations, all of which are aryl groups.

On the other hand, as A ₂ ^- , which is the anion part, B
F ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , ClO ₄ ⁻ , Cl ⁻
, Br ⁻ , tetraphenylborate, tetrakis(pentafluorophenyl)borate, benzenesulfonate anion, p-toluenesulfonate anion, trifluoromethanesulfonate anion and the like are exemplified, and the above-mentioned sulfonium cation and anion portion A ₂ ⁻ are Any combination can be used in the present invention.

The diaryliodonium salt represented by the general formula (8) is composed of a diaryliodonium cation and an arbitrary anion (A ₃ ⁻ ). Where R ₁₈ and R
Each ₁₉ independently represents an aryl group, but may have a substituent. Specific examples of the substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a methoxy group, an ethoxy group, and an n-propoxy group. , Isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, methylenedioxy group,
Examples of the benzyl group, phenethyl group, phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methylthio group, phenylthio group, cyano group, nitro group, fluoro group, chloro group, bromo group, etc. It is not limited to these examples.

Specific examples of the diaryliodonium cation include diphenyliodonium, anisylphenyliodonium, dianisyliodonium, ditolyliodonium, dimesityliodonium and di(4-tert).
Examples include -butylphenyl)iodonium, di(4-chlorophenyl)iodonium, di(3-nitrophenyl)iodonium, and naphthylphenyliodonium. On the other hand, as a specific example of A ₃ ⁻ which is an anion part,
F ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , ClO ₄ ⁻ , Cl
^-, Br ^-, tetraphenylborate, tetrakis (pentafluorophenyl) borate, benzene sulfonic acid anion, p- toluenesulfonate anion, trifluoromethanesulfonic acid anion, and the like. The above-mentioned diaryliodonium cation and anion part A ₃ ⁻ can be used in the present invention in any combination.

The N-alkoxypyridinium salt represented by the general formula (9) is composed of an N-alkoxypyridinium cation and an arbitrary anion (A ₄ ^- ). Here, in the general formula (9), R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each independently a hydrogen atom, a halogen atom, a cyano group,
Alkyl group, alkoxy group, aryl group, general formula (9)
In the heterocyclic group represented by, the alkyl group, the alkoxy group, the aryl group, and the heterocyclic group represented by the general formula (9) may have a substituent. Specific examples of such substituents include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, methoxy group, ethoxy group, n.
-Propoxy group, isopropoxy group, n-butoxy group,
sec-butoxy group, tert-butoxy group, methylenedioxy group, benzyl group, phenethyl group, phenyl group,
Examples thereof include a tolyl group, a xylyl group, a mesityl group, a naphthyl group, a methylthio group, a phenylthio group, a cyano group, a nitro group, a fluoro group, a chloro group, and a bromo group, but the present invention is not limited to these examples. Absent.

Specific examples of the N-alkoxypyridinium cation include N-ethoxypyridinium, N-ethoxy-2-picolinium, N-ethoxy-3-picolinium, N-methoxy-4-bromopyridinium and N-ethoxy-3-. Bromopyridinium, N-ethoxy-2-bromopyridinium, N-methoxy-4-chloropyridinium, N-ethoxy-3-chloropyridinium, N-ethoxy-2-chloropyridinium, N-ethoxy-4-
Methoxypyridinium, N-ethoxy-3-methoxypyridinium, N-methoxy-2-methoxypyridinium, N-ethoxy-4-phenylpyridinium, N-ethoxy-3-phenylpyridinium, N-ethoxy-2
-Phenylpyridinium, N-ethoxy-4-cyanopyridinium, N,N'-diethoxy-4,4'-bipyridinium and the like can be mentioned.

On the other hand, as the anion portion A ₄ ^- , B
F ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , Cl ⁻ , Br ⁻ ,
Examples include tetrakis(pentafluorophenyl)borate, benzenesulfonate anion, p-toluenesulfonate anion, trifluoromethanesulfonate anion, and the like. The above-mentioned N-alkoxypyridinium cation and anion moiety A ₄ ⁻ can be used in the present invention in any combination.

In the halogenated sulfone compound represented by the general formula (10), R ₂₆ represents an aryl group, but it may have a substituent. Specific examples of such a substituent include:
Methyl group, ethyl group, n-propyl group, isopropyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, benzyl group, phenyl group, tolyl group, xylyl group, mesityl group, nitro group, cyano group, Examples thereof include a fluoro group, a chloro group and a bromo group.

Specific examples of such compounds include trichloromethylphenyl sulfone, tribromomethylphenyl sulfone, trichloromethyl-4-chlorophenyl sulfone, tribromomethyl-4-nitrophenyl sulfone and 2,4-dichlorophenyltrichloromethyl sulfone. , 2-methyl-4-chlorophenyltrichloromethylsulfone and the like are exemplified.

In the organic peroxide represented by the general formula (11), R ₂₈ represents an aryl group, but may have a substituent. Specific examples of such a substituent include a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, benzyl group, phenethyl group, phenyl group,
Tolyl group, xylyl group, mesityl group, naphthyl group, fluoro group, chloro group, bromo group, tert-butylperoxycarbonyl group, isobutylperoxycarbonyl group, 3,4-bis(tert-butylperoxycarbonyl)benzoyl group , 3,4-bis(isobutylperoxycarbonyl)benzoyl group and the like, but the present invention is not limited to these examples. Also, R ₂₉
Represents an alkyl group, an aryl group, or a benzoyl group, but each may have a substituent, and specific examples of such a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n- group. Butyl group, sec-butyl group, ter
Examples thereof include t-butyl group, cyclohexyl group, benzyl group, phenethyl group, phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, fluoro group, chloro group, bromo group and benzoyl group. It is not limited to the example of.

Specific examples of such compounds include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, di(tert-butylperoxy)isophthalate and di(tert-butylperoxide). Oxy)terephthalate, di(tert-butylperoxy)phthalate,
2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 3,3′,4,4′-tetra(tert)
-Butylperoxycarbonyl)benzophenone and the like are exemplified.

In the triazine compound having a trihalomethyl group represented by the general formula (12), R ₃₀ , R ₃₁ and R ₃₂ each independently represent a trihalomethyl group, an alkyl group, an alkenyl group or an aryl group. 1
The individual is a trihalomethyl group. Here, the alkyl group, alkenyl group, and aryl group may have a substituent. Specific examples of such a substituent include a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, se
c-butyl group, tert-butyl group, cyclohexyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group,
tert-butoxy group, pentyloxy group, methylenedioxy group, amino group, dimethylamino group, diethylamino group, methylthio group, phenylthio group, benzyl group, phenethyl group, phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group , Anisyl group, 3,4-dimethoxyphenyl group, 2,4-dimethoxyphenyl group, 4-isopropoxyphenyl group, 4-pentyloxyphenyl group, 3-chloro-4-methoxyphenyl group, fluoro group, chloro group, Examples thereof include bromo group, but the present invention is not limited to these examples.

Specific examples of such compounds include 2,
4,6-Tris(trichloromethyl)-s-triazine, 2,4,6-Tris(tribromomethyl)-s-triazine, 2-propionyl-4,6-bis(trichloromethyl)-s-triazine, 2 -Benzoyl-4,6
-Bis(trichloromethyl)-s-triazine, 2-
(4-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(4-methoxyphenyl)-6-trichloromethyl-s-triazine,
2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-chlorostyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4 -Aminophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(4-methoxyphenyl)-6-trichloromethyl-s
-Triazine, 2,4-bis(3-chlorophenyl)-
6-trichloromethyl-s-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)
-S-triazine, 2-(4-aminostyryl)-4,
6-bis(dichloromethyl)-s-triazine and the like can be mentioned.

The above-mentioned polymerization accelerators represented by the general formulas (7) to (12) may be used alone or in combination of two or more kinds.

The photocurable composition of the present invention has a composition of 200 to 400 nm when the surface of the composition is cured in air.
It is preferable to use together with an ultraviolet light radical polymerization initiator that generates radicals by irradiating with ultraviolet light having a wavelength within the range. As the ultraviolet photo-radical polymerization initiator of the present invention, a usual photo-polymerization initiator of the type which is excited to generate a radical upon irradiation with ultraviolet light is used. As such a compound, a compound having a structure represented by the general formula (13) is shown. General formula (13);

[Chemical 35] (In the formula, Ar represents an aryl group, and X represents an alkyl group, an alicyclic group, a benzyl group, an alkoxycarbonyl group, a benzoyl group, an aryl group or a phosphinoyl group having a substituent.)

In Ar of the general formula (13), the aryl group may have an arbitrary substituent, and specific examples of such a substituent include a methyl group, an ethyl group, an n-propyl group, Isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-octyl group, n-dodecyl group, cyclohexyl group, phenyl group, tolyl group, anisyl group, naphthyl group, benzyl group,
Phenethyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, 2-hydroxyethoxy group, phenoxy group, naphthoxy group, benzyloxy group, hydroxy Group, acetoxy group, benzoyloxy group, acryloyloxy group, methacryloyloxy group,
Carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, benzoyl group, naphthoyl group, acetyl group,
Propionyl group, dimethylamino group, diethylamino group, morpholino group, methylthio group, phenylthio group, 2
-Furyl group, 2-furfuryl group, 2-thienyl group, 2-
Examples thereof include a pyridyl group, a 2-quinolinyl group, a fluoro group, a chloro group, and a bromo group, but the present invention is not limited to these examples.

In X of the general formula (13), the alkyl group, alicyclic group, benzyl group, alkoxycarbonyl group, benzoyl group and aryl group may have a substituent. Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-octyl group, n-dodecyl group, cyclohexyl group, phenyl. Group, tolyl group, anisyl group, naphthyl group, benzyl group, phenethyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, phenoxy group, Naphthoxy group, benzyloxy group, hydroxy group, acetoxy group, benzoyloxy group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, benzoyl group, naphthoyl group, acetyl group, propionyl group, dimethylamino group, diethylamino group, morpholino group, Examples thereof include a methylthio group, a phenylthio group, a 2-furyl group, a 2-furfuryl group, a 2-thienyl group, a 2-pyridyl group, a 2-quinolinyl group, a fluoro group, a chloro group, and a bromo group. It is not limited to the example.

Further, in X of the general formula (13), specific examples of the substituent of the phosphinoyl group having a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and a sec- group. Butyl group, isobutyl group, tert-butyl group, 2-ethylhexyl group, n-
Octyl group, 2,4,4-trimethylpentyl group, cyclohexyl group, phenyl group, tolyl group, 2,5-dimethylphenyl group, mesityl group, cumenyl group, benzyl group,
Phenethyl group, benzoyl group, 2,6-dichlorobenzoyl group, 2,4,6-trimethylbenzoyl group, 2,6
Examples thereof include a dimethoxybenzoyl group, a 2,6-diethoxybenzoyl group and a naphthoyl group, but the present invention is not limited to these examples.

Specific examples of the compound represented by the general formula (13) include benzoin compounds such as benzoin isobutyl ether, benzoin isopropyl ether, benzoin ethyl ether and benzyl dimethyl ketal, diethoxyacetophenone and 2-hydroxy-2-methyl. −
1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 4-tert-butyl-trichloroacetophenone, 2-methyl -1-[4-(methylthio)phenyl]
-2-morpholinopropanone-1,2-benzyl-2-
Acetophenone-based compounds such as dimethylamino-1-(4-morpholinophenyl)-butanone-1, glyoxyester-based compounds such as methylphenylglyoxylate,
Benzophenone compounds such as benzophenone, methyl benzoylbenzoate, hydroxybenzophenone, 4-phenylbenzophenone, and acrylated benzophenone,
2,4,6-Trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)
-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dichlorobenzoyl)-phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2 , 4,6-Trimethylbenzoyl)phenylphosphine oxide and other acylphosphine oxide compounds. Further, an ultraviolet light radical polymerization initiator having a structure other than the general formula (13), for example, a thioxanthone compound such as 2,4-diethylthioxanthone or 2-isopropylthioxanthone can be used.

In general, compounds called P1 type photoinitiators such as benzoin compounds, acetophenone compounds, glyoxyester compounds, and acylphosphine oxide compounds can be used alone, but P2
An ultraviolet photoradical polymerization initiator such as a benzophenone compound or a thioxanthone compound, which is a photoinitiator, is used in combination with a hydrogen donating compound. Even if the P1 type photoinitiator is used together with a hydrogen donor, the curability is further improved.

The hydrogen-donating compound is a compound capable of donating hydrogen to an initiator excited by light, for example, an aliphatic amine such as triethanolamine or methyldiethanolamine, 2-dimethylaminoethylbenzoic acid, 4-
Aromatic amines such as ethyl dimethylaminobenzoate, isobutyl 4-dimethylaminobenzoate and 4,4-dimethylaminobenzophenone can be mentioned.

These ultraviolet light radical polymerization initiators may be used alone or in admixture of two or more. In particular, a combination of a compound selected from a benzoin compound, an acetophenone compound and/or a benzophenone compound and an acylphosphine oxide compound is
Balanced surface curability and internal curability of the composition,
It is most preferable because a photocured product with a high appearance can be obtained.

The compound having an ethylenically unsaturated bond used in the present invention may be any compound as long as it has at least one radically polymerizable ethylenically unsaturated bond in the molecule. , Having a chemical form such as a polymer. These may be used alone, or may be a system in which two or more kinds are mixed at an arbitrary ratio for the purpose of improving physical properties and the like.

Examples of such compounds having a radical-polymerizable ethylenically unsaturated bond include those shown below. In the following, "(meta) acryl"
Means both “methacrylic” and “acry”.

Examples of the polymerizable monomer include esterified products of (meth)acrylic acid and monohydric alcohol, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, ( Isobutyl (meth)acrylate, tert-butyl (meth)acrylate,
Propyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate,
Cyclohexyl (meth), stearyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate,
Examples thereof include butoxyethyl (meth)acrylate and phenoxyethyl (meth)acrylate.

As the monomer, vinylbenzenes such as styrene, vinylstyrene, methylstyrene, chlorostyrene and divinylstyrene, vinyl ethers such as isobutyl vinyl ether, methyl vinyl ether and 2-ethylhexyl vinyl ether, and (meth)acryl. (Meth)acrylic compounds such as nitrile, (meth)acrylamide, methylenebis(meth)acrylamide, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, allyl alcohol, allyl acetate, diallyl phthalate, trimellitic acid Other vinyl compounds such as monomers containing an allyl group such as triallyl can also be used.

Further, examples of the monomer include carboxyl group-containing monomers such as (meth)acrylic acid, hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate, butyl isocyanate and phenyl isocyanate. Addition product of isocyanate compound and above-mentioned hydroxyl group-containing monomer, N
-Nitrogen-containing unsaturated monomers such as -vinylpyrrolidone, N-vinylcarbazole, N-vinylacetamide, and vinylpyridines can also be used.

Further, as the monomer, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butanediol di(meth)
Acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate Acrylate,
Multifunctional vinyl compounds such as pentaerythritol tetra(meth)acrylate and dipentaerythritol hexa(meth)acrylate, products obtained by reacting (meth)acrylic acid with an adduct of polyhydric alcohol and ethylene oxide or propylene oxide, A product obtained by reacting (meth)acrylic acid with an adduct of a polyhydric alcohol and ε-caprolactone, a phosphorus-containing polymerizable monomer, a (meth)acrylic functional polyorganosilsesquioxane, and the like are included.

The polymerizable oligomer includes an ethylenically unsaturated bond-containing resin, and specific examples thereof include polyester (meth)acrylate resin, unsaturated polyester resin, urethane (meth)acrylate resin and epoxy (meth)acrylate. Resin, phosphoric acid-modified epoxy (meth)acrylate resin, polybutadiene (meth)acrylate resin, silicone (meth)acrylate resin,
(Meth)acryloyl group-containing acrylic resin and the like can be mentioned.

The cationic dye represented by the general formula (1) is
The object of the present invention can be achieved by using 0.001 to 5 parts by weight with respect to 100 parts by weight of the compound having an ethylenically unsaturated bond. If it is less than 0.001 part by weight, the polymerization may not be sufficiently carried out and the curing may be insufficiently completed. If it exceeds 5 parts by weight, the photocured product is colored and the appearance of the photocured product is impaired. It is preferably 0.01 to 2 parts by weight.

The quaternary organic boron salt sensitizer represented by the general formula (6) is used in an amount of 0.005 to 10 parts by weight based on 100 parts by weight of the compound having an ethylenically unsaturated bond. The purpose can be achieved. 0.0
If the amount is less than 05 parts by weight, the polymerization may not be sufficiently performed, and the curing may be insufficiently completed, and at the same time, the decolorization reaction of the cationic dye may not sufficiently proceed and the cured product may be colored.
If it exceeds 10 parts by weight, the physical properties of the cured product may be deteriorated. It is preferably 0.05 to 5 parts by weight. The molar ratio of the cationic dye represented by the general formula (1) to the quaternary organoboron sensitizer represented by the general formula (6) is 1:
2-1:50 is preferable. When the molar ratio is less than 2, the radical polymerization initiation ability and the decolorizing property of the cationic dye cannot be sufficiently obtained. When the molar ratio exceeds 50, the residual quaternary organic boron salt sensitizer causes deterioration of the cured product. It is preferably in the range of 1:3 to 1:30.

The ultraviolet photo-radical polymerization initiator is 0.01 per 100 parts by weight of the compound having an ethylenically unsaturated bond.
By using 10 to 10 parts by weight, the object of the present invention can be achieved. If it is less than 0.01 part by weight, curing in air becomes difficult, and if it exceeds 10 parts by weight, physical properties of the cured product deteriorate, deterioration of the cured product due to residual ultraviolet photoradical polymerization initiator, and yellowing occur. Not preferable. Preferably 0.
It is in the range of 1 to 5 parts by weight.

The polymerization accelerators represented by the general formulas (7) to (12) are compounds 1 having an ethylenically unsaturated bond.
The object of the present invention can be achieved by using 0.005 to 10 parts by weight with respect to 00 parts by weight. If it is less than 0.005 part by weight, the effect of the polymerization accelerator will not be realized. Also,
If it exceeds 10 parts by weight, the physical properties of the cured product will be deteriorated, and the stability of the photocurable composition will be significantly deteriorated. It is preferably 0.01 to 5 parts by weight.

The photocurable composition of the present invention may cause color reversion of the cationic dye after photocuring depending on the composition. In that case, a compound having a substituent on at least one of the ortho positions of the carbon atom bonded to the phenolic hydroxyl group,
By mixing at least one selected from aromatic thiol compounds, amine compounds, and phosphorus compounds, it is possible to suppress color reversion of the cationic dye.

Specific examples of the compound having a substituent at at least one of the ortho positions of the carbon atom bonded to the phenolic hydroxyl group include 2,4,6-tri-tert-butylphenol and 2,6-di-tert-butyl. -P-cresol, N,N-hexamethylenebis(3,5-di-te
rt-butyl-4-hydroxy-hydrocinnamide),
4-tert-butylcatechol, octadecyl-3-
(3,5-Di-tert-butyl-4-hydroxyphenyl)propionate, 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4. 6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-tert-butyl-hydroxybenzyl)isocyanurate, 2,4
-Bis[(octylthio)methyl]-o-cresol,
2,2'-methylenebis(4-methyl-6-tert-
Butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,4,6-tris(dimethylaminomethyl)phenol, isooctyl-3-(3,5-di-tert-butyl-). 4-hydroxyphenyl)propionate, 2-(3,5-di-t
ert-Butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-tert-
Amyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2,4-di-te
rt-Butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4- Dodecyloxybenzophenone and the like are exemplified. For more details, see “12695 Chemical Products” (published by Kagaku Kogyo Nippo Ltd. in 1995) p969.
To p973, p977 to p981 compounds, “development of polymer additives and latest technology” (CMC Co., Ltd., published in 1992), p37 to p56 compounds, Po
lyfile (published by Taiseisha) 1997 Vol. Three
The phenolic compounds described in p22 to p30 can be used.

Specific examples of the aromatic thiol compounds include thiophenol, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole and 2,4,6-trimercapto. Examples include -s-triazine and 2-mercaptoimidazoline.

Examples of amine compounds include aliphatic amines such as triethanolamine and tributylamine, and N,N-.
Aromatic amines such as dimethylaniline and N,N-dimethyl-p-toluidine are exemplified, but bis(2,2,6,6)
6-Tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 2-(3,5-di-tert-butyl-4-hydroxybenzyl)- Bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-n-butylmalonate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl −
Hindered amine compounds such as 7,7,9,9-tetramethyl-1,3,8-trisazaspiro[4,5]decane-2,4-dione are particularly preferable. For more details, see “12695 Chemical Products” (Chemical Industry Daily 19
Published in 1995) The compounds described in p982 to p984 are exemplified.

Specific examples of phosphorus compounds include triphenylphosphine, tricyclohexylphosphine, trimethylphosphite, triethylphosphite, tributylphosphite, tridecylphosphite, triphenylphosphite, tris(2,4-di-). tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, cyclic neopentanetetraylbis(octadecylphosphite),2,2-methylenebis(4,6- The-tert-
Examples thereof include butylphenyl)octyl phosphite, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, and more specifically, “Development of polymer additives and latest technology” ( Compounds described in p60 to p66, etc. can be used.

The compound which suppresses the color reversion of these cationic dyes is added in an amount of 0.05 to 15 parts by weight based on 100 parts by weight of the compound having an ethylenically unsaturated group to achieve the purpose of suppressing the color reversion. You can If the amount is less than 0.05 parts by weight, color reversion cannot be completely suppressed.
If it exceeds 15 parts by weight, the curability is deteriorated or the physical properties of the cured product are deteriorated. It is preferably 0.2 to 10 parts by weight.

In the photocurable composition of the present invention, one or more kinds of coloring materials selected from coloring pigments, coloring dyes and bright pigments can be used. Color pigments include white pigments such as titanium white and zinc white, and black pigments such as carbon black and titanium black, as well as the "Revised New Edition Pigment Handbook".
Known organic and inorganic pigments described in (Edited by Japan Pigment Technology Association, published in 2001) can be used. As a coloring dye, "Handbook of Dyes" (edited by the Society of Synthetic Organic Chemistry, published in 1970)
The publicly known ones described in the above can be used. As the bright pigment, aluminum powder, aluminum paste, silver powder, titanium oxide-coated mica, mica-like iron oxide and the like can be used. These colorants can be added in an amount of 0 to 200 parts by weight based on 100 parts by weight of the compound having an ethylenically unsaturated bond.

Further, various extender pigments can be added to the photocurable composition of the present invention in order to suppress curing shrinkage and increase mechanical strength. As extender pigment, silica, silica-alumina, alumina, aluminum hydroxide, quartz, glass powder, glass beads, calcium carbonate,
Examples thereof include powders of kaolin, talc, mica, aluminum sulfate, calcium phosphate, and the like, and those whose surfaces are coated with a polyfunctional (meth)acrylate-based monomer or a silane coupling agent. Two or more different extender pigments may be added separately, or may be added after mixing, without any problem.

The photocurable composition of the present invention can be used by mixing it with a binder such as an organic polymer and coating it on a glass plate, an aluminum plate, another metal plate or a polymer film such as polyethylene terephthalate. Is. Polymers that can be used by mixing with the photopolymerizable composition of the present invention include polyacrylates, poly-α-alkyl acrylates, polyamides, polyvinyl acetals, polyurethanes, polycarbonates, polystyrenes, polyvinyl esters. And the like, and more specifically, polymethyl acrylate,
Polyethyl acrylate, polymethyl methacrylate,
Polyethylmethacrylate, polyvinylcarbazole,
Examples thereof include polyvinylpyrrolidone, polyvinyl butyral, polyvinyl acetate, novolac resin, phenol resin, epoxy resin and alkyd resin.

The photocurable composition of the present invention can be used as a solventless material and is expected to contribute to the improvement of the global environment. Of course, it can also be used in a form diluted with a conventional solvent. As the solvent used at that time, a general solvent used for applications such as conventional paints, for example, an aromatic hydrocarbon such as toluene or xylene, ethanol,
Alcohols such as 2-propanol and 1-butanol,
Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as diethylene glycol dimethyl ether and triethylene glycol dimethyl ether, esters such as ethyl acetate, butyl acetate and amyl acetate, ethylene glycol monoethers such as methyl cellosolve and ethyl cellosolve Etc. can be used.
These solvents may be used alone or in combination of two or more. The organic solvent reduces the viscosity of the material and improves workability, adhesion of the material to the base material, and the like.

The photocurable composition of the present invention may contain a thermal polymerization inhibitor for the purpose of preventing polymerization during storage. Specific examples of the thermal polymerization inhibitor that can be added to the photocurable composition of the present invention include p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, tert-butylcatechol, phenothiazine and the like.

The photocurable composition of the present invention further comprises an antifoggant, an antifading agent, a fluorescent whitening agent, a surfactant, a plasticizer, a flame retardant, an ultraviolet absorber, a foaming agent and a fungicide according to the purpose. Alternatively, an antistatic agent, a magnetic material, a conductive material, or the like may be used.

Light sources suitable for curing the photocurable composition of the present invention include high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, short arc metal halide lamps, xenon lamps, sodium lamps, halogen lamps, incandescent lamps, and sun lamps. Light, a semiconductor laser, an excimer laser, etc. are illustrated. The photocurable composition of the present invention is applied not only to paints, adhesives, and pressure-sensitive adhesives, but also to binders and other materials on a substrate to form various inks, electrophotographic materials, photographic materials such as hologram materials, and various recording materials such as microcapsules. It can also be used in media.

[0076]

EXAMPLES The present invention will be described below with reference to examples. Of course, the present invention is not limited to the examples shown below.

[Preparation of Various Paints] A white paint composition containing titanium oxide having the composition shown in Table 1 was prepared.

[0078]

[Table 1]

[Preparation of Samples and Comparative Samples] Photocurable samples containing various white paints, cationic dyes of the general formula (1), quaternary organic boron salt sensitizers and polymerization accelerators are shown in Table 2. Prepared with composition. Comparative samples in Table 2 were similarly prepared with the compositions shown in Table 3. Here, sample 1 and comparative sample 1, sample 2 and comparative sample 2,
Sample 3 and Comparative Sample 3, Sample 4 and Comparative Sample 4, Sample 5 and Comparative Sample 5, Sample 6 and Comparative Sample 6, Sample 7 and Comparative Sample 7, Sample 8
And Comparative sample 8, Sample 9 and Comparative sample 9, Sample 10 and Comparative sample 10, Sample 11 and Comparative sample 11, Sample 12 and Comparative sample 12, Sample 13 and Comparative sample 13, Sample 14 and Comparative sample 14, Sample 15 Comparative samples 15 correspond to each other. These components were the same except that they were mixed with equimolar amounts of different types of cationic dyes, and were prepared for the purpose of comparing differences in photocurability due to differences in cationic dyes. The cationic dyes used in Table 3 (general formula = D ₂ ⁺
The structure of D ₂ ⁺ of A ₅ ^- ) is shown in Table 4.

[0080]

[Table 2]

[0081]

[Table 3]

[0082]

[Table 4]

Photocurable samples containing various white paints, cationic dyes of the general formula (1), quaternary organic boron salt sensitizers, and ultraviolet photoradical polymerization initiators were prepared with the composition shown in Table 5. did. Further, the comparative sample in Table 5 was similarly prepared with the composition shown in Table 6. Here, sample 16 and comparative sample 16, sample 17 and comparative sample 17, sample 18 and comparative sample 18, sample 19 and comparative sample 19, sample 20 and comparative sample 20, sample 2
1 and comparative sample 21, sample 22 and comparative sample 2
2, sample 23 and comparative sample 23, sample 24 and comparative sample 24, sample 25 and comparative sample 25,
The sample 26 corresponds to the comparative sample 26, and the sample 27 corresponds to the comparative sample 27. These components were the same except that they were mixed with equimolar amounts of different types of cationic dyes, and were prepared for the purpose of comparing differences in photocurability due to differences in cationic dyes.

[0084]

[Table 5]

[0085]

[Table 6]

Table 7 shows photocurable samples containing various white paints, cationic dyes of the general formula (1), quaternary organic boron salt sensitizers, polymerization accelerators, and ultraviolet photoradical polymerization initiators. It was prepared with a compounding composition. In addition, comparative samples in Table 7 were similarly prepared with the compositions shown in Table 8. Here, sample 28 and comparative sample 28, sample 29 and comparative sample 29, sample 30 and comparative sample 30, sample 31
And Comparative sample 31, Sample 32 and Comparative sample 3
2, sample 33 and comparative sample 33, sample 34 and comparative sample 34, sample 35 and comparative sample 35,
The sample 36 corresponds to the comparative sample 36, the sample 37 corresponds to the comparative sample 37, the sample 38 corresponds to the comparative sample 38, and the sample 39 corresponds to the comparative sample 39. These components were the same except that they were mixed with equimolar amounts of different types of cationic dyes, and were prepared for the purpose of comparing differences in photocurability due to differences in cationic dyes.

[0087]

[Table 7]

[0088]

[Table 8]

[Curing Method for Each Sample] Curing Conditions A Samples 1 to 15 and Comparative Samples 1 to 15 had a thickness of 300 at both ends so that the cured coating film had a thickness of about 250 μm.
Aluminum plate with a spacer of μm (size 15
0×70 mm) and coated with a #30 bar coater.
After that, a PET film having a thickness of 30 μm is coated so that air does not enter the coated objects, and the coated objects of Samples 1 to 15 and Comparative Samples 1 to 15 are halogen lamps with an input power of 1.5 kW (manufactured by RDS Co., Ltd.). GSR-15-30
L) was used for irradiation at a distance of 30 cm for 5 minutes.

Curing condition B Samples 16 to 39 and comparative samples 16 to 39 were coated with a thickness of 300 μm on both ends so that the cured film thickness was about 250 μm.
Aluminum plate with m spacer (size 150
(×70 mm) was coated with a #30 bar coater. After that, the coated objects of Samples 16 to 39 and Comparative Samples 16 to 39 were treated with a metal halide lamp (UVL-6000M2-N1 manufactured by USHIO INC.) with an input power of 120 W/c.
Photocured in air at m). The metal halide lamp is incorporated in a belt conveyor type light irradiation device (UVC-5033 manufactured by Ushio Inc.), the distance between the metal halide lamp and the coated object is 25 cm, and the belt conveyor speed is 1.7 m/min. The light irradiation frequency is 1 to 4 times,
The coated object is divided into 4 parts, and each time it is passed once, it is divided into 1 part to shield the light from the aluminum foil, and the light irradiation amount is changed.
The cured state of the back surface side of the coating film after four irradiations was evaluated by peeling the coating film from the substrate. Under this light irradiation condition, a light amount of 1 J/cm ² (365 nm) will be irradiated if the light is irradiated once.

[Coating Film Evaluation Method] Curing Condition A Samples 1 to 15 cured with a halogen lamp were used in Example 1.
15 and Comparative Samples 1 to 15 are Comparative Examples 1 to 15,
"JIS K-5400 (General Test Method for Paint) 6.5
Using the evaluation method in "drying time", the cured state of the back surface of the coating film peeled from the aluminum substrate was evaluated. The results are shown in Table 9.

[0092]

[Table 9]

Curing condition B: Samples 16 to 39 cured with a metal halide lamp are Examples 16 to 39, and comparative samples 16 to 39 are Comparative Example 1.
6 to 39, the cured state by the light irradiation amount of the back surface of the coating film peeled from the aluminum substrate was evaluated in the same manner as the curing condition A. The results are shown in Tables 10 and 11.

[0094]

[Table 10]

[0095]

[Table 11]

From the above results, the cationic dyes having D ₁ ⁺ of the general formula (2), the general formula (3), the general formula (4) and the general formula (5) and the quaternary organic boron salt sensitizer Since the combination has higher sensitivity than the conventionally known combination of the cationic dye and the quaternary organic boron salt-based sensitizer, it may have high photocurability in the depth direction inside the composition having poor light transmittance. Was shown.

[0099]

The compound having an ethylenically unsaturated bond of the present invention and D ₁ ⁺ have the structures of the general formula (2), the general formula (3), the general formula (4) and/or the general formula (5). The photocurable composition comprising the cation dye and the quaternary organic boron salt-based sensitizer represented by the general formula (6) has a photocurable composition which is more excellent than the conventionally known combination comprising the cation dye/quaternary organic boron salt-based sensitizer. Since the composition has high sensitivity and high photoreactivity, the curability in the depth direction of the composition is good even if the composition contains a pigment or a coloring dye having a high hiding property. Therefore, the present curable composition is a paint, an adhesive, a pressure-sensitive adhesive,
It is possible to provide a good composition in the fields of ink, photoresist, hologram material and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C09D 4/00 C09D 4/00 5/00 5/00 C

Claims (14)

[Claims] 1. A compound (A) having an ethylenically unsaturated bond, (B) a cationic dye represented by formula (1), the general formula ^{_{(1); D 1 + ·}} A 1 - [wherein D ₁ ⁺ Represents the structure of the general formula (2), the general formula (3), the general formula (4) or the general formula (5), and A ₁ ⁻ represents any anion. ] General formula (2); (R ₁ and R ₂ represent an alkyl group.) General formula (3); (R ₃ and R ₄ represent an alkyl group.) General formula (4); (R ₅ , R ₆ and R ₇ represent an alkyl group.) General formula (5); (R ₈ , R ₉ and R ₁₀ represent an alkyl group.) and (C) Quaternary organic boron salt sensitizer represented by the general formula (6). General formula (6); (Wherein R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group or a halogen atom, and Z ⁺ is A photocurable composition comprising any cation). 2. The cation moiety (Z ⁺ ) of the quaternary organic boron salt sensitizer represented by the general formula (6) is a quaternary ammonium cation, a quaternary pyridinium cation, a quaternary quinolinium cation, or an imidazolium. Cation, tetrazolium cation, oxazolium cation, isoxazolium cation, thiazolium cation, pyrylium cation, oxonium cation, phosphonium cation,
Sulfonium cation, oxosulfonium cation,
The photocurable composition according to claim 1, which is an iodonium cation or a metal cation. 3. (A) 100 parts by weight of a compound having an ethylenically unsaturated bond, (B) 0.001 to 5 parts by weight of a cationic dye represented by the general formula (1), and (C) a general formula (6). 0.005 of a quaternary organic boron salt-based sensitizer represented by
The photocurable composition according to claim 1 or 2, which is composed of 10 to 10 parts by weight. 4. The molar ratio of the cationic dye represented by the general formula (1) to the quaternary organic boron salt sensitizer represented by the general formula (6) is 1:2 to 1:50. Item 4. The photocurable composition according to any one of Items 1 to 3. 5. The photocurable composition according to claim 1, wherein D ₁ ⁺ of the cationic dye of the general formula (2) has the structural formula (1). Structural formula (1); 6. The photocurable composition according to claim ₁ , wherein D ₁ ⁺ of the cationic dye of the general formula (3) has the structural formula (2). Structural formula (2); 7. The photocurable composition according to claim ₁ , wherein D ₁ ⁺ of the cationic dye of the general formula (4) has the structural formula (3). Structural formula (3); 8. The photocurable composition according to claim ₁ , wherein D ₁ ⁺ of the cationic dye of the general formula (4) has the structural formula (4). Structural formula (4); 9. The photocurable composition according to claim ₁ , wherein D ₁ ⁺ of the cationic dye of the general formula (5) has the structural formula (5). Structural formula (5); 10. R _{11 in the} general formula (6) is an alkyl group, R
_The photocurable composition according to claim 1, wherein ₁₂ , R ₁₃ and R ₁₄ are aryl groups. 11. R _{11 in the} general formula (6) has 1 to 8 carbon atoms.
The photocurable composition according to claim 10, which is one alkyl group. 12. At least one polymerization accelerator represented by formulas (7) to (12) is contained in an amount of 0.005 to 10 parts by weight per 100 parts by weight of a compound having an ethylenically unsaturated bond. The photocurable composition according to any one of claims 1 to 11. General formula (7); (In the formula, R ₁₅ and R ₁₆ represent an aryl group, R ₁₇ represents an alkyl group, an alkenyl group, an alicyclic group, an aryl group or an aralkyl group, and A ₂ ⁻ represents an anion.) General formula (8) ; (In the formula, R ₁₈ and R ₁₉ each independently represent an aryl group, and A ₃ ⁻ represents an arbitrary anion.) General formula (9); (In the formula, R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group,
It represents an alkoxy group, an aryl group or a heterocyclic group represented by the general formula (9), R ₂₅ represents an alkyl group, and A ₄ ⁻ represents an arbitrary anion. ) General formula (10); (In the formula, R ₂₆ represents an aryl group, and R ₂₇ represents a halogen atom.) General formula (11); (In the formula, R ₂₈ represents an aryl group, and R ₂₉ represents an alkyl group, an aryl group, or a benzoyl group.) General formula (12); (In the formula, R ₃₀ , R ₃₁ and R ₃₂ each independently represent a trihalomethyl group, an alkyl group, an alkenyl group or an aryl group, but at least one is a trihalomethyl group.) 13. An ultraviolet light radical polymerization initiator which generates radicals by absorbing light having a wavelength within a range of 200 to 400 nm with respect to 100 parts by weight of a compound having an ethylenically unsaturated bond is used in an amount of 0.01 to 10: The photocurable composition according to claim 1, wherein the photocurable composition is contained in an amount of part by weight. 14. The photocurable composition according to claim 13, wherein the ultraviolet photoradical polymerization initiator is a compound represented by the general formula (13). General formula (13); (In the formula, Ar represents an aryl group, and X represents an alkyl group, an alicyclic group, a benzyl group, an alkoxycarbonyl group, a benzoyl group, an aryl group or a phosphinoyl group having a substituent.)