JPH10306110A - Photo-setting composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve photo-setting sensitivity to thereby ensure sufficient curability even with a low photo-setting energy and make it possible to record an image at high speed by blending a radical-polymerizable unsaturated compound, a metal allene complex and an aromatic sulfonium salt. SOLUTION: A radical-polymerizable unsaturated compound comprising, e.g. a (meth)acrylic ester, an acrylamide, maleic anhydride or a maleic ester is blended with a metal allene complex of formula I (wherein M is a metal such as Fe, Ni or Co; X is a basic ionic substance such as BF4 , PF6 , AsF6 or SbF6 ; and Y is at least one group containing a benzene ring), in an amount of 0.01-20 wt.%, preferably 1-10 wt.%, an aromatic sulfonium salt of formula II (wherein X2 is a monovalent anion comprising, e.g. a halogen ion, OH, HSO4 , BF4 , PF6 , AsF6 or SbF6 ), and if necessary, a sensitizing dye comprising, e.g. xanthene dye, coumarin dye or merocyanine dye.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable composition used for recording inks, photocurable microcapsules for image recording, photosensitive coatings, etc., and more particularly to a photocurable composition exhibiting a highly sensitive curing reaction. It relates to a composition.

[0002]

2. Description of the Related Art Conventionally, photocurable compositions have been used for printing inks,
It has been developed for the purpose of printing plate, resist for printed circuit board, etc. Among them, particularly highly sensitive photocurable compositions include, for example, those using 2,4,5-triphenylimidazolyl dimer and a free radical generator in a photopolymerization initiation system, and 2,4,5-triene. Phenylimidazolyl dimer and p-
Those using aminophenyl ketone as a photopolymerization initiation system have been developed.

As photocurable compositions having sensitivity to visible light, for example, a complex initiation system of a dye and an aliphatic amine, a system of a hexaarylbiimidazole and a radical generator and a dye, a system of a hexaarylbiimidazole And p
-Dialkylaminobenzylidene ketone system, cyclic cis-α-dicarbonyl compound and dye system, carbonyl compound and tertiary amine system, substituted-triazine and merocyanine dye system, biimidazole and imidanone system, hexaarylbiimidazole and p-dialkylaminostilbene derivative system, hexaarylbiimidazole and p-dialkylaminocinnamylidene derivative system, triazine derivative and cyanine dye system, triazine derivative and thiapyrylium salt system, hexaarylbiimidazole and n-
Photopolymerization of dialkylstilbenzene derivatives or p-dialkylaminophenylbutadienyl derivatives and thiol compounds, ketone-substituted derivatives and organic peroxides, α-diketones and mercaptocarboxylic acids, α-diketones and polysulfides The one used for the starting system has been developed.

[0004]

However, the photocurable composition using the above-mentioned single or composite photopolymerization initiator has a poor photocuring sensitivity, and is not sufficiently cured in a short time in image recording. There was a problem.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problem, and can improve photocuring sensitivity, secure sufficient curability even with a small photocuring energy, and record an image at high speed. It is an object of the present invention to provide a photocurable composition that can be used.

[0006]

Means for Solving the Problems To achieve this object, the photocurable composition of the present invention is intended to be cured by irradiation with light, and particularly to a compound containing a radical polymerizable unsaturated group. , A compound having a metal arene complex and an aromatic sulfonium salt.

The photosensitive recording material according to the present invention having the above constitution is a compound having a radical polymerizable unsaturated group-containing compound, a metal arene complex, and an aromatic sulfonium salt, so that the photocuring sensitivity is improved. Thus, sufficient curability can be ensured even with a small light curing energy, and an image can be recorded at high speed.

[0008]

Embodiments of the present invention will be described below in detail.

The photo-curable composition used in the present invention is a compound having a radical polymerizable unsaturated group-containing compound, a metal arene complex and an aromatic sulfonium salt.

The radical polymerizable unsaturated group-containing compound is, for example, a compound having an ethylenically unsaturated group or a compound having an epoxy group. Especially desirable.

Compounds having an ethylenically unsaturated group include, for example, acrylic acid and salts thereof, acrylates,
Acrylamides, methacrylic acid and its salts, methacrylic esters, methacrylamides, maleic anhydride, maleic esters, itaconic esters, styrenes, vinyl ethers, vinyl esters, N-
Examples include vinyl heterocycles, allyl ethers, allyl esters, and derivatives thereof, and acrylates or methacrylates having a relatively high photopolymerization rate are particularly desirable.

Acrylic esters include, for example, butyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethyl acrylate, tricyclodecanyloxy acrylate, noniphenyloxyethyl acrylate, hexanediol acrylate,
1,3-dioxolan acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, tricyclodecane dimethylol diacrylate, tripropylene glycol diacrylate, bisphenol A diacrylate, pentaerythritol triacrylate Acrylate, dipentaerythritol hexaacrylate, hexaacrylate of caprolactone adduct of dipentaerythritol, trimethylolpropane triacrylate, triacrylate of propylene oxide adduct of trimethylolpropane, diacrylate of polyoxyethylenated bisphenol A, polyester acrylate, Polyurethane acrylate and the like.

The methacrylic acid esters include, for example, butyl methacrylate, cyclohexyl methacrylate, ethylhexyl methacrylate, benzyl methacrylate, furfuryl methacrylate, ethoxyethyl methacrylate, tricyclodecanyloxy methacrylate,
Noniphenyloxyethyl methacrylate, hexanediol methacrylate, 1,3-dioxolane methacrylate, hexanediol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, tricyclodecane dimethylol dimethacrylate,
Hexamethacrylate of tripropylene glycol dimethacrylate, bisphenol A dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, and a caprolactone adduct of dipentaerythritol.

The methacrylates include, for example, trimethylolpropane trimethacrylate, trimethacrylate of propylene oxide adduct of trimethylolpropane, dimethacrylate of polyoxyethylenated bisphenol A, polyester methacrylate, and polyurethane methacrylate.

These polymerizable compounds may be used alone or as a mixture of two or more.

In particular, the acrylates and methacrylates have at least three acryloyl groups which are unsaturated groups in the molecule, and are pentaerythritol triacrylate, dipentaerythritol hexaacrylate, and caprolactone addition of dipentaerythritol. It is desirable to include at least one of hexaacrylate, trimethylolpropane triacrylate, and a triacrylate of a propylene oxide adduct of trimethylolpropane.

Further, the photocurable composition has the following general formula:

[0018]

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(In the above general formula, M is Fe, Ni, Co
X represents BF ₄ , PF ₆ , AsF ₆ , Sb
It represents a basic ionic substance such as F ₆ , and Y represents a group containing at least one benzene ring. ) Is contained.

The radical polymerizable unsaturated group-containing compound contains the metal arene complex in a ratio of about 0.01 to about 20% by weight, more preferably 1 to 10% by weight. Usually 1
At a ratio of less than 10% by weight, the photopolymerization reaction hardly occurs.
At a ratio of 10% by weight or more, the sensitivity is not improved.

In order to improve the photosensitivity of the curable composition, in particular, the photosensitivity to wavelength, a sensitizing dye may be used in combination. The sensitizing dyes include xanthene dyes, coumarin dyes, merocyanine dyes, thiazine dyes,
Azine dyes, methine dyes, oxazine dyes, phenylmethane dyes, cyanine dyes, azo dyes, anthraquinone dyes, pyrazoline dyes, stilbene dyes, quinoline dyes and the like can be used.

Further, a pigment is used as a photochromic substance. Pigments may be commercially available or may be a book such as a pigment handbook (for example, "Latest Pigment Handbook" edited by the Japan Pigment Technical Association,
Among those described in the literature (1977) or in the literature, those having an appropriate hue are dispersed and used.

In particular, it is desirable to use monoazo, disazo, azocalcium lake and azobarium lake for yellow, quinacridone and calcium lake for magenta and phthalocyanine for cyan.

The photocurable composition of the present invention has the following general formula

[0025]

Embedded image

(In the above formula, X ₂ is a halogen ion, OH, HSO ₄ , BF ₄ , PF ₆ , AsF ₆ , SbF ₆
And the like. ) Is contained.

For example, triphenylsulfonium bromide,
It contains triphenylsulfonium chloride, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate and the like.

In addition, for the purpose of adjusting the solubility of the photocurable composition of the present invention, an organic solvent having an appropriate polarity can be used in combination.

The photocurable composition may further contain, if necessary, a heat polymerization inhibitor, a sensitizer, a surfactant and the like, but they may interfere with the photosensitive properties of the photosensitive material. must not.

Hereinafter, embodiments of the present invention will be described.

(Examples) (a) Radical polymerizable unsaturated group-containing compound (one to one compounding ratio) Dipentaerythritol polyacrylate phenylglycidyl ether acrylate 100% by weight in total (b) Photopolymerization initiator Iron arene complex 3% by weight aromatic sulfonium salt 1% by weight (c) wavelength sensitizing dye squarylium dye 0.3% by weight (d) sensitivity sensitizer 2,6-diisopropyl-N, N-dimethylaniline 1.5% by weight The mixture was mixed and heated and kneaded at 100 ° C. to produce a photocurable composition. The composition was applied to a 50 μm-thick polyester sheet with a bar coater, and the coated surface was covered with the same polyester sheet to prepare a sample.

This coating film exhibits a blue color due to the squarylium-based dye and has a peak sensitivity to red light. Therefore, the photocuring energy at a wavelength of 650 nm was measured with a spectral sensitometer to obtain a measure of sensitivity and curability. .

Table 1 shows the evaluation results of the examples and the comparative examples.

[0034]

[Table 1]

Comparative Example 1 A photocurable composition was produced in the same manner as in the example except that the aromatic sulfonium salt was omitted from the example. As a result, the photocuring energy at a wavelength of 650 nm was 2,100 erg · cm ⁻² .

Comparative Example 2 A photocurable composition was produced in the same manner as in the example except that the iron arene complex was omitted from the example. As a result, no photopolymerization reaction occurred and no curing occurred.

As is evident from Table 1, Examples 1 to 5 in which the aromatic sulfonium salt was added had lower photocuring energy values than Comparative Example 1 in which the aromatic sulfonium salt was not added. And it was confirmed that the composition was cured in a short time. With the same photocuring energy, the photocurable composition of this example has a faster curing speed than that of the comparative example.

Therefore, the photocurable composition cured by irradiation with light is a compound having a radical polymerizable unsaturated group-containing compound, a metal arene complex, and an aromatic sulfonium salt, so that the photocuring sensitivity can be improved. It was confirmed that sufficient curability can be secured even with a small light curing energy.

It should be noted that the present invention is not limited to the above-described embodiment, and that the configuration and operation can be changed without departing from the scope of the claims. For example, the photocurable composition of the present invention may be encapsulated in microcapsules.

The benzene ring of the metal arene complex may have a substituent, and the phenyl group of triphenylsulfonium may have a substituent.

Further, the phenyl group may be a polycyclic group such as naphthyl, which may have a substituent.

[0042]

As is apparent from the above description, the photocurable composition of the present invention is a compound having a radical polymerizable unsaturated group-containing compound, a metal arene complex, and an aromatic sulfonium salt. Therefore, the photocuring sensitivity is improved by the synergistic effect of the metal arene complex and the aromatic sulfonium salt, sufficient curability can be ensured even with a small photocuring energy, and an image can be recorded at high speed.

Claims (1)

[Claims] 1. A photocurable composition which is cured by irradiation with light, wherein the compound comprises a radical polymerizable unsaturated group-containing compound, a metal arene complex, and an aromatic sulfonium salt. Curable composition.