JPH10279614A - Photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymerizable composition excellent in sensitivity upon exposure to light in the visible region by mixing an ethylenically unsaturated addition-polymerizable compound with a photopolymerization system comprising dipyrromethene difluoroborate sensitizer and a radical generator which generates active radicals upon irradiation with light in the presence of the sensitizer. SOLUTION: The ethylenically unsaturated addition-polymerizable compound is exemplified by an unsaturated carboxylic acid, an alkyl ester thereof or an ester of an aliphatic or aromatic polyhydroxy compound, more particularly methyl (meth)acrylate or maleate. The photopolymerization initiation system comprises a sensitizer of formula I[wherein at least one of R<1> to R<7> is an alkyl branched in position α or β, and the rest are each hydrogen, cyano, chloro, a 1-10 C alkyl or the like; a substituted vinyl group of the formula II (wherein n is 0-4; R<8> is hydrogen or a 1-10 C alkyl: and R<9> is a 4-20 C heterocyclic group or the like) or the like] and a radical generator such as a titanocene compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a photopolymerizable composition. In particular, the present invention relates to a photopolymerizable composition having extremely high sensitivity to light in the visible region.

[0002]

2. Description of the Related Art Conventionally, many image forming methods using a photopolymerization system are known. For example, a photopolymerizable composition comprising an addition-polymerizable compound containing an ethylenic double bond, a photopolymerization initiator, and an organic polymer binder used as desired is prepared, and the photopolymerizable composition is supported. Create a light-sensitive material with a layer of photopolymerizable composition applied to the body, image-expose the desired image, polymerize and cure the exposed part, and dissolve and remove the unexposed part to form a cured relief image A photosensitive material provided with a layer of a photopolymerizable composition whose adhesive strength changes due to light between two supports, at least one of which is transparent, is subjected to image exposure from the transparent support side to reduce the adhesive strength by light. There is a method of forming an image by peeling the support after causing the change; and an image forming method utilizing a change in toner adhesion of the photopolymerizable composition layer due to light. As a photopolymerization initiator of the photopolymerizable composition applied to these methods, benzoin alkyl ether, benzyl ketal, benzophenone, anthraquinone, benzyl, Michler's ketone, and the like have been conventionally used.

[0003] However, these photopolymerization initiators are 4
Compared to the photopolymerization initiating ability for light in the ultraviolet region of 00 nm or less, that for light in the visible light region of 400 nm or more was significantly lower, and thus the application range of the photopolymerizable composition containing these was limited. . In recent years, with the development of image forming technology, there has been a strong demand for a photosensitive composition having a high sensitivity to light in the visible region. Its main use is, for example, a photosensitive material for non-contact projection exposure plate making or laser plate making using a visible light laser. Among them, in particular, YAG laser 532
A plate making method using a nm oscillation beam is considered to be one of the most promising techniques.

[0004] Several proposals have heretofore been made for a photopolymerization composition containing a photopolymerization initiation system capable of responding to light in the visible light region. For example, a system of hexaarylbiimidazole, a radical generator and a dye (Japanese Patent Publication No.
JP-A-37377), a system of hexaarylbiimidazole and (p-dialkylaminobenzylidene) ketone (JP-A-47-2528, JP-A-54-155292).
JP-A-48-15184, a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-84183), and a system of a substituted triazine and a merocyanine dye (JP-A-54-151024).
JP-A-52-1), a system of ketocoumarin and an activator (JP-A-52-1)
12681, JP-A-58-15503, JP-A-60-15
-88005), a system of a substituted triazine and a sensitizer (JP-A-58-29803, JP-A-58-40302).
), Hexaarylbiimidazole, styrene derivative, thiol system (JP-A-59-56403), and organic peroxide and dye system (JP-A-59-1402).
No. 03, JP-A-59-189340).

[0005] Examples of the use of titanocene in a photopolymerization initiation system are disclosed in JP-A-59-152396 and JP-A-6-152396.
1-1151197, JP-A-63-10602, JP-A-63-41484, JP-A-2-291, JP-A-3-291
-12403, JP-A-3-20293 and JP-A-3-20293
27393, JP-A-3-52050, and
A system in which a titanocene and a xanthene dye are further combined with an addition-polymerizable ethylenically unsaturated double bond-containing compound having an amino group or a urethane group (JP-A-4-221958)
JP-A-4-219756), a system of titanocene and 3-ketocoumarin dyes having excellent sensitivity near an argon ion laser at 488 nm (JP-A-63-221110).
JP-A-6-289335, JP-A-3-2335, and titanocene and a coumarin dye having a heterocyclic group at the 3-position.
39703). Further, a system of a pyrromethene dye having a specific substituent and a radical generator (JP-A-4-241338, JP-A-7-5885, JP-A-7-5685)
-225474) are also known.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photopolymerizable composition having high sensitivity to long wavelength light such as visible light. In particular, the present invention uses a photopolymerization initiation system comprising a combination of a sensitizer and a compound capable of generating an active radical upon irradiation with light.
It is an object of the present invention to provide a photopolymerizable composition having extremely excellent sensitivity to exposure near 0 nm.

[0007]

A photopolymerizable composition according to the present invention comprises an addition-polymerizable compound having at least one ethylenically unsaturated bond and a polymerization initiation system, and further comprises a polymerization initiation system. The system comprises a sensitizer represented by the following general formula (I) and a radical generator capable of generating an active radical when exposed to light in the presence of the sensitizer. is there.

[0008]

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Wherein at least ^one of R ^{1 to} R ⁷ is α-
And the other are each independently a hydrogen atom, a cyano group, a chlorine atom, a bromine atom or an allyl group, or a carbon number which may have a substituent. 1-10 alkyl groups, 1-10 carbon atoms
An alkoxy group, an acyl group having 2 to 15 carbon atoms, and 2 carbon atoms
To 15 alkoxycarbonyl groups or 6 to 2 carbon atoms
0 represents a cyclic hydrocarbon group or a substituted vinyl group represented by the following general formula [II] or [III]. However, at least one of R ³ and R ⁴ is a substituted vinyl group represented by the general formula [II] or [III].

[0010]

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[0011] (wherein, n represents an integer of 0 to 4, R ⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ⁹
Represents an optionally substituted heterocyclic group having 4 to 20 carbon atoms or a cyclic hydrocarbon group having 6 to 20 carbon atoms. )

[0012]

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(Wherein, p and m each represent an integer of 0 to 3, R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ¹¹ represents a hydrogen atom, a cyano group or An optionally substituted alkoxycarbonyl group having 2 to 15 carbon atoms, a phenoxycarbonyl group, or a carbon atom having 2 to 1 carbon atoms
5 represents an acyl group. )

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The addition-polymerizable compound having at least one ethylenically unsaturated bond (hereinafter abbreviated as “ethylenic compound”) contained as the first essential component in the photopolymerizable composition of the present invention refers to a photopolymerizable composition. A compound having an ethylenically unsaturated bond such that, when the product is irradiated with actinic rays, it undergoes addition polymerization by the action of the photopolymerization initiation system, which is the second essential component, and cures. It is a monomer having a bond or a polymer having an ethylenically unsaturated bond in a side chain or a main chain. The meaning of the monomer in the present invention is a concept corresponding to a so-called polymer substance, and therefore, a dimer other than a narrow amount of a monomer,
It also includes trimers and oligomers.

Examples of the monomer having an ethylenically unsaturated bond include unsaturated carboxylic acids and alkyl esters thereof, esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids, and aromatic polyhydroxy compounds with unsaturated carboxylic acids. And esters obtained by an esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound and aromatic polyhydroxy compound.

As the unsaturated carboxylic acid and its alkyl ester, acrylic acid, methacrylic acid, itaconic acid,
Examples thereof include crotonic acid, maleic acid, and alkyl esters having 1 to 5 carbon atoms of these carboxylic acids. Representative examples of such alkyl esters include methyl, ethyl, propyl, and butyl esters of acrylic acid or methacrylic acid.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate,
Acrylics such as trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate Acid esters, methacrylic acid esters in which the acrylic acid component of these acrylates is replaced with methacrylic acid, itaconic acid esters in the same way as itaconic acid, crotonic acid esters in the place of crotonic acid, maleic acid esters in the place of maleic acid, etc. No.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. The ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polycarboxylic acid and the polyhydric hydroxy compound is not always a single substance, but typical examples include condensation of acrylic acid, phthalic acid and ethylene glycol. Object, acrylic acid,
There are condensates of maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

Other examples of the ethylenic compound used in the present invention include acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate. Examples of the polymer having an ethylenically unsaturated bond in the main chain include a polyester obtained by a polycondensation reaction of an unsaturated divalent carboxylic acid and a hydroxy compound, and a polycondensation reaction of an unsaturated divalent carboxylic acid and a diamine. And the like. As the polymer having an ethylenically unsaturated bond in the side chain, a divalent carboxylic acid having an unsaturated bond in the side chain, for example, itaconic acid, propylidene succinic acid, ethylidene malonic acid, etc. and a condensation polymer of dihydroxy or diamine compound There is coalescence. Further, a polymer having a functional group having a reactive activity such as a hydroxy group or a methyl halide group in a side chain, for example, polyvinyl alcohol, poly (2-
Hydroxyethyl methacrylate), polyepichlorohydrin or the like and a polymer obtained by a polymer reaction of an unsaturated carboxylic acid such as acrylic acid, methacrylic acid or crotonic acid can also be suitably used.

Of the above-mentioned ethylenic compounds, monomers of acrylic esters or methacrylic esters can be particularly preferably used. Next, the photopolymerization initiation system, which is the second essential component of the photopolymerizable composition of the present invention, will be described. The photopolymerization initiation system used in the present invention is composed of a combination of two components of a sensitizer and an active radical generator, and the sensitizer has a substituent represented by the general formula [I]. Use dipyrromethene difluoroborate.

[0021]

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This dipyrromethene difluoroborate is a generally known compound, for example, US Pat.
4,339 and J.M. H. Boger et al, Het
room Chemistry, Vol. 1,5
389 (1990); U.S. Pat.
89029. For example, R ¹ , R ² , R ⁵ and R ^{6 in} the above general formula [I] suitable for use as a sensitizer in the present invention are all methyl groups, R ³ is hydrogen and R ⁷ Is a t-butylmethyl group, and R ⁴ is a 2-cyano-2-ethoxycarbonylvinyl group in the general formula [I], wherein R ¹ , R ² , R ⁵ and R ⁶ are all methyl groups. ,
It can be synthesized from a compound in which R ⁷ is a t-butylmethyl group and R ³ and R ⁴ are hydrogen and ethyl cyanoacetate as follows.

[0023]

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[0024]

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In the above reaction, 2-chlorobenzothiazole is subjected to Wittig reaction in the presence of triphenylmethylphosphonyl bromide and n-butyllithium in place of ethyl cyanoacetate. A compound having a 2-benzothiazolylvinyl group bonded to the 4-position suitable for use as a compound is obtained.

[0026]

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In the above general formula [I], R ^{1 to} R ⁷
At least one is an alkyl group branched at the α-position or β-position. This alkyl group has the following general formula (I
V] are preferred.

[0028]

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Wherein R ¹² and R ¹³ are each independently an alkyl group having 1 to 10 carbon atoms, R ¹⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and q is 0 Or 1] The alkyl group represented by the general formula [IV] has 3 to 2 carbon atoms.
It is preferably 0. Particularly preferred among the alkyl groups of the general formula [IV] are alkyl groups having a tertiary carbon atom at the α-position or the β-position and having 4 to 7 carbon atoms.
At least one of R ³ , R ⁴ and R ⁷ is the above α-
Particularly preferred is an alkyl group branched at the-or β-position.

The sensitizer used in the present invention in which an alkyl group having a secondary or tertiary carbon atom at the α-position or β-position is introduced, as compared with a sensitizer in which the corresponding alkyl group is linear.
The absorption wavelength peak is shifted to the longer wavelength side, and 48
8 nm argon ion laser or 532 nm YA
Sensitivity to the oscillation wavelength of the G laser is increased.
The sensitizer having the branched alkyl group introduced therein has good solubility in various coating solvents. Some of the alkyl groups branched at the α-position or β-position are exemplified below.

[0031]

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(In these formulas, q represents 0 or 1.)

In the general formula [I], when R ^{1 to} R ⁷ are not the above-mentioned alkyl groups branched at the α-position or β-position, R ^{1 to} R ⁷ represent a hydrogen atom, a cyano group, a chlorine atom, A bromine atom or an allyl group, or an optionally substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an acyl group having 2 to 15 carbon atoms, alkoxy having 2 to 15 carbon atoms It represents a carbonyl group, a cyclic hydrocarbon group having 6 to 20 carbon atoms, or a substituted vinyl group represented by the following general formula [II] or [III]. However, at least one of R ³ and R ⁴ is a substituted vinyl group represented by the general formula [II] or [III].

[0034]

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In the general formula (II), n represents an integer of 0 to 4, and R ⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms such as a methyl group or an ethyl group. R ⁹ is a heterocyclic group having 4 to 20 carbon atoms such as a pyran ring, a benzothiazole ring, a benzooxazole ring, a benzimidazole ring, a naphthooxazole ring, a naphthoimidazole ring, a furyl ring, and a thienyl ring which may have a substituent. Or a cyclic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0036]

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In the general formula [III], p and m are the total
Represents an integer of 0 to 3;^TenIs a hydrogen atom or methyl
Represents an alkyl group having 1 to 10 carbon atoms such as
You. R ¹¹Has a hydrogen atom, a cyano group, or a substituent
Good alkoxycarbonyl group having 2 to 15 carbon atoms, substituent
A phenoxycarbonyl group which may have
Represents an acyl group having 2 to 15 carbon atoms which may have a group;
You.

In the above, the optionally substituted alkyl and alkoxy groups represented by R ^{1 to} R ⁷ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group and an n-pentyl group. , N-heptyl group, n-octyl group, 2-hydroxyethyl group, 2-methoxyethyl group,
Examples thereof include a 2-vinyloxyethoxyethyl group, a benzyl group, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an i-butoxy group, an n-octoxy group, and a benzyloxy group.

Examples of the optionally substituted cyclic hydrocarbon group represented by R ^{1 to} R ⁷ and R ⁹ include an aryl group having 1 to 3 rings and a cycloalkyl group such as a phenyl group and a p-bromophenyl group. , Α-naphthyl group, cyclohexyl group,
Examples include a 2-phenanthryl group and a 2-tetralyl group. Examples of the optionally substituted alkoxycarbonyl group represented by R ^{1 to} R ⁷ and R ¹¹ include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, and an n-butoxycarbonyl group. , T-butoxycarbonyl group, benzyloxycarbonyl group, hydroxyethoxycarbonyl group,
Examples thereof include a fluoroethoxycarbonyl group, a chloroethoxycarbonyl group, and a bromoethoxycarbonyl group.

The acyl groups which may have a substituent represented by R ^{1 to} R ⁷ and R ¹¹ include acetyl, n-propionyl, i-butyryl, n-butyryl, 2,2
-Dimethylpropionyl, valeryl, benzoyl, p-methoxybenzoyl, p-chlorobenzoyl, p-fluorobenzoyl, p-bromobenzoyl, hydroxy-n-propionyl and the like.

R in the general formula [I]¹~ R⁷Preferred
One of the combinations is R¹, R^Two, R ^Five, R⁶Has 1 carbon
To 8, preferably an alkyl group having 1 to 5 carbon atoms, R⁷Is α
An alkyl group branched at the -position or the β-position, R^ThreeAnd R^Fourof
One is a hydrogen atom or 1 to 8 carbon atoms, preferably 1 carbon atom
To 5, and the other is a group represented by the general formula [II] or
It is a substituted vinyl group represented by [III].
Also, R¹, R^Two, R ^Five, R⁶Preferably has 1 to 8 carbon atoms
Or an alkyl group having 1 to 5 carbon atoms, R⁷Is hydrogen atom or charcoal
An alkyl group having 1 to 8, preferably 1 to 5 carbon atoms, R
^ThreeAnd R^FourOne of which is branched at the α-position or β-position
And the other is represented by the general formula [II] or [III]
What is a substituted vinyl group is also preferable.

Table 1 shows some of the dipyrromethene difluoroborate represented by the general formula [I]. In Table 1, Ph represents a phenyl group.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

[0046]

[Table 4]

[0047]

[Table 5]

[0048]

[Table 6]

[0049]

[Table 7]

[0050]

[Table 8]

[0051]

[Table 9]

[0052]

[Table 10]

[0053]

[Table 11]

[0054]

[Table 12]

The second component constituting the photopolymerization initiation system of the present invention is a radical generator that generates an active radical when irradiated with light in the presence of the above-mentioned sensitizer. Examples of the radical generator include halogenated hydrocarbon derivatives,
Diaryliodonium salt, organic peroxide, JP-A-59
Various kinds of titanocene compounds described in JP-A-152396 and JP-A-61-151197, various hexaarylbiimidazole compounds described in JP-B-6-29285, and the like can be used. Of these, titanocene compounds are preferred because they exhibit high photosensitivity.

Specific examples of titanocene compounds suitable for use in the present invention include, for example, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-
Ti-bis-phenyl, di-cyclopentadienyl-T
i-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, -Cyclopentadienyl-Ti-bis-2,4,
6-trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,6-di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4-di -Fluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,
5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6
-Tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti-
Bis-2,6-difluoro-3- (pyr-1-yl)-
Phenyl-1-yl, bis [cyclopentadienyl] bis [6-chloro-2-i-butylthio-4- (3-methylbut-1-oxy) pyrimidinyl] titanium, bis [cyclopentadienyl] bis [2 , 4-bis (1,1-dimethylpropoxy) pyrimidyl] titanium and the like.

The photopolymerizable composition according to the present invention may contain a compound having a dialkylaminophenyl group represented by the following general formula [V] or [VI] together with a radical generator for the purpose of increasing sensitivity. it can.

[0058]

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(Wherein, R ^{15 to} R ²¹ each have 1 to 1 carbon atoms)
Represents 10 alkyl groups. )

Such compounds include, for example, p-
Dimethylaminobenzoic acid ethyl ester, p-diethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isopropyl ester, p-dimethylaminobenzoic acid-n-butyl ester, p-dimethylaminobenzoic acid-n-octyl ester or p- Alkyl dialkylaminobenzoates such as ethyl di-n-butylaminobenzoate; 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone or 4,4'-bis (diisopropyl) Bisdialkylaminobenzophenones such as amino) benzophenone. Of these, alkyl dialkylaminobenzoates are particularly preferred.

The photopolymerizable composition according to the present invention further contains, in addition to the above components, an organic polymer substance as a binder for modifying the composition and improving physical properties after photocuring. Preferably. The binder may be appropriately selected depending on the purpose of improving the compatibility, the film-forming property, the developing property, the adhesive property and the like.
For example, to improve aqueous developability, acrylic acid copolymer, methacrylic acid copolymer, itaconic acid copolymer, partially esterified maleic acid copolymer, modified acid cellulose having a carboxyl group in the side chain, polyethylene oxide, It is preferable to contain polyvinylpyrrolidone and the like.

To improve the film strength and adhesion, polyether of epichlorohydrin and bisphenol A; soluble nylon; polyalkyl methacrylate or polyalkyl acrylate such as polymethyl methacrylate; alkyl methacrylate and acrylonitrile, acrylic Copolymers of acid, methacrylic acid, vinyl chloride, vinylidene chloride, styrene, etc .; copolymers of acrylonitrile with vinyl chloride, vinylidene chloride; copolymers of vinylidene chloride, vinyl chloride with vinyl acetate; polyvinyl acetate; Copolymer of acrylonitrile and styrene; copolymer of acrylonitrile and butadiene and styrene; polyvinyl alkyl ether; polyvinyl alkyl ketone; polystyrene; polyamide; polyurethane; polyethylene terephthalate isophthalate; Cellulose, that is contained chlorinated polyolefin and polyvinyl butyral or the like.

The amounts of the sensitizer that functions as the photopolymerization initiation system and the compound that can generate active radicals used in the photopolymerizable composition according to the present invention are determined by the amount of the organic polymer substance and the amount of the ethylenically unsaturated compound. The sensitizer is generally used in an amount of 0.05 to 20 parts by weight, preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the compound.
2 to 10 parts by weight, and the compound capable of generating an active radical is generally 0.1 to 30 parts by weight, preferably 0.5 to 30 parts by weight.
The amount of the compound having a dialkylaminophenyl group is generally 0 to 20 parts by weight, preferably 0.1 to 10 parts by weight. The weight ratio of the organic polymer substance to the ethylenically unsaturated compound is from 0:10 to 9: 1, preferably from 1: 9 to 9: 1.
8: 2.

The photopolymerizable composition according to the present invention may further contain, if necessary, a thermal polymerization inhibitor, a coloring agent, a plasticizer, a storage stabilizer,
A surface protective agent, a leveling agent, a coating aid and other assistants can be added. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-di-t-butyl-p-cresol, β
-Naphthol or the like is used, and as a coloring agent, for example, a phthalocyanine pigment, an azo pigment, carbon black,
Pigments such as titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes,
Cyanine dyes and the like are used. The addition amount of these thermal polymerization inhibitors and coloring agents is 0.04 to the total weight of the organic polymer substance and the ethylenically unsaturated compound.
1 to 3% by weight, and the colorant is preferably 0.1 to 60% by weight.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate and triacetyl glycerin. It is preferable to add in an amount of 10% by weight or less based on the total weight of the polymer compound and the ethylenically unsaturated compound.

When the photopolymerizable composition according to the present invention is used, it is usually dissolved in an appropriate solvent to form a solution, which is coated on a support and dried to prepare a photosensitive material. Examples of the solvent include methyl ethyl ketone, cyclohexanone, butyl acetate, amyl acetate, ethyl propionate, toluene, xylene, monochlorobenzene, carbon tetrachloride, trichloroethylene, trichloroethane, dimethylformamide, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, bentoxone, and propylene glycol monomethyl. Ether, propylene glycol monomethyl ether acetate and the like are used, and if desired, two or more kinds may be used in combination.

As the support, those usually used may be used. For example, a sheet of a metal such as aluminum, magnesium, copper, zinc, chromium, nickel, iron or an alloy containing these as a main component; woodfree paper, art paper, release paper Paper such as;
Inorganic sheets such as glass and ceramics; polymer sheets such as polyethylene terephthalate, polyethylene, polymethyl methacrylate, polyvinyl chloride, vinyl chloride-vinylidene chloride copolymer, polystyrene, 6-nylon, cellulose triacetate, cellulose acetate butyrate, etc. Can be

The photopolymerizable composition according to the present invention includes:
Further, known techniques for preventing adverse effects such as sensitivity reduction and storage stability deterioration due to oxygen, for example, providing a peelable transparent cover sheet on the photosensitive layer, a wax-like substance having low oxygen permeability, a water-soluble polymer, etc. Can be provided. Light sources for light irradiation include carbon arc,
High-pressure mercury lamp, xenon lamp, metal halide lamp,
General-purpose light sources including visible light of 400 nm or more, such as a fluorescent lamp, a tungsten lamp, a helium neon laser, a helium cadmium laser, an argon ion laser, and a YAG laser, can be used.

[0069]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Parts are parts by weight.

Synthesis Example 1 (Synthesis of sensitizer [S-1] 6.1 g of dimethylformamide and 20 g of dichloroethane
While stirring the mixed solvent at 10 ° C.,
12.8 g of phosphorus oxychloride was added dropwise over 15 minutes.
Subsequently, 1,3,5,7-tetramethyl-4-tert-butylmethylpyrromethenedifluoroborate 9.4
After adding g over 15 minutes, the reaction solution was heated to 80 ° C. and reacted for 60 minutes. This reaction solution was added with stirring to a mixed aqueous solution of 200 g of a 5% by weight aqueous potassium hydroxide solution and 200 g of ice. The precipitate was filtered and washed with a 30% by weight aqueous ethanol solution to obtain 4 g of 1,3,5,7-tetramethyl-4-tert-butylmethylpyrromethenedifluoroborate-2-carbaldehyde.

1,3,5,7-tetramethyl-4-tert-butylmethylpyrromethene difluoroborate
2.8 g of 2-carbaldehyde and ethyl cyanoacetate
2 g was added to 20 g of an ethanol solution containing 0.2 g of sodium methoxy, and reacted at 0 ° C. for 4 hours.
Return to room temperature. The reaction product was filtered and washed with a 30% by weight aqueous solution of ethanol to obtain 1.5 g of a sensitizer [S-1] shown in Table 1.

Examples 1 to 6 and Comparative Examples 1 to 5 A coating solution of a photosensitive composition having the following composition was applied to a grained and anodized aluminum sheet using a wheeler to a dry film thickness of 2 μm. Further, an aqueous solution of polyvinyl alcohol was applied on the surface so that the dry film thickness became 3 μm to prepare a photosensitive material sample.

[Photosensitive Composition Coating Solution] Methyl methacrylate / methacrylic acid / methyl acrylate copolymer 50 parts (weight average molecular weight 45,000, copolymerization ratio 80/7/13) trimethylolpropane triacrylate 50 parts Propylene glycol monomethyl ether acetate 200 parts Cyclohexanone 600 parts Sensitizer (described in Table 2) 3 parts Dicyclopentadienyl-Ti-bis-2,6-difluoro-3- (pyr-1-yl) -phenyl- 1-yl (active radical generator) 5 parts Additive (described in Table 2)

Next, a xenon lamp (UI-501C, manufactured by Ushio Electric Co., Ltd.) was used as the photosensitive material sample, and the light intensity was weakly logarithmically on the horizontal axis and logarithmically on the vertical axis using a spectral sensitivity measurement device manufactured by Narumi Corporation. Was irradiated for 10 seconds. The exposed sample was developed with an aqueous solution containing 0.5% by weight of sodium carbonate and 0.5% by weight of an anionic surfactant (Perex NBL, manufactured by Kao Corporation), and a photocured image was obtained from the height of the cured image obtained at 530 nm. The smallest exposure required for formation was calculated and defined as the sensitivity of the photosensitive composition. Table-
It is shown in FIG.

[0075]

[Table 13]

In Table 2, the symbols of sensitizers and additives indicate the following compounds.

[0077]

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[0078]

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Reference Example After the photosensitive composition coating solution of Example 1 was stirred and allowed to stand for 1 hour, the sensitizer was completely dissolved, and no precipitation was visually observed. On the other hand, when the coating solution of the photosensitive composition of Comparative Example 5 was similarly stirred and allowed to stand for 1 hour, 10% by weight or more of the sensitizer remained as a precipitate.

[0080]

The photopolymerizable composition according to the present invention has extremely high sensitivity to visible light, and enables extremely advantageous plate-making operations in both cost and required time. The photopolymerizable composition according to the present invention is useful for a wide range of applications, for example, lithographic, intaglio, making printing plates such as letterpress, photoresist for printed wiring and IC, dry film,
It can be used for image formation such as relief images and image duplication, photocurable inks, paints, adhesives, and the like.

Claims (7)

[Claims] 1. A photopolymerizable composition comprising an addition-polymerizable compound and a photopolymerization initiation system, wherein the addition-polymerizable compound has at least one ethylenically unsaturated bond. Comprises a sensitizer represented by the following general formula [I], and a radical generator capable of generating an active radical when exposed to light in the presence of the sensitizer. Composition. Embedded image (In the formula, at least ^one of R ^{1 to} R ⁷ is an alkyl group branched at the α-position or β-position, and the others each independently represent a hydrogen atom, a cyano group, a chlorine atom, a bromine atom. Atom or allyl group, or carbon atom 1 which may have a substituent
An alkyl group of 10 to 10, an alkoxy group having 1 to 10 carbon atoms,
It represents an acyl group having 2 to 15 carbon atoms, an alkoxycarbonyl group having 2 to 15 carbon atoms, a cyclic hydrocarbon group having 6 to 20 carbon atoms, or a substituted vinyl group represented by the following general formula [II] or [III]. However, at least 1 of R ³ and R ⁴
One is a substituted vinyl group represented by the general formula [II] or [III]. ) (In the formula, n represents an integer of 0 to 4, R ⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁹ represents a C 4-20 complex which may have a substituent. Ring group or carbon number 6
And -20 to 20 cyclic hydrocarbon groups. ) (In the formula, p and m represent an integer that is 0 to 3 in total,
R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R ¹¹ represents a hydrogen atom, a cyano group or an alkoxycarbonyl group having 2 to 15 carbon atoms which may have a substituent, a phenoxycarbonyl group, or It represents an acyl group having 2 to 15 carbon atoms. ) 2. The photopolymerizable composition according to claim 1, wherein the alkyl group branched at the α-position or the β-position is represented by the following general formula (IV). (In the formula, R ¹² and R ¹³ represent an alkyl group having 1 to 10 carbon atoms, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and q represents 0 or 1.) 3. At least one of R ³ , R ⁴ and R ⁷ is:
3. The photopolymerizable composition according to claim 1, which is an alkyl group branched at the α-position or the β-position. 4. The light according to claim 1, wherein R ⁷ is an alkyl group branched at the α-position or β-position, and one of R ³ and R ⁴ is hydrogen or a methyl group. Polymerizable composition. 5. One of R ^{3 and} R ⁴ is hydrogen or an alkyl group branched at the α-position or β-position, and the other is a substituted vinyl group represented by the general formula [II] or [III]. The photopolymerizable composition according to any one of claims 1 to 3, wherein 6. The photopolymerizable composition according to claim 1, wherein the radical generator is a titanocene compound. 7. The photopolymerizable composition according to claim 1, which contains at least one compound represented by the following general formula [V] or [VI]. Embedded image (In the formula, R ^{15 to} R ²¹ each represent an alkyl group having 1 to 10 carbon atoms.)