JPH10195118A - Photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photopolymerizable composition more highly sensitive to long-wavelength light such as visible light by mixing an addition- polymerizable compound having at least one ethylenic unsaturation with a photopolymerization initiator system comprising a pyran-ring-containing sensitizer and a compound which can generate active radicals upon irradiation in the presence of the sensitizer. SOLUTION: This composition comprises an addition-polymerizable compound having at least one ethylenic unsaturation and a photopolymerization initiator which comprises a sensitizer of formula I and a compound which can generate active radicals upon irradiation with light in the presence of this sensitizer. In formula I, R and R<1> , which are independent of each other, are each cyano, a phenyl or naphthyl group which may be substituted or the like; Y is H or a 1-15C alkyl; and X is a group of formula II [m is 0 or 1; n is 1 or 2; R<2> and R<3> are each H or a 1-10C alkyl; R<4> is H, an alkyl or the like; R<5> to R<7> are each H, a halogen or the like; and R<8> and R<9> are each H or a 1-16C alkyl].

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 is prepared from a compound containing an addition-polymerizable ethylenic double bond and a photopolymerization initiator, and an organic polymer binder used as desired, and then coated on a support. There is a method in which a photosensitive material having a layer of a photopolymerizable composition is prepared, a desired image is image-exposed on the photosensitive material, an exposed portion is polymerized and cured, and an unexposed portion is dissolved and removed to form a cured relief image. Further, after a photosensitive material in which a layer of a photopolymerizable composition is provided between two supports, at least one of which is transparent, is subjected to image exposure from the transparent support side to cause a change in adhesive strength due to light, There is a method of forming an image by peeling a support. Further, there is also an image forming method utilizing a change in toner adhesion due to light of the photopolymerizable composition layer. As the photopolymerization initiator of the photopolymerizable composition used in these methods, benzoin alkyl ether, benzyl ketal, benzophenone, anthraquinone, benzyl or Michler's ketone has been used. However, these photopolymerization initiators have a photopolymerization initiation capacity of 400
The application range of photopolymerizable compositions containing them has been limited, since they are extremely low for light in the visible light region of nm or more.

In recent years, with the development of image forming technology, there has been a strong demand for a photopolymerizable composition having high adaptability to light rays in the visible region. These are photosensitive materials suitable for, for example, non-contact type projection exposure plate making and laser plate making with a visible light laser. Among these techniques, a plate making method using an oscillating beam of visible light of an argon ion laser is considered to be one of the most promising techniques in the future.

Several proposals have been made for a photopolymerizable composition containing a photopolymerization initiation system that can respond to light in the visible light range. For example, a system of hexaarylbiimidazole, a radical generator and a dye (Japanese Patent Publication No. Sho 4
5-37377), 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).
JP-A-59-140403, JP-A-59-189340, a system of biimidazole, a styrene derivative, and a thiol (JP-A-59-56403); Publications).

[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 combining a titanocene with a xanthene dye and an addition-polymerizable ethylenically unsaturated bond-containing compound having an amino group or a urethane group (JP-A-4-221958 and JP-A-4-219756); Titanocene with excellent sensitivity around 488 nm and 3-
Ketocoumarin dye systems (JP-A-63-221110), titanocene and coumarin dye systems having a heterocyclic group at the 3-position (JP-A-6-289335, JP-A-3-239)
No. 703).

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photopolymerizable composition having higher sensitivity to long-wavelength light such as visible light, and in particular, has a very low sensitivity to exposure at around 488 nm. It is intended to provide a photopolymerizable composition having excellent heat resistance.

[0007]

The photopolymerizable composition according to the present invention is a photopolymerizable composition comprising an addition polymerizable compound having at least one ethylenically unsaturated bond and a photopolymerization initiation system. A sensitizer having a coumarin skeleton having a pyran ring bonded through at least one vinylene group, and a compound capable of generating active radicals by light irradiation in the presence of the sensitizer. It is characterized by containing.

[0008]

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, may be abbreviated as “ethylenic compound”), which is a polymerizable component of the photopolymerizable composition according to the present invention, refers to a photopolymerizable component. When the active composition is irradiated with actinic rays, it is a compound that is cured by addition polymerization by the action of a co-existing photopolymerization initiation system, for example, a monomer having an ethylenically unsaturated bond, or a side chain. Alternatively, it is a polymer having an ethylenically unsaturated bond in the main chain. In the present specification, the meaning of a monomer is a concept corresponding to a so-called high-molecular substance, and therefore includes a dimer, a trimer, and an oligomer in addition to a monomer in a narrow sense. It is.

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 an ester 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.

Representative examples of unsaturated carboxylic acids and alkyl esters thereof include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, and alkyl esters of these carboxylic acids having 1 to 5 carbon atoms, Methyl, ethyl, propyl, butyl esters and the like of (meth) acrylic acid. Examples of the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate,
Acrylic esters such as dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate; methacrylic esters in which the carboxylic acid portion of these esters is replaced by methacrylic acid; There are crotonic acid ester in place of acid and maleic acid ester in place of maleic acid.

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 polyhydroxy compound is not necessarily a single substance, but typical examples include acrylic acid, phthalic acid and ethylene glycol. Condensate, condensate of acrylic acid, maleic acid and diethylene glycol,
Condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin, and the like.

Other examples of the monomer having an ethylenically unsaturated bond used in the present invention include acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl acrylate; vinyl group-containing compounds such as divinyl phthalate And the like. 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,
There is a condensation polymer of propylidene succinic acid, ethylidene malonic acid or the like with a dihydroxy or diamine compound. 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, etc., and acrylic acid, methacrylic acid, crotonic acid, etc. A polymer obtained by a polymer reaction with an unsaturated carboxylic acid of formula (I) can also be suitably used.

[0013] Of these various ethylenic compounds, monomers of acrylic esters or methacrylic esters can be particularly preferably used. Next, the photopolymerization initiation system of the photopolymerizable composition according to the present invention will be described. This photopolymerization initiation system is composed of a combination of two types of components, and the first component is a sensitizer represented by the general formula [VII].

[0014]

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(Wherein, R and R ¹ each independently represent a cyano group, a phenyl or naphthyl group which may have a substituent or an alkoxycarbonyl group having an alkyl chain having 1 to 8 carbon atoms; X represents an alkylcarbonyl group or an alkylsulfonyl group, and X represents the following general formula [VI
II], wherein Y is a hydrogen atom or a group having 1 carbon atom
And 15 to 15 alkyl groups.

[0016]

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(Wherein m represents 0 or 1, n represents an integer of 1 or 2; R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; ⁴ represents a hydrogen atom, a halogen atom, an alkyl group, an acyl group, a cyano group or an alkoxycarbonyl group, R ⁵ to R ⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, R ⁸ And R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, but R ⁸ and R ⁹ may be bonded to each other to form a ring, and R ⁸ and R ⁶ And R ⁹ and R ⁷ may be bonded directly to each other or via an oxygen atom or a sulfur atom to form a ring.))

These sensitizers are known compounds. For example, as shown below, 3-cyano-7-dialkylamino-coumarin is reduced by Raney nickel by a conventional method, or The dialkylaminocoumarin can be synthesized by formylation using a Vilsmeier method to give 7-dialkylaminocoumarin-3-carbaldehyde, which is reacted with a dimethylpyran derivative in the presence of an acid or alkali catalyst.

[0019]

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In the above general formula [VIII], R ² , R ³
And R ⁵ is a hydrogen atom, R ⁴ is a hydrogen atom, a methyl group or a chlorine atom, m is 0 or 1, n is 1, and R ⁸ and R
⁹ is an alkyl group having 1 to 8 carbon atoms or is bonded to each other to form a piperidine ring, or R ^{6 to} R ^{9 of the} coumarin skeleton are bonded to each other to form a 9- or 7-membered ring, particularly an oil having the following structure: A compound forming a cyclic amino group is preferable because the sensitivity is remarkably improved.

[0021]

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In particular, in the general formula [VIII], R ⁸
And those in which the alkyl group of R ⁹ has 3 or more carbon atoms and those in which R ^{6 to} R ⁹ are bonded to each other to form an alicyclic amino group having the above structure, Excellent in dissolution stability in the photosensitive layer, those in which R ⁶ and R ⁸ or R ⁷ and R ⁹ are bonded to form an alicyclic amino group, the absorption wavelength peak shifts to a longer wavelength, It has the property of further improving sensitivity. Some of the sensitizers used in the present invention are shown in Table 1 below.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

The polymerization initiation system of the photopolymerizable composition according to the present invention comprises the above-described sensitizer and a compound capable of generating an active radical by light irradiation in the presence of the sensitizer. Although various compounds can be used as the compound capable of generating an active radical, a titanocene compound is preferably used.
As the titanocene compound, for example, JP-A-59-152
396, JP-A-61-151197, JP-A-6-4
It can be appropriately selected from various titanocene compounds described in each publication of No. 1170 and used. Preferred examples of the titanocene compound that generates an active radical in the present invention include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti -Bis-2,3
4,5,6-pentafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-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-methylcyclopentathienyl-
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 can be mentioned.

In the present invention, a compound capable of generating a radical other than the titanocene compound can be used. Such compounds include, for example, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl)
-4,4 ', 5,5'-tetra (p-carbethoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-bromophenyl ) Biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-
Dichlorophenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (O, o'-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4', 5,5'-tetraphenylbi Imidazole, 2,2'-bis (o-methylphenyl) -4,
Hexaarylbiimidazoles such as 4 ', 5,5'-tetraphenylbiimidazole.

Compounds that can generate radicals other than biimidazole include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,
6-di (trichloromethyl) -s-triazine, 2-
(P-methoxyphenyl) -4,6-di (trichloromethyl) -s-triazine, 2,2,2-trichloromethylacetophenone, tribromomethylphenylsulfone, 2-trichloromethyl-5- (p-methoxystyryl) And halogenated hydrocarbon derivatives such as -1,3,4-oxadiazole. Further, the photopolymerizable compound according to the present invention is disclosed in JP-A-58-29803 in order to increase the sensitivity.
Or a thiol compound or an amine compound described in Japanese Patent Application Laid-Open (JP-A) No. 6-222,086. In particular, it is preferable to add a dialkylamine derivative, and specific examples thereof include Michler's ketone and a compound having a dialkylaminophenyl group. Examples of the compound having a dialkylaminophenyl group include compounds represented by the following general formulas [IX] to [XII].

[0029]

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In the formula, R ^{10 to} R ²⁰ represent an alkyl group;
R ²¹ and R ²² each independently represent a hydrogen atom or an alkyl group. Preferably R ¹⁰ , R ¹¹ and R ^{13 to} R ²²
Represents a lower alkyl group, particularly an alkyl group having 1 to 4 carbon atoms, and R ¹² represents an alkyl group having 1 to 20 carbon atoms. These alkyl groups may be linear or branched. Also, R
¹² may be further substituted with a substituent, for example, a halogen atom, an aryl group, an acyl group, a carboxyl group, an alkoxy group and the like.

Some examples of the compounds represented by the general formulas [IX] to [XII] include ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, isopropyl p-dimethylaminobenzoate and p-dimethylaminobenzoate. Dialkylaminobenzoic acid alkyl esters such as -dimethylaminobenzoic acid-n-butyl ester, p-dimethylaminobenzoic acid-n-octyl ester and p-di-n-butylaminobenzoic acid ethyl ester;
4,4'-bis (dimethylamino) benzophenone,
Bis (dialkylamino) benzophenones such as 4,4'-bis (diethylamino) benzophenone and 4,4'-bis (diisopropylamino) benzophenone;
4'-bis (dimethylamino) benzyl and 4,4'-
Examples include bis (dialkylamino) benzyl such as bis (diethylamino) benzyl and N-phenylglycine. Among these, compounds represented by the general formula [IX] or [X], particularly alkyl dialkylaminobenzoate, are preferred.

The preferred amount of the sensitizer and the compound capable of generating an active radical constituting the photopolymerization initiation system used in the photopolymerizable composition of the present invention is 100 parts by weight of the ethylenically unsaturated compound. Sensitizer is preferably 0.05
The compound capable of generating an active radical is generally 0.1 to 3 parts by weight, more preferably 0.2 to 10 parts by weight.
0 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 0.5 to 10 parts by weight. The additive for high sensitivity is 0 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the ethylenically unsaturated compound.

The photopolymerizable composition according to the present invention consists essentially of the above-mentioned constituent components. In addition to these, an organic polymer substance is used for modifying the present composition and improving the physical properties after photocuring. Further, it is preferable to contain it. The type of the organic polymer compound may be appropriately selected depending on the purpose to be improved, such as compatibility, film forming property, developability, and adhesiveness. 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, Polyvinylpyrrolidone and the like are contained.

In order 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 and vinyl chloride, vinylidene chloride; copolymers of vinylidene chloride, chlorinated polyolefin, vinyl chloride and vinyl acetate; Polyvinyl acetate; copolymer of acrylonitrile and styrene; copolymer of acrylonitrile and butadiene, styrene; polyvinyl alkyl ether; polyvinyl alkyl ketone; polystyrene; polyamide; polyurethane; polyethylene terephthalate Sofutareto; it may be contained acetyl cellulose or polyvinyl butyral.
These organic polymer compounds are generally used in an amount of 500% by weight or less, preferably 200% by weight, based on the ethylenic compound.
Add in the following range.

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 additives can be added. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol, and the like. Examples of the coloring agent include phthalocyanine pigments and azo pigments. Pigments such as carbon black, titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The addition amount of these thermal polymerization inhibitors and coloring agents is 0.01 to 0.01% based on the total weight of the ethylenic compound and the organic polymer compound.
To 3% by weight, and the colorant is preferably 0.1 to 20% by weight.

As the plasticizer, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like are used.
It is preferable to add it so that it may be 10% by weight or less based on the total weight of the ethylenic compound and the above-mentioned organic polymer compound.

The photopolymerizable composition according to the present invention is usually dissolved in an appropriate solvent to form a solution, which is coated on a support,
It is dried and used in the form of 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 these can be used alone or in combination of two or more.

As the support, conventional ones can be used. For example, aluminum, magnesium, copper, zinc,
Sheets of metals such as chromium, nickel and iron or alloys containing these as main components; papers such as high-quality paper, art paper and release paper; inorganic sheets such as glass and ceramics; polyethylene terephthalate, polyethylene, polymethyl methacrylate, and poly Polymer sheets such as vinyl chloride, vinyl chloride-vinylidene chloride copolymer, polystyrene, 6-nylon, cellulose triacetate, and cellulose acetate butyrate are used.

Further, the photopolymerizable composition according to the present invention can be further prepared by a known technique for preventing adverse effects such as a decrease in sensitivity and a deterioration in storage stability due to oxygen, for example, a transparent cover sheet which can be peeled off on a photosensitive layer. Or a coating layer of a wax-like substance having a low oxygen permeability, a water-soluble polymer, or the like. As an exposure light source applicable to the photopolymerizable composition according to the present invention, a carbon arc, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a helium cadmium laser, an argon ion laser, a YAG laser, or more, 400 nm or more A general-purpose light source including visible light can be used.

[0040]

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. Reference Example 1 Synthesis of sensitizer Pyridine-acetic acid aqueous solution (water: acetic acid: pyridine = 1: 1: 1)
2) 0.7 g of a 3-cyanocoumarin derivative represented by the following formula (a) and sodium phosphinate 1.
After adding 4 g and dissolving completely, the solution was added to 40-
The temperature was raised to 45 ° C, a water suspension of Raney nickel 0.3g was added, and the mixture was stirred for 1.5 hours while maintaining the temperature at 40 to 45 ° C.

Next, 450 ml of chloroform was added to the supernatant.
To obtain 0.5 g of coumarin-3-carbaldehyde represented by the following formula (b). Subsequently, 0.5 g (0.019 mol) of the obtained coumarin-3-carbaldehyde was obtained.
Is a dimethylpyran derivative 0.4 represented by the following formula (c):
g (0.02 mol), 0.01 g of potassium n-butoxide
And 20 g of ethanol were mixed at 0 ° C. and stirred at this temperature for 6 hours. Then, the temperature was raised to 60 ° C. over 1 hour, and the mixture was stirred at this temperature for 10 hours to obtain a compound 0.3 of I-1 in Table 1.
g was obtained. Similarly, Compound I-3 in Table 1,
I-5 and I-7 were synthesized respectively.

[0042]

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Examples 1 to 8 and Comparative Examples 1 to 4 On a grained and anodized aluminum sheet, a coating solution of the photopolymerizable composition having the following composition was applied to a dry film thickness of 2 μm using a wheeler. Then, an aqueous solution of polyvinyl alcohol was applied on the surface so as to have a dry film thickness of 3 μm to prepare a photosensitive material.

[0044]

Table 2 Photopolymerizable composition coating solution 55 parts of methyl methacrylate / methacrylic acid / methyl acrylate copolymer (weight average molecular weight 45,000, copolymerization ratio 80/10/10) trimethylolpropanetri Acrylate 45 parts Methyl cellosolve 800 parts Tetrahydrofuran 50 parts Sensitizer (described in Table 3) Compound capable of generating active radical (described in Table 3)

Next, a xenon lamp (UI-501C, manufactured by Ushio Electric Co., Ltd.) was used as the light-sensitive material, and the wavelength was plotted on the horizontal axis and the light intensity was decreased logarithmically on the vertical axis using a spectral sensitivity measuring device manufactured by Narumi. Irradiated for 10 seconds. The exposed sample was developed with an aqueous solution containing 1% by weight of sodium silicate,
From the height of the cured image obtained at 88 nm, the minimum exposure required for the formation of a photocured image was calculated and defined as the sensitivity of the photopolymerizable composition. Table 3 shows the results.

[0046]

[Table 5]

The symbols in Table 3 indicate the following compounds.

[0048]

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[0049]

The photopolymerizable composition according to the present invention has extremely high sensitivity to visible light, and enables plate making operations which are extremely advantageous in terms of cost and time. Therefore, this photopolymerizable composition is useful in a wide range of application fields, for example, making printing plates such as flat plates, intaglio, letterpress, photoresists for making printed wiring and ICs, dry films, relief images and images. It is industrially extremely useful because it can be used for image formation such as reproduction, photocurable ink, paint, adhesive and the like.

Claims (3)

[Claims] 1. A photopolymerizable composition comprising an addition-polymerizable compound having at least one ethylenically unsaturated bond and a photopolymerization initiation system, wherein the photopolymerization initiation system is represented by the general formula [I]. A photopolymerizable composition comprising a sensitizer and a compound capable of generating an active radical upon irradiation with light in the presence of the sensitizer. Embedded image In the formula, R and R ¹ are each independently a cyano group, an optionally substituted phenyl or naphthyl group or an alkoxycarbonyl group having an alkyl chain having 1 to 8 carbon atoms, an alkylcarbonyl group or X represents an alkylsulfonyl group, X represents a group represented by the following general formula [II], and Y represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms. Embedded image (In the formula, m represents an integer of 0 or 1, n represents an integer of 1 or 2,
R ² and R ³ each independently represent a hydrogen atom or a carbon atom
Represents an alkyl group of 10 to 10, R ⁴ represents a hydrogen atom, a halogen atom, an alkyl group, an acyl group, a cyano group or an alkoxycarbonyl group, and R ^{5 to} R ⁷ each independently represent
A hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, R ⁸ and R ⁹ are each independently, represent a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, R ⁸ and R
⁹ may be bonded to each other to form a ring, also R ⁸
And R ⁶ and R ⁹ and R ⁷ may be bonded directly to each other or via an oxygen atom or a sulfur atom to form a ring. ). 2. The photopolymerizable composition according to claim 1, wherein the compound capable of generating an active radical is a titanocene compound. 3. The photopolymerizable composition according to claim 1, wherein the photopolymerizable composition further comprises at least one compound represented by the following general formulas [III] to [VI]. . Embedded image (Wherein, R ¹⁰ to R ²⁰ represents an alkyl group, R ²¹ and R
²² independently represent a hydrogen atom or an alkyl group)