JPH04184344A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To obtain a high-sensitivity photoinitiator by incorporating the compds. selected from a group consisting of an ethylenic unsatd. compd., the iron allene complex expressed by formula I, a titanocene compd., the 3-substd. cumarine expressed by formula II, the p-aminophenyl unsatd. ketone expressed by formula III, and the xanthene or thioxanthene expressed by formula IV. CONSTITUTION:At least one kind of the compds. selected from the group consisting of at least one kind of the ethylenic unsatd. compds. which are nongaseous at ordinary temp.; for example, pentaerythritol acrylate, etc., the iron allene complex expressed by the formula I, and the titanocene compd., the 3-substd. cumarine expressed by the formula II, the p-aminophenyl unsatd. ketone expressed by the III, and the xanthene or thioxanthene expressed by the formula IV are incorporated into the above compsn. In the formula II, R<3>, R<4>, R<5>, R<6> denote hydrogen, alkyl group, etc.; Z denotes an aryl group, heterocyclic group, etc. In the formula III, p and q are respectively 0 or 1; R<8> to R<13> denote a hydrogen atom or 1 to 24C org. group. In the formula IV, A denotes an oxygen atom or sulfur atom; B denotes a hydrogen atom or halogen atom; D denotes a carbon atom or nitrogen atom; E denotes an oxygen atom, alkoxy group, etc.; R<22> denotes an alkyl group, hydroxyalkyl group, etc.; R<23> denotes a hydrogen atom, alkoxy group, etc. The high-sensitivity photoinitiator is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel photopolymerizable composition that is sensitive to visible light.

BACKGROUND OF THE INVENTION Photopolymerizable compositions are widely used in numerous applications, including commercial use in printing, copying, resist formation, and others.

These compositions generally contain an ethylenically unsaturated compound or other type of polymerizable compound, a photoinitiator or photoinitiator system, and preferably a solvent-soluble or aqueous or alkali-soluble organic polymeric binder compound. However, the range of application of many of these known useful photopolymerizable compositions is currently limited because the initiators used are often not activated outside the ultraviolet region of the spectrum. It is.

Furthermore, image forming techniques are required to use visible light instead of ultraviolet rays as a light source, or to perform scanning exposure with a laser such as an argon ion laser that has a large oscillation intensity in the visible region. For this reason, there is a demand for photopolymerizable materials that are highly sensitive to visible light, and there is a demand for the development of photoinitiators that are highly sensitive to visible light.

Therefore, as a photoinitiator with high sensitivity, JP-A-54-1
No. 55292 discloses a system containing hexaarylbisimidazole, JP-A-58-15503 discloses an active halogen compound and a 3-ft-converted tsucoumarin compound system, and JP-A-5E3-4604 discloses a 3-ft coumarin compound system. A system of keto-substituted coumarin and N-phenylglycine, a combination of a 3-substituted coumarin and a quinazolinone conductor in JP-A-61-97850, and a combination of hexaarylbisimidazole and 3-substituted coumarin in JP-A-81-123803. - A photoinitiator system in combination with a ketorILyA coumarin is disclosed (Problem to be Solved by the Invention) However, the sensitivity of the photoinitiator system described above is insufficient, and a lower power laser is used to achieve higher speeds. In order to carry out scanning exposure with 200 nm, it is necessary to find a photoinitiator with even higher sensitivity.

(Means for Solving the Problems) In order to solve the above problems, that is, for the purpose of improving the sensitivity of photopolymerizable compositions to visible light, the present inventors have made extensive research and efforts regarding photoinitiator systems. As a result, we have finally completed the present invention. That is, the present invention provides (a) at least one ethylenically unsaturated compound that is non-gaseous at room temperature, (b) an iron allene complex represented by the following general formula (I), and (c) an iron allene complex represented by the following general formula (I).
Titanocene compound (d) (i) 3-substituted coumarin represented by the following general formula (IIa) (0) p-aminophenyl unsaturated ketone represented by the following general formula (IIb) (c) represented by the following general formula (IIc) This is a photopolymerizable composition characterized by containing at least one compound selected from the group consisting of (a), (b), and (c) of the xanthine or thioxanthene compounds shown.

(q (in the formula R'', R2 are the same or different groups, and R2 may form a fused polycyclic compound with a benzene ring.X
l is BF4. PFe, AsF5,5bFs.

FeCR4, SnCgs, 5bCQe, BiCQs are shown. ) (wherein R3, R', R', R'' are hydrogen, alkyl groups,
An alkoxy group, an alkylamino group, a dialkylamino group, a cyan group, or two may form a fused ring system or a fused heterocyclic ring system. Z represents an aryl group, a heterocyclic group, or -C-R7. R7 is an alkyl group, an alkoxy group,
Indicates an aryl group, an aryloxy group, and a heterocyclic group. ) (llb) CIIb In the formula, p and q are each 0 or 1, and R
81R91R"l R"I R121R" represents a hydrogen atom or an organic group having 1 to 24 carbon atoms.) R'4 is a methylidine group or a carbon number 1 that can be bonded to R" to form a ring with a carbonyl group. ~5 alkylene-iridine group, R15 is a carbon atom or a substituted or unsubstituted phenyl group, or a group that forms indanone, tetralone, or indanedione together with R'' and a carbonyl group; R'' is a hydrogen atom or a group having 1 to 24 carbon atoms;
is an organic group. ) [In the formula, A is an oxygen atom or a sulfur atom, B is a hydrogen atom or a halogen atom, and D is a carbon atom or a nitrogen atom (however, if D is a carbon atom, the space between adjacent carbon atoms (as indicated by the dotted line) ) is a double bond, and if D is a nitrogen atom, the bond with the adjacent carbon is a single bond.), E is the oxygen atom (in this case, the bond with the adjacent carbon is a double bond. ), an alkoxy group or an alkanoyloxy group, R22 is an alkyl group, a hydroxyalkyl group, an alkyl dialkyl group, a dialkylaminoalkyl group, or an aryl group, and R23 is a hydrogen atom, an alkoxy group, an alkyl group, or a dialkylamino group. be. ] The ethylenically unsaturated compound used in the present invention is
Monomers suitable for free radical initiated chain growth addition reactions, such as pentaerythritol triacrylate, polyethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glyfur dimethacrylate, tetraethylene glycol dimethacrylate, tri- Examples include methylolpropane triacrylate and trimethylolpropane trimethacrylate.

The second component (b) is an iron allene complex represented by the general formula (b) as described by Chesiker-Zeltung, 1
A large number of compounds are described in 08 Ro 1) 345-354 Ro 984).

In the general formula (I), R'', R2 is a C1-C1□ alkyl group, a C2-C1□ alkenyl group, a C2-CI
2 alkynyl group, C, #C, alkoxy group, cyan group, alkylthio group, phenoxy group% C2-C8 monocarboxylic acid and ester and amide, phenyl group%
It is selected from C2 to C5 alkanoyl groups, ammonium salts, pyridinium groups, nitro groups, alkylsulfinyl groups, alkylsulfonyl groups, and sulfamoyl groups.

Specifically, (η6-benzene)(η6-cyclopentadienyl)iron(II)-hexafluorophosphate, (
η6-toluene)(η5-cyclopentazinyl)iron(
n) hexafluorophosphate), (η6-cumene) (
(η5-cyclopentadienyl) Iron(II) hexafluorophosphate, (η6-benzene) (η5-cyclopentanoenyl) Iron(n) hexafluoroarsenate, (η8-benzene) (η5-cyclopentadienyl) ) Iron(II) tetrafluoroborate, (η6-naphthalene) (η6-naphthalene) (η5-cyclopentagenyl) iron(■) hexafluorophosphate, (η6-
anthracene) (η5-cyclopentagenyl) iron (
II) Hexafluorophosphate, (η6-pyrene)
(η5-cyclopentadienyl> Iron(II) hexafluorophosphate, (η6-benzene) (η5-cyanocyclopentadienyl) Iron(II) hexafluorophosphate, (η8-toluene) (η5-acetyl cyclopentagenyl) iron(II) hexafluorophosphate, (η6-cumene)(η5-chlorocyclopentagenyl) iron(If) tetrafluoroborate, (η6
-benzene) (η5-carboethquincyclohexagenyl)iron(n) hexafluorophosphate, (η6-
benzene) (η'-1,3-dichlorocyclohexagenyl)iron(n) hexafluorophosphate, (η6-
diatsubenzene)(η5-cyclohexagenyl)iron(
II) Hexafluorophosphate, (η6-acetophenone) (η5-cyclohexagenyl) Iron(II)
Hexafluorophosphate, (η8-methylbenzony)) (η5-cyclopentadienyl) Iron(II
) hexafluorophosphate, (η8-benzenesulfonamide)(η5-cyclopentadienyl)iron(II
) Tetrafluoroborate, (η8-benzamide) (
(η5-cyclopentadienyl) iron(II) hexafluorophosphate, (η6-diatubenzene) (η5-cyanocyclopentadienyl) iron(II) hexafluorophosphate, (ηe-chlornaphthalene) (η5-cyclopenta iron(II) hexafluorophosphate, (η6-anthracene)(η6-diacyclopentadienyl) iron(II) hexafluorophosphate, and the like. These compounds include Dokl,
It can be synthesized by the method described in Mukd, Nauk 5SSR149G15Ro9G3).

The third component (C) titanocene has the -M formula (III)
Compounds having the structure are preferred.

R24 and R'' are each a substituted or unsubstituted cyclopentadienyl group. R26 and R'' are each a substituted or unsubstituted phenyl group, and it is especially preferable that it be substituted with a halogen atom. . Third component (C)
Specific examples of titanocene are shown below.

Specifically, the 3-substituted coumarin represented by the general formula (IIa) of the fourth component (d) includes 7-dinithylamino-3-(2-benzothiazyl)-coumarin, 7-dinithylamino-3-(2-benzimidazolyl) ) - coumarin,
7-dinithylamino-3-(2-benzoxasilyl)
-coumarin, 7-ethylamino-3-(2-benzthiazolyl)-coumarin, 7-dinithylamino-3-benzoylcoumarin, 7-diethylamine-3-thienoylcoumarin, 7-diethylamine-3,3'-carponylvistamin, 3. 3'-carbonylbis(7-dinithylaminocoumarin), 9.9'-carbonylbithro,2,4,5-tetrahydro-3H,6H,IOH[
I-cobenzovirano[9,9a+1-gh]quinolazin-10-one) and the like. Synthetic methods for these compounds are described in Chemical Reviews aGl 945) and Tetrahedron 38 (9)
1203-1211 Ro982).

The p-aminophenyl unsaturated ketone of the fourth component (d) is represented by general formula (IIb). In general formula (IIb), p and q are each independently O or 1, and R''
lR9+R'. I R"I R"I R" each independently represents an alkyl group having a hydrogen atom of C3 to C12, a C2 to C12 alkyl group,
C1° alkenyl group, 02-CI2 alkynyl group%
C1-C8 alkoxy group, C1-C8 alkylthio group, C6-Coo aryloxy group, NC8-C20 substituted and unsubstituted aryl group, carboxyl group, cyan group, halogen atom, amino group, C1-Ct2 monoalkyl Amino group, C2-C24 dialkylamino group %C
I~C8□ cyanoalkyl group%C1~CI2 alkoxycarbonyl group, C2~C24 alkoxycarbonylalkyl group, 01~CI2 hydroxycarbonylalkyl group, CI''-CI2 anoxy group, or 02~C24 represents an acyloxycarbonylalkyl group, etc.

R14 is a methylidine group or a carbon atom number of 1 to 5 that can be bonded to R'' to form a ring with a carbonyl group.
The alkylene-iridine group R" is a carbon atom, a substituted or unsubstituted phenyl, or a group which together with R" and a carbonyl group forms an indanone, a tetralone, or an indanedione (wherein r is 0 or 1, R", R1
M, RIg, R'', R'' are each independently a hydrogen atom C
8-C1° alkenyl group, C2-CI2 alkynyl group, C,-C8 alkoxy X, C,-C8 alkylthio group, C6-C3° aryloxy group, 06-C2
0 substituted and unsubstituted aryl groups, carboxyl groups, cyan groups, halogen atoms, amino groups, C8-C1 □ substituted and unsubstituted monoalkylamino groups, C2-C24 substituted and unsubstituted dialkylamino groups, C, ~ C12 cyanoalkyl group, 01-C1□ alkoxycarbonyl group, 02-C24 alkoxycarbonyl alkyl M,
c.

~C1° hydroxycarbonylalkyl group, C1~C
It represents a t2 acyloxy group, a C2-C24 acyloxycarbonyl alkyl group, or the like. ).

Specifically, the compound represented by general formula (IIb) is:
2,5-bis(4'-diethylaminobenzylidene)cyclopentanone, 2,5-bis(4'-dimethylaminobenzylidene)cyclopentanone, 2,6-bis(4'
-diethylaminobenzylidene)cyclohexanone,
2,6-bis(4'-dimethylaminobenzylidene)cyclohexanone, 2,5-bis(4'-dimethylaminocinnamylidene)cyclopentanone, 2,8-bis(4
'-dimethylaminocinnamylidene) cyclohexanone, 1,3-bis(4'-dimethylaminobenzylidene)
Acetone, 2-(4'-diethylaminobenzylidene)-1-indanone, 2-(9'-julolylidene)
-1-indanone, 2-(4'-diethylaminobenzylidene)-1-tetralone, 4'-diethylamino-2
'-Methylbenzylidene-acetophenone, 2.5-bis(4'-N-ethyl-N-tribomethoxymethylaminobenzylidene)cyclopentanone, 2. 5-bis(
4'-N-Ethyl-N-hydroxymethylaminebenzylidene)pentanone and its sodium salt, 2,5
-bis(4' -N-methyl-N-cyanoethylaminobenzylidene)cyclopentanone, 2,5-bis(4'
-N-ethyl-N-10! cyclopentanone, 2,6-bis(4'-N-cyanoethylaminobenzylidene)cyclohexanone, 2
-(4'-N-ethyl-N-ruboquinomethylaminobenzylidene)-1-indanone, 2-(4'-N-
Ethyl-N-benzylidene)-
Sodium salt of 1-tetralone, 2- (4'-ethyl-N-cyanoethylaminobenzylidene)-1-indanone, 2- (4'-diethylaminobenzylidene)-1,3-indandione, 2- (4'-N -cyanoethyl)-N-ethylaminobenzylidene)-1,3
- Examples include indandione.

The xanthine or thioxanthene compound as the fourth component (d) is represented by the general formula (nc). In general formula (IIc), B is hydrogen, chlorine, bromine, etc., E is methoxy, ethoxy, propoxy, acetyloxy, propionyloxy, and R22 is methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl, methoxymethyl, methquinethyl. , methylaminomethyl, diethylaminopropyl, phenyl, xylyl, tolyl, anisyl, etc.
Examples of R23 include hydrogen, methoxy, ethoxy, methyl, ethyl, propyl, dimethylamino, and diethylamino.

A compound represented by the following general formula (III) and/or a cyclic diketone compound represented by the following general formula (IV) may be present in the composition of the present invention.

(In the formula, S is 0 or 1, R", R28, R" are the same or different groups, R28 may form a fused polycyclic compound with a benzene ring, R", R30 are benzene It can also be combined with a ring to form a ring.X2 is S
% S c v N R"R" represents hydrogen or a C1-C6 alkyl group. ) (In the formula, R'' is hydrogen or a substituted or unsubstituted alkyl or aralkyl group, and G is a divalent organic group.) The compound represented by the general formula (III) is N-
7-enylglycine, N-(p-methylphenyl)chrycine, N-(p-methoxyphenyl)glycine, N-(p-
-cyanophenyl)glycine, N-(p-chlorophenyl)glycine, N-(m-cyanophenyl)glycine,
N-methyl-N-phenylglycine, indoleacetic acid,
Examples include N-methylindoleacetic acid and 6-cyanindoleacetic acid.

The cyclic diketone compound represented by the general formula (IV) is a cyclic β-dicarbonyl compound having an active methylene group having an unstable hydrogen atom. In the formula, R32 is hydrogen, alkyl, substituted alkyl, or aralkyl, and G is a divalent organic group which may contain a heteroatom in the group chain, and optionally one or both of carbon and heteroatoms. may have a substituent.

In the above, the alkyl group is C, #C, 2 alkyl, and examples of the substituted alkyl include hydroxylalkyl, cyanoalkyl, haloalkyl, alfkynealkylene, alkylene 1,000, and aryloxyalkylene. The aryl part of the aralkyl group is 6
It may contain ~IO carbon atoms. Said divalent batter group G
completes the ring. This part is a heteroatom,
For example, it may contain nitrogen, oxygen and sulfur. Specific examples of these compounds include 5,5-dimethyl-1,3-cyclohexanedione, 2-methyl-1,3-cyclohexanedione, 2-methyl-1,3-cyclobendanedione, 2,4-diethyl -1,3-cyclobutanedione, 2
-Methyl-1,3-cyclobutanedione, 5-methyl-
2-thiobarbylic acid, barbylic acid, 3-ethyltetronic acid, 2゜4-dimethyl-3-oxo-5-hydroxy-5-methoxypentenoic acid δ-lactone, 1.3
．． 5-trimethylbarbic acid, 1,3-dimethyl 5
-Ethylbarbyric acid, 2-methyldimedone, 1.3
-Indandione, 2-methylindanone, bis-
(5-lo,3-dimethylbarbituryl)]methane, 1,
5-diphenyl-3-[2-(phenylthio)ethyl)
-2,4-pyrrolidinedione, 1-phenyl-3,5-
diketo-4-n-butyltetrahydropyrazole, 2,
2-dimethyl-m-dioxane-4,6-dione, 21
2.5-)samethyl-m-dioxane-4,6-dione, and the like.

A thermoplastic high molecular weight organic polymeric binder may preferably be present in the composition of the invention. Polymer binder types include: copolyesters based on terephthalic acid, isophthalic acid, sebacic acid, adipic acid and hexahydroterephthalic acid; Combined, (v) Cellulose ether % (Vi) Polyethylene, (vtr) Synthesis: / Mu, (V mouth 1
) Cellulose esters, (ix) polyvinyl esters, including polyvinyl acetate/acrylates and polyvinyl acetate/methacrylate copolymers, (X) polyacrylates and polyα-alkyl acrylate esters such as polymethyl methacrylate and polyethyl methacrylate, (xi)4. 000~4,000,0
High molecular weight ethylene oxide polymer (polyethylene glycol) having a weight average molecular weight of 0.00, (xit) polyvinyl chloride and its copolymers, (Xiii) polyvinyl acecool, (xiv) polyformaldehyde, (
XV) polyurethane, (xvi) polycarbonate and (xvl+) polystyrene.

Particularly preferred photopolymerizable binders in the compositions of the invention include those in which the unexposed photopolymerizable coating is soluble in primarily aqueous solutions, such as alkaline solutions;
Preferred are photopolymerizable binders that are relatively insoluble therein after exposure to actinic radiation. Polymers that typically meet these requirements are carboxylated polymers, such as vinyl addition polymers containing free carboxylic acid groups.

Examples include methacrylic acid copolymers, acrylic acid copolymers, crotonic acid copolymers, maleic acid copolymers, and partially esterified maleic acid copolymers. Further, there are cellulose having a carboxyl group in the side chain, and a polymer having a hydroxyl group in the side chain to which a cyclic acid hydrate is added.

Furthermore, it is desirable to add a small amount of a thermal polymerization inhibitor to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during production or storage of the photopolymerizable composition. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-phthyl p
Examples include -cresol, pyrogallol, di-t-butylcatechol, benzoquinone, 2-mercaptobenzimadazole, and cerous N-nitrophenylhydroxyamine. The amount of the thermal polymerization inhibitor added is preferably 0.01 to 5% based on the total composition.

If necessary, inert additives such as non-polymerizable plasticizers, dyes, pigments and fillers may be added to the extent that they do not significantly inhibit photopolymerizability.

The preferred blending ratio of the photopolymerizable composition of the present invention is the component (a
), the iron allene complex as component (b) is 0.01 to 50 parts by weight, particularly preferably 0.1 to 30 parts by weight, The titanocene compound which is component (c) is 0.01~
50 parts by weight, particularly preferably 0.1 to 30 parts by weight, component (d) of at least one compound selected from the group consisting of 3-tS coumarin, p-aminophenyl unsaturated ketone, xanthine or thioxanthene compounds; is 0.0
1 to 20 parts by weight, particularly preferably 0.1 to 20 parts by weight,
The compound represented by the general formula (III) or the cyclic diketone compound is each 0 to 20 parts by weight, particularly preferably 0
．． 1 to 20 parts by weight, and the binder is 0 to 1000 parts by weight, preferably 0 to 50 parts by weight.

The photopolymerizable composition of the present invention can be coated on a wide variety of substrates. By "substrate" is meant here any natural or synthetic support, preferably one which can be present in the form of an adhesive or rigid film or sheet. For example, the material may be metal sheet or foil, synthetic organic resin sheet material or film, cellulose paper,
<- may be a ford, etc. or a complex of two or more of these substances. Specific materials include aluminated aluminum, anodized aluminum, aluminated polyethylene terephthalate film, polyethylene terephthalate film, electrostatic discharge treated polyethylene terephthalate film, polyvinyl alcohol coated paper, cross-linked polyester coated paper, nylon, glass, cellulose acetate. Examples include film and others.

The particular material will generally be determined by the application purpose involved. For example, if printed circuits are being manufactured, the material may be a copper coated plate on fibreboard; in the manufacture of lithographic printing plates, the material may be anodized aluminum.

In the present invention, the thickness of the layer of the photopolymerizable composition is 0.1 μm.
-250μ, preferably 0.5-50μ.

The desired thickness is determined by the application.

A protective layer made of a polymer with excellent oxygen barrier properties such as polyvinyl alcohol is provided on the photopolymerizable composition layer provided on the substrate in order to prevent the polymerization inhibiting effect of oxygen in the air. Alternatively, a cover film such as polyethylene terephthalate film may be laminated.

The photopolymerizable composition of the present invention has high sensitivity to active light in a wide range from ultraviolet light to visible light.

Therefore, as a light source, lasers such as ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, alcone ion lasers, helium-cadmium lasers, fluorescent lamps,
Tungsten lamps and sunlight can be used.

(Example) The present invention will be specifically described below with reference to Examples, where parts and percentages are based on weight.

Examples 1 to 8, Comparative Examples 1 to 3 A photosensitive layer coating solution having the following composition was applied onto a 100μ thick transparent polyethylene terephthalate film having an undercoat layer, and dried at 90°C for 1 minute in a hot air dryer. , a coating film with a thickness of 3 μm was obtained. Next, an aqueous solution of 7% polyvinyl alcohol (completely saponified, degree of polymerization: 500) was applied thereon and dried in a hot air dryer at 100°C for 1 minute to form an overcoat layer with a thickness of 1 μm to obtain a sensitivity test piece. .

(g Light layer coating liquid composition) Poly(methyl methacrylate/methacrylic acid) 52 parts 70/30 molar ratio Tetraethylene glycol diacrylate 40 Component (b) 5 Component (C) 5 Component (d) 3 Component (e) (Compound represented by general formula (III) or cyclic diketone compound) 3 Methanol 200 Ethyl acetate
80 chloroform
120 2 as a negative film on the above sensitivity test piece
1v'2 Stenobutabble Note (Dainippon Screen Company lJ)
Gray film scale) and a xenon lamp (
Ushio Inc. UXL-500D-0), Toshiba interference filter KL-49 and the same color glass filter Y-4
After exposure for 5 minutes from a distance of 15 cm with a light source (490 nm) combined with 5, 0.7% carbonic acid at 30 ° C) I
After immersing the tablet in a Jium aqueous solution for 10 seconds, washing with water to remove the uncured portion, and drying, the number of complete curing stages (steps) of the 21.r2 step tablet was investigated, and the results are shown in Tables 1 and 2.

Comparative examples are also shown in Table 3. From Tables 1 to 3, it is clearly seen that Examples 1 to 8 of the present invention have higher sensitivity to 490 nm light than Comparative Examples 1 to 3.

Examples 1-4 Component (b) (η6-benzene) (η5-cyclopentadienyl) Iron(II) hexafluorophosphate component (c) Bis(cyclopentadienyl)-bis-[2,6-difluoro -3-(Pyr-noyl)-phenylftitane component (e) N-phenylglycine Table 1 Examples 5 to 8 Component (b) (η6-chlorobenzene) (η5-cyclopentadienyl) Iron(II) hexa Fluorophosphate component (c) Bis(7clopentazoenyl)-bis-[2,6-difluoro-3-(pyru-noyl)-phenyl phtitan component (e) N-phenylglycine Table 2 (Effects of the invention) This invention Because the photopolymerizable compositions of the invention exhibit high sensitivity to visible light, low energy exposure light sources can be used and a large number of masters can be exposed and developed in a given amount of time.

In addition, since the exposure source can be moved away from the original, the light rays are collimated, which brings about various advantages, such as the ability to form sharp halftone dots with vertical sides when forming halftone images. do.

Claims (1)

[Scope of Claims] (a) At least one ethylenically unsaturated compound that is non-gaseous at room temperature (b) An iron allene complex represented by the following general formula (I) (c) A titanocene compound (d) (a) The following 3-substituted coumarin represented by the general formula (IIa) (b) p-aminophyl unsaturated ketone represented by the following general formula (IIb) (c) xanthine or thioxanthene compound represented by the following general formula (IIc) ( A photopolymerizable composition comprising at least one compound selected from the group consisting of (a), (b), and (c). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (m+n≧0) (In the formula, R^1 and R^2 are the same or different groups, and R
^2 may form a fused polycyclic compound with a benzene ring. X^1 is BF_4, PF_6, AsF_6, SbF
_6FeCl_4, SnCl_6, SbCl__6, B
iCl_6 is shown. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IIa) (In the formula, R^3, R^4, R^5, R^6 are hydrogen, alkyl group, alkoxy group, alkylamino group, dialkylamino group, A cyano group or two may form a condensed ring system or a condensed heterocyclic ring system.Z represents an aryl group, a heterocyclic group, or ▲a numerical formula, a chemical formula, a table, etc.▼.R
^7 represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or a heterocyclic group. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IIb) (In formula IIb, p and q are each 0 or 1, and R^
8, R^9, R^1^0, R^1^1, R^1^2, R
^1^3 represents a hydrogen atom or an organic group having 1 to 24 carbon atoms. ) R^1^4 is a methylidine group or an alkylene-iridine group having 1 to 5 carbon atoms that can be combined with R^1^5 to form a ring with a carbonyl group, R^1^5 is a carbon atom or a substituted or unsubstituted phenyl group or R^1
Indicates a group that forms indanone, tetralone, or indanedione together with ^4 and a carbonyl group, and R^1^6
indicates ▲There are mathematical formulas, chemical formulas, tables, etc.▼, r is the number 0 or 1, R^1^7, R^1^8, R^1
^9, R^2^0, and R^2^1 are hydrogen atoms or organic groups having 1 to 24 carbon atoms. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IIc) [In the formula, A is an oxygen atom or a sulfur atom, B is a hydrogen atom or a halogen atom, and D is a carbon atom or a nitrogen atom (however, if D is a carbon atom, is a double bond between adjacent carbon atoms (indicated by a dotted line), and if D is a nitrogen atom, it is a single bond between adjacent carbon atoms.), E is an oxygen atom (this ), an alkoxy group or an alkanoyloxy group, R^2^2 is an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, a dialkylaminoalkyl group, or an aryl group. , R^2^3 is a hydrogen atom, an alkoxy group, an alkyl group, or a dialkylamino group. ]