JPH03210566A - Photopolymerizable composition sensitive to visible light - Google Patents

Abstract

PURPOSE:To improve the sensitivity to visible light by incorporating an ethylenic unsatd. compd. which is nongaseous at ordinary temp., a specific iron allen complex and a specific p-aminophenyl unsatd. ketone compd. into the above compsn. CONSTITUTION:The ethylenic unsatd. compd. which is nongaseous at ordinary temp., the iron allen complex expressed by formula I and the p-aminophenyl unsatd. ketone compd. expressed by formula II, etc., are incorporated into the compsn. In the formula I, R<1>, R<2> are the same or different groups and R<2> may form a condensed polycyclic compd. with a benzene ring; X' denotes BF4, PF6, AsF6, SbF6, FeCl4, SnCl6, SbCl6, BiCl6. In the formula II, (a), (b) denote 0 or 1 integer; R<3> to R<14> denote a hydrogen atom or 1 to 24C org. group; X<2>, X<3> denote a carbonyl group or a substituent contg. a cyano group; X<2> and X<3> may combine. The sensitivity is improved up to the region of visible light 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 a system containing an active halogen compound and a 3-keto-substituted coumarin compound, and JP-A-56-4604 discloses a system containing a 3-keto substituted coumarin compound. Substituted coumarin and N-
Phenylglycine system, JP-A-6197650 discloses a combination of 3-substituted coumarin and quinazolinone derivative,
JP-A-61-123603 discloses a photoinitiator system of a combination of hexaarylbisimidazole and a 3-keto substituted coumarin.

(Problem to be Solved by the Invention) However, the sensitivity of the photoinitiator systems described above is insufficient, and in order to perform scanning exposure at high speed with a lower output laser, it is necessary to find a photoinitiator with even higher sensitivity. is necessary.

(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;
A visible light-sensitive photopolymerizable composition characterized by containing an iron allene complex represented by the following general formula CI), and (c) a p-aminophenyl unsaturated ketone compound represented by the following general formula [II]. be.

(In the formula, RI Rz are the same or different groups, R1
may form a fused polycyclic compound with a benzene ring
X r is BF4, PH4, 8sFa, 5bFh, Fe
C1n, SnCli, 5bC1i, B1Cl1 are shown.

)(II In the formula, a, b represent O or the number of 1, and R3
~RI4 is a hydrogen atom or an organic group having 1 to 24 carbon atoms, X2 and x2 are substituents containing a carbonyl group or a cyano group, and x2 and x3 may be bonded. ) 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 glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylol Examples include propane triacrylate and trimethylolpropane trimethacrylate.

The iron allene complex represented by the general formula [I] as the second component (b) is Chesiker-Zeitung+1
08(11) 345-354 (1984).

In the general formula (1), R'R'' haCI-C+
x alkyl group, 02-C11 alkenyl group, C2
~C1□ alkynyl group, C1~CI alkoxy group,
Shea L alkylthio group, phenoxy group, 02-C6 monocarboxylic acid and ester and amide, phenyl group, C:-C2 alkanoyl group, ammonium salt, pyridinium group, nitro group, alkylsulfinyl group, alkylsulfonyl group, sulfamoyl selected from the following.

Specifically, (1-benzene) (η5-cyclopentadienyl) iron [II]-hexafluorophosphate, (
77'-toluene) (η5-cyclopentazinyl) iron (If) hexafluorophosphate, (P-cumene)
(η1-cyclopentadienyl) iron(If) hexafluorophosphate, (η6-benzene) (η5-cyclopentadienyl) iron[II] hexafluoroarsenate, (η6-benzene) (ηゝ-cyclopentagenyl) ) iron (If) tetrafluoroborate, (11″-naphthalene) (η5-cyclopentadienyl) Ik [II
] Hexafluorophosphate, (η1-anthracene-(η5-cyclopentadienyl) iron (If) hexafluorophosphate, (η6-pyrene) (η5-cyclopentadienyl) iron (U) hexafluorophosphate (η--benzene)(η5-cyanocyclopentadienyl)iron[II]hexafluorophosphate, (η
--Toluene) (η5-acetylcyclopentadienyl) iron (■) hexafluorophosphate, (η6-cumene) (η5-chlorocyclopentagenyl) iron [II]
Tetrafluoroborate, (η6-benzene) (η5-
Carboethoxycyclohexagenyl) iron [II] hexafluorophosphate, (η--benzene) (de!-
1,3-dichlorocyclohexagenyl) iron (■) hexafluorophosphate, (η1-cyanobenzene) (
η5-cyclohexagenyl) iron [II] hexafluorophosphate, (η6-acetophenone) (η5-cyclohexagenyl) iron (■) hexafluorophosphate, (η6-methylbenzoate) (η1-cyclopentagenyl) Iron (If) hexafluorophosphate, (vh-benzenesulfonamide) (ηゝ-cyclopentagenyl) iron [II] tetrafluoroborate, (
jh-benzamide) (η5-cyclopentadienyl)
Iron (U) hexafluorophosphate, (η6-diatubenzene)(η5-cyanocyclopentagenyl)iron [
II] Hexafluorophosphate, (η1-chlornaphthalene)(η5-cyclopentagenyl)iron [II]
Hexafluorophosphate, (η6-anthracene)
(77%-cyanocyclopentagenyl) iron (n) hexafluorophosphate and the like.

These compounds are Dokl, Akd, Nauk 5S
It can be synthesized by the method described in SR149615 (1963).

The third component (c) is a p-aminophenyl unsaturated ketone compound represented by the general formula [II].

In the general formula (If), a and b are each independently 0 or 1, R3R4R1, R6, RfR, R9,
RI@, R” R” R”, R eye is a hydrogen atom, C
l-Cl! Alkyl group of C mushroom to C, R alkenyl l
lt, C3-C1z alkynylli, c, ~C1 alkoxy group, C3-C- alkylthio group% C6-CI
Aryloxy group of *, substituted and unsubstituted aryl group of ch-cue, carboxyl group, cyano group, halogen atom, amino group, C3 to C1z monoalkylamino group,
C8-Cta dialkylamino group, C, AC, cyanoalkyl group, 01-C1! an alkoxycarbonyl group of 02 to Cta, an alkoxycarbonylalkyl group of 02 to Cta, a hydroxycarbonylalkyl group of C1 to C1, an acyloxy group of C8 to C11, or an acyloxycarbonyl group of 08 to C14.

8 X3 is each independently A group containing a carbonyl group or a cyano group such as X wealth xs is combine, You may also form a group such as

general formula ( ) Specific examples of compounds represented by Shown below.

υ 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, C is 0 or 1, RIB, RI6= R
1'? are the same or different groups, RIS may form a fused polycyclic compound with a benzene ring, R", R+
t can also be combined with a benzene ring to form a ring.

X3 is S, 5cN-R", RII is hydrogen or 0
1-C6 alkyl group) (Formula RI9 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-
Phenylglycine, N-(p-methylphenyl)glycine, 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-diathindoleacetic 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, where RIM is hydrogen, alkyl, substituted alkyl or aralkyl. ,
G is a divalent organic group which may contain a heteroatom in the side chain of the group, and where appropriate, one or both of the carbon and heteroatoms may have a substituent.
In the above, the alkyl group is C, ~CI! Substituted alkyl includes, for example, hydroxylalkyl, cyanoalkyl, haloalkyl, alkoxyalkylene, alkylentioether, and aryloxyalkylene. The aryl part of the aralkyl group is 6
May contain ~10 carbon atoms. The divalent organic 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-cyclopendanedione, 2,4-diethyl- 1,3-cyclobutanedione, 2
-Methyl-1,3-cyclobutanedione, 5-methyl-
2thiobarbituric acid, barbituric acid, 3-ethyltetronic acid, 2,4-dimethyl-3-oxo-5-human, waxy 5-methoxypentenoic acid δ-lactone, L3.5
- Trimethylbarbic acid, 1,3-dimethyl 5-
Ethylbarbic acid, 2-methyldimedone, 1.3-
Indanedione, 2-methylindandione, bis-[
5-(1,3-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, 2
．． 2.5-) samethyl-mdioxane-4,6-sion, and the like.

A thermoplastic high molecular weight organic polymeric binder may preferably be present in the composition of the invention. Polymeric binder types include (i) copolyesters based on terephthalic acid, isophthalic acid, sebacic acid, adipic acid and hexahydroterephthalic acid, (ii) polyamides, (iii) vinylidene chloride copolymers, (iv) ethylene/ Vinyl acetate copolymer, (V) cellulose ether, (■
) polyethylene, (vi) synthetic rubber, (vj) 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) high molecular weight ethylene oxide polymers (polyethylene glycol) having a weight average molecular weight of 4.000 to 4,000.00G, (xii) polyvinyl chloride and its copolymers, (xiii) polyvinyl acetal, (xiv) polyformaldehyde, (Xν) polyurethane, (xvi) polycarbonate and (xv
ii) Polystyrene can be mentioned.

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;
Photopolymerizable binders that are relatively insoluble after exposure to actinic radiation are preferred; typically polymers that meet these requirements are carboxylated polymers, such as vinyl addition polymers containing free carboxylic acid groups. It is a combination.

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 anhydride is added.

In addition, 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. Inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-
Cresol, pyrogallol, di-t-butylcatechol, benzoquinone, 2-mercaptopenzimadazole,
Examples include cerous N-nitrophenylhydroxyamine. The amount of the thermal polymerization inhibitor added is preferably 0.01 to 5% based on the total composition, and if necessary, inert additives such as non-polymerizable plasticizers, dyes, pigments, fillers, etc. may be added to the extent that photopolymerizability is not significantly inhibited.

The preferred blending ratio of the photopolymerizable composition of the present invention is the component (a
), the iron allene complex which is component (b) is 0.
．． 01 to 50 parts by weight, particularly preferably 0.1 to 30 parts by weight, and the p-aminophenyl compound as component (c) each contains 0.05 to 20 parts by weight, particularly preferably 0.1 to 2 parts by weight.
0 parts by weight, the compound represented by the general formula [I] 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 20 parts by weight. It is 50 parts by weight.

The photopolymerizable composition of the present invention can be coated on a wide variety of substrates. "Substrate" here means any natural or synthetic support, preferably in the form of a stirrable or rigid film or sheet. For example, the material may be a metal sheet or foil, a synthetic organic It can be a sheet or film of resin, cellulose paper, fiberboard, etc. or a composite of two or more of these materials. Specific materials include aluminoplast aluminum, anodized aluminum, aluminoplast polyethylene terenotalate film, polyethylene terephthalate film, electrostatic discharge treated polyethylene terephthalate film, polyvinyl alcohol coated paper, cross-linked polyester coated paper, nylon, glass, Examples include cellulose acetate film and others.

The particular material will generally be determined by the application purpose involved; for example, if printed circuits are to be manufactured, the material may be a copper coated plate on a fiberboard. 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 p.
-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 a 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, light sources include ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, lasers such as alcone ion lasers, helium cadmium lasers, fluorescent lamps, tungsten lamps, and You can use sunlight etc.

(Function) The sensitizer or component (c1) of the present invention is originally intended to efficiently absorb visible light that the photoinitiator or component (b) used in the present invention cannot absorb or exhibits very low absorbance. In that state, the sensitizer of the present invention acts on the photoinitiator used in the present invention, resulting in the generation of active radicals, which are then used to remove ethylenic compounds in the composition. It attacks unsaturated compounds and causes polymerization.

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

Examples 1 to 12, Comparative Examples 1 to 4 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. Then, a 7% polyvinyl alcohol (completely saponified, degree of polymerization 500) aqueous solution was applied on top of the coating film with a thickness of 3μ, and dried for 1 minute at 100°C in a hot air dryer to form an overcoat with a thickness of 1μ. A layer was applied to obtain a sensitivity test piece.

(Photosensitive layer coating liquid composition) Poly(methyl methacrylate/methacrylic acid) 52 parts 70/30 molar ratio Tetraethylene glycol diacrylate 40 Component (b) (shown in Tables 1 to 3) 5th order part (
c) (shown in BK-1 to BK-3) Tertiary component (d) (compound represented by general formula (III) or cyclic diketone compound) 3 methanol
200 ethyl acetate
80 chloroform 12
0 21.71 as a negative film on the above sensitivity test piece
”-Layer the step tablet (gray film scale manufactured by Dainippon Screen Co., Ltd.) and add the interference filter 1 manufactured by Toshiba Corporation [L-49 and the same color glass filter Y-45 to the xenon lamp (11XL-500D-0 manufactured by Ushio Inc.)
After exposure for 5 minutes from a distance of 15C11 using a light source (490n-Δ) that combines The number of steps for complete curing of the tablet was investigated and is shown in Table 1. Comparative examples are shown in Table 2. From Tables 1 to 2, it is clear that Examples 1 to 12 of the present invention are different from Comparative Examples 1 to 12. It can be seen that the sensitivity to light of 490 nm is higher than that of 4.

Table 2 (Effects of the Invention) The photopolymerizable composition of the present invention exhibits high sensitivity to visible light, so a low-energy exposure light source can be used, and a large number of light can be produced within a given time. The original plate can be exposed and developed.

In addition, since the exposure source can be moved away from the original, the light rays are collimated, and for example, when forming halftone images,
It has various advantages such as being able to form sharp halftone dots with vertical sides.

Claims (1)

[Claims] (1) (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) represented by the following general formula [II] p
- an aminophenyl unsaturated ketone compound. ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (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' is BF_4, PE_6, AsF_6, SbF_
6, FeCl_4, SnCl_6, SbCl_6, Bi
Indicates Cl_6. ) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼
[II] (In formula II, a, b represent the number 0 or 1, R^2~R
^1^4 is a hydrogen atom or an organic group having 1 to 24 carbon atoms, X^2 and X^3 are substituents containing a carbonyl group or a cyano group, and X^2 and X^3 are not bonded. It is a good thing. )