JPH07199466A - Photopolymeric composition - Google Patents

Abstract

PURPOSE:To enable a photopolymeric composition to have enhanced sensitivity to visible light by containing an ethylene unsaturated compound, a specific iron-allene complex and a sensitizer. CONSTITUTION:This photopolymeric composition contains at least one kind of ethylene unsaturated compound that is in non-gaseous form at room temperature, an iron-allene complex represented by the formula, and a sensitizer. In the formula, R<1> represents a C1 to C12 alkyl group; R<2> represents a C1 to C12 alkyl group, a C2 to C12 alkenyl group, a C2 to C12 alkynyl group, a C1 to C8 alkoxy group, a cyano group, an alkyltio group, a phenoxy group, a C2 to C6 monocarboxylic acid and ester, amide, or phenyl, group, a C2 to C5 alkanoyl group, an ammonium salt, a pyridinium group, a nitro group, an alkylsulfinyl group, an alkylsulfonyl group, or a sulfamoyl group; R<2> may form a benzene ring and a condensed polyvalent compound; X represents either BF4, PF6, AsF6, SbF6, Fecl4, SnCl6, or BiCl6; and R2 is preferably an electron withdrawing group which does not inhibit a polymerization reaction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photopolymerizable composition having sensitivity even in the visible light region.

[0002]

BACKGROUND OF THE INVENTION Photopolymerizable compositions are widely used in a number of applications, including printing, copying, resist formation and other commercial applications. 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, many of these known useful photopolymerizable compositions are limited in their application range because many of the initiators used are not activated outside the ultraviolet region of the spectrum. Is.

Further, it is required as an image forming technique to use visible light instead of ultraviolet light as a light source or perform scanning exposure with a laser having a large oscillation intensity in a visible region such as an argon ion laser. Therefore, a photopolymerizable material having high sensitivity to visible light is desired, and development of a photoinitiator having high sensitivity to visible light is desired.
Then, as a photoinitiator having high sensitivity, JP-A-54-1 is used.
55292 discloses a system containing hexaarylbisimidazole, JP-A-58-15503 discloses a system of an active halogen compound and a 3-keto-substituted coumarin compound, and JP-A-56-4604 discloses a 3-keto-substituted compound. Coumarin and N-
A system of phenylglycine, a combination of 3-substituted coumarin and a quinazolinone derivative in JP-A-61-97650, and a combination of hexaarylbisimidazole and a 3-keto-substituted coumarin in JP-A-61-123603. A photoinitiator system is disclosed.

[0004]

However, the above-mentioned photoinitiator system has insufficient sensitivity, and in order to perform scanning exposure with a laser having a lower output at a high speed, a photoinitiator system having a higher sensitivity is found. It is necessary.

[0005]

In order to solve the above problems, that is, to improve the sensitivity of the photopolymerizable composition to visible light, the present invention has been made as a result of earnest research, efforts and efforts on a photoinitiator system. Finally, the present invention has been completed. That is, the present invention is characterized by containing (a) at least one non-gaseous ethylenically unsaturated compound at room temperature (b) an iron allene complex represented by the following general formula 2 and (c) a sensitizer. Photopolymerizable composition

[0006]

[Chemical 2] (In the formula, R ¹ is a C _{1 to} C ₁₂ alkyl group, and R ² is C _{1 to} C 12.
₁₂ alkyl groups, C _{2 to} C ₁₂ alkenyl groups, C _{2 to} C
₁₂ alkynyl groups, C ₁ -C ₈ alkoxy groups, cyano groups, alkylthio groups, phenoxy groups, C ₂ -C ₆ monocarboxylic acids and esters and amides, phenyl groups,
R ² selected from a C _{2 to} C ₅ alkanoyl group, ammonium salt, pyridinium group, nitro group, alkylsulfinyl group, alkylsulfonyl group, sulfamoyl group, and R ²
May form a condensed polycyclic compound with a benzene ring.
X is BF ₄ , PF ₆ , AsF ₆ , SbF ₆ , FeC
One of l ₄ , SnCl ₆ and BiCl ₆ is shown. )

The ethylenically unsaturated compound used in the present invention is a monomer suitable for a free radical-initiated chain growth addition reaction, for example, pentaerythritol triacrylate, polyethylene glycol diacrylate, triethylene glycol. Examples thereof include diacrylate, polyethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate. The second component (b) is represented by the general formula 1 (formula 2). These compounds are Jour
nal of American Chemical Society, 103, 758 (1981)
It is synthesized by the method described in. R ² is preferably an electron-withdrawing group that does not inhibit the polymerization reaction.
This is because the iron allene complex having an alkyl group-substituted cyclopentaenyl group has difficulty in accepting electrons, and thus has difficulty interacting with the photosensitizer that has absorbed light. R
The electron withdrawing property of ² reduces this effect. Specific examples of the preferred second component (b) are shown below.

[0008]

[Chemical 3]

[0009]

[Chemical 4]

[0010]

[Chemical 5]

[0011]

[Chemical 6]

[0012]

[Chemical 7]

[0013]

[Chemical 8]

[0014]

[Chemical 9]

[0015]

[Chemical 10]

[0016]

[Chemical 11]

[0017]

[Chemical 12]

[0018]

[Chemical 13]

[0019]

[Chemical 14]

[0020]

[Chemical 15]

The third component (c) is a sensitizer, preferably cyanine, carbocyanine, merocyanine, aromatic carbonyl, styryl, acridine, thiazine, oxazine, coumarin, polycyclic aromatic hydrocarbon, polyarylamine, It is at least one dye selected from the group consisting of pyrylium, thiapyrylium, and xanthene. Specific examples of the particularly preferred third component (c) are shown below.

[0022]

[Chemical 16]

[0023]

[Chemical 17]

[0024]

[Chemical 18]

[0025]

[Chemical 19]

[0026]

[Chemical 20]

[0027]

[Chemical 21]

[0028]

[Chemical formula 22]

[0029]

[Chemical formula 23]

[0030]

[Chemical formula 24]

[0031]

[Chemical 25]

[0032]

[Chemical formula 26]

[0033]

[Chemical 27]

In the present polymerizable composition, the sensitizing property absorbs light and is excited to donate an electron to the iron allene complex cation, and the iron allene complex is reduced. The thermal stability of this reductant depends on the types of substituents on the cyclopentadienyl ring and the arene ring. Since the reductant of the iron allene complex of the present invention represented by the general formula 1 is extremely unstable, it easily decomposes to generate a free radical. The free radicals then polymerize the ethylenically unsaturated compound.

A compound represented by the following general formula 28 and / or a cyclic diketone compound represented by the following general formula 29 can be added to the composition of the present invention.

[0036]

[Chemical 28] 1 is 0 or 1, R ³ , R ⁴ and R ⁵ are the same or different groups, and R ³ and R ⁴ are selected from hydrogen or a C _{1 to} C ₁₂ alkyl group. Y is S, Se, N
-R R ^{6 6} represents a hydrogen or an alkyl group of C ₁ -C _6. Examples of the compound represented by the general formula 28 include 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, indole acetic acid,
Examples thereof include N-methylindole acetic acid and 6-cyanoindole acetic acid.

[0037]

[Chemical 29] (In the formula, R ⁷ is hydrogen or a substituted or unsubstituted alkyl or aralkyl group, and G is a divalent organic group.)

The cyclic diketone compound represented by the above general formula 29 is a cyclic β-dicarbonyl compound having an active methylene group having an unstable hydrogen atom. R in the formula
⁷ is hydrogen, alkyl, substituted alkyl, or aralkyl, G is a divalent organic group and may contain a heteroatom in the chain of the group, and optionally one or both of carbon and heteroatom. It may have a substituent. In the above, the alkyl group is C _{1 to} C ₁₂ alkyl, and examples of the substituted alkyl include hydroxylalkyl, cyanoalkyl, haloalkyl, alkoxyalkylene, alkylenethioether, aryloxyalkylene and the like. The aryl portion of the aralkyl group may contain 6 to 10 carbon atoms. The divalent organic group G completes the ring. This moiety may contain heteroatoms such as 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-cyclopentanedione, 2,4-diethyl-1,3-cyclobutanedione, 2-methyl-1,3-cyclobutanedione, 5-
Methyl-2-thiobarbituric acid, barbituric acid, 3
-Ethyltetronic acid, 2,4-dimethyl-3-oxo-5
-Hydroxy-5-methoxypentenoic acid delta-lactone,
1,3,5-Trimethylbarbituric acid, 1,3-Dimethyl-
5-ethylbarbituric acid, 2-methyldimedone, 1,3
-Indandione, 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-trimethyl-m -Dioxane-4,6-dione and the like.

A thermoplastic high molecular weight organic polymer binder may preferably be present in the composition of the present invention. Polymer binder types include (1) terephthalic acid, isophthalic acid, sebacic acid, adipic acid and hexahydroterephthalic acid based copolyesters, (2) polyamides,
(3) vinylidene chloride copolymer, (4) ethylene /
Vinyl acetate copolymer, (5) cellulose ether, (6) polyethylene, (7) synthetic rubber, (8) cellulose ester, (9) polyvinyl ester including polyvinyl acetate / acrylate and polyvinyl acetate / methacrylate copolymer, ( 10) Polyacrylates and poly α-alkyl acrylate esters such as polymethyl acrylate and polyethyl methacrylate, (11) high molecular weight ethylene oxide polymers having a weight average molecular weight of 4,000 to 4,000,000 (polyethylene glycol), (12) polyvinyl chloride and the like. The copolymer, (13) polyvinyl acetal, (14) polyformaldehyde, (15) polyurethane, (16) polycarbonate and (17) polystyrene are mentioned.

In the compositions of the present invention, a particularly preferred polymeric binder is one in which the unexposed photopolymerizable coating is soluble in predominantly aqueous solutions, such as alkaline solutions, but relatively after exposure to actinic radiation. Polymeric binders that are insoluble in it are preferred. Polymers that typically meet these requirements are carboxylated polymers, such as vinyl addition polymers containing free carboxylic acid groups. There are methacrylic acid copolymer, acrylic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer and the like. In addition, there are cellulose having a carboxyl group in the side chain, a polymer having a hydroxyl group in the side chain and a cyclic acid anhydride added thereto, and the like.

In addition, it is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during the production or storage of the photopolymerizable composition. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol and di-t.
-Butyl-p-cresol, pyrogallol, di-t-butylcatechol, benzoquinone, 2-mercaptobenzimidazole, N-nitrophenylhydroxyamine primary cerium and the like. The addition amount of the thermal polymerization inhibitor is preferably 0.01 to 5% with respect to the entire composition. Further, if necessary, an inert additive such as a non-polymerizable plasticizer, a dye, a pigment and a filler may be blended to such an extent that the photopolymerizability is not significantly impaired. When the preferred mixing ratio of the photopolymerizable composition of the present invention is expressed in parts by weight relative to 100 parts by weight of the ethylenically unsaturated compound which is the component (a), the iron allene complex which is the component (b) is 0.01 to 50 parts by weight, Particularly preferably 0.1 ~
30 parts by weight.

The compound represented by the general formula 28 and the cyclic diketone compound represented by the general formula 29 are 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, It is preferably 0 to 200 parts by weight. The photopolymerizable composition of the present invention can be coated on a wide variety of substrates. By "substrate" herein is meant any natural or synthetic support, preferably one that may be present in the form of a flexible or rigid film or sheet. For example, the material can be a metal sheet or foil, a synthetic organic resin sheet or film, cellulosic paper, fiberboard or the like or a composite of two or more of these materials. Specific materials include alumina plast aluminum, anodized aluminum, aluminum plast polyethylene terephthalate film, polyethylene terephthalate film, electrostatic discharge treated polyethylene terephthalate film, polyvinyl alcohol coated paper, cross-linked polyester coated paper,
Examples thereof include nylon, glass, cellulose acetate film and the like.

The particular material will generally be determined by the relevant application purpose. For example, if a printed circuit is manufactured,
The material can be a plate coated with copper on a fiberboard. In the manufacture of lithographic printing plates,
The material can be anodized aluminum. In the present invention, the thickness of the photopolymerizable composition is 0.1 to 250 μm, preferably 0.5 to 50 μm. The desired thickness is determined by the application. On the layer of the photopolymerizable composition provided on the substrate, a protective layer made of a polymer having an excellent oxygen barrier property, such as polyvinyl alcohol, is provided in order to prevent the polymerization inhibiting action by 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 actinic rays in a wide range from ultraviolet light to visible light. Therefore, as a light source, ultra-high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, argon ion laser, laser such as helium-cadmium laser, fluorescent lamp, tungsten lamp, and Sunlight can be used.

[0046]

EXAMPLES The present invention will be described in more detail with reference to the following examples, in which parts and% are based on weight. Examples 1 to 15 and Comparative Examples 1 to 3 A 100 μm thick transparent polyethylene terephthalate film having an undercoat layer was coated with a photosensitive layer coating solution having the following composition, and dried at 90 ° C. for 1 minute with a hot air dryer. A coating film having a thickness of 3 μm was obtained. Then, an aqueous solution of 7% polyvinyl alcohol (completely saponified, weight 500) was applied onto it, dried at 100 ° C. for 1 minute with a hot air dryer, and an overcoat layer with a thickness of 1 μm was provided 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 parts Component (b) 5 parts Component (c) 3 parts Methanol 200 parts Ethyl acetate 80 parts Chloroform 120 parts

As a negative film on the above sensitivity test piece
21√ (2) Stack step tablets (Dainippon Screen gray film scale) on a xenon lamp (USHIO Electric UXL-500 D-0) and Toshiba interference filter.
After exposing for 5 minutes from a distance of 15 cm with a light source (490 nm) combining KL-49 and the same color glass filter Y-45, 30
After immersing in 0.7% sodium carbonate aqueous solution for 10 seconds at ℃, washing with water to remove the uncured part, and drying, 21√ (2) step The number of steps (steps) of complete hardening of the tablet was investigated and shown in Table 1. It was Table 2 shows comparative examples in which the conventionally used iron allene complex (d) and the sensitizer (c) were simply combined in place of the component (b). The composition of the photosensitive layer coating liquid was 5 parts of the component (d) instead of 5 parts of the component (b) in the examples.
Tables 1 and 2 clearly show that Examples 1 to 15 of the present invention have higher sensitivity to light of 490 nm than Comparative Examples 1 to 3.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

Since the photopolymerizable composition of the present invention has high sensitivity to visible light, a low energy exposure light source can be used, and a large number of original plates can be exposed and developed within a given time. it can. Further, since the exposure source can be moved away from the original plate, its light rays are collimated, which has various advantages such as the ability to form sharp halftone dots having vertical sides when forming a halftone image. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location H05K 3/00 F 3/06 H

Claims (1)

[Claims] 1. At least (a) at least one non-gaseous ethylenically unsaturated compound at room temperature, (b) an iron allene complex represented by the following general formula 1, and (c) a sensitizer. A photopolymerizable composition characterized by: (In the formula, R ¹ is a C _{1 to} C ₁₂ alkyl group, and R ² is C _{1 to} C 12.
₁₂ alkyl groups, C _{2 to} C ₁₂ alkenyl groups, C _{2 to} C
₁₂ alkynyl groups, C ₁ -C ₈ alkoxy groups, cyano groups, alkylthio groups, phenoxy groups, C ₂ -C ₆ monocarboxylic acids and esters and amides, phenyl groups,
R ² selected from a C _{2 to} C ₅ alkanoyl group, ammonium salt, pyridinium group, nitro group, alkylsulfinyl group, alkylsulfonyl group, sulfamoyl group, and R ²
May form a condensed polycyclic compound with a benzene ring.
X is BF ₄ , PF ₆ , AsF ₆ , SbF ₆ , FeC
One of l ₄ , SnCl ₆ and BiCl ₆ is shown. )