JPH06161106A - Photo-polymerized composition - Google Patents

Abstract

PURPOSE:To expose and develop a number of original plates in a given time by containing specified ethylenic unsaturated compound and iron allene complex to show high sensitivity to visible light so that a low-energy exposure light source can be used. CONSTITUTION:At least one type of ethylenic unsaturated compound formed into non-gaseous shape at room temperature and iron allene complex shown by formula are contained. In formula, R<1>, R<2> are the same or different groups and selected out of C1-C12 alkyl groups and C2-C12 alkenyl groups, and R<2> can be condensation polycyclic compound with benzene rings. Dk<-> shows anionic pigments and (k) is 1 or 2. The anionic pigments are excited by absorbing light, electrons are supplied to iron allene complex cations, and free radicals are created to allow the polymerization of ethylenic double bonds. As components to give electrons and components to receive electrons form salts and exist in the vicinity, electrons are efficiently given and received to provide high sensitivity.

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. Also, use visible light instead of ultraviolet light as the light source,
Scanning exposure with a laser having a large oscillation intensity in the visible region such as an argon ion laser is required as an image forming technique. 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-54-15529
No. 2 discloses a system containing hexaarylbisimidazole, and JP-A No. 58-15503 discloses a system containing an active halogen compound and a 3-keto-substituted coumarin compound.
4604 discloses a system of 3-keto-substituted coumarin and N-phenylglycine, and JP-A 61-97650 discloses 3 system.
A combination of a substituted coumarin and a quinazolinone derivative, JP 61-123603 discloses a photoinitiator system of a combination of hexaarylbisimidazole and a 3-keto substituted coumarin.

[0003]

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.

[0004]

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 a photopolymerizable composition comprising (a) at least one non-gaseous ethylenically unsaturated compound at room temperature (b) an iron allene complex represented by the following general formula 2.

[0005]

[Chemical 2] (Wherein R ^1, R ² are the same or different groups, C ₁ ~
Alkyl C _12, alkenyl group of C ₂ ~C _12, C ₂ ~
C ₁₂ alkynyl group, C _{1 to} C ₈ alkoxy group, cyano group, alkylthio group, phenoxy group, C _{2 to} C ₆ monocarboxylic acid and ester and amide, phenyl group, C _{2 to} C ₅ alkanoyl group, Selected from ammonium salt, pyridinium group, nitro group, alkylsulfinyl group, alkylsulfonyl group, sulfamoyl group,
R ² may form a condensed polycyclic compound with a benzene ring. D ^k- represents an anionic dye, and k is 1 or 2. )

The ethylenically unsaturated compound used in the present invention is a monomer suitable for 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.

Anionic dye D in the general formula 2
^k- includes all dyes having an anion group, but typical examples are rose bengal, phloxine, erythrosine,
Examples include xanthene dyes such as eosin and fluorescein, coumarin dyes having a carboxylate anion group and a sulfonate anion group, and anthracene dyes. 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]

[0021]

[Chemical 16]

In the present polymerizable composition, the anionic dye absorbs light and is excited to donate an electron to the iron allene complex cation to generate a free radical. The free radical then polymerizes the ethylenic double bond. In this system, the electron-donating component and the electron-accepting component form a salt and are present in the vicinity, so that the electron transfer can be efficiently performed and the sensitivity becomes high. In addition, generally, there is back electron transfer as a reaction that prevents the formation of free radicals after electron transfer. However, in this system, since the anion and cation become neutral after the electron transfer, the ability to form a salt is lost and dissociated, so that it does not exist in the vicinity. Therefore, reverse electron transfer is less likely to occur, which is advantageous for high sensitivity. In the conventional initiator system, since the electron acceptor and the electron donor do not form a salt and do not exist in the vicinity,
Electron transfer does not occur unless the electron acceptor or electron donor absorbs light and is in an excited state without diffusing collision with a reacting partner. Therefore, electron transfer does not occur efficiently and free radicals do not occur efficiently. Therefore, the present polymerizable composition has higher sensitivity than the conventional polymerizable composition containing an initiator system.

In the composition of the present invention, the compound having the following general formula 17 and / or the cyclic diketone compound having the following general formula 18 is added to give higher sensitivity.

[Chemical 17] (In the formula, s is 0 or 1, and R ³ , R ⁴ , and R ⁵ are the same or different groups. R ³ may form a condensed polycyclic compound with a benzene ring, and R ⁴ , R 5 ⁵ can also combine with a benzene ring to form a ring, where X is S, Sc, N
In -R ^6, R ⁶ represents hydrogen or an alkyl group of C ₁ -C _6. )

[0024]

[Chemical 18] (In the formula, R ⁷ is hydrogen or a substituted or unsubstituted alkyl or aralkyl group, and G is a divalent organic group.) Examples of the compound represented by the general formula 17 include N-phenylglycine and 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, N -Methylindole acetic acid, 6-cyanoindole acetic acid and the like can be mentioned.

The cyclic diketone compound represented by the general formula 18 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 from 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 and 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 δ-lactone, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid 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-
Examples include Zeon.

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 preferable blending 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 as the component (a), the iron allene complex as the component (b) is 0.01 to 50 parts by weight. Parts by weight, particularly preferably 0.1 to 30 parts by weight. The compound represented by the general formula 17 or the cyclic diketone compound is 0 to 20 parts by weight, particularly preferably 0.1 to
20 parts by weight, the binder is 0 to 1000 parts by weight, preferably 0
It is 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,
Examples include electrostatic discharge treated polyethylene terephthalate film, polyvinyl alcohol coated paper, cross-linked polyester coated paper, nylon, glass, cellulose acetate film and the like.

The particular material is generally 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 a polymerization inhibitory 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.

[0033]

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 8 and Comparative Examples 1 to 4 A 100 μm thick transparent polyethylene terephthalate film having a subbing layer was coated with a photosensitive layer coating solution having the following composition, and dried at 90 ° C. for 1 minute in 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, and dried with a hot air dryer at 100 ° C. for 1 minute to form an overcoat layer having a thickness of 1 μm to obtain a sensitivity test piece. . (Composition of photosensitive layer coating liquid) Poly (methyl methacrylate / methacrylic acid) 52 parts 70/30 molar ratio Tetraethylene glycol diacrylate 40 parts Component (b) 5 parts Component (c) (represented by general formula 17) Compound or cyclic diketone compound) 3 parts Methanol 200 parts Ethyl acetate 80 parts Chloroform 120 parts As a negative film, a 21√ (2) step tablet (Dainippon Screen gray film scale) is overlaid on the above sensitivity test piece, and a xenon lamp ( Made by Ushio Electric
UXL-500 D-0) combined with Toshiba interference filter KL-49 and glass filter Y-45 of the same color (490 nm)
After exposure for 5 minutes from a distance of 15 cm, immerse in 0.7% sodium carbonate aqueous solution at 30 ° C for 10 seconds, wash with water to remove uncured portion, and dry. 21√ (2) Number of steps for complete curing of step tablet (Step) was examined and shown in Table 1. Further, Table 1 shows a comparative example in which the complex (d) in which the counter anion is not a dye and the dye (e) are simply combined in place of the component (b). The photosensitive layer coating liquid composition is the component (b) of the example.
Instead of 5 parts, the component (d) was 5 parts and the component (e) was 5 parts. It is apparent from Table 1 that Examples 1 to 8 of the present invention have higher sensitivity to light of 490 nm than Comparative Examples 1 to 4.

[0034]

[Table 1] Chemical formulas 19 to 34 in Table 1 are shown below.

[0035]

[Chemical 19]

[0036]

[Chemical 20]

[0037]

[Chemical 21]

[0038]

[Chemical formula 22]

[0039]

[Chemical formula 23]

[0040]

[Chemical formula 24]

[0041]

[Chemical 25]

[0042]

[Chemical formula 26]

[0043]

[Chemical 27]

[0044]

[Chemical 28]

[0045]

[Chemical 29]

[0046]

[Chemical 30]

[0047]

[Chemical 31]

[0048]

[Chemical 32]

[0049]

[Chemical 33]

[0050]

[Chemical 34]

[0051]

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. ⁵ Identification code Office reference number FI technical display location G03F 7/00 501 7124-2H 7/027 502 H01L 21/027

Claims (1)

[Claims] 1. A photopolymerizable composition comprising (a) at least one non-gaseous ethylenically unsaturated compound at room temperature (b) an iron allene complex represented by the following general formula 1. [Chemical 1] (Wherein R ^1, R ² are the same or different groups, C ₁ ~
Alkyl C _12, alkenyl group of C ₂ ~C _12, C ₂ ~
C ₁₂ alkynyl group, C _{1 to} C ₈ alkoxy group, cyano group, alkylthio group, phenoxy group, C _{2 to} C ₆ monocarboxylic acid and ester and amide, phenyl group, C _{2 to} C ₅ alkanoyl group, Selected from ammonium salt, pyridinium group, nitro group, alkylsulfinyl group, alkylsulfonyl group, sulfamoyl group,
R ² may form a condensed polycyclic compound with a benzene ring. D ^k- represents an anionic dye, and k is 1 or 2. )