JPH06332172A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To enhance sensitivity to the visible light by incorporating a specified ethylenically unsaturated compound, a specified iron allene complex, and a specified coumarin compound. CONSTITUTION:This photopolymerizable composition contains at least one kind of ethylenically unsaturated compound nongaseous at normal temperature, the iron allene complex represented by formula I, and at least one kind of coumarin compound represented by formula II, and in formulae I and II, each of R<1> and R<2> is, independently, 1-12 C alkyl, 2-12 C alkynvl, or the like; R<2> may form a condensed polycyclic compound with the benzene ring; X is BF4, PF6 or the like; each o R<3>-R<15> is H, alkyl, alkoxy, or the like; and Z<1> is an aryl or heterocyclic group or the like, thus permitting the obtained compound to exhibit high sensitivity to visible light, and to be able to use a low energy exposure light source, and to expose a large number of photosensitive materials and to develop them in a given time.

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 provides (a) at least one non-gaseous ethylenically unsaturated compound at room temperature (b) an iron allene complex represented by the general formula (1) (c) a coumarin compound represented by the general formula (2) or (4) A photopolymerizable composition comprising at least one.

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. The iron allene complex represented by the general formula 1 in the second component (b) is Chemiker-Zeitu.
ng, 108 (11) 345-354 (1984) describes many compounds.

In the general formula 1, R ¹ and R ² are C ₁ to
Alkyl C _12, alkenyl group of C ₂ ~C _12, C ₂ ~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, C
Alkanoyl group ₂ -C _5, an ammonium salt, a pyridinium group, a nitro group, an alkylsulfinyl group, alkylsulfonyl group, a sulfamoyl group, selected from halogen atoms.

Specifically, (η ⁶ -benzene) (η ⁵ -cyclopentadienyl) iron (2) hexafluorophosphate, (η ⁶ -toluene) (η ⁵ -cyclopentadienyl)
Iron (2) hexafluorophosphate, (η ⁶ -cumene)
(Η ⁵ -Cyclopentadienyl) iron (2) hexafluorophosphate, (η ⁶ -benzene) (η ⁵ -cyclopentadienyl) iron (2) hexafluoroarsenate,
(Η ⁶ -Benzene) (η ⁵ -Cyclopentadienyl) Iron (2) Tetrafluoroporate, (η ⁶ -Naphthalene)
(Η ⁵ -Cyclopentadienyl) iron (2) hexafluorophosphate, (η ⁶ -anthracene) (η ⁵ -Cyclopentadienyl) iron (2) hexafluorophosphate, (η ⁶ -pyrene) (η ^5- Cyclopentagenyl) iron (2) hexafluorophosphate, (η ⁶ -benzene) (η ⁵ -cyanocyclopentadienyl) iron (2) hexafluorophosphate, (η ⁶ -toluene) (η ^5-
Acetyl cyclopentadienyl) iron (2) hexafluorophosphate, (eta ⁶ - cumene) (eta ⁵ - cyclopentadienyl) iron (2) tetrafluoroborate, (eta ⁶ - benzene) (eta ⁵ over carboethoxy cyclohexanol Sadienyl) iron (2) hexafluorophosphate, (η ⁶ -benzene) (η ⁵ -1,3-dichlorocyclohexadienyl)
Iron (2) hexafluorophosphate, (η ⁶ -cyanobenzene) (η ⁵ -cyclohexadienyl) iron (2) hexafluorophosphate, (η ⁶ -acetophenone)
(Η ⁵ -Cyclohexadienyl) iron (2) hexafluorophosphate, (η ⁶ -methylbenzoate) (η ⁵ −
Cyclopentadienyl) iron (2) hexafluorophosphate, (η ⁶ -benzenesulfonamide) (η ⁵ -cyclopentadienyl) iron (2) tetrafluoroborate,
(Η ⁶ -benzamide) (η ⁵ -cyclopentadienyl)
Iron (2) hexafluorophosphate, (η ⁶ -cyanobenzene) (η ⁵ -cyanocyclopentadienyl) iron (2) Hexafluorophosphate (η ⁶ -chlornaphthalene) (η ⁵ -Cyclopentadienyl) iron ( 2) Hexafluorophosphate, (η ⁶ -anthracene) (η ⁵
-Cyanocyclopentadienyl) iron (2) hexafluorophosphate, (η ⁶ -chlorobenzene) (η ⁵ -cyclopentadienyl) iron (2) hexafluorophosphate, (η ⁶ -chlorobenzene) (η ^5- Examples include cyclopentadienyl) iron (2) tetrafluoroborate. These compounds are found in Dokl.Akd.Nauk SSSR 149 615 (1
963).

Specific examples of the coumarin compound represented by the general formula 2 of the third component (c) are shown below.

[0010]

[Chemical 6]

[0011]

[Chemical 7]

[0012]

[Chemical 8]

[0013]

[Chemical 9] Specific examples of the coumarin compound represented by the general formula 4 of the third component (c) are shown below.

[0014]

[Chemical 10]

[0015]

[Chemical 11]

[0016]

[Chemical 12]

[0017]

[Chemical 13]

The compound of the present invention contains a compound represented by the following general formula 14 and / or a cyclic diketone compound represented by the following general formula 15 for higher sensitivity.

[0019]

[Chemical 14] (In the formula, s is 0 or 1, and R ²⁷ , R ²⁸ , and R ²⁹ are the same or different groups. R ²⁷ may form a condensed polycyclic compound with a benzene ring, and R ²⁸ , R ²⁹ can also combine with a benzene ring to form a ring, where X is S, Se or N.
In -R ^30, R ³⁰ represents hydrogen or an alkyl group of C ₁ -C _6. )

[0020]

[Chemical 15] (In the formula, R ³¹ 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 14 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, N-methylindoleacetic acid, 6-cyanoindole Examples include acetic acid.

The cyclic diketone compound represented by the general formula 15 is a cyclic β-dicarbonyl compound having an active methylene group having an unstable hydrogen atom. R in the formula
³¹ 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 -C ₁₂ alkyl, and examples of the substituted alkyl include hydroxylalkyl, cyanoalkyl, haloalkyl, alkoxyalkyl, alkylthioether, aryloxyalkyl 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 and 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 δ
-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 can be mentioned.

A thermoplastic high molecular weight organic polymer binder may preferably be present in the composition of the present invention. Polymer binder types include (1) copolyesters based on terephthalic acid, isophthalic acid, sebacic acid, adipic acid and hexahydroterephthalic acid, (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 its The copolymer, (13) polyvinyl acetal, (14) polyformaldehyde, (15) polyurethane, (16) polycarbonate and (17) polystyrene can be 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 2 or 4 or the cyclic diketone compound is 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 200 parts by weight. Is.

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 will generally be determined by the relevant application purpose. For example, if a printed circuit is manufactured, the material can be a copper coated plate 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
It 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.

[0030]

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) 3 parts Component (d) (Compound represented by the general formula 14 or 15) 3 parts Methanol 200 parts Ethyl acetate 80 parts Chloroform 120 parts 21√ (2) step tablet (a gray film scale manufactured by Dainippon Screen) as a negative film on the above sensitivity test piece. ) Are stacked, and a xenon lamp (made by USHIO INC.
UXL-500 D-0) combined with Toshiba interference filter KL-49 and glass filter Y-45 of the same color (490 nm)
After exposing from a distance of 15 cm for 5 minutes, immerse it in a 0.7% sodium carbonate aqueous solution at 30 ° C for 10 seconds, wash it with water to remove the uncured portion, and dry it. 21√ (2) Number of steps for complete curing of step tablet (Step) was examined and shown in Tables 1 and 2. A comparative example is shown in Table 3. Clearly from Tables 1 to 3, Examples 1 to 8 of the present invention are compared with Comparative Examples 1 to 4.
It can be seen that it has high sensitivity to 490 nm light.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

The chemical formulas 16 to 25 of the components shown in the tables of the examples are shown below.

[Chemical 16]

[0036]

[Chemical 17]

[0037]

[Chemical 18]

[0038]

[Chemical 19]

[0039]

[Chemical 20]

[0040]

[Chemical 21]

[0041]

[Chemical formula 22]

[0042]

[Chemical formula 23]

[0043]

[Chemical formula 24]

[0044]

[Chemical 25]

[0045]

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 7/027 502 7/031 H01L 21/027

Claims (1)

[Claims] 1. An (a) at least one non-gaseous ethylenically unsaturated compound at room temperature (b) an iron allene complex represented by the following general formula (Formula 1) (c) the following general formula (Formula 2) or ( A photopolymerizable composition comprising at least a coumarin compound represented by Chemical formula 4). [Chemical 1] (Wherein R ^1, R ² are the same or different groups, C ₁ ~
Alkyl C _12, alkynyl group C ₂ ~C _12, C ₁ ~C
₈ alkoxy groups, cyano groups, alkylthio groups, phenoxy groups, C _{2 to} C ₆ monocarboxylic acid and ester groups,
C _{2 to} C ₅ alkanoyl group, ammonium salt, pyridinium group, nitro group, alkylsulfinyl group, alkylsulfonyl group, sulfamoyl group selected from halogen atoms, and R ² forms a condensed polycyclic compound with a benzene ring. You may have. X is BF ₄ , PF _6, As
F ₆ , SbF ₆ , FeCl ₄ , SnCl ₆ , SbCl ₆ , B
iCl ₆ is shown. ) [Chemical 2] (In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R
^{11, R 12, R 13,} R 14 R 1 5 is hydrogen, an alkyl group, an alkoxy group, an aryl group, a cyano group, a carboxyl group, an alkyloxycarbonyl group, Z ¹ is an aryl group, a heterocyclic group, Or chemical formula 3 is shown. R ^{16 in} Formula 3 represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or a heterocyclic group. ) [Chemical 3] [Chemical 4] (In the formula, R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ^23
24 and R ²⁵ are hydrogen, an alkyl group, an alkoxy group, an aryl group, a cyano group, a carboxyl group and an alkyloxycarbonyl group, and Z ² is an aryl group, a heterocyclic group, or the general formula 5. R ^{26 in} Chemical formula 5 represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or a heterocyclic group. ) [Chemical 5]