JPH0743896A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To enhance sensitivity to the visible light and to make possible exposure and development of a large number of printing plate materials in a given time by using a low energy exposure light source by incorporating a specified compound as a sensitizer. CONSTITUTION:The photopolymerizable composition comprising at least one kind of ethylenically unsaturated compound nongaseous at normal temperature, a photoinitiator, and the sensitizer represented by the formula in which each of R<1>-R<3> and R<6> and R<7> is H, alkyl, alkoxyalkyl, hydroxyalkyl, halogenoalkyl, alkoxy, alkoxyalkoxy, or the like; each of R<4> and R<5> is H or alkyl, and each may combine with R<2> and R<1> and R<6>; n is 0 or 1; each of R<9>-R<11> is alkyl: X is O, S, or NR<12>; R<12> is H or alkyl; and Y is H, alkylcarbonyl, alkoxycarbonyl, aryl, or the like.

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 provides a photopolymerizable composition containing at least one non-gaseous ethylenically unsaturated compound at room temperature, a photoinitiator and a sensitizer, as a sensitizer, the following general formula (I) A photopolymerizable composition comprising a novel compound represented by Chemical formula 2.

[0005]

[Chemical 2] (In the formula, R ¹ , R ² , R ³ , R ⁶ and R ⁷ are a hydrogen atom, an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, a halogenoalkyl group, an alkoxy group, an alkoxyalkoxy group, an alkylcarbonyl group, a carboxyl group, An alkoxycarbonyl group, a cyano group, or a halogen atom, which may be bonded to each other to form a ring, and R ⁴ and R ^{5 each} represent a hydrogen atom or an alkyl group, which may be bonded to R ² and R ^16. .n is 0 or ^{1, .X R 9, R 10} , R 11 is showing an alkyl group ^{O, S, NR 12 (R} 1 2 is hydrogen atom or an alkyl group) and, Y is a hydrogen atom, Alkylcarbonyl group, alkoxycarbonyl group, aryl group, arylcarbonyl group, aryloxycarbonyl group, alkoxycarbonylalkylcarbonyl group, alkoxycarbonylalkoxy It represents a heterocyclic group such as a carbonyl group, a cyano group, an unsubstituted or substituted benzimidazole group, a benzothiazole group, and a benzoxazole group.)

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 photoinitiator used in the present invention is not particularly limited, but α-carbonyl compounds, acyloin ethers, aromatic acyloin compounds,
Polynuclear quinone, hexaarylbisimidazole, trihalomethyl-S-triazine, acridine, phenazine,
Also included are onium salts such as triphenylsulfonium salts and diaryliodonium salts, titanocene, iron allene complexes, peroxides and the like. The amount used is preferably 0.2 to 20% by weight of the total composition of the photopolymerizable layer, more preferably 1 to 10%.
It is in the range of% by weight. The sensitizer used in the present invention is represented by the above general formula (I), and it is considered that it absorbs actinic rays and acts as an electron donor to the photoinitiator, and becomes a cation radical after electron transfer. . However, it is speculated that the cation radical of this compound is unstable and decomposes, liberating carbon dioxide and silyl cations and converting itself into radicals, which improves the efficiency of radical generation and increases the sensitivity of the photopolymerizable composition. Is expected to increase. Specific examples of preferable sensitizers are shown below.

[0007]

[Chemical 3] (D-1 in Example)

[0008]

[Chemical 4] (D-2 in Example)

[0009]

[Chemical 5] (D-3 in Examples)

[0010]

[Chemical 6] (D-4 in Examples)

[0011]

[Chemical 7] (D-5 in Examples)

[0012]

[Chemical 8] (D-6 in Examples)

[0013]

[Chemical 9] (D-7 in Examples)

[0014]

[Chemical 10] (D-8 in Examples)

[0015]

[Chemical 11] (D-9 in Examples)

[0016]

[Chemical 12] (D-10 in Examples) The sensitizer of the present invention is a novel compound, for example,
It can be produced by the reaction route shown in.

[0017]

[Chemical 13] N-substituted aminosuccinaldehyde (II) as a raw material and a cyanomethyl-substituted product are reacted in a polar solvent such as dimethylformamide in the presence of a base such as piperidine, and this is refluxed with dilute hydrochloric acid to give compound (IV). Is obtained. A thermoplastic high molecular weight organic polymer binder may preferably be present in the composition of the present invention. Polymer binder types include (i) terephthalic acid, isophthalic acid,
Copolyesters based on sebacic acid, adipic acid and hexahydroterephthalic acid, (ii) polyamides, (iii) vinylidene chloride copolymers, (iv) ethylene / vinyl acetate copolymers, (v) cellulose ethers, (vi)
Polyethylene, (vii) synthetic rubber, (viii) cellulose esters, (ix) polyvinyl esters including polyvinyl acetate / acrylate and polyvinyl acetate / methacrylate copolymers, (x) polyacrylates and poly α-alkyl acrylate esters such as polymethyl acrylate And polyethylmethacrylate, (x
i) high molecular weight ethylene oxide polymer (polyethylene glycol) having a weight average molecular weight of 4,000 to 4,000,000, (xii) polyvinyl chloride and its copolymer, (xii
i) polyvinyl acetal, (xiv) polyformaldehyde, (xv) polyurethane, (xvi) polycarbonate and
(xvii) polystyrene may 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, for example 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. Binder is 0
-80% by weight, preferably 30-70% by weight.

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% by weight based on the total 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.

In the present invention, the thickness of the photopolymerizable composition is
It is 0.01 to 250 μm, preferably 0 to 50 μm.
The desired thickness is determined by the application. The supports used in the present invention include all natural or synthetic supports, preferably those which may be present in the form of flexible or rigid films or sheets. For example, the material is a metal sheet or foil,
Synthetic organic resin sheet or film, cellulose paper,
It may be fiberboard or the like or a composite of two or more of these materials. Specific materials include alimina plast aluminum, anodized aluminum, alumin plast 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 film and the like can be mentioned. 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.

[0021]

EXAMPLES The present invention will be described in more detail with reference to the following examples, in which parts and% are based on weight. Example 1 A brush-polished aluminum plate having a thickness of 0.24 mm was immersed in 5% sodium hydroxide at 30 ° C. for 1 minute, washed with water, then neutralized with nitric acid and washed with water. The current density is 3A / d in 10% sulfuric acid.
It was anodized to a thickness of 3 g / m ² in m ^2. After that, the aluminum substrate was obtained by immersing in 70 ° C. 2% No. 3 water glass for 1 minute, washing with water and drying.

Next, a photosensitive layer coating liquid having the following composition was applied and dried at 100 ° C. for 1 minute with a hot air dryer to obtain a coating film having a thickness of 2.0 g / m ² . (Composition of photosensitive layer coating liquid) Poly (methyl methacrylate / methacrylic acid) 52 parts 85/15 molar ratio Molecular weight 80,000 Tetraethylene glycol diacrylate 40 parts 2,2 '-(O-chlorophenyl) -4,4', 5,5'-Tetraphenylbisimidazole 5 parts Sensitizer (shown in Table 1) 3 parts Methanol 200 parts Ethyl acetate 80 parts Chloroform 120 parts Next, apply a protective layer coating solution having the following composition and apply to a hot air dryer. hand
After drying at 100 ° C. for 1 minute, a protective layer having a thickness of 1 g / m ² was provided to obtain a test piece. (Protective layer coating liquid composition) Polyvinyl alcohol 100 parts (Complete saponification, degree of polymerization 500) Nonionic surfactant 1 part (Neugen EA150 Daiichi Kogyo Seiyaku Co., Ltd.) Water 900 parts 21 √ (2 as a negative film on the above test piece ) Stack step tablets (Dainippon Screen gray film scale) on top of each other, and then use a xenon lamp (UXL-UXL-
15) with a light source (490 nm) that combines a Toshiba interference filter KL-49 and a glass filter Y-45 of the same color with 500 D-0).
After exposing for 2 minutes from the distance of cm, the solution for negative PS plate (Fuji Photo Film DN-3C) was diluted with 1: 1 diluted solution at 30 ° C for 20 minutes.
Immerse for 2 seconds, wash with water to remove uncured part and dry,
21√ (2) The step number of complete curing of the step tablet was investigated, and it is shown in Table 1. As is clear from Table 1, the samples (1 to 7) according to the present invention have 490n in comparison with the samples (8 to 10) containing the conventionally known sensitizer.
It can be seen that it has high sensitivity to m light.

[0023]

[Table 1] The photosensitive layer coating liquid having the following composition was applied onto the aluminum substrate described in Example 1 and dried with hot air to obtain a coating film having a thickness of 1.8 g / m ² . (Photosensitive layer coating liquid composition) Poly (methyl methacrylate / methacrylic acid / n-hexyl methacrylate) 50 parts Molar ratio 65/15/20 40 parts tetraethylene glycol dimethacrylate (η ⁵ -cyclopetadienyl) ( η ⁶ -Toluene) iron (II) oxafluorophosphate 5 parts Sensitizer (shown in Table 2) 3 parts Methyl ethyl ketone 150 parts Dimethylformamide 150 parts Next, the same protective layer coating solution as in Example 1 is applied and dried with hot air. It was dried at 100 ° C. for 1 minute with a machine, and a protective layer having a thickness of 1.2 g / m ² was provided to obtain a test piece. The above test piece was exposed and developed in the same manner as in Example 1 to check the number of steps for complete curing. The results are shown in Table 2. As with Example 1, it can be seen that the sample according to the present invention has high sensitivity.

[0024]

[Table 2]

[0025]

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. .

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Claims (1)

[Claims] 1. A photopolymerizable composition comprising at least one non-gaseous ethylenically unsaturated compound at room temperature, a photoinitiator and a sensitizer, wherein the sensitizer is represented by the following general formula (I): A photopolymerizable composition comprising a novel compound represented by Chemical formula 1. [Chemical 1] (In the formula, R ¹ , R ² , R ³ , R ⁶ and R ⁷ are a hydrogen atom, an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, a halogenoalkyl group, an alkoxy group, an alkoxyalkoxy group, an alkylcarbonyl group, a carboxyl group, An alkoxycarbonyl group, a cyano group, or a halogen atom, which may be bonded to each other to form a ring, and R ⁴ and R ^{5 each} represent a hydrogen atom or an alkyl group, which may be bonded to R ² and R ^16. .n is 0 or ^{1, .X R 9, R 10} , R 11 is showing an alkyl group ^{O, S, NR 12 (R} 1 2 is hydrogen atom or an alkyl group) and, Y is a hydrogen atom, Alkylcarbonyl group, alkoxycarbonyl group, aryl group, arylcarbonyl group, aryloxycarbonyl group, alkoxycarbonylalkylcarbonyl group, alkoxycarbonylalkoxy It represents a heterocyclic group such as a carbonyl group, a cyano group, an unsubstituted or substituted benzimidazole group, a benzothiazole group, and a benzoxazole group.)