JPH0980750A - Photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure high photosetting property to visible light of a long wavelength by combining a titanocemne compd. with a compd. having a specified structure. SOLUTION: This compsn. contains an ethylenically unsatd. compd. which is not gaseous at ordinary temp., a titanocene compd., p-aminophenyl unsatd. diketone represented by formula I and a glycine deriv. represented by formula II. In the formula I, (a) is a natural number of 0-2 and each of R<1> -R<10> may be H or may be replaced by other group. In the formula II, each of R<11> -R<15> is H, optionally substd. acyl or halogen substd. alkyl but R<11> -R<15> are not simultaneously H. Since this compsn. has high photosetting property to visible light, especially light of >=500nm, a light source for exposure is selected from among more various light sources. Many original plates can be exposed in a time allowed because of high sensitivity.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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, an FD-YAG laser, and a helium-neon 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.

As a photoinitiator having high sensitivity, JP-A-54-155292 discloses a system containing hexaarylbisimidazole, and JP-A-58-15503 discloses an active halogen compound and a 3-keto-substituted coumarin. A system of compounds, a system of 3-keto-substituted coumarin and N-phenylglycine in JP-A-56-4604, JP-A-61-97.
Japanese Patent No. 650 discloses a photoinitiator system comprising a combination of a 3-substituted coumarin and a quinazolinone derivative, and Japanese Patent Application Laid-Open No. 61-123603 discloses a combination of a hexaarylbisimidazole and a 3-keto substituted coumarin. However, the photoinitiator system described above is not sufficiently sensitive. As a photopolymerizable composition having a high sensitivity to an oscillating light having a wavelength of 488 nm of an argon ion laser, there is one disclosed in JP-A-4-184344. The initiator system used here is a combination of an iron arene complex, a titanocene compound and a dye of a specific structure, but this composition has a wavelength of 50
Photosensitivity to light of 0 nm or more is insufficient.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a photopolymerizable composition having high photosensitivity to visible light, particularly not only oscillating light having a wavelength of 488 nm of an argon ion laser but also oscillating light having a wavelength of 515 nm of an argon ion laser. And FD
-To provide a photopolymerizable composition having high photosensitivity to oscillation light having a wavelength of 532 nm of a YAG laser.

[0005]

DISCLOSURE OF THE INVENTION In the present invention, as a result of earnestly researching and striving for a photoinitiator system for the purpose of solving the above problems, a combination of a titanocene compound and a compound having a specific structure has a long wavelength. Invented to give high curability to visible light. That is, the present invention is at least (a) at least one non-gaseous ethylenically unsaturated compound at room temperature (b) titanocene compound (c) p-aminophenyl unsaturated diketone represented by the following general formula 3 (d) It is a photopolymerizable composition containing the glycine derivative shown by Formula 4.

[0006]

Embedded image (In the chemical formula 3, a is a natural number of 0 to 2, and R ¹ , R ² , R ³ , R
⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ may be hydrogen atoms or may be substituted with other groups. )

[0007]

Embedded image (Wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are each independently a hydrogen atom, a substituted or unsubstituted acyl group, or a halogen-substituted alkyl group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ ,
R ¹⁵ is not a hydrogen atom at the same time. ) 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 thereof include propane triacrylate and trimethylolpropane trimethacrylate.

The titanocene compound as the second component (b) is preferably a compound represented by the following general formula 5.

[0009]

Embedded image (In Chemical Formula 5, R ¹⁶ and R ¹⁷ are each a substituted or unsubstituted cyclopentadienyl group. R ¹⁸ and R ¹⁹ are each a substituted or unsubstituted phenyl group, and are particularly substituted with a halogen atom. Specific examples of preferred second component (b) are shown below.

[0010]

[Chemical 6]

[0011]

[Chemical 7]

[0012]

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[0013]

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[0014]

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The third component (c), the p-aminophenyl derivative
The saturated diketone is represented by the general formula 1 (formula 3). General
In Formula 1, a is a natural number of 0 to 2 and R¹, R²,
R^Three, R^Four, R^Five, R⁶, R⁷, R⁸, R⁹, R^TenHaso
Each may be a hydrogen atom or may be substituted with another group.
Yes. Preferably, each independently a hydrogen atom, C₁~ C ₁₂
Alkyl group of C₂~ C₁₂Alkenyl group of C₂~ C₁₂
An alkynyl group of C₁~ C₈Alkoxy group of C₂~ C
₁₂An alkyloxyalkylene group of C₁~ C₈The archi
Luthio group, C₆~ C_TenAryloxy group, C₆~ C₂₀
Substituted and unsubstituted aryl groups, carboxyl groups, and
Roxy group, cyano group, halogen atom, amino group, C₁~
C₁₂Monoalkylamino group, C₂~ C_{twenty four}Dialkyl
Amino group, C₁~ C₁₂Cyanoalkyl group, C₁~ C₁₂
An alkoxycarbonyl group of C₂~ C_{twenty four}Alkoxyka
Rubonylalkyl group, C₁~ C₁₂Hydroxycarboni
Rualkyl group, C₁~ C₁₂Acyloxy group or C₂
~ C_{twenty four}Is an acyloxycarbonyl group. Also, R⁶
Is R⁹With R⁸Is R^TenWith C₂~ C_FiveAl
A xylene group may be formed. Compound represented by general formula 1
Specific examples include those having the following structures.

[0016]

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[0017]

[Chemical 12]

[0018]

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[0019]

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[0020]

[Chemical 15]

When an iron allene complex is present in the composition of the present invention, the curability may be deteriorated, so addition of the iron allene complex is not preferred. The glycine derivative of the fourth component (d) is represented by the general formula 2 (formula 4). In the general formula 2, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are each independently a hydrogen atom, a substituted or unsubstituted acyl group, or a halogen-substituted alkyl group, and R ¹¹ , R ¹² , and R ¹³ , R ¹⁴ , R ¹⁵
Are not simultaneously hydrogen atoms. Specific examples of the compound represented by the general formula 2 include N- (p-acetylphenyl) glycine, N- (m-trifluoromethylphenyl) glycine, N- (m-acetylphenyl) glycine and N-.
(P-trifluoromethylphenyl) glycine and the like can be mentioned.

A cyclic diketone compound represented by the following general formula 16 may be present in the composition of the present invention.

Embedded image (In the formula, R ²⁰ 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 general formula 16 is an unstable hydrogen atom. Is a cyclic β-dicarbonyl compound having an active methylene group. Wherein R ²⁰ 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 carbon or a heteroatom or Both of them may have a substituent. In the above, the alkyl group is C ₁ -C ₁₂ alkyl,
As the substituted alkyl, for example, hydroxylalkyl, cyanoalkyl, haloalkyl, alkoxyalkylene,
Examples thereof include alkylene thioether and aryloxy alkylene. The aryl part of the aralkyl group is 6-1
It may contain 0 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 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.

A thermoplastic high molecular weight organic polymer binder may preferably be present in the composition of the present invention. Polymeric binder types include (i) terephthalic acid, isophthalic acid, sebacic acid, adipic acid and hexahydroterephthalic acid based copolyesters, (ii) polyamides, (ii)
i) vinylidene chloride copolymer, (iv) ethylene / vinyl acetate copolymer, (v) cellulose ether,
(Vi) polyethylene, (vii) synthetic rubber, (viii) cellulose ester, (ix) polyvinyl ester including polyvinyl acetate / acrylate and polyvinyl acetate / methacrylate copolymer, (x) polyacrylate and poly α-alkyl acrylate ester, for example Polymethyl acrylate and polyethyl methacrylate, (xi) copolymer of (meth) acrylic acid and (meth) acrylic ester, (xii) high molecular weight ethylene oxide polymer having a weight average molecular weight of 4,000 to 4,000,000 (polyethylene glycol), (xiii) polyvinyl chloride and copolymers thereof, (xiv) polyvinyl acetal, (xv) polyformaldehyde, (xvi) polyurethane, (xvii) polycarbonate and (xviii) polystyrene.

In the compositions of the present invention, a particularly preferred photopolymerizable binder is one in which the unexposed photopolymerizable coating is soluble in predominantly aqueous solutions, for example alkaline solutions, but after exposure to actinic radiation a comparison is made. Polymer binders that are physically insoluble therein are preferred. Polymers that typically meet these requirements are carboxylated polymers,
For example, there are methacrylic acid copolymers, acrylic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, which are vinyl addition polymers containing free carboxylic acid groups. Further, there are cellulose having a carboxyl group in a side chain, and a product in which a cyclic acid anhydride is added to a polymer having a hydroxyl group in a side chain.

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. 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 which is the component (a), the titanocene compound which is the component (b) is 0.01 to 50 parts by weight. Part, particularly preferably 0.1 to 30 parts by weight, 0.01 to 20 parts by weight, particularly preferably 0.1 to 20 parts by weight, of the component (c), p-aminophenyl unsaturated diketone, and the glycine derivative as the component (d), 0.01 to 20 parts by weight, particularly preferably 0.1 to 20 parts by weight, 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. Parts by weight. The amount of the thermal polymerization inhibitor added was 0.
01-5% is preferable.

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, cellulose paper, fiberboard, 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, when a printed circuit is manufactured,
The material can be a plate coated with copper on 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 excellent oxygen barrier properties, such as polyvinyl alcohol, is provided in order to prevent a polymerization suppression effect due to 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 lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, argon ion lasers, FD-YAG lasers, helium-neon lasers, helium-cadmium lasers, etc. Laser,
A fluorescent lamp, a tungsten lamp, sunlight, etc. can be used.

[0029]

EXAMPLES The present invention will be described in more detail with reference to the following examples, in which parts and percentages are by weight. 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 drier to obtain a coating film having a thickness of 2 μm. Then, an aqueous solution of 7% polyvinyl alcohol (completely saponified, degree of polymerization 500) was applied on it, and heated at 90 ° C with a hot air dryer.
After drying for 1 minute, an overcoat layer having a thickness of 1 μm was provided to obtain a sensitivity test piece. A gray film scale was placed on this sensitivity test piece, and an Argon ion laser 51
Scanning exposure was performed with light of 5 nm. After that, it was immersed in a 0.7% sodium carbonate aqueous solution at 30 ° C. for 10 seconds, washed with water to remove the uncured portion, and dried, and then the number of stages (steps) of complete curing was examined. (Composition of photosensitive layer coating liquid) (Example 1) Poly (methyl methacrylate / methacrylic acid) 52 parts 70/30 molar ratio Tetraethylene glycol dimethacrylate 40 parts

[0030]

Embedded image 5 copies

[0031]

Embedded image 3 parts N- (p-acetylphenyl) glycine 3 parts Methanol 200 parts Ethyl acetate 80 parts Chloroform 120 parts (Example 2) Poly (methyl methacrylate / methacrylic acid) 52 parts 70/30 molar ratio Tetraethylene glycol dimethacrylate 40 Department

[0032]

Embedded image 5 copies

[0033]

Embedded image 3 parts N- (p-acetylphenyl) glycine 3 parts Methanol 200 parts Ethyl acetate 80 parts Chloroform 120 parts (Example 3) Poly (methyl methacrylate / methacrylic acid) 52 parts 70/30 molar ratio Tetraethylene glycol dimethacrylate 40 Department

[0034]

[Chemical 21] 5 copies

[0035]

Embedded image 3 parts N- (p-acetylphenyl) glycine 3 parts Methanol 200 parts Ethyl acetate 80 parts Chloroform 120 parts (Example 4) Poly (methyl methacrylate / methacrylic acid) 52 parts 70/30 molar ratio Tetraethylene glycol dimethacrylate 40 Department

[0036]

Embedded image 5 copies

[0037]

Embedded image 3 parts N- (p-acetylphenyl) glycine 3 parts Methanol 200 parts Ethyl acetate 80 parts Chloroform 120 parts (Example 5) Poly (methyl methacrylate / methacrylic acid) 52 parts 70/30 molar ratio Tetraethylene glycol dimethacrylate 40 Department

[0038]

Embedded image 5 copies

[0039]

[Chemical formula 26] 3 parts N- (p-acetylphenyl) glycine 3 parts Methanol 200 parts Ethyl acetate 80 parts Chloroform 120 parts The measurement results are shown in Table 1.

[0040]

[Table 1] As a comparative example, a photosensitive layer coating solution having the following composition was prepared, and the same experiment as that of the example was conducted. (Composition of photosensitive layer coating liquid) (Comparative Example 1) Poly (methyl methacrylate / methacrylic acid) 52 parts 70/30 molar ratio Tetraethylene glycol dimethacrylate 40 parts

[0041]

Embedded image 5 copies

[0042]

Embedded image 3 parts Methanol 200 parts Ethyl acetate 80 parts Chloroform 120 parts (Comparative Example 2) Poly (methyl methacrylate / methacrylic acid) 52 parts 70/30 molar ratio Tetraethylene glycol dimethacrylate 40 parts

[0043]

[Chemical 29] 3 parts N- (p-acetylphenyl) glycine 3 parts Methanol 200 parts Ethyl acetate 80 parts Chloroform 120 parts (Comparative Example 3) Poly (methyl methacrylate / methacrylic acid) 52 parts 70/30 molar ratio Tetraethylene glycol dimethacrylate 40 Department

[0044]

Embedded image 3 parts N- (p-acetylphenyl) glycine 3 parts Methanol 200 parts Ethyl acetate 80 parts Chloroform 120 parts (Comparative Example 4) Poly (methyl methacrylate / methacrylic acid) 52 parts 70/30 molar ratio Tetraethylene glycol dimethacrylate 40 Department

[0045]

[Chemical 31] 5 copies

[0046]

Embedded image 3 parts N- (p-acetylphenyl) glycine 3 parts Methanol 200 parts Ethyl acetate 80 parts Chloroform 120 parts The measurement results are shown in Table 2.

[0047]

[Table 2] As is clear from Table 1 and Table 2, Examples 1 to 5 of the present invention
It can be seen that is more sensitive to light of 515 nm than Comparative Examples 1 to 4.

[0048]

The photopolymerizable composition of the present invention has a high photocurability against visible light, particularly light having a wavelength of 500 nm or more.
The range of choice of exposure light source is expanded. Also, because of its high sensitivity,
Multiple masters can be exposed within a given time. Further, since the exposure source can be moved away from the original plate, its light rays are collimated, and when forming a halftone dot image, various advantages such as forming a sharp halftone dot having a vertical side portion are obtained. Have.

Claims (1)

[Claims] 1. At least: (a) at least one kind of non-gaseous ethylenic ethylene at room temperature
Saturated compound (b) Titanocene compound (c) p-aminophenyl compound represented by the following general formula 1
Saturated diketone (d) A photopolymerizable composition containing a glycine derivative represented by the following general formula 2. [Chemical 1]In chemical formula 1, a is a natural number from 0 to 2 and R¹, R², R^Three,
R^Four, R^Five, R⁶, R⁷, R ⁸, R⁹, R^TenIs a hydrogen atom
However, it may be substituted with another group. )R in chemical formula 2¹¹, R¹², R¹³, R¹⁴, R^FifteenAre independently
Hydrogen atom, substituted or unsubstituted acyl group, or halogen
R-substituted alkyl group, R¹¹, R¹², R¹³, R¹⁴, R
^FifteenAre not hydrogen atoms at the same time. )