JPH0925425A - Sensitizing coloring matter for photopolymer comprising benzopyran ring condensed compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject coloring matter, comprising a benzopyran ring condensed compound represented by a specific formula, having a spectral sensitivity over a wide wavelength region of about 430-650nm and useful as the second- harmonic wave of a yttrium aluminum garnet (YAG) laser. SOLUTION: This sensitizing coloring matter for a photopolymer comprises a benzopyran ring condensed compound represented by formula I [R1 and R2 are each an alkyl (which may have a side chain or a substituent group); either or both of R1 and R2 may be bonded to the benzene ring to which nitrogen atom is bonded to form a 5- or a 6-membered ring; R3 is a halogen, cyano, carboxy or an ester group of a carboxylic acid; R4 is same as R1 ; R5 and R6 are each H, an alkyl, an alkoxy, cyano, trifluoromethyl, sulfoxy or a halogen; X is a monovalent acid residue; Y is NH or 0; (n) is 0 or 1]. Furthermore, the compound is preferably obtained by reacting, e.g. a salicylaldehyde derivative of formula II with a benzimidazole derivative of formula III, thereby synthesizing an iminocoumarine derivative of formula IV and then reacting the synthesized iminocoumarine derivative of formula IV with malonitrile.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sensitizing dye for photopolymer comprising a benzopyran ring condensed compound.

[0002]

2. Description of the Related Art Photopolymer compositions are materials that exhibit changes in physical properties in light-irradiated and non-irradiated areas when they are exposed to light energy. They include printing, microfabrication of VLSI, printed circuit formation, UV-curable paints, inks, holograms. It has been put to practical use in a wide range of fields such as recording, and its use is expanding more and more.
This composition is basically composed of a photopolymerization initiator, a photopolymerizable compound and a binder resin, usually has a spectral sensitivity in an ultraviolet region, and is suitable for a g-line of a mercury lamp, an i-line or a high-power argon laser. Images are recorded using an ultraviolet oscillation line or the like. In recent years, the development of a technique for recording an image using visible laser light instead of ultraviolet light has been actively pursued, and the use of a sensitizing dye is an indispensable technical element in order to impart spectral sensitivity to the recording light. Has become. The characteristics of the sensitizing dye include (1) excellent solubility in a solvent, (2) large absorption coefficient at the wavelength of recording light, and (3) good sensitivity of the photosensitive wavelength to the wavelength of recording light. It is required that they agree with each other, (4) high sensitivity, (5) good storage stability, and (6) good compatibility with other components. The photopolymer composition basically comprises a binder polymer, a monofunctional to polyfunctional monomer, a polymerization initiator and a sensitizing dye. There are a great many kinds of each component other than the pigment, and the product composition is prepared in various combinations according to the use and the product grade and used. Therefore, in order to prepare a composition having the desired characteristics, the method of fixing other components and selectively using a dye suitable for this in accordance with recording light is the actual situation. A versatile dye having various properties capable of responding to a composition composed of such various kinds of combinations has not been found so far, and various kinds of useful sensitizing dyes are needed, and development thereof is desired. Has been done. To date, many types of sensitizing dyes for photopolymers have been proposed. For example, JP-A-54-151024 discloses a merocyanine dye, JP-A-58-29803 describes a cyanine dye, JP-A-59-56403 describes a stilbene derivative,
-23901: Coumarin compound, 64-33104
Describes a methylene blue derivative. In fact, it is difficult to find a dye having all the above-mentioned required characteristics among these known dyes.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention In the technical field of image recording by a visible laser using a photopolymerizable composition, various characteristics excellent in practical use are required due to the need for high speed scanning exposure recording and low power laser recording. A sensitizing dye provided is required. However, the molecular structure of sensitizing dyes, their interactions with each component, and the properties based on them have not been clarified at present, and the search for dyes is often difficult due to trial and error based on experience. However, it is not easy. Among coumarin compounds, 400-500 such as helium-cadmium and argon ion laser
Many useful sensitizing dyes exhibit high sensitivity to recording light having an oscillation line at nm. However, 500
It is hard to say that it exhibits sufficient sensitivity to recording light having an oscillation line in a long wavelength region of nm or more. Therefore, 500 nm
A sensitizing dye having high sensitivity in the above long wavelength region has been demanded. As a result of diligent studies, the present inventor has found that some dyes derived from the 3-benzimidazolyl-2-iminocoumarin compound exhibit useful properties.

[0004]

SUMMARY OF THE INVENTION The present invention provides a sensitizing dye for photopolymers comprising a benzopyran ring condensed compound represented by the following general formula (1).

Embedded image In the formula, R ₁ and R ₂ each independently represent an alkyl group, which may have a side chain or a substituent. Typical examples thereof are ethyl group, propyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, 1-methylpropyl group, 2-butoxyethyl group. , 2- (2-ethoxy)
Ethoxyethyl group, 6-bromohexyl group, 2-carboxyethyl group, 3-sulfoxypropyl group, 4-sulfoxybutyl group, 2-hydroxyethyl group, phenylmethyl group, 4-butoxyphenylmethyl group, 4-butyl There is a phenylmethyl group. Further, one or both of R ₁ and R ₂ may be bonded to a benzene ring to which a nitrogen atom is bonded to form a 5-membered or 6-membered ring. R ₃ is a halogen such as fluorine, chlorine, bromine, or iodine, a cyano group, a carboxy group, or a carboxylic acid such as an ethylcarboxy group, a butylcarboxy group, an octylcarboxy group, a 4-butylphenylcarboxy group, or a 4-hexylcyclohexylcarboxy group. Represents an ester group. R ₄ represents an alkyl group having the same meaning as R _1, and R ₅ represents R ₆ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen, a cyano group, a trifluoromethyl group or a sulfoxy group. X is CH ₃ SO ₄ , C ₂ H ₅ SO ₄ , Br, I, B
It represents a monovalent acid residue such as F ₄ or PF ₆ , and Y represents NH or 0. n represents an integer of 0 or 1, and when n is 0, neither R ₄ nor X exists.

As the photopolymerization initiator used in combination with the sensitizing dye of the present invention, various organic peroxides, triazine compounds represented by 2,4,6-trichloromethyl-s-triazine, benzoin alkyl ethers, and bisimidazoles. ,
Examples thereof include iron-allene complex, N-phenylglycine, diphenyliodonium salt and the like. Further, a multi-component initiator obtained by combining these several types may be used. Examples of organic peroxides include di-
t-butyldiperoxyisophthalate, 3,3'4,
4'-tetrakis (t-butyldioxycarbonyl) benzophenone, 2 as dialkyl peroxide,
5-dimethyl-2,5-bis (t-butyldioxy)-
2,3-Bis (hydroperoxy) -2,5-dimethylhexane, t-butylhydroperoxide as butyl-, and butyl-as peroxyacetal.
4,4-bis (t-butyldioxy) valerate, 1,
1-Bis (t-butyldioxy) -3,3,5-trimethylcyclohexane, and ketone peroxide include ethyl methyl ketone peroxide.

The photopolymerizable compound is composed of a photopolymerizable or photocrosslinkable monomer, oligomer, prepolymer or a mixture thereof having at least one ethylenically unsaturated double bond in one molecule. Examples of such compounds include ethyl acrylate, hydroxyethyl acrylate, ethylene glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, polyester methacrylate, polyurethane methacrylate, epoxy methacrylate, and the like. And the compounds used for the above.

Examples of the binder resin include poly-N-vinylpyrrolidone, polyvinyl acetate, polyvinyl butyral, polyvinyl carbazole, polystyrene, polymethyl methacrylate, polyethylene oxide,
Resins usually used in this technical field such as polybutylmethacrylate, styrene-maleic acid ester, polymethylmethacrylate-methacrylic acid-based resin, and poly-N-vinylpyrrolidone-glycidylmethacrylate-based resin can be mentioned.

The sensitizing dye according to the present invention is used at a ratio of 0.1 to 10 times the photopolymerization initiator, and a binder resin is added at a ratio of 0 to several hundred times with respect to the mixture thereof, and A polymerizable composition is prepared. If necessary, additives such as a thermal polymerization inhibitor and a plasticizer may be added to the composition.

Next, the present invention will be described in more detail with reference to examples. Specific examples of the sensitizing dye of the present invention include the following dyes.

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[Chemical 6]

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The dye according to the present invention is disclosed in German Patent Publication No. 225.
It can be manufactured based on the method described in Japanese Patent No. 3538. That is,

Embedded image And a salicylaldehyde derivative represented by

Embedded image By the reaction with the benzimidazole derivative represented by

Embedded image The target compound can be synthesized by synthesizing an iminocoumarin derivative represented by and reacting it with malonnitonyl. The R ₃ group can be derived by halogenating the iminocoumarin derivative represented by Chemical formula 19 by a conventional method, cyano-substituting the halogen, and further performing hydrolysis and esterification. By introducing this R ₃ group and then reacting it with malonnitrile, the target compound having the R ₃ group introduced can be synthesized. The target compound having R ₄ and X introduced thereinto can be synthesized by reacting the target compound thus obtained with a quaternizing agent represented by R ₄ X by a conventional method. At this time, when R ₄ X is propane sultone or butane sultone, it becomes an inner salt and X does not exist. The target compound in which Y is 0 can be obtained by hydrolyzing the target compound in the imino form with a mineral acid.

Next, the spectral sensitivity measurement will be described. Photosensitive solution formulation: Binder resin (XL-44) 100 parts Polyfunctional monomer (PETA) 100 parts Organic peroxide (BTTB) 8 parts Sensitizing dye 6 parts Ethyl cellosolve 900 parts Grain-finished aluminum plate surface-treated with the above photosensitive solution Was spin coated to form a photosensitive layer. An overcoat layer of polyvinyl alcohol was provided to avoid polymerization inhibition by oxygen. A 500 W xenon lamp was used as a light source for measuring the spectral sensitivity, and the photosensitive layer was exposed for 20 minutes. Thereafter, development was performed using an alkaline developer. The result is shown in FIG. The abbreviations have the following meanings. XL-44: Acrylic acid-methacrylic acid ester copolymer PETA: Pentaerythritol triacrylate BTTB: 3,3 ', 4,4'-Tetra (t-butylperoxycarbonyl) benzophenone

The λmax of the sensitizing dye of the present invention is in the range of about 540 to 600 nm in methanol, and the spectral sensitivity is in the wide range of about 430 to 650 nm. These dyes are sensitizing dyes with a new structure that have sensitivity in the long wavelength region, which is not sensitive to coumarin dyes.

In FIG. 1, dye 1 is about 435-602.
It can be seen that in the wavelength range of nm, the dye 13 has a spectral sensitivity in the wavelength range of about 467 to 605 nm. The other dyes of the present invention also have sensitivity up to around 430 nm on the short wavelength side and up to around 650 nm on the long wavelength side, depending on the shift of λmax and absorption band. The λmax of Dye 1 is 549 nm in methanol, that of the coumarin dye having the corresponding structure (Comparative Dye 1) is 459 nm, and the λmax of Dye 1 is 90 nm shifted by the long wavelength, and the long wavelength end of the spectral sensitivity. Is also shifted to the long wavelength side by about 80 nm. The other dyes of the present invention show almost the same relationship as the corresponding coumarin-based dyes.

[0014]

The present invention provides sensitizing dyes for photopolymers having spectral sensitivity over a wide wavelength range of about 430 to 650 nm, and these dyes are the second harmonic of YAG laser, halogen lamp and helium. -It is particularly useful for recording light such as a neon laser. Therefore, the dye of the present invention is useful as a sensitizing dye for PS plates for printing plate making using these as light sources, resists for printed circuit boards, digital color proofs, hologram recording materials, optical cure adhesives, paints and the like.

[Brief description of drawings]

FIG. 1 is a graph showing the spectral sensitivities of the dye of the present invention and the comparative dye.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigeo Yasui 566-139 Fujita Nishiki, Okayama City, Okayama Prefecture

Claims (1)

[Claims] 1. The following general formula (1): [In the above formula, R ₁ and R ₂ each independently represent an alkyl group, and may have a side chain or a substituent. Also, R
_One or both of ₁ and R ₂ may combine with a Benzen ring to which a nitrogen atom is bonded to form a 5- or 6-membered ring. R
₃ represents a halogen, a cyano group, a carboxy group or a carboxylic acid ester group, R ₄ represents an alkyl group having the same meaning as R _1, and R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group or an alkoxy group. , Cyano group, trifluoromethyl group, sulfoxy group or halogen. X represents a monovalent acid residue, and Y represents NH or 0. n
Represents an integer of 0 or 1, and when n is 0, neither R ₄ nor X exists. ] The sensitizing dye for photopolymers which consists of a benzopyran ring condensed compound represented by these.