JPS60202437A - Composition for forming photosensitive image - Google Patents

Abstract

PURPOSE:To obtain a compsn. having superior fundamental characteristics, such as photosensitive characteristics, heat stability, etc. and being safe to human body consisting primarily of a photochemical reaction initiator, radical generating agent, and addition polymerizable ethylenic unsatd. monomer, wherein said photochemical reaction initiator comprises 2,4,5-triaryl imidazolyl dimer expressed by the formula ( I ). CONSTITUTION:The compsn. consists primarily of a photochemical reaction initiator, a radical generating agent, and an addition polymerizable ethylenic unsatd. monomer wherein said photochemical reaction initiator is 2,4,5-triaryl imidazolyl dimer expressed by the formula ( I ). Specific examples for the photochemical reaction initiator expressed by the formula ( I ) is 2-(3-bromo-2-methoxy-1-phenyl)-4,5-diphenyl imidazolyl dimer, etc. Suitable radical generating agent is conventionally used amines, particularly, tertiary amines, or leuco dye, etc. Preferred proportion of a specified 2,4,5-triaryl imidazolyl dimer to radical generating agent is 2:1-1:5 by molar ratio.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to photosensitive imageable compositions. More specifically, the present invention relates to a photosensitive image-forming composition that has good sensitivity, excellent thermal stability, and is safe for the human body.

It is generally said that chemical substances in water systems can bioaccumulate in aquatic organisms and may eventually be transferred to the human body through the food chain. For this reason, the Ministry of International Trade and Industry requires testing of the concentration of new chemical substances in the bodies of fish under the Chemical Substances Examination and Regulation Law. In addition, when manufacturing or importing a "new chemical substance" for the purpose of preventing workers' health problems caused by chemical substances, it is necessary to carry out toxicity tests such as mutagenicity tests and submit a notification to the Minister of Labor in advance. Mandated by the Safety and Health Act.

By the way, as a photosensitive composition with good sensitivity, there is known a photographic image-forming acid combination in which a hexaary-μbiimidazole compound is used in combination with a radical generator, an ethylenically unsaturated monomer compound, and other additives. ing. Further, as a compound satisfying thermal stability, 2,2'-bis(
0-chlorpheni/l') -414'15+5'-
Tetrakisphenyl bi-imidazo-1v (hereinafter referred to as CI
-HABI) is known. However, this C
Since J-IIABI is almost insoluble in non-halogenated solvents, it is necessary to use halogenated solvents in coating dopes containing CJ-TIABI, which generally has the following drawbacks. In addition, the compounds that make up halogen paper are bioaccumulative and harmful (mutagenic).
It is generally known that they tend to be inferior in their suitability to non-halogenated solvents.

Therefore, the present inventors have made earnest efforts to obtain a composition that has excellent basic properties such as photosensitive performance and thermal stability as a photosensitive composition and is also safe for the human body, and as a result, has finally completed the present invention. It has arrived. That is, the present invention mainly consists of (A) a photoinitiator, (B) a radical generator, and (C) an addition polymerizable ethylenically unsaturated monomer, and the (A) photoinitiator is represented by the following general formula. A photosensitive image-forming composition characterized in that it is a 2,4,5-doaryrylimidazolyl dimer.

Specifically, the photoinitiator represented by the above general formula in the present invention includes 2-(3-bromo-2-methoxy-1-phenylene/k)-4,5-diphenylimidazolyl dimer, 2-
(4-chloro-2-ethoxy-1-phenyl)-4,5
-diphenylimidazolyl dimer, 2-(5-chloro/L
/-2-methoxy1-phenyl)-4,5-dinaphthylimidazolyl, 2-(6-fluoro1-2-methoxy1-phenyl/L/)-4,5-dinaphthylimidazolyl .

2-(2-chloro-3-ethoxy-1-phenyl)-4
, 5-dinaphthylimidazolyl divertebral body, 2-(2-chloroA/-4-butoxy-1-phenyl)-4゜5-diphenylimidazolyl dimer, 2-(2-chloroA/-5-methoxy-1 -phenyl) -4,5-diphenylimidazolyl dimer, 2-(2-bromo-6-medoxy1-
phenyl) -4,5-diphenylimidazolyl dimer, 2- (2-riT"1V-4,5-dimethoxy-1-
phenyl)-4,5-diphenylimidazolyl dimer,
2-(5-bromo-2,3-diethoxyV-1-phenyl)-4,5-diphenylimidazolyl dimer, 2-(2
, 3-dichloro-4,5,6-)dimethoxy-1-phenylene/L')-415-diphenylimidazolyl dimer and the like. t7tc, has an alkoxy group having 1 to 5-4 carbon atoms in the phenyl group at the 4.5-position. 2-(5-chloro-2-methoxy-1-phenyl)-4,5-bis(3-methoxy-1-pheny/I/)imidazolyl dimer.

2-(2-chloro-5-ethoxy-1-pheny/I/)
-4,5-bis(3-methoxy-1-phenyl)i.

Midazolyl dimer, 2-(2-bromo-4,5-dimethoxy-1-phenyl IV)-415-bis(3-ethoxy-1-phenyl)imidazolyl dimer isomer 1-phenyl)-4,5- Dinaphthylimidazolyl In the present invention, the radical generator includes Eirai 2μ compound.

from amines, especially tertiary amines, leuco dyes, halogenated hydrocarbons, N-phenylglycine, Michler's ketone,
Michler's thioketone, dimedone, thioureas, and the like are known, and any of them can be used in the present invention. In addition, as a result of thorough investigation of radical generators that exhibit remarkable effects in combination with the photoinitiator used in the present invention, dimedone,
Indo-61-acetic acid, N-naphthylglycine, 5-n-butylthioglycolic acid, 4,4'-bis(dimethylamino)benzyl, p-dialkylaminobenzoic acid ester, leuco crystal violet, indoginic acid, and these In addition to the compounds exemplified above, the radical generators used in the present invention include 1-chloroindoxylic acid, 2-chloroindoxylic acid, 4,4'-bis( diethylamino)benzyl, methyl p-diethylaminobenzoate, tri(p-diethylamino-0-tolyl)methane, tri(
Mention may be made of p-dimethylamino-o-tolyl)methane and 5-chloro-indole acetate.

In the present invention, the blending ratio of the specific 2.4.5-) realyl imidazolyl y dimer (A) and the radical generator is preferably in the range of 2:1 to 1:5 in terms of molar ratio. When the molar ratio exceeds 2:1, sensitivity decreases.

If the ratio is less than 2:1, the sensitivity will not change, but if the radical generator is added too much, there will be no effect, so the ratio is preferably 1:5 or more.

The photosensitive resin composition containing the novel photopolymerization initiator system of the present invention mainly contains an ethylenically unsaturated compound and, if necessary, a thermoplastic binder. In the present invention, the ethylenically unsaturated compounds that can form a polymer compound by chain-growth addition polymerization initiated by a free radical radical include cyclohexyl acrylate, decyl acrylate (.), alkyl acrylates such as lauryl acrylate, and 2 -2-hydroxyalkyl acrylates such as hydroxyethyl acrylate mtN+N-aminoalkyl acrylates such as N-dimethy7leaminoethyl acrylate, ether alkyl acrylates such as 2-methoxyethyl acrylate, grindyl acrylates, halogenated alkyl tV1 clv- Examples include polyfunctional acrylates such as trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and triethylene glycol dimethacrylate.

Thermoplastic polymers in which an ethylenically unsaturated group is present in the side chain substituent 1 For example, those represented by the formula % can also be mentioned. On the other hand, the thermoplastic binder is not an essential requirement of the present invention. However, various soluble polymers can be added to adjust the physical properties of the composition.

Together with the ethylenically unsaturated compound, a polymer (which may or may not be bonded to a photopolymerizable substance) becomes insoluble in a solvent as a whole upon irradiation with light.

For example, polyamide, polyacrylic acid ester, acrylic acid and acrylic acid alkyl ester copolymer, methacrylic acid and methacrylic acid alkyl ester copolymer, polyvinylphenol, polyvinyl ester, polyacrylamide, polyvinyl alcohol/I/, polyethylene oxide, gelatin.

9- Polymeric substances such as cellulose esters and cellulose ethers are used in combination as thermoplastic binders if necessary.

Suitable thermoplastic binders are nitrogen-containing polymers that can be quaternized with carboxyl groups, phenolic groups, sulfonic acid groups or halonic acid.

The former three can be developed with an aqueous alkaline solvent, and can be washed off and development can be stopped, ie, fixed, by washing with water. The latter can be developed with an aqueous acid solvent and fixed by washing with water.

Furthermore, a sensitizer is not an essential requirement of the present invention.

By adding the following substances, an 8-enhancing effect can be expected.

Hydroxyphthalein dye (fluorescein).

eosin etc.), aminoacridine dye (3,6-his(
alkylamino) acridines, etc.), carbocyan dyes (3,3'-diethyloxacarbocyanine iodide, etc.), coumarin (7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, etc.),
p-aminophenyl, furan, oxazole, diazole, aromatic hydrocarbons, perylene, pyrene, bis(p-aminophenyl)-α, β-unsaturated ketone, etc.

The photosensitive resin composition composition of the present invention can be used for printing-related materials such as 1-letterpress 1-lithographic printing plates, non-silver lithography films, and color proofing plates, or as liquid or film resists and solders. It can be used for electronic related materials such as masks.

The standard weight composition of the photosensitive resin composition for these uses is the specific 2.4.5-t! shown in formula (A). J phenylimidazolyl divalent body and dimedone, indole acetic acid,
N-naphthylglycine, S-alkylthioglycolic acid, 4.4'-bis(dialkylamino)benzi/L/
, I) -dialkylaminobenzoic acid ester, leuco crystal violet, indoxylic acid, and at least one compound selected from derivatives thereof. %), ethylenically unsaturated compound 30~80%, thermoplastic binder 0~
60%.

Preferably, a range of 10 to 60% is selected as a tentative standard.

In addition, various additives well known in the art may be added as necessary. These additives include carbon black, titanium oxide, powders of various metals and metal oxides, actinic ray absorbers such as various pigments and dyes, as well as various energy transfer dyes, oxygen scavengers, and chain transfer promoters. , thermal polymerization inhibitors, and the like. These additives are generally added in small amounts within 3% by weight of the total composition, but when pigments are added, they are added in amounts of 5 to 75% of the total composition, such as UV 1il coatings and inks. Furthermore, it is generally used as a composition for non-silver lithium film. The image-forming plate material can be produced by coating the above composition on a substrate or forming it into a sheet by a conventional coating technique. In the present invention, the effect is particularly remarkable when the thickness of the photosensitive resin layer is thin, usually 10 μm or less.

In general, the photopolymerizable image-forming plate material of the present invention is used by superimposing it on a suitable original image or pattern mask, exposing it to light, and then using it as a visible image through a mirror image process. As the photopolymerization initiator system of the present invention is soluble in non-halogenated solvents, there is no need to use halogenated solvents as coating dope solvents, so the coater and other equipment will not be harmed. 1 accumulation (concentration) and mutagenicity (Ames test), it also has excellent safety during production and handling. Moreover, because it has excellent thermal stability, its performance hardly changes over a long period of one year or two at room temperature.

The present invention will be specifically described below with reference to Examples.

Reference Example 1 The solubility of the photoinitiators shown in Table 1 in various solvents is also shown in Table 1.

13- Table 1 Reference Example 2゜The following composition containing a predetermined amount of the photoinitiator shown in Table 2 was
It was stored at ℃ for 2 days, and the residual rate (%) of the photoinitiator was measured. The results are also listed in Table 2.

Composition Components (f) Photoinitiator o, ooso' Dimedone 0.0030 Poly(methyl methacrylate/methacrylic acid 0.107
0/30 molar ratio) methylene chloride/methanol (3/1 weight ratio) 10.00
14-Table 2 As is clear from Table 2, the residual rate of the photoinitiator used in the present invention is 95% or more, which is a very high value compared to others, and it has excellent thermal stability in the solution. I understand that.

Reference Example 3 The photoinitiators shown in Table 3 were each placed in a separating funnel containing n-octyl alcohol and water, shaken several times, and allowed to stand still to measure the volume of the solution in 6 liquids. .

The distribution coefficient was calculated using the following formula. The results are also listed in Table 3.

Distribution coefficient (ρ) = pupil (0/W) Table 3 Note that the larger the partition coefficient, the greater the bioconcentration.

It is known that it accumulates in the human body, and it is safe if it is about 3 or less.

Reference Example 4 2-(5-chloro-2-
When the mutagenicity test (AmesTest) of the methoxy-1-phenyl)-4,5-diphenylimidazolyl monomer was conducted using Salmonella (TAIoo, Ta2O), no increase in Salmonella was observed compared to the blank, and the test was passed. Met. In addition, as a method, the photoinitiator and Salmonef bacteria were added to a solvent (dimethyl sulfoxide), and after culturing at 30°C for 48 hours, the increase in Salmonella bacteria compared to the blank was measured.

Example 1 The following is an example in which the photosensitive composition of the present invention was applied to a non-silver lithium film containing a UV blocker such as a pigment to a high degree in the photopolymerizable layer.

A composition for a photopolymerizable layer having the following composition was prepared on a biaxially stretched polyethylene terephthalate film having a thickness of 100 μm and having an undercoat layer.

A 4μ thick photopolymerizable layer was coated using a reverse coater. The optical density of the photopolymerizable layer is 350-400m
The average value was 2.6 in the μ range.

17- Furthermore, on top of the photopolymerizable layer, 10 tivolivinyl alcohol (
A protective layer having a thickness of 2 μm was provided by coating with an aqueous solution with a degree of saponification of 98 to 99 mo/I/% and a degree of polymerization of 500.

Next, a 21v'2 step tablet was placed on top of this lithographic film, and exposed using an ultra-high pressure mercury lamp (Oak Seisakusho Polymer Printer 3000.140W/#/). After that, wash with water to remove the storage layer, and add 2% carbonic acid)
The film was developed by immersing it in an IJum aqueous solution at 25° C. for 6 seconds, then immersing it in water and rubbing it with a sponge. Table 4 shows the optimum exposure time (exposure time required to cure 6 steps of the step tablet).

In addition, in order to examine thermal stability, the sample was stored in an incubator at 40°C for a certain period of time (1 month, 2 months), and a 2% sodium oxide aqueous solution was used to completely remove the photosensitive layer in the unexposed area. Measure the immersion time (at 25°C) and the optimal exposure time. The results are summarized in Table 4.

As is clear from Table 4, the photoinitiator used in the present invention is an excellent compound that does not change over time.

Patent applicant: Toyobo Co., Ltd. 19-

Claims (1)

[Claims] It mainly consists of (A) a photoinitiator, (B) a radical generator, and (C) an addition-polymerizable ethylenically unsaturated monomer, and the photoinitiator (A) is represented by the following general formula: −
A photosensitive image-forming composition characterized in that it is a triaryl imidazolyl di-stitched body.