JPS62294238A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. of a photocrosslinking type having high sensitivity by forming said compsn. of a polymer which has a maleimide group at the side chain and permits photonetworking and the compd. expressed by the specific formula. CONSTITUTION:The photosensitive compsn. of the photocrossling type having the high sensitivity is obtd. by the polymer which has the maleimide group at the side chain and permits photonetworking and the compd. expressed by the formula.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a photocrosslinkable composition that is crosslinked by a cycloaddition reaction, and more particularly relates to a photocrosslinkable composition having a maleimide group in its side chain. The present invention relates to a photosensitive composition comprising a polymer and a novel sensitizer, and particularly to a photosensitive composition useful for photosensitive layers of photosensitive printing plates, photoresists, etc.

[Conventional technology]

Photocrosslinkable materials that crosslink through cycloaddition reactions are well known, and these are used as main components of photosensitive compositions used in the production of photosensitive lithographic printing plates, photoresists, and the like. Among these crosslinked materials, photocrosslinkable polymers having maleimide groups in their side chains do not have sufficient photosensitivity with only photoreticular polymers, and in order to increase photosensitivity, thioxanthone and benzophenone are used as sensitizers. , Michler's ketone, anthraquinones, anthracene, chrysene, p-dinitrobenzene, 2-nitrofluorenone, and the like have been used. When these sensitizers are used, the sensitivity increases, but it is still not sufficient, and the image exposure during image formation requires a long time, resulting in poor workability. There were problems such as an image of good quality not being reproduced if there was vibration.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a highly sensitive photocrosslinkable photosensitive composition. More specifically, it is an object of the present invention to provide a photosensitive composition containing a sensitizer that increases the photocrosslinking rate of a photocrosslinkable photosensitive composition containing a phototunable polymer having a maleimide group in a side chain. .

[Structure of the invention]

The present inventor has conducted extensive research to achieve the above object, and found that a photocrosslinkable photosensitive composition in which a certain sensitizer includes a light modulating polymer having a maleimide group in its side chain. The present invention was achieved based on the discovery that the photocrosslinking rate of the compound can be increased.

The present invention provides (a) a phototunable polymer having a maleimide group in its side chain; Represents a nonmetallic atomic group, R is an aryl group, a substituted aryl group, a heterocyclic group,
Represents a substituted heterocyclic group. ) is a photosensitive composition characterized by containing a compound represented by:

The light modulating polymer having a maleimide group in its side chain in the composition of the present invention includes a maleimide group represented by the general formula ('A): ○ (wherein R1 and R2 are each a hydrogen atom) It represents a 10-gen atom or an alkyl group, and R1 and R2 may be taken together to form a 5-membered ring or a 6-membered ring. The alkyl groups for R1 and R2 preferably have 1 to 4 carbon atoms, and a methyl group is particularly preferred. Further, as the halogen atom, a chlorine atom, a bromine atom, and an iodine atom are preferable. ) in the side chain is exemplified. Such polymers are disclosed, for example, in JP-A-52-988 (corresponding U.S. Pat.
．． No. 079.041) Specification, West German Patent 2, 626.7
Specification No. 69, European Patent No. 21,019,
European Patent No. 3.552 and QieAngewandt
e Macromolekulare Chemi
) 115 (1983), pages 163 to 181, JP-A-49-128991 to JP-A-49-128993,
No. 50-5376 to No. 50-5380, No. 53-5
No. 298 to No. 53-5300, No. 50-50107, No. 51-47940, No. 52-13907, No. 5
No. 0-45076, No. 52-121700, No. 50-
No. 10884, No. 50-45087, West German Patent No. 2.
It is described in the specifications of No. 349.948 and No. 2.616.276. In the present invention, among these, the component (
As the polymer a), it is preferable to use one having an average of two or more maleimide groups per molecule in its side chain and an average molecular weight of 1000 or more. Such polymers, for example, have general formulas (B) to (D): (wherein, R1 and R2 have the same meanings as above, and n represents an integer, preferably from 1 to 6.) and a monomer having an alkali-soluble group in the molecule in a ratio of, for example, 9515 to 30/70, preferably 90/70.
It is easily prepared by copolymerizing at a ratio of /10 to 70/30 (mole ratio). In other words, polymers having acid groups are preferable because alkaline water can be used during development, and they are also advantageous in terms of pollution. The acid value of the maleimide polymer having acid groups is preferably in the range of 20 to 250, more preferably in the range of 50 to 150. still,
The copolymerizable monomers include vinyl monomers having carboxyl groups such as acrylic acid and methacrylic acid;
Examples include maleic anhydride and itaconic anhydride.

Among the above-mentioned polymers as component (a), di-
Angebante Macromoleklae Chemi (Die^ng
ewandte Makromolekulare C
A copolymer of N-(2-(methacryloyloxy)ethyl-2,3-dimethylmaleimide and methacrylic acid or acrylic acid) as described on pages 71 to 91 of 128 (1984), that is, an alkali-soluble group. A copolymer with a monomer having the above-mentioned vinyl monomer is preferable. A multi-component copolymer polymerized in the coexistence of a vinyl monomer different from the above-mentioned vinyl monomer is also preferable.

The polymer used as component (a) in the present invention preferably has a molecular weight of 1,000 or more, preferably 10,000 to 500,000, particularly preferably 20,000 to 300,000.

The amount of the polymer of component (a) added to the total composition is 1
0 to 99% by weight (hereinafter abbreviated as %), preferably 50%
~99%.

Next, the sensitizer (b), which is a significant feature in the photocrosslinkable composition of the present invention, will be explained.

In the compound represented by the general formula (I) used in the present invention, Z is a group of nonmetallic atoms necessary to form a nitrogen-containing heterocyclic nucleus. Examples of the nitrogen-containing heterocyclic nucleus formed with Z include thiazoles such as benzothiazole, α-naphthothiazole, and β-naphthothiazole, oxazoles such as benzoxazole and β-naphthoxazole, and selenazils such as benzoselenazole. , imidazoles such as imidazole and benzimidazole, isoindoles such as 3,3-dimethylindolenine, quinolines such as quinoline and inquinoline, 1,3.4-oxadiazole, 1,3.4-
In addition to diazoles such as thiadiazole and 1.3.4-selenadiazole, and triazoles such as 1.2.4-triazole, pyrazine, quinoxaline, S-)riazine, and phenanthridine can be mentioned. The nitrogen-containing heterocyclic nucleus formed together with Z may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group, a methoxy group, and an ethoxy group. an alkoxy group having 1 to 6 carbon atoms, such as a halogen atom such as chlorine or bromine, an amino group substituted with an alkyl group having 1 to 4 carbon atoms such as a cyano group, an amino group, or a dimethylamino group, or a carbomethoxy group. A carbalkoxy group having an alkyl group having 1 to 4 carbon atoms such as a phenyl group, a p-methoxyphenyl group, a p-chlorophenyl group having 6 to 1 carbon atoms, etc.
Examples include 0 substituted or unsubstituted aryl groups.

When R is an aryl group, it represents a monocyclic or polycyclic compound having 6 to 14 carbon atoms such as phenyl and naphthyl. In addition, in the case of a substituted aryl group, the substituent has 1 carbon number
~6 alkyl groups, alkoxy groups having 1 to 6 carbon atoms,
Aryl group having 6 to 10 carbon atoms, amino group, amine group substituted with alkyl group having 1 to 6 carbon atoms, fluorine,
Examples include halogen atoms such as chlorine and bromine. Further, the alkyl group used as the above-mentioned substituent may further have an alkoxy group having 1 to 2 carbon atoms such as methoxy or ethoxy, or a halogen atom such as chlorine as a substituent.

Preferred substituents for these substituted aryl groups include alkyl groups having 1 to 4 carbon atoms such as methyl group and ethyl group, alkoxy groups having 1 to 4 carbon atoms such as methoxy group and ethoxy group, and dimethylamino group. , an amino group substituted with an alkyl group having 1 to 4 carbon atoms such as diethylamino group, and halogen atoms such as fluorine, chlorine, and bromine.

When R is a substituted or unsubstituted heterocyclic group, the heterocycle is a monocyclic or polycyclic compound containing at least one of nitrogen, oxygen, and sulfur, preferably a 5- or polycyclic compound such as furan, pyrrole, or pyridine. It is a 6-membered ring heteroaromatic compound.

In the case of a substituted heterocyclic group, the same substituents as those used for the above-mentioned substituted aryl group can be mentioned.

Among the compounds represented by the general formula (I) used in the present invention, a more preferable compound is a compound represented by the following general formula (II).

In the above formula (If), Z' represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocyclic nucleus together with X.

X represents OlS and N-R', where R'
represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a substituted alkyl group, an aryl group having 6 to 10 carbon atoms, or a substituted aryl group. Like R shown in general formula (I), R represents an aryl group, a substituted aryl group, a heterocyclic group, or a substituted heterocyclic group.

Typical examples of the compound represented by the general formula (II) include thiazoles, oxazoles, imidazoles, oxadiazoles, triazoles, and the like.

The compound represented by the general formula (I) used in the present invention is disclosed in JP-A No. 60-162248 and U.S. Patent No. 4.5.
It can be synthesized using a known method, as described in No. 55.474.

The amount of the sensitizer (component (b)) added is 1 to 3 of the total composition.
It is preferably 0%, more preferably 3 to 15%.

Specific examples of the sensitizer represented by the general formula (1) used in the present invention are shown below.

Nα1 o2 Nα3 lα4 Nα5 Company 6 n 9 Nα10 11 Nα12 Nα13 α Nα15 Nα16 Nα17 The photocrosslinkable photosensitive composition of the present invention contains other sensitizers in addition to the sensitizer represented by the general formula (I). A sensitizer may also be included. In this case, a sensitizer is selected that further increases the photocrosslinking rate when used in combination with the sensitizer compound represented by general formula (I). Specific examples of such sensitizers include benzoin, benzoin methyl ether, benzoin ethyl ether, 2,2-dimethoxy-2-phenylacetophenone, 9-fluorenone, 2-chloro-9-
Fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-
9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,
10-anthraquinone, 2,6-dichloro-9,10-
anthraquinone, xanthone, 2-methylxanthone,
2-methoxyxanthone, dibenzalacetone, p-(
dimethylamino) phenylstyryl ketone, p-(dimethylamino)phenyl p-methylstyryl ketone, benzophenone, p-(dimethylamino)benzophenone (
or Michler's ketone), p-(diethylamino)benzophenone, and benzanthrone.

Furthermore, thioxanthone derivatives such as 2-chlorothioxanthone, 2-isopropylthioxanthone, dimethylthioxanthone, etc., German Patent No. 3018891 and German Patent No. 3117568, and European Patent No. 3372
Substituted thioxanthones such as those described in No. 0, GB 2,075,506 are preferably used. The amount of the sensitizer used in combination with the compound of general formula (I) is preferably 0.5 to 20% of the total composition, more preferably 3%.
~10%.

The photosensitive composition of the present invention may contain a binder if necessary, but it is usually appropriately selected from linear organic polymers. Specific examples of the binder include chlorinated polyethylene, chlorinated polypropylene, polyacrylic acid alkyl ester, copolymer of acrylic acid alkyl ester and at least one monomer such as acrylonitrile, vinylopestylene chloride, butadiene, polyamide, methyl cellulose, Examples include polyvinyl formal, polyvinyl butyral, methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, and diazo resins.

In addition to the above, it is preferable to further add a thermal polymerization inhibitor to the photosensitive composition, such as hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4
．． 4'-t-bis(3-methyl-6-t-butylphenol), 2゜2'-methylenebis(4-methyl-6
-t-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

In some cases, dyes or pigments such as methylene blue, crystal violet, rhodamine B1 fuchsin, auramine, azo dyes, anthraquinone dyes, titanium oxide, carbon black, iron oxide, phthalocyanine pigments, azo pigments, etc. are used for coloring purposes. May be added.

The photosensitive composition of the present invention is used by dissolving the above-mentioned various components in a solvent and coating the solution on a suitable support by a known method.

Solvents used when applying the photosensitive composition of the present invention include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, monochlorobenzene, toluene, xylene, propylene glycol monomethyl ether, 3- Examples include methoxypropanol, 3-methoxypropyl acetate, ethyl acetate, and butyl acetate.

These solvents may be used alone or in combination.

The photosensitive composition of the present invention is suitable as a photosensitive layer of a photosensitive lithographic printing plate. Suitable supports for photosensitive lithographic printing plates include hydrophilized aluminum plates, such as silicate-treated aluminum plates, anodized aluminum plates, and electrodeposited silicate aluminum plates;
Stainless steel plates, chromium-treated copper plates, and hydrophilized plastic films and paper can be cited.

The coating amount when producing a photosensitive lithographic printing plate is generally 0.1 to 10.0 g/m' as a solid content, and particularly preferably 0.5 to 5.0 g/rn'. .

Furthermore, when the composition of the present invention is used as a photoresist, various materials such as a copper plate, a copper plated plate, a stainless steel plate, a glass plate, etc. can be used as a support.

〔Example〕

The present invention will be explained in more detail below based on Examples.

Examples 1 to 4, Comparative Examples 1 to 3 After graining with a nylon brush, a silicate-treated aluminum plate was coated with a rotary coater at a rotation speed of 20 Or, p.
The following photosensitive solution using the sensitizer shown in Table 1 was applied at .

Methyl methacrylate)/N-(2-(methacryloyloxy)ethyl) -2,3-dimethylmaleimide/methacrylic acid = 15/65/20 (weight ratio) copolymer methyl ethyl ketone/2-methoxyethanol = 1/ 1 20% solution by weight ratio mixture (Resin V in JP-A-59-206425)
25 g Sensitizer shown in Table 1 0.5 g F-177 (manufactured by Dainippon Ink ■: fluorine-based nonionic surfactant) 0.02 g Copper phthalocyanine pigment (CI Pigment Blue
15) 10% dispersion of plasticizer 1.0g Aerosil R972 (manufactured by Nippon Aerosil ■: surface resin-treated silicic acid powder) 10% dispersion in ethylene glycol monomethyl ether 1.0g Methyl ethyl ketone 20 g Methanol 2g Ethylene glycol monomethyl ether acetate 28 For exposure, use a vacuum printing frame device, place a step wedge (density step difference 0, 15, number of density steps 15) on the prepared photosensitive plate, irradiate it with a 2KW ultra-high pressure mercury lamp for 16 seconds, and after exposure, use the following prescription. It was developed using a developer solution.

Developer Benzyl alcohol 4.5g 38% aqueous solution of sodium salt of isopropylnaphthalene sulfonic acid 4.5g Triethanolamine 1.5g Monoethanolamine 0.1g Sodium sulfite 0.3g Pure water
The highest number of step wedges corresponding to the 100g image is shown in Table 1 as the sensitivity of the sample. The higher the number of stages, the higher the sensitivity.

For comparison, 2,3-dimethylthioxanthone and Michler's ketone were added as sensitizers instead of the compound of the present invention as Comparative Examples (1) and (2), respectively, and Comparative Examples (2) were used without the addition of 2,3-dimethylthioxanthone and Michler's ketone. 3) and their sensitivities are also shown in Table 1.

Table 1 As shown in Table 1, when the sensitizer represented by the general formula (I) of the present invention was used, higher sensitivity was shown compared to Comparative Examples 1 to 3, and the present invention was achieved. The effects of the period were fully recognized.

Examples 5 to 10, Comparative Examples 4 to 6 The compounds shown in Table 2 below were used as the sensitizers represented by the general formula (I) of the present invention, and 7-methylthioxanthone- Ethyl 3-carboxylate 0
．． A coating solution was prepared using the same formulation as in Examples 1 to 4, except that 3 g was added to each, and a photosensitive plate was prepared using the same method, followed by exposure and development. The highest number of steps of the step wedge corresponding to the developed image is shown in Table 2 as the sensitivity of the sample.

In addition, Comparative Examples (4) and (5) used Michler's ketone and benzophenone instead of the sensitizer of the present invention, and Comparative Example (6) used ethyl 7-methylthioxanthone-3-carboxylate alone. ) and their sensitivities are also shown in Table 2.

As shown in Table 2, the sensitivity of Comparative Example (6) using the conventional sensitizer, ethyl 7-methylthioxanthone-3-carboxylate alone, or the combination of this and other conventional sensitizers. Compared to the sensitivity of comparative examples (4) and (5) when
When the sensitizer represented by the general formula (I') of the present invention is used in combination with a conventional sensitizer, the sensitivity is extremely high.

〔Effect of the invention〕

The photosensitive composition of the present invention has high sensitivity, and therefore can form an image with short exposure, and has excellent workability in plate making and the like.

Claims (1)

[Scope of Claims] A photosensitive composition comprising (a) a photoreticulable polymer having a maleimide group in its side chain; and (b) a compound represented by general formula (I). . ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocyclic nucleus, and R represents an aryl group, a substituted aryl group, a heterocyclic ring. (represents a substituted heterocyclic group)