JPH02173646A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To improve sensitivity of a photosensitive compsn., to enable to form a picture by a short time exposure and to improve workability of processing by using a specified photocrosslinking polymer and a specified sensitizer. CONSTITUTION:A photocrosslinking polymer (A) having maleimide groups in the side chains and a sensitizer (B) expressed by the formula I are contained in the subject photosensitive compsn. In the formula I, each Ar and Ar' is a substituted or unsubstituted aryl group; R is a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, etc. A compd. expressed by the formula II may be usable as the sensitizer. A copolymer of a monomer expressed by the formula III with a monomer (e.g. methacrylic acid) having an alkali-soluble group is usable as the polymer (A). In the formula III, each R<1> and R<2> is H, halogen, etc.; n is an integer.

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 particularly relates to a photocrosslinkable polymer having a maleimide group in its side chain and a novel sensitizing composition. The present invention relates to a photosensitive composition comprising a photosensitive agent, and particularly to a photosensitive composition useful for a photosensitive layer of a photosensitive printing plate, a photoresist, 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 crosslinkable materials, photocrosslinkable polymers having maleimide groups in their side chains alone do not have sufficient photosensitivity, and in order to increase photosensitivity, thioxanthone, benzophenone, Michler's ketone, anthraquinone, or sensitizers are used as sensitizers. Anthracene, chrysene, p-dinitrobenzene, 2-nitrofluorenone, etc. 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 photocrosslinkable polymer having a maleimide group in a side chain.

[Structure of the invention]

As a result of extensive research to achieve the above object, the present inventors have discovered that the photocrosslinking rate of a photocrosslinkable photosensitive composition containing a photocrosslinkable polymer having a maleimide group in its side chain using a certain sensitizer has been determined. The present invention has been developed based on the discovery that it is possible to increase the .

That is, the present invention provides a photosensitive composition comprising (a) a photocrosslinkable polymer having a maleimide group in its side chain; and (b) a compound represented by the following general formula (I): It is related to.

The present invention will be explained in detail below.

The crosslinkable polymer having a maleimide group in its side chain in the composition of the present invention is a maleimide group represented by the following general formula (A>): (wherein R1 and R2 are each a hydrogen atom, a halogen atom, or an alkyl group) and R' and R2 may be taken together to form a 5-membered ring or a 6-membered ring.The alkyl groups of R1 and R2 preferably have 1 to 4 carbon atoms, and in particular, A preferred example is a methyl group.Also, as a halogen atom, a chlorine atom, a bromine atom, or an iodine atom is preferred. No. 52-988 (corresponding U.S. Patent No. 4)
．． No. 079.041) Specification, West German Patent No. 2, 626.
No. 769, European Patent No. 21.019, European Patent No. 3.552, Die Angewante Macromolecules Chemi (DieAngewa
ndte Mackromolekulare
Chemi) 1 1 5 (1983) 16
Pages 3-181, JP-A-49-128991-4
No. 9-128993, No. 50-5376 to No. 50-5
No. 380, No. 53-5298 to No. 53-5300,
No. 50-50107, No. 51-47940, No. 52
-13907, 50-45076, 52-12
No. 1700, No. 50-10884, No. 50-4508
7, West German Patent No. 2.349.948, West German Patent No. 2.61
It is described in each specification of No. 6.276.

In the present invention, it is preferable to use, as the polymer of component (a), a polymer 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 a polymer may have the formula (B) to (
D): (In the formula, R1 and R2 have the same meanings as above, and n represents an integer, preferably 1 to 6.) A monomer represented by ゛ and a monomer having an alkali-soluble group in the molecule For example, it is easily prepared by copolymerizing these at a ratio of 9515 to 30/70, preferably 90/10 to 70/30 (molar 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 that grows acid groups is preferably in the range of 20 to 250, more preferably in the range of 50 to 150.

The above copolymerizable monomers include acrylic acid,
Examples include vinyl monomers having a carboxyl group such as methacrylic acid, maleic anhydride, itaconic anhydride, and the like.

As the polymer of component (a), among the above, di-
Angewante macromoleculae chemistry (Die A
ngewandte Mackromolekula
re Chemie) 128 (1984) 71~
A copolymer of N (2(methacryloyloxy)ethyl]-2,3-dimethylmaleimide and methacrylic acid or acrylic acid, such as a copolymer with a monomer having an alkali-soluble group, as described on page 91 is preferable. Furthermore, a multi-component copolymer polymerized in the coexistence of a vinyl monomer different from the above-mentioned vinyl monomers 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 5
It is 0-99%.

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

In the sensitizer represented by the general formula (I) used in the present invention, R is an alkyl group (e.g., methyl group, ethyl group, propyl group, etc.) or a substituted alkyl group (e.g., 2-hydroxyethyl group, 2-hydroxyethyl group, etc.). -Methoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2-sulfoethyl group, 3-sulfopropyl group, 2-carbomethoxyethyl group, benzyl group, phenethyl group, p-sulfophenethyl group , p-carboxyphenethyl group, vinylmethyl group) or aryl group (e.g. phenyl group, p-hydroxyphenyl group, p-methoxyphenyl group, p-chlorophenyl group, naphthyl group) or heterocyclic group (e.g. furyl group,
thienyl group, etc.).

The amount of the sensitizer (component et al.) added is preferably 1 to 30%, more preferably 2 to 10%.

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

The photocrosslinkable photosensitive composition of the present invention may further contain other sensitizers in addition to the sensitizer represented by -kill (1). In this case, a sensitizer is selected that further increases the photocrosslinking rate when used in combination with the sensitizer represented by -kill (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- Examples include methylstyryl ketone, benzophenone, p-(dimethylamino)benzophenone (or Michler's ketone), p-(diethylamine)benzophenone, and benzanthrone.

Furthermore, thioxanthone derivatives, such as 2-chlorothioxanthone, 2-isopropylthioxanthone, dimethylthioxanthone, etc., as well as German Patent No. 3018891 and German Patent No. 3117568, and European Patent No. 337
Substituted thioxanthones such as those described in British Patent No. 20, GB 2,075,506 are preferably used. - The amount of the sensitizer used in combination with the compound of killing (1) is preferably 0.5 to 20%, more preferably 3 to 10% of the total composition.

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 binders include chlorinated polyethylene, chlorinated polypropylene, polyacrylic acid alkyl esters, copolymers of acrylic acid alkyl esters and at least one monomer such as acrylonitrile, vinyl chloride, styrene, butadiene, polyamide, and methylcellulose. , polyvinylformanope, polyvinylbutyranope, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, diazo resin, and the like.

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'-thiobis(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 added for coloring purposes. You can.

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-methoxy Examples include propatool, 3-methoxypropyl acetate, ethyl acetate, butyl acetate, and the like.

These solvents may be used alone or in mixtures.

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 silicate electrodeposited aluminum plates, as well as zinc plates, stainless steel plates, and chromed copper plates. Examples include plastic films and paper that have been treated to make them hydrophilic.

- When producing a photosensitive lithographic printing plate, the appropriate coating amount is generally 0.1 to 10.0 g/m' in terms of solid content;
Particularly preferred is 0.5 to 5.0 g/m''.

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

〔Example〕

Hereinafter, the present invention will be explained in more detail based on Examples.

Examples 1 to 3, Comparative Examples 1 to 3 After graining with a nylon brush, an anodized aluminum plate was coated at a rotation speed of 20 Or
, p, m, the following photosensitive solution using the sensitizer shown in Table 1 was applied and dried at 100° C. for 2 minutes to give a dry film of about 1.5
A photosensitive plate was prepared by forming a photosensitive layer of μ.

Methyl methacrylate)/N-(2-(methacryloyloxy)ethyl-2,3-dimethylmaleimide/methagrylic acid = 15/65/20 (weight ratio) copolymer methyl ethyl ketone/2-methoxyethanol = 1/1 weight 20% solution of ratio mixture (Flli fat V
) 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% plasticizer dispersion 1.0g Aerosil R
972 (manufactured by Nippon Aerosil ■: surface resin-treated silicic acid powder) 10% dispersion of ethylene glycol monomethyl ether 1.0 g Methyl ethyl ketone 20 g Methanol 2 g Ethylene glycol monomethyl ether acetate 28 g Exposure was performed using a vacuum printing frame device. Step wedge on the board (density step 0.15, number of density steps 15)
The film was placed in a microwave oven and irradiated with a 2KW ultra-high pressure mercury lamp for 16 seconds, and after exposure, it was developed using a developer having the following formulation.

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

For comparison, thioxanthone and Michler's ketone were added as sensitizers in place of the compound of the present invention as Comparative Examples 1.2, and those without the addition were designated as Comparative Example 3. It is shown in Table 1.

Table 1 Examples 4 to 6, Comparative Examples 4 to 6 The compounds shown in Table 2 below were used as compounds represented by the general formula (I) of the present invention, and 7-methylthiosanthone was used as a sensitizer other than the present invention. -3-Ethyl carboxylate 0.3
Coating solutions were prepared using the same formulations as in Examples 1 to 3, except that 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 bensiphenone instead of the sensitizer of the present invention, and Comparative Example 6 used ethyl 7-methylthioxanthone-3-carboxylate alone. They are also shown in Table 2.

In Table 2, the sensitivity when a sensitizer and a conventional sensitizer are used together 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 photocrosslinkable 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) However, r and Ar' represent a substituted or unsubstituted aryl group, and R is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryl group. Or it represents an unsubstituted heterocyclic group.