JPH02236552A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To provide the photosensitive compsn. having a high sensitivity and having the sensitivity even light sources of long wavelengths by incorporating a sensitizer which increases the photocrosslinking speed of the photocrosslinking type photosensitive compsn. contg. a photocrosslinkable polymer having a maleimide group in the side chain and has the sensitivity even to the long wavelengths into the above-mentioned compsn. CONSTITUTION:The specific sensitizer is sensitive to a wide range of the light sources and increases the photocrosslinking speed of the photocrosslinking type photosensitive compsn. contg. the photocrosslinkable polymer having the maleimide group in the side chain. Namely, the photosensitive compsn. contains the photocrosslinkable polymer having the maleimide group in the side chain and the sensitizer expressed by formula I. In the formula, Z denotes the nonmetal atom group necessary for forming a heterocyclic nucleus contg. nitrogen; Y denotes the nonmetal atom group necessary for forming a ring; R1 denotes an alkyl group or substd. alkyl group; R2 and R3 respectively denote a hydrogen atom, alkyl group, substd. alkyl group, aryl group, substd. aryl group or halogen atom; n denotes 0 or 4 integer. This photosensitive compsn. has the high sensitivity and is sensitive to the light of the long wavelengths as well; therefore, the excellent workability in plate making, etc., and the good selectivity of various kinds of the light sources are obtd.

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 specifically, the present invention relates to a photocrosslinkable composition that is crosslinked by a cycloaddition reaction. This invention relates to a photosensitive composition comprising a sensitizer, and particularly to a photosensitive composition useful for photosensitive layers of photosensitive printing plates, photoresists, etc. (Prior art and problems to be solved) Photocrosslinkable materials that are crosslinked by cycloaddition reactions are well known, and these are used for the production of photolactic lithographic printing plates, photoresists, etc. It is used as a main component of compositions. Among these crosslinked materials, photocrosslinkable polymers having maleimide groups in their side chains do not have sufficient photolactic properties, and in order to increase photosensitivity, thioxanthone is used as a sensitizer. Penzophenone, Michler's ketone, anthraquinones, anthracene, chrysene, p-dinitrobenzene, 2-nitrofluorenone, etc. have been used.Using these sensitizers increases sensitivity, but it is still insufficient. However, since image exposure during image formation requires a long time, workability is poor, and in the case of detailed images, there are problems such as not being able to reproduce images of good quality if there is slight vibration in the operation. Ta.

Also, are the absorption wavelengths of these exacerbants short?
Since x is approximately 400 nm at most, there has been a problem in that the range of usable light sources is limited.

Therefore, in order to eliminate the above-mentioned drawbacks, JP-A No. 62-294238 discloses the formula -C: and R represents (substituted) aryl or (substituted) heterocycle) was proposed to be used as a stimulant.

However, the absorption wavelength of this stimulant is also short, and its λ
The ma% was at most about 400 nm, and the degree of anger was still insufficient, which was a problem.

Therefore, an object of the present invention is to provide a photosensitive composition that is highly sensitive and is sensitive even to long wavelength light sources. More specifically, the purpose of this invention is to increase the photocrosslinking rate of a photocrosslinkable photosensitive composition containing a photocrosslinkable polymer having a maleimide group in its side chain, and to develop a sensitizer that is sensitive to long wavelengths. An object of the present invention is to provide a photosensitive composition containing the following.

[Means to solve the problem]

As a result of intensive research to achieve the above object, the present inventors discovered that a certain sensitizer is sensitive to a wide range of light sources, and that a photo-crosslinkable polymer containing a maleimide group in its side chain is sensitive to a wide range of light sources. The present invention was achieved by discovering that the photocrosslinking rate of crosslinkable photosensitive compositions can be increased.

In other words, the present invention provides (a) a photocrosslinkable polymer having a maleimide group in its side chain; represents a necessary nonmetallic atom group, Y represents a nonmetallic atom group necessary to form a ring, R represents an alkyl group or a substituted alkyl group, R2
and R represent a hydrogen atom, an alkyl group, a substituted alkyl group, a substituted alkyl group, a substituted alkyl group, or a halogen atom, and n represents an integer from O to 4. ) It relates to a photolactic composition characterized by containing a multiplier represented by:

The present invention will be explained in detail below.

The photocrosslinkable 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 each represent a hydrogen atom, a halogen 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 of R' and R2 preferably have 1 to 4 carbon atoms, and are particularly preferred. is a methyl group.Also, as the /'t rogen atom, a chlorine atom, a bromine atom or an iodine atom is preferred.) Examples include polymers having these in the side chain. Such polymers are described, for example, in the specification of JP-A-52-988 (corresponding U.S. Pat. No. 4.079.041), West German Patent No. 2
．． 626,769, European Patent No. 21
．． No. 019, European Patent No. 3,552 and The Angewante Macromolecules Chemi (
Die Angewandte Mackromo
115 (I983
), pages 163-181, Japanese Patent Application Publication No. 4, 9-12899.
No. 1 to No. 4 9-128993, No. 5 0-537
No. 6 to No. 50-5380, No. 53-5298 to No. 53-5300, No. 50-50107,
No. 5 1-47940, No. 5 2-13907, No. 5 0-45076, No. 5 2-121700, No. 5 0-10884, No. 5 0-45087, West German Patent No. 2,349.948 No. 2,616. 276
It is stated in the specification of each issue. In the present invention, among these, as a polymer of component (Al), the polymer has an average of 2 or more maleimide groups per molecule in the side chain, and has an average molecular weight of 1
000 or more is preferable. Such polymers have, for example, general formulas (B) to (D): (wherein R' and R2 have the same meanings as above, and n represents an integer, preferably from 1 to 6). A monomer represented by and a monomer having an alkali-soluble group in the molecule are copolymerized in a ratio of, for example, 95/5 to 30/70, preferably 90/10 to 70/30 (molar ratio). It is easily prepared by 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. Examples of the above-mentioned copolymerizable monomers include carboxyl group-containing vinyl monomers such as acrylic acid and methacrylic acid, maleic anhydride, and itaconic anhydride. Among the above-mentioned polymers of component (al), Di Angewante Macromolecule Chemi (D
ie Angewandte Makromoleku
lare Chemie) 128 (I984) 71~
A copolymer of N-(2-(methacryloyloxy)ethyl)-2,3-dimethylmaleimide and methacrylic acid or acrylic acid, that is, 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 monomer is also preferable. The polymer of component (a) used in the present invention has a molecular weight of 1000 or more, preferably 10,000 to 10,000. It is desirable to use 500,000, particularly preferably 20,000 to 300,000.

The amount of the polymer of component (a) added to the total composition is 1
O to 99% by weight (hereinafter abbreviated as %), preferably 5
It is 0-99%.

Next, the exacerbating agent used in the photocrosslinkable composition of the present invention
I will explain about it. In the compound represented by the general formula (■) used in the present invention, Z is a nonmetallic atomic group necessary to form a nitrogen-containing petrocyclic nucleus usually used in cyanine dyes. The heterocyclic nucleus containing 2 and nitrogen is, for example, penzothiazoles (penzothiazole, 5-
Chloropenzothiazole, 6-chlorobenzothiazole, 4-methylbenzothiazole, 6-methylbenzothiazole, 5-phenylbenzothiazole, 6-methoxybenzothiazole, 4-ethoxybenzothiazole, 5
-hydroxybenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dimethoxybenzothiazole, etc.), naphthothiazoles (α naphthothiazole, β
-naphthothiazole, etc.), penzoselenazole (penzoselenazole, 5-chloropenzoselenazole, 6
-methylbenzoselenazole, 6-methoxybenzoselenazole, etc.), naphthoselenazole (α-naphthoselenazole, β-naphthoselenazole, etc.), penzoxazole (benzoxazole, 5-methylbenzoxazole, 5- Phenylbenzoxazole, 6-
methoxybenzoxazole), naphthoxazole (α-naphthoxazole, β-naphthoxazole)
, imidazoles (imidazole, penzimidazole, etc.), isoindoles (3,3-dimethylindolenine, etc.), quinolines (quinoline, isoquinoline),
Diazole M (I. 3.4-oxadiazole, 1,3.4-thiadiazole, 1.3.4-selenadiazole, etc.), triazoles, pyrazine, quinoxaline, S-}riazine, phenanthridine, etc. can be mentioned.

Y represents a group of nonmetallic atoms necessary to form a ring,
For example, a ring with the following structure is formed.

R is an alkyl group commonly known in cyanine dyes, a saturated or unsaturated linear or branched alkyl group having 1 or more carbon atoms (e.g., methyl group, ethyl group, probyl group, etc.) or a substituted alkyl group ( For example, 2-hydroxyenal group, 2-methoxyethyl group, carboxyzetyl group, 2-
Carboxyethyl group, 3-carboxybropyl group, 2-
sulfoethyl group, 3-sulfophene group, 2-carpomethoxyethyl group, benzyl group, phenethyl group, p-sulfophenethyl group, p-carboxyphenethyl group, vinylmethyl group, etc.). R2 and R each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a halogen atom. And n represents an integer from 0 to 4. The sensitizer represented by the general formula (I) used in the present invention can be synthesized using a known method. A typical synthesis method is, for example, "The Theory of Photography" by T. H. James.
．． James 'tJA''The Theory of
Photographic Process” 4th
Edition, Macmillan Co. ．． New York
(1977)) and “The Cyanine Soybean and Related Paper” by F.M. Hammer.
Comb Bounds (F. M. Hanger: ii' ”
The Cyanine Dyes and Rel
atedCompounds' John Wiley
& Sons Co. , New York (I96
4)).

Specific examples of the sensitizer of general formula (I) used in the present invention are shown below. Is it expressed as? ll■CHI C}IzCHzSO1-Na" C}13 CH2CH3 CH3 CH3 CL CI. ClhCH3 ■ CB! ! CI! Clh CH3 The photocrosslinkable photoconductive composition of the present invention has -i represented by formula (I) In addition to the exacerbating agent, other exacerbating agents may be further contained. In this case, an exacerbating agent that further increases the photocrosslinking rate when used in combination with the exacerbating agent compound represented by general formula (I) is selected. Specific examples of such sensitizers include benzoin, benzoin methyl ether, benzoin ethyl ether, 2,2-dimethoxy-2-phenylacetophenone, 9-fluorenone, 2-chloro9-
Fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-promo-9-anthrone, 2-ethyl-
9-anthrone, 9,10-anthraquinone, 2-ethyl-9.10-anthraquinone, 2-t-butyl9.
10-anthraquinone, 2,6-dichloro-9.10-
anthraquinone, xanthone, 2-methylxanthone,
2-methoxyxanthone, dibenzalacetone, p-(
Examples include dimethylamino) phenylstyryl ketone, p-(dimethylamino)phenyl'p-methylstyryl ketone, penzophenone, p-<dimethylamino)penzophenone (Michler's ketone), p-(diethylamino)penzophenone, benzanthrone, and the like. .

Furthermore, thioxanthone derivatives such as 2-chlorothioxanthone, 2-isoprobylthioxanthone, dimethylthioxanthone, etc., German Patent No. 3018891 and German Patent No. 3117568, and European Patent No. 337
It is preferable to use substituted thioxanthones such as those listed in Q in British Patent No. 2075506. The amount of the sensitizer that can be added in combination with the sensitizer of general formula (I) is 0.000% of the total composition. It is preferably 5 to 20%, more preferably 3 to 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, acrylic acid alkyl ester and a copolymer of at least one of the following monomers: acrylonitrile, hinyl chloride, styrene, butadienate, and polyamide. , methylcellulose, polyvinyl formal, polyvinyl butyral, methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, diazo resins, and the like.

It is preferable to further add a thermal polymerization inhibitor to the other photogenic compositions mentioned above, such as hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, penzoquinone,
．． 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 for coloring purposes, such as methylene blue, crystal bioleft, rhodamine B1 fuchsin, auramine, azo dyes, anthraquinone dyes, titanium oxide, carbon blank, iron oxide, cyanine pigments, azo pigments etc. may be added.

The photolactic 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 monoethyl ether, 3- Examples include methoxypropyl acetate, 3-methoxypropylacetate, ethyl acetate, and butyl acetate. These solvents may be used alone or in combination.

The photolactic composition of the present invention is suitable as a photosensitive layer of a photolactic 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.

In the case of manufacturing a photoreflective lithographic printing plate, the coating amount is -M plus 0.00% as a solid content. 1-1 0. A value of 0 g/g is appropriate, and a value of 0.0 g is particularly preferred. 5-5. 0 g/
It is g.

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, a more detailed explanation will be given based on an example.

Examples 1-6, Comparative Examples 1-3 Thickness 0. The surface of a 30 mrn aluminum plate was grained using a nylon brush and a water suspension of 400 mesh pumice stone, and then thoroughly washed with water.

After etching by immersing it in 10% sodium hydroxide at 70° C. for 60 seconds, it was washed with running water, neutralized with 20% L+NO, and washed with water. This was heated to 160°C in a 1% nitric acid aqueous solution using a sinusoidal alternating waveform current under the condition of Va = 12.7V.
Electrolytic surface roughening treatment was performed with an amount of electricity of coulomb/dn{.

When the surface roughness was measured, it was 0.6μ (Ra display)
Met. Followed by 30% H! So. After immersing in an aqueous solution and desmutting at 55°C for 2 minutes, 20% H.
P.O. Anodizing was carried out in an aqueous solution at a current density of 2 A/d m' for 5 minutes so that the amount of anodized film was 1.2 g/m'. Thereafter, it was immersed in a 2.5% sodium silicate aqueous solution at 70° C. for 1 minute, washed with water, and dried.

The following photosensitive solution containing the sensitizer shown in Table 1 was applied to the obtained aluminum plate using a spin coater and dried at 100°C for 2 minutes to form a photosensitive layer with a dry film thickness of about 1.5μ. , a photosensitive plate was created.

(Photosensitive solution) 0.5 g of sensitizer shown in Table 1 20 g of methyl ethyl ketone
Ta no nore
2g Brobylene glycol monomethyl ether 2
For 8g exposure (as a normal method), a vacuum printing frame device was used, a step wedge (density step 0.15, number of density steps 15) was placed on the photosensitive plate, and a 2κW ultra-high pressure mercury lamp was used for 16 seconds. After exposure, development was performed using a developer having the following formulation.

In addition, in order to examine the photosensitivity to long wavelengths, a 500 watt xenon lamp was used and a bandpass filter B. P
, 43 (transmission near 430 nm is maximum)
The film was exposed to light for 10 minutes using a step wedge, and developed.

(Developer) Benzyl alcohol 4.5g Table 1 Triethanolamine 1.5g Monoethanolamine O. lg Sodium sulfite 0.3g Pure water
The highest step number of the step wedge corresponding to the 100g image is taken as the sensitivity of the sample.
Shown in the table. The higher the number of stages, the higher the sensitivity.

For comparison, instead of the compound of the present invention as a sensitizer, 2
．． Comparative Examples (I) and (2) were those to which 3-dimethylthioxanthone and Michler's ketone were added, and Comparative Example (3) was to no additives, and their sensitivities are also shown in Table 1.

As shown in Table 1, when the aggravating agent represented by the general formula (I) of the present invention was used, the exacerbation level was higher even in response to longer wavelengths than in Comparative Examples 1 to 3. Ta.

Examples 7 to 9 Comparative Examples 4 to 6 Compounds shown in Table 2 below were used as exacerbating agents represented by general formula (I) of the present invention, and 7-methylthioxanthone-3-carvone was used as an exacerbating agent other than the present invention. Ethyl acid 0
．． A coating solution was prepared using the same formulation as in Examples 1 to 6, except that 3 g was added to each, and a photosensitive plate was prepared using the same method, and exposed and developed. The highest number of steps of the step wedge corresponding to the image that appeared is shown in Table 2 as the degree of perturbation of the sample.

Comparative Examples (4) and (5) were also prepared using Michler's ketone and penzophenone instead of the stimulant of the present invention.
) and a comparative example (6) in which ethyl 7-methylthioxanthone-3-carboxylate was used alone, and their sensitivities are also shown in Table 2.

As shown in Table 2, the degree of sensitization of Comparative Example (6) using ethyl 7-methylthioxanthone-3-carboxylate alone, which is a conventional stimulant, and that of other conventional sensitizers Compared to the sensitivity of comparative examples (4) and (5) when used in combination with
It can be seen that when the sensitizer represented by the one-shell formula (I) of the present invention is used in combination with a conventional sensitizer, the sensitivity is extremely high.

Example 10 Instead of the anodic oxidation method used as the method for producing aluminum plates in Examples 1 to 6, a current density of 2 A/2 in a 20% sulfuric acid aqueous solution was used.
dm'' to a thickness of 2.0 g/m for 2 minutes, and silicate treatment with sodium silicate.

Using the obtained aluminum plate, the following photosensitive liquid was applied using a spin coating machine, and dried at 100°C for 2 minutes to form a photosensitive layer with a dry film thickness of 1.5 μm, which was used as a photosensitive film. .

(Photosensitive solution) Sensitizer for patient I 0.1 gF, salt of condensate of diazodifenyl and formaldehyde 0.05 gF
- 1 7 7 0.02g
CI PigmentBl
ue 15) 10% plasticizer ¥'! ．． ? Fl
1. O g methyl ethyl ketone 20
g meku no nore
5 g ethylene glycol monomethyl ether + L
30 g exposure and development were performed in the same manner as in Examples 1-6.

The maximum number of steps of the step wedge was 9 steps.

〔Effect of the invention〕

The photosensitive composition of the present invention has high sensitivity and is also sensitive to long wavelength light, so it has excellent workability in plate making, etc., and has good selectivity for various light sources.

Claims (1)

[Scope of Claims] Photosensitivity characterized by containing (a) a photocrosslinkable polymer having a maleimide group in its side chain; and (b) a sensitizer represented by the following general formula (I). Composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, Z indicates a group of nonmetallic atoms necessary to form a heterocyclic nucleus containing nitrogen, and Y indicates a group of nonmetallic atoms necessary to form a ring. Represents a necessary nonmetallic atom group, R_1 represents an alkyl group or a substituted alkyl group, R_2 and R_3 each represent a hydrogen atom,
It represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a halogen atom, and n represents an integer from 0 to 4. )