JPS63116148A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To improve the plate wear of a lithographic printing plate by incorporating a high-molecular o-naphthoquinone diazide compd. into a titled compsn. CONSTITUTION:The high molecular compd. consisting of a structural unit -O-A- O-CH2-CH(-OX)-CH2- and structural unit -Y-B-Y-CH2-CH(-OX)-CH2- and having 500-500,000mol.wt. is added into the compsn. In the above-mentioned units, A, B denote (substd.)alkylene, (substd.)arylene, etc.; X denotes H, naphthoquinone-1,2-diazide-5-sulfonyl, etc.; Y denotes O, S. The high molecular compd. consisting of the structural units (a), (b) and (c) mol of the formulas I, II and III where c/(a+b+c)>=0.01 is preferably used as the above-mentioned compd. In the formulas, R' denotes bivalent and higher valent (unsatd.) hydrocarbon, etc., X denotes naphthoquinone-1,2-diazide-5-sulfonyl, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a photosensitive composition suitable for manufacturing lithographic printing plates, IC circuits and photomasks.

More specifically, the present invention relates to a photosensitive composition containing a polymeric 0-naphthoquinone diazide compound.

[Conventional technology]

A photosensitive composition composed of an 0-naphthoquinone diazide compound and a novolak type phenol resin has been used industrially as an extremely excellent photosensitive composition in the production of lithographic printing plates and as a photoresist.

[Problems to be solved by the invention] However, due to the nature of the novolac type phenolic resin used as the main component, it has poor adhesion to the substrate, brittle film, poor coating properties, poor abrasion resistance, and lithographic printing plates. There were issues that needed to be improved, such as insufficient printing durability when used for printing, and there were limits to its application.

In order to solve this problem, various polymer compounds have been investigated as binders. For example, special public relations
Although the polyhydroxystyrene or hydroxystyrene copolymer described in Japanese Patent No. 1050 did have improved film properties, it had the drawback of poor abrasion resistance.

Therefore, an object of the present invention is to provide a photosensitive composition that provides a lithographic printing plate with high printing durability.

Another object of the present invention is to provide a photosensitive composition that has good adhesion to a substrate, provides a flexible film, and has excellent coating properties.

As a result of various studies, the present inventors have discovered a photosensitive composition containing a polymeric naphthoquinonediazide compound useful for achieving the above object.

[Means for solving problems]

The present invention provides molecular weight 500-500.
000 polymer compounds (A and B are the same or different alkylene groups, substituted alkylene groups, alkenylene groups, substituted alkenylene groups, arylene groups, substituted arylene groups or groups, alkenylene groups, substituted alkenylene groups, arylene groups, represents a substituted arylene group; X is a hydrogen atom, naphthoquinone-1゜2-
diazido-5-sulfonyl group, naphthoquinone-1,2-
diazide-4-sulfonyl group or represents an unsubstituted hydrocarbon group, a substituted or unsubstituted unsaturated hydrocarbon group, a substituted or unsubstituted aromatic group, where l is an integer of 1 or more), is a group, and 1 equivalent or more of all X is a naphthoquinone-1゜2-diazido-5-sulfonyl group or a naphthoquinone-1,2-diazido-4-sulfonyl group;
Y is an oxygen or sulfur atom).

The polymer compound contained in the photosensitive composition of the present invention is more preferably a structural unit (a mole) represented by ! (However, R' is the same as defined above) Structural units (b moles) represented by (However, X is naphthoquinone-1,2-diazide-5-
Sulfonyl group or naphthoquinone-1,2-diazide-4
- Structural unit represented by (sulfonyl group) (C moles)
It consists of □≧0. O1 polymer compound with a molecular weight of 500 to a+b+C 500,000 (however, a and b are each an integer of 0 or more, and C is an integer of 1 or more)
It is.

A and B in the polymer compound contained in the photosensitive composition of the present invention are preferably the groups shown below.

Among the above groups, numbers 1, 2, 3 (n = 1 to 4), 4
．． The groups 5.6.10.11.13 (n=1-3), 14 and 15 are more preferred. In addition, the groups numbered 13 to 18 are
It is particularly preferably used when Y is an oxygen atom.

can be exemplified by the groups shown below.

Among the above groups, numbers 1 (n=1-3), 3 and 4 are particularly preferred.

Further, the number of X in the polymer compound contained in the photosensitive composition of the present invention is 1 or more per 100 X in one molecule, preferably 1 to 100 are naphthoquinone-1°2-diazide-5-
Sulfonyl group or naphthoquinone-1,2-diazide-4
- is a sulfonyl group.

Furthermore, the molecular weight of the polymer compound contained in the photosensitive composition of the present invention is 500 to 500,000, preferably 1.0.
00-100. 'OOO. Those with a molecular weight of less than 500 have little effect on improving printing durability, and those with a molecular weight of more than 500,000 have problems such as poor solvent solubility and are therefore unsuitable.

The polymer compound contained in the photosensitive composition of the present invention is a polymer compound obtained by reacting a compound having two active hydrogens in the molecule with a divalent glycidyl compound in the presence of a base. It is obtained by reacting with 1,2-naphthoquinone-2-diazido-4-sulfonyl chloride or 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride and an acid anhydride.

Compounds with active hydrogen during polymer synthesis include:
Bisphenol A1 Bisphenol B14.4'-Sulfonyldiphenol, bisphenol F, tetrachlorobisphenol A1 Tetrabromobisphenol A1 Catechol, divalent phenols such as resorcinol, ■, 2
-benzenedithiol, 1,3-benzenedithiol,
Dithiols such as ethanedithiol, dihydric alcohols such as ethylene glycol and diethylene glycol, terephthalic acid, phthalic acid, maleic acid, fumaric acid, malotic acid,
Examples include dibasic acids such as succinic acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid, and glutaric acid. Examples of the divalent glycidyl compound include glycidyl compounds of the above-mentioned active hydrogen-containing compounds. As the base, metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide, and amines such as triethylamine, tri-n-butylamine, and pyridine can be used.

More specifically, the reaction between a compound having active hydrogen and a divalent glycidyl compound can be carried out without a solvent or in a solvent such as an ether such as 1°4-dioxane or tetrahydrofuran, or a ketone such as methyl isobutyl ketone or methyl ethyl ketone. The reaction can be carried out at a temperature ranging from room temperature to 200° C. with stirring. Next, the obtained polymer and naphthoquinone-1,2-diazide-5-sulfonyl chloride or naphthoquinone-1,2-diazide-4-sulfonyl chloride were mixed in methylene chloride and in the presence of a base such as 4-dimethylaminopyridine or pyridine. A diazide group is introduced by reacting in a halogenated solvent such as chloroform at room temperature. Further, if necessary, the obtained polymer is mixed with maleic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, or naphthalene tetra in a solvent such as tetrahydrofuran, dioxane, or DMF in the presence of a base such as dimethylaminopyridine or pyridine. It can also be reacted with acid anhydrides such as carboxylic anhydrides.

Next, typical synthesis examples of the polymer compound in the present invention will be shown, but the present invention is not limited to these examples in any way.

Synthesis Example 1 Commercially available resin with repeating unit Epicor)-1009 (
Manufactured by Yuka Shell Co., Ltd., M, = 3800) 56.80g (0,
20 equivalents) and naphthoquinone-1゜2-diazide-5-
Dissolve 53.76 g (0.20 mol) of sulfonyl chloride in 200 methylene chloride, and add 1 mol of methylene chloride to this.
4-dimethylaminopyridine dissolved in 50rd 24.
44 g (0.20 mol) were added dropwise at room temperature over 30 minutes. After continued stirring for 2 hours at room temperature, the contents were reprecipitated into 2.5 ml of ethanol. The obtained polymer is T
After dissolving in HF 600mf and reprecipitating in water 71,
By drying under reduced pressure, 51.9 g of polymer was obtained. U* spectrum measurement of this polymer in THF solvent revealed that 27% of the hydroxyl groups in Epicote-1009 were converted to diazide groups.

Next, 14.17 g of this polymer (containing 0,0300 equivalents of hydroxyl groups), 22.58 g of trimellitic anhydride,
(0,120 mol) in 150 ml of tetrahydrofuran'
18.96 g of pyridine (0,24
After stirring at 50°C for 10 hours, the contents were mixed with 2.11 mol of water and 2.11 mol of methanol, O,'N! , acetic acid 0.21
It was reprecipitated in a mixed solution of

The obtained polymer was dissolved in 150 ml of THF, and 2 ml of water was added.
．． 11. 15.5 g of polymer was obtained by reprecipitating in a mixed solution of 0.71 methanol, washing with water, and drying under reduced pressure (i, = 11000). The acid value of this substance is 2.86
mj! q/g. The structural units of the obtained polymer are as follows.

U a:b:c=5:68:27 Synthesis Example 2 Polymers 14 and 17 obtained in the first step of Synthesis Example 1
Dissolve g in N,N-dimethylformamide 150-
To this was added 1.47 g of 4-dimethylaminopyridine (0,0
102 mol), triethylamine 10.91 g (0,1
0.08 mol) and 12.0 g (0.12 mol) of succinic anhydride were added, reacted at 70°C for 3 hours, and subjected to the same post-treatment as in Example 1 to give an acid value of 2.40 m12q / g V,
=5700 polymers were obtained, a:b:c=3:TO
:27.

Synthesis Example 3 Neopentyl glycol diglycidyl ether (SR-
NPC, manufactured by Hanhon Yakuhin Kogyo ■) 29.90g (0.10
0 mol), bisphenol A 22.84 g (0,10
0 mol) and triethylamine 0.40 g (0,004
1. mol) by heating at 70°C for 6 hours and then at 100°C for 4 hours. =5800 polymer was obtained. Next, a part of this polymer was purified in the same manner as in Synthesis Example 1 without purification, and naphthoquinone-1,2 to diazide-5
-Acid value 3.11 mj by reacting with sulfonyl chloride and then trimellitic anhydride! q/g.

"IW, = 17000 polymers were obtained. 1st
22% of the hydroxyl groups in the polymer obtained in the step reaction were converted to sulfonyl groups and 72% to ester groups, and the structural units are as follows.

\Ki/ Synthesis Example 4 Bisphenol A-diglycidyl ether (Nipikot-828, manufactured by Yuka Shell Co., Ltd., epoxy equivalent 188) 44
．． 80g (0,119 mol), malonic acid 12.40g
(0,119 mol) and tri-n-butylamine 0.4
■ By stirring 4g (0,00237 mol) at 85°C for 5 hours. =4700 polymers were obtained. The polymer obtained by reacting with naphthoquinone-1,2-diazide-4-sulfonyl chloride in the same manner as in Synthesis Example 1 without purifying a part of this polymer was measured by U spectrum in THF. It was found that 30% of the hydroxyl groups in the polymer obtained in the first step reaction were converted to sulfonyl groups and had the following structural units.

Synthesis Example 5 94.0 g (0.50 mol) of bisphenol A diglycidyl ether used in Synthesis Example 3 and 61.0 g (0.50 mol) of 1,4-butanedithiol. Og (0.5 mol) at 100°C in the presence of 3.7 g (0.02 mol) of tri-n-butylamine.
By reacting for a period of time, a polymer with -M''=12000 was obtained.

Naphthoquinone-1,2-diazide-5-
By reacting with sulfonyl chloride and then trimellitic anhydride, the acid value was 2.85 m1q/g, 1.
It was found that 30% of the hydroxyl groups in the polymer obtained in the first stage reaction were converted to sulfonyl groups and 65% to ester groups, and had the following structural units.

In the present invention, the O-naphthoquinone diazide compound may contain the following compounds in addition to the polymer compound of the present invention. The most preferred is the ester of naphthoquinone-1,2-diazosulfonic acid chloride and pyrogallol-acetone resin described in Japanese Patent Publication No. 43-28403. Other suitable orthoquinone diazide compounds include U.S. Pat.
No. 20 and No. 3,188.210, there are esters of naphthoquinone-1,2-diazonaphthoquinone sulfonic acid chloride with phenol-formaldehyde resins. Other useful 0-naphthoquinone diazide compounds are known and reported in numerous patents. For example, JP-A No. 47-5303,
The same town No. 48-63802, the same town No. 48-63803, the same town No. 48-96575, the same town No. 49-38701, the same town No. 48-13354, the same town No. 41-11222, the same town No. 45-9610, the same town No. 49-17481 , U.S. Patent No. 2.797.213, U.S. Patent No. 3,454.400
No. 3,544,323, No. 3.573.91
No. 7, No. 3,674.495, No. 3.785.8
25, British Patent No. 1,227,602, British Patent No. 1,251.345,
German Patent No. 1,267.005, German Patent No. 1.329.888, German Patent No. 1.330.932, German Patent No. 854.8
Examples include those described in various specifications such as No. 90.

The amount of the 0-naphthoquinonediazide compound in the photosensitive composition of the present invention is 10 to 50% by weight, more preferably 2% by weight.
It is 0 to 40% by weight. In the present invention, the proportion of the polymer compound in the photosensitive composition is 90 to 5% by weight, more preferably 60 to IO% by weight.

In addition to the polymer compound of the present invention, the composition of the present invention contains known alkali-soluble compounds such as phenolic thread formaldehyde resin, cresol formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, etc. A polymer compound can be contained. Such alkali-soluble polymer compound is used in an amount of 70% by weight or less of the total composition.

The composition of the present invention may contain a cyclic acid anhydride to increase sensitivity, a printout agent to obtain a visible image immediately after exposure, a dye as an image coloring agent, and other fillers. As the cyclic acid anhydride, U.S. Patent No. 4.115,
128, phthalic anhydride,
Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3.6-nindooxy-Δ4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic acid etc. By containing these cyclic acid anhydrides in an amount of 1 to 15% by weight based on the total composition, the sensitivity can be increased up to about 3 times. Typical print-out agents for obtaining a visible image immediately after exposure include a combination of a photosensitive compound that releases an acid upon exposure and an organic dye that can form a salt. Specifically, JP-A-50-36209, JP-A-53-81
The combination of 0-naphthoquinonediazide-4-sulfonic acid halide and a salt-forming organic dye described in JP-A No. 28, JP-A-53-36223, JP-A-Sho 54-74
The combination of a trihalomethyl compound and a salt-forming organic dye described in Japanese Patent No. 728 can be mentioned. In addition to the above-mentioned salt-forming organic dyes, other dyes can also be used as image coloring agents. Suitable dyes include oil-soluble dyes and basic dyes, including salt-forming organic dyes. Specifically, oil yellow #101, oil yellow #130, oil pink #312, oil green BG, oil blue BO31 oil blue #603
, Oil Black BY1 Oil Black BS, Oil Black T-505 (manufactured by Orient Chemical Industry Co., Ltd.) Crystal Violet (CI42555), Methyl Violet (CI42535), Rhodamine B (C
I45170B), malachite green (CI4200
0), methylene blue (CI52015), etc.

The composition of the present invention is applied onto a support after being dissolved in a solvent that dissolves each of the above components. The solvent used here is
Examples include ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, toluene, and ethyl acetate, and these solvents may be used alone or in combination. The concentration (solid content) of the above components is suitably 2 to 50% by weight. The coating amount varies depending on the application, but for example, for photosensitive planographic printing plates, the solid content is generally 0.
5 to 3.0 g/m'' is preferable.As the coating amount decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate.

When producing a lithographic printing plate using the photosensitive composition of the present invention, the support may be a hydrophilized aluminum plate, such as a silicate-treated aluminum plate, an anodized aluminum plate, a grained aluminum plate, or a silicate plate. There is a coated aluminum plate, zinc plate, stainless steel plate, chrome-treated steel plate, hydrophilized plastic film and paper.

Examples of developing solutions for the photosensitive composition of the present invention include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, diphosphoric acid, Aqueous solutions of inorganic alkaline agents such as ammonium acid, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. are suitable, and their concentration is 0.1 to 10% by weight,
It is preferably added in an amount of 0.5 to 5% by weight.

Moreover, a surfactant and an organic solvent such as alcohol can be added to the alkaline aqueous solution as required.

Next, the present invention will be explained in more detail by giving Examples. All percentages in the examples below are by weight unless otherwise specified.

Examples 1 to 5 An aluminum plate with a thickness of 0.30 and a nylon brush with a thickness of 40
The surface was grained using a water suspension of 0 mesh bumiston, and then thoroughly washed with water.

After etching by immersing in 10% sodium hydroxide at 70°C for 60 seconds, washing with running water and 20% HNO.

Neutralized and washed with water. This is VA=12. Electrolytic surface roughening treatment was carried out in a 1% nitric acid aqueous solution using a sinusoidal alternating waveform current under TV conditions with an anode specific electricity amount of 160 croons/dm'. When the surface roughness was measured, it was found to be 0.6μ
(Ra display). followed by 30% H,SO
, After being immersed in an aqueous solution and desmutted at 55°C for 2 minutes,
20% ll2SO in aqueous solution, current density 2. A/drn
No. 2 was anodized to a thickness of 2.7 g/m'.

The photosensitive solutions of Examples 1.2.3.4.5 and Comparative Examples having the components shown in Table 1 were coated onto the aluminum support thus obtained using a whirler.
It was dried at 00°C for 2 minutes.

The coating amount after drying was 2.1 g/m'. Each of these photosensitive lithographic printing plates was exposed for 40 seconds using a 2 KW metallographic lamp from a distance of 1 m through a positive transparent original.

This printing plate was developed by rubbing it with a sponge impregnated with a 1% aqueous solution of sodium metasilicate (nase hydrate). This printing plate was used to print on high-quality paper using a commercially available ink using a KOR type printing machine manufactured by Heidelberg Co., Ltd., and the final number of prints was determined. Table 1 shows the results.

(Effects of the Invention) The naphthoquinonediazide-containing resin of the present invention can print more sheets than conventional resins and has excellent printing durability.

Procedural amendment 61.12.10 Showa year month day 4.7 Literary and scientific figures 7. Contents of correction The following parts of the specification are corrected as follows.

Claims (2)

[Claims] (1) Molecular weight 500-500, consisting of the structural unit shown by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and the structural units shown by ▲ There are mathematical formulas, chemical formulas, tables, etc.
000 polymer compounds (A and B are the same or different alkylene groups, substituted alkylene groups, alkenylene groups, substituted alkenylene groups, arylene groups, substituted arylene groups, or ▲ mathematical formulas, chemical formulas, tables, etc.) ▼ is an alkylene group , substituted alkylene group, alkenylene group, substituted alkenylene group, arylene group, substituted arylene group); X is a hydrogen atom, naphthoquinone-1,2-diazido-5-sulfonyl group, naphthoquinone-1, 2-diazide-4-sulfonyl group or ▲ formula,
There are chemical formulas, tables, etc. ▼ (R' represents a substituted or unsubstituted hydrocarbon group with a valence of 2 or more, a substituted or unsubstituted unsaturated hydrocarbon group, a substituted or unsubstituted aromatic group, and l is 1 or more. ), which is an integer of X100 in one molecule.
At least one per piece is naphthoquinone-1,2-diazide-5
-Sulfonyl group or naphthoquinone-1,2-diazide-
4-sulfonyl group; Y is oxygen or sulfur atom). (2) The polymer compound is a structural unit (a mole) represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R' is defined in Claim No. 1) Structural units (b moles) shown as the same as those defined in section ▲Mathematical formulas, chemical formulas, tables, etc.▼ (However, X is naphthoquinone-1,2-diazido-5-sulfonyl group or naphthoquinone-1,2 -Diazide-4-
sulfonyl group), and has a molecular weight of 500 to 5, with C/(a+b+c)≧0.01.
00,000 (provided that a and b are each an integer of 0 or more, and c is an integer of 1 or more). sexual composition.