JPS59113433A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition having superior adhesive strength to metal and suitable especially for use in the formation of the photosensitive layer of a printing plate by adding a photosensitive resin having OH at a specified rate prepd. by reacting dicarboxylic acid having a photosensitive unsatd. double adjacent to an aromatic ring with polyol. CONSTITUTION:Dicarboxylic acid or its ester represented by formula I or II(where each of R1 and R1' is H, 1-4C alkyl, 1-4C alkoxy, halogen or NO2, R2 is 2-4C alkylene, (m) is 1-5, and each of (n) and n' is 1-4) is reacted with polyol to prepare photosensitive polyester resin having 0.3-2 OH groups per one dicarboxylic acid unit on the average and 3,000-70,000 weight average mol.wt. A photosensitive composition contg. the polyester resin is applied to a metallic substrate and dried to form a photosensitive layer. The resulting original plate for a printing plate is imagewise exposed, and the unexposed parts are removed to manufacture a printing plate having superior adhesive strength to its base metal.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive resin composition containing a photosensitive polyester resin with improved adhesion to metal as a film-forming component, and is particularly useful as a material for a layer in the printing plate. The present invention relates to a composition.

Is ro] a unique kojiki reaction? To this end, various photosensitive resins have been studied in which a cinnamic acid skeleton is introduced into the side chain or chain rC of the molecule. Examples include sulpolyvinyl alcohol-polyepichlorohydrin, polystyrene, acrylic resin, epoxy resin, and polyesters and polyamides having a cinnamic acid skeleton in the main chain, some of which have been put into practical use. Examples include polycinnamic acid vinyl ester produced by the reaction of polyvinyl alcohol and cinnamate chloride, and polyester produced by the condensation of diethyl phenylene diacrylate and 1,4-di-β-hydroxydicyclohexane. is used as an image forming material for printing plates, LSI devices, etc.

Among photodimerizable photosensitive resins such as those mentioned above, photosensitive polyester resins having a cinnamic acid skeleton in the molecular structure left behind by the condensation of phenylene diacrylic acid or its alkyl ester with glycol are relatively popular. It has a high photosensitivity, but on the other hand, it has the disadvantage of poor adhesion to metals. For example, a bath solution containing this type of resin is applied onto an aluminum plate whose surface has been polished by a physical, chemical or electrochemical method, and where the surface has been further anodized, and then dried. When a plate) is produced, the resin film adheres well to an aluminum plate that has been polished and anodized using special methods and conditions, but it does not adhere well to aluminum plates that have been polished and anodized using special methods and conditions. Unfortunately, the film does not adhere well to surface-treated aluminum plates. For this reason, the 28th edition made using the photosensitive polyester resin as described above,
It has the disadvantage that the skin in the image area often peels off due to the action of the developer during development.

Therefore, an object of the present invention is to provide a photosensitive resin composition that has improved adhesion to metals, particularly to aluminum plates used as substrates for printing plates. It is in.

Such an object of the present invention is to combine a dicarboxylic acid component containing a dicarboxylic acid having a photosensitive unsaturated double bond adjacent to an aromatic nucleus (hereinafter referred to as photosensitive unsaturated dicarboxylic acid) or an ester derivative thereof and a polyhydric alcohol component. The average number of dicarboxylic acid units obtained by the reaction is 0.
It is coupled with a photosensitive resin composition containing a photosensitive polyester resin having 6 to 2 hydroxyl groups as a skin restoration component.

Examples of photosensitive unsaturated dicarboxylic acids used in the invention include dicarboxylic acids represented by the following general formulas (11 to (7)), and ester derivatives of these dicarboxylic acids include Dimethyl ester, diethyl ester, and similar alkyl esters;
Di(alkylene glycol) such as di(ethylene glycol) ester and di(propylene glycol) ester
Can frost esters, etc.

(R1)m...(4) (In the above general formulas (1) to (7), R1 and R are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxyl group having 1 to 4 carbon atoms. represents a group, a halogen atom or a nitro group,
R2 represents an alkylene group having 2 to 4 carbon atoms, and m is 1 to 4.
represents an integer of 5, and h and n' each represent an integer of 1 to 4. ) Suitable examples of the above dicarboxylic acids or ester derivatives thereof include p-phenylene diacryl f9, m-phenylene diacryl e, 2,5-dimethoxy-p-phenylene diacryl 1i, 2-=) rho p-phenylene diacryl Acid, α,α′-dinitro p-phenylene diacrylic acid, α,α′-dimethyl-p-phenylene diacrylic acid, p-carboxycinnamic acid, cinnamylidenemalone 4
Bis(p-KatsuraFIWji) diethylene glycol ether, bisCP-carboxybenzal)zoclohexibunone, bis<p-carboxybenzal)cyclopentanone-p, p'-chalcone dicarboxylic acid, 5.5'-p
- Dicarboxylic acids such as phenylene dipentadienoic acid or hasonoester derivatives can be mentioned.As the dicarboxylic branch component, other polyhydric carboxylic acids or derivatives thereof are used in combination with the above photosensitive unsaturated dicarboxylic acids or ester derivatives thereof. Such compounds can be,
Succinic acid, adipic acid, azelaic acid, sepatic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, 5 - Dicarboxylic acids such as sodium sulfoisophthalic acid or its anhydrides or ester derivatives thereof can be used.

However, the use of large amounts of these other dicarboxylic acids or their derivatives should be avoided as it will cause a decrease in the photosensitivity of the resin. It is desirable that the amount of the ester derivative used be 60 to 100 mol% of the total dicarboxylic acid component.

On the other hand, as the polyhydric alcohol component, various types can be used without any particular restrictions, such as ethylene glycol, gelatin glycol, triethylene glycol, propylene glycol, diglobylene glycol, polyethylene glycol, holiflopylene glycol, Neopentyl glycol, 1.5-phthylene gelicol, 1.6
-hexanediol, 2-butene-1,4-diol,
2. ．． 2.4-Trimethyl-1,3-bentanediol% 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexane dimetatool, hydrogenated bisphenol A5 hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A, bispheno- /L/A propylene oxide adduct, bisphenol F ethylene oxide adduct, bisphenol F propylene oxide adduct, dihydric alcohol such as tricyclodecane dimetatool: 6-methylpentane-1,3,5-triol , trimethylolpropane, trimethylolethane, glycerin, diglycerin, pentaerythritol,
Alcohols having a valence of 6 or more such as dipentaerythritol and nrubitol can be used.

When reacting the polyhydric carboxylic acid component with the polyhydric alcohol component, the acidic acid is , select the mixing ratio of alcohol components. If the number of hydroxyl groups per polyvalent carboxylic acid unit is less than the average o.3, it is difficult to obtain a resin with sufficient density and thinness for metals, and if it is more than the average number of hydroxyl groups, the printing plate's sensitivity f, It is difficult to obtain a resin with sufficient ink receptivity (liposensitivity) necessary for use in a layer. The resin has no particular restrictions on molecular weight, but when used in the photosensitive layer of a printing plate, it has a molecular weight of 3,000 to 70.0'.
Those having a weight average molecular weight of OD are preferred.

Such photosensitive polyester (sub) resins can be produced by means known in the field of ordinary polyester synthesis, for example, "Lesson 1 Course on Polymerization Reactions 9, Polycondensation" by Ogata, published by Kagaku Dojinsha, or by US patents. It can be easily produced by the method described in No. 6.<S22.320.

That is, after the polyhydric carboxylic acid component and the polyhydric alcohol component are reacted (esterification reaction or transesterification reaction) in the presence of a catalyst and an inhibitor that are necessarily added, the amount of water in the reactor is gradually increased. It can be produced by reducing the pressure and distilling off excess glycol.

The reaction temperature is preferably 150 to 250C, and the reduced pressure is preferably 3 HIM) 1 g or less. As a catalyst,
For example, dibutyltin oxide, dibutyltin laurate,
Dibutyltin diacetate. Organometallic compounds such as lithium ethoxide, tetraisopropyl titanate, tetrabutoxytitanate; inorganic metal compounds such as titanium dioxide, zinc acetate, antimony trioxide, calcium oxide, etc. can be used, especially organic metal compounds such as dibutyltin oxide, dibutyltin laurate, etc. Tin compounds are preferred. The amount used is preferably 50 to 10,000 ppm as a metal component.

Inhibitors are used to minimize crosslinking and branching of photosensitive unsaturated double bonds that tend to occur during polycondensation reactions, and include, for example, phenothiazine, hydroquinone, hydroquinone monomethyl ether, 2
．． 6-di-tert-butyl-p-cresol, p-benzoquinone, etc. can be used. The amount used is 50 to 2,
000 ppm is preferred.

The photosensitive resin composition of the present invention is prepared by dissolving the photosensitive polyester resin produced as described above in an appropriate solvent, and optionally contains a sensitizer, pigment, dye, plasticizer, etc. Additives can be added.

Suitable solvents vary depending on the composition and molecular weight of the resin, but
Usually, chlorinated solvents such as methylene chloride, chloroform, trichloroethane, trichloroethylene, chlorobenzene, cyclobenzene, carbon tetrachloride; alcohols such as tetrahydrofurfuryl alcohol and benzyl alcohol;
P) Ether solvents such as lahydrofuran and dioxane Glycol monoalkyl ether solvents such as nigericol monomethyl ether and glycol monoethyl ether Ester thread solvents such as nigericol methyl ether acetate, glycol ethyl ether acetate, and ethyl acetate Solvent: methyl ethyl ketone , methyl isobutyl ketone, cyclohexanone, 4-methyl-4-methoxy-
Examples include ketone thread solvents such as 2-pentanone, nitrogen-containing compounds such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and nitrobenzene, and the above solvents can be used alone or in combination of two or more.

Any sensitizer that can be used in this field may be used, including benzophenone derivatives, benzanthrone derivatives, naphthothiazoline derivatives, aromatic carboxyl compounds such as quinones, aromatic nitro compounds, or bi-IJ. IJumo, Thiapyrylium salts, etc. can be used. Examples of such sensitizers include Michler's ketone, diethylamine ethylbenzophenone, benzanthrone, (3-methyl-1°3-diaza-1,9-benz)anthrone picramide, and 2-dibenzoylmethylene-3-
Methylnaphthothiazoline, 2-benzoylmethylene-1
-Methylnaphthothiazoline, 1,8-dimethoxyanthraquinone, 1,2-benzanthraquinone, 5-nitroacenaphthene, 2-nitrofluorene, 2,7-sinitrofluorene, 1-nitronaphthalene, 1,5-dinitronaphthalene, 2.4.6-)liphenylthiapyrylium verchlorate, 2.6-bis(p-ethoxyphenyl)-4-(p-n-amyloxyphenyl)-thiavirylium verchlorate, and the like.

The photosensitive resin composition of the present invention is formulated to have an appropriate viscosity so that it can be applied to conventional coating techniques,
The coating is applied to the support by a well-known coating method such as dip coating, curtain coating, roll coating, spray coating, air knife coating, doctor knife coating, spinner coating, etc.

Specific examples of the material to be coated include aluminum plates, zinc plates, copper plates, stainless steel plates, other metal plates, and composite materials in which a metal layer is provided on a synthetic resin film by techniques such as vacuum deposition and lamination.

After coating, if the coating solution is dried and solidified by a well-known method, a printing original plate having a photosensitive layer provided on a support can be obtained. The photosensitive layer of this printing original plate is subjected to imagewise exposure using a negative image to harden and insolubilize the exposed portions of the photosensitive layer, and then developed to remove the unexposed portions to form a corresponding image on the support. can be done.

Suitable light sources used for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, lasers, and the like.

As described above, the photosensitive resin composition of the present invention is extremely effective for forming the photosensitive layer of a printing plate, but the use of the composite acid of the present invention is not necessarily limited to the photosensitive layer of a printing plate. For example, it can also be used as a photoresist for various types of microfabrication.

Hereinafter, the present invention will be specifically explained using examples, but the present invention is not limited to the following examples as long as it does not exceed the purpose of reducing warpage.

Synthesis Example 1 Diethyl-p-phenylene diacrylate 274.9 (
1,0 mol), 3-methylpentane-1,3,5-)liol 161,9 (1,2 mol), 5 g of dibutyltin oxide and phenothiazine D, 5.9 in a stirrer,
The mixture was charged into a reactor equipped with an nitrogen inlet tube, a thermometer, and a dripping tube, stirred under a nitrogen atmosphere, and heated to 180C to start the reaction. After 6 hours, 21 additional portions of dibutyltin oxide were added, and the reaction was further continued for 6 hours. Thereafter, the pressure inside the reactor was gradually reduced at the same temperature to make it 1jI-rich Hf, and the dripping liquid was removed under this reduced pressure over 2 hours.

Thus, the intrinsic viscosity is 0.18 (tetrahydrofuran m??
! , 25C), Tf46C, weight average molecular weight 16,00
A photosensitive polyester commercial resin (N) having approximately one pendant hydroxyl group per one phenylene diacrylic acid unit with a molecular weight distribution dispersity of 6.4 was obtained.

Synthesis Example 2 Diethyl-p-phenylene diacryle) 274.9 (
1,0 mol), 6-methylpentane-1,3,5-)diol 6F, 0,10.5 mol), 1,4-di-β-hydroxyethoxycyclohexane 142 g (0,7 mol), dibutyl Tin oxide 5. ! I' and 0.5 g of phenothiazine were charged into a reactor, and the same operation as in Example fi1'1 was carried out. Thus, the intrinsic viscosity is 0.2[]
(] Detrahydrofuran solution 25C), T#43C, weight average molecule H1s, 5oO5 molecular weight distribution, photosensitive with approximately 0.5 pendant hydroxyl groups per phenylene diacrylic acid unit with dispersity of 6.2. Polynisder resin (Bl) was obtained.

Synthesis Example 6 Diethyl-p-phenylene diacrylate) 2749 (1
0 mol), trimethylolpronokone 134. ! i'(
1.0 mol), ethylene glycol 6411.0 mol)
, 5 g of dibutyltin oxide and 0.0 g of phenothiazine.
5 g was charged into the reactor of Example 1 and Mukaho, stirred under a nitrogen atmosphere, and heated to 180C to start the reaction. After 6 hours, after the dropwise amount of ethanol stopped, the pressure inside the reactor was gradually reduced to 1 s+mH at the same temperature, and the dropped liquid was removed. After 6 hours, the dripping stopped and 64.9 grams of ethylene glycol was recovered. Thus, the hydroxyl value is 172 K.
OH1l+1g/,! A photosensitive polyester resin (C1) having about one hydroxyl group per one phenylene diacrylic acid unit of i+ was obtained.

Synthesis Example 4 Diethyl-p-phenylene diac IJL'-t271 (
1,0 mol), pentaerythritol 102,10.7
5 mol), 1,4-di-β-hydroxycyclohexane 91.8, 1O, 45 mol), dibutyltin oxide 5
g and 0.5.9 g of phenothiazine were charged into the reactor, and the same operation as in Example 1 was performed. Thus hydroxyl group 1
Song 261 KOHil? /! i. A photosensitive polyester resin (Dl) having about 1.5 hydroxyl groups per 1 phenylene diacrylic acid unit was obtained.

Synthesis Example 5 Diethyl-2-nitro-p-phenylene diacrylate (31911.0 mol), 6-methylpentane-1,3,
5-triol 161.9 (1.2 mol), dibutyltin oxide 5y, and phenothiazine 0.5 g were charged, and the same operation as in Example 1 was carried out, and the weight average molecular weight was 13,500, and the molecular weight distribution dispersity was obtained. A photosensitive polyester resin (El) having approximately one pendant hydroxyl group per one 2-nitro-phenylene diacrylic acid unit of 39 was obtained.

Synthesis Example 6 Diethyl-p-carboxycinnamate 248.9 (1
,0 mol), 6-methylpentane-1,3,5-triol 161 g (1,2 mol), dibutyltin oxide 5
y and 0.5 g of phenothiazine into the reactor,
The same procedure as in Example 1 and li1 was carried out. Thus, p-
A photosensitive polyester resin CF+ having approximately one pendant hydroxyl group per carboxycinnamic acid unit was obtained.

Synthesis Example 7 Diethyl ester of bis(o-cinnamic acid) diethylene glycol ether 454.9 (1,0 mol), 6-methylpentane-1,3,5-) diol 134.11.0
mol), ethylene glycol 32 g (0.5 mol), dibutyltin oxide 5I and phenothiazine 0.5I
was charged into the reactor, and the same operation as in Example 6 was performed. Thus, the N weight average molecular weight is 19. A photosensitive polyester resin (Gl
I got it.

Synthesis Example 8 Diethyl-p-phenylene diacrylate 274M (1
0), 2,2,4-)dimethylbentane-1,6-
The same procedure as in Example 1 was carried out, except that 17511.2 mol of diol (17511.2 mol), dibutyltin oxide 5I and 0.5 g of phenothiazine were charged into the reactor and the reaction temperature was set at 210C. Thus, the weight average molecular weight of 14,000
A photosensitive polyester resin (Hl) having a terminal hydroxyl group of about 0.1 per phenylene diacrylic acid unit with a molecular weight distribution dispersity of 6.6 was obtained.

Examples 1 to 7 Take 4g of each of the above photosensitive polyester resins, d9-5
A photosensitive resin composition was prepared in which -nitro-acenaphthene was converted into 96.9% dichloroethane. This composition,
A photosensitive plate was prepared by coating a grained aluminum plate ("printing aluminum plate", manufactured by Dainippon Ink and Chemicals) with a whirler to a thickness of 1.5 μm and drying.

A step wedge with a step difference of 0.15 was brought into close contact with the thus obtained photosensitive plate, and the photosensitive plate was exposed for 60 seconds using a metal halide lamp with an output of 1 level, which was placed 1 rrL away from the step wedge. Thereafter, this photosensitive plate was developed with a mixed solution of γ-butyrolactone and 85% phosphoric acid (98/2 volume ratio). The highest number of unoxidized steps was defined as photosensitivity. In addition, the adhesion of the film to the aluminum plate was determined by the presence or absence of peeling of the image area film during development. The above results are shown in the table below.

Claims (1)

[Claims] 1. One dicarboxylic acid unit obtained by reacting a polyhydric alcohol component with a dicarboxylic acid component containing a dicarboxylic acid or its ester derivative having a photosensitive unsaturated double bond adjacent to an aromatic nucleus. 1. A photosensitive resin composition comprising a photosensitive polyester resin having an average of 0.3 to 2 hydroxyl groups in film form #:#:min. 2. A dicarboxylic acid or its ester derivative having a photosensitive unsaturated double bond adjacent to an aromatic nucleus has the following general formula (1
The composition according to claim 1, which is a dicarboxylic acid represented by (7) or an ester derivative thereof. (R1)n...(4) In the above general formulas (1) to (7), R1 and A are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. , represents a halogen atom or a nitro group, R
7 represents an alkylene group having 2 to 4 carbon atoms, m is 1 to 5
n and n' each represent an integer from 1 to 4. 6. The use of a dicarboxylic acid or its ester derivative having a photosensitive unsaturated double bond adjacent to an aromatic nucleus is used in an amount of 60 to 100 mol% of the total dicarboxylic acid component as described in claim 1 or 2. Composition of. 4 The weight average molecular weight of the photosensitive polyester resin is 3.0
00 to 70,000.