JPS59116650A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive resin composition for a printing plate with superior photosensitivity, printing resistance and sensitivity in printing by adding polyester resin having specified bicyclo or tricyclo rings and photosensitive unsatd. double bonds each adjacent to an aromatic ring in the molecular chain as a film forming component. CONSTITUTION:A compound having >=2 substituents selected from CH2OH, OH and COOR (R is H, alkyl or the like) on >=1 ring represented by formulae I - IIIis reacted with polyol and a compound represented by one of formulae IV- VII(where each of R1 and R1' is H, 1-4C alkyl, 1-4C alkoxy, halogen or NO2, R2 is 2-4C alkylene, each of (l) and (m) is 1-5, and (n) is 1-4) to obtain photosensitive polyester resin having >=1 kind of cyclic structures represented by the formulae I -III and photosensitive unsated. double bonds each adjacent to an aromatic ring represented by one of the formulae IV-VII in the molecular chain. A photosensitive layer is formed using a photosensitive resin composition contg. the photosensitive polyester resin to obtain a printing plate with superior photosensitivity, printing resistance and sensitivity in printing.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive resin composition. Specifically, the present invention relates to a photosensitive resin composition capable of forming a printing plate layer having excellent photosensitivity, printing durability, and oil sensitivity.

A photosensitive polyester resin having a photosensitive ethylenically unsaturated double bond adjacent to an aromatic nucleus in the main button of the molecule is known as one of the typical photocrosslinkable photosensitive resins. Such resins include dicarboxylic acids such as phenylene diacrylic acid, carboxycinnamic acid, chalcone dicarboxylic acid and ethylene glycol; propylene glycol, butylene glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol,
It is obtained by condensing glycerin with a polyhydric alcohol such as trimethylolpropane. However, although the above resins obtained using polyhydric alcohols have high photosensitivity, they have the disadvantage of poor printing durability. In other words, such resins are easily swollen by petroleum-based hydrocarbon bath agents that are commonly used as activators for printing inks, and are easily abraded by frictional forces. It is difficult to produce good printing plates. As a polyhydric alcohol, it is possible to obtain a resin with high photosensitivity by using a polyether-based glycol such as polytetraethylene glycol or polyethylene glycol. It has inferior disadvantages. Therefore, printing plates obtained using such resins have insufficient ink receptivity (commonly called ink transfer).

The present inventors conducted intensive research to improve the printing durability and oil sensitivity of the previously known photosensitive polyester resin without reducing its excellent photosensitivity, and as a result, the molecular butane structure of the resin was improved. The present invention has been achieved based on the discovery that the introduction of this method is extremely effective for achieving the above-mentioned improvements.

That is, the present invention contains, as a film-forming component, a photosensitive polyester resin containing in its molecular chain at least one type of ring structure selected from the group consisting of a photosensitive unsaturated double-linked ring structure adjacent to an aromatic nucleus. This invention relates to a photosensitive resin composition.

The photosensitive ethylenically unsaturated double bond contained in the photosensitive polyester resin of the present invention can be obtained by using a dicarboxylic acid or its ester derivative containing such an unsaturated double bond as a resin raw material. You can introduce it into the button. Examples of such dicarboxylic acids or ester derivatives thereof include the following general formulas +11 to (
7) Dicarboxylic acids or their dialkyl esters such as dimethyl ester and diethyl ester;
Di(ethylene glycol) ester, di(propylene gelylcol) ester, and similar xy(alkylene glycols)
Esters etc. can be used.

(Rt)n......(4) 9- In the above general formulas (1) to (7), R and R; are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. 4 represents an alkoxyl group, a halogen atom or a nitro group,
R7 represents an alkylene group having 2 to 4 carbon atoms, and l and m
each represents an integer of 1 to 5, and n represents an integer of 1 to 4. ) Among the above dicarboxylic acids or ester derivatives thereof, specific examples of particularly preferred ones include p-phenylene diacrylic acid, m-phenylene diacrylic acid, 2,5-dimethoxy-p-phenylene diacrylic acid, 2-nitro-p −
Phenylene diacrylic acid, α,α′-dinitro p-phenylene diacrylic acid, α,α′-dimethyl-p-phenylene diacrylic acid, p-carboxycinnamic acid, cinnamylidenemalonic acid, bis(p-cinnamic acid) Dicarboxylic acids such as diethylene glycol ether, bis(p-carboxybenzal)cyclohexanone, bis(p-carboxybenzal)cyclopentanone, and p,p'-rucondicarboxylic acid or ester derivatives thereof can be mentioned.

The halo type contained in the photosensitive polyester resin of the present invention is a polyhydric alcohol having such a ring structure as a resin raw material,
7-I can be introduced into the resin molecular chain by using a polycarboxylic acid or an ester derivative thereof, a hydroxycarboxylic acid or an ester derivative thereof.

As such a polyhydric alcohol, for example, the following tricyclodecanetriol can be used. The above-mentioned polyhydric carboxylic acid or its ester derivative represents, for example, a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. ) Carboxynorbornane acetic acid or its alkyl anhydride or its alkyl ester can be used. The above-mentioned hydroxycarboxylic acid or ester derivative thereof represents an alkyl group having 1 to 12 carbon atoms. ) Hydroxynorbornane acetic acid or its alkyl ester can be used.

In the production of the photosensitive polyester resin of the present invention, other polyhydric carboxylic acids or ester derivatives thereof and other polyhydric alcohols may be used in addition to the above-mentioned raw materials to the extent that they do not impair the achievement of the objects of the present invention. You can do it. Examples of such other polyhydric carboxylic acids or ester derivatives thereof include succinic acid, adipic acid, azelaic acid, cepatic acid,
Phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, het acid, maleic acid, fumaric acid, itaconic acid, trimellitic acid, pyromellitic acid, 5- polyhydric carboxylic acids such as sodium sulfoisophthalic acid or their anhydrides or their dimethyl esters,
Alkyl esters such as diethyl ester can be used;
Examples of other polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol,
Propylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1, 3-7-f Astragalus') -r-
1,6-hexanediol, 2-butene-1,4-
diol, 2.2.4-)limethylpentane-1.3-
Diol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexane dimetatool, to cyclo*
Su7-1, 4-diol, hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F ,
Ethylene oxide adduct of hydrogenated bisphenol A, 6
-Methylpentane-1,3,5-triol, glycerin, trimethylolpropane, trimethylolethane,
Polyhydric alcohols such as pentaerythritol, diglycerin, and dipentaerythritol can be used.

Regarding the characteristics and molecular weight of the photosensitive polyester resin of the present invention,
7:I No special restrictions, but 5. ODD~120,
Those having a weight average molecular weight of 000 are preferred.

The preferred content of the photosensitive unsaturated double bond adjacent to the aromatic nucleus in the photosensitive polyester resin of the present invention is 0.5 to 5.5 mol per 1000 g of resin, and the most preferred content is The amount is between 0.7 and 4.5 mol. Sufficiently high photosensitivity can be obtained within this range.

The preferred content of filtrate contained in the photosensitive polyester resin of the present invention is 1.2 to 5.0 mol per 100 p of the resin, and the most preferred content is 0.2 to 40 mol.

It is possible to obtain sufficient printing durability and oil sensitivity within this range.

Such photosensitive polyester resins can be prepared by means known in the field of conventional polyester synthesis, such as by standing,
It can be easily produced by the method described in "Lecture on Polymerization Reactions 9, Polycondensation" written by Ogata (published by Kagaku Kojinsha) or in U.S. Patent No. 3,622,320.For example, the above-mentioned acid and After the alcohol component is made to have an excess of hydroxyl groups relative to acid or ester groups and is reacted (esterification reaction or transesterification reaction) in the presence of a reaction catalyst and a polymerization inhibitor if necessary, the pressure of the reaction system is gradually reduced to remove excess alcohol. It can be produced by distilling off the components.The reaction temperature is 150~
250C is preferable, and the reduced pressure is at the final stage of polycondensation, 3 mm) (y
The following are preferred.

The photosensitive resin composition of the present invention is generally produced by dissolving the photosensitive polyester resin described above in a vehicle. Suitable solvents vary depending on the composition and molecular weight of the resin, but generally include chlorinated solvents such as methylene chloride, chloroform, trichloroethane, trichloroethylene, chlorobenzene, dichlorobenzene, and carbon tetrachloride; tetrahydrofurfuryl alcohol, benzyl alcohol, etc. Alcohol-based im; Ether thread solvents such as tetrahydrofuran and dioxane; Glycol monoalkyl ade A-based solvents such as nigericol monomethyl ether and glycol monoethyl ether; Ester thread solvents such as glycol methyl ether acetate, glycol ethyl ether acetate, and ethyl acetate ; Ketone thread solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-methyl-4-methoxy-2-pentanone. Containing thread solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and nitrobenzene; These solvents can be used alone or in combination.

The photosensitive resin composition of the present invention may contain various components other than the above components, for example, a sensitizer,
Contains pigments, dyes, fillers, printing durability improvers, lipophilicity improvers, binding aids, etc.

Any sensitizer that can be used in this field can be used, including benzophenone derivatives, benzanthrone derivatives, naphthothiazoline derivatives, aromatic carb-5zenyl compounds such as quinones, aromatic nitro compounds, and sensitizers. Hapi I
J IJ um salt, chiahi +) +) Lamb Hanawa chicken, etc. can be used. Specific examples of these include Michler's ketone, diethylamine ethylbenzophenone, benzanthrone, (
3-Mef-1,3-diaza-1,9-benz)anthrone picramide, 2-dibenzoylmethylene-ro-methylnaphthothiazoline, 2-benzoylmethylene-1-methylnaphthothiazoline, 1,8-dimethoxyanthraquinone , 1,2-benzanthraquinone, 5-nitroacenaphthene, 2-nitrofluorene 7.2.7-sinitrofluorene, 1-nitronaphthalene, 1.5-dinitronaphthalene, 2 +4 s 6-) IJ' phenylthiapyri 2.6-bis(p-ethoxyphenyl)4-(p-n-7miloxyphenyl) -
-y-Achyrillium 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 wall fabric technology,
The coating may be applied to the support by any 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 support that is the material to be coated include aluminum plates, zinc plates, stainless steel plates, and metal plates for that purpose; sheets and plates of synthetic resins such as polyethylene terephthalate, polycarbonate, and cellulose derivatives; synthetic resins. Various materials conventionally used as supports for narrow-mouth printing plates, such as paper coated with a synthetic resin bath or by melt-coating, composite materials in which a metal layer is applied to synthetic resin by JJL air vapor deposition, lamination, etc. be.

After coating, the coating solution is dried and solidified by a well-known method to obtain a printing original plate having a photosensitive layer provided on a support. The photosensitive layer of this printing original plate is imaged with a negative image to harden the exposed portion of the photosensitive layer and become obsolete, and then developed to remove the unexposed portion, resulting in a corresponding image on the support. Let it form.

Suitable light sources used for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, lasers, etc. 7).

As mentioned 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 composition 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 with reference to examples, but the present invention is not limited to the following examples unless it exceeds the scope of the invention.

Examples 1 to 6 Mixtures with various compositions were charged into a reactor equipped with a stirring device, a nitrogen gas introduction tube, a thermometer, and a notification tube, and stirred in a nitrogen gas atmosphere at 180C (however, In Geki Production Example 1, the reaction was started by heating to 22 DC). After that, heating and stirring were continued for 3 to 4 hours, and after the release of ethanol or methanol produced by the reaction stopped, the pressure in the reactor was gradually reduced to 111fiHy at the same temperature.

Thereafter, excess ethylene glycol or triethylene glycol was allowed to release under the above temperature and pressure for 6 to 4 hours, and after the release stopped, shedding was completed to obtain a photosensitive polyester resin. The above results are listed in Table 1.

A fat bath solution was prepared by dissolving each photosensitive polyester resin in dichloroethane, and a sensitizer and a phthalocyanine pigment were added to this f8g to prepare a photosensitive resin composition.

Each photosensitive resin composition was applied to an anodized aluminum base using a whirler, and this was dried to produce a printing original plate.

(A step wedge with a height difference of 0.15 was placed in close contact with each original plate of the original sensitivity, and the above original plate was exposed for 60 seconds using a so-called metal halide lung with output 1 installed at a position 1 m from the original plate.
Then, the original plate was γ-butyrolactone-85% phosphorous <9
8/2 volume addition ratio) mixture was used for development. The i sensitivity was indicated by the highest number of insolubilized plates.

(bl Printing durability and ink receptivity A negative film of the test chart was placed in close contact with each original plate, and the original plate was exposed for 60 seconds using a metal halide lamp with an output of 1 level installed at a distance of 1 m from the original plate, and then The original γ-butyrolactone-85% phosphoric acid (98/
Printing plates were produced by developing with a 2-volume/leaf ratio) mixed solution, and each of the printing plates thus produced was installed in a four-color lithographic printing machine, and a roll printing test was performed on the machine using standard ink. A printed image faithful to the original image could be obtained without thickening of halftone dots or plate blanking, etc., and printing durability was shown with a maximum number of prints of 2. The ink receptivity was judged to be good or bad based on whether or not a clear image was obtained without blurring or poor ink adhesion on the printed matter.

The above results are listed in Table 2.

Procedural amendment (voluntary) March 3, 1980 Commissioner of the Patent Office Kazuo Wakasugi 1. Indication of the case 1982 Patent Application No. 222968 2. Name of the invention Photosensitive resin composition 3. Person making the amendment Relationship to the incident Patent applicant 28-65-58 Sakashita 3-chome, Itabashi-ku, Tokyo 174
8) For the representative of Inu Nippon Ink Chemical Industry Co., Ltd.
Shigeru Kuni Mura 4, Agent 5, Dainippon Ink & Chemicals Co., Ltd., 3-7-20 Nihonbashi, Chuo-ku, Tokyo 106, Japan, ``Scope of Claims'' and ``Detailed Description of the Invention'' in the Statement of Subject of Amendment A ” Column 6, Contents of amendment (1) “Claims” of the specification attached to pages 1 to S
Amend as per page.

(2) Contains as a film-forming component a photosensitive polyester resin containing at least one ring structure in the molecular chain of the general formula (3) on page 9 of the same. photosensitive resin composition.

2. The photosensitive unsaturated double bond adjacent to the aromatic nucleus is derived from a dicarboxylic acid represented by the following formulas (1) to (7) or an ester derivative thereof. Compositions as described.

ti (JUshi... (4) In the above formulas (1) to (7), R1 and R,'u each represent a hydrogen atom, an argyl group having 1 to 4 carbon atoms, and an argyl group having 1 to 4 carbon atoms. R2 represents an alkylene group having 2 to 4 carbon atoms, 1 and m each represent an integer of 1 to 5, and n represents an integer of 1 to 4. ) The composition according to claim 1 or 2, which is derived from a compound represented by:

3. A composition according to claim 1 or 2, which is derived from a compound of the present invention.

The composition according to claim 1 or 2, wherein R and R4 each represent a hydrogen atom or an alkyl group.

(In the formula, R5, Ro and R71d each represent a hydrogen atom or an alkyl group.) 6. The weight average molecular weight of the photosensitive polyester resin is 5. O
The composition according to claims 1 to 5, which has a DD of 120,000.

Z The content of photosensitive unsaturated double bonds adjacent to the aromatic nucleus contained in the photosensitive polyester resin is 10% by weight of the resin.
00. 7. A composition according to claims 1 to 6, wherein the amount is 0.5 to 5.5 mol/g.

Fat weight 1000. ? 8. The composition according to claim 1, wherein the amount is 0.2 to 5.0 mol per mol. ” Procedural Amendment (Voluntary) October 1982 Kazuo Wakasugi, Commissioner of the Japanese Patent Office 1. Indication of the case, Patent Office No. 222968 of 1982. 2. Title of the invention: Photosensitive resin composition 3. Make amendments. Patent applicant: 3-35-58 Sakashita, Itabashi-ku, Tokyo 174 (2)
88) Dainippon Ink & Chemicals Co., Ltd. Representative: Shigeru Kuni Mura 4, Agent Address: 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Dainippon Ink & Chemicals Co., Ltd. Telephone: Tokyo (03) 272-4511 (Dainippon Ink & Chemicals Co., Ltd.) representative),
Mu-jin, 4・′” Correct.

(2) The description of "Hydroxynorfornanacetic acid" on page 12, line 14 of the specification has been changed to r-hydroxynorbornaline carbon (above).

Claims (1)

[Scope of Claims] A photosensitive resin composition comprising, as a film-forming component, a photosensitive polyester resin containing at least one type of ring structure in its molecular chain. 2. The composition according to claim 1, wherein the photosensitive unsaturated double bond adjacent to the aromatic nucleus is derived from a dicarboxylic acid represented by the following formulas +11 to (7) or an ester derivative thereof. . (R1) n (R1') n' (R1) n The above formula (
1) to (7), R1 and Rf each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkylene group having 1 to 4 carbon atoms, a halogen atom, or a nitro group, and R2 represents an atom having 2 carbon atoms.
-4 alkylene group, l and m each represent an integer of 1-5, and n represents an integer of 1-4. ) The composition according to claim 1 or 2, which is derived from a compound represented by: (In the formula, Rs and R4 each represent a hydrogen atom or an alkyl group.) 6. The composition according to claim 1 or claim 2, which is derived from a compound derived from a compound comprising: The weight average molecular weight of the resin is 5,
000 to 120,000. Z The content of photosensitive unsaturated double bonds adjacent to the aromatic nucleus contained in the photosensitive polyester resin is
oo! 7. A composition according to claims 1 to 6, wherein the amount is 0.5 to 5.5 mol/g. 8. The composition according to claim 1, wherein the composition is 0.2 to 5.0 mol per fat weight i o o'o +7.