JPS59206431A - Production of photosensitive polyester resin - Google Patents

Abstract

PURPOSE:To obtain the titled resin having a high MW and a small dispersion of an MW distribution, by reacting an OH-containing polyester precursor with a bis(N-acyllactam) compound or a bis(N-acylimide) compound. CONSTITUTION:A dicarboxylic acid having a photosensitive unsaturated double bond adjacent to an aromatic nucleus, such as a compound represented by formulas I -IV (wherein R3 and R3' are each H, a 1-4C alkyl, a 1-4C alkoxyl, a halogen, or nitro, R4 is a 2-4C alkylene, l and m are each 1-5, and n is 1- 4), or an ester derivative of this acid is reacted with a glycol (e.g., ethylene glycol) at 150-250 deg.C in a vacuum <=3mm.Hg to obtain an OH-containing polyester precursor of a weight-average MW>=5,000. This precursor is reacted with 0.1- 20wt% bis(N-acyllactam) compound of formula V or a bis(N-acylamide) compound of formula VI (wherein R1 is a 2-12C organic group, and R2 is a 1-11C aliphatic or aromatic hydrocarbyl group).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a photosensitive resin with improved photosensitivity.

In order to perform a unique photodimerization reaction, various photosensitive resins have been studied in which a cinnamic acid skeleton is introduced into the side chain or main chain of the molecule. Examples include polyvinyl alcohol, polyepichlorohydrin, polystyrene, acrylic resins, epoxy resins, and polyesters and polyamides having a cinnamic acid skeleton in the main chain, some of which have been put into practical use. for example,
There are polycinnamic acid vinyl esters produced by the reaction of polyvinyl alcohol and cinnamic acid chloride, and polyesters produced by the condensation of diethyl phenylene diacrylate and 1,4-di-β-hydroxyethoxycyclohexane. It is used as an image forming material for printing plates, LSI devices, etc.

Among the above-mentioned ex-dimerized type sensitive resins, photosensitive polyester resins having a cinnamic acid skeleton in the molecular main chain produced by condensation of phenylene diacrylic acid or its alkyl ester with glycol are relatively popular. Although it is said to have high photosensitivity, the current situation is that its sensitivity cannot necessarily be said to be at the same level as the current practical requirements. On the other hand, attempts have been made to increase the sensitivity of the photosensitive polyester resin by using a polyfunctional f) cinnamic acid ester or bisazide compound as a crosslinking agent, but such crosslinking agents generally do not interact with the resin. The bath compatibility is poor, and the resulting sensitivity of the resin is also insufficient.

Furthermore, in recent years, a simplified plate-making method has been proposed in which an image is directly printed on a photosensitive layer from an electrical image signal using a laser beam, instead of printing the image through a halftone film. However, the current photosensitive resins have insufficient photosensitivity, so a large, high-output laser must be used. For this reason, a photosensitive resin with even higher sensitivity is desired.

Photosensitive polyester resins are generally produced by a polycondensation reaction between a polyhydric carboxylic acid component having a cinnamic acid skeleton and a polyhydric alcohol component, and it is known that as the molecular weight increases, its photosensitivity improves. There is.

However, in the case of polycondensation reactions, it is generally difficult to obtain polymers with high molecular weight, and when the polycondensation reaction is carried out at high temperatures for a long period of time to increase the molecular weight, due to the presence of the cinnamic acid skeleton, Branching and crosslinking are likely to occur as side reactions, and polymers with a wide molecular weight distribution are likely to be produced.
Gels that are insoluble in common drugs are likely to form. These facts or development depend on the developability, resolution, and resolution of the photosensitive layer using the resin.
It has a negative effect on printing characteristics, etc.

The present inventors conducted extensive research aimed at obtaining a resin with high molecular weight and low molecular weight distribution dispersion in a method for producing a photosensitive polyester resin having a cinnamic acid skeleton. As a result, bis(N The inventors have discovered that the above objects can be achieved by using a (acyllactam) compound or a bis(N-acylimide) compound as a chain extender, and have thus arrived at the present invention.

That is, the present invention provides a polyester precursor by reacting 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 with a glycol component. The precursor is then treated with general formulas (1) and (2).
0 0 (wherein, R1 is an organic group having 2 to 12 carbon atoms, and
R7 is an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 11 carbon atoms. The present invention relates to a method for producing a photosensitive polyester resin characterized by reacting one type of compound.

As the photosensitive unsaturated dicarboxylic acid used in the present invention,
For example, dicarboxylic acids represented by the following general formulas (3) to (9) can be mentioned. Examples of ester derivatives of these dicarboxylic acids include dialkyl esters such as dimethyl ester and diethyl ester of these dicarboxylic acids, di(ethylene glycol ) ester, di(alkylene glycol) ester such as di(propylene glycol) ester, etc.

(6) (In the above general formulas (31 to (9), & and stripes are hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, alkoxyl groups having 1 to 4 carbon atoms, and halogen atoms, respectively) or represents a nitro group,
R4 represents an alkylene group having 2 to 4 carbon atoms, and l is 1 to 4.
represents an integer of 5, n represents an integer of 1 to 4, m represents 1
Represents an integer between ~5. ) Suitable examples of the above dicarboxylic acids or ester derivatives thereof include p-phenylene diacrylic acid, m-phenylene diacrylic acid, 2,5-dimethoxy-p-phenylene diacrylic acid, 2-=)t12-p-phenylene diacrylic acid, acrylic acid, α, α′-dini) O-p-phenylene diacrylic acid, α, a′-′) p-phenylene diacrylic acid, p-carboxycinnamic acid, cinnamylidenemalonic acid, bis( p-a acid) diethylene glycol ether, bis(p-carboxybenzal)cyclohexanone, bis(
p-carboxybenzal) cyclopentanone, p, p'
Mention may be made of dicarboxylic acids such as -chalcone dicarboxylic acid or their diesters as mentioned above.

As the dicarboxylic acid component, other polyhydric carboxylic acids or derivatives thereof can be used in combination with the photosensitive unsaturated dicarboxylic acids or ester derivatives thereof, and examples of such compounds include succinic acid, adipic acid, azelaic acid, Sepatenoic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrabromophthalic acid, tetrachloroheptatalic acid, maleic acid, 7
Dicarboxylic acids such as malic acid, itaconic acid, and 5-sodium sulfoisophthalic acid, or their 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 because it causes a decrease in the photosensitivity of the resin. It is desirable that the amount of the ester derivative used be 30 to 100 mol% of the total dicarboxylic acid component.

On the other hand, as the glycol component, various types can be used without particular limitation, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, and 1,5-phthylene glycol. Recall, 1,6-hexanediol, 2-butene-1,4-diol, 2,2.4
-trimethyl-1,3-bentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexane dimetatool, tricyclodecane dimetatool,
Hydrogenated bisphenol, p, hydrogenated bisphenol F1 bisphenol ethylene oxide adduct, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F, etc. can be used. .

In the reaction of the dicarboxylic acid component and the glycol component, preferably at least 1 equivalent of hydroxyl group per 1 equivalent of carboxyl group or ester group of the acid component so as to obtain a polyester precursor having hydroxyl groups at both ends of the molecule. It is desirable to select the blending ratio of both components so that the amount is 1.1 equivalent or more.

The polyester precursor can be prepared using any means known in the field of ordinary polyester synthesis, such as the method used in "Lecture on Polymerization Reactions 9, Polycondensation" written by Oman, published by Kagaku Dojinsha, or
US patent 3. (It can be easily produced by the method described in Publication No. 522,320. That is, the dicarboxylic acid component and the glycol component are reacted (esterification reaction or esterification reaction) in the presence of a catalyst and an inhibitor that are added as necessary. It can be produced by gradually reducing the pressure in the reactor to drain excess glycol.

The reaction temperature is preferably 150 to 250C, and the reduced pressure is preferably 5 milHg or less.

Catalysts used in producing the polyester precursor include, for example, dibutyltin oxide, diptyltin laurate, diptyltin diacetate, lithium ethoxide,
Organometallic compounds such as tetraisoglovir titanate, tetrabutoxytitanate; titanium dioxide, zinc acetate,
Inorganic metal compounds such as antimony trioxide and calcium oxide can be used. The amount used is 50 to 50% as a metal component.
110000pp is preferred.

Inhibitors are used to minimize the crosslinking and branching of ethylenically unsaturated groups that tend to occur during polycondensation reactions, and include, for example, phenothiazine, chloroquinone, hydroquinone monomethyl ether, 2.
6-di-tert-butyl-p-cresol, p-benzoquinone, etc. can be used. The amount used is 50 to 2000
ppm is preferred.

The polyester precursor produced in this way has 5,000
Those having a weight average molecular weight of 250 or more are suitable.
Those having a weight average molecular weight of 0 or more are more preferable.

When a polyester precursor having such a molecular weight is reacted with a bis(N-acyllactam) compound and/or a bis(N-acylimide) compound described below, it is possible not only to produce a high molecular weight resin but also to change the molecular weight distribution. This can be achieved by reducing the degree of dispersion.

Preferred examples of bis(N-acyllactam) compounds and bis(N-acylimide) compounds used in the present invention include terephthaloyl bis(N-caprolactam), inphthaloyl bis(N-caprolactam), adipoyl bis(N-caprolactam), and adipoyl bis(N-caprolactam). - caprolactam), adipoyl bis(N-caprolactam), sebacoyl bis(N-caprolactam),
Terephthaloyl bis(N-pyrrolidone), Isophthaloyl bis(N-pyrrolidone), Adipoyl bis(N-co/
- phosphoric acid imide), mono(coyl bis(N-succinimide), inphthaloyl bis(N-succinimide), sebacoyl bis(N-phthalimide) Tx, etc.

The above compound can be produced by a dehydrochloric acid reaction, and in some cases a desalting reaction, between a dibasic acid chloride compound and a lactam compound or an imide compound, and in some cases, an alkali metal salt thereof.

The amount of such a compound used is preferably 0.1 to 20% by weight based on the polyester precursor. If the amount is less than 0.1% by weight, the molecular weight will not increase sufficiently, and
If it exceeds 20% by weight, it is not preferable because no further effect can be expected or the degree of polymerization may be difficult to increase.

The reaction between a polyester precursor and a bis(N-acyllactam) compound and/or a bis(N-acylimide) compound is carried out by adding a predetermined amount of the compound to the melted polyester precursor, and then reacting under normal pressure or reduced pressure. Alternatively, the polyester precursor may be dissolved in an organic solvent and a predetermined amount of the compound may be added thereto to carry out the reaction. The reaction temperature is preferably 80C or more and 250C or less, and the reaction time is preferably 5 minutes or more, more preferably 10 minutes or more.

In addition, in the above reaction, tetra-n-butyltichnate, tetra-inglovir titanate, tri-n-butyl titanate, tri-n-butyl titanate, and
- Alkoxides of transition metals or Al such as butyl orthovanadate, tetrapropyl zirconate, triisopropylaluminate can be used.

Typical bath media that can be used in the above reaction include chlorinated vinegar solvents such as methylene chloride, chloroform, trichloroethane, trichloroethylene, monochlorobenzene, dichlorobenzene, and tetramerized carbon; ether thread bath solvents such as tetrahydrofuran and dioxane; Ester media such as recall methyl ether acetate, glycol ethyl ether acetate, ethyl acetate, butyl acetate; methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-
Ketone solvents such as methyl-4-methoxy-2-pentanone, dimethylformamide, dimethylacetamide, N
- Nitrogen-containing compounds such as methylpyrrolidone and nitrobenzene; dimethylsulfoxide, etc. The above solvents can be used alone or in a mixture of two or more.

According to the method of the present invention described above, 500 to 150
A photosensitive polyester resin having a weight average molecular weight of ,000 and a molecular weight distribution dispersity of 1.8 to 3.8 can be easily produced. It has a much higher photosensitivity than conventional photosensitive polyester resins.

The photosensitive polyester resin produced by the method of the present invention is usually prepared as a composition dissolved in a suitable solvent, or if necessary, a sensitizer, pigment, dye, filler, stabilizer, crosslinking agent, plasticizer, etc. It is used as a composition containing additives such as agents. Suitable solvents will vary depending on the composition and molecular cap of the resin, but will typically combine the polyester precursor and bis(N-
Organic solvents used in the reaction with acyllactam) compounds and/or bis(N-acylimide) compounds: Alcoholic solvents such as tetrahydrofurfuryl alcohol and benzyl alcohol; Glycol monomethyl ether, glycol monoethyl ether, etc. Glycol monoalkyl ether heating medium; ethylene glycol monophenyl ether etc. b'), the above solvent may be used alone or in combination
Used as a mixture of more than one species.

Any sensitizer that can be used in this field can be used, including benzophenone derivatives, benzanthrone derivatives, quinones, aromatic nitro compounds, naphthothiazoline derivatives, benzothiazoline derivatives, ketocoumarin compounds, or biryllium salts, Thiapyrylium salts and the like can be used. Examples of such sensitizers include Michler's ketone, diethylaminoethylbenzophenone, benzanthrone, (6-methyl-1,3-diaza-1,9
-benz) anthrone picramide, 6.11-dichlorobenzanthrone, 6-phenyl-benzanthrone %
1.8-dimethoxyanthraquinone, 1.2-benzanthraquinone, 5-nitroacenaphthene, 2-nitrofluorene, 2,7-sinitrofluorene, 1-nitronaphthalene, 1,5-dinitronaphthalene, p-nitrodiphenyl, 2-Diynsoylmethylene-3-methylnaphthothiazoline, 2-benzoylmethylene-1-methylnaphthothiazoline, 2-bis(furoyl)methylene-6-
Methylbenzothiazoline, 2-benzoylmethylene-6
-Methylbenzothiazoline, 3.6-carbonyl-bis(7-dinithylaminocoumarin), 2.4°6-dryphenylthiapyrylium perchlorate, 2.6-bis(
p-ethoxyphenyl)-4-(p-n-amyloxyphenyl)-thiapyrylium verchlorate and the like.

The photosensitive resin composition using the photosensitive polyester resin of the present invention is formulated to have an appropriate viscosity so that it can be applied to commonly used coating techniques such as whirler coating, dip coating, curtain coating, roll coating, Spray application, air knife application, doctor knife application, spinner application, etc.
It is applied to the support by well-known coating methods.

Specific examples of vL coating materials include aluminum plates, zinc plates, copper plates, stainless steel plates, and other metal plates; sheets and plates of synthetic resins such as polyethylene terephthalate, polycarbonate, and cellulose conductors; Examples include paper coated with bath melt coating or a synthetic resin bath liquid, and composite materials formed on synthetic resin by techniques such as metal Wt@vacuum deposition and lamination.

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 the support. The photosensitive layer of this printing original plate is subjected to imagewise exposure using a negative image to harden and insolubilize the exposed areas of the photosensitive layer, and then developed to remove the unexposed areas 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 mentioned above, the photosensitive resin of the present invention is extremely effective in forming the photosensitive layer of a printing plate, but the use of the composition of the present invention is necessarily limited to the photosensitive layer of a printing plate. For example, it can also be used as an otoresist for various microfabrication processes.

EXAMPLES 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 gist thereof.

Examples 1 to 5 (1) Production of polyester precursor Each mixture having the composition described in column A of Table 1 was mixed with a catalyst (5 L of diptyltin oxide) and an arrester (0.25 Ii of phenothiazine) in a stirring device, The mixture was charged into a reactor equipped with a nitrogen gas inlet tube, a thermometer, and a Mizoyama tube, and the reaction was started by heating to 180 C while stirring in a nitrogen gas atmosphere.

Thereafter, the mixture was heated and stirred for 3 hours, and after the ethanol produced by the reaction stopped flowing, the pressure inside the reactor was gradually reduced to 1 Ht at the same temperature. Thereafter, heating and stirring were continued for 4 hours under the same reduced pressure, and after the excess ethylene glycol had stopped forming, the pressure inside the reactor was lowered to normal pressure using nitrogen gas.

+21-1 Production of photosensitive resin (button extension method: a) The compound listed in column B of Table 1 was added to the polyester precursor of (1) above, and the pressure in the reactor was set to lmmHg again under a nitrogen atmosphere. After stirring was continued for 20 minutes at 180C under this pressure, the pressure was returned to normal and the resulting resin was taken out.

Production of f2+-2 photosensitive resin bath liquid (stretching method: b) Monochlorobenzene was added to the polyester precursor of (1) above to make a 30% by weight liquid. Next, the compounds listed in column B of Table 1 and tetra-n-butyl titanate (1% by weight based on the polyester precursor) were charged, and 140
After continuing stirring at C for 2 hours, the temperature inside the vessel was lowered to room temperature, and the single-formed resin solution was taken out.

Add monochlorobenzene to the resin solution of f21-1 or E(2+-2!) to prepare a 4% by weight bath solution, and add 5-nitroacenaphthene (10% to m fat) to this solution. A photosensitive composition was prepared by adding a phthalocyanin pigment (10% by weight based on the resin).This composition was applied to an anodized aluminum plate with a whiter, and it was dried to form a photosensitive plate. was created.

A step wedge with a step height of 0.15 was brought into close contact with the thus obtained photosensitive plate, and the photosensitive plate was exposed for 30 seconds using a metal halide lamp with an output of 1 cycle installed 1 m adjacent to the step wedge. Thereafter, this photosensitive plate was developed with a mixed solution of γ-butyrolactone and 85% phosphoric acid (98/2W ratio). The highest number of profane steps was defined as the light sensitivity.

For comparison, a resin of a comparative example was prepared by further reacting the polyester precursor (1) of each example under conditions of a reaction pressure of 11II H# and a reaction temperature of 180C for 5 hours. was measured. This was done for the purpose of producing m-fat with the highest molecular weight obtainable by conventionally known methods.

The contents and results of each side listed below are summarized in the first page.

Kazuo Wakasugi, Commissioner of the Patent Office1. Indication of the case 1982 Patent Application No. 81282 2, Title of the invention
7゜Production method of photosensitive polyester resin 3, relationship with the amended case Patent applicant: 3-35-58 Sakashita, Itabashi-ku, Tokyo 174 (28
8) Dainippon Ink & Chemicals Co., Ltd. Representative Yo Mura
Kuni Shigeru 4, Agent Address: Dainippon Ink & Chemicals Co., Ltd., 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Phone number: Tokyo (03) 272-4511 (Main representative) Patent in the inventor's column in the application and in the specification Scope of claims column 6, content of amendment q) Address of the sender of the application [5-l-1-304J, Hikarigaoka, Nerima-ku, Tokyo r 5-6-1-304 Hikarigaoka, Nerima-ku, Tokyo Correct to j.

(2. The statement of the scope of claims is amended as shown in the attached sheet.

List of attached documents (11 correction application form 1 copy (2) M delivery certificate 1 copy (3) Resident card
1 copy of 14 certificate of non-residence
1 letter (5) letter of reason
1 Claims after special amendment: ``1) A hydroxyl group obtained by reacting a dicarboxylic acid component containing a dicarboxylic acid having a photosensitive unsaturated double bond adjacent to an aromatic nucleus or an ester derivative thereof with a glycol component. The contained polyester precursor is reacted with at least one compound selected from the group consisting of bis(N-acyllactam) compounds and bis(N-acylimide) compounds represented by the following general formulas (11 and (2), respectively). A method for producing a photosensitive polyester resin, which is characterized by:

OO (In the formula, R1 is an organic group having 2 to 12 carbon atoms, and R2 is an aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 11 carbon atoms.) 2) Photosensitive material adjacent to the aromatic nucleus A dicarboxylic acid or its ester derivative having an unsaturated double bond is represented by the following general formula (3
) to (9) or an ester derivative thereof.

......-(6) (In the above general formulas (3) to (9), R3 and R1 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, halogen atom or nitro group, R4 represents an alkylene group having 2 to 4 carbon atoms, l represents an integer of 1 to 5, n represents an integer of 1 to 4, m
represents an integer from 1 to 5. 3) Claim 1 or 2 in which the amount of dicarboxylic acid or its ester derivative having a photosensitive unsaturated double bond adjacent to an aromatic nucleus is 60 to 100 mol% of the total dicarboxylic acid component. Method described.

4) The method according to claims 1 to 6, wherein the polyester precursor has hydroxyl groups at both ends of the molecule and has a weight average molecular weight of 5.000 or more.

5) Bis(N-acyllactam) compounds and/or bis(N-acyllactam) compounds represented by general formulas (1) and/or (2)
Claim 1: 0.1 to 20% by weight of a polyester precursor is reacted with a N-acyl(N-acyl) compound.
The method described in Items 1 to 4.
"that's all

Claims (1)

[Claims] 1) A polyester precursor containing a hydroxyl group obtained by reacting a dicarboxylic acid component containing a dicarboxylic acid or its ester derivative having a photosensitive unsaturated double bond adjacent to an aromatic nucleus with a glycol component. , characterized by reacting at least one compound selected from the group consisting of bis(N-acyllactam) compounds and bis(N-acylimide) compounds represented by the following general formulas (1) and (2), respectively. A method for producing photosensitive polyester resin. 0 0 111 0 0 (In the formula, R1 is an organic group having 2 to 12 carbon atoms, and R2 is an aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 11 carbon atoms.) 2) In the aromatic nucleus A dicarboxylic acid or its ester derivative having adjacent photosensitive unsaturated double bonds is represented by the following general formula (3
1. The method according to claim 1, wherein the dicarboxylic acid represented by 1 to (9) or an ester derivative thereof is used. (Rs)J...(6) (In the above general formulas (3) to (9), B and number are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms.
represents an alkoxyl group, a halogen atom or a nitro group, R4 represents an alkylene group having 2 to 4 carbon atoms, and ! is 1
n represents an integer of 1 to 4, and m represents an integer of 1 to 5. ) 6) Claim 1 or 2 in which the amount of dicarboxylic acid or its ester derivative having a photosensitive unsaturated double bond adjacent to an aromatic nucleus is 60 to 100 mol% of the total dicarboxylic acid component. Method described. 4) The method according to claims 1 to 3, wherein the polyester precursor has hydroxyl groups at both ends of the molecule and has a weight average molecular weight of 5.000 or more. 5) Bis(N-acyllactam) compounds and/or bis(N-acyllactam) compounds represented by general formulas (1) and/or (2)
5. The method according to claim 1, wherein the amount of the compound (N-acylimide) is 0.1 to 20% by weight based on the polyester precursor.