JPH0242211B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a photosensitive resin with improved photosensitivity.

[Formula] The skeleton (hereinafter referred to as the cinnamic acid skeleton) undergoes a unique photodimerization reaction, and therefore various photosensitive resins in which the cinnamic acid skeleton is introduced into the side chain or main chain of the molecule have been investigated. ing. 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, polyvinyl cinnamic acid ester produced by the reaction of polyvinyl alcohol and cinnamic acid chloride, diethyl phenylene diacrylate,
There are polyesters produced by condensation with 1,4-di-β-hydroxyethoxycyclohexane, and these are used as image-forming materials for printing plates, LSI devices, and the like. Among the photodimerizable photosensitive resins mentioned above, 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 expensive. Although it is said to have photosensitivity, the sensitivity cannot necessarily be said to be sufficient for current practical requirements. On the other hand, attempts have been made to increase the sensitivity of the photosensitive polyester resin by using a polyfunctional cinnamic acid ester as a crosslinking agent, but such crosslinking agents generally have poor compatibility with the resin. Furthermore, the sensitivity of the resin is not sufficiently improved by this method. 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 polycondensation reactions are carried out over a long period of time for the purpose of increasing the molecular weight, side reactions due to the presence of the cinnamic acid skeleton occur. ,
Branching and crosslinking are likely to occur, polymers with a wide molecular weight distribution are likely to be produced, and gelled products that are insoluble in solvents are likely to be produced. These facts or phenomena adversely affect the developability, resolution, printing characteristics, etc. of the photosensitive layer using the resin. The present inventors have conducted extensive research aimed at obtaining resins with high molecular weight and low molecular weight distribution dispersion in a method for producing photosensitive polyester resins having a cinnamic acid skeleton. The inventors have discovered that the above object can be achieved by using a diaryl phthalate compound, a diaryl phthalate compound, or a diaryl carbonate compound as a chain extender, and have 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. A method for producing a photosensitive polyester resin, which comprises producing a precursor, and then reacting the precursor with at least one compound selected from the group consisting of a diaryl oxalate compound, a diaryl phthalate compound, and a diaryl carbonate compound. It is something. Examples of the photosensitive unsaturated dicarboxylic acids used in the present invention include dicarboxylic acids represented by the following general formulas (1) to (7). Examples of ester derivatives of these dicarboxylic acids include dimethyl dicarboxylic acids of these dicarboxylic acids. Examples include esters, dialkyl esters such as diethyl ester, di(ethylene glycol) esters such as di(ethylene glycol) ester, and di(propylene glycol) ester. In the above general formulas (2) to (7), R ₁ and R' ₁ are hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, and 1 to 4 carbon atoms, respectively.
_R2 represents an alkylene group having 2 to 4 carbon atoms, l represents an integer of 1 to 5, and n represents an integer of 1 to 4.
represents an integer of 1 to 5, and m represents an integer of 1 to 5. Suitable examples of the above dicarboxylic acid or its ester derivative include p-phenylene diacrylic acid, m-
phenylene diacrylic acid, 2,5-dimethoxy-
p-phenylene diacrylic acid, 2-nitro-p-
phenylenedialkrylic acid, p-carboxycinnamic acid, cinnamylidenemalonic acid, bis(p-cinnamic acid) diethylene glycol ether, bis(p-
carboxybenzal)cyclohexanone, bis(p-carboxybenzal)cyclopentanone,
Mention may be made of dicarboxylic acids such as P,P'-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, Sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, maleic acid,
Dicarboxylic acids such as phthalic acid, itaconic acid, 5-sodium sulfoisophthalic acid, or their anhydrides or ester derivatives 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, and in order to obtain sufficiently high photosensitivity, photosensitive unsaturated dicarboxylic acids or their esters It is desirable that the amount of the derivative used be 30 to 100 mol% of the total dicarboxylic acid component. On the other hand, various glycol components can be used without particular limitation, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3
-butylene glycol, 1,6-hexanediol, 2-butene-1,4-diol, 2,2,4
-trimethyl-1,3-pentanediol, 1,
4-bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, Ethylene oxide adducts of bisphenol F, propylene oxide adducts of bisphenol F, etc. can be used. In the reaction of the dicarboxylic acid component and the glycol component, in order to obtain a polyester precursor having hydroxyl groups at both ends of the molecule, at least 1 equivalent of hydroxyl group is preferably used per 1 equivalent of carboxyl group or ester group of the acid component, preferably 1.1. It is desirable to select the blending ratio of both components so that the amount is ~2.0 equivalent. The polyester precursor can be prepared by means known in the art of conventional polyester synthesis, e.g.
It can be easily produced by the method described in "Lecture on Polymerization Reactions 9, Polycondensation" by Ogata, published by Kagaku Dojinsha, or by the method described in US Pat. No. 3,622,320. That is, the dicarboxylic acid component and glycol component are
It can be produced by carrying out a reaction (esterification reaction or transesterification) in the presence of a catalyst and an inhibitor that are added as necessary, and then gradually reducing the pressure in the reactor to distill off excess glycol. The reaction temperature is preferably 150 to 250°C, and the reduced pressure is preferably 3 mmHg or less. Examples of catalysts used in producing the polyester precursor include dibutyltin oxide, dibutyltin laurate, dibutyltin diacetate,
Organometallic compounds such as lithium ethoxide, tetraisopropyl titanate, and tetrabutoxytitanate; inorganic metal compounds such as titanium dioxide, zinc acetate, antimony trioxide, and calcium oxide, etc. can be used. The amount used is 50~ as a metal component.
10000ppm is preferred. Inhibitors are used to minimize crosslinking and branching of ethylenically unsaturated groups that tend to occur during polycondensation reactions, and include, for example, phenothiazine, hydroquinone, hydroquinone monomethyl ether, 2,6-ditert -Butyl-p-cresol, P-benzoquinone, etc. can be used. The amount used is preferably 50 to 2000 ppm. The polyester precursor produced in this way is
Those having a weight average molecular weight of 5,000 or more are preferable, and those having a weight average molecular weight of 7,500 or more are more preferable. When a polyester precursor having such a molecular weight is reacted with a diaryl oxalate compound, a diaryl phthalate compound, or a diaryl carbonate compound described below, it is possible not only to produce a high molecular weight resin in a short time, but also to disperse the molecular weight distribution. The degree can be reduced. The diaryl oxalate compound used in the present invention is a compound represented by the following general formula (8), and the diaryl phthalate compound is represented by the following general formula (9).
Examples of the compound represented by and the diaryl carbonate compound include compounds represented by the following general formula (10). (In the above general formulas (8) to (10), R ₃ and R ₄ each represent an aromatic hydrocarbon group which may have a substituent.) Specifications of R ₃ and R ₄ in each of the above general formulas As an example,

【formula】

[Formula] (n is 1~ 10 integers),

[Formula] (X is a halogen source Child),

[Formula] etc. can be mentioned. 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, no further effect can be expected, or the degree of polymerization may be difficult to increase, so it is preferable. do not have. The polycondensation reaction between the polyester precursor and the compounds of the general formulas (8) to (10) above is carried out by adding a predetermined amount of the compounds of the general formulas (8) to (10) to the molten polyester precursor, and then stirring these for a while. After stirring and mixing, the reaction is carried out under reduced pressure. The reaction temperature is preferably at least the melting point of the polyester precursor and at most 250°C, and the reaction time is preferably at least 5 minutes, more preferably at least 10 minutes. According to the method of the present invention described above, 7500~
A photosensitive polyester resin with a weight average molecular weight of 150,000 and a molecular weight distribution dispersion of 1.8 to 3.8 can be easily produced, and a photosensitive polyester resin with such a molecular weight and molecular weight distribution dispersion is different from conventional photosensitive polyester resins. It has a much higher light sensitivity. 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, additives such as sensitizers, pigments, dyes, fillers, and plasticizers are added. Used as an added composition. Suitable solvents vary depending on the composition and molecular weight of the resin, but are typically methylene chloride,
Chlorinated solvents such as chloroform, trichloroethane, trichloroethylene, chlorobenzene, dichlorobenzene, carbon tetrachloride; Alcohol solvents such as tetrahydrofurfuryl alcohol and benzyl alcohol; Ether solvents such as tetrahydrofuran and dioxane; Glycol monomethyl ether, glycol mono Glycol monoalkyl ether solvents such as ethyl ether; ester solvents such as glycol methyl ether acetate, glycol ethyl ether acetate, and ethyl acetate;
Methyl ethyl ketone, methyl isobutyl ketone,
Cyclohexanone, 4-methyl-4-methoxy-
Ketone 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 can be used, including benzophenone derivatives,
Aromatic carbonyl compounds such as benzanthrone derivatives, naphthothiazoline derivatives, quinones, aromatic nitro compounds, pyrylium salts, thiapyrylium salts, etc. can be used. Such sensitizers include, for example, Michler's ketone, diethylaminoethylbenzophenone, benzanthrone,
(3-methyl-1,3-diaza-1,9-benz)
Anthrone picramide, 2-dibenzoylmethylene-3-methylnaphthothiazoline, 2-benzoylmethylene-1-methylnaphthothiazoline, 1,
8-dimethoxyanthraquinone, 1,2-benzanthraquinone, 5-nitroacenaphthene, 2-
Nitrofluorene, 2,7-dinitrofluorene, 1-nitronaphthalene, 1,5-dinitronaphthalene, 2,4,6-triphenylthiapyrylium perchlorate, 2,6-bis(p-ethoxyphenyl)-4 -(p-n-amyloxyphenyl)-thiapyrylium perchlorate 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 conventional coating techniques,
The coating is applied to the support by a well-known coating method such as whirler coating, dip coating, curtain coating, roll coating, spray coating, air knife coating, doctor knife coating, or spinner coating. Specific examples of materials to be coated 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 derivatives; and melt-coated synthetic resins. Alternatively, examples include paper coated with a synthetic resin solution, and composite materials in which a metal layer is provided on a synthetic resin by vacuum deposition, lamination, or other techniques. 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 dissolve and 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 for forming a 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, but can also be used, for example, as a photoresist for various types of microfabrication. 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 4 (1) Production of polyester precursor Each mixture having the composition described in column A of Table 1 was mixed with a catalyst (5 g of dibutyltin oxide, 0.5 g of phenothiazine) using a stirring device, a nitrogen gas inlet tube, and a temperature The mixture was charged into a reactor equipped with a meter and a distillation tube, and the reaction was started by heating to 180° C. while stirring under a nitrogen gas atmosphere. After that, heating and stirring were continued for 3 hours, and after the distillation of ethanol produced by the reaction stopped, the pressure inside the reactor was gradually reduced to 1 mmHg at the same temperature. Thereafter, heating and stirring were continued for 4 hours under the same reduced pressure, and after distillation of the distillate had stopped, the pressure inside the reactor was lowered to normal pressure using nitrogen gas. (2) Production of photosensitive polyester resin Each compound listed in column B of Table 1 was charged into the above reactor, the pressure inside the reactor was again set to 1 mmHg, and the reaction was carried out at 180°C for 30 minutes under this pressure. After continued stirring, the temperature inside the vessel was lowered to room temperature. (3) Measurement of photosensitivity of photosensitive polyester resin A solution was prepared by dissolving 4 g of the resin in (2) above in 96 g of dichloroethane, and 0.4 g of 5-
A photosensitive composition containing nitroacenaphthene and 0.4 g of phthalocyanine pigment was prepared. This composition was applied to an anodized aluminum plate using a whirler and dried to produce a photosensitive plate. 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 kW 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 (98/2 volume ratio). The highest number of insolubilized steps was defined as the photosensitivity. For comparison, the polyester precursors of the above (1) of each example were further reacted for 4 hours at a reaction pressure of 1 mmHg and a reaction temperature of 180°C to produce resins of comparative examples. This was done with the aim of producing a resin with the highest molecular weight obtainable by conventionally known methods.

【table】

Claims (1)

[Scope of Claims] 1. A polyester precursor containing 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, 1. A method for producing a photosensitive resin, which comprises reacting at least one compound selected from the group consisting of a diarylphthalate compound, a diaryl phthalate compound, and a diaryl carbonate compound. 2. Claim 1, wherein the dicarboxylic acid or its ester derivative having a photosensitive unsaturated double bond adjacent to an aromatic nucleus is a dicarboxylic acid or its ester derivative represented by the following general formulas (1) to (7). The method described in section. In the above general formulas (1) to (7), R ₁ and R' ₁ are hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, and 1 to 4 carbon atoms, respectively.
_R2 represents an alkylene group having 2 to 4 carbon atoms, l represents an integer of 1 to 5, and n represents an integer of 1 to 4.
represents an integer of 1 to 5, and m represents an integer of 1 to 5. 3 The diaryl oxalate compound has the general formula (In the formula, R ₃ and R ₄ each represent an aromatic hydrocarbon group which may have a substituent.) The method according to claim 1 or 2, which is a compound represented by the following formula. 4 The diaryl phthalate compound has the general formula (In the formula, R ₃ and R ₄ each represent an aromatic hydrocarbon group which may have a substituent.) The method according to claim 1 or 2, which is a compound represented by the following formula. 5 The diaryl carbonate compound has the general formula (In the formula, R ₃ and R ₄ each represent an aromatic hydrocarbon group which may have a substituent.) The method according to claim 1 or 2, which is a compound represented by the following formula. 6. Claims 1 to 4, in which the amount of dicarboxylic acid or its ester derivative having a photosensitive unsaturated double bond adjacent to an aromatic nucleus used is 30 to 100 mol% of the total dicarboxylic acid component. Method. 7. The method according to claims 1 to 5, 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. 8. The method according to claims 1 to 6, wherein 0.1 to 20% by weight of a compound selected from the group consisting of a diaryl oxalate compound, a diaryl phthalate compound, and a diaryl carbonate compound is reacted with the polyester precursor.