JPS6223788B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel photosensitive resin and a positive photosensitive resin composition containing the same as an active ingredient. O-benzoquinone diazide compounds and o-
It is widely known that naphthoquinone diazide compounds can be used. These o-quinonediazide compounds can also be used in the form of sulfonic acids or carboxylic acids, and can also be used as sulfonic acid esters and carboxylic esters of various hydroxy compounds and o-quinonediazides of this type, as well as various amines. This type of amide compound with o-quinonediazide is also already used as a photosensitive material. These o-quinonediazide compounds are decomposed by light to produce free carboxyl groups, and when treated with an alkaline aqueous solution such as a tribasic sodium phosphate solution, the exposed areas are dissolved and an image is formed. It has the following characteristics. If these o-quinonediazide compounds are used alone as a light-sensitive material, not only will crystals precipitate, but the film-forming properties will also be poor and the mechanical strength of the image will be weak. Therefore, an alkali-soluble resin such as phenol formaldehyde resin (novolac type) is mixed with o-quinonediazide compounds, and the alkali resistance of the unexposed area is used to prevent the alkali-soluble resin from being dissolved by the alkaline solution. A method of forming a compound is also known, and this method is more frequently used, especially for pharmaceutical reasons. In particular, when etching an image obtained on a metal support or directly using an image obtained as a printing plate, it is important to use an alkali-soluble resin with excellent properties. By using o-quinonediazide compounds as the photosensitive layer, crystal precipitation in the photosensitive layer can be prevented and the mechanical strength of the image can be supplemented. For this reason, o-benzoquinonediazide sulfonyl chloride or o-
US Pat. No. 3,046,12 describes the condensation of naphthoquinonediazide sulfonyl chloride and an alkali-soluble novolac-type phenol formaldehyde resin or o- or m-cresol formaldehyde resin to form a polymer. However, the compounds described in the specification are
Image strength is poor due to dissolution of the image area by aqueous alkaline solution and poor adhesion to the support. Also, the oil sensitivity of the printed area is poor. The purpose of the present invention is to eliminate the drawbacks of conventional photosensitive compositions of this type and to provide a positive photosensitive resin composition having excellent developability, adhesiveness, oil sensitivity, and storage stability. be. That is, the present invention is based on the formula (): (In the formula, R means an alkyl group having 3 to 12 carbon atoms or a phenyl group) and phenol or its methyl substituted product or a mixture thereof in a molar ratio of 1:9. An alkali-soluble novolak-type phenolic resin obtained by condensing a mixed phenol containing a ratio of ~9:1 and formaldehyde in an amount of 50 to 100 mol% based on the mixed phenol in the presence of an acid catalyst, and a ~100
Formula for mole % amount () or (): (In the formula, X is a group represented by -SO ₂ Y, -COY,
The present invention provides a positive photosensitive resin composition containing as an active ingredient a photosensitive resin obtained by chemically condensing a photosensitive resin with an o-quinonediazide compound represented by (Y means a removable group). The photosensitive resin of the present invention is one in which o-quinonediazide sulfonic acid or o-quinonediazidecarboxylic acid is chemically combined with a co-condensed novolak type resin using an alkylphenol as one of the phenol components. When exposed to light, that area is rapidly developed in an alkaline aqueous solution, and the last exposed area has extremely strong alkali resistance, and the image will not collapse even if immersed in a solution with a pH of about 13 for a long time. In addition, it has good storage stability and excellent film-forming properties, and since it is substituted with a lipophilic group, the image area has excellent oil sensitivity, acid resistance, and mechanical strength. It can also be mixed with general novolac type resins in any proportion. The alkali-soluble cocondensation resin used in the present invention is characterized by containing both an alkylphenol represented by the formula () with a relatively large molecular weight and a phenol with a relatively small molecular weight and/or a methyl substituted product thereof. It is something. This resin composition can be determined depending on desired properties, such as required alkaline developability and oil sensitivity. When the resin is produced by condensation, the molar ratio of at least one alkylphenol to at least one selected from phenol and its methyl substituted product is 1:9 to 9:1. More specifically, when used in applications requiring oil sensitivity such as resists for printing plate materials such as PS plates and letterpress plates, the above ratio is preferably 4:6 to 8:2. On the other hand, when used as a second original image for copying such as a photomask, development stability is required rather than oil sensitivity, and therefore a 1:9 to 6:4 alkylphenol containing a small amount of alkylphenol is preferable. Those with a ratio of 4:6 to 6:4 have good properties in both oil sensitivity and development stability. In addition, the amount of formaldehyde used is the ratio used in the production of normal phenolic resins (for example, Nikkan Kogyo Shimbun, Plastic Materials Course [15]).
"Phenol Resin", published January 20, 1978, 141
- 142 pages), 50 to 100 mol%, preferably 60 to 100 mol%, based on the total number of moles of the alkylphenol and the phenol and/or its methyl substituted product.
It is said that Specific examples of the compound represented by formula () used in the present invention include phenylphenol, cyclohexylphenol, isopropylphenol, tert-butylphenol, n-butylphenol, tert-amylphenol, n-amylphenol, and tert-amylphenol. -Octylphenol, nonylphenol, dodecylphenol, hexylphenol and the like. Among these, the alkyl group is preferably located at the p-position of the hydroxy group. Further, as the methyl-substituted phenol, p-cresol, o-cresol, m-cresol, which are monomethyl substituted products, and various xylenols, which are dimethyl substituted products, are used. The above-mentioned alkylphenol, phenol or methyl substituted product, or a mixture thereof, and formaldehyde are condensed by a conventional method in the presence of a conventional acidic catalyst such as hydrochloric acid, oxalic acid, zinc acetate, magnesium acetate, etc. to form an alkali-soluble cocondensation. It can be a novolak type phenolic resin. Known reaction conditions are used at that time. The manufacturing method will be specifically explained using the following synthesis example. Synthesis Example A The following raw materials were charged into a three-necked flask (1) equipped with a sealed stirring bar, a condenser, and a thermometer. Phenol 2.3 mol p-tert-butylphenol 2.4 mol Formaldehyde (using 37% formalin)
3.9 mol 35% hydrochloric acid 0.5 ml The above mixture was heated to 100°C and stirred for 8 hours to produce novolak resin, and then heated to 180°C under reduced pressure.
Heating to ~190℃ removes the final reacted formaldehyde, monomer and water, yielding novolak resin 110℃.
Obtained in %. Incidentally, condensation products with other exemplified alkylphenols are also synthesized in the same manner as in this synthesis example. The o-quinonediazide compounds in the present invention include formulas () and (): (In the formula, X is a group represented by -SO ₂ Y or -COY, and Y means a removable group). is 4
For compounds of formula (), those substituted with the substituent X at the 4th or 5th position give preferable results. Preferred specific examples of the compound represented by formula () include 1,2-benzoquinonediazide (2)-4-carbonyl chloride. A preferred specific example of the compound represented by formula () is 1,2-naphthoquinone diazide.
(2)-5-sulfonyl chloride, 1,2-naphthoquinonediazide (2)-4-sulfonyl chloride,
1,2-naphthoquinone diazide (2)-5-carbonyl chloride, 1,2-naphthoquinone diazide (2)
-4-carbonyl chloride and the like. The photosensitive resin of the present invention is obtained by chemically condensing the co-condensed novolak resin described above with an o-quinonediazide compound represented by formula () or (). This condensation is carried out at room temperature in the presence of a base such as sodium carbonate or pyridine in an organic solvent that is freely miscible with water, such as acetone, or a mixed solvent of this organic solvent and water. It is carried out by reacting at a relatively low temperature. The o-quinonediazide sulfonyl group or the o-quinonediazidecarbonyl group is introduced into the resin in a proportion of about 20 to 100 mol%, preferably 20 to 80 mol%, based on the hydroxyl group in the co-condensed novolac type phenolic resin. . When it is lower than 20 mol%, the difference in alkali solubility between the exposed area and the least exposed area becomes small. Even if it exceeds 80 mol%, the desired effect will not improve any further considering the amount used, and there will be no merit. Next, the resin o-benzoquinonediazide or o
- A specific example of the synthesis of a condensation product of naphthoquinone diazide with sulfonyl chloride will be given. Synthesis Example B 24g of the cocondensation resin of Synthesis Example A was converted into 27g of 1,2-naphthoquinonediazide(2)-5-sulfonyl chloride.
Dissolve g in 400 ml of acetone and add 55 ml of IN-sodium carbonate solution while stirring at room temperature while keeping the pH below 8. After the dropwise addition, the reaction was continued for another 2 hours, and the reaction solution was poured into 3N HCl solution 1, and the precipitated oil was separated by decanting and stirred with a large amount of water, which eventually solidified. Separate this, wash with methanol, and dry at 45°C or less. Yield 27.4
g. The photosensitive resin thus obtained is usually used as a composition. That is, the positive photosensitive resin composition according to the present invention is
It is made of a material containing at least one kind of the photosensitive resin, to which a carrier and appropriate additives are added. The positive photosensitive composition of the present invention is usually used in the form of a coating solution. As a composition from this point of view,
It is prepared by dissolving a photosensitive resin in a suitable organic solvent. Examples of organic solvents used include acetone, methyl ethyl ketone, cellosolves, cellosolve acetates, dioxane, butyl acetate, and the like. The content of photosensitive resin in these solvents is, for example, 1 to 30% by weight. The positive photosensitive resin composition of the present invention may contain a polymer material, a dye, a pigment, a sensitizer, and other additives. Examples of polymeric materials include cellulose derivatives such as ethyl cellulose, methyl cellulose, propyl cellulose, and half esters of cellulose acetate, polyacrylic acid (ester), polymethacrylic acid (ester), acrylic acid having an alcoholic hydroxyl group, or acrylic acid with an alcoholic hydroxyl group. Examples include acrylic resins such as copolymers, maleic acid copolymers such as styrene-maleic anhydride copolymers, and methyl vinyl ether-maleic anhydride copolymers.
These are added for the purpose of improving coatability, acid resistance, corrosion resistance, strength, etc. of the coating film. Examples of pigments include chrome yellow and carbon black. Coloring is done to make the image easier to see and also to give the resulting image a light-shielding property so that it can be used as an original drawing. From this point of view, in addition to the above examples, other pigments,
Or dyes are used. Further, a general alkali-soluble novolak resin may be added. Depending on the amount added, the solubility of the photosensitive portion in the alkaline aqueous solution after the composition is exposed to light will be useful. Furthermore, a condensation product of an o-quinonediazide compound, which is a known photosensitive resin, and a general novolak type phenolic resin may be added. Additives (polymer materials, pigments, sensitizers, other additives, etc.) in the positive photosensitive resin composition of the present invention are used in an amount of 600 parts by weight or less per 100 parts by weight of the photosensitive resin. Since the positive photosensitive resin composition of the present invention has high chemical stability, it can be stored for a long period of time without deterioration in quality, and has excellent oil sensitivity. Therefore, the photosensitive resin composition of the present invention has a wide range of uses as a photosensitive material, for example, as a relief plate such as a Wipon plate or a PS plate, and as a resist as a printing plate material such as a letterpress plate or an intaglio plate, or as a metal etching mask, It is also used for photomasks and second original drawings for copying. The positive photosensitive resin composition of the present invention can be applied to a suitable support, such as a metal plate made of aluminum, zinc or copper, a plastic film made of polyester, polypropylene or cellulose acetate, paper, or paper laminated with the above film or metal plate. It is applied evenly to the surface. Examples of the coating method include a rotation method, a spray method, an impregnation method, and a coating method using a wheller or a roll. After coating, the coating film is dried to remove the organic solvent. A desired negative image is superimposed on the film surface of the photosensitive material thus produced, and actinic light is irradiated. For the irradiation, for example, carbon arc lamps, mercury lamps, xenon lamps, chemical lamps, tungsten lamps, etc. can be used. As a result, o-quinonediazide in the exposed portion of the photosensitive material changes into carboxylic acid due to the light and becomes soluble in the alkaline aqueous solution. Next, this photosensitive material is treated with an alkaline aqueous solution such as sodium metasilicate, sodium hydroxide, etc.
Aqueous solutions of potassium hydroxide, sodium carbonate, tribasic sodium phosphate, etc., or mixed aqueous solutions thereof, or, if desired, these alkali aqueous solutions and organic solvents such as methanol, ethanol, dioxane, etc., or these organic solvents and anions or nonions. Developed using a mixed solution with a surfactant. Next, the present invention will be explained in more detail with reference to Examples. In addition, in the following examples, % means weight %. Examples 1-2, Comparative Example 1 A ball-polished aluminum plate was heated for a sufficient time 5
Immersion treatment in ~10% aqueous solution of trisodium phosphate. After washing with water, it was immersed in a 70% nitric acid solution, thoroughly washed with water, then immersed in a 2% zirconium potassium fluoride aqueous solution for 2 minutes, and washed with water. A photosensitive solution having the composition shown below was coated on the aluminum plate which had been made hydrophilic in this way using a Whaler.

[Table] The above photosensitive resin was produced in the same manner as in Synthesis Example A and Synthesis Example B except that the phenol component was changed as described above. The coating thickness was 2.5μ, and the drying temperature was 70°C for 10 minutes. A negative film is placed on top of this photosensitive layer.
Exposure was performed for 50 seconds using a 2KW ultra-high pressure mercury lamp from a distance of 1m, and development was performed with a 4% sodium silicate aqueous solution at 30°C. Immediately after washing with water, the developing ink was placed on the printing plate surface, and it was rubbed lightly several times with a sponge.The adhesion of the printing ink in the image area after washing with water was compared to that of the photosensitive resin obtained from the ordinary phenol novolac resin alone in the comparative example. It was better than when used. Further, the development time during which the exposed areas were dissolved and removed was further extended, and the time until the last exposed areas began to dissolve was measured. Table 1 shows the results.
Shown below. As is clear from Table 1, it was found that when the positive photosensitive resin of the present invention was used, the stability of development, that is, the latitude, was significantly wider than that of Comparative Example 1, which was conventionally used. Furthermore, the coating film of the positive photosensitive resin composition described above was very stable, and almost no change was observed in its developability even after it was left at room temperature for several months. Example 3 1 part by weight of the photosensitive resin of Example 1 and 2 parts by weight of m-cresol novolak resin were mixed in a 1:1 mixture of methyl cellosolve acetate and methyl ethyl ketone.
It was dissolved in 50 parts by weight. This photosensitive solution was applied onto a grained aluminum metal sheet using a Whaler. The coated metal plate was exposed to carbon arc light for 3 minutes through a transparency and then developed with a 5% sodium metasilicate solution. When an oil-based printing ink was applied to the developed and water-washed metal plate and printed with an offset printer, printed matter with good ink adhesion was obtained. Example 4 30 parts by weight of a novolac type phenolic resin co-condensed in the same manner as in Synthesis Example A using 58 parts by weight of p-tert-butylphenol and 42 parts by weight of phenol and 1,2 parts by weight.
- 5 parts by weight of a photosensitive resin obtained by condensing 40 parts by weight of naphthoquinone diazide (2)-5-sulfonyl chloride in the same manner as in Synthesis Example B, metacresol novolak resin, and 1,2-naphthoquinone diazide. (2) 5 parts by weight of a photosensitive condensation resin with -5-sulfonyl chloride and 0.2 parts by weight of methyl violet are dissolved in 100 parts by weight of methyl cellosolve and filtered to make a photosensitive liquid. It was applied to a polished zinc plate using a rotary coating machine and allowed to dry. A positive film was placed in close contact with the photosensitive surface thus obtained, set in a fluorescent lamp vacuum printer, and exposed for 2 minutes. When this was developed with a 1.0% aqueous sodium hydroxide solution, the exposed areas were removed. The thus obtained zinc plate having a positive resist image with excellent acid resistance is powderless. It was corroded by the etching method and could be used as a photolithographic relief plate. Example 5 An organic coating layer made of alcohol-soluble polyamide containing a red organic coloring dye was dried to a thickness of 20 mm.
It was coated on a biaxially stretched polyethylene terephthalate film so that μ was obtained. The photosensitive solution of Example 3 was dried to a thickness of 3 μm on the obtained polyamide layer.
was coated to form a photosensitive photoresist layer. This photosensitive sheet material was exposed for 50 seconds through a negative film at a distance of 1.5 m from the light source of a 3KW ultra-high pressure mercury lamp, developed for 2 minutes with a 5% aqueous sodium metasilicate solution, and washed with water after development. The polyamide layer was then cleanly removed from the polyester film in the open image areas of the photoresist layer by gently rubbing the developed sheet material with absorbent cotton soaked in a treatment solution consisting of sodium toluenesulfonate, alcohol, and water. . The obtained image material was useful as a master for photoengraving. Example 6 24 parts by weight of the co-condensed resin obtained in Synthesis Example A,
2 parts by weight of a photosensitive resin obtained by reacting 16 parts by weight of 1,2-naphthoquinone diazide (2)-5-sulfonyl chloride according to Synthesis Example B and 2 parts by weight of m-cresol novolak resin were mixed with methyl ethyl ketone and methyl cellosolve. It was dissolved in 40 parts by weight of a 2:1 mixture of acetate to prepare a photosensitive solution. Thereafter, when the same operation as in Example 3 was performed, good printed matter was obtained. Example 7 2.0 mol of phenol, 0.3 mol of m-cresol,
A photosensitive resin was synthesized according to the method of Synthesis Example B using a phenol resin obtained by co-condensing 2.3 moles of p-tert-butylphenol and 3.0 moles of formaldehyde using the method of Synthesis Example A. When this resin was used in place of the photosensitive resin of Example 3 and the same operation was carried out, good printed matter was obtained.

Claims (1)

[Claims] 1 Formula (): (In the formula, R is an alkyl group having 3 to 12 carbon atoms or a phenyl group) A cocondensate of one or more compounds represented by the following, phenol or its methyl substituted product, or a mixture thereof, and formaldehyde. Alkali-soluble novolak type phenolic resin,
expression() or expression(): (In the formula, X is a group represented by -SO ₂ Y, -COY,
A positive photosensitive resin composition containing, as an active ingredient, a photosensitive resin obtained by chemically condensing an o-quinonediazide compound represented by (Y means a removable group). 2 The photosensitive resin consists of an alkali-soluble novolak type phenolic resin and a hydroxyl group in the resin of 20 to
The photosensitive resin composition according to claim 1, which is chemically condensed with 100 mol% of an o-quinonediazide compound represented by formula () or formula (). 3. The alkali-soluble novolak type phenolic resin is mixed with a mixed phenol and the mixed phenol.
The photosensitive resin composition according to claim 1, which is a condensate of 50 to 100 mol% of formaldehyde. 4 Mixed phenol is a mixture of phenols represented by formula () and phenol or its methyl substituted product or a mixture thereof in a molar ratio of 1:9 to 9:
1. The photosensitive resin composition according to claim 1.