TW200401167A - Positive photosensitive coating composition, preparation method of positive photosensitive resin and pattern-forming method - Google Patents

Abstract

The present application provides a positive type coating composition and forming method of pattern by using the said coating composition. The positive type sensitivity coating according to the present invention is characterized in that contains specific modified quinonediazido-sulfonamide as union based on the 100 parts by weight in one molecular, making the structure unit containing 0.1~0.9 mole concentration in 1 kg resin, and using the specific carboxylic sulfonamide derivative as the structure unit, which in 1 kg resin the structure unit containing 0.2~0.4 mole concentration positive type sensitivity resin with 1~50 parts by weight at least one component selected from the group of phenol resin phenol derivative and catechol.

Description

200401167 发明 、 Explanation of the invention _ ........,.... (The description of the invention should state: the prior art, the embodiment of the prior art, the content, and the simple description of the drawings) (1) FIELD OF THE INVENTION The present invention relates to a photoresist having excellent operation stability and high reliability in formation of a conductor image, and is particularly a positive-type photosensitive coating composition suitable for use as an etching photoresist for the manufacture of printed circuit boards. It also relates to a pattern forming method for a printed circuit board or the like using the positive photosensitive paint composition. (2) The printed circuit board used in the prior art electronic equipment is mainly a circuit formed by a screen printing method or an lithography using a photosensitive dry film on an insulating substrate having a conductive layer on the surface. Manufacture of patterns by subtractive layers. Recently, printed circuit boards have been miniaturized with increasing density and accuracy. Next, a manufacturing method corresponding to this requirement is proposed, and a method using a positive-type photosensitive electrodeposition photoresist is proposed. The positive photosensitive coating composition used for the positive photosensitive electrodeposition photoresist is prepared by adding an isocyanate of an isocyanate-containing monomer copolymer to a photosensitive substance and benzoic acid (see Japanese Patent Application No. 2000-056264). ). This positive-type photosensitive coating composition exhibits poor solubility in the exposed portion and the unexposed portion of the alkali developing solution due to exposure, whereby development can be performed. However, 'the sensitivity will decrease when the additive amount of the photosensitive substance is increased.' Conversely, although the sensitivity will be increased when the additive amount is decreased, the solubility of the alkali developer will not be sufficient. The problem. (3) Summary of the Invention The object of the present invention is to develop a positive photosensitive coating composition with high sensitivity and poor solubility in an alkali developer, and a pattern forming method using the same. [Disclosure of the Invention] When the present inventors and the like intensively studied to solve a conventional problem, they found that by blending a phenol resin, a phenol derivative, or a catechol derivative with a specific positive photosensitive resin, The present invention can complete the invention while maintaining sensitivity and improving pattern formation. In other words, the present invention relates to 1. A positive-type photosensitive coating composition characterized in that 100 parts by weight contains a modified quinonediazidesulfonamide represented by the following general formula (1) in a molecule. The unit is such that the structural unit contains a concentration of 0.1 to 0.9 mol in 1 kg of resin and a concentration of 0.2 to 4.0 mol in 1 kg of resin. For the resin, 1 to 50 parts by weight of at least one component selected from the group consisting of a phenol resin, a phenol derivative, and a catechol derivative is formulated, and the general formula (1)

-7-200401167 (wherein R1 represents a gas atom 'linear or branched fluorenyl group, aromatic hydrocarbon group, or alicyclic hydrocarbon group) General formula (2) [Chemical formula 4]

R3 a N

(Wherein, R2 and 1 ^ 3 each represent a hydrogen atom, a linear or branched alkyl group, an aromatic hydrocarbon group, or an alicyclic hydrocarbon group). 2. A pattern forming method, characterized in that it comprises (1) a step of applying a positive photosensitive coating composition as described in 1 above on a substrate to form a positive photosensitive coating film, and (2) directly or via a pattern light A step of exposing the positive photosensitive coating film, (3) a step of removing the coating film of the exposed portion with an alkaline developing solution to form a pattern, a pattern forming method, characterized in that (1) the substrate is A step of applying a positive photosensitive coating composition as described in the above item 1 to form a positive photosensitive coating film, (2) a step of exposing the positive photosensitive coating film directly or via a pattern mask, (3) using Step of removing the coating film of the exposed portion with an alkaline developer to form a pattern ~ 8-200401167 (4) Step of etching the exposed conductive film or metal plate '(5) Step of removing the photoresist coating film on the pattern . 4. The pattern forming method according to the above item 2 or 3, wherein the photosensitive coating composition according to the above item 1 is applied to a substrate or a metal plate having a conductive film by electrodeposition. (IV) Embodiment First, the positive photosensitive coating composition of the present invention will be described in detail. The positive photosensitive coating composition of the present invention is characterized by 100 parts by weight of the positive photosensitive resin as described above. 1 to 50 parts by weight is blended with at least one component selected from a phenol resin, a phenol derivative, and a catechol derivative (hereinafter simply referred to as a "phenol-based component"). Next, each component constituting the positive photosensitive resin will be described. The positive photosensitive resin component of the photosensitive resin is a structural unit containing a modified quinonediazide sulfaminamide represented by the general formula (!) In one molecule, and the structural unit contains 0.1 to 1 kg of resin. A positive-type photosensitive resin having a concentration of 0.9 mol and containing 1 to 2 mol of the structural unit represented by the above-mentioned general formula (2) in a concentration of C.2 to 4.0 mol. The concentration of the photosensitive group of the resin is not particularly limited, but the content of the modified I * azide diammine structural unit in the solid content of 丨 kg of resin in terms of photosensitivity, developability, and coating workability is 0. 1 to 0.9 Moore is more preferred, and 0.2 to 0.5 Moore is more preferred. 200401167 In the modified quinonediazide sulfonamide photosensitive group represented by the general formula (1), R is a monovalent organic group. R is a linear or branched alkyl group including methyl, ethyl, n-propyl, isopropyl and the like. Further, h is an aromatic hydrocarbon group including phenyl, tolyl, xylyl, and the like. R is an alicyclic hydrocarbon group including cyclohexyl and the like. The modified quinonediazide sulfonamide photosensitive group contains 0.1 to 0.9 moles, preferably 0.2 to 0.5 moles, in 1 kg of resin. If the content is less than 0.1 mol, the performance of photosensitivity and developability is not good, and if it is more than 0.9 mol, the sensitivity is reduced. In the structural unit represented by the general formula (2), R2 and R3 are monovalent organic groups. R2 | and R3 are, for example, the same as the above-mentioned R, a linear or branched alkyl group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group. The structural unit represented by the general formula (2) contains 0.2 to 4.0 moles of 1 kg of the positive-type photosensitive resin (solid content), and more preferably 0.6 to 1.5 moles. If the content is less than 0.2 mol, the alkali solubility is not good, and if it is more than 4.0 mol, the alkali resistance is not good. The positive-type photosensitive resin used in the present invention is not particularly limited as long as it has the above-mentioned constitution, and conventional materials can be used. · The positive-type photosensitive resin includes, for example, a quinonediazide sulfonamide (hereinafter referred to as a photosensitive group) and a compound having an amine group and a carboxyl group (hereinafter referred to as an amino acid compound) in one molecule by the following steps ( I), (II), or (丨 丨 丨) added to the resin. Step (I): (1) Copolymerizing an unsaturated monomer radical containing an unsaturated monomer having an isocyanate group-containing polymerizable vinyl group. -10 — 200401167 (2) Then, the hydroxy-containing quinone diazide compound is added by a urethane reaction. (3) Then, the amino acid compound is produced by addition reaction with a urea reaction. Step (II): (1) Adding a hydroxy-containing quinone diazide compound through a urethanation reaction and adding an amino acid compound through a urea reaction to a polymerizable ethylene having an isocyanate group Unsaturated monomers of various groups form various functional monomers. (2) Then, a polymerizable unsaturated monomer containing the synthesized monomer (1) is copolymerized with a free radical to produce it. Step (III) (1) Addition of a hydroxy-containing quinonediazide compound via a urethane bond, and addition of an amino acid compound via a urea bond to a polymerizable polymer having an isocyanate group Vinyl unsaturated monomers form various functional monomers. (2) Then, the monomer having (1) obtained is copolymerized with an isocyanate group-containing polymerizable vinyl group monomer and other monomer free radicals as necessary. (3) Then, it is produced by adding an amino acid compound to a urea reaction. Further, in order to react the hydroxyl group-containing diazide compound in the above-mentioned production steps (i) (2), react with an amino acid compound in the production steps (1) (3), or the production step (11) (1) Isocyanate group-containing vinyl monomers used when a β nitrogen compound and an amino acid compound which are one of the vial groups are reacted or reacted with an amino acid compound in the manufacturing steps (111) (2) are as follows. . 200401167 General formula (3) CH2 di c: / R4

-〇-CnH2n-NCO (wherein 'R4 is a hydrogen atom or a methyl group, and n is an integer of 1 to S) The monomers shown are, for example, diisocyanate (meth) acrylate and the like. Formula (4) [Chemical Formula 6] / R5

(Where 'R5 is a hydrogen atom or a methyl group, n is an integer of 1 to 8, is a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and R6 is the same straight line as the above 1 ^ A chain or branched alkyl group, suitably selected from the group consisting of 1 to 5 carbon atoms, such as m-propenyl-oc, α-dimethylbenzyl isocyanate, and the like. General formula (5) [Chemical formula 7]

G—〇 一 CnH2n ~ 〇H 200401167 (where I is a hydrogen atom or a methyl group, and n is an integer from i to 8) The (meth) acrylic acid ester-containing monomer shown in the formula 1 mole and two Monomer obtained by 1 mole reaction of isocyanate compound. Monomers represented by the general formula (5) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. Diisocyanate compounds such as aliphatic diisocyanates of hexamethylene diisocyanate or dimethylhexamethylene diisocyanate; alicyclic aliphatic diisocyanates of hydrogenated ditolyl diisocyanate or isophorone diisocyanate Type; phenylmethyl diisocyanate or aromatic diisocyanate of 4,4 diphenyl methyl diisocyanate itself, or each of these organic diisocyanates and polyols, and low molecular weight polymerization Additives such as ester resins and water, or cyclic polymers between organic diisocyanates as described above, and isocyanates and biurets. Among these are tolyl diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, m-xylylene diisocyanate, 1,3 with two isocyanates with different reactivity. -Diisocyanate_methylcyclohexane is preferred. The reaction of the isocyanate-containing vinyl monomer and hydroxyl-containing quinone diazide; for example, in an inert organic solvent, about 1 mole of isocyanate-containing vinyl monomer The hydroxy-containing quinone diazide in the ear is performed at room temperature and 80 ° C (preferably 60 ° C) for 0.5 to 20 hours. This reaction can be monitored by infrared spectrum analysis and measurement of the absorption of isocyanate groups in the vicinity of 2 2 5 0 c ηΓ 1. As the solvent used herein, an inert organic solvent that does not react with isocyanate and hydroxy groups of 13-200401167, such as ketone, ester, aromatic, aliphatic, ether, and the like can be used. These solvents can replace alcohol-based aqueous solvents as desolvents after the reaction. Further, the monomer compound obtained by reacting the isocyanate group-containing vinyl monomer and the hydroxy group-containing quinonediazide may be copolymerized with an unsaturated monomer having a salt-forming functional group. Examples of the amino acid compound used in the production steps (I) (3), (I I) (1), and (I I I) (3) are shown by the following general formula (6). Formula (6) NHR8

(Wherein R8 is a hydrogen atom, carbon number 1 to 15 (preferably 1 to 5, more preferably 1), branched alkyl group, aromatic hydrocarbon group, cyclic hydrocarbon group, and R9 series It is hydrogen, a carbon number of 1 to 15, may be a branched alkyl group, or a hydroxyl group, etc. Furthermore, the substituent of the 'amino group is, for example, meta, ortho or para. R9 is appropriately selected from the same as I The number of carbon atoms of the straight or branched chain alkyl group is from 15 to 15. In addition, the R8 is a carbon number of 1 to 15 appropriately selected from the same linear or branched chain group as the above I, and an aromatic hydrocarbon group. (Cycloaliphatic hydrocarbon group) Specific examples of the substance include, for example, p-aminobenzoic acid, m-methylaminobenzoic acid, etc. The monomer containing an isocyanate-containing monomer in the above manufacturing step (1) (1) -14-200401167 Total For polymerization, the monomers such as azobismethoxybutyronitrile, benzamidine peroxide, etc. are usually present in an inert organic solvent at about 80 to 150 ° C. Reactions are 1 to 20 lines. Appropriate organic solvents are soluble and are not limited. When used as an electrodeposition coating, a hydrophilic organic solvent is used as the solvent, for example, ethyl ketones such as diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, and ketones such as cyclohexanone, dimethyl carbonate, di, and propenyl. Carbonate and other carbonate-based, N-methylpyrrolidine-based. In the above manufacturing steps (1) and (2), the reaction with the isocyanate-containing hydroxyl-containing quinone diazide is continuously performed in the presence of a tin-based catalyst at ° C (preferably about 50 to 80 ° C). About 30 minutes is preferably 1 to 2 hours. In the above production methods (1), (3), (111) and (3), the reaction with the isocyanate-containing amino acid compound is continued at about 20 to 100 ° C, and the reaction is continuously performed at about 1 to 80 ° C. 2 to 10 hours, preferably; i 〇 In the above production methods (11) (1), (111) (1), the reaction between the isocyanate-containing monomer and the photosensitive group is in the presence of a tin-based catalyst. It is preferably about 50 to 80 ° C), and the reaction is continued for about 30 hours. In the above-mentioned production method (II) (1), the reaction of the ethylamino acid compound containing an isocyanate group is continued in the presence of a tin-based catalyst (about 20 to about 50 to 80 ° C) for about 30 minutes to the mixture It is advisable to add active hydrogen when the radical polymerizability is small. The organic acid type, methylamine carbonate, and other resins such as ammonium amine have a reaction time of about 20 to 100 to 3 hours, and the acid ester resin is about 40 to 3 to 4 hours. 0 to 10 〇〇C (minutes to 3 small alkenyl monomers and 100 ° C (preferably 3 hours, 200401167 {: ± 1 is 1 to 2 hours. The carboxyl group containing photosensitive obtained by the above method) There is no particular limitation on the formulation ratio of the acrylic resin monomer. For i kg of resin, Q. i ~ 0. 9 ear I stack, and for 丨 kg of resin, 0.2 ~ Molar hydroxyl group. The molecular weight of the carboxyl group-containing photosensitive acrylic resin obtainable by the production method is a number average molecular weight of about 10,000 to 100,000, and more preferably 3,000 to 50,000. When the carboxyl group concentration of the 〇〇〆 resin is less than 0.2 mol, the developing solution of the exposure 邰 in the developing step is not sufficiently soluble to form an image. In addition, it is generally not easy to neutralize, dissolve or dissolve the resin. Dispersed in water, a stable electrodeposition coating bath cannot be made. Moreover, it is larger than 4.0 mol for 1 kg of resin. At the ear, the image formation of the image was not able to form an image due to the "resistance to the developing solution of the unexposed part in the developing step being reduced and insufficient", and the coating efficiency (coulomb recovery amount) during electrodeposition coating was likely to decrease, and the obtained The surface of the photoresist film is prone to coating film abnormalities such as water marks. The photosensitive concentration of the resin is not particularly limited. In terms of photosensitivity, developability, and coating workability, it is 1 kg of resin solid content. The content of the modified quinonediazide sulfonamide structural unit is from 0.1 to 0.9 moles, especially from 0.2 to 0.5 moles. Face .... Ingredients: Phenol used in the present invention The component is used to improve the solubility resistance of the developing solution of the coating film of the unexposed part, that is, the additive that suppresses the solubility resistance of the developing solution, and can form a pattern with excellent image formation without reducing sensitivity. 16- 200401167 Phenol resins with phenolic components such as polyvinyl phenol, copolymers of vinyl phenol and other propionic acid monomers, acetaldehyde resins, etc. The phenol resin contains 4 to 9 in 1 kg of resin. 4 Mol phenolic hydroxyl group is preferred. Substances and catechol derivatives can be used as known, in particular, such as 4 '4' '5-trihydroxy-2,3', 5, -trimethyldiphenylmethane dinuclear phenols, 2 , 6-bis (2 '4-dihydroxybenzyl) -4-methylphenol, bis [4-hydroxy-3 (4-hydroxy-2-methylbenzyl) _5 —methylphenyl] Methane, bis [4-hydroxy-3 (2-hydroxy-5-methylbenzyl) _5_methylphenyl] methylamine, bis [4-hydroxy-3 (2'4-dihydroxybenzene) Methyl) _5-methylphenyl] methane linear phenols, bis (4,5-dihydroxy-2-methylphenyl) phenylmethane, bis (4,5-dihydroxy-2-methyl) Phenyl) -3 '4-dihydroxyphenylmethane Radial phenols. The molecular weight of the phenol-based component is about 500 to 100,000, preferably 1,000 to 20,000. . The addition amount of the phenol-based component is preferably 1 to 50 parts by weight based on 100 parts by weight of the positive photosensitive resin. If it is less than 1 part by weight, the solubility of the developer in the unexposed portion is insufficient, and good pattern formation properties cannot be obtained. If it is more than 50 parts by weight, the light-shielding effect of the phenol-based component is large, the light transmittance of the photoresist film is reduced, it is the cause of the residual film in the exposed portion, and the sensitivity is reduced. The positive-type photosensitive coating composition of the present invention can be manufactured by blending the above-mentioned positive-type photosensitive resin and phenol-based component, and can be compounded with a sensitizer, a dye, a solvent, a neutralizing agent, an extender, and others as needed. Additives, etc. In addition, the positive photosensitive coating composition of the present invention can be used as a neutralizing agent for a positive resin in a complex of the above-mentioned positive photosensitive resin and a phenol component. An aqueous positive photosensitive coating composition dispersed in water. This material can be used as a positive photosensitive coating composition for anion electrodeposition. The neutralizers are, for example, monoethanolamine, diethanolamine, triethanolamine, and the like; alkylamines such as monoethylamine, diethylamine, triethylamine, trimethylamine, and diisobutylamine; and dimethylamine. Alkyl alkanolamines such as ethanolamine; cycloaliphatic amines such as cyclohexylamine; alkali metal hydroxides such as caustic soda and caustic potassium; ammonium and the like; these can be used alone or as a mixture. In the present invention, in order to improve the fluidity of the water-solubilized or water-dispersible electrodeposition coating, a hydrophilic solvent may be added, such as isopropanol, n-butanol, 3-butanol, methoxyethanol, and ethoxylate. Ethyl alcohol, butoxyethanol 'ethylene glycol dimethyl ether, diethylene glycol, methyl ether, dioxane, tetrahydrofuran and the like. These hydrophilic solvents are usually used in an amount of 100 parts by weight or less for 100 parts by weight of the electrodeposition coating composition. In addition, in order to increase the coating amount of the coating object, a hydrophobic solvent such as toluene, xylene and other petroleum solvents can be added; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate and acetic acid Esters such as butyl ester; hydrophobic alcohols such as 2-ethylhexanol 'benzyl alcohol; hydrophobic ethers such as ethylene glycol dibutyl ether, diethylene glycol dibutyl ether, propylene glycol phenyl ether, etc. The amount of the isotropic solvent used is usually 30 g parts or less to the solid content of the electrodeposition coating composition. Depending on the resins required in addition to the above, the electrodeposition coating can be adjusted appropriately, and dyes or pigments can be added. The positive photosensitive coating composition of the present invention can be used for conventional applications, such as lithography applications. -18- 200401167 Next, a pattern forming method according to the present invention will be described. The pattern forming method of the present invention is characterized by including (1) a step of applying a positive-type photosensitive coating composition as described above on a substrate to form a positive-type photosensitive coating film, and (2) directly or through a pattern mask. Step of exposing positive photosensitive coating film> (3) A step of removing a coating film of an exposed portion with an alkaline developing solution to form a pattern. Furthermore, it also includes a pattern forming method, which is characterized by (1) applying a positive photosensitive coating composition as described above on a substrate to form a positive photosensitive coating film, and (2) directly or through a pattern mask. The step of exposing the positive photosensitive coating film (3) a step of removing the coating film of the exposed portion with an alkaline developer to form a pattern, (4) a step of etching the surface of the exposed conductive film or metal plate, (5) Step of removing the photoresist coating film on the pattern. In the step (1), the substrate is, for example, a substrate having a conductive film such as a copper-clad laminated board (printed circuit board, etc.). The coating can be applied by, for example, electrodeposition coating, roll coating, spray coating, curtain coating, dip coating, or the like. The electrodeposition coating is performed by immersing a printed wiring board as an anode in an electrodeposition coating bath (bath solid content concentration: 3 to 30% by weight), and energizing with a direct current at a maximum applied voltage of 20 to 400V. The power-on time is 30 seconds to 5 minutes. After the electrodeposition coating, the object to be coated is drawn from the electrodeposition bath and washed with water, and then the water contained in the electrodeposition coating film is removed by hot air or the like. 200401167 The coating film thickness of the positive photosensitive coating composition is 1 to 100 μm in dry film thickness, preferably 3 to 20 μm in dry film thickness. The coating method other than the above-mentioned electrodeposition coating may be followed by drying the coated surface with hot air or the like, and removing the solvent and water to form a coating film. The above step (2) is to expose active light rays such as visible light and ultraviolet rays directly or through a patterned mask (photo positive type) on the surface of the positive-type photosensitive coating film formed in step (1) for exposure. The active light used for the exposure is light having a wavelength of 300 to 450 nm. Such light sources are, for example, sunlight, mercury lamps, M gas lamps, arc lamps, and the like. Irradiation with active light is usually 50 to 800rajcm-2 '. In the present invention, in order to reduce the concentration of the photosensitive group, it is performed in the range of 30 to 300mJcm.2. The developing process in the above step (3) is usually performed by spraying dilute alkali water 'on the coating film surface to clean the photosensitive portion of the coating film. Dilute alkaline water can usually be neutralized with caustic soda, caustic potassium, sodium silicate, sodium carbonate, ammonium water and other free carboxylic acids in the coating film, pH 値 8 ~ 12, which can impart water solubility to those skilled in the art. In the step (4) described above, the copper foil portion (non-circuit portion) on the substrate is exposed by the development process and then removed by a general etching process such as using an aqueous ferric chloride solution. Then, the unexposed part of the circuit pattern is a cellosolve solvent such as ethyl cellosolve, ethyl cellosolve acetate; aromatic hydrocarbon solvents such as toluene and xylene: methyl ethyl ketone, methyl Ketone solvents such as isobutyl ketone; acetate solvents such as ethyl acetate and butyl acetate; chlorine solvents such as trichloroethane; or when using an anionic electrodeposition coating, pH ≥ 1 1 can be used A caustic soda aqueous solution, a caustic potassium aqueous solution, etc. are dissolved and removed to form a printed circuit on a substrate. -20- 200401167 [Effect of the invention] The positive-type photosensitive coating composition of the present invention can be exposed to active light rays such as visible light and ultraviolet rays on the positive-type photosensitive coating film surface formed by the object. The exposed naphthoquinonediazepine compound can form carboxylic acid through ketene, and can be removed by developing solution such as alkaline aqueous solution. In addition, it can be formed by the naphthalene azide in the unexposed area. In addition, the photoresist effect formed by the phenolic component and hydrogen bond in the alkali developing solution can be maintained while maintaining the structure (3). With resistance to dissolution. As a result, the remarkable effect of forming a fine high-resolution pattern can be exhibited through steps (丨). [Examples] The present invention will be described more specifically with reference to examples and the like in the following. "Parts" and "%" are based on weight. The invention is not limited by these. The following abbreviations are used for the following chemical substances. These are described below. IEM: Isocyanoethyl methacrylate DNDDG: Dipropylene glycol dimethyl ether ADVN ·· 2,2'-Azobis (2,4-dimethylpentamyl) NAU-8: 1 '2-naphthalene -2-Diazide-5-sulfonic acid methyl · N_ (2-Ethylethyl) amidamine (manufactured by Toyo Sangyo Co., Ltd.) NM ·· Ν -methyl-2 -pyrrolidone DBTDL: two Butyltin dilaurate PABA: p-aminobenzoic acid 200401167 In a 4-neck flask, add 3 3 5 parts of DFDDG under a nitrogen gas stream and stir. After raising the temperature to 1 17 ° c, add styrene dropwise over 3 hours. 60 parts of methyl methacrylate 150 parts of n-butyl acrylate 1 15 parts of n-butyl methacrylate. 33 parts of isocyanoethyl methacrylate 142 parts of ADVN 17 parts of the mixture, and then in 3 hours A mixture of 45 parts of ADVN and 180 parts of DFDDG was added dropwise into the mixture and kept for 1 hour. After reducing the temperature to 60 ° C, add 85 parts of NAU-8, 125 parts of DMFDG, 130 parts of NMP and stir for 1 hour, add 500PPM DBTDL and stir for another hour. Then, 85 parts of PABA, 70 parts of DFDDG, and 15 parts of NMP were added and stirred for 4 hours' to obtain a positive-type photosensitive resin solution having a resin solid content of 52% and a Gardner viscosity of Z3Z4. The acid value (KOHmg / g, the same below) of the obtained resin was 51. The DNQ concentration (diazonaphthoquinone mole concentration, the same below) was 0.40 mole / kg, and the number average molecular weight was 20.7. . Production Example 2 In a 4-necked flask, 3, 3 and 5 parts of DFDDG were added and stirred under a nitrogen gas flow, and the temperature was raised to 1 17 t. Then, 60 parts of styrene and 150 parts of methyl methacrylate were added dropwise within 3 hours. Butyl propionate 丨 丨 M fraction n-butyl methacrylate 40 parts isocyanoethyl methacrylate 135 parts

ADVN is a mixture of 17 parts 200401167, and then a mixture of 45 parts of ADVN and 180 parts of DFDDG is added dropwise over 3 hours and kept for 1 hour. After reducing the temperature to 60 ° C, add 74 parts of NAU-8, 116 parts of DMFDG, 1 28 parts of NMP and stir for 1 hour, add 5 00PPM DBTDL and stir for another hour. Then, 85 parts of PABA, 70 parts of DFDDG, and 15 parts of NMP were added and stirred for 4 hours to prepare a positive-type photosensitive resin solution having a resin solid content of 51% and Gardner viscosity Z4. The acid value of the obtained resin was 5 2. The DNQ concentration was 0.35 mol / kg and the number average molecular weight was 22,000. Production Example 3 In a 4-necked flask, 3, 3 and 5 parts of DFMDG were added and stirred under a nitrogen gas flow, and the temperature was raised to 17 ° C. Then, 60 parts of styrene and 150 parts of methyl methacrylate were added dropwise within 3 hours. Butyl acrylate 1 1 5 parts n-butyl methacrylate 48 parts isocyanoethyl methacrylate 127 parts ADVN 25 parts mixture, and then a mixture of 45 parts ADVN and 1 80 parts DFMDG was added dropwise over 3 hours' Hold for 1 hour. After the temperature was lowered to 60 ° C, 60 parts of N A U-8, 125 parts of 01 \ ^ 00, and 130 parts of ?? were added and stirred for 1 hour, 50000% 03but01 was added and stirred for another 1 hour. Then, "85 parts of PABA, 70 parts of DFDDG, 15 parts of NMP, and stirred for 4 hours" were prepared to obtain a positive photosensitive resin solution having a resin solid content of 51% and Gardner viscosity Z3. The obtained resin had an acid value of 5 丨, a dNq concentration of 0-30 mol / kg, and a number average molecular weight of 19,000. Manufacturing Example 4 -23- 200401167 Under nitrogen gas flow, 3, 3 and 5 parts of DFDDG were added to a 4-necked flask, and the mixture was stirred and heated to 1 17 ° C. Then 60 parts of styrene methyl methacrylate was added dropwise within 3 hours. Ester 150 parts of n-butyl acrylate 1 15 parts of n-butyl methacrylate 25 parts of isocyanoethyl methacrylate 150 parts of ADVN 17 parts of the mixture, then 45 parts of ADVN, 1 A mixture of 80 parts of DFDDG ^ was held for 1 hour. After lowering the temperature to 60 ° C, ‘85 parts of N A U-8, 1 25 parts of DMFDG, and 1 30 parts of NMP were added and stirred for 1 hour, and 50 OPPM DBTDL was vigorously added and stirred for another 1 hour. Then, 85 parts of PABA, 70 parts of DFDDG, and 15 parts of NMP were added and stirred for 4 hours to prepare a positive-type photosensitive resin solution having a resin solid content of 50% 'Gardner viscosity Z3. The obtained resin had an acid value of 49, a DNQ concentration of 0.45 mol / kg, and a number average molecular weight of 21,000. Example 1 For 100 parts by weight (solid content) of the production example], a positive photosensitive resinous resin was mixed with 2.5 parts by weight of a phenol having an average molecular weight of 4,000 and a hydroxyl value (KOHmg / g) of 110.酣 It resin, after adding Q.40 equivalents of MDEA to the residue to neutralize it, deionized water was added to make the solid content be 10%. 'The electrodeposition coating solution of Example 1 was prepared. Examples 2 to 10 In the same manner as in Example 1, the electrodeposition coating solutions of Examples 2 to 10 were prepared at the mixing ratios shown in Table 丨. Example 1 1 -24- 200401167 The positive photosensitive resin shown in Production Example 1 was blended with a phenol resin at the compounding ratio shown in Table 1 to obtain a liquid photoresist of Example 11. Comparative Example 1 After adding 0.40 equivalents of MDEA to the carboxyl group to the positive photosensitive resin shown in Production Example 1, neutralized water was added, and deionized water was added to a solid content of 10% to prepare an electrodeposition coating solution. Comparative Example 2 For 100 parts by weight of the positive-type photosensitive resin shown in Production Example 1, 60 parts by weight of a weight average molecular weight of 40 00 and a phenolic novolac resin having a hydroxyl value (KOHmg / g) of 110 were added, and the carboxyl group was added to 0.35 After the equivalent of MDEA was neutralized, deionized water was added to make the solid content 10% to prepare an electrodeposition coating solution. Example 1 2 For 100 parts by weight (solid content) of the positive-type photosensitive resin shown in Production Example 1, 5.0 parts by weight of a catechol derivative solution 3 3% bis (4 '5-bis Hydroxy-2-methylphenyl) phenylmethane / DMFDG, after adding 0.40 equivalents of MDEA to the carboxyl group to neutralize it, deionized water was added to make the solid content 10%, and the electrodeposition of Example 12 was obtained. Coating solution. Examples 1 to 2 1 were prepared in the same manner as in Example 12 at the compounding ratios shown in Table 2 to prepare electrodeposition coating solutions of Examples 1 to 3 to 21. Comparative Example 3 An electrodeposition coating solution of each Comparative Example 3 was prepared at the mixing ratio 'shown in Table 2. Test result 25- 200401167 The steel laminate for printed wires was immersed in the electrodeposition coating solution shown in Examples 1 to 1 0 ′ 1 2 to 2 1 as an anode, and a 500 Am-2 direct current was applied at a bath temperature of 35 ° c. A current was applied for 6 to 5 seconds for electrodeposition coating. The coating film was washed with water and dried at 9CTC for 10 minutes to form a non-adhesive, smooth photosensitive film with a thickness of 8 μm. The photoresist liquid observed in Example 11 was applied to a steel laminate for printing and wiring, and dried at 90 ° C for 10 minutes to form a non-adhesive, smooth photosensitive film with a thickness of 8 μm. Then, the positive film was adhered to the coated surface with a vacuum device, and an ultra-high pressure mercury lamp of 10 kw was used, and both sides were irradiated with 300 m] -2. Next, the exposed portion was washed out with a 1% sodium carbonate aqueous solution for development, and after washing with water, the copper foil was etched with an aqueous solution of ferric chloride to remove it, and then the unexposed portion was removed with a 5% sodium hydroxide aqueous solution. Make a pattern. These evaluations are shown in Table 1.

-26- 200401167 Table 1 Compounding amount (solid content ratio) Evaluation results Photosensitivity 13 ί Resin phenol resin * Manufacturing example 1 Manufacturing example 2 Manufacturing example 3 Manufacturing example 4 ABCD Sensitivity line forming example 1 100.0 2.5 〇〇2 100.0 2.5 〇〇3 100.0 2.5 〇〇4 100.0 2.5 〇〇5 100.0 2.5 〇〇6 100.0 2.5 〇07 100.0 2.5 〇〇8 100.0 5.0 〇09 100.0 7.5 〇10 100.0 10.2 〇〇11 100.0 2.5 〇Comparative Example 1 100.0 〇X 2 100.0 60.0 X 〇

* The weight average molecular weight of phenol resin is based on the basic value (KOHmg / g) A: phenol resin lacquer 4000 4000 B: cresol novolac resin 8800 120 (methyl para-mixture) C: polyvinyl phenol resin 4200 460 D: poly Vinylphenol 4800 230 copolymer resin (styrene copolymerization)

200401167 Table 2 Compounding amount (solid content ratio) Evaluation results Photosensitive resin phenol resin * Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 ABCD Sensitivity Line Forming Example 12 100.0 5.0 〇〇13 100.0 5.0 〇〇14 100.0 5.0 〇〇15 100.0 5.0 〇〇16 100.0 5.0 〇〇17 100.0 — 5.0 〇〇18 — ** ———— 100.0 5.0 〇19 100.0 2, 5 〇〇20 100.0 10.0 〇〇21 100.0 5.0 〇〇 Comparative example 3 100.0 60.0 X 〇 * phenol resin A: bis (4 '5-dihydroxy-2-methylphenyl) phenylmethane B: 4,4,5'-trihydroxy-2,3', 5, -tri Methyldiphenylmethane C: bis (4-hydroxy-3- (2-hydroxy-2-methylbenzyl) -5 -methylphenyl) methane D: bis (4-hydroxy-3- 3- (4 -Hydroxy-2-methylbenzyl) -5 -methylphenyl) methane evaluation results. Sensitivity. · The superimposed graded sheet (21 steps) made by the Stern method (21 steps) was superimposed on the coating film. , Evaluated by its number of segments. A good sensitivity is 0 'A low sensitivity is X. Line-drawing formability: Using a line and space pattern film ', the image was developed after exposure, and the state of the line-drawing was observed by optics and SEM. Those with good line formation are 0, those with poor 200401167 are χ. In addition, the electrodeposition coating bath was subjected to a storage promotion test at 30 ° C. for one month, and then the appearance change of the coating bath was observed. As a result, the coating bath was completely free from abnormalities such as precipitation and agglomeration of resin components, and the coating system was good. A printed circuit board was prepared in the same manner as described above by using the coating bath subjected to the storage promotion test. As a result, in Examples 1 to 10 and 12 to 21, printed circuit boards having a good pattern and a good pattern were obtained in the same manner as in the initial stage. (V) Schematic description: None

Claims (1)

200401167 Filing and applying for a patent 1. A positive photosensitive coating composition 'characterized in that one part by weight contains a modified quinonediazidesulfonamide represented by the following general formula (1) in one molecule The following general formula (2) is a structural unit such that the structural unit contains Q. 丨 ~ 0.9-Moore's concentration 'in 1 kg of resin and 0.2 ~ 4.0 Moore's concentration in 1 kg of resin- 1 to 50 parts by weight of at least one component selected from the group consisting of a phenol resin, a phenol derivative, and a catechol derivative, is used for the positive photosensitive resin of the structural unit shown in [), [Chem. 1] · (Wherein R1 represents a hydrogen atom, a linear or branched alkyl group, an aromatic hydrocarbon group, or an alicyclic hydrocarbon group) [Chemical Formula 2] R3-—N (Wherein 'L and R3 each represent a hydrogen atom, a linear or branched alkyl group, an aromatic hydrocarbon group' or an alicyclic hydrocarbon group). -30- 200401167 2. —A pattern forming method, characterized in that it comprises (1) a step of coating a substrate with a positive photosensitive coating composition as described in the first patent application scope to form a positive photosensitive coating film, ( 2) The step (3) of exposing the positive photosensitive coating film directly or through a pattern mask to a pattern by removing the coating film of the exposed portion with an inspection developing solution. 3. A pattern forming method, characterized by (1) a step of applying a positive photosensitive coating composition such as the first patent application scope on a conductive film or a metal plate to form a positive photosensitive coating film, (2) a step of exposing the positive photosensitive coating film directly or via a pattern mask (3) a step of removing the coating film of the exposed portion with an alkaline developing solution to form a pattern, and (4) exposing the exposed conductive film Or a step of etching the surface of the metal plate, (5) a step of removing the photoresist coating film on the pattern. 4. The pattern forming method according to item 2 or 3 of the scope of patent application, wherein the photosensitive coating composition as described in item 1 of the scope of patent application is applied to a substrate or a metal plate having a conductive film by electrodeposition. 5. A method for producing a positive photosensitive resin, which is characterized by the following steps in order: copolymerizing unsaturated monomer free radicals including unsaturated monomers having an isocyanate group-containing polymerizable vinyl group A step of adding a hydroxy-containing quinonediazide compound through a urethanation reaction, and a step of adding an amino acid compound by a urea reaction; -31-200401167 sequentially by the following steps Finished: AL ·. A; ri is based on the addition of isocyanate group-containing polymerizable vinyl groups, and @ 日 日 梦 from the urethane bond to the hydroxyl-containing quinone diazide compound 'Urea bond The step of adding an amino acid compound to form each functional monomer 11 Θ ¥ step and copolymerizing 13 of the polymerizable unsaturated monomer containing the obtained monomer free radicals; or sequentially by the following steps: The unsaturated monomer having a polymerizable vinyl group containing an isocyanate group is formed by adding a urethane bond to a hydroxy-containing quinone diazide compound and a urea bond to add an amino acid compound. A step of each functional monomer, a step of copolymerizing other monomer radicals as necessary, and a step of adding an amino acid compound by a urea reaction. -32- 200401167 Lu, (a), the designated representative of this case is: Figure _ (b), the representative symbols of this representative map are simply explained: 柒 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention. -4-