TWI224718B - 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 to 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 to 0.4 mole concentration positive type sensitivity resin with 1 to 50 parts by weight at least one component selected from the group of phenol resin phenol derivative and catechol.

Description

1224718 发明 Description of the invention (the description of the invention should state: the technical field, prior art, content, embodiments, and drawings of the invention briefly) (1) the technical field to which the invention belongs The invention relates to a conductor with excellent operation stability and a conductor Reliable photoresist for image formation, in particular, a positive photosensitive coating composition suitable as an etching resist for printed circuit board manufacturing, and a printed circuit board using the positive photosensitive coating composition And other pattern formation methods. (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. 2000-0 5). 6264). 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, when the additive amount of the photosensitive substance is increased, there is a problem that sensitivity is reduced. On the contrary, when the additive amount is decreased, the sensitivity is increased, but the solubility of the alkali developing solution is poor, which is not 1224718 points, resulting in a reduction in pattern formation. 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 a molecule containing a modified quinonediazide sulfonamide represented by the following general formula (1) in one part by weight is: The structural unit 'is such that the structural unit contains a concentration of from 0.1 to 0.9 moles in 丨 kg of resin and a concentration of 0.2 to 4.0 moles in 1 kg of resin, as shown by the following general formula (2) The positive photosensitive resin of the structural unit is blended with 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, and the general formula (1)

-7- 1224718 (One of the "I" represents a hydrogen atom, a straight or branched chain radical, an aromatic meridian group, or an alicyclic hydrocarbon group) General formula (2) [Chemical formula 4]

R3——N

(Wherein "R2 and r3" 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 forming a positive photosensitive coating film by applying a positive photosensitive coating composition as described in 1 above on a substrate, 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 a test imaging 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 part to form a pattern with an alkaline developing solution-8-1224718 (4) Step of engraving the exposed conductive film or metal plate with uranium, (5) Removing the photoresist coating film on the pattern step. 4. The pattern forming method according to item 2 or 3 above, wherein the photosensitive coating composition according to item 1 above is applied to a substrate or a metal plate having a conductive film by electrodeposition. (IV) Embodiment First, the positive-type photosensitive coating composition of the present invention will be described in detail. The positive-type photosensitive coating composition of the present invention is characterized in that, for 1,000 parts by weight of the positive-type photosensitive resin described above, In other words, 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") is blended i to 50 parts by weight. Next, each component constituting the positive photosensitive resin will be described. Positive-type photosensitive resin The positive-type photosensitive resin component contains a modified quinonediazide sulfaminamide represented by the general formula (1) in one molecule as a structural unit, and the structural unit contains 0.1 in 1 kg of resin. A positive photosensitive resin having a concentration of ~ 0.9 mol and containing 0.2 to 4.0 mol in the structural unit represented by the above-mentioned general formula (2) in 1 kg of resin. The photosensitivity of the tree β is not specifically limited, but in terms of photosensitivity, developability, coating workability, etc., it is a modified unit of acetic acid and azide diammine in 1 kg of resin solid content. The content is preferably from 0.1 to 0.9 moles, and more preferably from 0.2 to 0.5 moles. 9 ~ 1224718 In the modified quinonediazide sulfonamide photosensitive group represented by general formula (i), h is a monovalent organic group. R! Is a linear or branched alkyl group including methyl, ethyl, n-propyl, isopropyl, and the like. R! 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 mol to 0.9 mol, preferably 0.2 mol to 0.5 mol in 1 kg of resin. If the content is less than 0 ·! Mor, the performance of the photosensitivity and developability is not good, and if it is more than 0.9 Moore, the sensitivity decreases. In the structural unit represented by the general formula (2), R2 and R3 are monovalent organic groups. 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, preferably 0.6 to 1.5 moles, in 1 kg of a positive photosensitive resin (solid content). 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 resistance is poor. 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 contains, for example, a compound having a quinonediazide sulfonamide (hereinafter referred to as a photosensitive group) and 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 (III) added to the resin. Step (I): (1) copolymerizing an unsaturated monomer radical containing an unsaturated monomer having a polymerizable vinyl group containing an isocyanate group. -1 0-1224718 (2) Then, a 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) Adding an amino group-containing diazide compound via a urethane bond and adding 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. In addition, in order to react the hydroxyl group-containing diazide compound in the above-mentioned production steps (1) (2), react with an amino acid compound in the production steps (1) (3), or the production step (II) (1) The isocyanate group-containing vinyl monomer used in the reaction of a diazide compound and an amino acid compound containing a hydroxyl group, or a reaction with an amino acid compound in the manufacturing step (I 1 1) (2), such as the following Show. 1224718 general formula (3) CH2 di c; 7R4

, G-0-CnH2n-NCO (wherein, r4 is a hydrogen atom or a methyl group, and n is an integer of 1 to 8), such as diisocyanate (ethyl methacrylate) and the like. Formula (4) [Chemical Formula 6] / R5

(Wherein R5 is a hydrogen atom or a methyl group, η is an integer of 1 to 8, R6 is a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and R6 is the same linear chain as above Or a branched alkyl group, suitably selected from monomers having 1 to 5 carbon atoms), such as m-propenyl-α, α-dimethylbenzyl isocyanate, and the like. General formula (5) [Chemical formula 7]

—〇-CnH2rv ~ 0H 1224718 (where R? Is a hydrogen atom or a methyl group, and n is a stroke number of 1 to 8) The hydroxyl group-containing (meth) acrylate monomer 1 mole and diiso Monomer obtained from the moire reaction of the gas acid compound 1. The monomer represented by the general formula (5) is, for example, 2-hydroxyethyl (meth) acrylate, 2-transpropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. Diisocyanate compounds such as aliphatic diisocyanates of hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; alicyclic aliphatic monoisocyanates of hydrogenated xylenyl diisocyanate or isophorone diisocyanate Class; methylbenzene diisocyanate or 4,4, -diphenyl methyl diisocyanate aromatic diisocyanate organic diisocyanate itself, or each of these organic diisocyanates and polyols, and low molecular weight polyester resins Or adducts such as water, or cyclic polymers between the organic diisocyanates as described above, and isocyanates and biurets. Among these are tolyl diisocyanate, isophorone diisocyanate, methylcyclohexane, 2,4-diisocyanate, m-xylylene diisocyanate, 1, which have two isocyanates with different reactivity. 3-Diisocyanate methylcyclohexane and the like are preferred. The reaction of the isocyanate-containing vinyl monomer with a hydroxyl-containing quinone diside nitrogen compound is, for example, about 1 mole of hydroxyl-containing quinone diester for 1 mole of isocyanate-containing vinyl monomer in an inert organic solvent. Nitrogen is carried out at a temperature of 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 around 22 50 cm · 1. The solvent used here may be an inert organic solvent which does not react with cyanic acid -13-! 224718 acetic acid group and hydroxyl group, such as ketone-based, ester-based, aromatic-based, aliphatic-based, ether-based solvents. 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). General formula (6) [Chemical formula 8] 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, R 9 It is hydrogen, a carbon number of 1 to 15, or a branched alkyl group, or a hydroxyl group, etc. In addition, the substituent of the amine group is, for example, meta, ortho or para. R9 is appropriately selected from the above R! The number of carbon atoms of the same linear or branched alkyl group is 1 to i 5. In addition, 'Rs is appropriately selected from the number of carbon atoms of 1 to 15 the same linear or branched alkyl group as the above Ri, And aromatic hydrocarbon group, alicyclic hydrocarbon group) Specific examples of the substance include, for example, p-aminobenzoic acid, m-methylaminobenzoic acid, etc. The above-mentioned production #Step (1) (1) A monomer containing an isocyanate-containing monomer One 1 4 one 1224718 copolymerization reaction, usually in the presence of a monomer starting agent such as azobismethoxybutyronitrile, benzamyl peroxide, etc. in an inert organic solvent, at about 80 ~ 1 The reaction takes about 1-20 rows at 50 ° C. 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 are reacted with isocyanate-containing hydroxyl-containing quinonediazide in the presence of tin-based catalyst in the production steps (1) (2) above, ° C ( It is preferably performed at about 50 to 80 ° C. for about 30 minutes, and more preferably 1 to 2 hours. In the above production methods (1), (3) and (111) (3), the reaction with the isocyanate-containing amino acid compound is continued at about 20 to 100 ° C, which is more than 1 to 80 ° C. The reaction takes about 2 to 10 hours, preferably negative. 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, and preferably about 1 to 2 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 ether type, methylamine ketone, and other resins such as ammonium amines have a reaction time of about 20 to 100 to 3 hours, and the resins of the acid esters are about 40 to 3-4 to 4 hours. ~ 100 ° C (minutes ~ 3 small alkenyl monomers and 100 ° C (preferably 3 hours, -15-1224718 is better) 1 ~ 2 hours. The carboxyl group-containing photosensitivity obtained by the above method The blending ratio of the acrylic resin monomer is not particularly limited. For 1 kg of the resin, 0.1 to 0,9 molquinone diester, and for 1 kg of the resin, 0.2 to 0.4 mol. The molecular weight of the carboxyl group-containing photosensitive acrylic resin obtainable by this production method is a number-average molecular weight of about 10,000 to 100,000, preferably 3,000 to 50,000. When the carboxyl group concentration of the resin is less than 0.2 mol, the developing solution in the exposed portion is insufficiently soluble in the developing step and cannot form an image. In addition, it is generally difficult to neutralize, dissolve or disperse the resin in the developing step. In water, a stable electrodeposition coating bath cannot be made. Moreover, it is larger than 4.0 ohms for 1 kg of resin. 'In the developing step, the developing solution of the unexposed part has poor solubility resistance, is insufficient, and cannot form an image. In addition, the coating efficiency (coulomb recovery amount) is easily reduced during electrodeposition coating, and the obtained The photoresist film surface is prone to abnormal coating films such as water marks. The photosensitive concentration of this resin is not particularly limited. In terms of photosensitivity, developability, and coating workability, it is improved for 1 kg of resin solid content. The content of the structural unit of the quinone-azidesulfonamide is preferably 0.1 to 0.9 mol, especially 0.2 to 0.5 mol. Phenol-based component: The phenol-based component used in the present invention is to improve the coating film on the unexposed part. The developer is used for the solubility resistance of the developing solution, that is, an additive that suppresses the solubility of the developing solution, and can form a pattern with excellent image formation without reducing sensitivity. -16-1224718 A phenolic resin such as polyphenol Vinyl phenol, copolymers of vinyl phenol and other acrylic monomers, phenolic lacquer resin, etc. The phenol resin preferably contains 4 to 9.4 mole phenolic hydroxyl groups in 1 kg of resin. In addition, phenol derivatives Catechol-derived The substance can be used by a person skilled in the art, in particular, such as a 4,2,5-trihydroxy-2,3,5, -trimethyldiphenylmethane 2-nucleus tritium classification, 2,6-bis (2, 4-Dioxetylbenzyl) -4 -methylamidine, bis [4-hydroxy-3-(4-hydroxy-2-methylbenzyl) -5 -methylphenyl] methane, bis [ 4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5 -methylphenyl] methane, bis [4-hydroxy-3 (2,4-dihydroxybenzyl) -5 -Methylphenyl] linear phenols of methane, bis (4,5-dihydroxy-2-methylphenyl) phenylmethane, bis (4,5-dihydroxy-2-methylphenyl) The molecular weight of the radial phenolic phenol-based component of -3,4-dihydroxyphenylmethane is about 500 to 100,000, and more 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 phenolic 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 basic neutralizing agent for a positive resin 455 1224718 photosensitive resin, and dispersed in a mixture of the positive photosensitive resin and a phenol-based component, and dispersed in Water-based positive photosensitive coating composition in water. This material can be used as a positive photosensitive coating composition for anion electrodeposition. The neutralizing agent is, for example, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; alkylamines such as monoethylamine, diethylamine, triethylamine, trimethylamine, and diisobutylamine; 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, which can be used alone or as a mixture. In the present invention, in order to improve the fluidity of water-solubilized or water-dispersible electrodeposition coatings, a hydrophilic solvent may be added, such as isopropanol, n-butanol, 3-butanol, methoxyethanol, and ethoxylate. Ethyl alcohol, butoxy ethanol, 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; and hydrophobic ethers such as ethylene glycol dibutyl ether, diethylene glycol dibutyl ether, and propylene glycol phenyl ether. The use amount of these hydrophobic solvents is usually 30 parts by weight or less based on 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- 1224718 Next, the pattern forming method of 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. The step (3) of exposing the positive photosensitive coating film to a pattern by removing the coating film of the exposed portion with a diagnostic developer. And 'also includes a pattern forming method, which is characterized by (1) a step of 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 patterned photomask 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 above 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. -19- 1224718 The coating film thickness of the positive photosensitive coating composition is 1 to 100 μΐΏ, preferably 3 to 20 μΐΏ 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, gas lamps, arc lamps, and the like. Irradiation of active light is usually 50 to 800 m 2 cm-2 'in the present invention to reduce the concentration of the photosensitive group within the range of 30 to 300 mjcm · 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 with pH 値 8 ~ 12, which can impart water solubility to those skilled in the art. In the step (4) 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 portion of the circuit pattern is made of a cellosolve solvent such as ethyl cellosolve, ethylcellosolve acetate; aromatic hydrocarbon solvents such as toluene and xylene; methyl ethyl ketone, methyl Ketone-based solvents such as isobutyl ketone; acetate-based solvents such as ethyl acetate and butyl acetate; chlorine-based solvents such as trichloroethane, or when using anionic electrodeposition coatings, pH ≥ 1 1 or higher A caustic soda aqueous solution, a caustic potassium aqueous solution, etc. are dissolved and removed to form a printed circuit on a substrate. -20- 1224718 [Effect of the invention] The positive-type photosensitive coating composition of the present invention can be exposed to active light such as visible light and ultraviolet rays on the positive-type photosensitive coating film surface formed by the object. The exposed naphthoquinonediazide compound can form a carboxylic acid through ketene, and can be removed by developing solution such as an aqueous alkali solution. In addition, it is formed by the naphthoquinonediazide portion of the unexposed part. The compounded phenolic component is hydrogen-bonded, maintains its structure, and has solubility resistance to an alkali developing solution. As a result, the photoresist formed in steps (丨) to (3) can exert a remarkable effect of forming a fine high-resolution pattern. [Examples] The present invention will be described more specifically with 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-dimethylvaleronitrile) NAU-8: 1,2-naphthoquinone- 2-Diazide-5-sulfonic acid methyl (2-hydroxyethyl) amidamine (manufactured by Toyo Sangyo Co., Ltd.) NMP: N-methyl-2-pyrrolidone DBTDL: dibutyltin dilaurate PABA: Production of p-aminobenzoic acid positive-type photosensitive resin Manufacturing Example 1 -21-1224718 Add 3 3 5 parts of DFDDG to a 4-necked flask under a nitrogen gas stream and stir, and raise the temperature to 11 71 after 3 hours 60 parts of styrene 60 parts of methyl methacrylate 150 parts of n-butyl acrylate 1 15 parts of n-butyl methacrylate 3 3 parts of isocyanoethyl methacrylate 1 42 parts of ADVN The mixture was then added dropwise with a mixture of 45 parts of ADVN and 180 parts of DFDDG over 3 hours and held 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 prepare a positive-type photosensitive resin solution having a resin solid content of 52% and a Gardner viscosity of Z3Z4. The acid value (K0Hmg / g, the same below) of the obtained resin was 51. The DNQ concentration (diazonaphthoquinone mole concentration, below) was 0.40 ng / kg, and the number average molecular weight was 20,700. 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 17 ° C. Then, 60 parts of styrene and 150 parts of methyl methacrylate were added dropwise within 3 hours. N-butyl acrylate 1 15 parts n-butyl methacrylate 40 parts isocyanoethyl methyl propionate 135 parts ADVN 17 parts 1224718 A mixture, then 45 parts ADVN, 180 parts DFMDG are added dropwise within 3 hours The mixture was held for 1 hour. After reducing the temperature to 60 ° C, add 74 parts of N A U-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. N-butyl acrylate 1 1 5 parts n-butyl methacrylate 4 8 parts isocyanoethyl methacrylate 127 parts ADVN 25 parts mixture, then 45 parts ADVN, 1 80 parts DMFDG are added dropwise within 3 hours The mixture was held for 1 hour. After reducing the temperature to 60 ° C, add 60 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 prepare a positive-type photosensitive resin solution having a resin solid content of 51% and Gardner viscosity Z3. The obtained resin had an acid value of 51, a DNQ degree of 0.30 mol / kg, and a number average molecular weight of 19,000. Production Example 4 -23-1224718 Add 3 3 5 parts of DFDDG to a 4-necked flask under a stream of nitrogen and stir. After raising the temperature to 1 17 ° C, 60 parts of styrene methacrylic acid was added dropwise within 3 hours. Methyl ester 150 parts of n-butyl acrylate 1 15 parts of n-butyl methacrylate 2 5 parts of isocyanoethyl methacrylate 1 50 parts of ADVN 17 parts of the mixture, and then 45 parts are added dropwise within 3 hours Mixture of ADVN, 180 parts of DFDDG, hold for 1 hour. After reducing the temperature to 60 ° C, add 85 parts of NAU-8, 1 25 parts of DMFDG, 1 30 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 50% and a 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 positive photosensitive resin shown in Production Example 1, 2.5 parts by weight of a phenol novolac resin having a weight average molecular weight of 4000 and a hydroxyl value (KOHmg / g) of 110 were mixed. After adding the equivalent of MDEA to the carboxyl group for neutralization, deionized water was added to make the solid content be 0% to prepare the electrodeposition coating solution of Example 1. 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 1, respectively. Example 1 1 1224718 The positive-type photosensitive resin shown in Production Example 1 was mixed with a phenol resin at the compounding ratio shown in Table 1 to prepare a liquid photoresist of Example π. Comparative Example 1 After adding 40 equivalents of MDEA to the positive photosensitive resin shown in Production Example 1 to neutralize the carboxyl group, deionized water was added to make the solid content 10% to prepare an electrodeposition coating solution. Comparative Example 2 For 100 parts by weight of the positive photosensitive resin shown in Production Example 1, 60 parts by weight of a phenol novolac resin having an average molecular weight of 4000 and a hydroxyl value (KOHmg / g) of 110 were mixed, and 0.35 equivalents of MDEA was added to the carboxyl group. After neutralization, deionized water was added so that the solid content was 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 33% bis (4,5-dihydroxy- 2-methylphenyl) phenylmethane / DMFDG, after adding 0.440 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 compounding ratio shown in Table 2. Test results-25- 1224718 The steel laminate for printed wires was immersed in the electrodeposition coating solution shown in Examples 1 to 10 and 12 to 21 as an anode, and a direct current of 500 Am_2 was energized at a bath temperature of 35 ° C 6 5 Electrodeposition was applied in seconds. The coating film was washed with water and dried at 9 ° C. 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 at 90 ° C. Dry at 10 ° C for 10 minutes to form a non-adhesive, smooth photosensitive film with a thickness of 8 μm. Then, make a positive film tightly adhere to the coating surface with a vacuum device, and use an ultra-high pressure mercury lamp of 1 Okw, irradiate 300 on each side -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 the unexposed portion by 5% sodium hydroxide. The aqueous solution was removed to produce a pattern. These evaluations are as shown in Table 丄.

-2 6-4 Μ 1224718 Table 1 Compounding amount (solid content ratio) Evaluation results Photosensitive ΰ Tri-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 〇〇10 10 2.5 Comparative Example 1 100.0 〇 X 2 100.0 60.0 X 〇

* Phenol resin weight average molecular weight hydroxyl 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: Polyethylene 4800 230 copolymer resin (styrene copolymerization)

27 1224718 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 〇〇19 100.0 2.5 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

• 4,4,5, trihydroxy_2,3,, trimethyldiphenylmethane C · bis (4-hydroxy_3- (2-hydroxy-2-methylbenzyl) -5-methyl Phenyl) methane D • Bis (4-hydroxy · 3- (4-hydroxy-2-methylbenzyl) -5 -methylphenyl) methane Evaluation Results Sensitivity ·· Stone system classification Sheets (21 segments) were superimposed on the coating film and developed after exposure. The number of segments was evaluated. The sensitivity is 0, and the sensitivity is X. Formability of line drawing: Use line and space pattern film, visualize after exposure, draw line state by optical and SEM observation. Line drawing is good for 0, poor -28-1224718 is 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

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Claims (1)

1224718, patent application range 92 1 07685 "Positive photosensitive coating composition, manufacturing method and pattern forming method of positive photosensitive resin" patent case (93 t April 1 'revised' version) 1. A positive Type photosensitive coating composition, characterized in that 1 to 50 parts by weight of a positive type photosensitive resin is blended with 1 to 50 parts by weight of a phenol component selected from the group consisting of a phenol tree, a phenol derivative, and a catechol derivative. Wherein, one molecule of the positive photosensitive resin contains a modified quinonediazidosulfonamide as a structural unit, and the structural unit contains 0.1 to 0.9 moles in 1 kg of resin. Concentration of the ear and a structural unit represented by the following general formula (2) at a concentration of 0.2 to 4.0 moles in 1 kg of resin, [化 1] Q (Wherein R1 represents a hydrogen atom, a linear or branched Ci6 alkyl group, a C6-8 aromatic hydrocarbon group, or a c3-6 alicyclic hydrocarbon group) [Chemical Formula 2] R3—N 1224718 (wherein I and I each represent a hydrogen atom, a linear or branched 6-alkyl f group, an aromatic hydrocarbon group, or a c3 6 cycloaliphatic hydrocarbon group) ^ 2 A pattern forming method including (1 ) Coating the substrate with a positive photosensitive coating composition as described in the first patent application to form a positive photosensitive coating film, (2) exposing the positive photosensitive coating film directly or via a pattern mask Step (3) A step of removing a coating film of the exposed portion with an alkaline developing solution to form a pattern. 3. A pattern forming method, characterized in that φ (1) a step of applying a positive-type photosensitive coating composition such as item 1 of the scope of patent application on a conductive film or metal plate to form a positive-type photosensitive coating film (2) the step of exposing the positive photosensitive coating film directly or via a pattern mask (3) the step of removing the coating film of the exposed portion with an alkaline developer to form a pattern, and (4) the conductive conductivity of the exposure (5) a step of removing the photoresist coating film on the pattern. φ 4. The pattern forming method according to the second or third item of the patent application, wherein the photosensitive coating composition as the first item of the patent application is applied to a substrate or a metal plate having a conductive film by electrodeposition. 5. A method for producing a positive-type photosensitive resin, characterized in that ^ is sequentially formed by the following steps: Step (I): sequentially includes ① making unsaturated unsaturated polymerizable vinyl groups having a polymerizable vinyl group containing an isocyanate group-2 -Unsaturated monomer mixture of 1224718 monomer, the step of radical copolymerization in the presence of a radical polymerization initiator, ② the radical-containing diazide compound in the presence of a tin catalyst 'through amine The formate formation reaction addition step, and ③ the amino acid compound is added at a temperature of 20 to 100 ° C with a urea formation reaction addition step; step (II): sequentially including ① Isocyanate-based polymerizable vinyl unsaturated monomers react in the presence of various tin-based catalysts to add hydroxy-containing quinone diazide compounds through urethane bonding and amine groups through urea bonding. An acid compound to form each functional monomer, ② a step of radical copolymerization of a polymerizable unsaturated monomer mixture containing the obtained monomer in the presence of a radical polymerization initiator; or step (III): sequentially including ① For polymers with isocyanate groups Unsaturated vinyl monomers react in the presence of tin-based catalysts to form functional monomers through the addition of urethane bonds to hydroxy-containing quinone diazide compounds. ② The obtained monomers and Isocyanate-based polymerizable vinyl monomers and other polymerizable unsaturated monomers, if necessary, are radically copolymerized in the presence of a radical initiator. ③ The amino acid compound is reacted in the presence of a tin-based catalyst. Step of urea addition reaction.