KR20060092260A - Aqueous resist composition - Google Patents

Abstract

There is provided a novel resist composition used for production of printed boards. The aqueous resist composition of the present invention comprises (A) a resin soluble in water or an aqueous alkali solution, (B) a cellulose derivative, (C) water and (D) a hydroxyl group-containing organic solvent, wherein the content of the cellulose derivative (B) in the resist composition is within a range from 0.001 to 1.0% by weight, the content of water (C) is within a range from 25 to 65% by weight, and the content of the hydroxyl group-containing organic solvent (D) is within a range from 15 to 50% by weight. According to the present invention, it is made possible to form an aligned pattern having a smooth surface with high accuracy while maintaining excellent adhesion and good tack of a resist by using a specific amount of water and a specific solvent even if a very small amount of a cellulose derivative is used.

Description

Aqueous resist composition {AQUEOUS RESIST COMPOSITION}

(Cross-reference of related applications)

This application claims the benefit of U.S. Provisional Application No. 60/605532, filed August 31, 2004, under section 35 U.S.C. 119 (e).

The present invention relates to a resist composition used for the production of a printed board, in particular, an aqueous solution or a dispersion type resist composition and a method for producing a resist-coated substrate using the same.

Conventionally, a printed circuit board has a resist coating film formed on an insulating substrate having a conductive metal layer such as copper foil (may contain a metal other than copper, hereinafter also referred to as "copper clad substrate"), and the resist coating film has a desired pattern. It has been manufactured by exposing through a photomask, developing the exposed resist coating film with water or alkaline water, etching the conductive metal layer in the portion where the resist does not remain with an etching solution, and then removing the resist to form a desired wiring pattern. .

Examples of the method of forming a resist layer on the copper clad substrate include a dry film method and a liquid resist coating method. As a liquid resist coating method, a dip coating method is known in addition to a method of applying a liquid resist on a copper clad substrate by roll coating or screen printing. According to this method, the copper clad substrate is immersed in a large amount of a resist composition solution (generally a solution), the substrate is taken out, and then the solvent is evaporated by drying to form a resist coating film on the copper clad substrate.

Organic solvents having high volatility have been used in liquid resist compositions used in the dip coating method. Because of concerns about negative effects on the human body and the environment, for example, a resist composition containing water as a solvent disclosed in Japanese Patent Laid-Open No. 05-27437 has been proposed.

However, since the aqueous resist composition contains water having a low evaporation rate as a solvent, much time is required to dry the resist composition after coating. Therefore, so-called "sagging" occurs during drying of the resist solution, causing problems such as uneven thickness of the coating film.

In order to prevent "sagging", it is known to add a thixotropic agent (thixotropy-imparting agent) or a thickener to the resist composition. For example, Japanese Patent Laid-Open No. 2003-233183 proposes a composition using an inorganic thickener. have. Even if the thickness of the coating film is kept uniform, the smoothness and adhesion strength of the coating film are not necessarily sufficient. In particular, further improvement is required in the smoothness of the coating film in order to obtain a highly accurate wiring pattern.

Conventionally, it is proposed to use a cellulose derivative such as hydroxyalkyl cellulose as an organic thixotropic agent or a thickener (see, for example, Japanese Patent Application Laid-Open No. 55-045725 and Japanese Patent Application Laid-open No. Hei 11-174667). However, since the cellulose derivative in the aqueous solution of the cellulose derivative causes reversible gelation at a given temperature, the cellulose derivative precipitates out of the aqueous solution above the above temperature, so that the viscosity of the aqueous solution rapidly decreases. Therefore, when an aqueous resist containing cellulose derivative is applied, and then dried above the gelling temperature, severe "sagging" occurs due to a decrease in viscosity during drying. Moreover, since the decrease in viscosity during drying changes the dispersion state of the composition, the smoothness of the coating film is degraded. Depending on the type of cellulose derivative, the gelation temperature is generally significantly lower than the boiling point of water, so that it has been difficult to solve the above problems.

Japanese Patent Laid-Open No. 2000-292922 discloses a photosensitive composition containing 0.05 to 4.0 of a hydrophobic polymer and a water-soluble polymer in a weight ratio (hydrophobic polymer / water-soluble polymer), and hydroxyalkyl cellulose can be used as a water-soluble polymer. It is described. However, for compositions containing large amounts of cellulose derivatives, the surface coated with the aqueous composition is not sufficiently dried due to the hydrophilicity of the cellulose, so that the coated surface exhibits excessive viscosity. In addition, the addition of water degrades the smoothness of the coated surface, so that problems such as reducing the resolution of the pattern are not solved.

An object of the present invention is to provide a resist composition containing water as a solvent and capable of forming a wiring pattern having a high precision and smooth surface while maintaining excellent adhesion and good viscosity of the resist.

As a result of earnestly examining by the present inventors, even if a very small amount of cellulose derivative is used for the resist composition containing water-soluble or alkali-soluble resin and a cellulose derivative, the said objective can be achieved by using a specific amount of water and a specific solvent. This invention was completed. The present invention is described in the following [1] to [9].

[1] An aqueous resist composition containing (A) a resin soluble in water or an aqueous alkali solution, (B) a cellulose derivative, (C) water, and (D) a hydroxy group-containing organic solvent, wherein (B) in the resist composition ) The content of cellulose derivative is in the range of 0.001 to 1.0% by weight, (C) the content of water is in the range of 25 to 65% by weight, and (D) the content of the hydroxy group-containing organic solvent is in the range of 15 to 50% by weight. Aqueous resist composition.

[2] (A) Resin soluble in water or aqueous alkali solution, (B) cellulose derivative, (C) water, (D) hydroxy group-containing organic solvent, (E) polymerizable unsaturated compound and (F) photopolymerization initiator As an aqueous resist composition containing, the content of the (B) cellulose derivative in the resist composition is in the range of 0.001 to 1.0% by weight, the content of (C) water is in the range of 25 to 65% by weight, and (D) a hydroxyl group -The content of the organic solvent containing the aqueous resist composition in the range of 15 to 50% by weight.

[3] The aqueous resist composition according to [1] or [2], wherein the weight ratio (A) / (B) of the resin (A) soluble in water or alkali aqueous solution to the (B) cellulose derivative is in the range of 10 to 1000. .

[4] The aqueous resist composition according to any one of [1] to [3], wherein the resin (A) soluble in water or an aqueous alkali solution is a copolymer containing (meth) acrylic acid as one of its constituent monomers.

[5] The aqueous resist composition according to any one of [1] to [4], wherein the cellulose derivative (B) is hydroxyalkyl cellulose.

[6] The compound according to any one of [1] to [5], wherein the (D) hydroxy group-containing organic solvent is a monoalkyl ether of a diol compound, a monoester of an diol compound and an aliphatic carboxylic acid and an α-hydroxy. An aqueous resist composition that is at least one of the carboxylate esters.

[7] A method for producing a resist coated substrate comprising immersing a heat transfer substrate containing a conductive metal in the aqueous resist composition according to any one of [1] to [6].

[8] A method for producing a printed circuit board, comprising using the aqueous resist composition according to any one of [1] to [6].

[9] A printed circuit board manufactured by using the aqueous resist composition according to any one of [1] to [6].

The present invention will now be described in detail.

(A) Resin soluble in water or alkali aqueous solution

The resin (A) soluble in water or aqueous alkali solution (hereinafter also referred to as "water or alkali-soluble resin") used in the resist composition of the present invention refers to a resin that can be dissolved in water or an aqueous alkali solution, such as an aqueous sodium carbonate solution. The water or alkali-soluble resin of the present invention has a property of being soluble in a developer and slightly soluble in an etching solution, and is preferably a component containing a resin having a carboxyl group or an anhydride group in a molecule thereof. Examples of the resin having a carboxyl group or an anhydride group in the molecule include an acrylic resin which is a copolymer containing (meth) acrylic acid and (meth) acrylate ester as a monomer, a copolymer of (meth) acrylic acid and ethylene, a maleic anhydride, ethylene or styrene The copolymers of are enumerated. Acrylic resins are particularly preferred in terms of adhesion and viscosity.

(Meth) acrylic acid means methacrylic acid and / or acrylic acid.

(A) Water or alkali-soluble resins are preferably photopolymerizable resins capable of causing photopolymerization under ultraviolet, X-ray, or electron beam exposure in the presence or absence of a photopolymerization initiator, for example polymerization in the molecule such as ethylenically unsaturated bonds. Lists of plural genitalia are listed.

As photopolymerizable resin, well-known resin can be used individually or in combination, It can select from the group of following (1)-(5).

(1) a reaction product of an unsaturated hydroxy compound with a resin having at least one functional group selected from a carboxyl group, a carboxylic anhydride group, an isocyanate group and an epoxy group;

(2) a reaction product of an unsaturated epoxy compound with a resin having at least one functional group selected from a carboxyl group, a carboxylic anhydride group, an isocyanate group, an amino group and a hydroxy group;

(3) a reaction product of an unsaturated carboxylic acid or an unsaturated carboxylic anhydride with a resin having at least one functional group selected from hydroxy, amino, isocyanate and epoxy groups;

(4) a reaction product of an unsaturated amino compound with a resin having at least one functional group selected from carboxyl groups, carboxylic acid anhydride groups, formyl groups, keto groups, isocyanate groups and epoxy groups; And

(5) A reaction product of an unsaturated isocyanate compound and a resin having at least one functional group selected from a carboxyl group, a carboxylic anhydride group, an amino group, a hydroxyl group and an epoxy group.

Although the weight average molecular weight and acid value (mgKOH / g) of these photopolymerizable resins are not specifically limited, The weight average molecular weight is preferably in the range of 500 to 100,000, more preferably in the range of 1,000 to 50,000, more preferably in the range of 2,000 to 20,000. Most preferably, the acid value is preferably in the range of 20 to 350, more preferably in the range of 50 to 250, and most preferably in the range of 80 to 200.

The weight average molecular weight is measured by gel permeation chromatography, and the acid value is measured in the order defined in JIS K5601.

Specific examples of the unsaturated hydroxy compound include polyethylene glycol mono (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, diethylene glycol monoacrylate, triethylene glycol Polyethylene glycols such as mono (meth) acrylate, polyethylene such as 1,4-butanediol mono (meth) acrylate, ethylene glycol mono (meth) allylether and diethylene glycol mono (meth) allylether Glycol mono (meth) allylether, N-methylolacrylamide, allyl alcohol, metaallyl alcohol, hydroxystyrene, hydroxymethylstyrene and allyl phenol.

Specific examples of unsaturated epoxy compounds include glycidyl (meth) acrylate, allyl glycidyl ether, and 3,4-epoxycyclohexyl methyl (meth) acrylate.

As unsaturated carboxylic acid and its anhydride, it is (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, sorbic acid, tetrahydrophthalic acid, cinnamic acid, nad acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, li Kanic acid, ricinoleic acid, arachidonic acid and its anhydrides can be used.

Examples of unsaturated amino compounds include the reaction products of allylamine, diallylamine, aminostyrene, aminomethylstyrene, acrylamide and unsaturated carboxylic acids or derivatives thereof and polyamines such as ethylenediamine.

As the unsaturated isocyanate compound, a reaction product of 2-isocyanate ethyl (meth) acrylate, allyl isocyanate and unsaturated hydroxy compound and polyisocyanate such as toluene diisocyanate or xylene diisocyanate can be used.

The resin having at least one functional group used in (1) to (5) is at least one homo selected from unsaturated carboxylic acids, unsaturated carboxylic anhydrides, unsaturated isocyanate compounds, unsaturated epoxy compounds, unsaturated carboxy compounds and unsaturated amino compounds. Polymer or copolymer.

Examples of the resin having a carboxyl group as a functional group include poly (meth) acrylic acid, (meth) acrylic acid-methyl (meth) acrylate copolymer, (meth) acrylic acid-styrene copolymer, styrene maleic anhydride copolymer, and ethylene (meth) acrylic acid And (anhydrous) carboxylic acid addition products of copolymers, terminal carboxylated polybutadienes, terminal carboxylated butadiene-acrylonitrile copolymers and phenol resins.

Examples of the resin having a hydroxy group include polyhydroxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate-styrene copolymer, hydroxyethyl (meth) acrylate-methyl methacrylate copolymer, novolac type Phenolic resins, polyvinyl alcohols, partially saponified ethylene-vinyl acetate copolymers, polyglycerols, polyvinylphenols, carboxylic acid addition products of epoxy resins, polyethylene glycols, polypropylene glycols, terminal hydroxylated (hydrogenated) polybutadienes, terminal hydroxides (Hydrogenation) Petroleum resins and reaction products of polyhydric alcohols with polyhydric isocyanates are listed.

Examples of the resin having an epoxy group include polyglycidyl (meth) acrylate, glycidyl (meth) acrylate-styrene copolymer, glycidyl (meth) acrylate-methyl methacrylate copolymer, and novolak type phenol The reaction product of resin and epichlorohydrin, the reaction product of polyhydric phenol and epichlorohydrin, and the reaction product of polyhydric alcohol and epichlorohydrin are listed.

Examples of resins having amino groups include polyacrylamide, polyallylamine, saponified products of polyvinylformamide, saponified products of polyvinylacetamide, polyaminostyrene, aminostyrene-styrene copolymers, carboxyl group-containing resins and polyhydric amines. Reaction products, urea resins and melamine resins are listed.

Examples of the resin having an isocyanate group include reaction products of poly-2-isocyanate ethyl (meth) acrylate, 2-isocyanate ethyl (meth) acrylate-methyl (meth) acrylate copolymer, and polyhydric isocyanate compound and polyhydric hydroxy compound. Listed.

Specific examples of the more preferable resin among the resins of (1) to (5) are:

(1-1) a reaction product of an unsaturated hydroxy compound with a resin having a carboxylic anhydride group, for example, a reaction product of hydroxyethyl acrylate and a styrene-maleic anhydride copolymer and the reaction product further reacted with a base Obtained reaction product;

(1-2) reaction product of an unsaturated hydroxy compound and a resin having an isocyanate group;

(2-1) Reaction products of unsaturated epoxy compounds and resins having carboxyl groups, for example, reaction products of glycidyl acrylate and methacrylic acid-methyl methacrylate copolymers, 3,4-epoxy-cyclohexyl methylacrylic Reaction products of the rate and methacrylic acid-methyl methacrylate copolymers and reaction products obtained by further reacting these reaction products with a base;

(3-1) Reaction products of unsaturated carboxylic acids or unsaturated carboxylic anhydrides of resins having epoxy groups, for example reaction products of acrylic acid and polyglycidyl methacrylate and acrylic acid and glycidyl methacrylate-methyl Reaction product of methacrylate copolymer.

In these, the copolymer containing (meth) acrylic acid is preferable as a kind of constituent monomer, and the acrylic resin containing the copolymer or modified substance of (meth) acrylic acid and its ester is more preferable. Specific examples thereof include reaction products of glycidyl acrylate and methacrylic acid-methyl methacrylate copolymers, reaction products of 3,4-epoxy-cyclohexyl methylacrylate and methacrylic acid-methyl methacrylate copolymers, and There are reaction products obtained by further reacting these reaction products with bases.

As the photopolymerized resin, in addition to the resins (1) to (5), the following may be used:

(6) homopolymers or copolymers of conjugated diene compounds such as polybutadiene and modified products thereof;

(7) Polymerizable unsaturated resin obtained by adding unsaturated dicarboxylic acid or its anhydride to the unsaturated bond in the fatty acid chain of the ether product of an epoxy resin and an unsaturated fatty acid;

(8) polymerizable unsaturated resins containing unsaturated fatty acid-modified high acid value alkyd resins; And

(9) A mixture of maleated oil and a polymerizable unsaturated resin containing an ethylenically unsaturated compound having at least one polymerizable unsaturated bond in the molecule.

The content of the resin (A) in the aqueous resist composition of the present invention is usually in the range of 5 to 40% by weight, preferably in the range of 7 to 30% by weight, particularly preferably in the range of 9 to 25% by weight. If the content is less than 5% by weight, the thickness of the coating film formed on the insulating substrate is too thin, there may occur a problem that the strength of the coating film is lowered. If the content exceeds 40% by weight, the thickness of the coating film is too thick, there may be a problem that the viscosity increases rapidly and the drying time is long.

(B) cellulose derivative

In the cellulose derivative (B) of the present invention, an alkyl group, a hydroxyalkyl group or a carboxyl alkyl group is introduced into the hydroxy group of cellulose. Known cellulose derivatives can be used without limitation, and hydroxyalkyl cellulose is preferred. Examples of the alkyl group include methyl group, ethyl group, propyl group and butyl group; Examples of the hydroxyalkyl group include a hydroxyethyl group, a hydroxypropyl group and a hydroxybutyl group; In addition, examples of the carboxyalkyl group include a carboxymethyl group. Specific examples of cellulose derivatives include alkyl ethers of celluloses such as methyl cellulose, ethyl cellulose and benzyl cellulose; Hydroxyalkyl ethers of hydroxyethyl cellulose and hydroxypropyl cellulose; Alkyl hydroxyalkyl ethers of methyl hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, methyl ethyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and ethyl hydroxypropyl cellulose; Carboxycarboxylose such as carboxymethyl cellulose; And cellulose esters such as cellulose acetate. Although the amount of the alkyl group or the hydroxyalkyl group to be introduced can be set within an arbitrary range depending on the purpose, it is usually within the range of 0.05 to 2.5 equivalents per glucose contained in the cellulose.

Among these, methyl cellulose, ethyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, ethyl hydroxypropyl cellulose and hydroxypropyl cellulose are preferable, and hydroxypropyl cellulose is particularly preferable.

Commercially available cellulose derivatives can be used, for example, HEC DAICEL (product of DAICEL CHEMICAL INDUSTRIES, LTD.), Belmocoll (product of Akzo Nobel Co., Ltd.), HEC (product of SUMITOMO SEIKA CHEMICALS CO., LTD.), KLUCEL (Manufactured by Sansyo Co., Ltd.), Metolose (manufactured by Shin-Etsu Chemical Co., Ltd.), Nisso HPC (manufactured by Nippon Soda Co., Ltd.), and Tylose (manufactured by Clarit Japan Co., Ltd.). .

The content of the (B) cellulose derivative is in the range of 0.001 to 1.0% by weight based on the aqueous resist composition of the present invention. If a component is not in the said range, the effect of this invention is hard to be obtained. When the content exceeds 1.0% by weight, not only the surface smoothness of the coating film is degraded, but also the coating film obtained exhibits excessive viscosity. If the content is less than 0.001% by weight, the thickness of the coating film obtained is nonuniform and unsatisfactory appearance such as cissing or nonuniformity appears, and the smoothness of the coating film surface is further deteriorated.

In this invention, the weight ratio (A) / (B) of the (B) cellulose derivative with respect to (A) water or alkali-soluble resin has a preferable inside of the range of 10-1000. When the weight ratio of (A) / (B) exceeds 350, the content of component (A) is preferably 15% by weight or more.

(C) water

The aqueous resist composition of this invention contains (C) water as a solvent. The amount of organic solvent with high volatility can be reduced by containing (C) water. In addition, the flash point of the resist composition can be increased, thereby increasing safety during storage and transportation.

The content of (C) water in the aqueous resist composition of the present invention is necessary to control the gelation of the cellulose derivative to obtain a coating film having a good shape, and is in the range of 25 to 65% by weight based on the aqueous resist composition, and is 25 to 60% by weight. The range of% is preferable, The range of 30-56 weight% is more preferable, The range of 35-52 weight% is more preferable, The inside of 35-50 weight% is the most preferable. When the content of water exceeds the above range, gelation of the cellulose derivative is likely to occur, so that the coating film has poor smoothness, and it is difficult to obtain a pattern of high precision. If the water content is less than the above range, since the solubility of the cellulose derivative is deteriorated, the smoothness of the coating film is deteriorated, making it difficult to obtain a pattern of high precision.

(D) Hydroxyl group -Organic solvent

The (D) hydroxy group-containing organic solvent of the present invention is a compound having at least one hydroxy group in a molecule, and known organic solvents can be used without limitation. Among these organic solvents, alcohol compounds, diol compounds, monoalkyl ethers of diol compounds, monoesters and aliphatic carboxylic acids and α-hydroxycarboxylate esters of diol compounds are preferable. In addition, these hydroxyl group-containing organic solvents may be used alone or in combination.

The content of component (D) in the aqueous resist composition of the present invention is in the range of 15 to 50% by weight, preferably in the range of 20 to 55% by weight, more preferably in the range of 20 to 45% by weight, based on the aqueous resist composition of the present invention. Preferably, the inside of the 25-45 weight% range is more preferable, and the inside of the 25-40 weight% range is the most preferable. If the content of the component (D) is less than 15% by weight, it is difficult to suppress gelation of the cellulose derivative caused by heating, so that the coating film has poor smoothness and it is difficult to obtain a pattern of high precision. Moreover, "sagging" occurs during drying, resulting in deterioration of the uniformity of the coating film thickness. If the content exceeds 50% by weight, the solubility of the cellulose derivative is deteriorated, so that the coating film has a bad smoothness and it is difficult to obtain a pattern of high precision.

Specific examples of the (D) hydroxy group-containing organic solvent include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 1-pentanol, ethylene glycol, propylene glycol, glycerin, 1,2-propanediol, diethylene Glycol, triethylene glycol, tetraethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tri Ethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, ethylene glycol monoacetate, diethylene glycol monoacetate, triethylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Glycol mono Propylene ether monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, propylene glycol monoacetate and dipropylene glycol monoacetate. .

1,3-propanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-butanediol, 3 -Methyl-1,3-butanediol, 1,3-pentanediol, 2,4-pentanediol, 1,3-hexanediol, 2,4-hexanediol, trimethylol propane, pentaerythritol, 3-methoxy -1-propanol, 2-methyl-3-methoxy-1-propanol, 2,2-dimethyl-3-methoxy-1-propanol, 3-methoxy-1-butanol, 3-methoxy-3-methyl -1-butanol, the methoxy group of the organic solvent being substituted with an ethoxy group or another alkoxy group, 3-acetoxy-1-propanol, 2-methyl-3-acetoxy-1-propanol, 2,2-dimethyl- It is also possible to use 3-acetoxy-1-propanol, 3-acetoxy-1-butanol, 3-acetoxy-3-methyl-1-butanol and the acetoxy group of the organic solvent substituted with other acyloxy groups.

As the (D) hydroxy group-containing organic solvent, α-hydroxycarboxylate esters can also be used, and known α-hydroxycarboxylate esters can be used without limitation. Specific examples of the α-hydroxycarboxylate esters include methyl glycolate, ethyl glycolate, n-propyl glycolate, isopropyl glycolate, n-butyl glycolate, isobutyl glycolate, n-pentyl glycolate, n- Glycolate esters such as hexyl glycolate and cyclohexyl glycolate; Methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, n-hexyl lactate, cyclohexyl lactate and Lactate esters such as benzyl lactate; Methyl α-hydroxybutyrate, ethyl α-hydroxybutyrate, n-propyl α-hydroxybutyrate, isopropyl α-hydroxybutyrate, n-butyl α-hydroxybutyrate, isobutyl α-hydroxybutyrate, n- Α-hydroxybutyrate esters such as pentyl α-hydroxybutyrate, n-hexyl α-hydroxybutyrate and cyclohexyl α-hydroxybutyrate; And methyl α-hydroxy valerate, ethyl α-hydroxy valerate, n-propyl α-hydroxy valerate, isopropyl α-hydroxy valerate, n-butyl α-hydroxy valerate, isobutyl α- Α-hydroxy valerate esters such as hydroxy valerate, amyl α-hydroxy valerate, n-hexyl α-hydroxy valerate and cyclohexyl α-hydroxy valerate are listed.

Other known organic solvents may be added to the resist composition of the present invention if necessary. Examples of the solvent include ketones such as acetone, methylethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, ethylbenzene and tetramethylbenzene; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl Glycol ethers such as ethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol dibutyl ether; Acetate esters such as methyl acetate, ethyl acetate and butyl acetate; Methyl 3-methoxy-propionate, ethyl 3-methoxy-propionate, methyl 3-methoxy-butyrate, ethyl 3-methoxy-butyrate, methyl 3-methyl-3-methoxy-butyrate, ethyl 3 -Methyl-3-methoxy-butyrate, methyl 2-methoxy-cyclohexanecarboxylate, 3-methoxy-1-propyl acetate, 2-methyl-3-methoxy-1-propyl acetate, 2,2- Dimethyl-3-methoxy-1-propyl acetate, 3-methoxy-1-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, in which the methoxy group of the solvent is replaced by an ethoxy group or another alkoxy group Those in which the acetoxy group of the solvent is substituted with other acyloxy groups, aliphatic hydrocarbons such as octane, decane and cyclohexane; And petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha.

(E) Polymerizable  Unsaturated compounds

The aqueous resist composition of the present invention preferably further contains (E) a polymerizable unsaturated compound in addition to the components (A) to (D). The polymerizable unsaturated compound (E) is not particularly limited as long as it is a compound polymerizable in the presence of the photopolymerization initiator (F), and known polymerizable unsaturated compounds may be used alone or in combination. The content of the (E) polymerizable unsaturated compound in the resist composition of the present invention is preferably in the range of 0.5 to 7% by weight, and preferably in the range of 1 to 5% by weight, based on the aqueous resist composition of the present invention. Most preferred. If the content of the polymerizable unsaturated compound (E) is less than 0.01% by weight, the photopolymerization may not proceed sufficiently, and it may be difficult to maintain the performance suitable for use as a resist. If the content exceeds 10% by weight, not only the properties of the coating film deteriorate, but also the coating film exhibits excessive viscosity.

Examples of polymerizable unsaturated compounds include unsaturated hydroxy compounds, unsaturated epoxy compounds, unsaturated carboxylic acids or unsaturated carboxylic anhydrides, unsaturated amino compounds, unsaturated isocyanate compounds, styrene, vinyltoluene, divinylbenzene, methyl methacrylate, ( (Meth) acrylate esters of polyhydric alcohols such as alkyl) or aryl esters) and allyl ethers of polyhydric alcohols.

Examples of (meth) acrylate esters of polyhydric alcohols include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and ethoxylated pentaerythritol tetra (meth ) Acrylates are listed. Examples of allyl ethers of polyhydric alcohols include ethylene glycol diallyl ether, diethylene glycol diallyl ether, diallyl ether, polyethylene glycol diallyl ether, trimethylolpropane triallyl ether, glycerin triallyl ether and pentaerythritol tetraallyl ether Are listed.

(F) Photopolymerization Initiator

As the photopolymerization initiator (F), known photopolymerization initiators can be used. Specific examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzyl, diphenyl disulfide, tetramethylthiuram sulfide, diacetyl, eosin, thionine, Michler's ketone, anthraquinone, chloroanthraquinone , Methyl anthraquinone, α-hydroxyisobutylphenone, p-isopropyl-α-hydroxyisobutylphenone, α, α'-dichloro-4-phenoxyacetophenone, 1-hydroxy-1-cyclohexylaceto Phenone, 2,2-dimethoxy-2-phenylacetophenone, methylbenzoyl formate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzophenone, Thioxanthone, 2-chlorothioxanthone, 2,4-diethyl thioxanthone, 2-isopropyl thioxanthone, 4-benzoyl-4'-methyldiphenyl sulfide, ethyl N, N-dimethylaminobenzo Ate, pentyl N, N-dimethylaminobenzoate and triethanolamine. These photopolymerization initiators can be used alone or in combination.

The content of the photopolymerization initiator is within the range of 0.01 to 10% by weight, preferably within the range of 0.1 to 5% by weight, and most preferably within the range of 0.5 to 3% by weight based on the aqueous resist composition of the present invention. When content of a photoinitiator is less than 0.01 weight%, photopolymerization does not advance enough and it becomes difficult to maintain the performance suitable for use as a resist. If the content exceeds 10% by weight, the properties of the coating film may be deteriorated.

The photosensitive composition of the present invention may contain photopolymerization initiators to maintain stability during storage and processing. As the photopolymerization initiator, a conventionally known photopolymerization initiator can be used. Examples include phenol (eg 3,5-ditert-butyl-4-hydroxytoluene), hydroquinone (eg hydroquinone and hydroquinone monomethyl ether) and catechol (eg catechol) Cole, tert-butylcatechol and pyrogallol).

If necessary, known colorants such as acid blue, phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black and naphthalene black; Silicone, fluorine and polymerizable defoamers and / or leveling agents; And adhesion promoters such as imidazole, thiazole, triazole and silane coupling agents.

Surfactants for controlling surface tension can be added to the resist composition of the present invention. The surfactant is not particularly limited and known surfactants can be used. Examples include anionic surfactants (eg ammonium salts of sodium dodecylbenzenesulfonate, sodium laurate and polyoxyethylene alkyl ether sulfates), nonionic surfactants (eg polyoxyethylene alkyl ethers, polyoxy) Ethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkylamines and polyoxyethylene alkylamides) and acetylene glycol surfactants. In the present invention, these surfactants may be used alone or in combination.

As for the viscosity in 25 degreeC of the resist composition of this invention, the inside of the range of 5-500 mPa * S is preferable, The inside of the 10-300 mPa * S range is more preferable, The inside of the 15-200 mPa * S range is still more preferable, The mPaS range is most preferred. When the viscosity is low, thixotropy hardly appears. If the viscosity is high, it is difficult to control the thickness of the coating film during dip coating. Viscosity can be measured by a commercial B type rotary viscometer.

The resist composition of the present invention can be prepared by mixing the above components according to any method, for example, each of the components while stirring in a container equipped with a stirring blade. Each component may be put into a mixing container simultaneously or sequentially. Each component may be put in a batch or divided several times. The temperature during the mixing is not particularly limited, and is usually in the range of 5 to 50 ° C, and preferably in the range of 10 to 40 ° C. Each component may be mixed at a given temperature or mixed with varying temperatures.

The resist composition of the present invention can be applied to any coating method, but is particularly useful for the dip coating method. The dip coating method is a known method and a coating substrate can be prepared by placing a large amount of resist composition in a container, immersing a heat transfer substrate including a conductive metal layer such as a copper clad substrate, and pulling the heat transfer substrate vertically at an arbitrary speed. Can be. In this case, the resist composition in a container can be set to arbitrary temperatures, and the temperature is preferable in the range of 10-50 degreeC.

The device used in the dip coating method is not particularly limited, and known devices may be used. In order to form a uniform film, an apparatus capable of changing the ascent rate during take out is preferably used. Examples of commercial dip coating devices include Full Automatic Dip Coater AD-7200, Semi Automatic Dip Coater SD-6200 and Five Coater SZC-720 (manufactured by SAZMA Communication Industry Co., Ltd.).

Printed circuit boards having a predetermined wiring pattern are usually manufactured from copper coated substrates obtained by a dip coating method through a process of drying, exposure, development, etching, and removal of a resist film and, if necessary, another additional process.

The following were used as each component (A)-(F) of a resist.

(A) water or alkali soluble resin

3,4-Epoxy-cyclohexylmethyl acrylate modified resin of methacrylic acid-methyl methacrylate copolymer (Product name: DAICEL CHEMICAL INDUSTRIES, LTD. 17,000)

(B) cellulose derivative

(b-1) hydroxyethyl cellulose (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

(b-2) Methyl cellulose (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

(b-3) hydroxypropyl cellulose (manufactured by Nippon Soda Co., Ltd.)

(b-4) Methyl hydroxypropyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd.)

(b-5) ethylhydroxyethyl cellulose (manufactured by Akzo Nobel Co., Ltd.)

(D) Hydroxyl group -Organic solvent

(d-1) ethylene glycol monobutyl ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

(d-2) Propylene Glycol Monomethyl Ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

(d-3) 3-methoxy-3-methyl-1-butanol (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

(E) Polymerizable  Unsaturated compounds

(e-1) Polyethylene Glycol Diacrylate (manufactured by KYOEISHA CHEMICAL Co., Ltd.)

(e-2) trimethylolpropane triacrylate (manufactured by KYOEISHA CHMICAL Co., Ltd.)

(F) Photopolymerization Initiator

(f-1) 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemical Co., Ltd.)

(f-2) diethyl thioxanthone (manufactured by Ciba Specialty Chemical Co., Ltd.)

(Other ingredients)

Triethylamine (TEA)

N-methyl morpholine (NMM)

( Hydroxyl group -Organic solvents other than organic solvents)

Propylene Glycol Monomethyl Ether Acetate (PGMA)

( Thixotropic agent )

Oxypropylene Ammonium-Modified Smectite (SMC)

< Example  1>

One) Resist  Preparation of the composition

Each component shown in Table 1 except (B) a cellulose derivative and (C) water was mixed in the ratio shown in Table 1, and the uniform solution was obtained. Then, the amount of (C) water shown in Table 1 was added dropwise over 2 hours with vigorous stirring of the mixture. In addition, the amount of the (B) cellulose derivative shown in Table 1 was added, followed by stirring for 15 hours to prepare an aqueous resist composition.

2) measurement of viscosity

TOKI SANGYO CO., LTD. Using a Type B viscometer (Model BL, NO. 1 rotor) of the product, the viscosity was measured at rotor rotation conditions of 6 rpm at 25 ° C.

3) Resist  Of composition Dip coating

SAZMA Comunication Industry Co., Ltd., while maintaining the resist composition prepared in 1) at 35 ℃. Using a dip coater (trade name: Five Coater FC-7500), the resist composition was dip coated onto a double-sided copper clad substrate (substrate thickness: 130 μm, copper foil thickness: 18 μm, 400 mm × 510 mm), and then the substrate was 80 It dried at 15 degreeC for 15 minutes, and obtained the coating substrate which has a coating film which consists of a resist composition. The thickness of the coating substrate was adjusted to about 8 μm by changing the extraction rate during coating.

4) evaluation of viscosity

The two dried coated substrates obtained in 3) were superimposed on one another so that the coating surfaces faced each other, and inserted between two stainless steels of 400 mm × 510 mm × 1 mm, respectively, and then allowed to stand horizontally. After standing in this state for 2 days (23 ° C., relative humidity: 60%), the two substrates were slowly removed. The laminated coating surface was divided into 1 cm x 1 cm crosscuts, respectively, and the peeling state was evaluated by the number of crosscuts including the peeling parts according to the following criteria. The results are shown in Table 1 below.

A: the number of crosscuts including the peeling portion occupies less than 2% of the total crosscuts

B: the number of crosscuts including the peeled portion occupies 2% or more and less than 5% of the total crosscuts

C: the number of crosscuts including the peeled portion occupies 5% or more and less than 10% of the total crosscuts

D: the number of crosscuts including the peeled portion occupies 10% or more of the total crosscuts

5) Measurement of adhesion

ELCOMETER INC. The peeling strength of the coating film was measured at room temperature using the coating film adhesion tester of the product (adhesion tester, MODEL F106, a device for measuring the peel strength when peeling the aluminum cylinder adhered on the coating surface).

6) measurement of gloss

It was measured using a commercially available gloss meter (TESTER SANGYO CO., LTD., Product, OP-102), and the measured value was expressed as a relative value to gloss value 1 of Example 1. The results are shown in Table 1 below.

7) Measurement of line shape and resolution

Post-development evaluation

The coated substrate obtained in the above 3) was subjected to a photomask having 5 line-and-space patterns (hereinafter sometimes abbreviated as L / S) patterns of 20 μm / 20 to 80 μm / max 80 μm line width and 10 μm pitch, respectively. After exposure to ultraviolet light (ultra high pressure mercury lamp, dominant wavelength: 365 nm, 80 mJ / cm ² ), the solution was immersed in a 1% aqueous sodium carbonate solution at 30 ° C. for 60 seconds and then washed with water at 25 ° C. The linearity of the resist line was evaluated by scanning electron micrograph of the substrate obtained according to the following criteria. Among the patterns obtained without causing chipping of lines and developing residue, developability was expressed by the smallest L / S value.

The results are shown in Table 1 below.

A: line sidewall is almost straight

B: curvature is observed in part of the line sidewall

C: curvature is observed throughout the line sidewalls

D: Remarkable curvature is observed on the line sidewalls

Evaluation of Etching

After development, the coated substrate was etched and washed with an aqueous copper chloride solution at 45 ° C. for 60 seconds. The shape of the remaining five resist lines of L / S = 40/40 was observed by scanning electron micrograph of the obtained substrate, and then evaluated according to the following criteria. The results are shown in Table 1 below.

A: Number of 0 to 1 patterns with chipping and warping among 5 patterns

B: 2 to 3 patterns with chipping and warping out of 5 patterns

C: 4 out of 5 patterns with chipping and warping

D: Number of 5 patterns with chipping and warping out of 5 patterns

Post uninstall

After etching, the resist film was removed at 45 ° C. with 3% by weight aqueous sodium hydroxide solution, and then washed and dried to obtain a substrate having a copper wiring pattern. The line shape of the copper wiring of L / S = 40/40 was observed with the scanning electron micrograph of the obtained board | substrate, and it evaluated according to the following criteria. The results are shown in Table 1 below.

A: 0 to 1 pattern among 5 patterns in which copper remains between copper wirings

B: 2 to 3 patterns in which copper remains between copper wirings among 5 patterns

C: 4-5 patterns in which copper remains between copper wirings among 5 patterns

D: Number of 5 patterns in which copper remains between copper wirings among 5 patterns

< Example  2 to 6>

An aqueous resist composition was prepared in the same manner as in Example 1, except that the ingredients shown in Table 1 were used in the amounts described in Table 1 as the respective ingredients. It evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

< Comparative example  1>

An aqueous resist composition was prepared in the same manner as in Example 1 except that hydroxyethyl cellulose was not used. It evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

< Comparative example  2>

An aqueous resist composition was prepared in the same manner as in Example 1, except that the amount of hydroxyethyl cellulose was 2.0 parts by weight. It evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

< Example  7-16

An aqueous resist composition was prepared in the same manner as in Example 1 except that the components shown in Table 2 were used in the amounts shown in Table 2 as the respective components. It evaluated in the same manner as in Example 1. The results are shown in Table 2 below.

< Comparative example  3 to 7 and Example  17-21>

An aqueous resist composition was prepared in the same manner as in Example 1 except that the components described in Tables 3a and 3b were used in the amounts described in Tables 3a and 3b as respective components. It evaluated in the same manner as in Example 1. The results are shown in Tables 3a and 3b below.

The aqueous resist composition of the present invention can provide a printed circuit board having excellent adhesion, viscosity and surface smoothness, and having a high precision wiring pattern formed thereon.

Claims (9)

An aqueous resist composition comprising (A) a resin soluble in water or an aqueous alkali solution, (B) a cellulose derivative, (C) water, and (D) a hydroxy group-containing organic solvent, wherein (B) cellulose in the resist composition The content of the derivative is in the range of 0.001 to 1.0% by weight, the content of (C) the water is in the range of 25 to 65% by weight, and the content of the (D) hydroxy group-containing organic solvent is in the range of 15 to 50% by weight. An aqueous resist composition made into. (A) Resin soluble in water or aqueous alkali solution, (B) cellulose derivative, (C) water, (D) hydroxy group-containing organic solvent, (E) polymerizable unsaturated compound and (F) photopolymerization initiator As an aqueous resist composition, the content of the (B) cellulose derivative in the resist composition is in the range of 0.001 to 1.0% by weight, (C) the content of the water is in the range of 25 to 65% by weight, and (D) the hydroxy group-containing organic Content of a solvent exists in 15 to 50weight% of a range, The aqueous resist composition characterized by the above-mentioned. The aqueous resist according to claim 1 or 2, wherein the weight ratio (A) / (B) of the resin soluble in (A) water or an aqueous alkali solution to the (B) cellulose derivative is in the range of 10 to 1000. Composition. The aqueous resist composition according to claim 1 or 2, wherein the resin (A) soluble in water or an aqueous alkali solution is a copolymer containing (meth) acrylic acid as one of the composition monomers. The aqueous resist composition according to claim 1 or 2, wherein the cellulose derivative (B) is hydroxyalkyl cellulose. The organic group-containing organic solvent according to claim 1 or 2, wherein the (D) hydroxy group-containing organic solvent is selected from monoalkyl ethers of diol compounds, monoesters of diol compounds and aliphatic carboxylic acids, and α-hydroxycarboxylate esters. An aqueous resist composition, characterized in that more than two. A method for producing a resist-coated substrate, wherein the heat-transfer substrate containing the conductive metal is immersed in the aqueous resist composition according to claim 1. A method for manufacturing a printed circuit board comprising using the aqueous resist composition according to claim 1. A printed circuit board manufactured by using the aqueous resist composition according to claim 1.