JP3406526B2 - Photosensitive resin composition, photosensitive element using the same, method for producing resist pattern, and method for producing printed wiring board - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a method for producing a resist pattern, and a method for producing a printed wiring board.

[0002]

2. Description of the Related Art Conventionally, in the field of printed wiring board manufacturing, as a resist material used for etching, plating, etc., a photosensitive resin composition and a photosensitive element obtained by using a support and a protective film therefor are widely used. Has been. In printed wiring boards, a photosensitive element is laminated on a circuit-forming board, and after pattern-wise exposure, the unexposed area is removed with a developer to form a resist pattern, which is used as a mask for etching or plating. Is applied to form a circuit, and then the cured portion is peeled off from the substrate to be manufactured. As a developing solution for removing the resist in the unexposed area, an alkaline developing type using sodium carbonate or the like is mainly used from the viewpoint of environment and safety, and the developing solution is usually a photosensitive resin composition to some extent. If it has the ability to dissolve the physical layer, it can be used, and the photosensitive resin composition is dissolved or dispersed in the developing solution at the time of development.

With the recent increase in density of printed wiring boards,
Better resolution is required. Further, since the contact area between the circuit-forming substrate and the photosensitive resin composition layer on which the resist pattern is formed is small, the photosensitive element is
Excellent adhesion, mechanical strength, chemical resistance and flexibility are required in the developing, etching or plating process. Further, from the viewpoint of workability, it is desirable that the imaging property, which is the difference in color contrast between the exposed portion and the unexposed portion, is large in order to make it easy to confirm whether or not the pattern is properly formed after exposure.

Japanese Unexamined Patent Publication (Kokai) No. 1-2224747 discloses a photoresist composition containing a binder polymer containing styrene and a specific unsaturated urethane compound containing an isopropylene oxide group as a block structure. This resist composition has succeeded in improving the gold plating resistance by containing a binder polymer containing styrene and a specific unsaturated urethane compound, but from the viewpoint of resolution, it can be used as a printed wiring board. It is difficult to deal with higher density.

Further, JP-A-5-241340 discloses a photopolymerizable composition containing styrene / acrylic acid or styrene / methacrylic acid. This photopolymerizable composition has succeeded in improving the peelability and the edge fusion resistance, but from the viewpoint of resolution and adhesiveness, it is difficult to cope with high density printed wiring boards. Further, JP-A-5-72734 discloses a photosensitive resin composition containing a binder polymer containing styrene. This photosensitive resin composition,
It is a photosensitive resin composition for flexographic printing plates, and has completely different uses.

Further, Japanese Patent Application Laid-Open No. 10-198033 discloses a photopolymerizable composition containing a binder polymer containing styrene or a styrene derivative.
The application of this photopolymerizable composition is for processing iron-based metal substrate, and from the viewpoint of resolution, it is difficult to deal with higher density of printed wiring boards.

[0007]

The inventions described in claims 1, 2 and 3 provide a photosensitive resin composition which is extremely excellent in resolution, adhesion and imaging properties. The invention according to claim 4 provides a photosensitive resin composition having excellent peeling characteristics in addition to the effects of the inventions according to claims 1, 2 and 3. The invention according to claim 5 provides a photosensitive element which is extremely excellent in resolution, adhesion, imaging property and workability. The invention according to claim 6 provides a method for producing a resist pattern having extremely excellent resolution, adhesion, imaging property and workability, which is extremely useful for increasing the density of printed wiring and automating the production of printed wiring boards. . The invention according to claim 7 provides a method for producing a printed wiring board having a resist pattern with extremely excellent resolution, adhesion, imaging property and workability, which is extremely useful for increasing the density of printed wiring and automating the production of printed wiring boards. It is provided.

[0008]

That is, the present invention is
(A) a carboxyl group-containing binder polymer containing styrene or a styrene derivative as a copolymerization component, (B) a photopolymerizable unsaturated compound having at least one polymerizable ethylenically unsaturated bond in the molecule, (C) photopolymerization Initiator and (D) general formula (I)

[Chemical 3] (In the formula, X is a halogen atom, a hydrogen atom, or a carbon number of 1 to 20.
Alkyl group, C3-10 cycloalkyl group, amino group or phenyl group which may be substituted with C1-20 alkyl group, aryl group such as naphthyl group, amino group, mercapto group, carbon number 1 to 10 is an alkylmercapto group, a carboxyalkyl group having an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a heterocyclic group, wherein m and n are integers of 2 or more. And n is an integer of 0 or more and is an integer selected so that m + n = 6, and when n is an integer of 2 or more, Xs of 2 or more may be the same or different. The present invention relates to a photosensitive resin composition containing the compound represented.

In the present invention, the photopolymerizable unsaturated compound (B) having at least one polymerizable ethylenically unsaturated bond in the molecule is represented by the general formula (II)

[Chemical 4] (In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Y ¹ and Y ² each independently represent an alkylene oxide group having 2 to 6 carbon atoms, Z is
The present invention relates to the above-mentioned photosensitive resin composition containing a compound represented by a hydrocarbon group having 1 to 16 carbon atoms and p and q each independently being an integer of 1 to 28) as an essential component.

The present invention also provides the above-mentioned components (A) and (B).
The use ratio of the component, the component (C) and the component (D) is (A)
The component is 40 to 80 parts by weight with respect to the total amount of 100 parts by weight of the component (A) and the component (B), and the component (B) is with respect to 100 parts by weight of the total amount of the components (A) and (B). 20 to 20
60 parts by weight, the component (C) is 0.1 to 20 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B),
The component (D) is 100 in total of the components (A) and (B).
The present invention relates to the photosensitive resin composition which is 0.001 to 3 parts by weight with respect to parts by weight.

In the present invention, the (A) component carboxyl group-containing binder polymer containing styrene or a styrene derivative as a copolymerization component contains 0.1 to 30% by weight of styrene or a styrene derivative as a copolymerization component. The present invention relates to the photosensitive resin composition which is a group-containing binder polymer.

The present invention also relates to a photosensitive element obtained by applying the above-mentioned photosensitive resin composition onto a support, drying and laminating. Further, the present invention, the photosensitive element, while peeling off the protective film in some cases, is laminated so that the photosensitive resin composition layer is in close contact with the circuit-forming substrate, irradiated with actinic rays imagewise, The present invention relates to a method for producing a resist pattern, which comprises photo-curing an exposed portion and removing an unexposed portion by development. The present invention also relates to a method for manufacturing a printed wiring board, characterized in that the circuit forming substrate having the resist pattern manufactured is etched or plated by the method for manufacturing the resist pattern.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The components contained in the photosensitive resin composition of the present invention will be described in detail below. A carboxyl group-containing binder polymer containing styrene or a styrene derivative as the component (A) in the present invention is a copolymer component.
In order to improve both the adhesion and the peeling property by using a styrene derivative or styrene as a copolymerization component, the content is preferably 0.1 to 30% by weight, more preferably 1 to 28% by weight, and 1.5 to It is particularly preferable to contain 27% by weight. If this content is less than 0.1% by weight, the adhesion tends to be poor, and if it exceeds 30% by weight, the peeled pieces tend to be large and the peeling time tends to be long. Examples of the styrene derivative include α-methylstyrene, p-methylstyrene, p-ethylstyrene, p-methoxystyrene and p-methylstyrene.
-Ethoxystyrene, p-chlorostyrene, p-bromostyrene, and the like. Further, in these styrenes or styrene derivatives, the benzene ring has a nitro group, a nitrile group,
It may be substituted with a functional group such as an alkoxyl group, an acyl group, a sulfone group, a hydroxyl group and a halogen atom,
It is preferably substituted with a single alkyl group such as a methyl group and a tert-butyl group. From the viewpoint of adhesion, styrene and p-methylstyrene are preferred. These styrenes or styrene derivatives are used alone or in combination of two or more.

Further, the copolymer containing styrene or a styrene derivative contained in the carboxyl group-containing binder polymer containing styrene or a styrene derivative as the component (A) in the present invention can be copolymerized with styrene or a styrene derivative. And a vinyl monomer other than styrene or a styrene derivative. Examples of the carboxyl group-containing binder polymer include acrylic acid, α-bromoacrylic acid, α
-Acrylic acid derivatives such as chloroacrylic acid, β-furylacrylic acid, β-styrylacrylic acid, methacrylic acid,
α-bromomethacrylic acid, α-chloromethacrylic acid, β
-Furryl methacrylic acid, methacrylic acid derivatives such as β-styryl methacrylic acid, maleic acid, maleic anhydride,
Maleic acid monoesters such as monomethyl maleate, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like can be mentioned. These carboxyl group-containing monomers are used alone or in combination of two or more.

Examples of vinyl monomers other than styrene and styrene derivatives include 2,2,3,3-tetrafluoropropyl acrylate acrylamide,
Examples thereof include acrylamides such as 2,2,3,3-tetrafluoropropyl methacrylate acrylamide and diacetone acrylamide, esters of vinyl alcohol such as acrylonitrile and vinyl-n-butyl ether, alkyl acrylates, and methacrylic acid alkyl esters. Examples of the acrylic acid alkyl ester or methacrylic acid alkyl ester include those represented by the general formula (III)

[Chemical 5] (In the formula, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group having 1 to 12 carbon atoms) and the like.

Examples of R ⁴ in the above general formula (III) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and an undecyl group. , Dodecyl groups and their structural isomers. Examples of the monomer represented by the general formula (III) include acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid propyl ester, acrylic acid butyl ester, acrylic acid pentyl ester, acrylic acid hexyl ester, and acrylic acid. Heptyl ester, acrylic acid octyl ester, acrylic acid 2-ethylhexyl ester, acrylic acid nonyl ester, acrylic acid decyl ester, acrylic acid undecyl ester, acrylic acid dodecyl ester, methacrylic acid methyl ester, methacrylic acid ethyl ester,
Methacrylic acid propyl ester, methacrylic acid butyl ester, methacrylic acid pentyl ester, methacrylic acid hexyl ester, methacrylic acid heptyl ester, methacrylic acid octyl ester, methacrylic acid 2-ethylhexyl ester, methacrylic acid nonyl ester, methacrylic acid decyl ester, methacrylic acid ester Examples thereof include decyl ester and methacrylic acid dodecyl ester.

These vinyl monomers other than styrene and styrene derivatives may be used alone or in combination of two or more. In addition, the carboxyl group-containing binder polymer containing styrene or the styrene derivative of the component (A) in the present invention is used alone or in combination of two or more kinds. Also, (A)
It may be used in combination with a carboxyl group-containing binder polymer other than the carboxyl group-containing binder polymer containing the component styrene or a styrene derivative as a copolymerization component.

The carboxyl group-containing binder polymer containing the styrene or styrene derivative as the component (A) in the present invention is soluble or swellable in an alkaline aqueous solution from the viewpoint of developability, environmental protection and the like. Since it is desirable to have a carboxyl group, it is necessary to have a carboxyl group, and the acid value is preferably 100 to 500 mgKOH / g, and particularly preferably 100 to 300 mgKOH / g. When the acid value is less than 100 mgKOH / g, the developing time tends to be delayed, and when it exceeds 500 mgKOH / g, the developing solution resistance of the photocured resist tends to decrease.

The carboxyl group-containing binder polymer containing styrene or styrene derivative as the component (A) in the present invention has a weight average molecular weight of 20,000 to polystyrene measured by gel permeation chromatography. It is preferably 300,000, particularly preferably 40,000 to 150,000. When the weight average molecular weight is less than 20,000, the developing solution resistance of the photocured resist tends to decrease, and when it exceeds 300,000, the developing time tends to be long.

Examples of the photopolymerizable unsaturated compound having at least one polymerizable ethylenically unsaturated group in the molecule of the component (B) in the present invention include polyethylene glycol diacrylate (the number of ethylene groups is 2 to
14), polyethylene glycol dimethacrylate (having 2 to 14 ethylene groups), trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethanetri Acrylate, tetramethylol methane trimethacrylate, tetramethylol methane tetraacrylate, tetramethylol methane tetramethacrylate, polypropylene glycol diacrylate (having 2 to 14 propylene groups), polypropylene glycol dimethacrylate (having 2 to 14 propylene groups) ), Dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentae Compounds obtained by reacting α, β-unsaturated carboxylic acids with polyhydric alcohols such as thylitol hexaacrylate and dipentaerythritol hexamethacrylate, bisphenol A dioxyethylene diacrylate, bisphenol A dioxyethylene dimethacrylate, bisphenol A Bisphenol A polyoxyethylene diacrylate such as trioxyethylene diacrylate, bisphenol A trioxyethylene dimethacrylate, bisphenol A decaoxyethylene diacrylate, bisphenol A decaoxyethylene dimethacrylate, bisphenol A polyoxyethylene dimethacrylate, trimethylolpropane Such as triglycidyl ether triacrylate and bisphenol A diglycidyl ether acrylate α in Rishijiru group-containing compound, compounds obtained by adding β- unsaturated carboxylic acid, 2,2-bis (4-methacryloxy pentaethoxy phenyl) propane, methyl acrylate,
Methacrylic acid methyl ester, acrylic acid ethyl ester, methacrylic acid ethyl ester, acrylic acid butyl ester, methacrylic acid butyl ester, acrylic acid 2-
Examples thereof include acrylic acid alkyl esters such as ethylhexyl ester and methacrylic acid 2-ethylhexyl ester, and methacrylic acid alkyl esters. These photopolymerizable unsaturated compounds are used alone or in combination of two or more kinds.

The photopolymerizable unsaturated compound having at least one polymerizable ethylenic unsaturated group in the molecule of the component (B) in the present invention is an unsaturated urethane compound from the viewpoint of adhesion, resolution and the like. It is preferable to include the compound, and more preferable to include the compound represented by the general formula (II).

The unsaturated urethane compound can be produced by various methods, and the production method is not particularly limited, but for example, a polyisocyanate compound having two or more isocyanate groups in the molecule is used. A group having an active hydrogen selected from a hydroxyl group, an amino group, an imino group, an amide group, an imide group, and a mercapto group (hereinafter referred to as an active hydrogen group) in a molecule and a compound having a carbon-carbon double bond Obtained by reaction. It can also be obtained by reacting a compound having an isocyanate group and a carbon-carbon double bond in the molecule with a compound having two or more active hydrogen groups in the molecule. Further, a compound having an active hydrogen group and a carbon-carbon double bond in the molecule, and an isocyanate group and a carbon-
It can also be obtained by reaction with a compound having a carbon double bond.

In the general formula (II), R ¹
And R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group and an isopropyl group, and Y 1 and Y 2 are an ethylene oxide group, a propylene oxide group and an isopropylene oxide. Group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, and the like represent an alkylene oxide group having 2 to 6 carbon atoms, Z represents a hydrocarbon group having 2 to 16 carbon atoms, and p and q each independently. It is an integer of 1-28.

The isopropylene group in the above isopropylene oxide group is

[Chemical 6] In the isopropylene oxide group, there are two types of bonding directions in the case where the methylene group is bonded to oxygen and the case where the methylene group is not bonded to oxygen. Good or two kinds of bonding directions may be mixed. When the repeating unit of Y is 2 or more, 2
The above Ys may be the same or different, and Y is 2
When composed of one or more alkylene oxide groups, Y
May exist at random or may exist in blocks.

Examples of the hydrocarbon group having 2 to 16 carbon atoms include alkylene groups such as ethylene group, hexylene group, 2-ethylhexylene group, trimethylhexylene group, decylene group, cyclohexylene group and bicyclohexylene. Examples thereof include a cycloalkylene group such as a group, a phenylene group, a biphenylene group, and an arylene group such as a naphthylene group.

In the compound represented by the general formula (II), from the viewpoint of developability or peeling property, the general formula (IV)

[Chemical 7] (In the formula, R ¹ , R ² , Y ¹ , Y ² and Z are the same as those in the general formula (I), W is an ethylene oxide group, and h, i, s and t are , 1 to 14 independently
Is an integer) is particularly preferable. Further, these compounds represented by the general formula (IV) are used alone or in combination of two or more kinds. Examples of commercially available compounds include Shin-Nakamura Chemical Co., Ltd., trade names UA-11 and UA-13.

Examples of the photopolymerization initiator as the component (C) in the present invention include benzophenone, N, N'-
Tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,4'-
Diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone,
Aromatic ketones such as phenanthrenequinone, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and other benzoin ethers, methylbenzoin, ethylbenzoin and other benzoin compounds, benzyl dimethyl ketal and other benzyl derivatives, 2- (o-
Chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-
Methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p -Methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4
-Di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl)-
2,4,5-Diphenylimidazole dimers, etc.
Examples include acridine derivatives such as -triarylimidazole dimer, 9-phenylacridine, and 1,7-bis (9-acridinyl) heptane. These are used alone or in combination of two or more.

X in the compound represented by the general formula (I) which is the component (D) in the present invention is a halogen atom, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 3 to 10 carbon atoms.
Cycloalkyl group, an amino group or an aryl group such as a phenyl group which may be substituted with an alkyl group having 1 to 20 carbon atoms, a naphthyl group, an amino group, a mercapto group, an alkylmercapto group having 1 to 10 carbon atoms, an alkyl group The group is represented by a carboxyalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a heterocycle, and an alkyl group is particularly preferable.

Examples of the halogen atom include fluorine, chlorine, bromine, iodine and astatine.
Examples of the alkyl group having 1 to 20 carbon atoms include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group,
Hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, tridecyl group, tetradecyl group,
Pentadecyl group, octadecyl group, nonadecyl group, icosyl group and the like can be mentioned.

Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl group, cyclobutyl group,
Examples thereof include a cyclopentyl group, a cyclohexyl group and a cyclooctyl group. Examples of the aryl group substituted with an alkyl group having 1 to 20 carbon atoms include a methylphenyl group, an ethylphenyl group and a propylphenyl group.

Examples of the alkylmercapto group having 1 to 10 carbon atoms include a methylmercapto group, an ethylmercapto group and a propylmercapto group. Examples of the carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, and a carboxybutyl group.

Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, propoxy group,
Examples thereof include butoxy group. Examples of the group composed of the above heterocycle include an ethylene oxide group, a furan group, a thiophene group, a pyrrole group, a thiazole group, an indole group and a quinoline group. Further, m and n in the general formula (I) are integers of which m is 2 or more, n is 0 or more, and are selected so that m + n = 6. When n is an integer of 2 or more, Xs of 2 or more may be the same or different. If m is less than 2, the resolution will deteriorate.

Examples of the compound represented by the general formula (I) of the component (D) of the present invention include catechol, resorcinol (resorcinol), 1,4-hydroquinone, 2-methylcatechol and 3-methyl. Catechol,
4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4 -N-butylcatechol, 2-tert
-Butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-
alkyl catechol such as tert-butyl catechol,
2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol (orcin), 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol,
2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-
alkylresorcinol such as tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone,
Examples thereof include alkylhydroquinone such as 2,5-di-tert-butylhydroquinone, pyrogallol, and phloroglucin.

The content of the carboxyl group-containing binder polymer containing styrene or styrene derivative as the component (A) in the present invention is 40 to 100 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). The amount is preferably 80 parts by weight, particularly preferably 40 to 60 parts by weight. If this content is less than 40 parts by weight, the photocured product tends to be brittle, and the coating property tends to be poor when used as a photosensitive element, and if it exceeds 80 parts by weight, the sensitivity tends to be insufficient. .

The content of the photopolymerizable unsaturated compound having at least one polymerizable ethylenically unsaturated bond in the molecule of the component (B) in the present invention is the same as that of the components (A) and (B). The amount is preferably 20 to 60 parts by weight, and particularly preferably 40 to 60 parts by weight, based on 100 parts by weight. If this content is less than 20 parts by weight,
The sensitivity tends to be insufficient, and when it exceeds 60 parts by weight, the photocured product tends to become brittle.

Further, the content of the photopolymerization initiator of the component (C) in the present invention is such that the total amount of the components (A) and (B) is 1
It is preferably 0.1 to 20 parts by weight, and particularly preferably 0.2 to 10 parts by weight, based on 00 parts by weight. If this content is less than 0.1 parts by weight, the sensitivity tends to be insufficient, and if it exceeds 20 parts by weight, the absorption on the surface of the photosensitive composition during exposure increases and the internal photocured product is increased. Tends to be insufficient.

The content of the compound represented by the general formula (I) in the component (D) in the present invention is 0.001 to 3 relative to 100 parts by weight of the total amount of the components (A) and (B).
It is preferably part by weight, and particularly preferably 0.01 to 0.1 part by weight. If the content is less than 0.001, the resolution tends not to be improved, and if it exceeds 3 parts by weight, the sensitivity tends to be insufficient.

In the photosensitive resin composition of the present invention, if necessary, dyes, color formers, thermal color inhibitors such as glycidyl ether compounds, plasticizers, pigments, fillers, defoamers and flame retardants. , A stabilizer, an adhesion promoter, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, etc., per 0.01 parts by weight of the total amount of the components (A) and (B).
Can be contained in an amount of about 20 parts by weight.

Examples of the above dyes include fuchsin, auramine base, chalcoside green S, paramagenta, crystal violet, methyl orange, night blue 2B, Victoria blue, malachite green,
Examples include basic blue 20, iodging green, night green B, trivalosan, numagenta, acid violet RRH, red violet 5RS, ethyl violet, methylene blue, new methylene blue GG, phthalocyanine green, diamond green, rhodamine B and the like.

Examples of the color former include tribromomethylphenyl sulfone, leuco crystal violet and the like. Examples of the plasticizer include hydrocarbon oils such as naphthene oil and paraffin oil, and a molecular weight of 3000.
The following low molecular weight polystyrene, α-methylstyrene-vinyltoluene copolymer, petroleum resin, dialkyl phthalate, alkyl phosphate, polyethylene glycol,
Polyethylene glycol ester, polyethylene glycol ether, polyacrylate, polyester resin,
Polyterpene resin, polyisoprene and hydrogenated products thereof, p
-Toluenesulfonic acid, p-toluenesulfonamide,
Liquid 1,2-polybutadiene, 1,4-polybutadiene and terminal modified products thereof, hydroxides or carboxylates thereof, liquid acrylonitrile-butadiene copolymers and carboxylates thereof, liquid styrene-butadiene copolymers, ethylene Examples thereof include glycol-propylene glycol block copolymers.

Examples of the pigment include phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone red, indanthrene blue, titanium white, silica, talc, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, aluminum hydroxide. , Precipitated barium carbonate, barium titanate, and the like.

Examples of the filler include silica, calcium carbonate, kaolin, calcined kaolin, diatomaceous earth,
Talc, titanium oxide, zinc oxide, aluminum hydroxide,
Polystyrene resin, urea-formalin resin, styrene-
Examples thereof include methacrylic acid copolymers, styrene-butadiene copolymers, and inorganic or organic fillers such as hollow plastic pigments. Examples of the defoaming agent include silicon compounds and hydrocarbon compounds.

Examples of the stabilizer include hydroxy aromatic compounds such as p-methoxyphenol and 2,6-di-tert-butyl-p-cresol, and quinones such as phenybenzoquinone, p-toluquinone and p-xyloquinone. ,
Amines such as nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and phenyl-α-naphthylamine, heterocyclic compounds such as phenothiazine and pyridine, nitrobenzene, dinitrobenzene, chloranil, aryl force fight, 2,2′-methylenebis (4- Ethyl-6-tert-butylphenol),
2,2'-methylenebis (4-methyl-6-tert-butylphenol), cuprous chloride and the like can be mentioned.

As the above-mentioned antioxidant, for example, 2,6
-Alkylated phenols such as di-tert-butyl-4-methylphenol, 2,2-methylenebis (4-methyl-)
6-tert-butylphenol) and other alkylated bisphenols, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2-4- Hydroxy-3,5-di-tert
-Butylanilino-4,6-bis (n-octylthio)
Examples include -1,3,5-triazine, dilaurylthiodipropionate benzotriazole, benzotriazole hydrochloride, benzotriazole organic acid salt, and aminobenzothiazole.

The photosensitive resin composition may contain aliphatic alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, n-pentanol and hexanol, allyl alcohol, benzyl alcohol and anisole, if necessary. , Hydrocarbons such as phenetole, n-hexane, cyclohexane, heptane, octane, nonane, and decane, diacetone alcohol, 3-methoxy-1-butanol, 4-methoxy-1-butanol, 3-ethoxy-1-butanol, 3-methoxy-3
-Methyl-1-butanol, 3-methoxy-3-ethyl-1-pentanol-4-ethoxy-1-pentanol, 5-methoxy-1-hexanol, acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl Isobutyl ketone, methyl pentyl ketone,
Methylhexylketone, ethylbutylketone, dibutylketone, cyclopentanone, cyclohexanone, methylcyclohexanone, γ-butyrolactone, 3-hydroxy-2-butanone, 4-hydroxy-2-butanone, 4
-Hydroxy-2-pentanone, 5-hydroxy-2-
Pentanone, 4-hydroxy-3-pentanone, 6-hydroxy-2-hexanone, 3-methyl-3-hydroxy-2-pentanone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, ethylene glycol monoacetate , Ethylene glycol diacetate,
Propylene glycol monoacetate, propylene glycol diacetate, MC, EC, butyl cellosolve,
Ethylene glycol alkyl ethers such as phenyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, MC acetate and EC acetate, and their acetates, diethylene glycol monomethyl ether, monoethyl ether, mono i-propyl ether, monobutyl ether, Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether acetate and its acetates, DMD
G, DEDG, DBDG, MEDG, and other diethylene glycol dialkyl ethers, monomethyl ether, monoethyl ether, dimethyl ether, diethyl ether, methyl ethyl ether, and other triethylene glycol alkyl ethers, monomethyl ether, monoethyl ether, n-propyl ether, Propylene glycol alkyl ethers such as monobutyl ether, dimethyl ether, diethyl ether, monomethyl ether acetate and monoethyl ether acetate, and dipropylene such as acetate, monomethyl ether, monoethyl ether, n-propyl ether, monobutyl ether, dimethyl ether and diethyl ether. Glycol alkyl ethers, ethyl formate, propyl formate, butyl formate, formate Le, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate,
Carboxylic esters such as ethyl propionate, methyl butyrate, ethyl butyrate, dimethylformamide, dimethyl sulfoxide, dioxane, tetrahydrofuran, methyl lactate, ethyl lactate, methyl benzoate, ethyl benzoate,
It can be applied as a solution by dissolving it in a solvent such as propylene carbonate or a mixed solvent thereof.

The photosensitive resin composition of the present invention has a metal surface, for example, an iron-based alloy such as copper, a copper-based alloy, nickel, chromium, iron and stainless steel, preferably copper, a copper-based alloy, an iron-based alloy. On the surface of, after being applied as a liquid resist and dried,
It is preferably used after being covered with a protective film, or in the form of a photosensitive element.

The thickness of the photosensitive resin composition layer varies depending on the use, but the thickness after drying is preferably 1 to 100 μm, and particularly preferably 1 to 30 μm. If it is less than 1 μm, industrial coating tends to be impossible, and if it exceeds 100 μm, the effect of the present invention tends to be small and the sensitivity tends to be insufficient. When the liquid resist is coated with a protective film, an inert polyolefin film such as polyethylene or polypropylene is used as the protective film. The photosensitive element can be obtained by applying a photosensitive resin composition onto a polymer film made of polyethylene terephthalate, polypropylene, polyethylene, polyester or the like as a support and drying it. Since these polymer films must be removable from the photosensitive resin composition layer later, they may be those that have been subjected to a surface treatment such that they cannot be removed, or materials. I won't. The thickness of these polymer films is preferably 1 to 100 μm, more preferably 1 to 30 μm. Further, one of these polymer films may be laminated on both sides of the photosensitive resin composition layer as a support film for the photosensitive resin composition layer and the other one as a protective film of the photosensitive resin composition layer. .

As a method for producing a resist pattern using the photosensitive element of the present invention, when the above-mentioned protective film is present, the protective film is removed and then the photosensitive resin composition layer is heated. Examples thereof include a method of laminating by press-bonding to a circuit forming substrate such as a copper clad laminate. The surface to be laminated is usually a metal surface, but there is no particular limitation. The heating temperature of the photosensitive resin composition layer is not particularly limited and is preferably 90 to 130 ° C. The pressure for pressing the photosensitive resin composition layer is not particularly limited and is preferably 1 to 10 kgf / cm ² .

If the photosensitive resin composition layer is heated to 90 to 130 ° C. as described above, it is not necessary to preheat the circuit-forming substrate in advance, but in order to further improve the stackability, It is also possible to preheat the circuit-forming substrate.

The photosensitive resin composition layer thus laminated is irradiated with actinic rays imagewise through a negative or positive mask pattern called an artwork. At this time, when the polymer film present on the photosensitive resin composition layer is transparent, it may be irradiated with actinic rays as it is, and when it is opaque, it is of course necessary to remove it. From the viewpoint of protecting the photosensitive resin composition layer, it is preferable that the polymer film is transparent and the actinic ray is irradiated through the polymer film while the polymer film remains. As the light source of the actinic ray, a known light source such as a carbon arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp that effectively radiates ultraviolet rays is used.
In addition, a flood light bulb for photography, a solar lamp or the like that effectively radiates visible light is also used.

Next, after the exposure, if a support is present on the photosensitive resin composition layer, after removing the support,
A resist pattern is manufactured by using a developer such as an alkaline aqueous solution to remove the unexposed portion and develop it by a known method such as spraying, rocking dipping, brushing, scraping or the like. As the developer, a safe and stable developer having good operability such as an alkaline aqueous solution is used. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium or potassium hydroxides, alkali carbonates such as lithium, sodium or potassium carbonates or bicarbonates, alkali metals such as potassium phosphate and sodium phosphate. Alkali metal pyrophosphates such as phosphates, sodium pyrophosphate, potassium pyrophosphate and the like are used. As the alkaline aqueous solution used for the development, a dilute solution of 0.1 to 5 wt% sodium carbonate, a dilute solution of 0.1 to 5 wt% sodium hydroxide,
A dilute solution of 0.1 to 5% by weight sodium tetraborate is preferred. The pH of the alkaline aqueous solution used for development is
It is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. Further, a surface active agent, a defoaming agent, a small amount of an organic solvent for accelerating development may be mixed in the alkaline aqueous solution. Development methods include a dip method and a spray method, and the high pressure spray method is most suitable for improving the resolution.

As a processing after development, if necessary, 80 to
The resist pattern may be further cured and used by heating at about 250 ° C. or exposure at about 0.2 to 5 mJ / cm ² . For etching the metal surface after development, a ferric chloride solution, a ferric chloride solution, an alkaline etching solution, or a hydrogen peroxide-based etching solution can be used, but ferric chloride is preferable because of its good etching factor. It is desirable to use a solution.

When a printed wiring board is manufactured using the photosensitive element of the present invention, the surface of the circuit-forming board is treated by a known method such as etching or plating using the developed resist pattern as a mask. Then, the resist pattern is usually stripped with an aqueous solution having a stronger alkaline property than the alkaline solution used for the development. As the strongly alkaline aqueous solution, for example, a 1 to 5 wt% sodium hydroxide aqueous solution, a 1 to 5 wt% potassium hydroxide aqueous solution, or the like is used. Further, the printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board.

[0054]

EXAMPLES The present invention will be described below with reference to examples. Examples 1 to 10 and Comparative Examples 1 to 8 The binder polymer, the photopolymerizable unsaturated compound, the compound of the component (D) or the monohydric phenol compound shown in Table 1, Table 3 and Table 4 were mixed, and Table 2 was added thereto. The photopolymerization initiator and other additives shown in 1 above were mixed and dissolved in a solvent to obtain a solution of the photosensitive resin composition.

[0055]

[Table 1]

The photopolymerizable unsaturated compounds in Table 1 are shown below. * 1: Bisphenol A (pentamethyleneoxymethacrylate) represented by the following formula (V)

[Chemical 8] * 2: EO-modified urethane dimethacrylate represented by the following formula (VI)

[Chemical 9] * 3: EO, PO modified urethane dimethacrylate represented by the following formula (VII)

[Chemical 10]

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

[Table 4]

Next, 1 part of this photosensitive resin composition solution was added.
6 μm thick polyethylene terephthalate film (Teijin
GS type, manufactured by Co., Ltd.) was uniformly applied and dried in a hot air convection dryer at 100 ° C. for 10 minutes to obtain a photosensitive element. The film thickness of the photosensitive resin composition layer after drying is 20 μm.
Met. On the other hand, a copper-clad laminate, which is a glass epoxy material in which copper foil (thickness 35 μm) is laminated on both sides (Hitachi Chemical Industry
Co., Ltd., product name MCL-E-61) copper surface # 600
Polishing was performed using a polishing machine (manufactured by Sankei Co., Ltd.) having an appropriate brush, washed with water, and then dried with an air stream. Then, after heating the copper-clad laminate to 80 ° C., the photosensitive element obtained above was adhered to the photosensitive resin composition layer on the copper surface at 120 ° C. under a pressure of 4 kgf / cm ² . Laminated.

Next, the copper clad laminate laminated with the photosensitive element was cooled, and when it reached 23 ° C., a photo tool having a 21-step step tablet of a stouffer and a negative for adhesion evaluation were formed on the polyethylene terephthalate surface. Line width / space width is 10/400 to 50/400
A phototool having a wiring pattern of (unit: μm) is brought into close contact, and a 3 KW high-pressure mercury lamp (Oak Seisakusho Co., Ltd., product name HMW-590) is used to determine the number of remaining steps after development of a 21-step step tablet of a stouffer. The exposure was performed with an energy amount of 7.0. For the evaluation of resolution, a photo tool having a 21-step step tablet of Stofer and a photo tool having a wiring pattern of line width / space width of 10/10 to 50/50 (unit: μm) as a negative for resolution evaluation are used. Using. Here, the adhesiveness was evaluated by the smallest value of the line width of the thin line which was in close contact after the unexposed portion was removed by the developing treatment.
Further, the resolution was evaluated by the smallest value of the space width between the line widths which was able to cleanly remove the unexposed portion by the development processing. The smaller the numerical values are, the better the evaluations of the adhesiveness and the resolution are.

Then, the polyethylene terephthalate film was removed, and an unexposed portion was removed by spraying a 1.0 wt% sodium carbonate aqueous solution at 30 ° C. for 30 seconds. The imaging property is a numerical representation of the amount of change in color, and indicates the difference in color contrast between the exposed portion and the unexposed portion. The photosensitive element thus prepared is exposed with an amount of energy such that the number of remaining step steps after development of the 21-step step tablet of the stofer becomes 7.0, and the exposure is carried out.
After that, the amount of change of the photosensitive element itself was measured using a color difference meter (manufactured by Tokyo Denshoku Co., Ltd., product name Color Ace TC-1). The value of this color change is taken as the imaging amount, and the larger the value, the more the color of the photosensitive element changes,
It serves as a standard for negative shift check during exposure and completion of exposure.

The results of the obtained resolution, adhesion and imaging properties are summarized in Tables 6 and 7. Next, the binder polymer shown in Table 5, the photopolymerizable unsaturated compound and the compound of the component (D) are mixed, and the photopolymerization initiator and other additives shown in Table 2 are mixed with this and dissolved in a solvent to be exposed. A solution of the resin composition was prepared and a photosensitive element was obtained by the above method. Then, the photosensitive element was laminated on the copper clad laminate by the above method. Then, the resist exposed by the energy amount such that the residual step number after development of the 21-step step tablet of Stofer is 7.0 is immersed in a 3% sodium hydroxide aqueous solution heated to 45 ° C. to cure the cured surface of the copper surface. The peeling time was measured and used as the peeling time. The results of the obtained peeling time are shown in Table 8. In addition, the results of resolution, adhesion and imaging properties are summarized in Table 6 by the above method.

[0064]

[Table 5]

[0065]

[Table 6]

[0066]

[Table 7]

[0067]

[Table 8]

As is clear from Table 5 and Table 6, the resolution of the photosensitive resin compositions used in Comparative Examples 1 to 8 was 15 or 20 μm, and the photosensitive resin compositions used in Examples 1 to 10 were Since the resolution of the product is 12 μm, it can be seen that the resolution of the photosensitive resin composition of the present invention is extremely excellent. Moreover, the adhesiveness of the photosensitive resin compositions used in Comparative Examples 1 to 8 is 15 to 20 μm, and the adhesiveness of the photosensitive resin compositions used in Examples 1 to 10 is 15 to 18 μm.
Therefore, it can be seen that the photosensitive resin composition of the present invention satisfies the requirement for adhesiveness.

The imaging properties of the photosensitive resin compositions used in Comparative Examples 1-8 are 30-45, and the imaging properties of the photosensitive resin compositions used in Examples 1-10 are 45. From this, it is understood that the photosensitive resin composition of the present invention satisfies the requirements required for imaging properties.
On the other hand, as is clear from Table 8, Example 8 to Example 10
The peeling time of the photosensitive resin composition used in 1 is 10 seconds, 1
From 6 seconds and 19 seconds, it is understood that the photosensitive resin composition of the present invention satisfies the requirement for the peeling time.
From the above, the photosensitive resin composition of the present invention is excellent in adhesiveness and imaging property, and is extremely excellent in resolution. Also, the peeling property is excellent.

[0070]

EFFECTS OF THE INVENTION The photosensitive resin composition according to the first, second and third aspects is extremely excellent in resolution, adhesion and imaging properties, and is very suitable for use as a liquid resist and a photosensitive element. The photosensitive resin composition according to claim 4 is excellent in peeling properties in addition to the effect of the invention according to claim 1, 2 or 3, and is very suitable for use as a liquid resist and a photosensitive element. The photosensitive element according to claim 5 has extremely excellent resolution, adhesion, imaging property and workability, and is extremely useful for increasing the density of printed wiring and automating the production of printed wiring boards.
The method for producing a resist pattern according to claim 6 is a method for producing a resist pattern, which has extremely excellent resolution, adhesion, imaging properties and workability, which are extremely useful for increasing the density of printed wiring and automating the production of printed wiring boards. The method for producing a printed wiring board according to claim 7 is a method for producing a printed wiring board which is extremely useful for high density of printed wiring and automation of production of the printed wiring board, which is extremely excellent in resolution, adhesion, imaging property and workability. is there.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI G03F 7/033 G03F 7/033 H05K 3/00 H05K 3/00 F (56) Reference JP-A-61-134756 (JP, A, JP ) JP-A-7-281437 (JP, A) JP-A-7-325398 (JP, A) JP-A-5-241331 (JP, A) JP-A-7-319153 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) G03F 7/004 C08F 2/44 C08F 2/48 C09D 4/06 G03F 7/028 G03F 7/033 H05K 3/00

Claims (7)

(57) [Claims] 1. A carboxyl group-containing binder polymer containing (A) styrene or a styrene derivative as a copolymerization component, (B) a photopolymerizable unsaturated compound having at least one polymerizable ethylenic unsaturated bond in the molecule,
(C) photopolymerization initiator and (D) general formula (I) (In the formula, X is a halogen atom, a hydrogen atom, or a carbon number of 1 to 20.
Alkyl group, C3-10 cycloalkyl group, amino group or phenyl group which may be substituted with C1-20 alkyl group, aryl group such as naphthyl group, amino group, mercapto group, carbon number 1 to 10 is an alkylmercapto group, a carboxyalkyl group having an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a heterocyclic group, wherein m and n are integers of 2 or more. And n is an integer of 0 or more and is an integer selected so that m + n = 6, and when n is an integer of 2 or more, Xs of 2 or more may be the same or different. A photosensitive resin composition containing the compound represented by the above, wherein a carboxyl group-containing binder polymer containing styrene or a styrene derivative as the component (A) as a copolymerization component contains styrene or a styrene derivative. It is a carboxyl group-containing binder polymer containing 0.1 to 30% by weight as a polymerization component, and the content of the compound represented by the general formula (I) of the component (D) is the same as that of the components (A) and (B). The photosensitive resin composition is 0.001 to 3 parts by weight based on 100 parts by weight in total. 2. The photosensitive resin composition according to claim 1, wherein X in the general formula (I) of the component (D) is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 3. The photopolymerizable unsaturated compound (B) having at least one polymerizable ethylenic unsaturated bond in the molecule is represented by the general formula (II): (In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Y ¹ and Y ² each independently represent an alkylene oxide group having 2 to 6 carbon atoms; Z
Represents a hydrocarbon group having 1 to 16 carbon atoms, and p and q are
The photosensitive resin composition according to claim 1 or 2, further comprising a compound represented by each independently an integer of 1 to 28) as an essential component. 4. The use ratio of the component (A), the component (B) and the component (C) is 40 to 40 parts by weight based on 100 parts by weight of the total amount of the component (A) and the component (B). 80 parts by weight,
The component (B) is 100 in total of the components (A) and (B).
20 to 60 parts by weight with respect to parts by weight, the component (C) is
The photosensitive resin composition according to any one of claims 1 to 3, which is 0.1 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (B). 5. A photosensitive element formed by applying the photosensitive resin composition according to any one of claims 1 to 4 on a support, drying the support, and laminating the composition. 6. The photosensitive element according to claim 5 is laminated on a circuit-forming substrate so that the photosensitive resin composition layer is in close contact with the protective film if necessary, and the actinic rays are imaged. Irradiate, light cure the exposed area,
A method for producing a resist pattern, which comprises removing an unexposed portion by development. 7. A method of manufacturing a printed wiring board, which comprises etching or plating a circuit-forming substrate having a resist pattern manufactured by the method of manufacturing a resist pattern according to claim 6.