JP2000314957A - Photosensitive resin composition, photosensitive element using same and manufacture of resist pattern and printed circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which is excellent intent reliability and yields little sludge due to underdevelopment and to provide a photosensitive element and methods for manufacturing resist patterns and printed circuit boards having this pattern. SOLUTION: The photosensitive resin composition contains a binder polymer and a compound represented by the formula and further contains a photopolymerizable compound having a polymerizable ethylenically unsaturated group in the molecule, and a photopolymerization initiator. The photosensitive element is formed by coating a support with this composition and drying it. The resist pattern is formed by peeling the protective film of the element and laminating the element on a substrate for forming the circuit and irradiating the assembly with active rays to optically cure the exposed parts, and removing the unexposed parts by development. Furthermore, the printed circuit board is obtained by etching or plating the substrate. In the formula, for example, each of R1 and R2 is an H atom; each of A1 and A2 is an ethylene group; each of R3-R5 is a hexylene group; and each of (k) and (m) is 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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, there are two methods of manufacturing a printed wiring board, a tenting method and a plating method. The tenting method is a method in which a copper through hole for mounting a chip is protected by a resist, and an electric circuit is formed through etching and resist peeling. On the other hand, in the plating method, copper is deposited in through holes by electroplating, protected by solder plating,
In this method, an electric circuit is formed by removing and etching a resist. As the resist, a photosensitive resin composition and a photosensitive element using the same are used, and an alkali developing type in which an uncured portion is removed with an alkaline aqueous solution is mainly used. Therefore, the photosensitive resin composition to be used is required to have a tenting property, that is, a tent reliability, which is not broken by a developing solution or a spray pressure of water washing.

[0003] JP-A-5-271129 discloses a photosensitive resin composition having good tent reliability using a vinyl urethane compound for such a purpose. However, in such a photosensitive resin composition, development sludge tends to increase, causing short circuit failure. This is presumed to be due to the fact that the isocyanate residue portion having a urethane bond is not so excellent in developability.

In order to reduce development sludge, the solubility of the photosensitive resin composition in a developer is improved, that is, a polyethylene glycol group ((OCH ₂ CH ₂ ) _n ) is contained in the structure of the photopolymerizable compound. It is known that it is effective to introduce a hydrophilic group represented by, for example, on the other hand, if the hydrophilicity of the photosensitive resin composition is excessively improved, the cured film becomes brittle, so that the tent reliability is increased. There was a problem of the decrease.

[0005]

SUMMARY OF THE INVENTION The inventions according to claims 1 and 2 provide a photosensitive resin composition having extremely excellent tent reliability and low developing sludge property. Claim 3
The described invention provides a photosensitive element having extremely excellent tent reliability, low developing sludge property and workability. The invention according to claim 4 provides a method of manufacturing a resist pattern having extremely excellent tent reliability, low developing sludge property and workability, which is extremely useful for increasing the density of printed wiring and automating the manufacture of printed wiring boards. is there. According to a fifth aspect of the present invention, there is provided a method of manufacturing a printed wiring board having a resist pattern having extremely excellent tent reliability, low developing sludge property and workability, which is extremely useful for increasing the density of printed wiring and automating the manufacture of the printed wiring board. Is provided.

[0006]

The present invention comprises (A) a binder polymer, (B) a compound of the general formula (I)

Embedded image (Wherein, R ¹ and R ² each independently represent a hydrogen atom or a carbon atom
And A ¹ and A ² each independently represent an alkylene group having 2 to 6 carbon atoms, and R ³ , R ⁴ and R ⁵ each independently represent an alkylene group having 1 to 10 carbon atoms. , K and m are each independently an integer of 1 to 15), and a photopolymerizable compound having a polymerizable ethylenically unsaturated group in the molecule and (C) a photopolymerization initiator. The present invention relates to a photosensitive resin composition contained therein.

In the present invention, the use ratio of the component (A), the component (B) and the component (C) is such that the component (A) is used in a total amount of 100 parts by weight of the component (A) and the component (B). 40-80
Parts by weight, the component (B) is 20 to 60 parts by weight, the component (C) is 0.01 to 5 parts by weight, and the compound represented by the above general formula (I) in the component (B) is ( B) Total amount of components 1
The photosensitive resin composition is contained in an amount of 25 to 100 parts by weight based on 00 parts by weight.

[0008] The present invention also relates to a photosensitive element obtained by applying the photosensitive resin composition on a support and drying the composition. Further, the present invention provides the photosensitive element, wherein the photosensitive resin composition layer is laminated on the circuit-forming substrate while peeling off a protective film which may be present in some cases, and irradiating actinic rays imagewise. The present invention also relates to a method for producing a resist pattern, which comprises curing an exposed portion with light and removing an unexposed portion by development. Further, the present invention relates to a method for manufacturing a printed wiring board, wherein a circuit forming substrate on which a resist pattern is manufactured is etched or plated by the method for manufacturing a resist pattern.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The binder polymer as the component (A) in the present invention is not particularly limited, and examples thereof include an acrylic resin, a methacrylic resin, a styrene resin, an epoxy resin, an amide resin, an amide epoxy resin, an alkyd resin, and phenol. And the like. From the viewpoint of alkali developability, an acrylic resin or a methacrylic resin is preferred. These can be used alone or in combination of two or more.

The binder polymer (A) in the present invention can be produced, for example, by radically polymerizing a polymerizable monomer.

[0011] The polymerizable monomer is not particularly limited.
For example, styrene, vinyltoluene, a polymerizable styrene derivative substituted at the α-position or an aromatic ring such as α-methylstyrene or styrene, 2,2,3,
Acrylamide such as 3-tetrafluoropropyl acrylate acrylamide, 2,2,3,3-tetrafluoropropyl methacrylate acrylamide, diacetone acrylamide, esters of vinyl alcohol such as acrylonitrile, vinyl-n-butyl ether, alkyl acrylate, methacryl Alkyl acid ester, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, glycidyl acrylate, methacrylic acid Acid glycidyl ester, 2,2,2-trifluoroethyl acrylate, 2,2 -Trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, acrylic acid, methacrylic acid, α-bromoacrylic acid, α-chloroacrylic acid, β-furylacrylic acid, β-styrylacrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate and other maleic acid monoesters, fumaric acid, cinnamic acid, α-cyanocinnamate acid,
Examples include itaconic acid, crotonic acid and propiolic acid.

Examples of the alkyl acrylate or alkyl methacrylate include, for example, those represented by the general formula (II)

Embedded image (Wherein, R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents an alkyl group having 1 to 12 carbon atoms), and a hydroxyl group, an epoxy group, a halogen group, etc. And an acrylate or methacrylate ester substituted with methacrylate. These can be used alone or in combination of two or more. As R ⁷ in the general formula (II), for example, a methyl group, an ethyl group,
Examples include a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and structural isomers thereof.

The monomers represented by the above general formula (II) include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate , Heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, methacryl Propyl acrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, methacrylate Acrylic acid 2-ethylhexyl ester, methacrylic acid nonyl ester, decyl methacrylate esters, methacrylic acid undecyl ester, and methacrylic acid dodecyl ester.

The binder polymer (A) in the present invention preferably contains a carboxyl group from the viewpoint of alkali developability. For example, a polymerizable monomer having a carboxyl group and another polymerizable monomer may be used. It can be produced by radical polymerization of a monomer. Further, the binder polymer as the component (A) in the present invention preferably contains styrene or a styrene derivative as a polymerizable monomer from the viewpoint of flexibility. These binder polymers are used alone or in combination of two or more.

The polymerization average molecular weight of the binder polymer (A) in the present invention is from 20,000 to 300, from the viewpoint of balance between mechanical strength and alkali developability.
000, preferably 40,000 to 200,
000, more preferably 60,000 to 12
Particularly preferably, it is set to 0000. If the weight average molecular weight is less than 20,000, mechanical strength tends to be poor, and if it exceeds 300,000, alkali developability tends to be poor. The weight average molecular weight in the present invention is a value measured by a gel permeation chromatography method and converted by a calibration curve created using standard polystyrene.

The carboxyl group content of the binder polymer (A) in the present invention is preferably from 15 to 50 mol%, and more preferably from 15 to 30 mol%, from the viewpoint of the balance between alkali developability and alkali resistance. More preferably, it is more preferably 15 to 25 mol%. If the carboxyl group content is less than 15 mol%, alkali developability tends to be poor, and if it exceeds 50 mol%, alkali resistance tends to be poor. In addition, the carboxyl group content in the present invention is a ratio of a polymerizable monomer having a carboxyl group to all polymerizable monomers used.

The photopolymerizable compound having a polymerizable ethylenically unsaturated group in the molecule of the component (B) in the present invention must contain the compound component represented by the general formula (I). In the general formula (I), R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and an n group.
-Propyl group, isopropyl group and the like. Also,
A ¹ and A ² are each independently an alkylene group having 2 to 6 carbon atoms. Examples of the alkylene group having 2 to 6 carbon atoms include an ethylene group, an n-propylene group, an isopropylene group, a butylene group, a pentylene group, and a hexylene group. R ³ , R ⁴ and R ⁵ are each independently an alkylene group having 1 to 10 carbon atoms, and examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, an n-propylene group, Propylene group, butylene group, pentylene group,
Examples include a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, and structural isomers thereof.
If the alkylene group has more than 10 carbon atoms, the hydrophilicity decreases and the development sludge increases.

The above isopropylene group is represented by --CH (CH ₃ )
CH ₂ — is a group represented by the formula (I)
In (A ¹ -O)-and-(A ² -O)-, there are two types of bonding directions: a case where the methylene group is bonded to oxygen and a case where the methylene group is not bonded to oxygen. Or two kinds of bonding directions may be mixed. Also,-
When the repeating units of (A ¹ -O)-and-(A ² -O)-are 2 or more, two or more A ¹ and two or more A ² may be the same or different; ^{When 1} and A ² are composed of two or more types of alkylene groups, two or more types of-(A ¹ -O)
- and - (A ² -O) - it may exist at random or may be present blockwise. In addition, the general formula (I)
K and m in the above are each independently an integer of 1 to 15. When this value exceeds 15, the hydrophilicity becomes too high, and the developing solution resistance of the obtained resist decreases.

The compound represented by the general formula (I) is, for example, k and m are 3, R ¹ and R ² are hydrogen atoms, and R ³ , R ⁴ and R ⁵ are hexylene. Acrylate compound (Shin-Nakamura Chemical Co., Ltd., prototype name,
NK ester A-SDL-3E) and the like.

The photopolymerizable compound having a polymerizable ethylenically unsaturated group in the molecule of the component (B) in the present invention is:
Components other than the compound represented by the general formula (I) can be contained.

Examples of the components other than the compound represented by the general formula (I) include polyhydric alcohols, compounds obtained by reacting polyhydric alcohols with α, β-unsaturated carboxylic acids, 2,2- Bis (4- (acryloxypolyethoxy) phenyl) propane, 2,2-bis (4- (methacryloxypolyethoxy) phenyl) propane, and a compound containing a glycidyl group are reacted with an α, β-unsaturated carboxylic acid. Compound, urethane monomer, nonylphenyldioxylene acrylate, nonylphenyldioxylene methacrylate, γ-chloro-β-hydroxypropyl-β′-acryloyloxyethyl-o-phthalate, γ-chloro-β-hydroxypropyl-β′- Methacryloyloxyethyl-o-phthalate, β-hydroxyethyl-β′-acryloy Oxyethyl -o- phthalate, beta-hydroxyethyl -β'- methacryloyloxyethyl -o- phthalate, acrylic acid alkyl esters, alkyl esters, and the like methacrylic acid.

Compounds obtained by reacting the above polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example,
Polyethylene glycol diacrylate having 2 to 14 ethylene groups, polyethylene glycol dimethacrylate having 2 to 14 ethylene groups, polypropylene glycol diacrylate having 2 to 14 propylene groups, and the number of propylene groups 2-14 which are polypropylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropaneethoxytriacrylate, trimethylolpropaneethoxytrimethacrylate, tetramethylol Methane triacrylate, tetramethylol methane trimethacrylate, tetramethylol methane tetraacrylate, Tiger methylol methane tetramethacrylate, polypropylene glycol diacrylate number of propylene is 2 to 14, polypropylene glycol dimethacrylate number of propylene is 2 to 14, dipentaerythritol pentaacrylate,
Examples thereof include dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate.

As the α, β-unsaturated carboxylic acid,
For example, acrylic acid and methacrylic acid are used. Examples of the 2,2-bis (4- (acryloxypolyethoxy) phenyl) propane include, for example, 2,2-bis (4
-(Acryloxydiethoxy) phenyl) propane,
2,2-bis (4- (acryloxytriethoxy) phenyl) propane, 2,2-bis (4- (acryloxypentaethoxy) phenyl) propane, 2,2-bis (4
-(Acryloxydecaethoxy) phenyl) and the like. Examples of the 2,2-bis (4- (methacryloxypolyethoxy) phenyl) propane include, for example, 2,2
-Bis (4- (methacryloxydiethoxy) phenyl)
Propane, 2,2-bis (4- (methacryloxytriethoxy) phenyl) propane, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane,
2,2-bis (4- (methacryloxydecaethoxy) phenyl) propane and the like, and 2,2-bis (4-
(Methacryloxypentaethoxy) phenyl) propane is BPE-500 (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.)
It is commercially available as

Examples of the glycidyl group-containing compound include, for example, trimethylolpropane triglycidyl ether triacrylate, trimethylolpropane triglycidyl ether trimethacrylate, 2,2-bis (4-
Acryloxy-2-hydroxy-propyloxy) phenyl, 2,2-bis (4-methacryloxy-2-hydroxy-propyloxy) phenyl and the like can be used. Examples of the urethane monomer include addition of an acrylic monomer having an OH group at the β-position or a methacrylic monomer corresponding thereto, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Reactant, tris (methacryloxytetraethylene glycol isocyanate hexamethylene isocyanurate, E
O-modified urethane dimethacrylate, EO, PO-modified urethane dimethacrylate and the like. EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. Also, PO
Represents propylene oxide, and the PO-modified compound has a propylene oxide group block structure.

Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like. Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like. These can be used alone or 2
Used in combination of more than one type.

Examples of the photopolymerization initiator (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-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2
Aromatic ketones such as ethylanthraquinone and phenanthrenequinone; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin compounds such as methyl benzoin and ethyl benzoin; benzyl derivatives such as benzyl dimethyl ketal; , 5-triarylimidazole dimer, 9-phenylacridine, acridine derivatives such as 1,7-bis (9,9'-acridinyl) heptane, N-phenylglycine and the like.

From the viewpoint of adhesion and sensitivity,
4,5-triarylimidazole dimer is preferred,
For example, 2,2'-bis (o-chlorophenyl) -4,
5,4 ', 5'-tetraphenyl-1,2'-imidazole dimer, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-chlorophenyl) imidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2,2' -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-fluorophenyl) imidazole dimer, 2,2'-bis (o-bromophenyl) -4,4', 5, 5'-tetra (p-chlorop-methoxyphenyl) imidazole dimer, 2,
2'-bis (o-chlorophenyl) -4,4 ', 5
5'-tetra (o, p-dichlorophenyl) imidazole dimer, 2,2'-bis (o-chlorophenyl)-
4,4 ', 5,5'-tetra (o, p-dibromophenyl) imidazole dimer, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p- Chloronaphthyl) imidazole dimer, 2,2'-bis (m,
p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylimidazole dimer, 2,2'-bis (o, p
Dichlorophenyl) -4,4 ', 5,5'-tetraphenylimidazole dimer, 2,2'-bis (o, p-
Dichlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) 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) -4,5-diphenylimidazole dimer, 2-
(P-methylmercaptophenyl) -4,5-diphenylimidazole dimer, 2,2′-bis (p-bromophenyl) -4,4 ′, 5,5′-tetraphenylimidazole dimer, 2, 2'-bis (o-bromophenyl)
-4,4 ', 5,5'-tetra (o, p-dichlorophenyl) imidazole dimer, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetra (p -Iodophenyl) imidazole dimer, 2,2'-bis (m
-Bromophenyl) -4,4 ', 5,5'-tetraphenylimidazole dimer, 2,2'-bis (m, p-dibromophenyl) -4,4', 5,5'-tetraphenylimidazole And dimers. These are used alone or in combination of two or more.

In the present invention, the amount of the component (A) is from 40 to 80 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B) from the viewpoint of the balance between coating properties and photocurability. Parts by weight, more preferably 50 to 70 parts by weight, particularly preferably 55 to 65 parts by weight. If the amount is less than 40 parts by weight, the resulting photosensitive element tends to have poor coating properties, and if it exceeds 80 parts by weight, the photocurability tends to be insufficient.

The total amount of the component (B) in the present invention is preferably 20 to 60 parts by weight, and more preferably 30 to 5 parts by weight, based on 100 parts by weight of the total of the components (A) and (B).
It is more preferably 0 parts by weight, particularly preferably 35 to 45 parts by weight. If the amount is less than 20 parts by weight, the photocurability tends to be insufficient, and if it exceeds 60 parts by weight, the coating properties tend to deteriorate.

The compounding amount of the compound represented by the general formula (I) in the present invention is preferably 25 to 100 parts by weight, preferably 50 to 100 parts by weight, based on 100 parts by weight of the total amount of the component (B).
It is more preferably 75 parts by weight, particularly preferably 60 to 65 parts by weight. If the amount is less than 25 parts by weight, the effect of the present invention tends to be small.

The amount of the component (C) in the present invention is as follows:
The amount is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the total of the components (A) and (B), and is preferably 0.0 to 5 parts by weight.
It is more preferably 5 to 4 parts by weight, particularly preferably 0.1 to 3 parts by weight. If the amount is 0.0
If the amount is less than 1 part by weight, the sensitivity tends to be insufficient.
When the amount exceeds the weight part, the resolution tends to be deteriorated.

The photosensitive resin composition of the present invention may contain, if necessary, a dye such as malachite green, a coloring agent such as leuco crystal violet, a thermal coloring inhibitor, and a plasticizer such as p-toluenesulfonic acid amide. , Pigments, fillers, defoamers, flame retardants, stabilizers, adhesion promoters, leveling agents,
A peeling accelerator, an antioxidant, a fragrance, an imaging agent, a thermal crosslinking agent and the like can be contained in an amount of about 0.01 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (B). These are used alone or in combination of two or more.

The photosensitive resin composition of the present invention may be dissolved, if necessary, in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, dimethylformamide or a mixture thereof to obtain a solid content. It can be applied as a solution of about 30 to 60% by weight.

The photosensitive resin composition of the present invention is not particularly limited, but is preferably a metal surface, for example, an iron-based alloy such as copper, a copper-based alloy, nickel, chromium, iron, or stainless steel, and preferably copper or a copper-based alloy. Preferably, it is applied as a liquid resist on the surface of the iron-based alloy and dried, and then coated with a protective film if necessary, or used in the form of a photosensitive element.

The thickness of the photosensitive resin composition layer varies depending on the application, but is preferably from 1 to 200 μm, more preferably from 1 to 100 μm, and more preferably from 1 to 30 μm in terms of thickness after drying. Is particularly preferred. If the thickness is less than 1 μm, it tends to be industrially difficult to apply,
If it exceeds 00 μm, the effect of the present invention tends to be small and the sensitivity tends to be insufficient. If it exceeds 200 μm, the photocurability at the bottom of the resist tends to deteriorate. When a liquid resist is coated with a protective film, the protective film is, for example, an inactive polyolefin film such as polyethylene and polypropylene.However, from the standpoint of releasability from the photosensitive resin composition layer, a polyethylene film is used. preferable.

The photosensitive element is obtained by coating and drying a photosensitive resin composition on a heat- and solvent-resistant polymer film such as polyethylene terephthalate, polypropylene, polyethylene or polyester as a support. Can be From the viewpoint of transparency, it is preferable to use a polyethylene terephthalate film. The coating can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, a bar coater, and a sleigh coater.
Further, the drying temperature is preferably from 50 to 175 ° C, more preferably from 70 to 110 ° C. If the drying temperature is lower than 50 ° C., a large amount of the organic solvent tends to remain in the photosensitive resin composition layer, and if it exceeds 175 ° C., the color of the photosensitive resin composition layer tends to change. The drying time is preferably 30 to 900 seconds, and 30 to 900 seconds.
More preferably, it is 600 seconds. This drying time is 3
If the time is less than 0 second, the amount of the organic solvent remaining in the photosensitive resin composition layer tends to increase, and if it exceeds 900 seconds, the color of the photosensitive resin composition layer tends to change.

Since these polymer films must be removable from the photosensitive resin composition layer later, they may be subjected to a surface treatment that makes removal impossible, or may be made of a material. Don't be. The thickness of these polymer films is preferably 1 to 100 μm, more preferably 1 to 30 μm. If the thickness is less than 1 μm, the mechanical strength tends to decrease, and problems such as breakage of the polymer film during coating tend to occur. If the thickness exceeds 30 μm, the resolution tends to decrease and the price tends to increase. Further, one of these polymer films may be laminated on both surfaces of the photosensitive resin composition layer as a support film of the photosensitive resin composition layer, and the other one may be used as a protective film of the photosensitive resin composition layer. . As the protective film, one having a smaller adhesive force between the photosensitive resin composition layer and the protective film than the adhesive force between the photosensitive resin composition layer and the support is preferable.

The photosensitive element of the present invention comprising the two layers of the photosensitive resin composition layer and the polymer film thus obtained may be further provided with a protective film as it is or on the other surface of the photosensitive resin composition layer. They are stacked, wound into a roll, and stored. Further, the amount of the residual organic solvent in the photosensitive resin composition layer is preferably 2% by weight or less from the viewpoint of preventing the diffusion of the organic solvent in a later step.

In producing a resist pattern using a photosensitive element, if the above-mentioned protective film is present, the protective film is removed, and the substrate for circuit formation is heated while heating the photosensitive resin composition layer. And a method of laminating by pressure bonding, and it is preferable to laminate under reduced pressure from the viewpoint of adhesion and followability. The surface to be laminated is usually a metal surface, but is not particularly limited. The heating temperature of the photosensitive resin composition layer is preferably from 70 to 130 ° C., and the pressing pressure is from 0.1 to 1 MPa (1 to 10 kg / cm).
² ) is preferable, but these conditions are not particularly limited. Further, as described above, the photosensitive resin composition layer
If the substrate is heated to 0 to 130 ° C., it is not necessary to pre-heat the circuit-forming substrate in advance, but the circuit-forming substrate can be pre-heated to further improve the lamination property.

The photosensitive resin composition layer thus completed is irradiated with actinic rays imagewise through a negative or positive mask pattern called artwork. At this time, when the polymer film present on the photosensitive resin composition layer is transparent, it may be irradiated with actinic light as it is, and when it is opaque, it is necessary to remove it naturally. From the viewpoint of protecting the photosensitive resin composition layer, it is preferable that the polymer film is transparent, and that the polymer film is irradiated with actinic rays through the polymer film while remaining.

As the light source of the actinic ray, a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, or the like that effectively emits ultraviolet rays is used. In addition, those that effectively emit visible light, such as a flood light bulb for photography and a sun lamp, are also used. The sensitivity of the photopolymerization initiator contained in the photosensitive resin composition layer is usually maximum in the ultraviolet region. In this case, it is preferable to use an active light source that effectively emits ultraviolet light. In contrast, when a photopolymerizable initiator such as 9,10-phenanthrenequinone which is highly sensitive to visible light is used in combination, an actinic light source that should emit visible light effectively should be used. Is preferred.

Next, after exposure, if a support is present on the photosensitive resin composition layer, after removing the support,
Using a developing solution such as an aqueous alkaline solution, the unexposed portion is removed and developed by a known method such as spraying, rocking immersion, brushing, and scraping to produce a resist pattern. As the developer, a safe and stable one having good operability, such as an alkaline aqueous solution, is used. As the base of the alkaline aqueous solution, for example, alkali hydroxides such as lithium, sodium or potassium hydroxide, alkali carbonates such as lithium, sodium, potassium or ammonium carbonate or bicarbonate, potassium phosphate, phosphoric acid Alkali metal phosphates such as sodium and alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate are used.

Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1 to 5% by weight of sodium carbonate,
Dilute solution of 0.1-5% by weight potassium carbonate, 0.1-5%
Weight% dilute solution of sodium hydroxide, 0.1-5% by weight
A dilute solution of sodium tetraborate or the like is preferred. In addition, the pH of the alkaline aqueous solution used for development needs to be within an appropriate pH range in which the photosensitive resin composition layer in the unexposed portion is removed and the photosensitive resin composition layer in the exposed portion remains on the substrate as a resist. For this reason, the temperature is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. A surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution. Development methods include a dip method, a battle method, a spray method, brushing, and slapping, and a high-pressure spray method is most suitable for improving resolution.

As processing after development, 60-
The resist pattern may be further cured by heating at about 250 ° C. or exposure at about 0.2 to 10 mJ / cm ² .

For etching the metal surface after the development, a cupric chloride solution, a ferric chloride solution, an alkali etching solution, and a hydrogen peroxide-based etching solution can be used. It is desirable to use a ferric solution.

When a printed wiring board is manufactured using the photosensitive element of the present invention, the surface of the circuit forming substrate is treated by a known method such as etching or plating using the developed resist pattern as a mask. Examples of the plating method include copper plating such as copper sulfate plating and copper pyrophosphate, solder plating such as high-throw solder plating,
There are nickel plating such as Watt bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating, and gold plating such as hard gold plating and soft gold plating. Next, the resist pattern is usually stripped with a more alkaline aqueous solution than the alkaline aqueous solution used for development. As the strong alkaline aqueous solution, for example, 1 to
A 5% by weight aqueous solution of sodium hydroxide, a 1 to 5% by weight aqueous solution of potassium hydroxide and the like are used. Further, the printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board.

[0047]

The present invention will be described below with reference to examples. Examples 1 to 3 and Comparative Examples 1 to 4 The components (A), (C), additives and solvents shown in Tables 1 and 2 were blended, and the component (B) shown in Table 3 was dissolved therein. A solution of the photosensitive resin composition was obtained.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3]

Next, using a knife coating method, a solution of the photosensitive resin composition was uniformly applied on a 25 μm-thick polyethylene terephthalate film (GS type, manufactured by Teijin Limited), and a hot air convection dryer at 100 ° C. For 10 minutes to obtain a photosensitive element. The dried film thickness of the photosensitive resin composition layer was 40 μm.

Next, a copper clad laminate (Hitachi Chemical Industries, Ltd.) which is a glass epoxy material under laminated copper foil (thickness: 35 μm) on both sides
Copper surface of # 600 manufactured by MCL-E-61)
Polished using a polishing machine with a considerable brush (manufactured by Sankei Co., Ltd.), washed with water, dried in an air stream, and the obtained copper-clad laminate was heated to 80 ° C. Layer of the photosensitive resin composition on the copper surface using
Lamination was performed at 0 ° C. and 0.4 MPa (4 kgf / cm ² ).

After the lamination, the copper-clad laminate was cooled, and when the temperature of the copper-clad laminate reached 23 ° C., a phototool (a 21-step step tablet of a stofer was brought into close contact with the polyethylene terephthalate surface, Using an exposure machine (model HMW-201GX, 5 kW ultra-high pressure mercury lamp), the line / space is 30/400 to 250/400 (adhesion, unit:
A photo tool having a wiring pattern of (μm) was brought into close contact, and exposed with an energy amount such that the number of remaining steps after development of the 21-step tablet of the stofer was 8.0. After exposure, leave at room temperature for 15 minutes, then peel off the polyethylene terephthalate film from the copper-clad laminate,
The development was carried out by spraying a 1.0% by weight aqueous solution of sodium carbonate at 30 ° C.

Thereafter, based on the result, the exposure amount at which the number of remaining steps after development was 8.0 was accurately obtained.
The amount of development sludge was determined by separating and filtering the sludge generated in this development step by a centrifugal separator.
After drying at 4 ° C. for 4 hours, the weight of the sludge was measured and evaluated. The tent reliability is based on a 1.6mm thick copper clad laminate with 3 holes of 4mm diameter in a row (see Fig. 1).
The laminated body of the photosensitive resin composition was laminated on both sides, exposed at an exposure amount such that the number of remaining steps after development was 8.0, and development was performed twice for 60 seconds. After the development, the number of broken holes at the locations shown in 1 in FIG. 1 (a total of 18 three-diameter φ4 mm holes) was measured and evaluated as a deformed tent breaking ratio (the following formula), which was defined as tent reliability.

(Equation 1) Table 4 summarizes the above results.

[0055]

[Table 4]

[0056]

The photosensitive resin compositions according to claims 1 and 2 are extremely excellent in tent reliability and low developing sludge property,
Very suitable for use as liquid resists and photosensitive elements. The photosensitive element according to the third aspect is extremely excellent in tent reliability, low developing sludge property and workability, and is extremely useful for increasing the density of printed wiring and automating the production of printed wiring boards. The method of manufacturing a resist pattern according to claim 4 is a method of manufacturing a resist pattern having extremely excellent tent reliability, low developing sludge property and workability, which is extremely useful for increasing the density of printed wiring and automating the manufacture of printed wiring boards. . The method for manufacturing a printed wiring board according to the fifth aspect provides a tent reliability which is extremely useful for increasing the density of printed wiring and automating the manufacture of printed wiring boards.
This is a method for producing a printed wiring board having extremely excellent low developing sludge properties and workability.

[Brief description of the drawings]

FIG. 1 is an enlarged view of an external appearance and a triple hole of an evaluation board used for evaluating a deformed tent tear rate in Examples.

[Explanation of symbols]

 1. Triple hole

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 2H025 AA04 AA13 AB11 AB15 AC01 BC14 BC43 CB13 CB14 CB43 FA40 FA43 5E339 BE11 CC01 CC10 CD01 CE12 CE16 CF01 CF16 CF17 DD02 FF01 FF10 GG01 GG02 5E343 AA02 AA12 BB21 BB71

Claims (5)

[Claims] (A) a binder polymer, (B) a general formula (I) (Wherein, R ¹ and R ² each independently represent a hydrogen atom or a carbon atom
And A ¹ and A ² each independently represent an alkylene group having 2 to 6 carbon atoms, and R ³ , R ⁴ and R ⁵ each independently represent an alkylene group having 1 to 10 carbon atoms. , K and m are each independently an integer of 1 to 15), and a photopolymerizable compound having a polymerizable ethylenically unsaturated group in the molecule and (C) a photopolymerization initiator. A photosensitive resin composition comprising: 2. The use ratio of component (A), component (B) and component (C) is such that the total amount of component (A) and component (B) is 100
Component (A) is 40 to 80 parts by weight, and (B)
20 to 60 parts by weight of the component and 0.01 to 5 of the component (C)
Parts by weight, and the above-mentioned general formula (I) in the component (B)
The photosensitive resin composition according to claim 1, wherein the compound represented by the formula (I) is contained in an amount of 25 to 100 parts by weight based on 100 parts by weight of the total amount of the component (B). 3. A photosensitive element obtained by applying and drying the photosensitive resin composition according to claim 1 on a support. 4. The photosensitive element according to claim 3, which is laminated on a circuit-forming substrate such that the photosensitive resin composition layer adheres to the circuit-forming substrate while removing a protective film that may be present in some cases. A method for producing a resist pattern, comprising: irradiating an exposed portion, photocuring an exposed portion, and removing an unexposed portion by development. 5. A method for manufacturing a printed wiring board, comprising etching or plating a circuit-forming substrate on which a resist pattern has been manufactured by the method for manufacturing a resist pattern according to claim 4.