JP2003035953A - Photosensitive resin composition for high density and high resolution and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition useful to increase the density and resolution of a printed wiring board and having excellent photosensitivity, adhesion, resolution, chemical resistance, mechanical strength, peeling property and flexibility. SOLUTION: The photosensitive resin composition contains a copolymer comprising a styrene and its derivative, a photopolymerizable compound, a photopolymerization initiator and carboxylbenzotriazole or its derivative of formula (I) (where R<1> is H or a <=20C alkyl or aminoalkyl). Its use is provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition useful for high density and high resolution, its use, a photosensitive element using the same, a resist pattern and a printed wiring board, and particularly to resolution. , A composition excellent in adhesion and plating solution resistance.

[0002]

2. Description of the Related Art In the manufacture of printed wiring boards, a conductive layer is formed by forming a resist layer on a metal foil, exposing, developing and patterning, etching / plating, and removing unnecessary resist. It is removed by peeling. As such a resist material, a photosensitive element having a three-layer structure in which a photosensitive resin composition is applied to a support, dried, and the resin layer is covered with a protective film is widely used. Then, the photosensitive element is heated and pressure-bonded to the metal foil to be engaged.

The developing solution is mainly of the alkaline developing type using a sodium hydrogen carbonate solution or the like. Here, the developer is
Generally, it can be used as long as it has the ability to dissolve the photosensitive resin composition layer to some extent, and the photosensitive resin composition can be dissolved or dispersed in a developer during development.

With the recent increase in density of printed wiring boards,
Since the contact area between the copper substrate and the patterned photosensitive resin composition layer is small, the photosensitive resin composition has excellent adhesion in the development, etching or plating treatment step,
Chemical resistance, mechanical strength, peeling characteristics, flexibility, etc. are required, and in addition, high adhesion and high resolution are required.

In order to improve the adhesion and the peeling property, it has been attempted to include a styrene component in the polymer binder. JP-A-2000-181056 discloses a photosensitive resin containing a polymer binder containing styrene or a derivative thereof, a conventional photopolymerization initiator, and a photopolymerizable compound having a long-chain ethylenically unsaturated group. The composition is described. However, if the dispersity of the binder polymer is large, there is a drawback that the adhesiveness and the resolution are lowered.

Japanese Unexamined Patent Publication No. 2000-214583 discloses that
A photosensitive resin composition containing a polymer binder containing styrene or a derivative thereof, a conventional photopolymerization initiator, and a photopolymerizable compound which is a bisphenol A compound having a specific structure is described. However, if the dispersity of the binder polymer is large, there is a drawback that the adhesiveness and the resolution are lowered. Therefore, there is a demand for a photosensitive resin composition having improved adhesiveness and capable of coping with higher density.

[0007]

In order to solve the above problems, the object of the present invention is to provide excellent photosensitivity, adhesion, resolution, chemical resistance, mechanical strength, peeling characteristics and flexibility, and to improve printed wiring. The present invention provides a photosensitive resin composition useful for densification and high resolution and its use.

[0008]

The present invention comprises (A) a polymeric binder, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in the molecule, and (C) a photopolymerizable compound. In the photosensitive resin composition containing an initiator and an additive (D), the component (A) is a copolymerization component composed of styrene and / or a derivative thereof; and the component (D).
Has the general formula (I):

[0009]

[Chemical 2]

A photosensitive resin composition characterized by being a carboxylbenzotriazole and / or a derivative thereof represented by the formula (wherein R ¹ is hydrogen, an alkyl group having 20 or less carbon atoms or an aminoalkyl group). Regarding things.

DETAILED DESCRIPTION OF THE INVENTION

In the present invention, "(meth) acrylic acid"
Means acrylic acid and methacrylic acid corresponding thereto, "(meth) acrylate" means acrylate and corresponding methacrylate, and "(meth) acrylate" means
The "acryloyl group" means an acryloyl group and a corresponding methacryloyl group.

"EO" represents ethylene oxide, and E
The O-modified compound has a block structure of an ethylene oxide group. Further, “PO” represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide group.

The component (A) polymer binder of the present invention is a polymerizable styrene derivative substituted in the α-position or aromatic ring such as styrene, vinyltoluene, 1-methylstyrene (isopropenylbenzene). is there. For example, it can be produced by radically polymerizing a polymerizable monomer. Further, the component (A) of the present invention preferably contains a carboxyl group in consideration of the alkali developability, and for example, a polymerizable monomer having a carboxyl group and other polymerizable monomer are radically polymerized. It can be manufactured.

Weight average molecular weight M _w of component (A) of the present invention
Is 2.0 × 10 considering the developing solution resistance and the developing time.
^{4 to} 3.0 × 10 ⁵ , preferably 4.0 × 10
More preferably, it is ^{4 to} 1.5 × 10 ⁵ .

The component (A) of the present invention is 1.0 to 3.0 in consideration of the influence of the dispersity (weight average molecular weight M _w / number average molecular weight M _n ) on the adhesiveness and the resolution. It is more preferably 1.5 to 2.5. In addition, the weight average molecular weight and the number average molecular weight in the present invention are measured by gel permeation chromatography, and standard polystyrene converted values are used. The dispersity is a measure of the molecular weight heterogeneity of the sample.

The acid value of the component (A) of the present invention is preferably 100 to 500 mg / KOH in order to satisfy both the shortening of the developing time and the resistance of the photocured resist to the developing solution.
More preferably, it is from 00 to 300 mg / KOH.

As the component (A) of the present invention, styrene or a styrene derivative or another polymer binder may be used in combination of two or more kinds. Here, the dispersity when two or more binder polymers are combined is the dispersity of the entire component (A) (polymer mixture). When two or more kinds are used in combination, examples of the polymer binder include two or more kinds of polymer binders composed of different copolymerization components, two or more kinds of polymer binders having different weight average molecular weights, different dispersions. Two or more types of polymer binders and the like. In this case, the dispersity is preferably 1.0 to 3.0, more preferably 2.0 to 3.0. Further, in order to improve both the adhesion and the peeling property by using styrene and / or a styrene derivative as a copolymerization component, the content is preferably 0.1 to 50% by weight, more preferably 1 to 30% by weight, It is particularly preferable to contain 1.5 to 27% by weight.

Other polymer binders that can be used as the component (A) of the present invention include, for example, acrylic resins, styrene resins, epoxy resins, amide resins,
Examples thereof include amide epoxy resin, alkyd resin, phenol resin, and mixtures thereof. Considering the alkali developability, acrylic resin is preferable. These may be used alone or in combination of two or more.

For example, (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2, 2,
2-trifluoroethyl (meth) acrylate, 2,
2,3,3-Tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, 1-bromo (meth) acrylic acid, 1-chloro (meth) acrylic acid, 2-furyl (meth) acrylic acid, 2-styryl (Meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate,
Maleic acid monoesters such as monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, 1-
Examples thereof include cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid.

Examples of the alkyl (meth) acrylic acid ester include those represented by the general formula (II)

[0021]

[Chemical 3]

(Wherein R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an optionally substituted alkyl group having 1 to 12 carbon atoms), and compounds thereof. A compound in which the hydroxyl group, epoxy group, halogen group or the like is substituted on the alkyl group of

Examples of the monomer represented by the general formula (II) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, and (meth) acrylic acid. Butyl ester,
(Meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth)
Acrylic acid nonyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester,
(Meth) acrylic acid dodecyl ester and the like can be mentioned.
These may be used alone or in combination of two or more.

According to the present invention, the compounding amount of the component (A) is
To improve both the mechanical strength and photosensitivity of the photocured product per 100 parts by weight of the total amount of components (A) and (B), 4
The amount is preferably 0 to 80 parts by weight, more preferably 45 to 70 parts by weight. The mechanical strength of the photocured product affects the coating property when used as a photosensitive element.

At least 1 in the molecule of component (B) of the present invention
Known materials can be used as the photopolymerizable compound having two polymerizable ethylenically unsaturated bonds. For example,
A bisphenol A (meth) acrylate compound, a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, a compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid, Urethane monomers such as (meth) acrylate compounds having a urethane bond, nonylphenyldioxylene (meth) acrylate, 3-chloro-2-hydroxypropyl-2'-
(Meth) acryloyloxyethyl-o-phthalate,
2-hydroxyethyl-2 '-(meth) acryloyloxyethyl-o-phthalate, 2-hydroxypropyl-2'-(meth) acryloyloxyethyl-o-phthalate, (meth) acrylic acid alkyl ester, EO-modified nonylphenyl (Meth) acrylate etc. are mentioned. These can be used alone or in combination of two or more.

Examples of the bisphenol A (meth) acrylate compound include 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane and 2,2-bis.
2,2-bis (4-((meth)) such as bis (4- (methacryloxypentadecaethoxy) phenyl) propane
Acryloxypolyalkoxy) phenyl) propane,
2,2 such as 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane
-Bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane and the like.

Examples of the compound obtained by reacting the above polyhydric alcohol with α, β-unsaturated carboxylic acid include:
Polyethylene glycol di (meth) acrylate having 2-14 ethylene groups, 2-1 propylene groups
4 polypropylene glycol di (meth) acrylate, (meth) acrylic acid such as tetramethylolmethane tetra (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, and the like. Can be fisted. Examples of the glycidyl group-containing compound include trimethylolpropane triglycidyl ether tri (meth) acrylate and 2,2-bis (4- (meth) acrylate.
Acryloxy-2-hydroxy-propyloxy) phenyl etc. can be fisted.

Examples of urethane monomers include β-
Addition reaction product of a (meth) acrylic monomer having an OH group at the position with a diisocyanate compound such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate; tris ((meta ) Acryloxytetraethylene glycol isocyanate) Hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate; EO, PO-modified urethane di (meth) acrylate and the like.

According to the present invention, the blending amount of component (B) is
To improve both the mechanical strength and photosensitivity of the photocured product per 100 parts by weight of the total amount of components (A) and (B), 2
The amount is preferably 0 to 60 parts by weight, more preferably 30 to 55 parts by weight.

As the component (C) photopolymerization initiator of the present invention,
Known ones can be used. For example, benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone. Benzophenones; 2-benzyl-2-dimethylamino-1
Aromatic ketones such as-(4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1; 2-ethylanthraquinone, phenanthrenequinone, 2 -T-butyl anthraquinone, octamethyl anthraquinone,
1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2
-Methylanthraquinone, 1,4-naphthoquinone, 9,
Quinones such as 10-phenantharaquinone, 2-methyl-1,4-naphthoquinone and 2,3-dimethylanthraquinone; benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and other benzoin ether compounds; benzoin, methylbenzoin, ethyl Benzoin compounds such as benzoin; benzyl derivatives such as benzyl dimethyl ketal; 2- (o-chlorophenyl)
-4,5-diphenylimidazole dimer, 2- (o-
Chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl)-
Optionally substituted 2,4,5-triarylimidazole dimer such as 4,5-diphenylimidazole dimer, 2- (o- or p-methoxyphenyl) -4,5-diphenylimidazole dimer Acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9'-acridinyl) heptane; N-phenylglycine, N-phenylglycine derivatives; coumarin compounds and the like. These may be used alone or in combination of two or more. Considering adhesion and sensitivity, 2-
(O-Chlorophenyl) -4,5-diphenylimidazole dimer and optionally substituted 2,4,5-triarylimidazole dimer such as N, N'-tetraethyl-4,4'-diaminobenzophenone The body is more preferred.

According to the present invention, the blending amount of component (C) is
To improve both internal photocuring and photosensitivity per 100 parts by weight of the total amount of components (A) and (B), 0.01
It is preferably from 10 to 10 parts by weight, more preferably from 0.2 to 5.0 parts by weight.

The component (D) carboxybenzotriazole of the present invention has the general formula (I):

[0033]

[Chemical 4]

(Wherein R ¹ is hydrogen, an alkyl group having 20 or less carbon atoms or an aminoalkyl group) and is a carboxylbenzotriazole and / or a derivative thereof. The photosensitive resin composition of the present invention 0.005 to 4.0 per 100 parts by weight of the total amount of the components (A) and (B).
Includes parts by weight. For example, 5-carboxybenzotriazole and 4-carboxybenzotriazole are mentioned, and 5-carboxybenzotriazole is preferable.

The carboxylbenzotriazole derivative as the component (D) includes, for example, 1- [N, N-bis (2-containing an optionally substituted aminomethyl group.
Ethylhexyl) aminomethyl] -5-carboxylbenzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] -4-carboxylbenzotriazole, 1- [N, N-bis (2-ethylhexyl)
Aminoethyl] -5-carboxylbenzotriazole, 1- [N, N-bis (isopropyl) aminomethyl] -5-carboxylbenzotriazole, 1- [N
-Hydro-N-3- (2-ethylhexyloxy) -1
-Propylaminomethyl] -5-carboxylbenzotriazole, 1- [N, N-bis (1-octyl) aminomethyl] -5-carboxylbenzotriazole, 1-
[N, N-bis (2-hydroxypropyl) aminomer] -5-carboxylbenzotriazole and the like can be mentioned.

According to the present invention, the blending amount of component (D) is
In order to improve the adhesion, the resolution and the deposition of the plating per 100 parts by weight of the total amount of the components (A) and (B), 0.0
The amount is 05 to 4.0 parts by weight, and more preferably 0.01 to 2.0 parts by weight.

According to the present invention, the compounding amount of the component (A) is 40 per 100 parts by weight of the total amount of the components (A) and (B).
To 80 parts by weight, and the compounding amount of the component (B) is 20 to 6
It is 0 parts by weight, and the compounding amount of the component (C) is 0.01 to
6.0 parts by weight, and the compounding amount of component (D) is
It is preferably 0.005 to 4.0 parts by weight.

According to the present invention, the compounding amount of the component (A) is 45 per 100 parts by weight of the total amount of the components (A) and (B).
To 70 parts by weight, and the blending amount of the component (B) is 30 to 5
5 parts by weight, and the compounding amount of the component (C) is 0.2 to 5.
0 parts by weight, and the compounding amount of component (D) is 0.0
It is more preferably 1 to 2.0 parts by weight.

In the photosensitive resin composition of the present invention, if necessary, a dye such as malachite green, a photocoloring agent such as tribromophenyl sulfone or leuco crystal violet, a thermal color-preventing agent, p-toluene sulfone. Plasticizers such as amides, pigments, fillers, defoamers, flame retardants, stabilizers,
An adhesion promoter, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, a thermal crosslinking agent, etc. can be contained. According to the present invention, it is preferable that the amount of each component (A) and (B) is 0.005 to 20 parts by weight per 100 parts by weight. These may be used alone or in combination of two or more.

The photosensitive resin composition of the present invention contains, if necessary, alcohols such as methanol and ethanol; benzenes such as toluene; ketones such as acetone and methyl ethyl ketone; N, N-dimethylformamide; Dissolve in a solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, alkylene glycol monoalkyl ether such as propylene glycol monomethyl ether or a mixed solvent thereof, and apply as a solution having a solid content of about 30 to 60% by weight. You can

Further, according to the present invention, the thickness of the photosensitive resin composition layer varies depending on the use, but in order to improve both industrial coatability and resolution and adhesion, the thickness after drying is required. Is preferably 1 to 100 μm, and more preferably 1 to 50 μm.

According to the present invention, the transmittance of the photosensitive resin composition layer for ultraviolet rays having a wavelength of 365 nm is preferably 5 to 75%, and 7 to 7%, in order to improve both adhesion and resolution. 60% is more preferable, and 10 to 4
It is particularly preferably 0%. The transmittance can be measured by a UV spectrometer, and examples of the UV spectrometer include a 228A type W beam spectrophotometer manufactured by Hitachi, Ltd.

The photosensitive resin composition of the present invention is applied as a liquid resist on the surface of a support, dried and then coated with a protective film, if necessary, or used in the form of a photosensitive element. Is preferred. The support is not particularly limited, for example, copper, copper-based alloy, nickel, chromium,
Examples of the metal surface include iron-based alloys such as iron and stainless steel, and copper, copper-based alloys and iron-based alloys are preferable. Further, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene and polyester can be used.

According to the present invention, the thickness of the support is preferably 5 to 25 μm in order to improve both the peel strength and the resolution of the support before development when used as a photosensitive element. It is more preferably ˜20 μm, and particularly preferably 10 to 16 μm. Further, according to the present invention, the protective film for the photosensitive element preferably has a thickness of 5 to 30 μm, and preferably 10 to 28 μm, in order to satisfy both the mechanical strength and the low cost of the protective film in the laminate. Is more preferable and 15 to 25 μm is particularly preferable. Also,
It is preferable that such a support and a protective film can be removed from the photosensitive resin composition layer later. If necessary, surface treatment such as antistatic treatment can be performed.

A photosensitive element comprising two layers of the support and the photosensitive resin composition layer thus obtained, and a photosensitive element comprising three layers of the support, the photosensitive resin composition layer and the protective film. Can be stored as it is, or can be stored in the form of a roll by further laminating a protective film on the other surface of the photosensitive resin composition layer.

In the case of producing a resist pattern using the photosensitive element of the present invention, when the above-mentioned protective film is present, after removing the protective film, the photosensitive resin composition layer is heated while the circuit is being formed. A method of laminating by pressure bonding to a forming substrate is mentioned, and it is preferable to laminate under reduced pressure in consideration of adhesion and followability. 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 preferably 70 to 130 ° C., and the compression pressure is about 0.1 to 1.0 MPa (about 1 to 10 kPa).
gf / cm ² ) is preferable, but these conditions are not particularly limited. Further, if the photosensitive resin composition layer is heated to 70 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 laminate property, It is also possible to preheat the substrate.

The photosensitive resin composition layer thus laminated 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 rays as it is, and when it is opaque, it is of course necessary to remove it. 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 radiates ultraviolet rays can be used. Further, a flood light bulb for photography, a solar lamp, or the like that effectively radiates visible light can also be used.

Then, after the exposure, if a support is present on the photosensitive resin composition layer, after removing the support,
The unexposed portion is removed by wet development, dry development, or the like, and development is performed to manufacture a resist pattern. In the case of wet development, using a developer corresponding to the photosensitive resin composition such as an alkaline aqueous solution, an aqueous developer or an organic solvent, for example, a known method such as spraying, rocking dipping, brushing, scraping or the like is used. can do. As the developing solution, a safe and stable one having good operability such as an alkaline aqueous solution can be used. Examples of the base of the alkaline aqueous solution include, for example, alkali hydroxide such as lithium, hydroxide of sodium or potassium; lithium;
Use alkali carbonates such as sodium, potassium or ammonium carbonates or bicarbonates; alkali metal phosphates such as potassium phosphate and sodium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate. You can As the alkaline aqueous solution used for development, sodium carbonate, potassium carbonate, sodium hydroxide having a concentration of 0.1 to 5% by weight,
A dilute solution of sodium tetraborate is preferred. The pH of the alkaline aqueous solution used for development 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 can be mixed in the alkaline aqueous solution. The aqueous developer comprises water or an aqueous alkaline solution and one or more organic solvents. Here, as the alkaline substance,
In addition to the above substances, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol- 2-morpholine and the like can be mentioned. The pH of the developer is preferably as low as possible within the range where the resist can be sufficiently developed, and is preferably pH 8 to 12, and pH 9 to 10.
Is more preferable. Examples of the organic solvent include 3-acetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol,
Butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and the like can be mentioned. These may be used alone or in combination of two or more. The concentration of the organic solvent is usually 2 to 90.
The amount is preferably wt%, and the temperature can be adjusted according to the developability. Further, a small amount of a surfactant, a defoaming agent or the like can be mixed in the aqueous developer. As the organic solvent-based developer used alone, for example,
1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone and the like can be mentioned. These organic solvents contain 1 to prevent ignition.
It is preferable to add water in the range of 20 wt%. Further, two or more developing methods can be used in combination, if necessary. Development methods include dip method, battle method,
There are spraying methods, brushing, slapping, etc., and the high pressure spraying method is the most preferable for improving the resolution.

As a process after the development, about 6 if necessary
The resist pattern can be further cured and used by heating at 0 to 250 ° C. or exposure at about 0.2 to 10 mJ / cm ² .

A cupric chloride solution, a ferric chloride solution, an alkaline etching solution, or a hydrogen peroxide-based etching solution can be used for etching the metal surface after the development, but chloride is used because of its good etching factor. 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 board can be 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 sulfate plating, copper plating such as copper pyrophosphate plating, solder plating such as high-throw solder plating, and Watts bath (nickel sulfate-nickel chloride).
Plating, nickel plating such as nickel sulfamate plating, and gold plating such as hard gold plating and soft gold plating. Then, the resist pattern can be stripped with, for example, a stronger alkaline aqueous solution than the alkaline aqueous solution used for the development. As the strongly alkaline aqueous solution, for example, an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide having a concentration of 1 to 10% by weight can be used. Examples of the peeling method include a dipping method and a spraying method. The dipping method and the spraying method can be used alone or in combination.
The printed wiring board having the resist pattern formed thereon may be a multilayer printed wiring board.

[0052]

EXAMPLES The present invention will be described in detail below with reference to examples, but these examples do not limit the present invention in any sense.

Synthesis Example 1 6 of ethylene glycol monomethyl ether / toluene
/ 4 (weight ratio) solution containing 60% by weight of methacrylic acid / methyl methacrylate / ethyl acrylate / styrene (26
/ 34/20/20 (weight ratio)) was formed (M _w = 6.7 × 10 ⁴ , solid content 60.0).

Synthesis Example 2 6 of ethylene glycol monomethyl ether / toluene
An A2 solution having methacrylic acid / methyl methacrylate / styrene (25/50/25 (weight ratio)) was formed in 60% by weight / 4 (weight ratio) solution (M _w = 5.0 × 1).
0 ⁴ , solid content 60.0).

Synthesis Example 3 6 of ethylene glycol monomethyl ether / toluene
/ 4 (weight ratio) solution containing 60% by weight of methacrylic acid / methyl methacrylate / methyl acrylate (18/48/3
4) was formed (M _w = 7.5 × 1)
0 ⁴ , solid content 60.0).

Example 1 (a) The raw materials shown in Table 1 were mixed to obtain a solution 1 of a photosensitive resin composition.

[0057]

[Table 1]

(B) The solution 1 of the photosensitive resin composition obtained in the above step (a) was uniformly applied onto a polyethylene terephthalate film (G2-16, manufactured by Teijin Ltd.) having a thickness of 16 μm, It was dried for 10 minutes by a hot air convection dryer at 100 ° C. Then, a polyethylene protective film (NF-1
3, Tama Poly Co., Ltd.) were laminated and protected to obtain a photosensitive resin composition laminate (photosensitive element) 1. The film thickness of the photosensitive resin composition layer after drying was 40 μm. (c) A copper-clad laminate (MCL-E-) in which copper foil (thickness 35 μm) is laminated on both sides of a glass-based epoxy resin prepreg.
61, manufactured by Hitachi Chemical Co., Ltd.) was polished with a polishing machine (manufactured by Sankei Co., Ltd.) equipped with a brush having a roughness of # 600 and washed with water. Then, it is dried with an air stream, this roughened copper-clad laminate is heated to 80 ° C., the photosensitive element 1 obtained in the above step (b) is peeled off the protective film on the copper surface, Using a heat roll at 120 ° C., lamination was performed at a speed of 1.5 m / min to obtain a copper clad laminate 1 on which photosensitive elements were laminated. Next, using a light exposure machine (HMW-201B, manufactured by Oak Co., Ltd.) having a high-pressure mercury lamp, a Stofer 21-step step tablet was placed on the test piece as a negative and exposed at 60 mJ / cm ² . The polyethylene terephthalate film was peeled off, a 1 wt% sodium carbonate aqueous solution was sprayed at 30 ° C. for 60 seconds, and the unexposed portion was removed to obtain a printed wiring board 1 on which a conductor pattern (resist pattern) was formed.
The photosensitive element, the resist pattern and the printed wiring board thus obtained were evaluated for photosensitivity, resolution and adhesion. The results are shown in Table 2.

Photosensitivity: The photosensitivity of the photosensitive resin composition was evaluated by measuring the number of steps of the step tablets of the photocured film formed on the copper clad laminate. The light sensitivity is
It is indicated by the number of steps of the step tablet, and the higher the number of steps of this step tablet, the higher the photosensitivity.

Resolution: A phototool having a 21-step step tablet of Stofer and a line width / space width of 30/30 to 200/200 as a negative for resolution evaluation.
A phototool having a wiring pattern (unit: μm) was brought into close contact, and exposure was performed with an energy amount such that the number of remaining step steps after development of the 21-step step tablet of the Stofer was 8.0. Here, 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 value, the better the evaluation of resolution.

Adhesion: 21-step step of Stofer 21-step step of Stofer and a phototool having a tablet with a wiring pattern having a line width of 6 to 47 (unit: μm) as a negative for adhesion evaluation are adhered. After the development of the tablet, exposure was performed with an energy amount such that the number of remaining step steps was 8.0. Here, the adhesion was evaluated by the value of the smallest line width of the exposed portion after the development processing. The smaller the numerical value is, the better the evaluation of adhesiveness is.

[0062]

[Table 2]

Examples 2 to 4 and Comparative Examples 1 to 3 Photosensitization was carried out in the same manner as in Example 1 except that the types of the component (A) and the composition of (D) were as shown in Table 3 below. The photosensitive element, the resist pattern and the printed wiring board were obtained, and the photosensitivity, resolution and adhesion were evaluated. Table 2
The results are shown in.

[0064]

[Table 3]

As is clear from Table 2, Examples 1 to 4
Has excellent photosensitivity and performance similar to that of conventional products, is excellent in resolution and adhesion, and has all the required properties. Comparative Examples 1 to 3 are inferior in resolution and adhesion, and as a result, high-performance final products cannot be obtained.

[0066]

The present invention provides a photosensitive resin composition having excellent photosensitivity, adhesion, resolution, chemical resistance, mechanical strength, peeling property and flexibility, and the composition of the present invention. It is intended to provide a printed wiring board material which is useful for increasing the density and resolution of the printed wiring by using.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05K 3/06 H05K 3/06 H 3/18 3/18 DF term (reference) 2H025 AA01 AA02 AA06 AA07 AA08 AA13 AA14 AB11 AB15 AC01 AD01 BC32 BC42 BC85 CA01 CA20 CA27 CA28 CB13 CB16 CB51 CB55 CB56 FA03 4J011 PA65 PA69 PB22 PB40 PC02 PC08 4J026 AA17 AA43 AA45 AA5 CF15 CDA5 CD06 DB02 DB01 CA15 CD06 DB02 DB06 DB02 CA06 DA00 DB02 DB06 CA02 DA06 DB02 DB06 BB71 CC62 ER11 ER16 GG01 GG16

Claims (12)

[Claims] 1. A polymer binder (A), a photopolymerizable compound (B) having at least one polymerizable ethylenically unsaturated bond in the molecule, (C) a photopolymerization initiator and (D) an additive. In the photosensitive resin composition containing, the component (A) is
A copolymerization component comprising styrene and / or a derivative thereof; and the component (D) is represented by the general formula (I): A photosensitive resin composition comprising a carboxylbenzotriazole represented by the formula (wherein R ¹ is hydrogen, an alkyl group having 20 or less carbon atoms or an aminoalkyl group) and / or a derivative thereof. 2. The photosensitive resin composition according to claim 1, wherein the component (A) is 0.1 to 50% by weight based on the total amount of the copolymerization component of the component (B). 3. The photosensitive resin according to claim 1, wherein the component (D) is 0.005 to 4.0 parts by weight per 100 parts by weight of the total amount of the components (A) and (B). Composition. 4. The component (A) is 40 to 80 parts by weight and the component (B) is 20 to 60 parts by weight per 100 parts by weight of the total amount of the components (A) and (B). The photosensitive resin composition according to claim 1, wherein the component (C) is 0.01 to 6.0 parts by weight. 5. The weight average molecular weight of the component (A) is 2 ×.
The photosensitive resin composition according to any one of claims 1 to 4, which has a viscosity of 10 ^{4 to} 3 × 10 ⁵ . 6. The dispersity of the component (A) is 1.0 to 3.
The photosensitive resin composition according to any one of claims 1 to 5, which is 0. 7. The acid value of the component (A) is 100 to 500.
The photosensitive resin composition according to any one of claims 1 to 6, which is mg / KOH. 8. The photosensitive material according to claim 1, wherein the component (A) is a mixture of styrene and / or a derivative thereof and (meth) acrylic acid and / or a derivative thereof. Resin composition. 9. The photosensitive resin composition according to claim 1, wherein the component (B) contains a carboxyl group. 10. A photosensitive element formed by using the photosensitive resin composition according to claim 1. 11. A resist pattern formed using the photosensitive resin composition according to claim 1. 12. A printed wiring board using the photosensitive resin composition according to claim 1.