JP2002182381A - Photosensitive resin composition, photosensitive element using the same, method for producing resist pattern and method for producing printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in adhesion and resolution, suppressing the occurrence of scum and useful to increase the density of a printed wiring board and to provide a photosensitive element, a method for producing a resist pattern and a method for producing a printed wiring board. SOLUTION: The photosensitive resin composition contains (A) a binder polymer, (B) a compound of formula (I) (where R1 is H or methyl; X1 is a 2-6C alkylene; (m) is an integer of 4-20; and (n) is an integer of 1-15) and (C) a photopolymerization initiator. The photosensitive element uses the photosensitive resin composition. In the method for producing a printed wiring board, the method for producing a resist pattern is adopted.

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, a photosensitive element comprising a support and a layer of a photosensitive resin composition has been used as a resist used in the fields of printed wiring boards, precision processing of metals, and the like. The photosensitive element is generally formed by laminating a layer of a photosensitive resin composition on a support, and in many cases, further laminating a protective film on the layer of the photosensitive resin composition. The applications of the photosensitive element can be roughly classified into two types, one for circuit formation and the other for solder resist.

A photosensitive element for forming a circuit is used to form a circuit by a method called a subtractive method or an etched foil method. The subtractive method is a method of forming a circuit by using a circuit forming substrate such as a glass epoxy substrate whose surface and inner walls of through holes are covered with a copper layer and removing excess copper by etching. The method is further divided into a method called a tenting method and a method called a plating method.

In the tenting method, a copper through hole for mounting chip components is protected with a resist, etched,
The circuit is formed after the resist is peeled off. For this reason, it is desirable that the resist has a high coating strength. On the other hand, the plating method, contrary to the tenting method, covers the resist except for the through-hole portion and the portion that is to be a circuit, solder-plates the copper surface not covered with the resist, and peels the resist. Then, a pattern of solder plating is formed, and etching is performed using the pattern of solder plating as a resist for an etching solution to form a circuit.

In the tenting method, the adhesion between the resist and the copper is important in order to prevent the etchant from infiltrating between the resist and the copper. When the etchant infiltrates between the resist and the copper, the desired portion of the copper is etched, and the circuit is disconnected.

In the plating method as in the tenting method, in order to prevent the plating from passing between the resist and the copper,
The adhesion between the resist and copper is important. If plating is stripped between the resist and copper, a plating pattern is formed in an undesired portion, and copper in an undesired portion remains in the subsequent etching.

A method for producing a printed wiring board using a photosensitive element of the subtractive method is as follows. First, after the protective film is peeled off, the photosensitive element is laminated on a circuit-forming substrate such as a copper-clad laminate. Next, the support is peeled off, if necessary, and exposed through a positive or negative film such as a wiring pattern mask film to cure the exposed portion of the resist. If there is a support after exposure, peel off the support if necessary, dissolve or disperse the unexposed portion of the photosensitive resin composition layer with a developer,
A cured resist image is formed on a circuit forming substrate.
As the layer of the photosensitive resin composition, an alkali developing type using an alkaline aqueous solution as a developing solution and a solvent developing type using an organic solvent are known. Demand is growing. The developer is usually used as long as it has the ability to dissolve the layer of the photosensitive resin composition to some extent, and the photosensitive resin composition is dissolved or dispersed in the developer at the time of use.

The cured resist formed by exposure and development is peeled off by etching or plating with an aqueous alkali solution such as sodium hydroxide. The peeling speed is preferably high from the viewpoint of workability, handleability and productivity. In addition, the resist cured film is affected by the impact of spray etc.
If it does not break, the resist sticks to the transport roll of the peeling machine, so that cleaning work must be performed, and the workability is reduced. Furthermore, with the recent increase in the density of printed wiring,
Since the contact area between the copper substrate and the patterned photosensitive resin composition is reduced, excellent adhesion, mechanical strength, chemical resistance, flexibility, etc. are required in the development, etching or plating process, and resolution is required. Is required.

Among the properties of this type, for improving the chemical resistance, for example, those using a binder polymer obtained by copolymerizing a styrene monomer are disclosed in JP-B-55-38961.
JP-B-54-25957, JP-A-2-289607, JP-A-Hei.
This is described in, for example, JP-A-4-347859 and JP-A-4-285960. However, since these resists have improved chemical resistance, the resolution is poor, and it tends to be difficult to cope with high density printed wiring boards.

[0010] Another problem is the generation of aggregates in the developer in which the photosensitive resin composition is dissolved or dispersed. This aggregate is dispersed in the developer and is sprayed by a spray pump or the like.
It adheres to the printed wiring board developed again and causes unnecessary defects in the subsequent etching and plating steps. In order to prevent the cause of the occurrence of this defect, good dispersion stability of the photosensitive resin composition in a developer is required.

Japanese Patent Application Laid-Open No. 2-26971 discloses peeling fragmentation,
As a photosensitive resin composition having a good stripping time and the like, an ethylenically unsaturated compound that is a polypropylene glycol group alone is exemplified, and JP-A-5-11446 discloses that a polypropylene glycol group and a polyethylene glycol group are blocked. However, when these compounds having a polypropylene glycol group in the molecule are used in the photosensitive resin composition, they are easily separated in an alkali developing solution, causing scum and causing If adhered, there is a problem that causes a short circuit or disconnection.

[0012]

SUMMARY OF THE INVENTION Claims 1, 2, 3,
The inventions described in 4, 5, and 6 are excellent in adhesion and resolution,
An object of the present invention is to provide a photosensitive resin composition which suppresses generation of scum and is useful for increasing the density of a printed wiring board. An object of the present invention is to provide a photosensitive element which is excellent in adhesion and resolution, suppresses the occurrence of scum, and is useful for increasing the density of a printed wiring board.

An eighth aspect of the present invention is to provide a method of manufacturing a resist pattern which is excellent in adhesion and resolution, suppresses the occurrence of scum, and is useful for increasing the density of a printed wiring board. The invention according to claim 9 is excellent in adhesion and resolution,
An object of the present invention is to provide a method for manufacturing a printed wiring board which suppresses the occurrence of scum and is useful for increasing the density of the printed wiring board.

[0014]

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

Embedded image (R ¹ represents a hydrogen atom or a methyl group, and X ¹ has 2 to 2 carbon atoms.
6 represents an alkylene group, m is an integer of 4 to 20,
n is an integer of 1 to 15), and (C) a photopolymerization initiator.

The present invention also relates to the photosensitive resin composition wherein the binder polymer (A) contains styrene or a styrene derivative as a copolymer component. Also, the present invention
(A) The binder polymer is (a) methacrylic acid 20
To 40% by weight, 2 to 40% by weight of styrene and 20 to 78% by weight of alkyl (meth) acrylate as a copolymer component. Further, the present invention relates to the photosensitive resin composition, wherein X ¹ is an ethylene group. Further, the present invention relates to the photosensitive resin composition wherein m is 6 to 18.

The present invention also relates to the photosensitive resin composition wherein (C) the photopolymerization initiator is a 2,4,5-triarylimidazole dimer. The present invention also relates to a photosensitive element obtained by applying the photosensitive resin composition on a support and drying the composition.

Further, according to the present invention, the photosensitive element is laminated on a circuit-forming substrate so that a layer of the photosensitive resin composition is in close contact with the photosensitive element, and is irradiated with actinic rays in an image-like manner. The present invention relates to a method for producing a resist pattern, which comprises curing and removing an unexposed portion by development. Also,
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.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto,
(Meth) acrylate means acrylate and its corresponding methacrylate, and (meth) acryloyl group means acryloyl and its corresponding methacryloyl group.

The photosensitive resin composition of the present invention comprises (A) a binder polymer, (B) a compound represented by the above general formula (I), and (C) a photopolymerization initiator. Examples of the binder polymer (A) include an acrylic resin, a styrene resin, an epoxy resin, an amide resin, an amide epoxy resin, an alkyd resin, and a phenol resin. From the viewpoint of alkali developability, an acrylic resin is preferred. These can be used alone or 2
More than one species can be used in combination.

The binder polymer (A) can be produced, for example, by radically polymerizing a polymerizable monomer. As the polymerizable monomer, for example, styrene, vinyl toluene, α-methylstyrene,
Polymerizable styrene derivatives such as p-methylstyrene, p-ethylstyrene, p-methoxystyrene, p-ethoxystyrene, p-chlorostyrene, p-bromostyrene, acrylamide, acrylonitrile, vinyl-n-
Esters of vinyl alcohol such as butyl ether,
Alkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2 -Trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β -Furyl (meth) acrylic acid, β-
Styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid,
Examples include itaconic acid, crotonic acid and propiolic acid. These are used alone or in combination of two or more.

Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and the like.
Butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, structural isomers thereof and the like Is mentioned. These can be used alone or in combination of two or more.

The (A) binder polymer preferably contains a carboxyl group from the viewpoint of alkali developability. For example, the polymerizable monomer having a carboxyl group is radically polymerized with another polymerizable monomer. It can be manufactured by the following. The polymerizable monomer having a carboxyl group is preferably methacrylic acid.
The (A) binder polymer preferably contains styrene or a styrene derivative such as p-methylstyrene as a polymerizable monomer from the viewpoint of flexibility.

From the viewpoint of adhesion and resolution, (A) the binder polymer comprises 20 to 40% by weight of methacrylic acid, 2 to 40% by weight of styrene and 20 to 78% by weight of alkyl (meth) acrylate as a copolymer component. It is preferable that

The copolymerization ratio of the methacrylic acid is 20 to 40.
% By weight, more preferably from 24 to 35% by weight, and particularly preferably from 26 to 30% by weight. If the copolymerization ratio is less than 20% by weight, the minimum development time is prolonged, and the cured resist film tends not to be cracked and the workability tends to be deteriorated. If it exceeds 40% by weight, the adhesion tends to be reduced.

The copolymerization ratio of the styrene is 2 to 40% by weight.
Is preferably, more preferably 10 to 30% by weight, and particularly preferably 15 to 25% by weight. If the copolymerization ratio is less than 2% by weight, the resist tends to swell and the adhesion during development tends to decrease.
If it exceeds 0% by weight, the minimum development time is prolonged, and the cured resist film tends not to be cracked and the workability tends to be deteriorated.

The copolymerization ratio of the alkyl (meth) acrylate is preferably from 20 to 78% by weight, more preferably from 35 to 66% by weight, and preferably from 45 to 66% by weight.
More preferably, it is 59% by weight. If the copolymerization ratio is less than 20% by weight, the resist becomes brittle and the cross-cutting property tends to deteriorate, and if it exceeds 78% by weight, the adhesion tends to deteriorate.

The binder polymer (A) has a weight average molecular weight of 20,000 from the viewpoint of coating properties and resolution.
~ 120,000, preferably 30,000
~ 80,000, more preferably 40,00
It is particularly preferably from 0 to 60,000. If the weight average molecular weight is less than 20,000, the coating properties tend to deteriorate, and if it exceeds 120,000, the resolution tends to deteriorate. In the present invention, the weight average molecular weight is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

In the above general formula (I), R ¹ is a hydrogen atom or a methyl group, preferably a methyl group.
In the general formula (I), X ¹ represents an alkylene group having 2 to 6 carbon atoms, and examples thereof include an ethylene group, a propylene group, a butylene group, a pentylene group, and structural isomers thereof. Preferably, there is. In the general formula (I), m is an integer of 4 to 20, preferably 4 to 18, more preferably 6 to 18, from the viewpoint of scum generation and developer resistance. It is particularly preferable that the number is from 18 to 18. In the general formula (I), n is 1 to
It is an integer of 15, and is preferably 4 to 10, and more preferably 7, from the viewpoints of scum generation and developer resistance.

Examples of the compound represented by the general formula (I) include n-octyl alcohol ethylene oxide-modified (meth) acrylate, n-octyl alcohol propylene oxide-modified (meth) acrylate, and n-octyl alcohol propylene oxide-modified (meth) acrylate.
Butyl alcohol ethylene oxide modified (meth) acrylate, n-butyl alcohol propylene oxide modified (meth) acrylate, n-pentyl alcohol ethylene oxide modified (meth) acrylate, n-pentyl alcohol propylene oxide modified (meth) acrylate, n-hexyl alcohol Ethylene oxide-modified (meth) acrylate, n-hexyl alcohol propylene oxide-modified (meth) acrylate and the like, but from the viewpoint of scum resistance, n-octyl alcohol ethylene oxide-modified (meth) acrylate,
N-octyl alcohol propylene oxide-modified (meth) acrylate and the like are preferred.

Examples of the available compound represented by the general formula (I) include, for example, R ¹ in the general formula (I).
= Methyl group, X ¹ = ethylene group, m = 18 and n = 7, OC-18E (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., n-
Octyl alcohol ethylene oxide-modified methacrylate), in the general formula (I), R ¹ = methyl group, X ¹
= Ethylene group, m = 9 and n = 7, and OC-9E (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., n-octyl alcohol ethylene oxide-modified methacrylate).

The photosensitive resin composition of the present invention may contain a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in a molecule other than the component (B).

As the photopolymerizable compound, for example, a compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol, 2,2-bis (4-((meth) acryloxypolyethoxy)) Phenyl) propane, 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2- Bisphenol A-based (meth) acrylate compounds such as bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, compounds obtained by reacting an α, β-unsaturated carboxylic acid with a glycidyl group-containing compound, Urethane monomers such as (meth) acrylate compounds having a urethane bond in the molecule, nonylphenoxypolyethyleneoxyacrylic Over DOO, .gamma.-chloro -β- hydroxypropyl-beta '- (meth) acryloyloxyethyl -o- phthalate, beta-hydroxyalkyl -β'-
Phthalic acid compounds such as (meth) acryloyloxyalkyl-o-phthalate, alkyl (meth) acrylates and the like, and bisphenol A (meth)
It is preferable to use an acrylate compound or a (meth) acrylate compound having a urethane bond in the molecule as an essential component. These are used alone or in combination of two or more.

Examples of the photopolymerization initiator (C) include benzophenone, N, N'-tetramethyl-4,
N, N'-tetraalkyl-4,4'-diaminobenzophenone such as 4'-diaminobenzophenone (Michler's ketone), 2-benzyl-2-dimethylamino-1-
Aromatic ketones such as (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, quinones such as alkylanthraquinone, benzoin alkyl ethers and the like Benzoin ether compounds, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer,
(O-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2-
(O-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5
2,4,5-triarylimidazole dimer such as -diphenylimidazole dimer, acridine derivative such as 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane, N-phenylglycine, N-phenylglycine derivatives, coumarin-based compounds and the like can be mentioned. Further, the substituents of the aryl groups of the two 2,4,5-triarylimidazoles may be the same to give a target compound, or different asymmetric compounds may be given.
Further, from the viewpoint of adhesion and sensitivity, 2,4,5-triarylimidazole dimer is more preferable. These are used alone or in combination of two or more.

The amount of the component (A) is as follows:
It is preferably 40 to 80 parts by weight, more preferably 45 to 70 parts by weight, and more preferably 50 to 65 parts by weight, based on 100 parts by weight of the total of the component (B) and the photopolymerizable compound other than the component (B). It is particularly preferred that the amount is by weight. When the amount is less than 40 parts by weight, the photocured product becomes brittle, and when used as a photosensitive element, the coating properties tend to be inferior. When the amount exceeds 80 parts by weight, the adhesion and the resolution tend to decrease.

The compounding amount of the photopolymerizable compound other than the components (B) and (B) is 100 parts by weight of the total amount of the photopolymerizable compounds other than the components (A), (B) and (B). On the other hand, it is preferably 20 to 60 parts by weight,
The amount is more preferably from 55 to 55 parts by weight, particularly preferably from 35 to 50 parts by weight.

The amount of the component (B) is as follows:
It is preferably 2 to 20 parts by weight, more preferably 3 to 15 parts by weight, and more preferably 5 to 15 parts by weight, based on 100 parts by weight of the total of the component (B) and the photopolymerizable compound other than the component (B).
Particularly preferred is 10 to 10 parts by weight. If the amount is less than 2 parts by weight, good dispersion stability of the photosensitive resin composition in the developer cannot be obtained, and scum tends to be generated,
If it exceeds 20 parts by weight, sufficient adhesion tends not to be obtained.

The amount of the component (C) is as follows:
The amount is preferably 0.1 to 20 parts by weight, more preferably 0.15 to 15 parts by weight, based on 100 parts by weight of the total amount of the component (B) and the photopolymerizable compound other than the component (B). , 0.2 to 10 parts by weight. If the amount is less than 0.1 part by weight, the sensitivity tends to be insufficient. If the amount is more than 20 parts by weight, the light absorption on the surface of the composition during exposure increases and the internal photocuring becomes insufficient. Tends to be sufficient.

The above-mentioned photosensitive resin composition may contain, if necessary, a photopolymerizable compound having at least one cationically polymerizable cyclic ether group in the molecule (eg, oxetane compound), a cationic polymerization initiator, malachite green, etc. Dyes, photochromic agents such as tribromophenylsulfone and leucocrystal violet, thermal coloring inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, defoamers, flame retardants, stabilizers, and adhesion imparting Agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc., each containing about 0.01 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (B). can do. These are used alone or in combination of two or more.

The photosensitive resin composition may be used, if necessary,
Methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene,
It can be dissolved in a solvent such as N, N-dimethylformamide, propylene glycol monomethyl ether or a mixed solvent thereof and applied as a solution having a solid content of about 30 to 60% by weight.

The photosensitive resin composition is not particularly limited, but is applied as a liquid resist on a metal surface such as copper, copper-based alloy, iron, and iron-based alloy, dried, and then, if necessary, a protective film. Is preferably used in the form of a photosensitive element.

The thickness of the photosensitive resin composition layer varies depending on the use, but it is preferably about 1 to 100 μm in thickness after drying. When using a liquid resist covered with a protective film, examples of the protective film include polymer films such as polyethylene and polypropylene.

The photosensitive element can be obtained, for example, by applying a photosensitive resin composition on a polymer film such as polyethylene terephthalate, polypropylene, polyethylene or polyester as a support and drying it. 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, and a bar coater. Drying can be performed at 70 to 150 ° C. for about 5 to 30 minutes. 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.

The thickness of these polymer films is 1 to 1
It is preferably set to 00 μm. One of these polymer films may be laminated on both sides of the photosensitive resin composition layer as a support for the photosensitive resin composition layer, and the other 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, and a low fisheye film is preferable.

The photosensitive element has an intermediate layer and a protective layer such as a cushion layer, an adhesive layer, a light absorbing layer and a gas barrier layer in addition to the photosensitive resin composition layer, the support and the protective film. You may.

The photosensitive element is stored, for example, as it is or after being further laminated with a protective film on the other surface of the photosensitive resin composition layer and wound around a cylindrical core. At this time, it is preferable that the support is wound up so as to be the outermost side. An end face separator is preferably provided on the end face of the roll-shaped photosensitive element roll from the viewpoint of end face protection, and a moisture-proof end face separator is preferably provided from the viewpoint of edge fusion resistance. In addition, as a packing method, it is preferable to wrap in a black sheet having low moisture permeability.

Examples of the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).

In producing a resist pattern using the photosensitive element, if the protective film is present, after removing the protective film, the photosensitive resin composition layer is heated to about 70 to 130 ° C. About 0.1 to 1 MPa (about 1 to 10 kgf / cm ² ) on the circuit forming substrate while heating
For example, a method of laminating by pressing under pressure, and lamination under reduced pressure is also possible. The surface to be laminated is usually a metal surface, but is not particularly limited.

The photosensitive resin composition layer thus laminated is irradiated with actinic rays imagewise through a negative or positive mask pattern. As the light source of the actinic ray, a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, a xenon lamp, or the like that effectively emits ultraviolet light, visible light, or the like is used. It is also used for the laser direct writing exposure method.

Next, after the exposure, if a support is present on the photosensitive resin composition layer, after removing the support,
A resist pattern can be manufactured by removing unexposed portions and developing by wet development using a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, or dry development. Examples of the alkaline aqueous solution include a dilute solution of 0.1 to 5% by weight of sodium carbonate, a dilute solution of 0.1 to 5% by weight of potassium carbonate, and a dilute solution of 0.1 to 5% by weight of sodium hydroxide. Can be PH of the above alkaline aqueous solution
Is preferably in the range of 9 to 11, and the temperature is
It is adjusted according to the developability of the photosensitive resin composition layer. Further, a surfactant, an antifoaming agent, an organic solvent and the like may be mixed in the alkaline aqueous solution. Examples of the developing method include a dip method, a spray method, brushing, slapping, and the like.

As processing after development, if necessary,
The resist pattern may be further cured by heating at about 250 ° C. or exposing at about 0.2 to 10 J / cm ² . For the etching of the metal surface performed after the development, for example, a cupric chloride solution, a ferric chloride solution, an alkali etching solution, or the like can be used.

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, solder plating, nickel plating, and gold plating. Next, the resist pattern can be stripped with, for example, a more alkaline aqueous solution than the alkaline aqueous solution used for development. As the strong alkaline aqueous solution, for example, 1 to 10% by weight
An aqueous sodium hydroxide solution, a 1 to 10% by weight aqueous potassium hydroxide solution, or the like is used. Examples of the peeling method include a dipping method and a spray method. Further, the printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board or may have a small diameter through hole.

[0052]

The present invention will be described below with reference to examples.

Examples 1 to 8, Comparative Examples 1 and 2 The component (A) shown in Table 1, the component (C) shown in Table 2 and other additive components were mixed, and the component (B) was added to Table 3. And it melt | dissolved by the compounding quantity shown in Table 4, and obtained the solution of the photosensitive resin composition.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3]

[0057]

[Table 4]

The materials used in Tables 3 and 4 are shown below. * 1 BPE-200: 2,2'-bis (4-methacryloxypentaethoxyphenyl) propane, trade name of Shin-Nakamura Chemical Co., Ltd. * 2 APG-400: polypropylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd. * 3 OC-18E: In the general formula (I), R ¹ =
Methyl group, X ¹ = ethylene group, n-octyl alcohol ethylene oxide modified methacrylate in which m = 18 and n = 7, trade name of Shin-Nakamura Chemical Co., Ltd. * 4 OC-9E: In the general formula (I) R ¹ = methyl group, X ¹ = ethylene group, n = 9 and n = 7
-Octyl alcohol ethylene oxide modified methacrylate, trade name of Shin-Nakamura Chemical Co., Ltd.

Next, the solution of the photosensitive resin composition was added to 2
The photosensitive element was obtained by uniformly coating on a polyethylene terephthalate film having a thickness of 0 μm and drying with a hot air convection dryer at 100 ° C. for 10 minutes. The dried film thickness of the layer of the photosensitive resin composition was 25 μm.

On the other hand, a copper-clad laminate (Hitachi Chemical Industries, Ltd.) which is a glass epoxy material in which copper foil (thickness: 35 μm) is laminated on both sides
(Co., Ltd., trade name MCL-E-679) copper surface # 60
Polishing using a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to 0, washing with water, drying with an air flow, heating the obtained copper-clad laminate to 80 ° C. Using the obtained photosensitive element, a layer of the photosensitive resin composition is formed on the copper surface by one layer.
Lamination was performed at 20 ° C. and 0.4 MPa.

Next, 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 and a 3 kW high-pressure mercury lamp (( HMW-590 (manufactured by Oak Manufacturing Co., Ltd.), a liner / space width of 6/6 to 47/47 (unit: μm) (unit: μm) (a smaller value is better) as a 21-step step tablet of a stofer and a resolution evaluation negative. A phototool having a wiring pattern was brought into close contact with the stoker and exposed at an energy amount such that the number of remaining steps after development of the 21-step tablet of the stofer was 7.0. Width is 6/400 to 47/400 (unit: μm)
A photo tool having a wiring pattern (the smaller the numerical value, the better) was used.

Next, the polyethylene terephthalate film was removed, and an unexposed portion was removed by spraying a 1.0% by weight aqueous solution of sodium carbonate at 30 ° C. for 30 seconds. Table 5 summarizes the results of the obtained adhesion and resolution. In addition, the scum was taken out of the photosensitive resin composition layer of the obtained photosensitive element only by 1.0 m ² ,
A 1.0% by weight aqueous solution of sodium carbonate was added, and the mixture was stirred at room temperature for 2 hours with a stirrer. A predetermined amount of a polypropylene-based antifoaming agent was added to the obtained emulsion to a concentration of 0.1% by weight, and further stirred for 30 minutes. After one day and night, the occurrence of scum was observed. Table 5 summarizes the results. ○: No scum was generated, Δ: A small amount of scum was generated, ×: A large amount of scum was generated

[0063]

[Table 5]

[0064]

The photosensitive resin compositions according to the first, second, third, fourth, fifth and sixth aspects are excellent in adhesion and resolution, suppress the occurrence of scum, and are useful for increasing the density of printed wiring boards. is there. The photosensitive element according to claim 7 is excellent in adhesion and resolution, suppresses the occurrence of scum, and is useful for increasing the density of a printed wiring board.

The method of manufacturing a resist pattern according to claim 8 is as follows:
It has excellent adhesion and resolution, suppresses scum, and is useful for increasing the density of printed wiring boards. The method for manufacturing a printed wiring board according to the ninth aspect is excellent in adhesion and resolution, suppresses the occurrence of scum, and is useful for increasing the density of the printed wiring board.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) G03F 7/031 G03F 7/031 5E343 7/033 7/033 H05K 3/06 H05K 3/06 H 3/18 3/18 DF term (reference) 2H025 AA14 AB15 AC01 AD01 BC14 BC34 CA28 CB14 CB16 4J011 PA65 PA69 PC02 QB16 SA21 SA22 SA25 SA31 SA41 SA51 SA78 VA01 WA01 4J026 AA17 AA43 AA45 BA27 GA09 4J027 AC02 AC06 CA03 CE12 CD10 5E343 AA02 AA12 BB24 BB67 BB71 CC62 CC65 DD32 ER11 ER16 ER18 GG01

Claims (9)

[Claims] (A) a binder polymer, (B) a general formula (I) (R ¹ represents a hydrogen atom or a methyl group, and X ¹ has 2 to 2 carbon atoms.
6 represents an alkylene group, m is an integer of 4 to 20,
n is an integer of 1 to 15), and (C) a photopolymerization initiator. 2. The photosensitive resin composition according to claim 1, wherein (A) the binder polymer contains styrene or a styrene derivative as a copolymer component. 3. The method according to claim 1, wherein (A) the binder polymer comprises (a) 20 to 40% by weight of methacrylic acid and 2 to 40% by weight of styrene.
3. The photosensitive resin composition according to claim 1, wherein 20 to 78% by weight of (meth) acrylic acid alkyl ester is obtained as a copolymer component. 4. The photosensitive resin composition according to claim 1, wherein X ¹ is an ethylene group. 5. The photosensitive resin composition according to claim 1, wherein m is from 6 to 18. 6. The photopolymerization initiator (C) is a 2,4,5-triarylimidazole dimer.
6. The photosensitive resin composition according to 4 or 5. 7. A photosensitive element obtained by applying the photosensitive resin composition according to claim 1, 2, 3, 4, 5 or 6 on a support and drying. 8. The photosensitive element according to claim 7, which is laminated on a circuit-forming substrate so that a layer of the photosensitive resin composition is in close contact with the photosensitive element, and is irradiated with actinic rays in an image-like manner. A method for producing a resist pattern, comprising curing and removing an unexposed portion by development. 9. 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 8.