JP3487294B2 - Photosensitive resin composition and its use - Google Patents

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, in the field of manufacturing printed wiring boards, as a resist material used for etching, plating and the like, a photosensitive resin composition and a photosensitive element obtained by laminating a support and a protective film thereon are widely used. It is used. A printed wiring board has a photosensitive element laminated on a copper substrate, and after pattern exposure, the unexposed portion is removed with a developer, and etching or plating treatment is applied to form a pattern, and then the cured portion is removed. It is manufactured by a method of peeling and removing from the substrate. As a developing solution for removing the unexposed portion, an alkaline developing type using a sodium hydrogen carbonate solution or the like is mainly used, and the developing solution usually has a capability of dissolving the photosensitive resin composition layer to some extent. The photosensitive resin composition is dissolved or dispersed in the developer at the time of use.

With the recent increase in the density of printed wiring boards, the contact area between the copper substrate and the patterned photosensitive resin composition layer becomes smaller, so that various characteristics required for the photosensitive resin composition layer are obtained. It is required to be highly advanced and have excellent sensitivity, resolution, and releasability in the development, etching, or plating treatment steps, as well as low scum generation resistance (developer resistance) and plating resistance (chemical resistance).

[0004]

However, until now, a photosensitive resin composition having low scum generation property and plating resistance and a good balance of various properties has not yet been developed. Therefore, an object of the present invention is to provide a photosensitive resin composition and a photosensitive element which are excellent in sensitivity, resolution, peeling property, low scum generation property, and plating resistance. Another object of the present invention is to provide a method for producing a resist pattern laminated substrate on which a resist pattern having excellent sensitivity, resolution, peeling property, low scum generation property and plating resistance is formed. Still another object of the present invention is to provide a method for producing a printed wiring board using a resist pattern having excellent sensitivity, resolution, peeling property, low scum generation property and plating resistance.

[0005]

In order to solve the above-mentioned problems, the photosensitive resin composition according to the present invention comprises (A) a binder polymer, (B1) 2,2-bis (4-((meth) acryloyloxy). Polyethoxy) phenyl) propane,
(B2) containing 2,2-bis (4-((meth) acryloyloxypolyalkyleneoxy) phenyl) propane having at least one ethoxy group and one propoxy group in the molecule and (C) a photopolymerization initiator It will be. Thus, in the present invention, as the photopolymerizable compound,
Since the component (B1) and the component (B2) are combined with each other, they are excellent in sensitivity, resolution, peeling property, low scum generation property, and plating resistance, such as resist patterns of printed wiring boards. Can be suitably used as.

The photosensitive element according to the present invention has a resist layer comprising the above-mentioned photosensitive resin composition of the present invention formed on a support.

The method of manufacturing a resist pattern laminated substrate according to the present invention comprises the following steps: (1) a step of laminating a resist layer comprising the photosensitive resin composition of the present invention on a substrate; And (3) selectively removing the resist layer in the unexposed area by development to form a resist pattern.

The method for manufacturing a printed wiring board according to the present invention is
The following steps: (1) a step of laminating a resist layer comprising the photosensitive resin composition according to the present invention on a circuit-forming substrate; (2) irradiating an actinic ray imagewise to the resist in the exposed portion. A step of photo-curing the layer; (3) a step of selectively removing the resist layer in the unexposed portion by development to form a resist pattern; (4) a processing of the circuit forming substrate using the resist pattern as a mask Etching or selectively plating the layer on the layer to be processed.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive resin composition of the present invention comprises
(A) Binder polymer, (B1) 2,2-bis (4
-((Meth) acryloyloxypolyethoxy) phenyl) propane, (B2) 2,2-bis (4 having at least one ethoxy group and one propoxy group in the molecule
-((Meth) acryloyloxypolyalkyleneoxy) phenyl) propane and (C) a photopolymerization initiator. Here, (meth) acrylic acid in the present invention means acrylic acid and methacrylic acid corresponding thereto, and (meth) acrylate means acrylate and methacrylate corresponding thereto.

Examples of the (A) binder polymer in the present invention include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. From the viewpoint of alkali developability, acrylic resins are preferred. These may be used alone or in combination of two or more. Examples of combinations of two or more binder polymers include two or more binder polymers composed of different copolymerization components, two or more binder polymers having different weight average molecular weights, two or more binder polymers having different dispersities. To be Further, a polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used. The binder polymer may have a photosensitive group, if necessary.

The (A) binder polymer can be produced, for example, by radically polymerizing a polymerizable monomer. As the polymerizable monomer, for example,
Styrene, vinyltoluene, α-methylstyrene, p-
Polymerizable styrene derivatives such as methylstyrene and p-ethylstyrene, vinyl alcohol esters such as acrylamide, acrylonitrile and vinyl-n-butyl ether, (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, α-bromo (meth) acrylic acid, α-
Chlor (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid,
Maleic acid anhydrides, maleic acid monoesters such as monomethyl maleate, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like can be mentioned. These may be used alone as a homopolymer, or as a copolymer by combining two or more kinds.

Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
Butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and their structural isomers Is mentioned. These may be used alone or in combination of two or more.

The binder polymer (A) preferably contains a carboxyl group from the viewpoint of alkali developability. For example, a polymerizable monomer having a carboxyl group and another polymerizable monomer are radically polymerized. It can be manufactured by Methacrylic acid is preferable as the polymerizable monomer having a carboxyl group.
From the viewpoint of flexibility, the binder polymer (A) is preferably a copolymer containing styrene or a styrene derivative as a polymerizable monomer. In order to improve both the adhesiveness and the peeling property, the styrene or styrene derivative used as the copolymerization component is preferably contained in the copolymer in an amount of 3 to 30% by weight, preferably 4 to 28.
More preferably, it is more preferably 5% by weight, and particularly preferably 5 to 27% by weight. If the content is less than 3% by weight, the adhesion tends to be poor, and if it exceeds 30% by weight, the peeled pieces tend to be large and the peeling time tends to be long.

The acid value of the binder polymer (A) is preferably 30 mgKOH / g or more from the viewpoint of developing time, and 2 from the viewpoint of resistance to a developing solution of a photocured resist.
It is preferably 00 mgKOH / g or less and 45 to
More preferably, it is 150 mgKOH / g. When solvent development is performed as the development step, it is preferable to prepare a small amount of the polymerizable monomer having a carboxyl group.
(A) Weight average molecular weight of the binder polymer (measured by gel permeation chromatography (GPC),
It is preferably 20,000 or more from the viewpoint of developing solution resistance, and is preferably 300,000 or less from the viewpoint of developing time, and is 25,000 to 150, as calculated by a calibration curve using standard polystyrene. It is more preferably 000.

In the present invention, (B1) 2,2-bis (4
Examples of-((meth) acryloyloxypolyethoxy) phenyl) propane include compounds represented by the general formula (I):

[Chemical 3] The compound represented by is preferable. In formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. A plurality of X's represent an ethylene group. m and n are m
It is preferably a positive integer such that + n = 2 to 40, more preferably m + n = 4 to 30, and m.
+ N = 8-20 is particularly preferable, and 8-15 is extremely preferable.

Examples of the 2,2-bis (4-((meth) acryloyloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloyloxyethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloyloxydiethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytriethoxy) phenyl) propane,
2,2-bis (4-((meth) acryloyloxytetraethoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloyloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxyhexaethoxy) phenyl) propane, 2,
2-bis (4-((meth) acryloyloxyheptaethoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloyloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxynonaethoxy) phenyl) propane, 2,2
-Bis (4-((meth) acryloyloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxyundecaethoxy) phenyl)
Propane, 2,2-bis (4-((meth) acryloyl oxide decaethoxy) phenyl) propane, 2,2-
Bis (4-((meth) acryloyloxytridecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-(( (Meth) acryloyloxypentadecaethoxy) phenyl) propane,
2,2-bis (4-((meth) acryloyloxyhexadecaethoxy) phenyl) propane and the like can be mentioned.
2,2-bis (4- (methacryloxypentaethoxy)
Phenyl) propane is commercially available as BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name),
2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (Shin-Nakamura Chemical Co., Ltd. product name).

In the present invention, (B2) has at least one ethoxy group and at least one propoxy group in the molecule;
The 2-bis (4-((meth) acryloyloxypolyalkyleneoxy) phenyl) propane may have at least one ethoxy group and one propoxy group, and has 4 or more carbon atoms other than the ethoxy group and the propoxy group. It may contain an alkyleneoxy group.

The component (B2) is preferably represented by the general formula (II):

[Chemical 4] The compound represented by can be used. In formula (II), R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group. A plurality of Y's represent an ethylene group, an n-propylene group or an iso-propylene group, and a plurality of Z's represent an ethylene group, an n-propylene group or an iso-propylene group. However, one of Y and Z is an ethylene group, and the other is an n-propylene group or an iso-propylene group. t and u are preferably positive integers such that t + u = 2-40, more preferably t + u = 5-30, particularly preferably t + u = 8-20, and 8-15. Is most preferable. s and v are preferably positive integers such that s + v = 2-40, more preferably s + v = 5-30, particularly preferably s + v = 8-20, and 8-15. Is most preferable.

Since the alkyleneoxy group in the component (B1) is only an ethoxy group (hydrophilic group),
In some cases, the component (1) alone may not provide sufficient developer resistance and plating resistance, but in the present invention, as the above (B2), an alkyleneoxy group having 3 or more carbon atoms (hydrophobic group) is included in the molecule. (Including at least one propoxy group)
Since the components are used in combination, it is considered that these characteristics can be improved.

[0020] In iso- propylene group is represented by formula _{(II), -CH (CH 3} ) CH 2 - is a group represented by the the formula - (Y-O) - or - (Z-O) - There are two kinds of bonding directions in the case where the methylene group is bonded to oxygen and the case where the methylene group is not bonded to oxygen.
Either one of the binding directions may be used, or the two types of binding directions may be mixed. Further, when s, t, u and v are respectively 2 or more, 2 or more-(YO)-and 2 or more-(ZO) -may exist at random, or in a block manner. May exist.

Specific examples of the component (B2) include 2,
2-bis (4-((meth) acryloyloxydiethoxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloyloxyhexaethoxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydipropoxydiethoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloyloxytetrapropoxytetraethoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloyloxyhexapropoxyhexaethoxy) phenyl) propane and the like. These are used alone or in combination of two or more. Available as BPA-5PO10EO
DM (Hitachi Chemical Co., Ltd. sample name), BPA-16
EO5PODM (Hitachi Chemical Co., Ltd. sample name), B
PA-20PO10EODM (Hitachi Chemical Co., Ltd. sample name), RMA-473 (BA10 (PO) 10-D)
MA) (Japan Emulsifier Co., Ltd. sample name) and the like.

The photosensitive resin composition of the present invention may contain a photopolymerizable compound other than the components (B1) and (B2). Examples of these include polyhydric alcohols with α,
a compound obtained by reacting a β-unsaturated carboxylic acid,
2,2-bis (4-((meth) acryloyloxypolypropoxy) phenyl) propane, 2,2-bis (4-
(Bisphenol A-based (meth) acrylate compounds such as ((meth) acryloyloxypolybutoxy) phenyl) propane, compounds obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid, and a urethane bond in the molecule. Urethane monomers such as (meth) acrylate compounds having, nonylphenoxy polyethyleneoxy acrylate, γ-chloro-β-hydroxypropyl-
Examples include phthalic acid compounds such as β ′-(meth) acryloyloxyethyl-o-phthalate and β-hydroxyalkyl-β ′-(meth) acryloyloxyalkyl-o-phthalate, and (meth) acrylic acid alkyl ester. . These are used alone or in combination of two or more.

Examples of the (C) photopolymerization initiator in the present invention include N, N'-tetraalkyl-4, such as benzophenone and N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone). 4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2
-Methyl-1- [4- (methylthio) phenyl] -2-
Aromatic ketones such as morpholino-propanone-1, quinones such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin,
Benzoin compounds such as alkylbenzoin, benzyl derivatives such as benzyldimethylketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer,
2- (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, 9-phenylacridine, acridine derivative such as 1,7-bis (9,9′-acridinyl) heptane, N-phenylglycine, Examples thereof include N-phenylglycine derivatives and coumarin compounds. The substituents on the aryl groups of the two 2,4,5-triarylimidazoles may be the same and may give the target compound, or may be different and give an asymmetric compound. Also,
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 blending amount of the component (A) is as follows.
It is preferable that the amount is in the range of 40 to 80 parts by weight with respect to 100 parts by weight of the total amount of the components 1) and (B2).
More preferably, the amount is 5 to 70 parts by weight. If the blending amount is less than 40 parts by weight, the photocured product tends to be brittle, and when used as a photosensitive element, the coating property tends to be poor, and if it exceeds 80 parts by weight, the sensitivity tends to be insufficient. .

The blending amount of the component (B1) is as follows:
The total amount of the components (B1) and (B2) is 100 parts by weight, preferably 10 to 40 parts by weight, more preferably 20 to 30 parts by weight. If the amount is less than 10 parts by weight, the resolution tends to decrease, and if it exceeds 40 parts by weight, the peeling time tends to be long, the plating resistance tends to be low, and edge fusion tends to occur.

The blending amount of the component (B2) is as follows:
The total amount of the components (B1) and (B2) is preferably 5 to 40 parts by weight based on 100 parts by weight,
More preferably, it is 10 to 30 parts by weight. If the amount is less than 5 parts by weight, the peeling time tends to be long, the plating resistance tends to be low, and edge fusion tends to occur. If it exceeds 40 parts by weight, the development scum tends to occur.

The blending amounts of the component (C) are the components (A) and (B).
It is preferably 0.1 to 20 parts by weight, and 0.2 to 10 parts by weight based on 100 parts by weight of the total of the components 1) and (B2).
It is preferably 10 parts by weight. This compounded amount is 0.1
If it is less than parts by weight, the sensitivity tends to be inadequate, and if it exceeds 20 parts by weight, absorption on the surface of the composition during exposure tends to increase, and internal photocuring tends to be insufficient.

The photosensitive resin composition containing the above essential components may further contain at least 1 in the molecule, if necessary.
Photopolymerizable compound having one cationically polymerizable cyclic ether group (oxetane compound, etc.), cationic polymerization initiator, dye such as malachite green, photocoloring agent such as tribromophenyl sulfone, leuco crystal violet, thermal color developing agent, Plasticizers such as p-toluenesulfonamide, pigments, fillers, defoamers, flame retardants, stabilizers, adhesion promoters, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc. 0.01 parts each for 100 parts by weight of the total amount of the components (A) and (B).
Can be contained in an amount of about 20 parts by weight. These are used alone or in combination of two or more.

The photosensitive resin composition of the present invention containing the above components can be obtained, for example, by uniformly kneading and mixing the blended components with a roll mill, a bead mill or the like. Further, if necessary, it is dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether or a mixed solvent thereof to obtain a solid content of 30 It can be applied as a solution of about 60% by weight.

The application of the obtained photosensitive resin composition is not particularly limited, but after application as a liquid resist on a metal surface such as copper, copper-based alloy, iron, iron-based alloy, etc. and drying, it is necessary. Accordingly, it is preferably used by being coated with a protective film or in the form of a photosensitive element which will be described in detail later. The thickness of the photosensitive resin composition layer applied varies depending on the use, but it is preferably about 1 to 100 μm after drying. When the protective film is applied after being applied as a liquid resist and then used as a protective film, for example, a polymer film of polyethylene, polypropylene or the like can be mentioned.

Next, a photosensitive element according to the present invention, that is, a photosensitive element in which a resist layer comprising the above-mentioned photosensitive resin composition of the present invention is formed on a support, will be described with reference to the drawings. To do. FIG. 1 schematically shows an embodiment of a photosensitive element. The photosensitive element 1 includes a support 11 and a resist layer (photosensitive resin composition layer) 12 formed thereon. Is included. As the support 11, for example, a polymer film of polyethylene terephthalate, polypropylene, polyethylene, polyester or the like can be preferably used. The thickness of the polymer film is preferably about 1 to 100 μm. Resist layer 1 on support 11
The method for forming 2 is not particularly limited, but it can be preferably carried out by applying a solution of the photosensitive resin composition and drying. The thickness of the photosensitive resin composition layer applied varies depending on the use, but it is preferably about 1 to 100 μm after drying. 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. In addition, the amount of the residual organic solvent in the resist layer 12 is to prevent the diffusion of the organic solvent in a later step,
It is preferably 2% by weight or less. The polymer film used as a support is a protective film (not shown)
The surface of the resist layer may be coated with The protective film preferably has 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, and is also preferably a low fish eye film. Further, the photosensitive element is
In addition to the photosensitive resin composition layer, the support and the protective film, it may have an intermediate layer such as a cushion layer, an adhesive layer, a light absorbing layer, a gas barrier layer or a protective layer.

The produced photosensitive element is stored, for example, as it is or after further laminating a protective film on the surface of the photosensitive resin composition layer and winding it on a cylindrical winding core. At this time, it is preferable that the support is wound so that it is on the outside. An end face separator is preferably installed 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 installed from the viewpoint of edge fusion resistance. In addition, as a packing method, it is preferable to wrap the product 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, ABS resin (acrylonitrile-butadiene-styrene copolymer).

Next, a method of manufacturing a resist pattern laminated substrate according to the present invention is schematically shown in FIG.
Will be described with reference to. First, in step (1), a resist layer made of the above-described photosensitive resin composition of the present invention is formed on a substrate (circuit forming substrate). As the forming method, the above-described coating method is used, and as shown in FIG. 2A, the photosensitive element 1 is formed on the circuit forming substrate 2 and the resist layer 12 is formed on the circuit forming substrate 2. It can be laminated so as to be in close contact with the surface. Prior to lamination, if a protective film is present on the resist layer 12 of the photosensitive element 1, the protective film is removed. As a lamination method, for example, the resist layer 12 is
About 0.1 to 1 MPa (about 1 to 10 kgf / cm ₂ ) on the circuit forming substrate 2 while heating to about 0 to 130 ° C.
Examples of the method include laminating by pressure bonding under pressure, and laminating under reduced pressure is also possible. As the circuit forming substrate 2, a substrate having a metal layer (not shown) as a layer to be processed on its surface is generally used, and the substrate 2 surface on which the photosensitive element 1 is laminated is usually a metal surface. But
There is no particular limitation.

After the lamination of the photosensitive elements is completed, as a step (2), an actinic ray is imagewise irradiated to photo-cur the resist layer in the exposed portion. As a method of irradiating the active ray imagewise, as shown in FIG. 2B, the active layer imagewise is irradiated onto the resist layer 12 through the mask pattern 3 to photo-cur the resist layer 12 in the exposed portion. be able to. The mask pattern 3 may be a negative type or a positive type, and a generally used one can be used. As the light source of the actinic ray, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, a xenon lamp, or the like that effectively radiates ultraviolet rays, visible light, or the like is used. Further, laser direct drawing exposure can be performed without using a mask pattern.

After the exposure, in step (3), the resist layer in the unexposed portion is selectively removed by development to form a resist pattern 121 as shown in FIG. Is obtained. The exposure in the step (2) can be performed in the state where the support 11 is present as long as the light irradiation to the resist layer 12 is not hindered. In that case, the support 11 is removed prior to the development. . The development is performed by removing the unexposed portion by wet development, dry development or the like with a developing solution such as an alkaline aqueous solution, an aqueous developing solution or an organic solvent. The above alkaline aqueous solution can be preferably used, for example, 0.1 to 5
Examples thereof include a dilute solution of sodium carbonate by weight, a dilute solution of 0.1 to 5 wt% potassium carbonate, a dilute solution of 0.1 to 5 wt% sodium hydroxide, and the like. The pH of this alkaline aqueous solution is preferably in the range of 9 to 11, and its temperature is adjusted according to the developability of the photosensitive resin composition layer. Further, a surface active agent, a defoaming 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, and slapping. As a treatment after development, by heating at about 60 to 250 ° C. or exposing at about 0.2 to 10 J / cm ₂ as necessary,
The formed resist pattern may be further cured.

Next, a method for manufacturing a printed wiring board according to the present invention will be described with reference to FIGS. 3 and 4 which schematically show the steps as one embodiment. The steps up to forming the resist pattern include the step of laminating the photosensitive element 1 on the circuit forming substrate 2 (1), the exposure step (2),
It includes the developing step (3) and is the same as that described in the method of manufacturing the resist pattern. However, in the method of manufacturing a printed wiring board, as shown in FIGS. 3 (A) and 4 (A), a circuit forming substrate 2 having a thin processed layer 21 made of copper or the like on its surface is used. use. FIG. 3 shows a circuit forming process by a subtractive method using etching, and FIG. 4 shows a circuit forming process by a semi-additive method using plating.

After the resist pattern 121 is formed,
As the step (4), as shown in FIG. 3B, the processed layer 21 of the circuit forming substrate 2 is etched using the formed resist pattern 121 as a mask, or as shown in FIG. 4B. As described above, the layer to be processed 21 is selectively plated to form a plating layer (22) made of copper or the like. For etching the layer to be processed 21 having a metal surface, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, or the like can be used. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.

Finally, as shown in FIGS. 3C and 4C, the resist pattern 12 remaining on the substrate 2 is formed.
1 can be peeled off with a stronger alkaline aqueous solution than the alkaline aqueous solution used for the development, and the printed wiring board 5 on which the circuit 211 is formed can be obtained. Further, in the case of the semi-additive method, as shown in FIG. 4D, after the resist pattern is peeled off, the processed layer 21 is also removed by, for example, a quick etching method or the like. As the strongly alkaline aqueous solution, for example, 1 to 10 wt% sodium hydroxide aqueous solution, 1 to 10 wt% potassium hydroxide aqueous solution, etc. are 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.

[0039]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples without departing from the technical idea of the present invention. (1) Preparation of Binder Polymer Solution The following components were mixed to obtain a binder polymer solution. [(A) component] Methacrylic acid / methyl methacrylate / styrene / butyl methacrylate / ethyl acrylate (30/22/30 /
8/10 weight ratio) copolymer (weight average molecular weight = 5000)
0, acid value = 194 mgKOH / g) in methylcellosolve-toluene solution (solid content = 48% by weight): 120 g (solid content 58 g) [(C) component] 2,2′-bis (2-chlorophenyl) -4, 4 ',
5,5'-Tetraphenylbisimidazole: 3.2 g 4,4'-bis (diethylamino) benzophenone:
0.06 g [color former] leuco crystal violet: 0.4 g [polymerization inhibitor] 4-tert-butylcatechol (TBC): 0.04
g [Dye] Malachite Green: 0.04 g [Solvent] Acetone: 10 g Toluene: 7 g N, N-Dimethylformamide: 3 g Methanol: 3 g

(2) Examples 1 to 4 and Comparative Examples 1 to 4
Preparation of photosensitive resin composition The binder polymer solution obtained above is shown in Table 1.
(B1) component and (B2) component are dissolved and each
The photosensitive resin compositions of Examples and Comparative Examples were prepared. In Table 1
The compounds used are shown below. "BPE500" (trade name of Shin-Nakamura Chemical Co., Ltd.):
In the above general formula (I), R¹, R^Two= CH_Three, M +
A compound (2,2-bis (4- (methacrylic acid)
Royloxypentaethoxy) phenyl) propane) "BP (EO) 14MA": the general formula (I)
And R¹, R^Two= CH_Three, M + n≈14
(2,2-bis (4- (methacryloyloxyheptae
Toxy) phenyl) propane) "BPA-5PO10EODM": the above general formula (II)
Where R^Three, R^Four= R = CH_Three, Y: ethylene group,
Z: n-propylene group or iso-propylene group
, A compound having t + u≈5 and s + v≈10 (2,2-
Bis (4-((meth) acryloyloxypolyethoxy)
Polypropoxy) phenyl) propane) "BPA-10PO10EODM": the general formula (I
In I), R^Three, R ^Four= R = CH_Three, Y: ethylene
Group, Z: n-propylene group or iso-propylene group
And a compound in which t + u≈10 and s + v≈10
(2,2-bis (4-((meth) acryloyloxypox
Lyethoxypolypropoxy) phenyl) propane) "BPA-16EO5PODM": the above general formula (II)
Where R^Three, R^Four= R = CH_Three, Y: n-propylate
Or an iso-propylene group, Z: an ethylene group
, T + u≈16, s + v≈5 (2,2-
Bis (4-((meth) acryloyloxypolypropoxy)
Cipolyethoxy) phenyl) propane) "4-tert
-Butylcatechol "(manufactured by Wako Pure Chemical Industries, Ltd.)

(3) Preparation of cured film A solution of the obtained photosensitive resin composition was applied to a 16 μm thick poly
Apply evenly on ethylene terephthalate film and
Photosensitive by drying in a hot air convection dryer at 00 ° C for 10 minutes
Got the element. Film thickness after drying of photosensitive resin composition layer
Was 30 μm. On the other hand, copper foil (thickness 35 μm)
Copper-clad laminate made of glass epoxy material laminated on both sides
(Hitachi Chemical Co., Ltd. product name "MCL-E-67")
Polish the copper surface of the machine with a brush equivalent to # 600 (Sankei
(Manufactured by K.K.), washed with water, and dried with an air stream.
It was The obtained copper-clad laminate was heated to 80 ° C.
On the surface, the photosensitive resin composition layer of the photosensitive element
Was laminated while being heated to 110 ° C. Then high
Parallel light exposure machine with high pressure mercury lamp (Oak Seisakusho)
Using EXM1201 manufactured by Co., Ltd. as a negative
Place the fur 41-step step tablet on the test piece.
60 mJ / cm^Two, 120 mJ / cm^Two, 240m
J / cm ^TwoExposed. After exposure, polyethylene terephthalate
Peel off the rate film and use 1 wt% sodium carbonate water solution
Unexposed by spraying the solution at 30 ℃ for 40 seconds
The portion was removed.

(4) Evaluation of cured film [Sensitivity] The step of the photo-cured film formed on the copper clad laminate
By measuring the number of steps of the tablet
The sensitivity of the composition was evaluated and the 41-step step tablet (Δ
O. D. = 0.05) required to cure 15 stages
Exposure (mJ / cm^Two) Was taken as the sensitivity. The number is small
However, it has high sensitivity. [Resolution] Glass negative mask on test piece (Hitachi Chemical
41-step step tab
Exposure required to cure the 15th stage of the let (mJ /
cm ^Two) Exposed. Observe the pattern after development and
Line width (μm) left as a space and space
, The resolution (μm) was obtained. The smaller the number, the resolution
Is high. [Peeling time] Exposure amount corresponding to each sensitivity (15 steps
/ 41) irradiated sample with 1 wt% sodium carbonate
It was developed using an aqueous solution. After standing for one day and night, 3% by weight hydroxy acid
Keep the sodium chloride solution at 50 ° C and stir with a stir bar
While soaking, the time (seconds) when peeling started was measured.
The shorter the peeling time, the better.

[Scum Generation] Unexposed Film 0.5
m ² was dissolved in 1 liter of a 1% by weight aqueous sodium carbonate solution, and the solution was circulated in a spray developing machine at 30 ° C. for 90 minutes. After standing for 2 minutes, the oily product adhering to the wall surface of the developing machine was observed, and the scum generating property was evaluated according to the following criteria. The larger the number, the better in terms of characteristics. 3: No oily product 2: Small amount of oily product 1: Large amount of oily product [Plating resistance] The copper-clad laminate was laminated with the above-mentioned photosensitive resin composition layer according to the above-mentioned method, and each of them had a corresponding sensitivity. The plate was exposed to light with an exposure amount (15 steps / 41) using a plating resistance evaluation mask, and developed by the above method. This sample was degreased, washed with water, plated with copper sulfate at 3.0 A / dm ² for 30 minutes, washed with water and immersed in borofluoric acid, and then 1.5 A / dm ^2.
Solder plated for 10 minutes and washed with water. Water was removed with an airbrush, and cellophane tape (manufactured by Sekisui Chemical Co., Ltd., 24 mm width) was adhered and peeled off rapidly, and the presence or absence of peeling was examined. A: No peeling X: Peeling The obtained evaluation results are also shown in Table 1.

[0044]

[Table 1] From Table 1, (B1) component and (B
2) In the photosensitive resin composition of the example containing both components,
Excellent balance was shown in all of sensitivity, resolution, peeling time, scum generation, and plating resistance.
It was found that the photosensitive resin composition of Comparative Example containing only one of the component (B1) or the component (B2) lacks the balance of these characteristics.

[0045]

Since the photosensitive resin composition of the present invention uses two specific components as the photopolymerizable compound, it has excellent sensitivity, resolution, releasability, low scum generation and plating resistance. Both are excellent. Therefore, the photosensitive element using this photosensitive resin composition as a resist layer has sensitivity, resolution, releasability, low scum occurrence,
A resist pattern having excellent plating resistance can be provided, which is useful for increasing the density of printed circuit boards and improving workability in manufacturing. Further, according to the method for manufacturing a printed wiring board of the present invention, a printed wiring board having a densified circuit can be manufactured with good workability.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing one embodiment of a photosensitive element.

FIG. 2 is a schematic view showing an example of a manufacturing process of a resist pattern laminated substrate.

FIG. 3 is a schematic diagram showing an example of a manufacturing process of a printed wiring board.

FIG. 4 is a schematic view showing another example of a manufacturing process of a printed wiring board.

[Explanation of symbols] 1 Photosensitive element 11 Support 12 Resist layer (photosensitive resin composition layer) 2 substrates (circuit forming substrate) 121 resist pattern 4 Resist pattern laminated substrate 211 circuits 5 printed wiring board

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI G03F 7/004 512 G03F 7/004 512 7/028 7/028 7/033 7/033 7/40 521 7/40 521 H05K 3 / 06 H05K 3/06 H 3/18 3/18 D

Claims (10)

(57) [Claims] 1. A binder polymer (A), (B1)
2,2-bis (4-((meth) acryloyloxypolyethoxy) phenyl) propane, (B2) 2,2-bis (4-((meth)) having at least one ethoxy group and one propoxy group in the molecule A photosensitive resin composition comprising acryloyloxypolyalkyleneoxy) phenyl) propane and (C) a photopolymerization initiator. 2. The (B1) 2,2-bis (4-((meth) acryloyloxypolyethoxy) phenyl) propane is represented by the general formula (I): (In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, plural Xs represent an ethylene group, and m and n are positive integers such that m + n = 2 to 40). The photosensitive resin composition according to claim 1. 3. The (B2) 2,2-bis (4-((meth) acryloyloxypolyalkyleneoxy) phenyl) propane having at least one ethoxy group and one propoxy group in the molecule is represented by the general formula (II). : [Chemical 2] (In the formula, R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, a plurality of Ys represent an ethylene group, an n-propylene group or an iso-propylene group, and a plurality of Zs represent an ethylene group, n-propylene. Represents a group or an iso-propylene group, t and u are positive integers such that t + u = 2 to 40, and s and v are positive integers such that s + v = 2 to 40, provided that either Y or Z. One is an ethylene group and the other is an n-propylene group or an iso-propylene group.) The photosensitive resin composition according to claim 1 or 2. 4. The photosensitive resin composition according to claim 1, wherein the binder polymer (A) is a copolymer containing styrene or a styrene derivative as an essential copolymerization component. 5. The photosensitive resin composition according to claim 1, which is for etching or plating. 6. A photosensitive element comprising a support and a resist layer comprising the photosensitive resin composition according to claim 1. 7. A method for producing a resist pattern laminated substrate including the following steps: (1) a step of laminating a resist layer comprising the photosensitive resin composition according to any one of claims 1 to 5 on the substrate; (2) A step of irradiating an actinic ray imagewise to photo-cure the exposed resist layer; (3) A step of selectively removing the unexposed resist layer by development to form a resist pattern. . 8. The resist pattern laminated substrate according to claim 7, wherein the step (1) is performed by laminating the photosensitive element according to claim 6 so that a resist layer thereof is in close contact with the substrate. Manufacturing method. 9. A method for manufacturing a printed wiring board, which comprises the steps of: (1) Laminating a resist layer comprising the photosensitive resin composition according to any one of claims 1 to 5 on a circuit-forming substrate. Step; (2) Step of irradiating actinic rays imagewise to photo-cure the resist layer in the exposed part; (3) Forming a resist pattern by selectively removing the resist layer in the unexposed part by development (4) A step of etching or selectively plating the layer to be processed of the circuit forming substrate with the resist pattern as a mask. 10. The printed wiring according to claim 9, wherein the step (1) is performed by laminating the photosensitive element according to claim 6 so that a resist layer thereof is in close contact with the circuit forming substrate. Board manufacturing method.