KR20080052686A - Photosensitive resin composition, photosensitive element, and method for manufacturing printed wiring board - Google Patents

Abstract

Disclosed is a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound having a polymerizable ethylenically unsaturated group, and (C) a photopolymerization initiator. The component (B) of this photosensitive resin composition contains a specific bisphenol A (meth)acrylate compound, a specific alkoxylated trimethylolpropane tri(meth)acrylate compound, and a specific nonylphenyl polyalkyleneglycol (meth)acrylate compound. Also disclosed are a photosensitive element using such a photosensitive resin composition and a method for manufacturing a printed wiring board.

Description

Photosensitive resin composition, photosensitive element, and manufacturing method of printed wiring board {PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE ELEMENT, AND METHOD FOR MANUFACTURING PRINTED WIRING BOARD}

This invention relates to the photosensitive resin composition, the photosensitive element, and the manufacturing method of a printed wiring board.

Background Art Conventionally, in the field of manufacturing printed wiring boards, metal plating is performed on circuits for the purpose of protecting circuits, reducing contact resistance, and the like. In addition, with the spread of portable electronic devices, the form of mounting components used is rapidly increasing in chip scale packages (CSPs) and ball grid arrays (BGAs), which are advantageous for miniaturization. Such a mounting component forms a surface resin layer (solder resist) on the entire surface of a circuit conductor of a printed wiring board except for mounting pads (solder pads) and the like, performs metal plating on parts of the pads, and is plated pads and solder. It is connected with a wiring board by a ball. In many cases, gold plating is used for metal plating in order to ensure a good metal bond.

And the gold plating method in the said field is rapidly moving from the electrolytic plating method to the electroless plating method. This is based on the progress of miniaturization and high density of printed wiring boards, the need for electrode plated wires to be necessary, and the uniform plating film thickness and smooth surface to be obtained. The transition to electroless plating is based on substrates for portable electronic devices. Especially notable.

By the way, in the board | substrate used for portable electronic devices, such as a mobile telephone which the market is rapidly expanding in recent years, mounting components, such as CSP and BGA, are easy to fall out from the board surface by drop impact and the bending by the force which presses an input key. Although such a problem occurs, one of the factors is considered to be that the printed wiring board by the electroless plating method has a lower solder ball connection reliability than the electroplating method. In order to solve this problem, a method of electroless plating to other portions without copper plating on a portion (copper circuit) on which the mounting components are mounted has been proposed (Patent Document 1).

In addition, in order to provide a photosensitive resin composition which not only has excellent resolution, adhesion, photosensitivity and plating resistance, but also can sufficiently reduce the contamination of the plating bath, a binder polymer and at least one polymerizable ethylenically unsaturated bond in the molecule are used. The photosensitive resin composition which contains the photopolymerizable compound, a photoinitiator, and a coloring agent, and whose total light transmittance in an uncured state is 60% or more is disclosed (for example, refer patent document 2).

Patent Document 1: International Publication No. 98/04407 Pamphlet

Patent Document 2: Japanese Patent Laid-Open No. 2004-12812

Disclosure of the Invention

Problems to be Solved by the Invention

The printed wiring board which can perform surface mounting of electronic components, such as CSP and BGA with high reliability, is a laminated board in which the surface resin layer (solder resist) was formed in the predetermined pattern on the circuit formation board (substrate with a circuit pattern formed). The cured product layer (resist pattern) of the photosensitive resin composition is formed on the circuit pattern so that the circuit pattern is exposed, and after electroless plating is performed on the circuit pattern, it is manufactured by the method of removing the cured product layer (resist pattern). I think I can.

However, conventionally, the peelability from the surface resin layer of the cured product layer (resist pattern) after electroless plating is not sufficient, and a part of the cured product layer is not removed but a resist residue that remains on the surface resin layer occurs. There was.

Therefore, an object of the present invention is to provide a photosensitive resin composition which is capable of obtaining sufficient peelability when used to form a cured product layer (resist pattern) on a surface resin layer formed on a circuit-forming substrate. Moreover, an object of this invention is to provide the photosensitive element using this photosensitive resin composition, and the manufacturing method of the printed wiring board using the same.

Means to solve the problem

The present invention provides a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound having a polymerizable ethylenically unsaturated group, and (C) a photopolymerization initiator, wherein (B) component is represented by the following general formula (1) Bisphenol-A (meth) acrylate compound shown, the alkoxylated trimetholpropane triacrylate compound represented by following General formula (2), and the nonylphenyl polyalkylene glycol acrylate represented by following General formula (3) It includes a compound.

[Formula 1]

In formula (1), X <^1> and X <^2> respectively independently show the alkylene group which is 2-6, R <^1> and R <^2> respectively independently represent a hydrogen atom or a methyl group, p and q are p + q = 4-40 The positive integer to be represented is represented, In formula (2), X <^3> , X <^4> and X <^5> show a 2-6 alkylene group each independently, R <^3> , R <^4> and R <^5> are respectively independently a hydrogen atom or a methyl group In the formula (3), X ⁶ represents an alkylene group having 2 to 6 carbon atoms, R ⁶ represents a hydrogen atom or a methyl group, and k, m and n represent a positive integer such that k + m + n = 3 to 30. and r represent the integer of 1-20.

The photosensitive element of this invention is equipped with a support body and the photosensitive layer which consists of the photosensitive resin composition of the said invention provided on the said support body.

When the photosensitive resin composition and the photosensitive element of this invention are used for forming hardened | cured material layer (resist pattern) on the surface resin layer formed on the circuit formation board | substrate by using together the said specific compound as a photopolymerizable compound, a sufficient shape It has become possible to obtain followability and peelability.

In the photosensitive resin composition and the photosensitive element of this invention, it is preferable that (C) component contains 2,4,5-triaryl imidazole dimer. Moreover, when the total amount of (A) component and (B) component is 100 weight part, the quantity of (A) component is 40-80 weight part, the quantity of (B) component is 20-60 weight part, (C It is preferable that the quantity of the component is 0.1-20 weight part.

As for the photosensitive layer of the photosensitive element of the said invention, it is more preferable that the transmittance | permeability with respect to the ultraviolet-ray of wavelength 365nm is 5-75%.

The present invention provides a first laminate comprising a circuit forming substrate having a circuit forming substrate and a circuit pattern formed on the circuit forming substrate and a surface resin layer formed to expose the circuit pattern on the circuit forming substrate. On the surface of the surface resin layer side of a board | substrate, the 1st process of laminating | stacking the previously formed photosensitive layer which consists of said any one photosensitive resin composition, and developing and patterning after irradiating actinic light to the predetermined part of the photosensitive layer A second step of forming a cargo layer, obtaining a second laminated substrate having a surface resin layer and a cured product layer in this order on the circuit forming substrate, and electroless plating to the second laminated substrate, It is a manufacturing method of the printed wiring board provided with the 3rd process of forming a plating layer on a circuit pattern.

In this manufacturing method, it is preferable that the hardened | cured material layer is patterned so that a part of circuit pattern may expose and to form a plating layer on the whole surface of the part which a circuit pattern exposes.

Effects of the Invention

When the photosensitive resin composition and the photosensitive element of this invention are used in order to form hardened | cured material layer (resist pattern) on the surface resin layer formed on the circuit formation board | substrate, sufficient peelability can be obtained. Moreover, the photosensitive resin composition and the photosensitive element of this invention are excellent also in the point of the resolution, adhesiveness, plating tolerance, and shape following.

Moreover, the manufacturing method of the printed wiring board of this invention is good in the embedding property of the photosensitive layer (photosensitive resin composition layer), and the peelability of hardened | cured material layer (resist pattern), and is enough to prevent the contamination of a plating bath. Can be reduced.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows one Embodiment of the photosensitive element of this invention.

2 is a flowchart showing one embodiment of a method for manufacturing a printed wiring board of the present invention.

It is process drawing which shows another embodiment (until the 2nd process) of the manufacturing method of the printed wiring board of this invention.

It is process drawing which shows another embodiment (third process) of the manufacturing method of the printed wiring board of this invention.

Fig. 5 is a top view showing a lattice phototool (mask pattern).

Explanation of the sign

One… Photosensitive element, 10... Support 20... Photosensitive layer, 22... Exposure section 24... Cured product layer (resist pattern), 30... Protective film, 40... Circuit forming substrate, 50, 51... Circuit pattern, 50a, 51a... Exposed portion, 55... Plating layer, 55a... Ni plated layer, 55b... Au plating layer, 60... Surface resin layer, 70... Opening, 80... Circuit forming substrate, 90... Mask pattern, 90a... Shield, 90b... Transparent portion, 92... Active light, 100.. First laminated substrate, 200... Second laminated substrate, 300... Printed wiring board

Implement the invention  Best form for

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described in detail. In addition, (meth) acrylic acid in this specification means acrylic acid and methacrylic acid corresponding to it, (meth) acrylate means acrylate and methacrylate corresponding to it, and the (meth) acryloyl group It means acryloyl group and the methacryloyl group corresponding to it.

As the binder polymer of the component (A) in the present invention, any polymer that functions as a binder of the photosensitive resin composition can be used without particular limitation. Specific examples thereof include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenolic resins. In view of alkali developability, acrylic resins are preferred. These are used individually or in combination of 2 or more types.

A binder polymer can be manufactured by radically polymerizing a polymerizable monomer, for example. As said polymerizable monomer, For example, acrylamide, acrylonitrile, such as the polymerizable styrene derivative substituted by the alpha-position or aromatic ring, such as styrene, vinyltoluene, (alpha) -methylstyrene, diacetone acrylamide, Esters of vinyl alcohols such as vinyl-n-butyl ether, (meth) acrylic acid alkyl esters, (meth) acrylic acid tetrahydrofulfuryl esters, (meth) acrylic acid dimethylaminoethyl esters, (meth) acrylic acid diethylaminoethyl esters, (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-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, male There may be mentioned phosphoric acid mono-isopropyl maleate such as monomethyl ester, fumaric acid, cinnamic acid, α- cyano-cinnamic acid, itaconic acid, crotonic acid, propionic olsan.

The said (meth) acrylic-acid alkylester is represented by following General formula (4), for example. In formula (4), R <^7> represents a hydrogen atom or a methyl group, and R <^8> represents the C1-C12 alkyl group which may have a substituent. As a substituent which R <^8> has, there are a hydroxyl group, an epoxy group, a halogen group.

[Formula 2]

Examples of the alkyl group in R ⁸ include a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and structural isomers thereof. Can be.

As a specific example of the (meth) acrylic-acid alkylester represented by Formula (4), (meth) acrylic-acid methyl ester, (meth) acrylic-acid ethyl ester, (meth) acrylic-acid propyl ester, (meth) acrylic-acid butyl ester, (meth) acrylic-acid pentyl Ester, (meth) acrylic acid pentyl 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 and (meth) acrylic acid dodecyl ester are mentioned. These are used individually or in combination of 2 or more types.

It is preferable that a binder polymer has a carboxyl group from an alkali developable viewpoint. The binder polymer which has a carboxyl group can be manufactured by radically polymerizing the polymerizable monomer which has a carboxyl group, and another polymerizable monomer, for example.

In addition, the binder polymer preferably contains styrene or a styrene derivative as a monomer unit in view of chemical resistance. In order for both adhesiveness and peelability to be favorable by making a styrene or a styrene derivative into a copolymerization component, it is preferable that a binder polymer contains these 2-40 weight%, It is more preferable that it contains 3-28 weight%, It is 5-27 It is particularly preferable to comprise by weight. When this content is less than 2 weight%, there exists a tendency for adhesiveness to fall, and when it exceeds 40 weight%, a peeling piece becomes large and there exists a tendency for peeling time to become long.

It is preferable that it is 20000-30000O, and, as for the weight average molecular weight of a binder polymer, it is more preferable that it is 40000-150000. When this weight average molecular weight is less than 20000, there exists a tendency for developing solution resistance to fall, and when it exceeds 300000, there exists a tendency for developing time to become long.

It is preferable that it is 30-250 mgKOH / g, and, as for the acid value of a binder polymer, it is more preferable that it is 50-200 mgKOH / g. If the acid value is less than 30 mgKOH / g, the developing time tends to be long, and if it exceeds 250 mgKOH / g, the developing solution resistance of the photocured resist pattern tends to decrease.

These binder polymers are used individually or in combination of 2 or more types. As a combination of the binder polymers when using combining two or more types, for example, two or more types of binder polymers which consist of another copolymerization component, two or more types of binder polymers of different weight average molecular weight, and two or more types of binders of different dispersion degrees And polymers.

The photopolymerizable compound which has a polymerizable ethylenically unsaturated group which is (B) component is the bisphenol-A (meth) acrylate compound represented by the said General formula (1), and the alkoxylated trimetholol represented by the said General formula (2). A propane triacrylate compound and the nonylphenyl polyalkylene glycol acrylate compound represented by the said General formula (3) are included.

In formula (1), X <^1> and X <^2> represent a C2-C6 alkylene group each independently, R <^1> and R <^2> respectively independently represent a hydrogen atom or a methyl group, p and q are p + q = 4-40 The positive integer to become. When the carbon number of X ¹ or X ² is not in the range of 2 to 6 or p + q is not in the range of 4 to 40, it is difficult to sufficiently obtain the adhesiveness of the photosensitive layer or the peeling time of the cured product layer (resist pattern). This tends to be long. It is preferable that X <^1> and X <^2> are an ethylene group from a viewpoint of adhesiveness and peelability, and it is preferable that p + q is 10-30.

Suitable specific examples of the compound of formula (1) include bisphenol A polyoxyethylene dimethacrylate (2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane). As 2, 2-bis (4- ((meth) acryloxy polyethoxy) phenyl) propane, it is 2, 2-bis (4- ((meth) acryloxy diethoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy Heptaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonaethoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecethoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4 -((Meth) acryloxy Tetradecaethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane. 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is commercially available as BPE-500 (manufactured by Shinnakamura Chemical Co., Ltd., brand name), and 2,2-bis (4- ( Methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (made by Shin-Nakamura Chemical Co., Ltd., brand name). These are used individually or in combination of 2 or more types.

In formula (2), X <^3> , X <^4> and X <^5> represent a C2-C6 alkylene group each independently, R <^3> , R <^4> and R <^5> show a hydrogen atom or a methyl group each independently, k, m And n represents a positive integer consisting of k + m + n = 3 to 30. When the carbon number of X ³ , X ^4, or X ⁵ is not in the range of 2 to 6 or is not in the range of k + m + n = 3 to 30, the toughness and peelability of the cured product layer (resist pattern) tend to be lowered. From the viewpoint of improving both the toughness and the peelability of the cured product layer (resist pattern), an ethylene group is preferable as X ³ , X ⁴ and X ⁵ . Moreover, it is preferable to exist in the range of k + m + n = 6-27, and it is more preferable to exist in the range of 9-27. As a suitable specific example of the compound of Formula (2), there is ethoxylated trimetholol propane triacrylate.

In formula (3), X <^6> represents a C2-C6 alkylene group, R <^6> represents a hydrogen atom or a methyl group, and r represents the integer of 1-20. When the carbon number of X ⁶ is not in the range of 2 to 6, or r is not in the range of 1 to 20, the peeling residue of the cured product layer (resist pattern) occurs or the peeling time tends to be long. From the viewpoint of improving the peeling residue and the peelability of the cured product layer (resist pattern) at the same time, an ethylene group is preferable as X ⁶ . Moreover, it is preferable that r is in the range of 2-16, and it is more preferable to exist in the range of 4-12. Suitable specific examples of the compound of formula (3) include nonylphenyl polyethylene glycol acrylate.

(B) component may further contain the photopolymerizable compound of that excepting the above. As another photopolymerizable compound, the compound obtained by making (alpha), (beta)-unsaturated carboxylic acid react with polyhydric alcohol, the compound obtained by making (alpha), (beta)-unsaturated carboxylic acid react with glycidyl group containing compound, (gamma)-chloro- (beta)-hydroxypropyl -(beta)-(meth) acryloyloxyethyl-o-phthalate, (beta) -hydroxyethyl- (beta) '-(meth) acryloyloxyethyl-o-phthalate, the (meth) acrylic-acid alkylester, etc. are mentioned. .

As a photoinitiator of (C) component, for example, benzophenone, N, N'- tetramethyl-4,4'- diamino benzophenone (mihiraketone), N, N'- tetraethyl-4,4 '-Diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1 Aromatic ketones such as-[4- (methylthio) phenyl] -2-morpholino-propane-1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1 , 2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, Quinones such as 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, benzoin such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether Benzoin compounds such as ether compounds, benzoin, methyl benzoin, ethyl benzoin, benzyl dimethyl ketal, etc. Of benzyl derivatives, 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-methoxy 2,4,5-triarylimidazole dimers such as phenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7-bis (9,9'-acrididi Acridine derivatives such as nil) heptane, N-phenylglycine, N-phenylglycine derivatives, and coumarin compounds. In addition, the thioxanthone type compound and the tertiary amine compound may be combined in such a manner as to combine diethyl thioxanthone and dimethylaminobenzoic acid. These are used individually or in combination of 2 or more types.

Among these, 2,4,5-triarylimidazole dimer is especially preferable among these. The 2,4,5-triarylimidazole dimer may be a symmetrical compound having the same substituent on the aryl groups of two 2,4,5-triarylimidazoles or an asymmetric compound having different substituents.

The amount of the binder polymer is preferably 40 to 80 parts by weight, more preferably 45 to 70 parts by weight in 100 parts by weight of the total amount of the components (A) and (B). When this compounding quantity is less than 40 weight part, a photocured product is easy to be soft, and when it uses as a photosensitive element, there exists a tendency for coating film property to fall, and when it exceeds 80 weight part, there exists a tendency for photosensitivity to fall.

It is preferable to set it as 20-60 weight part in 100 mass parts of total amounts of (A) component and (B) component, and, as for the quantity of the photopolymerizable compound of (B) component, it is more preferable to set it as 30-55 weight part. When this amount is less than 20 weight part, there exists a tendency for photosensitivity to fall, and when it exceeds 60 weight part, there exists a tendency for a photocured product to fall off.

It is preferable that the content rate of the bisphenol-A (meth) acrylate compound represented by General formula (1) is 10 weight%-50 weight% in the total amount of (B) component, and is 15 weight%-40 weight% It is more preferable. If it is less than 10 weight%, the effect of suppression of peeling residual of a hardened | cured material layer (resist pattern) will tend to become small, and if it exceeds 50 weight%, plating deterioration by the inadequate adhesion of a photosensitive layer will tend to generate | occur | produce.

It is preferable that the content rate of the alkoxylated trimetholpropane tri (meth) acrylate compound represented by General formula (2) in the total amount of (B) component is 20 weight%-80 weight%, and 25 weight%- It is more preferable that it is 75 weight%, and it is especially preferable that it is 30 weight%-65 weight%. If it is less than 20 wt%, plating deterioration tends to occur due to insufficient adhesion of the photosensitive layer, and if it exceeds 80 wt%, peeling residue of the cured product layer (resist pattern) may occur or the cured product layer (resist pattern) may recede. There is a tendency.

It is preferable that the content rate of the nonylphenyl polyalkylene glycol (meth) acrylate compound represented by General formula (3) is 10 weight%-40 weight% in the total amount of (B) component, 15 weight%- It is more preferable that it is 30 weight%. When it is less than 10 weight%, there exists a tendency for the peelability of hardened | cured material layer (resist pattern) to deteriorate, and when it exceeds 40 weight%, there exists a tendency for the lack of adhesion of a photosensitive layer.

It is preferable that it is 0.1-20 weight part with respect to 100 weight part of total amounts of (A) component and (B) component, and, as for the quantity of the photoinitiator of (C) component, it is more preferable that it is 0.2-10 weight part, and it is 2-5 weight Particularly preferred is denial. When this amount is less than 0.1 part by weight, the photosensitivity tends to decrease, while when it exceeds 20 parts by weight, absorption on the surface of the photosensitive layer increases during exposure and tends to be insufficient for internal photocuring.

The photosensitive resin composition, in addition to the above components, if necessary, dyes such as malachite green, photochromic agents such as tribromophenyl sulfone, leuco crystal violet, thermochromic agents, plasticizers such as p-toluenesulfonamide, pigments, It may contain a filler, an antifoaming agent, a flame retardant, a stabilizer, an adhesion imparting agent, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, a thermal crosslinking agent and the like. It is preferable that the quantity of these components is about 0.01-20 weight part with respect to 100 weight part of total amounts of (A) component and (B) component, respectively. These are used individually or in combination of 2 or more types.

The photosensitive resin composition of this invention is solvent, such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N- dimethylformamide, and propylene glycol monomethyl ether as needed. Or it melt | dissolves in these mixed solvents and is used suitably in the solution state about 30 to 60 weight% of solid content.

The solution of the photosensitive resin composition is, for example, coated on a metal surface, dried to form a photosensitive layer, and coated with a protective film as necessary to form a cured product layer (resist pattern). Although there is no restriction | limiting in particular as a metal in this case, Iron-type alloys, such as copper, a copper-type alloy, nickel, chromium, iron, stainless steel, are mentioned, Copper in terms of adhesiveness with a hardened | cured material layer (resist pattern), and an electronic conductivity It is preferable that they are a copper type alloy and an iron type alloy.

Or the photosensitive resin composition of this invention is used suitably in the photosensitive element state. 1: is a schematic cross section which shows suitable embodiment of the photosensitive element of this invention. The photosensitive element 1 shown in FIG. 1 is comprised from the support body 10, the photosensitive layer 20 provided on the support body 10, and the protective film 30 provided on the photosensitive layer 20. As shown in FIG.

The photosensitive layer 20 consists of the photosensitive resin composition of this invention mentioned above. Although the thickness of the photosensitive layer 20 changes with a use, it is preferable that it is 1-100 micrometers, and it is more preferable that it is 1-50 micrometers. When this thickness is less than 1 micrometer, there exists a tendency for coating to become industrially difficult, and when it exceeds 100 micrometers, since the effect of this invention becomes less, there exists a tendency for adhesive force and the resolution to fall.

It is preferable that the transmittance | permeability with respect to the ultraviolet-ray of wavelength 365nm is 5 to 75%, as for the photosensitive layer 20, it is more preferable that it is 7 to 60%, and it is especially preferable that it is 10 to 40%. If this transmittance is less than 5%, the adhesiveness tends to decrease, and if it exceeds 75%, the resolution tends to decrease. This transmittance can be measured by a UV spectrometer. As a UV spectrometer, the Hitachi Corporation make 228A type W-beam spectrophotometer etc. are mentioned.

It is preferable that the photosensitive layer 20 prepares the solution of the photosensitive resin composition mentioned above, and apply | coats it on the support body 10, and is formed. Application | coating can be performed by well-known methods, such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, and a bar coater, for example. In addition, drying can be performed in 70-150 degreeC and about 5 to 30 minutes.

It is preferable that the support body 10 is 5-25 micrometers in thickness, It is more preferable that it is 8-20 micrometers, It is especially preferable that it is 10-16 micrometers. When this thickness is less than 5 micrometers, it exists in the tendency to become fragile at the time of peeling a support body before image development, and when it exceeds 25 micrometers, there exists a tendency for the resolution to fall.

It is preferable that the haze of the support body 10 is 0.001-5.0, It is more preferable that it is 0.001-2.0, It is especially preferable that it is 0.01-1.8. When this haze exceeds 2.0, there exists a tendency for the resolution to fall. The haze is measured in accordance with JIS K 7105 and can be measured by a commercially available turbidimeter such as NDH-1001DP (manufactured by Nippon Denshoku Industries Co., Ltd., brand name).

As the support 10 and the protective film 30, polymer films, such as polyethylene terephthalate, polypropylene, polyethylene, and polyester, are used suitably because they are excellent in the point of heat resistance and solvent resistance.

It is preferable that the thickness of the protective film 30 is 5-30 micrometers, It is more preferable that it is 10-28 micrometers, It is especially preferable that it is 15-25 micrometers. When this thickness is less than 5 micrometers, the protective film 30 will tend to be broken at the time of lamination, and when it exceeds 30 micrometers, it will be inferior to inexpensiveness.

It is preferable that the tensile strength of the long direction of the protective film 30 is 13 MPa or more, It is more preferable that it is 13-100 MPa, It is more preferable that it is 14-1OOMPa, It is still more preferable that it is 15-100 MPa, It is 16-100 MPa It is further more preferable. If this tensile strength is less than 13 MPa, there exists a tendency for the protective film 30 to be easily broken at the time of lamination.

It is preferable that the tensile strength of the protective film 30 in the width direction is 9 MPa or more, It is more preferable that it is 9-100 MPa, It is more preferable that it is 10-100 MPa, It is still more preferable that it is 11-100 MPa, 12-100 MPa It is further more preferable that it is. If this tensile strength is less than 9 MPa, there exists a tendency for the protective film 30 to be easily broken at the time of lamination.

The tensile strength can be measured according to JIS C 2318-1997 (March. 3), and can be measured by a commercially available tensile strength tester manufactured by Dongyang Baldwin Co., Ltd., product name Tenshiron.

Since the support body 10 and the protective film 30 must be removable from the photosensitive layer 20 later, the surface treatment should not be carried out so that removal is impossible, but there is no restriction | limiting in particular and a process is performed as needed. You may carry out. The support 10 and the protective film 30 may be subjected to an antistatic treatment as necessary.

The photosensitive element of this invention is not limited to the said embodiment, In addition to the photosensitive layer, a support body, and a protective film, you may have intermediate layers and protective layers, such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer.

The photosensitive element 1 is stored, for example, as it is or by further laminating the protective film 30 on the other side of the photosensitive layer 20 and wound in a cylindrical core.

Next, one Embodiment of the manufacturing method of the printed wiring board using the photosensitive resin composition of this invention is described. In the manufacturing method of the printed wiring board of this embodiment, a circuit formation board | substrate is contained in a printed wiring board and has a circuit formation board and a circuit pattern (circuit lead). The circuit forming substrate may have a through hole or the like, and may have a multilayer structure.

In this embodiment, a resist is used. A resist is a coating material which masks or protects a specific area | region of a printed wiring board in order to selectively perform etching, soldering, or film formation, and also functions as a plating protective film. Usually, a photoresist is used, and the photosensitive property is used to coat and form a fine and accurate pattern in a predetermined region to a high degree, thereby protecting the object to be protected. In the manufacturing method of the printed wiring board of this invention, a resist is divided into two types according to the objective.

On the other hand, it is a soldering resist (surface resin layer), for example, it is apply | coated and exposed so that only the area | region which forms a junction part by solder bonding may be exposed, and it is formed so that it may have a desired coating (protection) pattern. That is, a soldering resist (surface resin layer) is formed so that the whole surface of a circuit forming board except a circuit pattern may be covered.

Another is a plating resist. A plating resist is a hardened | cured material layer (resist pattern) formed so that the photosensitive layer may be laminated | stacked using the photosensitive element, and it has a coating | covering (protection) pattern such that only the area | region which exposes and performs electroless plating is exposed. That is, this hardened | cured material layer (resist pattern) is formed so that the adhesion of metal by plating, such as a part of a mounting pad, may coat | cover the whole surface of the circuit formation board which is not preferable.

EMBODIMENT OF THE INVENTION Below, this embodiment is described in detail using drawing. 2 is a flowchart showing one embodiment of a method for manufacturing a printed wiring board of the present invention. In the embodiment shown in FIG. 2, first, the circuit forming substrate 80 on which the circuit pattern 50 is formed on the circuit forming substrate 40 and the surface resin layer (solder resist) formed on the circuit forming substrate 80 ( A first laminated substrate 100 having 60 is prepared (FIG. 2A). In the surface resin layer 60, an opening 70 exposed by the exposed portion 50a of the circuit pattern 50 is formed. Then, the photosensitive element 1 is laminated on the surface on the surface resin layer 60 side of the first laminated substrate 100 such that the photosensitive layer 20 is in close contact with the surface resin layer 60 (( b)).

Subsequently, the active light rays 92 are irradiated onto the image via the mask pattern 90 with respect to the photosensitive layer 20 laminated on the circuit forming substrate 80 (FIG. 2C). The mask pattern 90 has the shielding part 90a which shields the actinic ray 92, and the transparent part 90b which permeate | transmits the actinic ray 92. As shown in FIG. Thereby, a part (exposed part 22) of the photosensitive layer 20 is exposed and the hardened | cured material of the photosensitive resin composition is formed. After exposure, the support 10 and the unexposed portion are removed and developed to form a patterned cured product layer (resist pattern) 24 (FIG. 2 (d)). In this way, the second laminated substrate 200 having the surface resin layer 60 and the cured product layer (resist pattern) 24 on the circuit-forming substrate 80 in this order is obtained. The cured product layer (resist pattern) 24 is formed for the purpose of plating resist so that the exposed portion 50a of the circuit pattern 50 is exposed. This hardened | cured material layer (resist pattern) 24 can be arbitrarily post-cured after that.

Ni electroless plating is performed on the second laminated substrate 200 using the surface resin layer 60 and the cured product layer (resist pattern) 24 as a mask, and the plating layer 55 is formed on the circuit pattern 50. ) (FIG. 2E). Subsequently, the cured product layer 24 is removed from the second electroless plated laminated substrate 200 to obtain a printed wiring board 300 (FIG. 2 (f)).

FIG.3 and FIG.4 is process drawing which shows another embodiment of the manufacturing method of the printed wiring board of this invention, FIG. 3 is the process drawing which shows the 2nd process, and FIG. 4 shows the 3rd process. In the first process shown in FIG. 3, first, the number of surfaces formed on the circuit forming substrate 80 and the circuit forming substrate 80 on which the circuit patterns 50 and 51 are formed on the circuit forming substrate 40. The first laminated substrate 100 having the ground layer 60 is prepared (FIG. 3A). In the surface resin layer 60, an opening 70 exposed by the exposed portions 50a and 51a of the circuit patterns 50 and 51 is formed. Then, the photosensitive element 1 is laminated on the surface of the first laminated substrate 100 on the surface resin layer 60 side so that the photosensitive layer 20 is in close contact with the surface resin layer 60 (Fig. 3 ( b)).

In the second step, the active light rays 92 are irradiated onto the image via the mask pattern 90 with respect to the photosensitive layer 20 laminated on the circuit forming substrate 80 (FIG. 3C). . The mask pattern 90 has a shielding portion 90a that shields the active light ray 92 and a transparent portion 90b that transmits the active light ray 92. Thereby, a part (exposure part 22) of the photosensitive layer 20 is exposed, and the hardened | cured material of the photosensitive resin composition is formed. After exposure, the support 10 and the unexposed portion are removed and developed to form a patterned cured product layer (resist pattern) 24 (FIG. 3 (d)). In this way, the second laminated substrate 200 having the surface resin layer 60 and the cured product layer (resist pattern) 24 on the circuit forming substrate 80 in this order is obtained. The cured product layer (resist pattern) 24 exposes only the circuit pattern 50 for performing electroless plating, and the plating resist covers an area such as a circuit pattern 51 for which metal adhesion by plating is not preferable. Function as. This hardened | cured material layer (resist pattern) 24 can be arbitrarily post-cured after that.

In the 3rd process shown in FIG. 4, Ni electroless plating is performed with respect to the 2nd laminated board 200 using the surface resin layer 60 and the hardened | cured material layer (resist pattern) 24 as a mask, The Ni plating layer 55a is formed on the surface of the unmasked circuit pattern 50 (FIG. 4E). Subsequently, substituted Au plating is performed to form an Au plating layer 55b on the Ni plating layer (Fig. 4 (f)). In this way, the metal plating process is performed only on the necessary portions, and the cured product layer (resist pattern) 24 is peeled off to obtain a printed wiring board 300 (FIG. 4G) which is excellent in reliability of the mounting component. .

As for the 1st laminated board | substrate 100 shown to FIG. 2 and FIG. 3, the photosensitive element 1 is carried out on the circuit formation board | substrate 40, and the photosensitive layer 20 is the circuit formation board | substrate 40, for example. And forming a patterned surface resin layer 60 by etching and plating the active light onto an image, and etching or plating the surface resin layer 60 as a mask. It is produced via the process of forming the circuit pattern 50.

In the said 1st process, after removing the protective film 30, the photosensitive element 1 is laminated | stacked by pressing on the surface resin layer 60, heating the photosensitive layer 20. FIG. At this time, it is preferable to laminate | stack under reduced pressure from the standpoint of adhesiveness and followability. More specifically, during the lamination, it is preferable to heat the photosensitive layer 20 at 70 to 130 ° C., and the pressing pressure is preferably about 0.1 to 1.OMPa (about 1 to 10 kgf / cm ² ). When the photosensitive layer 20 is heated at 70 to 130 ° C in this manner, it is not necessary to preheat the circuit forming substrate in advance, but in order to further improve the lamination property, the circuit forming substrate may be preheated.

As the light source of the active light 92, 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. The mask pattern 90 is a negative or positive mask pattern called art work.

The development after exposure is performed by removing the unexposed portion by wet development, dry development, or the like by a developing solution corresponding to a photosensitive resin composition such as an alkaline aqueous solution, an aqueous developer, and an organic solvent. The developing method includes a dip method, a battle method, a spray method, a brushing, a slapping, and the like, and a high pressure spray method is most suitable for improving the resolution.

As the developing solution, an alkaline aqueous solution or the like is preferably used because it is safe and stable and has good operability. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as hydroxides of lithium, sodium or potassium, alkali carbonates such as carbonates or bicarbonates of lithium, sodium, potassium or ammonium, alkali metal phosphates such as potassium phosphate and sodium phosphate, and fatigue. Alkali metal pyrophosphates, such as sodium phosphate and potassium pyrophosphate, etc. are used. The development method includes a dip method, a battle method, a spray method, brushing, and slapping, and a high pressure spray method is most suitable for improving resolution.

The alkaline aqueous solution is more specifically, a lean solution of 0.1-5% by weight of sodium carbonate, a lean solution of 0.1-5% by weight of potassium carbonate, a lean solution of 0.1-5% by weight of sodium hydroxide, and 0.1-5% by weight of sodium tetraborate. Lean solutions and the like are preferred. Moreover, it is preferable to make pH of alkaline aqueous solution into the range of 9-11, and the temperature is adjusted according to the developability of the photosensitive layer.

In alkaline aqueous solution, you may mix surface active agent, an antifoamer, a small amount of organic solvents for promoting image development, etc. Alkali substances used in this case include borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propane in addition to the above substances. Diol, 1,3-diaminopropanol-2, morpholine and the like. It is preferable to make pH of a developing solution as small as possible in the range which can fully develop a resist, It is preferable to set it as pH8-12, and it is more preferable to set it as pH9-10.

As said organic solvent, for example, acetone alcohol, acetone, ethyl acetate, alkoxy ethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether and diethylene glycol monobutyl ether are mentioned. These are used individually or in combination of 2 or more types. It is preferable to make the density | concentration of the organic solvent into 2 to 90 weight% normally, and the temperature can be adjusted according to developability. Moreover, a small amount of surfactant, an antifoamer, etc. can also be added to the aqueous developing solution in which the organic solvent was mixed.

As the organic solvent developer used alone, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ- Butyrolactone is mentioned. It is preferable to add water in these organic solvents in the range of 1-20 weight% in order to prevent flammability. Moreover, you may use together 2 or more types of developing methods as needed.

As a process after image development, you may further harden a hardened | cured material layer (resist pattern) by performing the heating of about 60-250 degreeC, or exposure of about 0.2-10mJ / cm <^2> as needed.

As electroless plating, electroless Ni plating is mentioned. Metal plating, such as gold, silver, palladium, platinum, rhodium, copper, and tin, may be performed on electroless Ni plating.

Removal of the cured product layer (resist pattern) after electroless plating can be performed, for example, by peeling with a strongly alkaline aqueous solution than the alkaline aqueous solution used for development. As a strongly alkaline aqueous solution, 1-10 weight% sodium hydroxide aqueous solution, 1-10 weight% potassium hydroxide aqueous solution, etc. are used, for example. As a peeling system, an immersion system, a spray system, etc. are mentioned.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these examples.

Example  1-8 and Comparative example  1 ~ 4

(bookbinder Polymer  1, compound)

Methacrylic acid, methyl methacrylate, and styrene were copolymerized in the ratio of the weight ratio 28:60:12, and the copolymer (binder polymer 1) of the weight average molecular weight 60000, glass transition temperature of 124 degreeC, and acid value 68 mgKOH / g was obtained. The binder polymer 1 was dissolved in methyl cellosolve / toluene (6: 4, weight ratio) so as to be 50% by weight of a nonvolatile component (solid content) to obtain a solution of the binder polymer 1.

(bookbinder Polymer  2, composite)

As a copolymerization monomer, 130 g of methacrylic acid, 170 g of methyl methacrylate, 100 g of ethyl acrylate, and 100 g of styrene and 3.Og of azobisisobutyronitrile were mixed to prepare a solution α. To a flask equipped with a stirrer, a reflux condenser, a hygrometer, a dropping lot, and a nitrogen gas inlet tube, 500 g of a mixture of methyl cellosolve and toluene in a weight ratio of 3: 2 was added, stirred while blowing nitrogen gas, and heated to 85 ° C. The solution (alpha) was dripped there over 4 hours, and it kept warm for 2 hours, stirring at 85 degreeC.

In addition, a solution in which 0.5 g of azobisisobutyronitrile was dissolved in 150 g of a compound containing methyl cellosolve and toluene having a weight ratio of 3: 2 was added dropwise into the flask over 10 minutes. The solution after dropping was kept at 85 ° C for 5 hours with stirring, followed by cooling to obtain a solution of Binder Polymer 2. The nonvolatile component (solid content) of the solution of the binder polymer 2 was 50.0 wt%, and the weight average molecular weight of the binder polymer 2 was 100000.

In addition, the weight average molecular weight was derived by measuring by gel permeation chromatography (GPC) method and converting using the analytical curve of standard polystyrene. The measurement conditions of GPC are shown below.

( GPC  Measuring conditions)

Pump: Hitachi L-6000 type (manufactured by Hitachi Co., Ltd.)

Column: GelpackGL-R420 + GelpackGL-R430 + GelpackGL-R440 (3 in total) (above, manufactured by Hitachi Chemicals, Ltd., trade name)

Eluent: Tetrohydrofuran

Measurement temperature: room temperature

Flow rate: 2.05 mL / min

Detector: Hitachi L-3300 RI (manufactured by Hitachi, Ltd.)

Table 1 and Table 2 show the mixing ratio of the component (A), the component (B), the component (C) and other additive components. As shown in Table 1 and Table 2, (A) component and the other additive component were mixed, (B) component and (C) component were melt | dissolved in this mixture, and the solution of the photosensitive resin composition was obtained.

TABLE 1

TABLE 2

1: weight as solid content

2: bisphenol A polyoxyethylene dimethacrylate: Shin Nakamura Chemical Co., trade name (in the compound represented by the general formula ^(1), R 1 is a methyl group, X ¹ and X ² is the average value of the ethylene group, p + q is About 10)

3: bisphenol A polyoxyethylene dimethacrylate: Shin Nakamura Chemical Co., trade name (in the compound represented by the general formula ^(1), R 1 is a methyl group, X ¹ and X ² is the average value of the ethylene group, p + q is About 30)

4: Ethoxylated trimethylolpropane triacrylate: Nippon Kayaku Co., Ltd. product name (In the compound of General formula (2), R <^3> , R <^4> and R <^5> is a hydrogen atom, X <^3> , X <^4> and X <^5> Ethylene group, average value of k + m + n is about 9

5: nonyl phenyl polyethylene glycol acrylate: Toagosei Co., Ltd. Product name (in the compound represented by the general formula (3), R ⁶ is a hydrogen atom, X ⁶ is an ethylene group, the average value of r of about 4)

6: nonylphenyl polyethyleneglycol acrylate: Shin-Nakamura Chemical Co., Ltd. product name (In the compound of General formula (3), R <^6> is a hydrogen atom, X <^6> is an ethylene group, and the average value of r is about 8.)

7: Polypropylene glycol diacrylate: Shin-Nakamura Chemical Co., Ltd. Product name: Shin-Nakamura Chemical Co., Ltd.

8: trimethylolpropane triacrylate: Shinnakamura Chemical Co., Ltd.

(Photosensitive Element  making)

The solutions of the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 4 were evenly applied onto a polyethylene terephthalate film (base: 1.7%, trade name GS-16, manufactured by Teijin Co., Ltd.) having a thickness of 16 µm. After drying for 10 minutes with the hot air convection type dryer of 100 degreeC, it protected by the polyethylene protective film and obtained the photosensitive element. The thickness after drying of the photosensitive layer was 50 micrometers.

(Production of circuit forming substrate)

12.5cm, 20cm in width and 1.6mm thick double-sided copper foil epoxy laminated board (Hitachi Chemical Co., Ltd. make, brand name: MCL-E-61) leaving a 1 cm periphery on the copper foil surface of the cross section, and has a predetermined pattern An etching resist was formed. The copper foil of the part which is not covered by the etching resist was etched away, and the circuit pattern which has a metal terminal (pad) and wiring was formed. The remaining etching resist was peeled off to obtain a circuit forming substrate. The back surface was etched all over, leaving the glass epoxy surface exposed.

(Formation of Surface Resin Layer)

On the circuit surface of the obtained circuit formation board | substrate, the photoresist (Taiyo Ink Co., Ltd. make, brand name: PSR-4000) was apply | coated to the whole surface leaving 1 cm of circumferences, and it dried at 80 degreeC for 30 minutes. Then, the whole surface except the mounting pad part to plate | plate was exposed using the exposure machine (The Oak Corporation make, brand name: HMW-590) through a phototool. The unexposed portion was spray-developed for 60 seconds in a 1% by weight aqueous sodium carbonate solution (30 ° C), the photoresist on the pad portion was removed, a pattern was formed, and then thermally cured by heating at 150 ° C for 1 hour to form a circuit. The surface resin layer (solder resist) was formed on the board | substrate.

( Of the cured product layer (resist pattern)  formation)

The photosensitive layer (photosensitive resin composition layer) of the photosensitive element obtained in Examples 1-8 and Comparative Examples 1-4 was put on both surfaces of the circuit formation board | substrate with a surface resin layer at a pressure of 0.4 Mpa, the temperature of 110 degreeC, and the lamination rate 1.5. It laminated by m / min and laminated | stacked. The whole surface was exposed except the circuit pattern which performs an electroless-plating process among the laminated photosensitive layers, it spray-developed for 80 second in 1weight% sodium carbonate aqueous solution (30 degreeC), and the hardened | cured material layer (resist pattern) was formed.

About the photosensitive element obtained by the above, and a laminated board | substrate, the characteristic evaluation was performed by the following method. Table 3 and Table 4 show the evaluation result.

( Plating resistance )

The laminated board | substrate obtained by Examples 1-8 and Comparative Examples 1-4 was immersed in Pro Select SF (Art-Tech Japan Co., Ltd. product, brand name) for 5 minutes at 50 degreeC, and the degreasing process was performed. After washing with running water for 1 minute at room temperature, it was immersed in Micro Etch SF (Art-Tech Japan Co., Ltd. make, brand name) for 1 minute at 30 degreeC, and the soft etching process was performed. After washing with running water for 1 minute at room temperature, the solution was immersed in 5% sulfuric acid solution for 1 minute at room temperature and subjected to an acid washing treatment.

Then, the laminated board | substrate was immersed in the catalyst solution Orotech 1000 (Art-Tech Japan Co., Ltd. make, brand name) for electroless plating at room temperature for 90 second, and was activated. After washing with running water for 2 minutes at room temperature, it was immersed for 40 minutes at 83 ° C. in Orotech HP (Arttech Japan Co., Ltd. product) which was a Ni-P plating solution, and electroless Ni plating was performed.

After rinsing with running water for 2 minutes at room temperature, to Orotech CS4000 (made by Arttech Co., Ltd., Orotech CS4000: 150 mL / L, gold potassium cyanide: 1.47 g / L, Orotech SF: 1 mL / L), at 85 ° C It was immersed for 10 minutes and substituted electroless Au plating was performed. As a post-treatment, it washed with water and dried at 85 degreeC for 15 minutes.

In this way, in the laminated substrate in which the plating layer was formed, the presence or absence (in particular, the pad part periphery) of the hardened | cured material layer (resist pattern) was visually determined by the criteria shown below, and plating resistance was evaluated. The evaluation results are shown in Table 3 and Table 4. In addition, evaluation of plating property means that it is good that there is no breakage and swelling.

Criteria

A: No front break and swell B: Some break and swell C: Front break and swell

( Peelability )

Photoresist (TAIYO Ink Manufacturing Co., Ltd. product PSR-4000) was put on one side of double-sided copper foil epoxy laminated board (Hitachi Chemical Co., Ltd. make, brand name: MCL-E-61) of 4cm in width 5cm in thickness. The whole surface was apply | coated and dried for 30 minutes at 80 degreeC.

About the laminated board which apply | coated the said photoresist, whole surface exposure was performed through the grid | lattice-shaped phototool (mask pattern) 90 shown in FIG. The grid-shaped phototool (mask pattern) 90 has a plurality of shielding portions 90a for shielding actinic rays and a transparent portion 90b for transmitting actinic rays. The shielding portion 90a has a width of 2.6 mm and a length (B of FIG. 5) of 0.8 mm, and a line of 0.45 mm spacing (C of FIG. 5). The exposure machine (The Oak Corporation make, brand name: HMW-590) was used for exposure.

After exposure, the unexposed part was spray-developed for 60 second in 1weight% sodium carbonate aqueous solution (30 degreeC). Subsequently, it heated at 150 degreeC for 1 hour and thermosetted, and formed the surface resin layer (solder resist) on the said laminated board. In this surface resin layer, the opening part which copper of one part of the said laminated board exposes is formed.

The photosensitive layers of the photosensitive elements of Examples 1-8 and Comparative Examples 1-4 were laminated on both surfaces of the laminated board provided with the said surface resin layer on conditions of the pressure of 0.4 MPa, the temperature of 110 degreeC, and the lamination rate of 1.5 m / min. , Laminated. About the laminated photosensitive layer, the whole surface exposure was performed by the energy exposure amount which becomes 8.0 of the remaining step number after image development in the stopper 21-stage step tablet, and the hardened | cured material layer was formed. Thus, the laminated board for evaluation in which the hardened | cured material layer covered the upper and lower surfaces of the laminated board provided with the said surface resin layer was obtained.

About this laminated board for evaluation, it sprayed for 80 second with 1 weight% sodium carbonate aqueous solution (30 degreeC), and plating process was performed by the method similar to the said plating resistance evaluation. Then, peelability was evaluated by immersing in 3 weight% sodium hydroxide aqueous solution heated at 50 degreeC, and measuring the time until the hardened | cured material layer peels from the laminated board provided with the said surface resin layer. The evaluation results are shown in Table 3 and Table 4. Peelability evaluation means that it is so good that time is short.

( Resist  Exfoliation residue)

Adhesion of the hardened | cured material layer adhered to the side wall (2.6 mm of vertical 0.8 mm height 30 micrometers in height) of the opening part of a surface resin layer (solder resist) so that peeling cannot be carried out completely using the said laminated board for evaluation after peelability evaluation. The area was observed. SEM (Hitachi Instruments Service Co., Ltd. SE-2100) was used for the observation of the adhesion area. The value obtained by dividing the obtained adhesion area by the side wall area (2.6 mm x 0.8 mm x 30 µm) of the openings was obtained, and the average value of the values obtained in the five openings selected at random was determined from the residue of the cured product layer (resist residue). ). According to the ratio of the obtained resist residue, the resist peeling residual was evaluated as follows. The evaluation results are shown in Table 3 and Table 4. Moreover, it means that it is so good that there are few resist residues.

standard

A: The resist residue is less than 10% B: The resist residue is 10% or more but less than 50% C: The resist residue is 50% or more

( Plating bath Pollutant )

Examples 1-8 and Comparative Example 1, the photosensitive elements obtained in the 0.5m ² ~ 4, after peeling the PET film and a polyethylene film, a Ni-P plating solution 83 ℃ Oro Tech HP (Art Tech Japan Co., Ltd., commercial name) Was immersed for 5 hours, and electroless Ni plating was performed.

Using this plating treatment liquid, the process from the same degreasing treatment to the electroless Ni plating as in the evaluation method of the above plating resistance was performed on the test substrate, and the Ni-P plating film thickness (precipitation thickness) deposited on the substrate was measured. Measured. When the new Ni-P plating solution Orotech HP was used instead of the plating treatment liquid, the plating bath contamination was evaluated by the relative value of the deposition film thickness when the deposition film thickness of the blank was 100. The evaluation results are shown in Table 3 and Table 4. In addition, plating bath contamination is calculated | required by the following formula.

Plating bath contamination (%) = Precipitation film thickness of each sample (μm) / Precipitation film thickness of blank (μm)

(Sensitivity)

The photosensitive layer in the photosensitive element obtained from Examples 1-8 and Comparative Examples 1-4 was laminated | stacked and laminated | stacked on the said copper foil laminated board on the conditions of the pressure of 0.4 MPa, the temperature of 110 degreeC, and the lamination rate of 1.5 m / min. The stopper 21-stage step tablet is arrange | positioned as a negative on the obtained laminated body, and it is a 21-stage step tablet in the same developing conditions as the above using the exposure machine (201GX, Inc. make) which has a high pressure mercury lamp. Sensitivity was evaluated by the exposure energy amount (mJ / cm <^2> ) required in order to harden | cure 8.0 steps of. The evaluation results are shown in Table 3 and Table 4. Further, the lower the exposure energy amount, the higher the sensitivity.

TABLE 3

TABLE 4

In Table 3 and Table 4, it turned out that the photosensitive resin composition of Examples 1-8 is preferable in the plating resistance, peelability, and plating bath contamination property at the time of forming hardened | cured material layer (resist pattern). Moreover, the shape followability with respect to the surface resin layer of these photosensitive elements was also favorable.

Claims (7)

A photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound having a polymerizable ethylenically unsaturated group, and (C) a photopolymerization initiator, (B) the component, Bisphenol A system (meth) acrylate compound represented by following General formula (1), An alkoxylated trimetholpropane tri (meth) acrylate compound represented by the following General Formula (2), and The photosensitive resin composition containing the nonylphenyl polyalkylene glycol (meth) acrylate compound represented by following General formula (3). [Formula 1]

[In Formula (1), X <^1> and X <^2> represent a C2-C6 alkylene group each independently, R <^1> and R <^2> respectively independently represent a hydrogen atom or a methyl group, p and q are p + q = 4 ~ Represents a positive integer equal to 40, In formula (2), X <^3> , X <^4> and X <^5> represent a C2-C6 alkylene group each independently, R <^3> , R <^4> and R <^5> show a hydrogen atom or a methyl group each independently, k, m and n represent a positive integer such that k + m + n = 3-30, In formula (3), X <^6> represents a C2-C6 alkylene group, R <^6> represents a hydrogen atom or a methyl group, r shows the integer of 1-20.] The photosensitive resin composition of Claim 1 in which (C) component contains a 2,4,5-triarylimidazole dimer. The method of claim 1, When the total amount of the component (A) and the component (B) is 100 parts by weight, The amount of (A) component is 40-80 weight part, The amount of (B) component is 20-60 weight part, The photosensitive resin composition whose amount of (C) component is 0.1-20 weight part. A photosensitive element provided with a support body and the photosensitive layer which consists of the photosensitive resin composition of any one of Claims 1-3 provided on the said support body. The photosensitive element of Claim 4 whose transmittance | permeability with respect to the ultraviolet-ray of wavelength 365nm is 5-75% of the said photosensitive layer. A first laminate comprising a circuit forming substrate having a circuit forming substrate and a circuit pattern formed on the circuit forming substrate, and a surface resin layer formed so as to expose the circuit pattern on the circuit forming substrate. A first step of laminating a photosensitive layer formed of the photosensitive resin composition according to any one of claims 1 to 3 on a surface of the substrate on the surface resin layer side; Irradiating an actinic ray to a predetermined portion of the photosensitive layer and then developing to form a patterned cured product layer, and forming a second laminated substrate having the surface resin layer and the cured product layer in this order on the circuit forming substrate. The second process to obtain, A third step of forming an plating layer on the circuit pattern by performing electroless plating on the second laminated substrate The manufacturing method of the printed wiring board provided with. The manufacturing method of the printed wiring board of Claim 6 in which the said hardened | cured material layer is patterned so that a part of said circuit pattern may be exposed and the said plating layer is formed in the whole surface of the part by which the said circuit pattern is exposed.

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