JP4752840B2 - Photosensitive resin composition, photosensitive element, and method for producing printed wiring board - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a photosensitive element, and a method for producing a printed wiring board.

  Conventionally, in the printed wiring board manufacturing field, metal plating is performed on a circuit for the purpose of protecting the circuit and reducing contact resistance. In addition, with the spread of portable electronic devices, the form of mounted components used is rapidly increasing in the chip scale package (CSP) and the ball grid array (BGA), which are advantageous for downsizing. For such mounting parts, a surface resin layer (solder resist) is formed on the entire surface of the circuit conductor of the printed wiring board excluding the mounting pads (solder pads), etc. The printed circuit board and the solder ball are connected to the wiring board. 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 | area is changing rapidly from the electroplating method to the electroless-plating method. This is based on the progress of miniaturization and higher density of printed wiring boards, the need for electrode lead wires and the uniform plating film thickness and smooth surface. The transition is particularly noticeable in portable electronic device substrates.

  By the way, in a substrate used for a portable electronic device such as a cellular phone whose market has been rapidly expanding in recent years, a mounting component such as CSP or BGA is likely to fall off the surface of the substrate due to a drop impact or bending due to a force of pressing an input key. However, it is considered that the printed wiring board by the electroless plating method has lower solder ball connection reliability than that by the electrolytic plating method. In order to solve this problem, a method has been proposed in which electroless plating is not performed on a portion (copper circuit) on which a mounting component is mounted, and electroless plating is performed on other portions (Patent Document 1).

In addition, in order to provide a photosensitive resin composition that not only has excellent resolution, adhesion, photosensitivity and plating resistance, but can sufficiently reduce the contamination of the plating bath, the binder polymer and at least one in the molecule Photosensitive resin containing a photopolymerizable compound having a polymerizable ethylenically unsaturated bond, a photopolymerization initiator, and a colorant, and having a total light transmittance of 60% or more in an uncured state A composition is disclosed (for example, see Patent Document 2).
International Publication No. 98/04407 Pamphlet JP 2004-12812 A

  A printed wiring board that can perform surface mounting of electronic components such as CSP and BGA with higher reliability is a surface resin layer (solder resist) in a predetermined pattern on a circuit-formed substrate (substrate on which a circuit pattern is formed). ) Is formed so that the circuit pattern is exposed on the laminated substrate on which the photosensitive resin composition is formed, and electroless plating is performed on the circuit pattern. It is thought that it can be manufactured by a method of removing the cured product layer (resist pattern).

  However, conventionally, the cured resin layer (resist pattern) after electroless plating is not sufficiently peelable from the surface resin layer, and there is a resist residue that remains on the surface resin layer without peeling off a part of the cured material layer. There was a problem that it occurred.

  Therefore, the present invention is a photosensitivity capable of obtaining sufficient peelability when used to form a cured product layer (resist pattern) on a surface resin layer formed on a circuit-formed substrate. It aims at providing a resin composition. Another object of the present invention is to provide a photosensitive element using the photosensitive resin composition and a method for producing a printed wiring board using the photosensitive element.

The present invention is a photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound having a polymerizable ethylenically unsaturated group, and (C) a photopolymerization initiator, wherein (B) The components are represented by the bisphenol A-based (meth) acrylate compound represented by the following general formula (1), the alkoxylated trimethylolpropane triacrylate compound represented by the following general formula (2), and the following general formula (3). Nonylphenyl polyalkylene glycol acrylate compound.

In formula (1), X ¹ and X ² each independently represent an alkylene group having 2 to 6 carbon atoms, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and p and q are p + q = 4. A positive integer of ˜40, and in formula (2), X ³ , X ⁴ and X ⁵ each independently represents an alkylene group having 2 to 6 carbon atoms, and R ³ , R ⁴ and R ⁵ are each independently Represents a hydrogen atom or a methyl group, k, m and n represent a positive integer such that k + m + n = 3 to 30, in 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 r represents an integer of 1 to 20.

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

  In the photosensitive resin composition and photosensitive element of the present invention, a cured product layer (resist pattern) is formed on a surface resin layer formed on a circuit-formed substrate by using the specific compound in combination as a photopolymerizable compound. When used for forming, sufficient shape followability and peelability can be obtained.

  In the photosensitive resin composition and photosensitive element of the present invention, the component (C) preferably contains a 2,4,5-triarylimidazole dimer. Moreover, when the total amount of (A) component and (B) component is 100 mass parts, the quantity of (A) component is 40-80 mass parts, and the quantity of (B) component is 20-60 mass parts. It is preferable that the amount of the component (C) is 0.1 to 20 parts by mass.

  More preferably, the photosensitive layer of the photosensitive element of the present invention has a transmittance of 5 to 75% for ultraviolet rays having a wavelength of 365 nm.

  The present invention includes a circuit forming substrate, a circuit formed substrate having a circuit pattern formed on the circuit forming substrate, and a surface resin layer formed so that the circuit pattern is exposed on the circuit formed substrate. A first step of laminating a pre-formed photosensitive layer made of any one of the above photosensitive resin compositions on the surface of the first laminated substrate having the surface resin layer side; and an actinic ray on a predetermined portion of the photosensitive layer A second step of obtaining a second laminated substrate having a surface resin layer and a cured product layer in this order formed on the circuit-formed substrate by forming a patterned cured product layer after irradiation And a third step of forming a plating layer on the circuit pattern by performing electroless plating on the two laminated substrates.

  In this manufacturing method, it is preferable that the cured product layer is patterned so that a part of the circuit pattern is exposed, and a plating layer is formed on the entire exposed part of the circuit pattern.

  When the photosensitive resin composition and photosensitive element of the present invention are used to form a cured product layer (resist pattern) on a surface resin layer formed on a circuit-formed substrate, sufficient peelability is obtained. It is possible to obtain The photosensitive resin composition and photosensitive element of the present invention are also excellent in terms of resolution, adhesion, plating resistance, and shape followability.

  Moreover, the method for producing a printed wiring board of the present invention has good embedding property of the photosensitive layer (photosensitive resin composition layer) and releasability of the cured product layer (resist pattern), and further sufficiently contaminates the plating bath. Can be reduced.

It is sectional drawing which shows one Embodiment of the photosensitive element of this invention. It is process drawing which shows one Embodiment of the manufacturing method of the printed wiring board of this invention. It is process drawing which shows other embodiment (until a 2nd process) of the manufacturing method of the printed wiring board of this invention. It is process drawing which shows other embodiment (3rd process) of the manufacturing method of the printed wiring board of this invention. It is a top view which shows a grid | lattice-like phototool (mask pattern).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support body, 20 ... Photosensitive layer, 22 ... Exposure part, 24 ... Hardened | cured material layer (resist pattern), 30 ... Protective film, 40 ... Substrate for circuit formation, 50, 51 ... Circuit pattern, 50a, 51a ... exposed portion, 55 ... plated layer, 55a ... Ni plated layer, 55b ... Au plated layer, 60 ... surface resin layer, 70 ... opening, 80 ... circuit-formed substrate, 90 ... mask pattern, 90a ... shielding Part, 90b ... transparent part, 92 ... active light, 100 ... first laminated substrate, 200 ... second laminated substrate, 300 ... printed wiring board

Hereinafter, preferred embodiments of the present invention will be described in detail. In this specification, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto, (meth) acrylate means acrylate and corresponding methacrylate, and (meth) acryloyl group means acryloyl group. And the corresponding methacryloyl group.

  As the binder polymer of the component (A) in the present invention, any polymer that functions as a binder for the photosensitive resin composition can be used without particular limitation. Specific examples include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. From the viewpoint of alkali developability, an acrylic resin is preferable. These are used alone or in combination of two or more.

  The binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives substituted at the α-position or aromatic ring such as styrene, vinyl toluene, α-methylstyrene, acrylamide such as diacetone acrylamide, acrylonitrile, vinyl, and the like. -Esters of vinyl alcohol such as 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) acryl Acid, α-chloro ( T) Acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate and the like, Examples include fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid.

The (meth) acrylic acid alkyl ester is represented by, for example, the following general formula (4). In Formula (4), R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents an alkyl group having 1 to 12 carbon atoms that may have a substituent. Examples of the substituent that R ⁸ has include a hydroxyl group, an epoxy group, and a halogen group.

Examples of the alkyl group in R ⁸ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. Isomers.

  Specific examples of the (meth) acrylic acid alkyl ester represented by the formula (4) include (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 hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid Nonyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester may be mentioned. These are used alone or in combination of two or more.

  The binder polymer preferably has a carboxyl group from the viewpoint of alkali developability. The binder polymer having a carboxyl group can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer.

  The binder polymer preferably contains styrene or a styrene derivative as a monomer unit from the viewpoint of chemical resistance. In order to improve both adhesion and peelability using styrene or a styrene derivative as a copolymerization component, the binder polymer preferably contains 2 to 40% by mass, more preferably 3 to 28% by mass, It is particularly preferable to contain 27% by mass. If this content is less than 2% by mass, the adhesion tends to decrease, and if it exceeds 40% by mass, the peel piece tends to be large and the peel time tends to be long.

  The weight average molecular weight of the binder polymer is preferably 20,000 to 300,000, and more preferably 40000 to 150,000. When the weight average molecular weight is less than 20,000, the developer resistance tends to decrease, and when it exceeds 300,000, the development time tends to be long.

  The acid value of the binder polymer is preferably 30 to 250 mgKOH / g, and more preferably 50 to 200 mgKOH / g. When the acid value is less than 30 mg KOH / g, the development time tends to be long, and when it exceeds 250 mg KOH / g, the developer resistance of the photocured resist pattern tends to be lowered.

  These binder polymers are used alone or in combination of two or more. Examples of combinations of binder polymers when two or more types are used in combination include, for example, two or more types of binder polymers comprising different copolymerization components, two or more types of binder polymers having different weight average molecular weights, and two types having different dispersities. The above binder polymers are mentioned.

  The photopolymerizable compound having a polymerizable ethylenically unsaturated group as the component (B) is represented by the bisphenol A-based (meth) acrylate compound represented by the general formula (1) and the general formula (2). An alkoxylated trimethylolpropane triacrylate compound, and a nonylphenyl polyalkylene glycol acrylate compound represented by the above general formula (3).

In formula (1), X ¹ and X ² each independently represent an alkylene group having 2 to 6 carbon atoms, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and p and q are p + q = 4. A positive integer of ~ 40 is indicated. Or the number of carbon atoms of X ¹ or X ² is not within the range of 2 to 6, or if p + q is not within the range of 4 to 40, or adhesion of the photosensitive layer is hardly sufficiently obtained cured product layer ( The stripping time of the resist pattern tends to be long. From the viewpoint of adhesion and peelability, X ¹ and X ² are preferably ethylene groups, and p + q is preferably 10-30.

  A preferred specific example of the compound of formula (1) is bisphenol A polyoxyethylene dimethacrylate (2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane). Examples of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) 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) acryloxyheptaethoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy nonaethoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ( (Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane. 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is commercially available as BPE-500 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 2,2-bis (4 -(Methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). These may be used alone or in combination of two or more.

In formula (2), X ³ , X ⁴ and X ⁵ each independently represent an alkylene group having 2 to 6 carbon atoms, R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, k , M, and n are positive integers such that k + m + n = 3-30. When the carbon number of X ³ , X ⁴ or X ⁵ is not within the range of 2 to 6 or is not within the range of k + m + n = 3 to 30, the toughness and peelability of the cured product layer (resist pattern) are reduced. Tend to. From the viewpoint of improving both the toughness and peelability of the cured product layer (resist pattern), X ³ , X ⁴ and X ⁵ are preferably ethylene groups. 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. A preferred specific example of the compound of formula (2) is ethoxylated trimethylolpropane triacrylate.

In 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 r represents an integer of 1 to 20. When the number of carbon atoms of X ⁶ is not within the range of 2 to 6 or r is not within the range of 1 to 20, there is a tendency that the remaining peel of the cured product layer (resist pattern) occurs or the peeling time becomes long. is there. X ⁶ is preferably an ethylene group from the viewpoint of improving both the peeling residue and the peelability of the cured product layer (resist pattern). Moreover, r is preferably in the range of 2 to 16, and more preferably in the range of 4 to 12. A preferred specific example of the compound of formula (3) is nonylphenyl polyethylene glycol acrylate.

  The component (B) may further contain a photopolymerizable compound other than the above. Other photopolymerizable compounds include compounds obtained by reacting polyhydric alcohols with α, β-unsaturated carboxylic acids, compounds obtained by reacting glycidyl group-containing compounds with α, β-unsaturated carboxylic acids, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β ′-(meth) acryloyloxyethyl-o-phthalate, (meth) acrylic acid alkyl ester, etc. Is mentioned.

  Examples of the photopolymerization initiator (C) include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-Methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2- Aromatic ketones such as morpholino-propanone-1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2 , 3-Diphenylanthraquinone, 1-chloroa Quinones such as traquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin ether compounds such as phenyl ether, benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 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 2,4,5-triarylimidazole dimer such as 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) ) Acridine derivatives such as heptane, N-phenylglycine, N-phenylglycine derivatives, and coumarin compounds. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid. These are used alone or in combination of two or more.

  Among these, the component (C) is particularly preferably a 2,4,5-triarylimidazole dimer. The 2,4,5-triarylimidazole dimer may be a symmetric compound in which the substituents of the aryl groups of two 2,4,5-triarylimidazoles are the same, or an asymmetric with different substituents. It may be a compound.

  The amount of the binder polymer is preferably 40 to 80 parts by mass and more preferably 45 to 70 parts by mass in 100 parts by mass of the total amount of the component (A) and the component (B). If this blending amount is less than 40 parts by mass, the photocured product tends to be brittle, and when used as a photosensitive element, the coating properties tend to be reduced, and if it exceeds 80 parts by mass, the photosensitivity tends to decrease.

  The amount of the photopolymerizable compound of component (B) is preferably 20 to 60 parts by mass, and preferably 30 to 55 parts by mass, in 100 parts by mass of the total amount of component (A) and component (B). More preferred. If this amount is less than 20 parts by mass, the photosensitivity tends to decrease, and if it exceeds 60 parts by mass, the photocured product tends to be brittle.

  In the total amount of component (B), the content of the bisphenol A-based (meth) acrylate compound represented by the general formula (1) is preferably 10% by mass to 50% by mass, and 15% by mass to 40% by mass. It is more preferable that If the amount is less than 10% by mass, the effect of suppressing the remaining peeling of the cured product layer (resist pattern) tends to be small, and if it exceeds 50% by mass, plating due to insufficient adhesion of the photosensitive layer tends to occur.

  In the total amount of the component (B), the content ratio of the alkoxylated trimethylolpropane tri (meth) acrylate compound represented by the general formula (2) is preferably 20% by mass to 80% by mass, and preferably 25% by mass to More preferably, it is 75 mass%, and it is especially preferable that it is 30 mass%-65 mass%. If it is less than 20% by mass, there is a tendency for plating to be peeled due to insufficient adhesion of the photosensitive layer, and if it exceeds 80% by mass, the cured product layer (resist pattern) is not peeled off and the cured product layer (resist pattern) tends to be brittle. There is.

  In the total amount of component (B), the content ratio of the nonylphenyl polyalkylene glycol (meth) acrylate compound represented by the general formula (3) is preferably 10% by mass to 40% by mass, and 15% by mass to 30%. More preferably, it is mass%. If it is less than 10% by mass, the peelability of the cured product layer (resist pattern) tends to deteriorate, and if it exceeds 40% by mass, insufficient adhesion of the photosensitive layer tends to occur.

  The amount of the photopolymerization initiator of the component (C) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B), and 0.2 to 10 It is more preferable that it is a mass part, and it is especially preferable that it is 2-5 mass parts. If this amount is less than 0.1 parts by mass, the photosensitivity tends to decrease, and if it exceeds 20 parts by mass, the absorption on the surface of the photosensitive layer increases during exposure and the internal photocuring tends to be insufficient. Tend.

  In addition to the components described above, the photosensitive resin composition may include, if necessary, a dye such as malachite green, a photochromic agent such as tribromophenyl sulfone or leuco crystal violet, a thermochromic inhibitor, p-toluenesulfonamide. Contains plasticizers, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion-imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc. Also good. It is preferable that the quantity of these components is about 0.01-20 mass parts, respectively with respect to 100 mass parts of total amounts of (A) component and (B) component. These are used alone or in combination of two or more.

  If necessary, the photosensitive resin composition of the present invention may be 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. It is preferably used in the state of a solution having a solid content of about 30 to 60% by mass.

  The solution of the photosensitive resin composition is applied to, for example, a metal surface and dried to form a photosensitive layer, and a protective film is coated as necessary to form a cured product layer (resist pattern). . The metal in this case is not particularly limited, and examples thereof include copper, copper-based alloys, iron-based alloys such as nickel, chromium, iron, and stainless steel, and adhesion to a cured product layer (resist pattern) and electronic conductivity. From the above viewpoint, copper, a copper-based alloy, and an iron-based alloy are preferable.

  Or the photosensitive resin composition of this invention is used suitably in the state of the photosensitive element. FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention. The photosensitive element 1 shown in FIG. 1 includes a support 10, a photosensitive layer 20 provided on the support 10, and a protective film 30 provided on the photosensitive layer 20.

  The photosensitive layer 20 is made of the above-described photosensitive resin composition of the present invention. Although the thickness of the photosensitive layer 20 changes with uses, it is preferable that it is 1-100 micrometers, and it is more preferable that it is 1-50 micrometers. If the thickness is less than 1 μm, it tends to be difficult to apply industrially, and if it exceeds 100 μm, the effect of the present invention is reduced, and the adhesive force and resolution tend to be reduced.

  The photosensitive layer 20 preferably has a transmittance for ultraviolet rays having a wavelength of 365 nm of 5 to 75%, more preferably 7 to 60%, and particularly preferably 10 to 40%. If this transmittance is less than 5%, the adhesion tends to decrease, and if it exceeds 75%, the resolution tends to decrease. This transmittance can be measured by a UV spectrometer. Examples of the UV spectrometer include a 228A type W beam spectrophotometer manufactured by Hitachi, Ltd.

  The photosensitive layer 20 is preferably formed by preparing a solution of the above-described photosensitive resin composition and applying it to the support 10. 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, or a bar coater. Moreover, drying can be performed at 70-150 degreeC and about 5 to 30 minutes.

  The support 10 preferably has a thickness of 5 to 25 μm, more preferably 8 to 20 μm, and particularly preferably 10 to 16 μm. If this thickness is less than 5 μm, the substrate tends to be broken when the support is peeled off before development, and if it exceeds 25 μm, the resolution tends to decrease.

  The haze of the support 10 is preferably 0.001 to 5.0, more preferably 0.001 to 2.0, and particularly preferably 0.01 to 1.8. When this haze exceeds 2.0, the resolution tends to decrease. The haze is measured according to JIS K 7105 and can be measured with a commercially available turbidimeter such as NDH-1001DP (trade name, manufactured by Nippon Denshoku Industries Co., Ltd.).

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

  The protective film 30 preferably has a thickness of 5 to 30 μm, more preferably 10 to 28 μm, and particularly preferably 15 to 25 μm. If the thickness is less than 5 μm, the protective film 30 tends to be broken during lamination, and if it exceeds 30 μm, the cost tends to be inferior.

  The tensile strength in the longitudinal direction of the protective film 30 is preferably 13 MPa or more, more preferably 13 to 100 MPa, still more preferably 14 to 100 MPa, and still more preferably 15 to 100 MPa, It is still more preferable that it is 16-100 MPa. When the tensile strength is less than 13 MPa, the protective film 30 tends to be easily broken during lamination.

  The tensile strength in the width direction of the protective film 30 is preferably 9 MPa or more, more preferably 9 to 100 MPa, still more preferably 10 to 100 MPa, still more preferably 11 to 100 MPa, Even more preferably, it is 12-100 MPa. If the tensile strength is less than 9 MPa, the protective film 30 tends to be easily broken during lamination.

  The tensile strength can be measured according to JIS C 2318-1997 (5.3.3), and can be measured with a commercial tensile strength tester such as Toyo Baldwin Co., Ltd. It is.

  Since the support 10 and the protective film 30 must be removable from the photosensitive layer 20 later, the support 10 and the protective film 30 should not have been subjected to a surface treatment that makes removal impossible, but are not particularly limited and necessary. Processing may be performed according to the above. The support 10 and the protective film 30 may be subjected to antistatic treatment as necessary.

  The photosensitive element of the present invention is not limited to the above embodiment, and has an intermediate layer and a protective layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer in addition to the photosensitive layer, the support and the protective film. May be.

  The photosensitive element 1 is stored, for example, as it is or by further stacking a protective film 30 on the other surface of the photosensitive layer 20 and winding it around a cylindrical core.

  Next, an embodiment of a method for producing a printed wiring board using the photosensitive resin composition of the present invention will be described. In the printed wiring board manufacturing method of this embodiment, the circuit-formed board is included in the printed wiring board and includes a circuit forming board and a circuit pattern (circuit conductor). The circuit formed substrate may have a through hole or the like, or may have a multilayer structure.

  In this embodiment, a resist is used. The resist is a coating material that masks or protects a specific area of the 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 a fine and accurate pattern is coated on a predetermined region with high accuracy by utilizing its photosensitivity to protect the object to be protected. In the method for producing a printed wiring board of the present invention, the resist is classified into two types depending on the purpose.

  One of them is a solder resist (surface resin layer), for example, it is formed by applying and exposing so that only the region where the joint part is formed is exposed by soldering and having a desired coating (protection) pattern It is. That is, the solder resist (surface resin layer) is formed so as to cover the entire surface of the circuit-formed substrate excluding the circuit pattern.

  The other is a plating resist. The plating resist is a cured product layer (resist pattern) formed so as to have a coating (protection) pattern that exposes only the region where electroless plating is performed by exposing a photosensitive layer using a photosensitive element. is there. That is, the cured product layer (resist pattern) is formed so as to cover the entire surface of the circuit-formed substrate where metal adhesion by plating such as a mounting pad portion is not desirable.

  Hereinafter, the present embodiment will be described in more detail with reference to the drawings. FIG. 2 is a process diagram showing an embodiment of a method for producing a printed wiring board of the present invention. In the embodiment shown in FIG. 2, first, a circuit formed substrate 80 on which a circuit pattern 50 is formed on a circuit forming substrate 40 and a surface resin layer (solder resist) 60 formed on the circuit formed substrate 80 are provided. A first laminated substrate 100 is prepared (FIG. 2A). The surface resin layer 60 has an opening 70 through which the exposed portion 50a of the circuit pattern 50 is exposed. 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 ((b) of FIG. 2).

  Next, the photosensitive layer 20 laminated on the circuit-formed substrate 80 is irradiated with an actinic ray 92 in an image form through the mask pattern 90 ((c) of FIG. 2). The mask pattern 90 includes a shielding portion 90 a that shields the active light beam 92 and a transparent portion 90 b that transmits the active light beam 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 the exposure, the support 10 and the unexposed portion are removed and developed to form a patterned cured product layer (resist pattern) 24 ((d) in FIG. 2). Thus, the 2nd multilayer substrate 200 provided with the surface resin layer 60 and the hardened | cured material layer (resist pattern) 24 in this order on the circuit-formed board | substrate 80 is obtained. The cured product layer (resist pattern) 24 is formed for the purpose of a plating resist so that the exposed portion 50a of the circuit pattern 50 is exposed. The cured product layer (resist pattern) 24 can be optionally post-cured thereafter.

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

  3 and 4 are process diagrams showing another embodiment of the method for manufacturing a printed wiring board according to the present invention. FIG. 3 shows the process up to the second process, and FIG. 4 shows the process of the third process. It is. In the first step shown in FIG. 3, first, a circuit-formed substrate 80 in which circuit patterns 50 and 51 are formed on a circuit-forming substrate 40 and a surface resin layer 60 formed on the circuit-formed substrate 80 are formed. A first laminated substrate 100 is prepared (FIG. 3A). The surface resin layer 60 has openings 70 through which the exposed portions 50a and 51a of the circuit patterns 50 and 51 are exposed. 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 ((b) of FIG. 3).

  In the second step, the photosensitive layer 20 laminated on the circuit-formed substrate 80 is irradiated with actinic rays 92 in an image form through the mask pattern 90 ((c) of FIG. 3). The mask pattern 90 includes a shielding portion 90 a that shields the active light beam 92 and a transparent portion 90 b that transmits the active light beam 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 the exposure, the support 10 and unexposed portions are removed and developed to form a patterned cured product layer (resist pattern) 24 ((d) in FIG. 3). Thus, the 2nd multilayer substrate 200 provided with the surface resin layer 60 and the hardened | cured material layer (resist pattern) 24 in this order on the circuit-formed board | substrate 80 is obtained. The cured product layer (resist pattern) 24 functions as a plating resist that covers a region such as the circuit pattern 51 where only the circuit pattern 50 for performing electroless plating is exposed and metal adhesion by plating is not preferable. The cured product layer (resist pattern) 24 can be optionally post-cured thereafter.

  In the third step shown in FIG. 4, 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 circuit pattern 50 is not masked. An Ni plating layer 55a is formed on the surface of the substrate ((e) of FIG. 4). Subsequently, substitution Au plating is performed to form an Au plating layer 55b on the Ni plating layer ((f) in FIG. 4). In this way, metal plating is applied only to a required portion, the cured product layer (resist pattern) 24 is peeled off, and the printed wiring board 300 ((g) in FIG. 4) having excellent reliability of the mounted component is obtained. obtain.

  2 and 3, for example, the photosensitive element 1 is laminated on a circuit forming substrate 40 so that the photosensitive layer 20 is in close contact with the circuit forming substrate 40, and the active light beam. Is formed through a process of forming a patterned surface resin layer 60 by a method of developing after irradiating the film in an image form and a process of forming a circuit pattern 50 by etching or plating using the surface resin layer 60 as a mask. The

In the first step, the photosensitive element 1 is laminated by removing the protective film 30 and then pressing the photosensitive layer 20 on the surface resin layer 60 while heating. At this time, it is preferable to laminate under reduced pressure from the viewpoint of adhesion and followability. More specifically, during lamination, the photosensitive layer 20 is preferably heated to 70 to 130 ° C., and the pressure is preferably about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ). If the photosensitive layer 20 is heated to 70 to 130 ° C. in this way, it is not necessary to pre-heat the circuit-formed substrate in advance, but in order to further improve the stackability, the circuit-formed substrate is pre-heated. May be.

  As the light source of the actinic ray 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 emits ultraviolet light, visible light, or the like is used. The mask pattern 90 is a negative or positive mask pattern called artwork.

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

  As the developer, an alkaline aqueous solution or the like is preferably used in terms of safety and stability and good operability. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium or potassium hydroxide, alkali carbonates such as lithium, sodium, potassium or ammonium carbonate or bicarbonate, potassium phosphate, sodium phosphate And alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate. Development methods include a dip method, a battle method, a spray method, brushing, and slapping, and the high pressure spray method is most suitable for improving the resolution.

  More specifically, the alkaline aqueous solution is a dilute solution of 0.1 to 5% by mass sodium carbonate, a dilute solution of 0.1 to 5% by mass potassium carbonate, a dilute solution of 0.1 to 5% by mass sodium hydroxide, A dilute solution of 0.1 to 5% by mass sodium tetraborate is 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 a photosensitive layer.

  In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed. In addition to the above substances, the alkaline substance used in this case includes borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol. 1,3-diaminopropanol-2, morpholine and the like. The pH of the developer is preferably as low as possible within a range where the resist can be sufficiently developed, preferably pH 8-12, more preferably pH 9-10.

  Examples of the organic solvent include triacetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether is mentioned. These are used alone or in combination of two or more. The concentration of the organic solvent is usually preferably 2 to 90% by mass, and the temperature can be adjusted according to the developability. A small amount of a surfactant, an antifoaming agent, or the like can be added to the aqueous developer mixed with an organic solvent.

  Examples of the organic solvent-based developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. These organic solvents preferably add water in the range of 1 to 20% by mass in order to prevent ignition. Moreover, you may use together 2 or more types of image development methods as needed.

As a treatment after development, the cured product layer (resist pattern) may be further cured by heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 mJ / cm ² as necessary.

  Examples of the electroless plating include electroless Ni plating. Metal plating such as gold, silver, palladium, platinum, rhodium, copper, and tin may be performed on the electroless Ni plating.

  The removal of the cured product layer (resist pattern) after the electroless plating can be performed, for example, by peeling with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development. As the strong alkaline aqueous solution, for example, a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution and the like are used. Examples of the peeling method include an immersion method and a spray method.

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

Examples 1-6 and comparative examples 7, 8, 1-4
(Synthesis of binder polymer 1)
Methacrylic acid, methyl methacrylate and styrene are copolymerized in a mass ratio of 28:60:12 to obtain a copolymer (binder polymer 1) having a weight average molecular weight of 60,000, a glass transition temperature of 124 ° C., and an acid value of 68 mgKOH / g. It was. The binder polymer 1 was dissolved in methyl cellosolve / toluene (6: 4, mass ratio) so that the nonvolatile component (solid content) was 50% by mass to obtain a solution of the binder polymer 1.

(Synthesis of Binder Polymer 2) As a comonomer, 130 g of methacrylic acid, 170 g of methyl methacrylate, 100 g of ethyl acrylate and 100 g of styrene were mixed with 3.0 g of azobisisobutyronitrile to prepare a solution α. did. To a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 500 g of a mixture of methyl cellosolve and toluene having a mass ratio of 3: 2 was added and stirred while blowing nitrogen gas, Heated to 85 ° C. The solution α was dropped therein over 4 hours, and the mixture was kept warm at 85 ° C. for 2 hours with stirring.

  Further, a solution in which 0.5 g of azobisisobutyronitryl was dissolved in 150 g of a mixture of methyl cellosolve and toluene having a mass ratio of 3: 2 was dropped into the flask over 10 minutes. The solution after dropping was kept at 85 ° C. for 5 hours with stirring, and then cooled to obtain a solution of binder polymer 2. The nonvolatile component (solid content) of the solution of the binder polymer 2 was 50.0% by mass, and the weight average molecular weight of the binder polymer 2 was 100,000.

The weight average molecular weight was measured by a gel permeation chromatography (GPC) method and was derived by conversion using a standard polystyrene calibration curve. The measurement conditions for GPC are shown below.
(GPC measurement conditions)
・ Pump: Hitachi L-6000 type [manufactured by Hitachi, Ltd.]
-Column: GelpackGL-R420 + GelpackGL-R430 + GelpackGL-R440 (3 in total) (above, product name, manufactured by Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran Measurement temperature: Room temperature Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI [manufactured by Hitachi, Ltd.]

  Tables 1 and 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, the component (A) and other additive components are mixed, and the component (B) and the component (C) are dissolved in this mixture to obtain a solution of the photosensitive resin composition. It was.

1: Mass as solid content 2: Bisphenol A polyethyleneethylene dimethacrylate: trade name of Shin-Nakamura Chemical Co., Ltd. (in the compound of general formula (1), R ¹ is a methyl group, X ¹ and X ² are ethylene Group, the average value of p + q is about 10)
3: Bisphenol A polyoxyethylene dimethacrylate: trade name of Shin-Nakamura Chemical Co., Ltd. (in the compound of general formula (1), R ¹ is a methyl group, X ¹ and X ² are ethylene groups, and the average value of 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 are hydrogen atoms, X ³ , X ⁴ and X ⁵ are ethylene The average value of k + m + n is about 9)
5: Nonylphenyl polyethylene glycol acrylate: Toa Gosei 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 4)
6: Nonylphenyl polyethylene glycol acrylate: Product name of Shin-Nakamura Chemical Co., Ltd. (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. Product name 8: Trimethylolpropane triacrylate: Shin-Nakamura Chemical Co., Ltd.

(Production of photosensitive element)
A solution of the photosensitive resin composition of Examples 1 to 6 and Comparative Examples 7, 8, and 1 to 4, a 16 μm thick polyethylene terephthalate film (haze: 1.7%, trade name GS-16, manufactured by Teijin Ltd.) ) Uniformly coated on the substrate, dried for 10 minutes with a hot air convection dryer at 100 ° C., and then protected with a polyethylene protective film to obtain a photosensitive element. The film thickness after drying of the photosensitive layer was 50 μm.

(Production of circuit-formed board)
12.5 cm long, 20 cm wide, 1.6 mm thick double-sided copper-clad epoxy laminate (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-61), leaving a 1 cm rim on the copper foil surface on one side Then, an etching resist having a predetermined pattern was formed. A portion of the copper foil not covered with the etching resist was removed by etching to form a circuit pattern having metal terminals (pads) and wiring. The remaining etching resist was peeled off to obtain a circuit-formed substrate. The entire back surface was etched so that the glass epoxy surface was exposed.

(Formation of surface resin layer)
Photoresist (manufactured by Taiyo Ink Manufacturing Co., Ltd., trade name: PSR-4000) was applied to the entire surface of the circuit-formed substrate obtained, leaving a peripheral edge of 1 cm, and dried at 80 ° C. for 30 minutes. . Then, the whole surface except the mounting pad part to plate was exposed using the exposure machine (Oak Manufacturing Co., Ltd. make, brand name: HMW-590) through the photo tool. The unexposed area is spray-developed with a 1% by weight aqueous sodium carbonate solution (30 ° C) for 60 seconds, the photoresist on the pad is removed to form a pattern, and then heated at 150 ° C for 1 hour to thermally cure. A surface resin layer (solder resist) was formed on the circuit-formed substrate.

(Formation of cured product layer (resist pattern))
Pressure is applied to the photosensitive layer (photosensitive resin composition layer) of the photosensitive element obtained in Examples 1 to 6 and Comparative Examples 7, 8, and 1 to 4 on both surfaces of the circuit-formed substrate provided with the surface resin layer. Lamination was performed at 0.4 MPa, a temperature of 110 ° C., and a laminating speed of 1.5 m / min. Of the laminated photosensitive layer, the entire surface excluding the circuit pattern to be subjected to electroless plating was exposed and spray-developed with a 1% by mass aqueous sodium carbonate solution (30 ° C.) for 80 seconds to form a cured product layer (resist pattern). .

  About the photosensitive element and laminated substrate which were obtained by the above, characteristic evaluation was performed with the following method. Tables 3 and 4 show the evaluation results.

(Plating resistance)
The laminated substrates obtained in Examples 1 to 6 and Comparative Examples 7, 8, and 1 to 4 were immersed in Pro Select SF (manufactured by Atotech Japan Co., Ltd., trade name) for 5 minutes at 50 ° C., and degreased. Went. After washing with running water for 1 minute at room temperature, it was immersed in Micro Etch SF (manufactured by Atotech Japan Co., Ltd., trade name) for 1 minute at 30 ° C. and subjected to a soft etching treatment. After washing with running water for 1 minute at room temperature, it was immersed in a 5% sulfuric acid solution for 1 minute at room temperature to perform pickling treatment.

  Thereafter, the multilayer substrate was immersed in electroless plating catalyst solution Aurotech 1000 (manufactured by Atotech Japan Co., Ltd., trade name) for 90 seconds at room temperature to activate. After washing with running water for 2 minutes at room temperature, electroless Ni plating was performed by immersing in Aurotech HP (trade name, manufactured by Atotech Japan Co., Ltd.) which is a Ni-P plating solution at 83 ° C. for 40 minutes.

  After washing with running water for 2 minutes at room temperature, 85% in Aurotech CS4000 (manufactured by Atotech Co., Ltd., Aurotech CS4000: 150 mL / L, potassium gold cyanide: 1.47 g / L, Aurotech SF: 1 mL / L) The substrate was immersed for 10 minutes at a temperature of 0 ° C., and substituted electroless Au plating was performed. As a post-treatment, it was washed with water and dried at 85 ° C. for 15 minutes.

About the laminated substrate in which the plating layer was formed in this manner, the presence or absence of tearing and swelling of the cured product layer (resist pattern) (particularly around the pad portion) was determined by the following criteria to evaluate the plating resistance. The evaluation results are shown in Tables 3 and 4. In addition, evaluation of plating property means that it is better that there is no tearing and swelling.
Judgment criteria A: No torn or swollen B: Some torn or swollen C: All torn or swollen

(Peelability)
Double-sided copper-clad epoxy laminate with 4cm length and 5cm thickness and 1.6mm thickness (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-61), a photoresist (manufactured by Taiyo Ink Manufacturing Co., Ltd., PSR) -4000) was coated on the entire surface and dried at 80 ° C. for 30 minutes.

  The entire surface of the laminated plate coated with the photoresist was exposed through a lattice-like phototool (mask pattern) 90 shown in FIG. The lattice-like phototool (mask pattern) 90 has a plurality of shielding portions 90a that shield active light rays and a transparent portion 90b that transmits active light rays. The shielding portions 90a are 2.6 mm in width (A in FIG. 5), 0.8 mm in length (B in FIG. 5), and are arranged with an interval of 0.45 mm (C in FIG. 5). An exposure machine (trade name: HMW-590, manufactured by Oak Manufacturing Co., Ltd.) was used for the exposure.

  After exposure, the unexposed part was spray-developed with a 1% by mass aqueous sodium carbonate solution (30 ° C.) for 60 seconds. Then, it heated at 150 degreeC for 1 hour, was hardened, and formed the surface resin layer (solder resist) on the said laminated board. The surface resin layer is formed with an opening through which a part of the copper of the laminated plate is exposed.

The photosensitive layers of the photosensitive elements of Examples 1 to 6 and Comparative Examples 7, 8, and 1-4 were applied to both sides of the laminate provided with the surface resin layer at a pressure of 0.4 MPa, a temperature of 110 ° C., and a laminating speed of 1. Lamination was performed under the condition of 5 m / min. The laminated photosensitive layer was subjected to overall exposure with an energy exposure amount such that the number of remaining steps after development in the stove 21-step tablet was 8.0, thereby forming a cured product layer. In this way, the evaluation laminated board which a hardened | cured material layer covers the upper and lower surfaces of the laminated board provided with the said surface resin layer was obtained.

  The laminate for evaluation was sprayed with a 1% by mass aqueous sodium carbonate solution (30 ° C.) for 80 seconds, and a plating treatment was performed in the same manner as in the evaluation of plating resistance. Then, it was immersed in 3 mass% sodium hydroxide aqueous solution heated at 50 degreeC, and peelability was evaluated by measuring time until a hardened | cured material layer peels from the laminated board provided with the said surface resin layer. The evaluation results are shown in Tables 3 and 4. The evaluation of peelability means that the shorter the time, the better.

(Resist stripping residue)
Adhering to the side wall (width 2.6 mm, height 0.8 mm, height 30 μm) of the opening portion of the surface resin layer (solder resist) by using the evaluation laminate after the peelability evaluation, without being completely peelable. The adhesion area of the cured product layer was observed. SEM (Hitachi Instrument Service Co., Ltd. SE-2100) was used for the observation of the adhesion area. A value obtained by dividing the obtained adhesion area by the side wall area (2.6 mm × 0.8 mm × 30 μm) of the opening is obtained, and an average value of values obtained for the five randomly selected openings is obtained. The ratio of the residue of the cured product layer (resist residue) was used. Based on the ratio of the obtained resist residue, the resist stripping residue was evaluated according to the following criteria. The evaluation results are shown in Tables 3 and 4. In addition, it means that it is so favorable that there are few resist residues.
Criteria A: Resist residue is less than 10% B: Resist residue is 10% or more and less than 50% C: Resist residue is 50% or more

(Plating bath contamination)
After peeling off the PET film and the polyethylene film from the photosensitive element 0.5 m ² obtained in Examples 1 to 6 and Comparative Examples 7, 8, and 1-4, the Ni-P plating solution Aurotech HP (Atotech Japan ( The product was immersed in a product name (trade name) at 83 ° C. for 5 hours, and an electroless Ni plating treatment was performed.

Using this plating treatment solution, the same processing as the above-described evaluation method for plating resistance, from the degreasing treatment to the electroless Ni plating, was performed on the test substrate, and the Ni-P plating film thickness (deposited film) deposited on the substrate. Thickness) was measured. The case where a new Ni-P plating solution Aurotech HP was used instead of the plating treatment solution was used as a blank, and the plating bath contamination was evaluated based on the relative value of the deposited film thickness when the deposited film thickness of the blank was 100. The evaluation results are shown in Tables 3 and 4. The plating bath contamination is determined by the following formula.
Plating bath contamination (%) = deposited film thickness of each sample (μm) / deposited film thickness of blank (μm)

(sensitivity)
The above-described copper-clad laminates were used for the photosensitive layers in the photosensitive elements obtained from Examples 1 to 6 and Comparative Examples 7, 8, and 1-4 under the conditions of pressure 0.4 MPa, temperature 110 ° C., and lamination speed 1.5 m / min. Laminated on a plate and laminated. On the obtained laminate, a stove 21-step tablet is placed as a negative, and using an exposure machine having a high-pressure mercury lamp lamp (201GX, manufactured by Oak Seisakusho), under the same development conditions as above, The sensitivity was evaluated by the amount of exposure energy (mJ / cm ² ) required to cure 8.0 step of the 21 step step tablet. The evaluation results are shown in Tables 3 and 4. Note that the lower the exposure energy amount, the higher the sensitivity.

From Table 3 and Table 4, it is clear that the photosensitive resin compositions of Examples 1 to 6 have good plating resistance, peelability and plating bath contamination when a cured product layer (resist pattern) is formed. It became. Moreover, these photosensitive elements also had good shape followability to the surface resin layer.

Claims (7)

A photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound having a polymerizable ethylenically unsaturated group, and (C) a photopolymerization initiator,
(B) component is
The bisphenol A-based (meth) acrylate compound represented by the following general formula (1) is 15% by mass to 40% by mass in the total amount of the component (B) .
The alkoxylated trimethylolpropane tri (meth) acrylate compound represented by the following general formula (2) is 30% by mass to 65% by mass in the total amount of the component (B) , and nonylphenyl represented by the following general formula (3) The photosensitive resin composition which contains a polyalkylene glycol (meth) acrylate compound in 15 mass%-30 mass% in the total amount of (B) component .

[In Formula (1), X ¹ and X ² each independently represent an alkylene group having 2 to 6 carbon atoms, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and p and q are p + q = Indicates a positive integer between 4 and 40,
In formula (2), X ³ , X ⁴ and X ⁵ each independently represent an alkylene group having 2 to 6 carbon atoms, R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, k , M and n are positive integers such that k + m + n = 3 to 30,
In 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 r represents an integer of 1 to 20. ]   The photosensitive resin composition of Claim 1 in which (C) component contains a 2,4,5-triaryl imidazole dimer. When the total amount of component (A) and component (B) is 100 parts by mass,
(A) The quantity of a component is 40-80 mass parts,
(B) The quantity of a component is 20-60 mass parts,
The photosensitive resin composition of Claim 1 whose quantity of (C) component is 0.1-20 mass parts.   A photosensitive element provided with a support body and the photosensitive layer which consists of the photosensitive resin composition as described in any one of Claims 1-3 provided on this support body.   The photosensitive element according to claim 4, wherein the photosensitive layer has a transmittance of 5 to 75% for ultraviolet rays having a wavelength of 365 nm. A circuit-forming substrate, a circuit-formed substrate having 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-formed substrate. The 1st process of laminating | stacking the photosensitive layer which consists of the photosensitive resin composition as described in any one of Claims 1-3 on the surface by the side of the said surface resin layer of a 1st multilayer substrate, and ,
A second portion of the photosensitive layer is irradiated with actinic rays and then developed to form a patterned cured product layer, and the surface resin layer and the cured product layer are provided in this order on the circuit-formed substrate. A second step of obtaining a laminated substrate of
A third step of performing electroless plating on the second laminated substrate to form a plating layer on the circuit pattern;
A method of manufacturing a printed wiring board comprising:   The manufacturing method according to claim 6, wherein the cured product layer is patterned so that a part of the circuit pattern is exposed, and the plating layer is formed on the entire exposed part of the circuit pattern.

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