KR101799845B1

KR101799845B1 - Photosensitive resin composition, dry film, and printed wiring board

Info

Publication number: KR101799845B1
Application number: KR1020167030261A
Authority: KR
Inventors: 미치야 히구치; 소이치 하시모토; 다카시 아라이; 히로노부 가와사토; 신지 이나바
Original assignee: 고오 가가쿠고교 가부시키가이샤; 신닛테츠 수미킨 가가쿠 가부시키가이샤
Priority date: 2015-11-02
Filing date: 2016-01-28
Publication date: 2017-11-22
Also published as: CN106796396A; WO2017077662A1; CN106796396B; TWI620012B; KR20170065463A; TW201716856A

Abstract

It is an object of the present invention to provide a photosensitive resin composition containing a carboxyl group-containing resin having a bisphenol fluorene skeleton, which is excellent in developability and in which cracks are not easily generated during repeated temperature changes in the cured product. The photosensitive resin deposit according to the present invention contains a carboxyl group-containing resin (A), an unsaturated compound, a photopolymerization initiator, and an epoxy compound. (A1) which is a reaction product of an epoxy compound having a bisphenol fluorene skeleton represented by the following formula (1) with an unsaturated group-containing carboxylic acid as a reactant and an acid anhydride, the carboxyl group-containing resin (A) Lt; / RTI > The epoxy compound contains a crystalline epoxy resin and an amorphous epoxy resin.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a dry film, a printed wiring board,

The present invention relates to a photosensitive resin composition, a dry film and a printed wiring board. More particularly, the present invention relates to a photosensitive resin composition suitable for forming an electrically insulating layer such as a solder resist layer, a plating resist layer, an etching resist layer, Compositions and the like.

BACKGROUND ART Conventionally, an electric insulating resin composition is used for forming an electric insulating layer such as a solder resist layer, a plating resist layer, an etching resist layer, and an interlayer insulating layer of a printed wiring board. Such a resin composition is, for example, a photosensitive resin composition.

It has been proposed to incorporate a carboxyl group-containing resin having a bisphenol fluorene skeleton in the photosensitive resin composition in order to impart high heat resistance to the layer formed by the photosensitive resin composition. For example, Japanese Patent No. 4508929 discloses the use of a carboxyl group-containing resin having a fluorene skeleton obtained by reacting fluorene epoxy (meth) acrylate with a polyvalent carboxylic acid or anhydride thereof.

However, the developability of a photosensitive resin composition containing a carboxyl group-containing resin having a bisphenol fluorene skeleton is low. By using such a photosensitive resin composition, an electric insulating layer such as a solder resist layer or an interlayer insulating layer can be formed by photolithography , It was difficult to manufacture the film with sufficient thickness. Further, even if the heat resistance of the layer formed of the above-described photosensitive resin composition can be improved, cracks may occur in such a layer during repeated temperature changes including temperature rise and temperature drop.

Japanese Patent No. 4508929

It is an object of the present invention to provide a photosensitive resin composition which can obtain excellent developability even when the photosensitive resin composition contains a carboxyl group-containing resin having a bisphenol fluorene skeleton and can prevent cracks from easily occurring during repeated temperature changes in the cured product A printed wiring board having a solder resist layer containing a cured product of the photosensitive resin composition, and an interlayer insulating layer containing a cured product of the photosensitive resin composition A printed wiring board, and a process for producing the photosensitive resin composition.

The photosensitive resin composition according to one aspect of the present invention is a photosensitive resin composition comprising a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenic unsaturated bond in one molecule, a photopolymerization initiator (C) (1), R ₁ to R ₈ are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, and a bisphenol Containing resin (A1) which is a reaction product of an epoxy compound (a1) having a fluorene skeleton and an unsaturated group-containing carboxylic acid (a2) and an acid anhydride,

The epoxy compound (D) contains a crystalline epoxy resin and an amorphous epoxy resin, wherein the amount of the crystalline epoxy resin and the amount of the amorphous epoxy resin contained in the amorphous epoxy resin relative to 1 equivalent of the carboxyl group contained in the carboxyl- And the total amount of equivalents of epoxy groups is in the range of 0.7 to 2.5.

The dry film according to one aspect of the present invention contains the above photosensitive resin composition.

A printed wiring board according to one aspect of the present invention comprises an interlayer insulating layer containing a cured product of the photosensitive resin composition.

A printed wiring board according to one aspect of the present invention comprises a solder resist layer containing a cured product of the photosensitive resin composition.

Figs. 1A to 1E are cross-sectional views showing a step of manufacturing a multilayered printed circuit board according to an embodiment of the present invention.

Hereinafter, an embodiment of the present invention will be described. In the following description, "(meth) acrylic" means at least one of "acrylic" and "methacrylic". For example, (meth) acrylate means at least one of acrylate and methacrylate.

The photosensitive resin composition according to the present embodiment is a photosensitive resin composition comprising a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenic unsaturated bond in one molecule, a photopolymerization initiator (C) .

The carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1) having a bisphenol fluorene skeleton.

The carboxyl group-containing resin (A1) is, for example, a reaction product of an intermediate compound which is a reaction product of an epoxy compound (a1) and an unsaturated group-containing carboxylic acid (a2) and an acid anhydride. The epoxy compound (a1) is represented by the following formula (1), and in the formula (1), R ₁ to R ₈ each independently represent a hydrogen, an alkyl group having 1 to 5 carbon atoms, or a halogen, and a bisphenol fluorene skeleton.

The carboxyl group-containing resin (A1) is synthesized by reacting the epoxy compound (a1) with an unsaturated carboxylic acid (a2), and reacting the resulting intermediate with an acid anhydride.

Each of R ₁ to R ₈ in the formula (1) may be hydrogen, but may be an alkyl group having 1 to 5 carbon atoms or halogen. This is because even if the hydrogen in the aromatic ring is substituted with a low molecular weight alkyl group or halogen, the physical properties of the carboxyl group-containing resin (A1) are not adversely affected, and rather the heat resistance of the cured product of the photosensitive resin composition Or the flame retardancy may be improved.

The carboxyl group-containing resin (A1) will be described in more detail. In order to synthesize the carboxyl group-containing resin (A1), an intermediate is synthesized by first reacting at least part of the epoxy group (see Formula (2)) of the epoxy compound (a1) with the carboxylic acid (a2) containing an unsaturated group. The intermediate has a structure (S3) represented by the following formula (3), which is formed by a ring-opening addition reaction between an epoxy group and an unsaturated group-containing carboxylic acid (a2). That is, the intermediate has a secondary hydroxyl group formed in the structure (S3) by a ring-opening addition reaction between an epoxy group and an unsaturated carboxylic acid (a2). In the formula (3), A is an unsaturated group-containing carboxylic acid residue.

Next, a secondary hydroxyl group in the intermediate is reacted with an acid anhydride. Thus, the carboxyl group-containing resin (A1) can be synthesized.

The acid anhydride may contain at least one of the acid dianhydride (a3) and the acid anhydride (a4). When the acid anhydride contains the acid anhydride (a4), the carboxyl group-containing resin (A1) has the bisphenol fluorene skeleton (S1) represented by the formula (1) and the structure (S4) represented by the following formula .

The structure S4 is formed by reacting a secondary hydroxyl group in the structure (S3) of the intermediate and an acid anhydride group in the acid anhydride (a4). In the formula (4), A is an unsaturated group-containing carboxylic acid residue and B is a aniline anhydride residue.

When the acid anhydride contains an acid anhydride (a3), the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton (S1) and a structure (S5) represented by the following formula (5).

The structure S5 is formed by reacting two acid anhydride groups in the acid dianhydride (a3) and two secondary hydroxyl groups in the intermediate, respectively. That is, the structure S5 is formed by crosslinking the acid anhydrides a3 between two secondary hydroxyl groups. There may be a case where two secondary hydroxyl groups existing in one molecule of the intermediate are crosslinked and a case where two secondary hydroxyl groups respectively present in two molecules of the intermediate are crosslinked. When two secondary hydroxyl groups present in two molecules of the intermediate are cross-linked, the molecular weight increases. In the formula (5), A is an unsaturated group-containing carboxylic acid residue, and D is an acid anhydride residue.

The carboxyl group-containing resin (A1) can be obtained by reacting a secondary hydroxyl group in the intermediate with an acid anhydride. When the acid anhydride contains the acid anhydride (a3) and the acid anhydride (a4), a part of the secondary hydroxyl group in the intermediate is reacted with the acid anhydride (a3), and a part of the secondary hydroxyl group in the intermediate and the acid anhydride a4) is reacted. Thus, the carboxyl group-containing resin (A1) can be synthesized. In this case, the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton (S1), a structure (S4) and a structure (S5).

The carboxyl group-containing resin (A1) may also have the structure (S6) represented by the following formula (6). The structure (S6) is formed by reacting only one of the two acid anhydride groups in the acid dianhydride (a3) with a secondary hydroxyl group in the intermediate. In the formula (6), A is an unsaturated group-containing carboxylic acid residue and D is an acid anhydride residue.

In the case where a part of the epoxy group in the epoxy compound (a1) remains unreacted during the synthesis of the intermediate, the carboxyl group-containing resin (A1) may have the structure (S2) represented by the formula (2) . Further, in the case where a part of the structure (S3) in the intermediate remains unreacted, the carboxyl group-containing resin (A1) may have the structure (S3).

When the acid anhydride contains the acid anhydride (a3), the number of the structure (S2) and the number of the structure (S6) in the carboxyl group-containing resin (A1) is reduced by optimizing the reaction conditions in the synthesis of the carboxyl group- , Or the structure (S2) and the structure (S6) are almost removed from the carboxyl group-containing resin (A1).

As described above, the carboxyl group-containing resin (A1) has a structure (S4) when it has a bisphenol fluorene skeleton (S1) and the acid anhydride contains the acid anhydride (a4), the acid anhydride is the acid anhydride ), It may have structure S5. When the acid anhydride contains the acid anhydride (a4), the carboxyl group-containing resin (A1) may have at least one of the structure (S2) and the structure (S3). When the acid anhydride contains the acid anhydride (a3), the carboxyl group-containing resin (A1) may have at least one of the structure (S2) and the structure (S6). When the acid anhydride contains the acid anhydride (a4) and the acid dianhydride (a3), the carboxyl group-containing resin (A1) has at least one of the structure (S2), the structure (S3) and the structure (S6) .

When the epoxy compound (a1) itself has a hydroxyl group having a secondary hydroxyl group, that is, for example, when n = 1 or more in the formula (7) described below, the carboxyl group- ) May be formed by reacting a hydroxyl group of a second grade with an acid anhydride.

The structure of the above-mentioned carboxyl group-containing resin (A1) is reasonably deduced based on technical common sense, and it is practically impossible to specify the structure of the carboxyl group-containing resin (A1) by analysis. The reason for this is as follows. When the epoxy compound (a1) itself has a secondary hydroxyl group (for example, when n is 1 or more in the formula (7)), depending on the number of secondary hydroxyl groups in the epoxy compound (a1) (A1) is greatly changed. When the intermediate and the acid anhydride (a3) react with each other, as described above, when two secondary hydroxyl groups present in one molecule of the intermediate are cross-linked with the acid dianhydride (a3) There may be a case where the two secondary hydroxyl groups present in each molecule are cross-linked with the acid anhydride (a3). For this reason, the finally obtained carboxyl group-containing resin (A1) contains a plurality of molecules having different structures from each other and the structure thereof can not be specified even when the carboxyl group-containing resin (A1) is analyzed.

The carboxyl group-containing resin (A1) has an ethylenically unsaturated group derived from an unsaturated group-containing carboxylic acid (a2) and thus has photoreactive properties. Therefore, the carboxyl group-containing resin (A1) can impart photosensitivity (specifically, ultraviolet curable property) to the photosensitive resin composition. Further, since the carboxyl group-containing resin (A1) has a carboxyl group derived from an acid anhydride, it is possible to impart developability to the photosensitive resin composition by an alkaline aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide. When the acid anhydride contains the acid anhydride (a3), the molecular weight of the carboxyl group-containing resin (A1) depends on the number of bridges by the acid dianhydride (a3). Therefore, a carboxyl group-containing resin (A1) having an acid value and a molecular weight appropriately adjusted can be obtained. When the acid anhydride contains the acid dianhydride (a3) and the acid anhydride (a4), the amount of the acid dianhydride (a3) and the acid anhydride (a4) and the amount of the acid anhydride (a4) relative to the acid dianhydride (a3) , A carboxyl group-containing resin (A1) having a desired molecular weight and acid value can be easily obtained.

The weight average molecular weight of the carboxyl group-containing resin (A1) is preferably in the range of 1000 to 5000. When the weight average molecular weight is 1000 or more, the tackiness of the film formed from the photosensitive resin composition is further suppressed, and the insulation reliability and corrosion resistance of the cured product are further improved. When the weight average molecular weight is 5,000 or less, the developability of the photosensitive resin composition with the alkaline aqueous solution is particularly improved.

It is preferable that the solid content of the carboxyl group-containing resin (A1) is in the range of 60 to 140 mgKOH / g. In this case, the developability of the photosensitive resin composition is particularly improved. The solid content is more preferably in a range of 80 to 135 mgKOH / g, and still more preferably in a range of 90 to 130 mgKOH / g.

The weight average molecular weight (Mw) of the carboxyl group-containing resin (A1) is calculated from the molecular weight measurement result by gel permeation chromatography. Molecular weight measurement in gel, permeation, and chromatography can be performed, for example, under the following conditions.

GPC apparatus: SHODEX SYSTEM 11 manufactured by Showa Denko KK,

Column: SHODEX KF-800P, KF-005, KF-003 and KF-001 are connected in series.

Mobile phase: THF,

Flow rate: 1 ml / min,

Column temperature: 45 캜,

Detector: RI,

Conversion: Polystyrene.

The reaction conditions in the synthesis of the raw material of the carboxyl-containing resin (A1) and the carboxyl-containing resin (A1) will be described in detail.

The epoxy compound (a1) has, for example, a structure (S7) represented by the following formula (7). N in the formula (7) is, for example, a number in the range of 0 to 20. To make the molecular weight of the carboxyl-containing resin (A1) to a suitable value, it is particularly preferable that the average of n is within the range of 0 to 1. When the average of n is in the range of 0 to 1, particularly when the acid anhydride contains the acid dianhydride (a3), the increase in the excess molecular weight due to the addition of the acid dianhydride (a3) tends to be suppressed.

The unsaturated group-containing carboxylic acid (a2) may contain, for example, a compound having only one ethylenically unsaturated group in one molecule. More specifically, the unsaturated group-containing carboxylic acid (a2) may be, for example, acrylic acid, methacrylic acid, omega -carboxy-polycaprolactone (n≈2) monoacrylate, crotonic acid, cinnamic acid, 2- Acryloyloxyethylphthalic acid, 2-acryloyloxypropylphthalic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethylphthalic acid, 2- Methacryloyloxyethyl maleic acid,? -Carboxyethyl acrylate, 2-acryloyloxyethyltetrahydrophthalic acid, 2-methacryloyloxypropyl methacrylate, 2-acryloyloxyethyl methacrylate, At least one compound selected from the group consisting of ethyltetrahydrophthalic acid, 2-acryloyloxyethylhexahydrophthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid. The unsaturated group-containing carboxylic acid (a2) preferably contains acrylic acid.

In the reaction of the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2), a known method may be employed. For example, a reactive solution is obtained by adding an unsaturated carboxylic acid (a2) to a solvent solution of the epoxy compound (a1), and if necessary, a thermal polymerization inhibitor and a catalyst are added and stirred. This reaction solution is reacted by a conventional method, preferably at a temperature of 60 to 150 캜, particularly preferably at a temperature of 80 to 120 캜 to obtain an intermediate. Examples of the solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbon solvents such as toluene and xylene; and aromatic hydrocarbons such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, At least one component selected from the group consisting of acetic acid esters such as carbitol acetate and propylene glycol monomethyl ether acetate, and dialkyl glycol ethers. The heat polymerization inhibitor contains, for example, at least one of hydroquinone and hydroquinone monomethyl ether. Examples of the catalyst include, for example, tertiary amines such as benzyldimethylamine and triethylamine, quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride, triphenylphosphine, and triphenylphosphine And at least one kind of component selected from the group consisting of

It is preferred that the catalyst contains, in particular, triphenylphosphine. That is, it is preferable to react the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2) in the presence of triphenylphosphine. In this case, the ring-opening addition reaction of the epoxy group with the unsaturated group-containing carboxylic acid (a2) in the epoxy compound (a1) is particularly promoted, and the reaction rate of 95% or more, 97% Rate)) can be achieved. As a result, an intermediate having structure (S3) can be obtained in high yield. Further, the occurrence of ion migration in the layer containing the cured product of the photosensitive resin composition is suppressed, and the insulation reliability of the same layer is further improved.

The amount of the unsaturated group-containing carboxylic acid (a2) relative to 1 mole of the epoxy group of the epoxy compound (a1) when the epoxy compound (a1) is reacted with the unsaturated group-containing carboxylic acid (a2) is preferably within a range of 0.8 to 1.2 moles . In this case, a photosensitive resin composition having excellent photosensitivity and storage stability can be obtained.

The epoxy compound (a1) and the unsaturated group-containing carboxylic acid (a2) are preferably reacted under air bubbling. In this case, the addition polymerization reaction of the unsaturated group is suppressed, so that the increase of the molecular weight of the intermediate and the gelation of the solution of the intermediate can be suppressed. In addition, excessive coloring of the carboxyl group-containing resin (A1) as the final product can be suppressed.

The intermediate thus obtained has a hydroxyl group generated by the reaction between the epoxy group of the epoxy compound (a1) and the carboxyl group of the unsaturated carboxylic acid (a2).

The acid dianhydride (a3) is a compound having two acid anhydride groups. The acid dianhydride (a3) may contain an anhydride of the tetracarboxylic acid. The acid dianhydride (a3) is, for example, 1,2,4,5-benzene tetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, methylcyclohexene tetracarboxylic dianhydride, tetracarboxylic dianhydride, naphthalene -1,4,5,8-tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride, glycerin bisanhydrotrimellitate mono Acetate, ethylene glycol bisanhydrotrimellitate, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro- 1,2-c] furan-1,3-dione, 1,2,3,4-butane tetracarboxylic dianhydride, and 3,3 ', 3,3'- 4,4'-biphenyltetracarboxylic dianhydride, and 4,4'-biphenyltetracarboxylic dianhydride. It is particularly preferable that the acid dianhydride (a3) contains 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride. That is, it is preferable that D in the formulas (5) and (6) includes a 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride residue. In this case, the adhesiveness of the film formed from the photosensitive resin composition can be further suppressed while ensuring good developability of the photosensitive resin composition, and the insulation reliability and corrosion resistance of the cured product can be further improved. The amount of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride to the entire acid dianhydride (a3) is preferably in the range of 20 to 100 mol%, more preferably in the range of 40 to 100 mol% , And is not limited to the above-mentioned range.

The acid anhydride (a4) is a compound having one acid anhydride group. The acid anhydride (a4) may contain an anhydride of dicarboxylic acid. The acid anhydrides (a4) include, for example, phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, At least one selected from the group consisting of anhydride, methylsuccinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, &Lt; / RTI > species. It is particularly preferable that the acid anhydride (a4) contains 1,2,3,6-tetrahydrophthalic anhydride. That is, it is preferable that the acid anhydride contains 1,2,3,6-tetrahydrophthalic anhydride. That is, it is preferable that the carboxyl group-containing resin (A1) has the structure (S4) and the B in the formula (4) includes the 1,2,3,6-tetrahydrophthalic anhydride residue. In this case, it is possible to further suppress the tackiness of the film formed of the photosensitive resin composition while ensuring good developability of the photosensitive resin composition, and further improve the insulation reliability and corrosion resistance of the cured product. The amount of 1,2,3,6-tetrahydrophthalic anhydride is preferably in the range of 20 to 100 mol%, more preferably in the range of 40 to 100 mol%, based on the entirety of the acid anhydride (a4) But is not limited to the range.

In the reaction of the intermediate and the acid anhydride, a known method may be employed. For example, an acid anhydride is added to a solvent solution of an intermediate, and if necessary, a thermal polymerization inhibitor and a catalyst are added and stirred to obtain a reactive solution. The reaction solution is reacted at a temperature of preferably 60 to 150 占 폚, particularly preferably 80 to 120 占 폚 by a conventional method to obtain a carboxyl group-containing resin (A1). The solvent, the catalyst and the polymerization inhibitor may be appropriately used, and the solvent, catalyst and polymerization inhibitor used in the synthesis of the intermediate may be used as they are.

The catalyst is particularly preferably containing triphenylphosphine. That is, it is preferable to react the intermediate with an acid anhydride in the presence of triphenylphosphine. In this case, the reaction between the secondary hydroxyl group and the acid anhydride in the intermediate is particularly promoted, so that a reaction rate (conversion rate) of 90% or more, 95% or more, 97% or more, or almost 100% can be achieved. Therefore, a carboxyl group-containing resin (A1) having at least one of the structure (S4) and the structure (S5) can be obtained in a high yield. Further, the occurrence of ion migration in the layer containing the cured product of the photosensitive resin composition is suppressed, and the insulation reliability of the same layer is further improved.

When the acid anhydride contains the acid dianhydride (a3) and the acid anhydride (a4), the amount of the acid dianhydride (a3) is preferably in the range of 0.05 to 0.24 mol per mol of the epoxy group of the epoxy compound (a1). The amount of the acid anhydride (a4) is preferably in the range of 0.3 to 0.7 mole based on 1 mole of the epoxy group of the epoxy compound (a1). In this case, a carboxyl group-containing resin (A1) having an acid value and a molecular weight appropriately adjusted can be easily obtained.

The carboxyl group-containing resin (A) may contain only the carboxyl group-containing resin (A1) or may further contain a carboxyl group-containing resin (hereinafter also referred to as a carboxyl group-containing resin (F)) other than the carboxyl group-containing resin (A1).

The carboxyl group-containing resin (F) may contain, for example, a compound having a carboxyl group and no photopolymerization (hereinafter referred to as component (F1)). The component (F1) contains, for example, a polymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated compound having a carboxyl group may contain a compound such as acrylic acid, methacrylic acid, omega -carboxy-polycaprolactone (n 2) monoacrylate, and the like. The ethylenically unsaturated compound having a carboxyl group may also contain a reaction product of pentaerythritol triacrylate, pentaerythritol trimethacrylate, and the like with a dibasic anhydride. The ethylenically unsaturated monomer is selected from the group consisting of 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, a linear or branched aliphatic or alicyclic (Meth) acrylic acid esters, which may have an unsaturated bond, or an unsaturated ethylenic unsaturated compound having no carboxyl group.

The carboxyl group-containing resin (F) may also contain a compound having a carboxyl group and an ethylenically unsaturated group (hereinafter referred to as a (F2) component). The carboxyl group-containing resin (F) may contain only the component (F2). The component (F2) is selected from, for example, an intermediate which is a reaction product of an epoxy compound (g1) having two or more epoxy groups in one molecule with an ethylenically unsaturated compound (g2), a polyvalent carboxylic acid and an anhydride thereof (Referred to as a first resin (g)) which is a reaction product with at least one kind of compound (g3). The first resin (g) is obtained, for example, by adding a compound (g3) to an intermediate obtained by reacting an epoxy group in the epoxy compound (g1) with a carboxyl group in the ethylenically unsaturated compound (g2). The epoxy compound (g1) may contain an appropriate epoxy resin such as cresol novolak type epoxy resin, phenol novolak type epoxy resin and the like. The epoxy compound (g1) may contain a polymer of the ethylenically unsaturated compound (h). The ethylenically unsaturated compound (h) contains, for example, a compound (h1) having an epoxy group such as glycidyl (meth) acrylate or an epoxy group such as 2- (meth) acryloyloxyethyl phthalate Containing compound (h2). The ethylenically unsaturated compound (92) preferably contains at least one of acrylic acid and methacrylic acid. The compound (g3) contains, for example, at least one compound selected from the group consisting of polyvalent carboxylic acids such as phthalic acid, tetrahydrophthalic acid and methyltetrahydrophthalic acid and anhydrides of these polyvalent carboxylic acids.

The component (F2) may contain a resin (referred to as a second resin (i)) which is a reaction product of a polymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated compound having a carboxyl group and an ethylenically unsaturated compound having an epoxy group . The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group. The second resin (i) is obtained by reacting an ethylenically unsaturated compound having an epoxy group with a part of the carboxyl groups in the polymer. The ethylenically unsaturated monomer may further contain an ethylenic unsaturated compound having no carboxyl group. Examples of the ethylenically unsaturated compound having a carboxyl group include acrylic acid, methacrylic acid,? -Carboxy-polycaprolactone (n? 2) monoacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate &Lt; / RTI > Examples of the ethylenically unsaturated compound having no carboxyl group include 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, a linear or branched aliphatic or alicyclic (Meth) acrylate ester of an alicyclic group (which may have some unsaturated bonds in the ring). The ethylenically unsaturated compound having an epoxy group preferably contains glycidyl (meth) acrylate.

The carboxyl group-containing resin (A) contains only the carboxyl group-containing resin (A1) or contains the carboxyl group-containing resin (A1) and the carboxyl group-containing resin (F). The carboxyl group-containing resin (A) preferably contains 30 mass% or more of the carboxyl group-containing resin (A1), more preferably 50 mass% or more, and further preferably 100 mass%. In this case, the heat resistance and insulation reliability of the cured product of the photosensitive resin composition can be particularly improved. Further, the adhesiveness of the coating film formed from the photosensitive resin composition can be sufficiently reduced. Further, the developability of the photosensitive resin composition with an alkaline aqueous solution can be secured.

Next, components other than the carboxyl group-containing resin (A) contained in the photosensitive resin composition according to the present embodiment will be described.

As described above, the photosensitive resin composition is prepared by mixing the carboxyl group-containing resin (A), the unsaturated compound (B) having at least one ethylenic unsaturated bond in one molecule, the photopolymerization initiator (C) .

The unsaturated compound (B) can impart photo-curability to the photosensitive resin composition. The unsaturated compound (B) includes, for example, monofunctional (meth) acrylate such as 2-hydroxyethyl (meth) acrylate; Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (Meth) acrylate such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (metha) acrylate, epsilon -caprolactone-modified pentaerythritol hexaacrylate, and tricyclodecanedimethanol di (Meth) acrylate, and the like.

In particular, the unsaturated compound (B) preferably contains a trifunctional compound, that is, a compound having three unsaturated bonds in one molecule. In this case, the resolution when the film formed from the photosensitive resin composition is exposed and developed is improved, and the developability of the photosensitive resin composition with the alkaline aqueous solution is particularly improved. The trifunctional compound may be, for example, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated isocyanuric acid tri (Meth) acrylate and ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate and ethoxylated glycerin tri (meth) acrylate.

It is also preferable that the unsaturated compound (B) contains a phosphorus-containing compound (phosphorus-containing unsaturated compound). In this case, the flame retardancy of the cured product of the photosensitive resin composition is improved. The phosphorus-containing unsaturated compound is, for example, 2-methacryloyloxyethyl acid phosphate (specific name light ester P-1M and light ester P-2M manufactured by Kyowa Chemical Industry Co., Ltd.), 2 -Acryloyloxyethyl acid phosphate (specific examples are L-acrylate P-1A manufactured by Kyowa Chemical Industry Co., Ltd.), diphenyl-2-methacryloyloxyethyl phosphate Manufactured by Showa Denko K.K.), and HFA series manufactured by Showa Highpolymer Co., Ltd. (specific examples include dipentaerythritol hexaacrylate and HCA (9,10-dihydro-9-oxa-10 (HFA-6003, HFA-6007), caprolactone-modified dipentaerythritol hexaacrylate and HCA (9,10-dihydro-9-oxa-10- Phosphaphenanthrene-10-oxide) and It may contain at least one compound selected from the group consisting of addition reaction, such as the part number HFA-3003, and HFA-6127).

The unsaturated compound (B) may contain a prepolymer. The prepolymer may contain at least one compound selected from the group consisting of, for example, a prepolymer obtained by polymerizing a monomer having an ethylenically unsaturated bond and then adding an ethylenically unsaturated group, and an oligomer (meth) acrylate prepolymer . Examples of the oligomeric (meth) acrylate prepolymers include epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) (Meth) acrylate, and a spirane resin (meth) acrylate.

The photopolymerization initiator (C) contains, for example, an acylphosphine oxide-based photopolymerization initiator (C1). That is, the photosensitive resin composition contains, for example, an acylphosphine oxide-based photopolymerization initiator (C1). In this case, although the photosensitive resin composition contains the carboxyl group-containing resin (A1), the photosensitive resin composition can impart high photosensitivity to ultraviolet rays. Further, the occurrence of ion migration in the layer containing the cured product of the photosensitive resin composition is suppressed, and the insulation reliability of the same layer is further improved.

In addition, the acylphosphine oxide-based photopolymerization initiator (C1) hardly hinders the electrical insulation of the cured product. Therefore, a cured product having excellent electrical insulation can be obtained by exposure curing the photosensitive resin composition. The cured product is preferably used as, for example, a solder resist layer, a plating resist layer, an etching resist layer, and an interlayer insulating layer .

Examples of the acylphosphine oxide-based photopolymerization initiator (C1) include monoacylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzoylethylphenylphosphinate (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) Bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylphenyl) phosphine oxide, bis- Trimethylbenzoyl) phenylphosphine oxide, and (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide, and the like as a group consisting of a bisacylphosphine oxide-based photopolymerization initiator Is selected site may contain a component of at least one. In particular, the acylphosphine oxide-based photopolymerization initiator (C1) preferably contains 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the acylphosphine oxide-based photopolymerization initiator (C1) - trimethylbenzoyldiphenylphosphine oxide alone.

The photopolymerization initiator (C) preferably contains a hydroxyketone-based photopolymerization initiator (C2) in addition to the acylphosphine oxide-based photopolymerization initiator (C1). That is, the photosensitive resin composition preferably contains a hydroxyketone-based photopolymerization initiator (C2). In this case, as compared with the case where the hydroxyketone-based photopolymerization initiator (C2) is not contained, a further higher photosensitivity can be imparted to the photosensitive resin composition. Thus, when the coating film formed from the photosensitive resin composition is cured by irradiating ultraviolet rays, it becomes possible to sufficiently cure the coating film from its surface to the deep portion. Examples of the hydroxyketone-based photopolymerization initiator (C2) include 1-hydroxy-cyclohexyl-phenyl-ketone, phenylglyoxyacid methyl ester, 1- [4- (2-hydroxyethoxy) Hydroxy-2-methylpropan-1-one, 2-hydroxy-1- {4- [4- (2- Methyl-prop-1-one and 2-hydroxy-2-methyl-1-phenyl-propan-1-one.

The mass ratio of the acylphosphine oxide-based photopolymerization initiator (C1) to the hydroxyquat-based photopolymerization initiator (C2) is preferably in the range of 1: 0.01 to 1:10. In this case, the curability near the surface of the coating film formed from the photosensitive resin composition and the curability at the deep portion can be improved to a good balance.

It is also preferable that the photopolymerization initiator (C) contains bis (diethylamino) benzophenone (C3). That is, when the photosensitive resin composition contains an acylphosphine oxide photopolymerization initiator (C1) and bis (diethylamino) benzophenone (C3), or an acylphosphine oxide photopolymerization initiator (C1), a hydroxyketone photopolymerization initiator (C2) and bis (diethylamino) benzophenone (C3). In this case, when the coating film formed from the photosensitive resin composition is partially exposed and then developed, the curing of the unexposed portion is suppressed, so that the resolution is particularly high. Therefore, a cured product of the photosensitive resin composition in a very fine pattern can be formed. Particularly, in the case where an interlayer insulating layer of a multilayer printed wiring board is manufactured from a photosensitive resin composition, and a small-diameter hole for a through hole is formed in this interlayer insulating layer by photolithography (see FIG. 1 ), It is possible to precisely and easily form a hole with a small diameter.

The amount of bis (diethylamino) benzophenone (C3) relative to the acylphosphine oxide-based photopolymerization initiator (C1) is preferably within a range of 0.5 to 20 mass%. When the amount of bis (diethylamino) benzophenone (C3) relative to the acylphosphine oxide-based photopolymerization initiator (C1) is 0.5% by mass or more, the resolution is particularly high. When the amount of bis (diethylamino) benzophenone (C3) relative to the acylphosphine oxide-based photopolymerization initiator (C1) is 20 mass% or less, the electric insulation of the cured product of the photosensitive resin composition is changed to bis (diethylamino) Phenon (C3) is difficult to inhibit.

The photosensitive resin composition may also contain known photopolymerization accelerators, sensitizers, and the like. For example, the photosensitive resin composition may include benzoin and its alkyl ethers; Acetophenones such as acetophenone and benzyl dimethyl ketal; Anthraquinones such as 2-methyl anthraquinone; Dioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone and 2,4- ; Benzophenones such as benzophenone and 4-benzoyl-4'-methyldiphenyl sulfide; Xanthones such as 2,4-diisopropylxanthone; And 2-hydroxy-2-methyl-1-phenylpropan-1-one; A compound containing a nitrogen atom such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone or the like . The photosensitive resin composition may contain, together with the photopolymerization initiator (C), a known photopolymerization accelerator such as a tertiary amine type such as p-dimethylbenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester or 2-dimethylaminoethyl benzoate A sensitizer, and the like. The photosensitive resin composition may contain at least one of a photopolymerization initiator for visible light exposure and a photopolymerization initiator for near-infrared exposure, if necessary. The photosensitive resin composition may contain, in addition to the photopolymerization initiator (C), a coumarin derivative such as 7-diethylamino-4-methylcoumarin as a sensitizer for the laser exposure method, a carbanian pigment system, a xanthene pigment system and the like.

The epoxy compound (D) can impart thermosetting property to the photosensitive resin composition. As described above, the epoxy compound (D) contains a crystalline epoxy resin and an amorphous epoxy resin. Here, "crystalline epoxy resin" is an epoxy resin having a melting point, and "amorphous epoxy resin" is an epoxy resin having no melting point.

The crystalline epoxy resin is, for example, 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) , A hydroquinone type crystalline epoxy resin (specific name: YDC-1312 manufactured by Shin-nettetsu Sumikin Kagaku Kogyo Co., Ltd.), a biphenyl-type crystalline epoxy resin (specific examples include Mitsubishi Kagaku Kogyo K.K. (Trade name YX-4000), diphenyl ether type crystalline epoxy resin (specifically, YSLV-80DE manufactured by Shinnitetsu Sumikin Kagaku KK), bisphenol type crystalline epoxy resin (Trade name: YTRV-80XY manufactured by Kagaku Kogyo K.K.), tetrakisphenol ethane-type crystalline epoxy resin (specific example: GTR-1800 manufactured by Nippon Yakuza Co., Ltd.), bisphenol fluorene type crystalline epoxy resin An epoxy resin having a structure (S7) as a specific example) That contains one or more components selected from the preferred.

The crystalline epoxy resin preferably has two epoxy groups in one molecule. In this case, it is possible to make cracks harder to occur in the cured product during repeated temperature changes.

The crystalline epoxy resin preferably has an epoxy equivalent of 150 to 300 g / eq. This epoxy equivalent is the gram weight of the crystalline epoxy resin containing one gram equivalent of epoxy group. The crystalline epoxy resin has a melting point. The melting point of the crystalline epoxy resin is, for example, from 70 to 180 캜.

In particular, the epoxy compound (D) preferably contains a crystalline epoxy resin having a melting point of 110 캜 or lower. In this case, the developability by the alkaline aqueous solution of the photosensitive resin composition is particularly improved. The crystalline epoxy resin having a melting point of 110 占 폚 or less can be obtained by using, for example, a biphenyl-type epoxy resin (the product number YX-4000 manufactured by Mitsubishi Kagaku Kabushiki Kaisha as a specific example), a biphenyl ether type epoxy resin (Part number YSLV-80DE manufactured by Tetsu Sumikin Kagaku Co., Ltd.) and bisphenol-type epoxy resin (specific part YSLV-80XY manufactured by Shinnitetsu Sumikin Kagaku), bisphenol fluorene type crystalline epoxy resin And an epoxy resin having a structure (S7) as a specific example).

Examples of the amorphous epoxy resin include phenol novolak type epoxy resin (specific EPICLON N-775 manufactured by DIC Corporation), cresol novolak type epoxy resin (specific example, manufactured by DIC Kabushiki Kaisha) Bisphenol A novolak type epoxy resin (specific example: EPICLON N-865 manufactured by DIC Corporation), bisphenol A type epoxy resin (specific example, manufactured by Mitsubishi Kagaku Kogyo K.K.) Bisphenol F type epoxy resin (specific example: part number jER4004P manufactured by Mitsubishi Kagaku KK), bisphenol S type epoxy resin (specific EPICLON EXA-1514 manufactured by DIC Corporation) Bisphenol AD type epoxy resin, biphenyl novolak type epoxy resin (specific example: NC-3000 manufactured by Nihon Yakushin Kogyo Co., Ltd.), hydrogenated bisphenol A type epoxy resin Naphthalene type epoxy resin (specific EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770, manufactured by DIC Corporation), which is manufactured by Shinnetsu Tetsu Sumikin Kagaku Kogyo Co., , a tertiary butyl catechol type epoxy resin (specific EPICLON HP-820 manufactured by DIC Corporation), a dicyclopentadiene type epoxy resin (specific EPICLON HP-7200 manufactured by DIC) (Specific examples: ADAMANTATE XE-201 manufactured by Idemitsu Kosan Co., Ltd.), a special bifunctional epoxy resin (specific examples include YL7175-500 and YL7175-M manufactured by Mitsubishi Kagaku Co., Ltd.) EPICLON EXA-4822, EPICLON EXA-4822, and EPICLON EXA-4822 manufactured by DIC Corporation, EPICLON TSR-960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA- -9726; (Product number MX-156 manufactured by KANEKA KOGYO Co., Ltd.), a core-shell polymer modified bisphenol A type epoxy resin (specific example, manufactured by Shin-Etsu Chemical Co., Ltd.), YSLV- Rubber-modified core-shell polymer modified bisphenol F type epoxy resin (specific example MX-136 manufactured by KANEKA K.K.), and rubber particle-containing bisphenol F type epoxy resin (specific examples are available from KANEKA CO., LTD. No. CN-130). It is preferable to contain at least one kind of component selected from the group consisting of polyvinyl alcohol

The epoxy compound (D) may contain a phosphorus-containing epoxy resin. In this case, the flame retardancy of the cured product of the photosensitive resin composition is improved. The phosphorus-containing epoxy resin may be contained in the crystalline epoxy resin, or may be contained in the amorphous epoxy resin. Examples of phosphorus-containing epoxy resins include phosphoric acid-modified bisphenol F type epoxy resins (specific EPICLON EXA-9726 and EPICLON EXA-9710 manufactured by DIC Corporation), Shinnitetsu Sumikin Kagaku KK The phototypical FX-305 is available in the part number manufactured by NEC Electronics.

The amorphous epoxy resin preferably contains an epoxy resin (da) having a bisphenol structural unit (d1) and a structural unit (d2). When the amorphous epoxy resin contains the epoxy resin (da), the thermal shock resistance of the cured product of the photosensitive resin composition can be improved.

Examples of the structural unit (d1) include structural units derived from bisphenol A, bisphenol F, and bisphenol S. Specific examples of the structural unit (d1) include units other than the terminal OH groups and units represented by the following formula (8). In addition, a part of the phenylene group and the phenyl group in the unit represented by the formula (8) may be hydrogenated. The phenylene group and the phenyl group in the unit represented by the formula (8) may have a substituent such as a hydrocarbon group, an alkoxyl group, an aryl group, an aryloxy group, or a hydroxyl group.

The structural unit (d2) is selected from the group consisting of a linear hydrocarbon structural unit (d21) having 4 to 20 carbon atoms and a polyalkylene ether structural unit (d22) having 3 to 20 ether oxygen atoms At least one kind.

The straight chain hydrocarbon structural unit (d21) is a structural unit in which _{y of} - (CH ₂ ) _y - is 4 or more and 20 or less. y is preferably from 4 to 10. A substituent such as a hydroxyl group may be contained instead of a hydrogen atom in the structural unit in which _{y of} - (CH ₂ ) _y - is 4 or more and 20 or less. At least one of the hydrogen atoms in the structural unit in which _{y of} - (CH ₂ ) _y - is 4 or more and 20 or less may be substituted with a hydrocarbon group, an alkoxyl group, an aryl group, or an aryloxy group. The hydrocarbon and the alkoxyl group as the substituent preferably have 4 or less carbon atoms. The aryl group and the aryl group in the aryloxy group are preferably phenyl groups. The linear hydrocarbon structural unit (d21) may have these substituents in a range that does not impair the flexibility of the structural unit (d2).

As the polyalkylene ether structural unit (d22), the number of ether oxygen atoms is 3 or more and 20 or less, preferably 3 to 10. Specific examples of the polyalkylene ether structural unit (d22) include one or more alkylene oxides selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, neopentylene oxide, tetramethylene oxide and the like And a structural unit derived from a polymer. One or more hydrogen atoms of the alkylene oxide may be substituted with, for example, a hydroxyl group, an alkoxyl group, an aryl group, an aryloxy group, a hydrocarbon group, or the like. The hydrocarbon and the alkoxyl group as the substituent preferably have 4 or less carbon atoms. The aryl group and the aryl group in the aryloxy group are preferably phenyl groups. The polyalkylene ether structural unit (d22) may have these substituents in a range that does not impair the flexibility of the structural unit (d2).

The molar ratio of the structural unit (d1) to the structural unit (d2) is preferably from 10: 1 to 1: 5, more preferably from 5: 1 to 1: 3. When the molar ratio of the structural unit (d1) is higher than the above-mentioned range, the amorphous epoxy resin does not have sufficient flexibility, and cracks may easily occur in the cured product of the photosensitive resin composition. When the molar ratio of the structural unit (d1) is lower than the above-mentioned range, the Tg of the amorphous epoxy resin is too low, which may lower the heat resistance of the cured product of the photosensitive resin composition.

Specifically, the epoxy resin (da) preferably has at least one structure represented by the following structural formulas (9-i) to (9-iv). In addition, a plurality of hydroxyl groups of the structural formulas shown below may undergo a crosslinking reaction, and oxygen atoms of the hydroxyl group may be nodule (unspecified).

In the structural formulas (9-i) to (9-iv), Ar ₁ and Ar ₂ are structural units (d1) which may have a substituent and may be hydrogenated. Ar ₁ and Ar ₂ may be the same or different. X is at least one member selected from the group consisting of a straight chain hydrocarbon group having 4 to 20 carbon atoms and a polyalkylene ether structure having 1 to 18 ether oxygen atoms. When X is a linear hydrocarbon group having 4 to 20 carbon atoms, X constitutes the structural unit (d2). When X is a polyalkylene ether structure having an ether oxygen atom number of 1 or more and 18 or less, -OXO- constitutes the structural unit (d2). N is an average value of repeating units of 1 to 30.

Examples of the method for obtaining such an epoxy compound (da) include a method of curing a predetermined epoxy resin with a curing agent.

As the predetermined epoxy resin, there may be mentioned a method using an epoxy compound having the structural unit (d1) and the structural unit (d2) as described above; A method of using an epoxy compound having a structural unit (d1) and an epoxy compound having a structural unit (d2) in combination; A method of using an epoxy compound having a structural unit (d1) and a chain extender capable of giving the structural unit (d2) by reaction to the epoxy compound in combination.

Specific examples of the epoxy compound (da) include the part numbers EPICLON EXA4816 and EPICLON EXA4822 manufactured by DIC Corporation, the parts numbers YL7175-500 and YL7175-1000 manufactured by Mitsubishi Kagaku Kogyo Co.,

The epoxy equivalent of the epoxy compound having the structural unit (d1) and the structural unit (d2) is preferably 200 to 800 g / eq, more preferably 350 to 650 g / eq.

The amorphous epoxy resin preferably contains an epoxy resin (db) having a novolac structure and a biphenyl skeleton. In the photosensitive resin composition containing the epoxy resin (db), the electrical insulation performance of the cured product is enhanced. Therefore, the photosensitive resin composition is particularly suitable as an insulating material for printed wiring boards in which high reliability such as line-to-line insulation and interlayer migration resistance is required. The epoxy resin (db) is preferably an amorphous biphenyl novolak type epoxy resin (part number NC-3000, part number NC-3000-L, part number NC-3000-H manufactured by Japan Chemical Industry Co., -3000-FH-75M, CER-3000-L).

The photosensitive resin composition according to the present embodiment may contain melamine (E). In this case, the adhesion between the cured product of the photosensitive resin composition and a metal such as copper increases. Therefore, the photosensitive resin composition is particularly suitable as an insulating material for a printed wiring board. Also, the resistance to electrolytic plating of the cured product of the photosensitive resin composition, that is, the whitening resistance upon electroless nickel / gold plating treatment, is improved.

The photosensitive resin composition according to the present embodiment may contain an organic solvent. The organic solvent is used for the purpose of liquefying or varifying the photosensitive resin composition, adjusting the viscosity, adjusting the coating property, and adjusting the film formability.

The organic solvent includes, for example, linear, branched, secondary or multivalent alcohols such as ethanol, propyl alcohol, isopropyl alcohol, hexanol, and ethylene glycol; Ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene and xylene; Petroleum aromatics mixed solvents such as Swazol series (manufactured by Maruzen Petrochemical Co., Ltd.) and sorbet series (manufactured by Exxon Chemical Co., Ltd.); Cellosolve such as cellosolve and butyl cellosolve; Carbitols such as carbitol and butyl carbitol; Propylene glycol alkyl ethers such as propylene glycol methyl ether; Polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; Acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate and carbitol acetate; And at least one compound selected from the group consisting of dialkyl glycol ethers.

The amount of the component in the photosensitive resin composition is appropriately adjusted so that the photosensitive resin composition can be developed into an alkaline solution with photo-curable properties.

The amount of the carboxyl group-containing resin (A) relative to the solid content of the photosensitive resin composition is preferably in the range of 5 to 85 mass%, more preferably in the range of 10 to 75 mass%, more preferably in the range of 30 to 60 mass% .

The amount of the unsaturated compound (B) relative to the carboxyl group-containing resin (A) is preferably within a range of 1 to 50 mass%, more preferably within a range of 10 to 45 mass%, and more preferably within a range of 21 to 40 mass% More preferable.

The amount of the photopolymerization initiator (C) relative to the carboxyl group-containing resin (A) is preferably within a range of 0.1 to 30 mass%, more preferably within a range of 1 to 25 mass%.

As to the amount of the epoxy compound (D), it is preferable that the total equivalent weight of the epoxy group contained in the epoxy compound (D) is in the range of 0.7 to 2.5 relative to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A) More preferably within a range of from 1.0 to 2.3, and still more preferably within a range of from 0.7 to 2.0.

When the total amount of the equivalents of the crystalline epoxy resin and the epoxy group contained in the amorphous epoxy resin relative to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A) is 2.5 or less, the developability can be improved. The total amount of equivalents of the crystalline epoxy resin and the epoxy group contained in the amorphous epoxy resin relative to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A) is more preferably 0.7 to 2.3, and even more preferably 0.7 to 2.0.

The equivalent amount of the epoxy group of the crystalline epoxy resin to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A) is preferably in the range of 0.2 to 1.9. In this case, the developability of the photosensitive resin composition can be particularly improved. The equivalence of the epoxy group of the crystalline epoxy resin to one equivalent of the carboxyl group contained in the carboxyl group-containing resin (A) is more preferably in the range of 0.3 to 1.7.

The equivalent of the epoxy group contained in the amorphous epoxy resin relative to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A) is preferably within a range of 0.05 to 1.5. In this case, it is possible to improve the developability of the photosensitive resin composition, and particularly improve the crack resistance of the cured product during repeated temperature changes. The equivalent amount of the epoxy group contained in the amorphous epoxy resin relative to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A) is more preferably 0.1 to 1.2.

When the photosensitive resin composition contains melamine (E), the amount of melamine (E) relative to the carboxyl group-containing resin (A) is preferably in the range of 0.1 to 10 mass%, more preferably 0.5 to 5 mass% desirable.

When the photosensitive resin composition contains an organic solvent, the amount of the organic solvent is adjusted so that the organic solvent quickly volatilizes when the coating film formed from the photosensitive resin composition is dried, that is, the organic solvent does not remain in the dried film . In particular, the amount of the organic solvent in the entire photosensitive resin composition is preferably in the range of 0 to 99.5 mass%, more preferably in the range of 15 to 60 mass%. Since the preferable proportion of the organic solvent differs depending on the application method and the like, it is preferable that the ratio is suitably controlled by the application method.

The solid content is the total amount of all components obtained by removing volatile components such as a solvent from the photosensitive resin composition.

As long as the effect of the present embodiment is not impaired, the photosensitive resin composition may further contain components other than the above-mentioned components.

For example, the photosensitive resin composition may contain an inorganic filler. In this case, the curing shrinkage of the film formed from the photosensitive resin composition is reduced. The inorganic filler may contain at least one material selected from the group consisting of, for example, barium sulfate, crystalline silica, nanosilica, carbon nanotubes, talc, bentonite, aluminum hydroxide, magnesium hydroxide, and titanium oxide . The photosensitive resin composition and the cured product thereof may be whitened by adding a white material such as titanium oxide or zinc oxide to the inorganic filler. The proportion of the inorganic filler in the photosensitive resin composition is appropriately set, but the amount of the inorganic filler to the carboxyl group-containing resin (A) is preferably in the range of 0 to 300 mass%.

Examples of the photosensitive resin composition include blocked isocyanate-based blockers such as tolylene diisocyanate, morpholine diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate blocked with caprolactam, oxime and malonic acid ester; Amino resins such as melamine resin, n-butylated melamine resin, isobutylated melamine resin, butylated urea resin, butylated melamine urea cocondensed resin, and benzoguanamine cocondensed resin; Various thermosetting resins other than those described above; Ultraviolet ray curable epoxy (meth) acrylate; A resin obtained by adding (meth) acrylic acid to an epoxy resin such as bisphenol A type, phenol novolac type, cresol novolak type, or alicyclic type; And at least one resin selected from the group consisting of a diallyl phthalate resin, a phenoxy resin, a urethane resin, and a fluorine resin.

The photosensitive resin composition may contain a curing agent for curing the epoxy compound (D). The curing agent is, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, Imidazole derivatives such as cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- compound; Hydrazine compounds such as adipic acid hydrazide and sebacic acid hydrazide; Phosphorus compounds such as triphenylphosphine; Acid anhydrides; phenol; Mercaptans; Lewis acid amine complex; And an onium salt may be contained. Commercially available products of these components include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all of which are trade names of imidazole compounds) manufactured by Shikoku Chemical Co., DBT, DBN, U-CATSA102 and U-CAT5002 (all of bicyclic amidine compounds and salts thereof).

The photosensitive resin composition may contain an adhesion-imparting agent other than melamine (E). Examples of the adhesion-imparting agent include guanamine, acetoguanamine, benzoguanamine, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl- Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl- And S-triazine derivatives such as azine isocyanuric acid adducts.

The photosensitive resin composition comprises a curing accelerator; coloring agent; Copolymers such as silicone and acrylate; A leveling agent; Adhesion-imparting agents such as silane coupling agents; Thixotropic agents; A polymerization inhibitor; Antihalation agents; Flame retardant; Defoamer; Antioxidants; Surfactants; And a polymeric dispersing agent.

The content of the amine compound in the photosensitive resin composition is preferably as small as possible. In this case, the electric insulating property of the layer made of the cured product of the photosensitive resin composition is hardly damaged. In particular, the amount of the amine compound relative to the carboxyl group-containing resin (A) is preferably 6% by mass or less, more preferably 4% by mass or less.

The photosensitive resin composition may be prepared by mixing the raw materials of the photosensitive resin composition as described above and kneading them by a known kneading method using, for example, 3 rolls, a ball mill, a sand mill or the like. When the raw material of the photosensitive resin composition contains a liquid component and a component having a low viscosity, a portion of the raw material other than the liquid component and the low viscosity component is first kneaded, and a liquid component, a low viscosity component Are added and mixed to prepare a photosensitive resin composition.

The second agent may be prepared by preparing a first agent by mixing a part of the components of the photosensitive resin composition in consideration of storage stability and the like and mixing the remainder of the components. That is, the photosensitive resin composition may include a first agent and a second agent. In this case, for example, the first agent is prepared by previously mixing and dispersing the unsaturated compound (B) in the components of the photosensitive resin composition, a part of the organic solvent, and the thermosetting component, The second agent may be prepared by mixing and dispersing the components. In this case, a desired amount of the first agent and the second agent are mixed in a timely manner to prepare a mixed solution, and the mixed solution is cured to obtain a cured product.

The photosensitive resin composition according to the present embodiment is suitable for an electrically insulating material for a printed wiring board. Particularly, the photosensitive resin composition is suitable for a material of an electrically insulating layer such as a solder resist layer, a plating resist layer, an etching resist layer, and an interlayer insulating layer.

It is preferable that the photosensitive resin composition according to the present embodiment has properties that can be developed with an aqueous solution of sodium carbonate even if the coating has a thickness of 25 mu m. In this case, since it is possible to produce a sufficiently thick electrically insulating layer from the photosensitive resin composition by the photolithography method, the photosensitive resin composition can be widely applied for producing an interlayer insulating layer, a solder resist layer, and the like in a printed wiring board Yes. Of course, an electrically insulating layer thinner than 25 占 퐉 in thickness can also be produced from the photosensitive resin composition.

Whether or not the coating film having a thickness of 25 mu m can be developed with an aqueous solution of sodium carbonate can be confirmed by the following method. A wet coating film is formed by applying a photosensitive resin composition on an appropriate base material, and the wet film is heated at 80 占 폚 for 40 minutes to form a film having a thickness of 25 占 퐉. The coating is irradiated with ultraviolet rays under conditions of 500 mJ / cm < ² > in a state in which the exposed film is in direct contact with a negative mask having an unexposed portion for shielding ultraviolet rays. After the exposure, a 1% Na ₂ CO ₃ aqueous solution at 30 ° C is sprayed onto the coating at an injection pressure of 0.2 MPa for 90 seconds, and then pure water is sprayed for 90 seconds at an injection pressure of 0.2 MPa. As a result of observing the film after this treatment, it can be judged that the film having a thickness of 25 mu m can be developed with an aqueous solution of sodium carbonate when the portion corresponding to the non-exposed portion in the film is removed and the residue is not recognized.

Hereinafter, an example of a method for producing a printed wiring board having an interlayer insulating layer formed from the photosensitive resin composition according to the present embodiment will be described with reference to Figs. 1A to 1E. In the present invention, a through hole is formed in the interlayer insulating layer by photolithography.

First, the core material 1 is prepared as shown in Fig. 1A. The core material 1 has at least one insulating layer 2 and at least one conductor wiring 3, for example. The conductor wiring 3 provided on one surface of the core material 1 will be referred to as a first conductor wiring 3 hereinafter. As shown in Fig. 1 (B), a film 4 is formed from the photosensitive resin composition on one surface of the core material 1. The coating film 4 may be formed by, for example, a coating method or a dry film method.

In the coating method, for example, a photosensitive resin composition is applied onto the core material 1 to form a wet coating film. The method of applying the photosensitive resin composition is selected from the group consisting of a known method such as a dipping method, a spraying method, a spin coating method, a roll coating method, a curtain coating method, and a screen printing method. Subsequently, in order to volatilize the organic solvent in the photosensitive resin composition, the wet film is dried, for example, at a temperature in the range of 60 to 120 占 폚 to obtain the film (4).

In the dry film method, first, a photosensitive resin composition is applied onto a suitable support made of polyester or the like and then dried to form a dry film, which is a dried product of the photosensitive resin composition, on the support. Thereby, a laminate including a dry film and a support for supporting the dry film can be obtained. After the dry film in this laminate is superimposed on the core material 1, pressure is applied to the dry film and the core material 1, and then the support is peeled off from the dry film, ). As a result, a film 4 made of a dry film is provided on the core material 1.

The coating 4 is partly cured as shown in Fig. 1C by exposing the coating 4. Fig. To this end, for example, after the negative mask is brought into contact with the coating 4, the coating 4 is irradiated with ultraviolet rays. The negative mask has an exposed portion for transmitting ultraviolet rays and an unexposed portion for shielding ultraviolet rays, and the unexposed portion is provided at a position coinciding with the position of the through hole 10. The negative mask is, for example, a photo tool such as a mask film or a dry plate. The ultraviolet light source is selected from the group consisting of, for example, a chemical lamp, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp and a metal halide lamp.

The exposure method may be a method other than a method using a negative mask. For example, the coating film 4 may be exposed by a direct imaging method in which ultraviolet rays emitted from the light source are irradiated only to the exposed portion of the coating film 4. [ For example, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a g-line (436 nm), an h-line (405 nm), an i-line (365 nm) And a combination of two or more of i-lines.

In the dry film method, after the dry film in the laminate is superimposed on the core material 1, ultraviolet rays are irradiated to the film 4 made of a dry film through the support without peeling the support, And then the support may be peeled off from the film 4 before the development processing.

Subsequently, the coating 4 is subjected to a developing treatment to remove the unexposed portion 5 of the coating 4 shown in Fig. 1C, whereby the through hole 10 Is formed at the position where the hole 6 is formed. In the developing treatment, a developer suitable for the composition (composition) of the photosensitive resin composition can be used. The developing solution is, for example, an alkaline aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide, or an organic amine. More specifically, the alkaline aqueous solution includes, for example, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogen carbonate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide and lithium hydroxide At least one kind of component selected from the group consisting of The solvent in the alkaline aqueous solution may be water alone or a mixture of water and a hydrophilic organic solvent such as lower alcohols. The organic amine contains, for example, at least one component selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine.

The developing solution is preferably an alkaline aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide, particularly preferably an aqueous solution of sodium carbonate. In this case, it is possible to improve the working environment and alleviate the burden of the waste treatment.

Subsequently, the coating 4 is cured by heating. The heating conditions are, for example, within a range of a heating temperature of 120 to 200 DEG C and a heating time of 30 to 120 minutes. When the film 4 is thermally cured in this way, the performance such as strength, hardness, and chemical resistance of the interlayer insulating layer 7 is improved.

If necessary, the coating film 4 may be irradiated with ultraviolet rays at one of the time before heating and the time after heating, or at both time points. In this case, the photocuring of the coating film 4 can be further promoted.

As a result, the interlayer insulating layer 7 made of the cured product of the photosensitive resin composition is formed on the core material 1. A second conductor wiring 8 and a hole plating 9 can be provided on the interlayer insulating layer 7 by a known method such as an additive process. As a result, as shown in FIG. 1E, the interlayer interlayer interposed between the first conductor interconnection 3, the second conductor interconnection 8, the first conductor interconnection 3 and the second conductor interconnection 8, The printed wiring board 11 having the insulating layer 7 and the through holes 10 for electrically connecting the first conductor wirings 3 and the second conductor wirings 8 can be obtained. 1E, the hole plating 9 has a cylindrical shape covering the inner surface of the hole 6, but the hole 6 may be filled with the hole plating 9 as a whole.

An example of a method of manufacturing a printed wiring board having a solder resist layer formed from the photosensitive resin composition according to the present embodiment will be described.

First, prepare the core material. The core material includes, for example, at least one insulating layer and at least one conductor wiring. A film is formed from the photosensitive resin composition on the side where the conductor wiring of the core is provided. As a method of forming the film, there are a coating method and a dry film method. As the coating method and the dry film method, the same method as in the case of forming the above-described interlayer insulating layer can be employed. The film is partially cured by exposure. The same method as in the case of forming the above-described interlayer insulating layer can be adopted for the exposure method. Subsequently, the coating is subjected to a development treatment to remove a portion which is not exposed in the coating, whereby the exposed portion of the coating remains on the core. Next, the coating film on the core material is heat-cured by heating. The developing method and the heating method may be the same as those in the case of forming the above-described interlayer insulating layer. If necessary, ultraviolet rays may be further irradiated to the coating at one of the time before the heating and the time after the heating, or both the points. In this case, the photocuring of the coating film can be further promoted.

Thus, a solder resist layer made of a cured product of the photosensitive resin composition is formed on the core material. This makes it possible to obtain a printed wiring board comprising a core material having an insulating layer and a conductor wiring thereon, and a solder resist layer partially covering the surface on which the conductor wiring is provided in the core material.

Example

Hereinafter, the present invention will be described in detail with reference to examples.

[Synthesis of Synthesis Examples A-1 to A-10 and B-1 to B-2]

(1) Synthesis Examples A-1 to A-10 and B-2

The raw material components described in the "first reaction" column in Tables 1 and 2 were added to a four-necked flask equipped with a reflux condenser, a thermometer, a tube for blowing air, and a stirrer, and these were stirred under air bubbling to prepare a mixture. This mixture was heated in a four-necked flask while stirring under air bubbling at the reaction temperature and the reaction time shown in the "Reaction Conditions" column. Thus, a solution of the intermediate was prepared.

Subsequently, the raw material components described in the "second reaction" column of Tables 1 and 2 were introduced into the solution of the intermediate in the four-necked flask, and while stirring the solution in the four-necked flask under air bubbling, The reaction temperature and the reaction time described were heated. Subsequently, except for the synthesis example B-2, the solution in the four-necked flask under air bubbling was heated with the reaction temperature and reaction time described in the column of "reaction condition (2)" while stirring. Thus, a 65 mass% solution of the carboxyl group-containing resin was obtained. The weight average molecular weight and the acid value of the carboxyl group-containing resin are the same as those described in Tables 1 and 2. The molar ratios between the components are also shown in Tables 1-2.

Details of the components listed in column (a1) in Tables 1 and 2 are as follows.

Epoxy Compound 1: A bisphenol fluorene epoxy compound having an epoxy equivalent of 250 g / eq, represented by Formula (7), wherein R ₁ to R ₈ in Formula (7) are all hydrogen.

Epoxy Compound 2: Bisphenol represented by the formula (7) and having an epoxy equivalent of 279 g / eq in which R ₁ and R ₅ in the formula (7) are all methyl, R ₂ to R ₄ and R ₆ to R ₈ are both hydrogen Fluorene type epoxy compound.

(2) Synthesis Example B-1

48 parts by mass of methacrylic acid, ω-carboxy-polycaprolactone (n≈2) monoacrylate (manufactured by Toa Synthetic Chemical Co., Ltd.) was added to a four-necked flask equipped with a reflux condenser, a thermometer, 50 parts by mass of a thermoplastic resin (Aronix M-5300), 92 parts by mass of methyl methacrylate, 10 parts by mass of styrene, 430 parts by mass of dipropylene glycol monomethyl ether and 3.5 parts by mass of azobisisobutyronitrile. The solution in the four-necked flask was heated at 75 DEG C for 5 hours under a nitrogen stream to proceed a polymerization reaction to obtain a copolymer solution having a concentration of 32%.

Subsequently, 0.1 part by mass of hydroquinone, 64 parts by mass of glycidyl methacrylate and 0.8 parts by mass of dimethylbenzylamine were added to the copolymer solution, and the addition reaction was carried out by heating at 80 DEG C for 24 hours. Thus, a 38% by mass solution of the carboxyl group-containing resin (B-1) was obtained. The acid value of the carboxyl group-containing resin (B-1) was 67 mgKOH / g.

[Table 1]

[Table 2]

[Preparation of Examples X1 to X22, Examples Y1 to Y19, Examples Z1 to Z21, Comparative Examples X1 to X11, Comparative Examples Y1 to Y5, and Comparative Examples Z1 to Z7)

The components described in the "Composition" column of Tables 3 to 13 to be described later were kneaded in three rolls, and these components were stirred and mixed in a flask to obtain a photosensitive resin composition. The details of the components are as follows. The following crystalline epoxy resin was previously pulverized by a jet mill or a mortar to make the average particle diameter thereof 20 mu m or less.

Unsaturated Compound A: trimethylolpropane triacrylate.

Unsaturated compound B:? -Caprolactone-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., part number DPCA-60).

Unsaturated compound C: tricyclodecane dimethanol diacrylate (Shin-Nakamura Chemical Co., Ltd., Part A-DCP).

Unsaturated compound D:? -Caprolactone-modified dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., part number KAYARAD DPCA-20.

Photopolymerization initiator A: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (product number Irgacure TPO, manufactured by BASF).

Photopolymerization initiator B: 1-hydroxycyclohexyl phenyl ketone (product number: Irgacure 184, manufactured by BASF).

Photopolymerization initiator C: 4,4'-bis (diethylamino) benzophenone.

Crystalline epoxy resin A 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) Type, melting point 150 to 158 占 폚, epoxy equivalent 99 g / eq).

Crystalline epoxy resin B: Hydroquinone type crystalline epoxy resin (trade name: YDC-1312, manufactured by Shinnitetsu Sumikin Kagaku KK, melting point: 138 to 145 deg. C, epoxy equivalent: 176 g / eq).

Crystalline epoxy resin C: biphenyl-type crystalline epoxy resin (YX-4000, product of Mitsubishi Chemical Corporation, melting point 105 캜, epoxy equivalent 187 g / eq).

Crystalline epoxy resin D: Diphenyl ether type crystalline epoxy resin (part number YSLV-80DE, manufactured by Shinnitetsu Sumikin Kagaku KK, melting point 80 to 90 占 폚, epoxy equivalent 163 g / eq).

Crystalline epoxy resin E: bisphenol-type crystalline epoxy resin (trade name YSLV-80XY, manufactured by Shinnitetsu Sumikin Kagaku KK, melting point 75 to 85 ° C, 192 g / eq).

Amorphous biphenyl novolac epoxy resin (product name: NC-3000, softening point: softening point: 53 to 63 캜, epoxy equivalence: 280 g / eq, manufactured by Nippon Kayaku Co., Ltd.) Solution of amorphous epoxy resin A: (Epoxy equivalent of epoxy resin having a novolac structure and a biphenyl skeleton) dissolved in diethylene glycol monoethyl ether acetate at a solid content of 80% (equivalent epoxy equivalent of solid content of 80% is 350 g / eq).

Solution of amorphous epoxy resin B: bisphenol A type epoxy resin containing long chain carbon chain (manufactured by DIC, EPICLON EXA-4816, liquid resin, epoxy equivalent 410 g / eq, structural unit (d1): bisphenol A Skeleton, structural unit (d2): containing a straight chain hydrocarbon having 6 carbon atoms) in diethylene glycol monoethyl ether acetate at a solid content of 90% (epoxy equivalent of 455.56 g / eq in terms of 90% solids) .

Amorphous epoxy resin C: Rubber core shell polymer modified bisphenol F type epoxy resin (MX-136 manufactured by Kaneka Corporation, liquid resin, epoxy equivalent: 220 g / eq).

Solution of amorphous epoxy resin D: cresol novolak type epoxy resin, manufactured by DIC, part number EPICLON N-695, softening point 90-100 占 폚, epoxy equivalent 214 g / eq was dissolved in diethylene glycol monoethyl ether acetate The dissolved solution (epoxy equivalent of 75% solids, 285 g / eq)

(Preparation of DIC, part number EPICLON EXA-4822, liquid resin, epoxy equivalent 389 g / eq, structural unit (d1): bisphenol A skeleton, structural unit (epoxy equivalents in terms of 85% solids: 457.65 g / eq) of polyethylene glycol (d2): polyethylene glycol, ether oxygen atoms: 4) in 85% solids in diethylene glycol monoethyl ether acetate,

Solution of amorphous epoxy resin F: amorphous biphenyl novolak type epoxy resin (epoxy resin having novolak structure and biphenyl skeleton), product name NC-3000H manufactured by Nippon Kayaku Co., Ltd., softening point 65 to 75占 폚, and an epoxy equivalent of 290 g / eq in a diethylene glycol monoethyl ether acetate at a solid content of 80%. The epoxy equivalents in terms of 80% solids were 362.5 g / eq.

Melamine: fine powder melamine produced by Nissan Chemical Industries, Ltd.

Antioxidant: Hindered phenolic antioxidant (manufactured by BASF, part number IRGANOX 1010).

· Blue pigment: phthalocyanine blue.

Yellow pigment: 1,1 '- [(6-phenyl-1,3,5-triazine-2,4-diyl) bis (imino)] bis (9,10-anthracenedione).

Barium sulphate: manufactured by Sakai Chemical Industry Co., Ltd .;

Talc: Made by Japan Talc, part number SG-2000.

Bentonite: manufactured by Reox Corporation, part number Bentone SD-2. Antifoaming agent: Shin-Etsu Silicone Co., product number KS-66.

· Surfactant: manufactured by DIC, part number Megapack F-477.

Rheology Control agent: BYK-430, manufactured by BICKEM Japan Co., Ltd.

Solvent A: Diethylene glycol monoethyl ether acetate.

Solvent B: methyl ethyl ketone.

[Preparation of test pieces using Examples X1 to X22 and Comparative Examples X1 to X11]

For Examples X1 to X16, Examples X18 to X22, and Comparative Examples X1 to X11, test pieces were prepared as follows.

A glass epoxy copper clad laminate (FR-4 type) having a copper foil with a thickness of 35 mu m was prepared. A comb-shaped electrode having a line width / space width of 50 mu m / 50 mu m as a conductor wiring was formed on the glass epoxy copper clad laminate by a subtractive process to obtain a core material . A wet coating film was formed by applying a photosensitive resin composition on the entire surface of one side of the core material by a screen printing method. This wet coating film was heated at 80 DEG C for 40 minutes and preliminarily dried to form a film having a thickness of 25 mu m. The coating was irradiated with ultraviolet rays under conditions of 500 mJ / cm ² in a state in which the negative mask having a non-visible portion having a pattern including a circular shape with a diameter of 50 탆 was directly in contact with the coating. The exposed film was subjected to development processing. In the developing treatment, 1% Na ₂ CO ₃ aqueous solution at 30 ° C was sprayed onto the coating film for 90 seconds at an injection pressure of 0.2 MPa. Subsequently, pure water was sprayed onto the coating film at an injection pressure of 0.2 MPa for 90 seconds to clean the coating. As a result, a portion not exposed in the film was removed to form a hole. Subsequently, the coating film was irradiated with ultraviolet rays under the condition of 1000 mJ / cm ² , and then heated at 160 캜 for 60 minutes. As a result, a layer composed of the cured product of the photosensitive resin composition was formed on the core material. Thus, a test piece was obtained.

In Example X17, a test piece was prepared as follows.

The photosensitive resin composition was applied onto a film made of polyethylene terephthalate with an applicator and then dried by heating at 95 DEG C for 25 minutes to form a 25 mu m thick dry film on the film. Further, the dry film was heat laminated on the whole surface of one side of the same core material as in Examples X1 to X16, Examples X18 to X22, and Comparative Examples X1 to X11 with a vacuum laminator. The conditions of the heated laminate were 0.5 MPa and 80 DEG C for 1 minute. Thus, a film of a dry film and having a thickness of 25 mu m was formed on the core material. This film was subjected to exposure, development, and ultraviolet irradiation under the same conditions as those described above. After the exposure, before the development, the film made of polyethylene terephthalate was peeled from the dry film (coating film). As a result, a layer made of a cured product of a photosensitive resin composition (which may be referred to as a cured product of a dry film) was formed on the core material. Thus, a test piece was obtained.

[Production of Test Specimens Using Examples Y1 to Y19 and Comparative Examples Y1 to Y5, and Examples Z1 to Z21 and Comparative Examples Z1 to Z7]

With respect to Examples Y1 to Y18 and Comparative Examples Y1 to Y5, and Examples Z1 to Z20 and Comparative Examples Z1 to Z7, test pieces were prepared as follows.

The same procedure as in Examples X1 to X22 and Comparative Examples X1 to X11 was conducted to obtain a core material. A portion of the surface layer (surface layer) having a thickness of about 1 mu m in the conductor wiring of this core material was dissolved and removed with a part number CZ-8100 manufactured by MEC COMPANY LTD. To roughen the conductor wiring . Thereafter, the same processes as in Examples X1 to X22 and Comparative Examples X1 to X11 were carried out to form a layer composed of the cured product of the photosensitive resin composition on the core material. Thus, a test piece was obtained.

When the photosensitive resin compositions of Examples Y19 and Z21 were used, test pieces were prepared as follows. Was carried out in the same manner as in Example X17 to form a dry film. The dry film was heat laminated on the whole surface of one side of the core material as in the case of Examples Y1 to Y18 and Comparative Examples Y1 to Y5 and Examples Z1 to Z20 and Comparative Examples Z1 to Z7 with a vacuum laminator. The conditions of the heated laminate are the same as in the case of Example X17. Thereafter, the same treatment as in Example X17 was carried out to obtain a test piece.

[Evaluation test]

(1) Tackiness

With respect to Examples and Comparative Examples except for Example X17, Example Y19 and Example Z21, the degree of stickiness of the coating film when the negative mask was removed from the coating film after exposure of the coating film at the time of producing the test piece was evaluated as follows I appreciated.

A: When the negative mask is removed from the film, resistance can not be felt, and no adhesion mark is recognized in the film after removing the negative mask.

B: Resistance was felt when the negative mask was removed from the film, and the adhesion mark was recognized in the film after removing the negative mask.

C: It is difficult to remove the negative mask from the film, and if the negative mask is forcibly removed, the film is broken.

The evaluation of the following (2) to (8) was not carried out for Comparative Example X5, Comparative Example X9 and Comparative Example X11 in which the tackiness evaluation was C. In addition, evaluation was not carried out for Comparative Example Y4 and Comparative Example Y5 and Comparative Example Z6 in which the tackiness evaluation was C, the following (3) to (8). In addition, for Example X17, Example Y19 and Example Z21, a film was formed from a dry film, and thus no evaluation of the tackiness was performed.

(2) Developability

A wet coating film was formed by applying a photosensitive resin composition to the entire surface of one side of a printed wiring board by screen printing, with respect to Examples and Comparative Examples except for Example X17, Example Y19 and Example Z21. This wet coating film was heated at 80 占 폚 for 40 minutes and 60 minutes to form a film having a thickness of 25 占 퐉. This coating was subjected to development without exposure. In the developing treatment, 1% Na ₂ CO ₃ aqueous solution at 30 ° C was sprayed for 90 seconds at an injection pressure of 0.2 MPa, and pure water was sprayed for 90 seconds at an injection pressure of 0.2 MPa. The printed wiring board after the treatment was observed, and the results were evaluated as follows.

A: Even when the heating time of the wet coating film was 40 minutes or 60 minutes, the film was completely removed.

B: When the heating time of the wet coating film was 40 minutes, all the coating films were removed, but at 60 minutes, part of the coating film remained on the printed wiring board.

C: A part of the coating remained on the printed wiring board even in the case where the heating time of the wet coating film was 40 minutes or 60 minutes.

In Comparative Examples X4 and X7, Comparative Examples Y4 and Y5 in which the developability evaluation was C, the following evaluations (3) to (8) were not performed.

In addition, for Example X17, Example Y19, and Example Z21, evaluation of developability was not performed because a film was formed from a dry film. In Example X17, Example Y19, and Example Z21, no problem was observed in the developing step after exposure.

(3) Resolution

The holes formed in the layer made of the cured product in the test pieces of the examples and comparative examples were observed, and the results were evaluated as follows.

A: The diameter of the bottom of the hole is 40 占 퐉 or more.

B: The diameter of the bottom of the hole is 25 占 퐉 or more and less than 40 占 퐉.

C: The diameter of the bottom of the hole was less than 25 占 퐉, or no reliable hole was formed.

(4) Venus Venus

A nickel plating layer was formed on a portion of the test piece of Examples and Comparative Examples exposed to the outside in the conductor wiring using a commercially available electroless nickel plating bath and then a gold plating layer was formed using a commercially available electroless gold plating bath Respectively. Thus, a metal layer composed of a nickel plating layer and a gold plating layer was formed. The layer comprising the cured product and the metal layer were observed with the naked eye. Further, the layer made of the cured product was subjected to the cellophane adhesive tape peeling test. The results were evaluated as follows.

A: No abnormality was recognized in the appearance of the layer made of the cured product and the metal layer, and the layer made of the cured product by the cellophane adhesive tape peeling test was not peeled.

B: Discoloration was observed in the layer made of the cured product, but no peeling of the layer made of the cured product by the cellophane adhesive tape peeling test occurred.

C: Float of the layer composed of the cured product was recognized, and peeling of the layer composed of the cured product was caused by the cellophane adhesive tape peeling test.

(5) Line insulation

The conductor wirings (comb-shaped electrodes) in the test pieces of Examples X1 to X22, Comparative Examples X1 to X11, Examples Y1 to Y19, Comparative Examples Y1 to Y5, Examples Z1 to Z21 and Comparative Examples Z1 to Z7, While the bias voltage was applied, the printed wiring board was exposed for 150 hours (Examples Z1 to Z21 and 200 hours for the test pieces of Comparative Examples Z1 to Z7) under the test environment of 121 占 폚 and 97% RH. The electric resistance value between the comb-shaped electrodes of the layer made of the cured product under the test environment was measured at all times, and the result was evaluated according to the following evaluation criteria.

A: The electrical resistance value was always maintained at 10 ⁶ Ω or more for 150 hours from the start of the test (200 hours for the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7).

B: The electric resistance value was always maintained at 10 ⁶ Ω or more from the start of the test to 150 hours (180 hours relative to the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7), but 150 hours (200 hours for the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7), the electric resistance value was less than 10 ⁶ Ω.

C: The electric resistance value was less than 10 ⁶ Ω after elapse of 100 hours from the start of the test (180 hours for the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7).

(6) Interlayer insulation

A conductive tape was adhered onto the layers of the cured products in the test pieces of Examples X1 to X22, Comparative Examples X1 to X11, Examples Y1 to Y19, Comparative Examples Y1 to Y5, Examples Z1 to Z21, and Comparative Examples Z1 to Z7 Respectively. While the bias voltage of DC 100 V was applied to the conductive tape, the test piece was exposed for 60 hours under the test environment of 121 占 폚 and 97% R.H. (for the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7 for 80 hours). The electric resistance value between the conductor wiring of the layer made of the cured product and the conductive tape under this test environment was measured at all times and the result was evaluated according to the following evaluation criteria.

A: The electric resistance value was always kept at 10 ⁶ Ω or more until the elapse of 60 hours from the start of the test (80 hours for the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7).

B: The electrical resistance value was always maintained at 10 ⁶ Ω or more from the start of the test to 50 hours (70 hours for the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7), but 60 hours (80 hours for the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7), the electric resistance value was less than 10 ⁶ Ω.

C: The electric resistance value was less than 10 ⁶ Ω after elapse of 50 hours from the start of the test (70 hours for the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7).

(7) PCT (pressure cooker test)

The test pieces of Examples X1 to X22, Comparative Examples X1 to X11, Examples Y1 to Y19, Comparative Examples Y1 to Y5, Examples Z1 to Z21 and Comparative Examples Z1 to Z7 were heated at 121 占 폚 and 100% RH for 100 hours After the test pieces of Examples Z1 to Z21 and Comparative Examples Z1 to Z7 were left for 150 hours), the appearance of the cured layer was evaluated according to the following evaluation criteria.

A: No abnormality was observed in the layer made of the cured product.

B: Discoloration was observed in the layer made of the cured product.

C: A large discoloration was observed in the layer made of the cured product, and a part of the layer was swollen.

(8) Cooling cycle

The test pieces of Examples X1 to X22, Comparative Examples X1 to X11, Examples Y1 to Y19, Comparative Examples Y1 to Y5, Examples Z1 to Z21 and Comparative Examples Z1 to Z7 were cooled at -65 DEG C for 10 minutes, Lt; 0 > C for 10 minutes was repeated 1000 times. The appearance of the layer composed of the cured product in the test piece at the time when the treatment was performed 500 times and when the treatment was performed 1000 times was evaluated according to the following evaluation criteria.

A: No cracks at 500 times or 1000 times.

B: There is no crack at 500 times of processing, but there is a crack at 1000 times of processing.

C: Cracks were observed at 500 times or 1000 times.

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

[Table 11]

[Table 12]

[Table 13]

As has been found from the above-described embodiment, the photosensitive resin composition according to the first aspect,

A resin composition comprising a carboxyl group-containing resin (A)

An unsaturated compound (B) having at least one ethylenic unsaturated bond in one molecule,

A photopolymerization initiator (C)

The epoxy compound (D)

&Lt; / RTI >

The carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1) which is a reaction product of an epoxy compound (a1) and an unsaturated group-containing carboxylic acid (a2)

Wherein the epoxy compound (a1) has a bisphenol fluorene skeleton represented by the formula (1), wherein R ₁ to R ₈ are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, Lt; / RTI >

The epoxy compound (D) contains a crystalline epoxy resin and an amorphous epoxy resin,

The total amount of equivalents of the epoxy group of the crystalline epoxy resin and the epoxy group of the amorphous epoxy resin relative to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A) is within a range of 0.7 to 2.5.

This photosensitive resin composition contains a bisphenol fluorene skeleton represented by the formula (1) derived from the epoxy compound (a1), so that the photosensitive resin composition containing the carboxyl group-containing resin (A1) High heat resistance and insulation reliability can be imparted to the cargo. When the epoxy compound (D) contains a crystalline epoxy resin, the developability of the photosensitive resin composition can be improved. When the epoxy compound (D) contains only crystalline epoxy resin, cracks tend to occur in the cured product of the photosensitive resin composition during repeated temperature changes including temperature rise and temperature drop. However, in the present embodiment, since the epoxy compound (D) contains the crystalline epoxy resin and the amorphous epoxy resin in the above-described predetermined ratio, cracks are generated in the cured product of the photosensitive resin composition It can be difficult. When the total amount of the equivalents of the crystalline epoxy resin and the epoxy group contained in the amorphous epoxy resin relative to one equivalent of the carboxyl group contained in the carboxyl group-containing resin (A) is 0.7 or more, insulation of the layer containing the cured product of the photosensitive resin composition Reliability can be improved, and crack resistance of the cured product during repeated temperature changes can be improved. When the total amount of the equivalents of the crystalline epoxy resin and the epoxy group contained in the amorphous epoxy resin relative to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A) is 2.5 or less, the developability can be improved. Therefore, even when the photosensitive resin composition of the present embodiment contains a carboxyl group-containing resin having a bisphenol fluorene skeleton, excellent developability can be obtained, and cracks easily occur during repeated temperature changes in the cured product of the photosensitive resin composition It can be difficult.

In the photosensitive resin composition according to the second aspect, the equivalent amount of the epoxy group of the crystalline epoxy resin with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A) is preferably within a range of 0.2 to 1.9.

This photosensitive resin composition can improve the developing property as compared with the case where the equivalent amount of the epoxy group contained in the crystalline epoxy resin is out of the range of 0.2 to 1.9.

In the photosensitive resin composition according to the third aspect, it is preferable that the crystalline epoxy resin has two epoxy groups in one molecule.

This photosensitive resin composition can make it more difficult for the cured product of the photosensitive resin composition to generate cracks during repeated temperature changes.

The photosensitive resin composition according to the fourth aspect is characterized in that the amorphous epoxy resin comprises a bisphenol structural unit (d1), a linear hydrocarbon structural unit having 4 or more carbon atoms and 20 or less ether oxygen atoms, (D2) of at least one polyalkylene ether structural unit represented by the following formula (1).

This photosensitive resin composition can improve the thermal shock resistance of the cured product as compared with the case of not containing the epoxy resin (da).

In the photosensitive resin composition according to the fifth aspect, the amorphous epoxy resin preferably contains an epoxy resin (db) having a novolac structure and a biphenyl skeleton.

This photosensitive resin composition is particularly suitable as an insulating material for a printed wiring board which requires high reliability, such as line-to-line insulation and interlayer migration resistance, because the electrical insulation property of the cured product becomes high.

In the photosensitive resin composition according to the sixth aspect, it is preferable that the acid anhydride contains an acid dianhydride.

In this case, the molecular weight is adjusted by the fact that the carboxyl group-containing resin (A1) is crosslinked by the acid anhydride (a3). Therefore, a carboxyl group-containing resin (A1) having an acid value and a molecular weight appropriately adjusted can be obtained. By controlling the amount of the acid dianhydride (a3), the molecular weight and the acid value of the carboxyl group-containing resin (A1) are easily adjusted.

In the photosensitive resin composition according to the 7th aspect, the acid dianhydride preferably contains 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride.

This photosensitive resin composition can easily obtain a coating with reduced adhesiveness while securing good developability, and can easily obtain a cured product having improved insulation reliability and resistance to electrolysis.

In the photosensitive resin composition according to the eighth aspect, the weight average molecular weight of the carboxyl group-containing resin (A1) is preferably within a range of 1000 to 5000.

In this case, the tackiness of the film formed of the photosensitive resin composition can be easily suppressed, and the insulation reliability and electrolytic resistance of the cured product formed from the photosensitive resin composition can be easily improved, and the developability of the photosensitive resin composition in an alkaline aqueous solution .

In the photosensitive resin composition according to the ninth aspect, the solid content of the carboxyl group-containing resin (A1) preferably falls within a range of 60 to 140 mgKOH / g.

In this case, the developability of the photosensitive resin composition tends to be improved.

In the photosensitive resin composition according to the 10th aspect, the acid anhydride preferably contains 1,2,3,6-tetrahydrophthalic anhydride.

In this case, the tackiness of the film formed of the photosensitive resin composition is easily suppressed, and the insulation reliability and resistance to electrolysis of the cured product formed from the photosensitive resin composition are easily improved.

The dry film according to the eleventh aspect is characterized by being a dried product of the photosensitive resin composition.

In this case, even if the dry film contains a carboxyl group-containing resin having a bisphenol fluorene skeleton, it has excellent developability and cracks are not readily generated while the temperature change is repeated in the cured product.

The printed wiring board according to a twelfth aspect is characterized by having a solder resist layer containing a cured product of the photosensitive resin composition.

In this case, the solder resist layer is not easily cracked while the temperature change is repeated.

The printed wiring board according to the thirteenth aspect is characterized by including an interlayer insulating layer containing a cured product of the photosensitive resin composition.

In this case, the interlayer insulating layer is not easily cracked while the temperature change is repeated.

Production method of the photosensitive resin composition according to the fourteenth aspect, it is represented by the formula (1), formula (1) of, R ₁ ~R ₈ are each independently hydrogen, halogen or a bisphenol fluorene group having 1 to 5 carbon atoms Containing resin (A1) is synthesized by reacting an epoxy compound (a1) having an omega skeleton with an unsaturated group-containing carboxylic acid (a2) and reacting the thus obtained intermediate with an acid anhydride to obtain a carboxyl- (B) having at least one ethylenic unsaturated bond in one molecule, a photopolymerization initiator (C) and an epoxy compound (D), wherein the resin (A) Wherein the epoxy compound (D) contains a crystalline epoxy resin and an amorphous epoxy resin, wherein the amount of the crystalline epoxy resin and the amorphous epoxy resin relative to 1 equivalent of the carboxyl group contained in the carboxyl group- And the total amount of equivalents of epoxy groups contained in the qualitative epoxy resin is in the range of 0.7 to 25.

In the photosensitive resin composition obtained by this production method, the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton derived from the epoxy compound (a1) and represented by the formula (1), whereby the photosensitive resin composition containing the carboxyl group- High heat resistance and insulation reliability can be imparted to the cured product of the resin composition. When the epoxy compound (D) contains a crystalline epoxy resin, the developability of the photosensitive resin composition can be improved. When the epoxy compound (D) contains only crystalline epoxy resin, cracks tend to occur in the cured product of the photosensitive resin composition during repeated temperature changes including temperature rise and temperature drop. However, in the present embodiment, since the epoxy compound (D) contains the crystalline epoxy resin and the amorphous epoxy resin in the above-mentioned predetermined ratio, the cured product of the photosensitive resin composition is cracked It can be made easily. When the total amount of the equivalents of the crystalline epoxy resin and the epoxy group contained in the amorphous epoxy resin relative to one equivalent of the carboxyl group contained in the carboxyl group-containing resin (A) is 0.7 or more, insulation of the layer containing the cured product of the photosensitive resin composition Reliability can be improved, and crack resistance of the cured product during repeated temperature changes can be improved. When the total amount of the equivalents of the crystalline epoxy resin and the epoxy group contained in the amorphous epoxy resin relative to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A) is 2.5 or less, the developability can be improved. Therefore, even when the photosensitive resin composition of the present embodiment contains a carboxyl group-containing resin having a bisphenol fluorene skeleton, excellent developability can be obtained, and cracks are easily generated during repeated temperature changes in the cured product of the photosensitive resin composition You can do it.

Claims

As the photosensitive resin composition,
A carboxyl group-containing resin (A);
An unsaturated compound (B) having at least one ethylenic unsaturated bond in one molecule;
A photopolymerization initiator (C); And
And an epoxy compound (D)
The carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1) which is a reaction product of an epoxy compound (a1) and an unsaturated group-containing carboxylic acid (a2)
Wherein the epoxy compound (a1) has a bisphenol fluorene skeleton represented by the following formula (1), wherein R ₁ to R ₈ are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, Lt; / RTI >
The epoxy compound (D) contains a crystalline epoxy resin and an amorphous epoxy resin,
Wherein the total amount of equivalents of the epoxy group of the crystalline epoxy resin and the epoxy group of the amorphous epoxy resin relative to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A) is in the range of 0.7 to 2.5,

.

The method according to claim 1,
Wherein the equivalent amount of the epoxy group of the crystalline epoxy resin with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A) is within a range of 0.2 to 1.9.

The method according to claim 1,
Wherein the crystalline epoxy resin has two epoxy groups in one molecule.

The method according to claim 1,
Wherein the amorphous epoxy resin is at least one of a bisphenol structural unit (d1), a linear hydrocarbon structural unit having 4 to 20 carbon atoms and a polyalkylene ether structural unit having 3 to 20 ether oxygen atoms , And an epoxy resin (da) having a unit (d2).

The method according to claim 1,
Wherein the amorphous epoxy resin contains an epoxy resin (db) having a novolac structure and a biphenyl skeleton.

The method according to claim 1,
Wherein the acid anhydride contains an acid dianhydride.

The method according to claim 6,
Wherein said acid dianhydride contains 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride.

The method according to claim 1,
Wherein the weight average molecular weight of the carboxyl group-containing resin (A1) is in the range of 1000 to 5000.

The method according to claim 1,
And the solid acid value of the carboxyl group-containing resin (A1) is within a range of 60 to 140 mgKOH / g.

The method according to claim 1,
Wherein the acid anhydride contains 1,2,3,6-tetrahydrophthalic anhydride.

A dry film, which is a dried product of the photosensitive resin composition according to any one of claims 1 to 10.

A printed wiring board comprising a solder resist layer containing a cured product of the photosensitive resin composition according to any one of claims 1 to 10.

A printed wiring board comprising an interlayer insulating layer containing a cured product of the photosensitive resin composition according to any one of claims 1 to 10.