JP2017191204A - Photosensitive resin composition, dry film, and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having high photosensitivity and also excellent resolution even when containing a carboxyl group-containing resin with a bisphenol fluorene skeleton.SOLUTION: A photosensitive resin composition contains a carboxyl group-containing resin (A), an unsaturated compound (B), a photopolymerization initiator (C), and an epoxy compound (D). The carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1) that is a reactant of: an intermediate that is a reactant of an epoxy compound (a1) and an unsaturated group-containing carboxylic acid (a2); and an acid anhydride. The epoxy compound (a1) has a bisphenol fluorene skeleton. The photopolymerization initiator (C) contains an oxime ester photopolymerization initiator (C1), and the amount of the oxime ester photopolymerization initiator (C1) is 0.05-60 mass% relative to the total amount of the photopolymerization initiator (C).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a photosensitive resin composition, a dry film, and a printed wiring board. Specifically, an electrically insulating layer such as a solder resist layer, a plating resist layer, an etching resist layer, or an interlayer insulating layer is formed on the printed wiring board. A photosensitive resin composition suitable for carrying out, a dry film which is a dried product of the photosensitive resin composition, a printed wiring board comprising an interlayer insulating layer containing a cured product of the photosensitive resin composition, and the photosensitive resin composition The present invention relates to a printed wiring board including a solder resist layer containing a cured product.

  Conventionally, for the production of printed wiring boards, various electrically insulating resin compositions have been used to form electrically insulating layers such as solder resist layers, plating resist layers, etching resist layers, and interlayer insulating layers. For example, a photosensitive resin composition is used as the resin composition.

  In order to give high heat resistance to the layer formed from the photosensitive resin composition, it has been proposed to add a carboxyl group-containing resin having a bisphenolfluorene skeleton to the photosensitive resin composition. For example, Patent Document 1 discloses using a carboxyl group-containing resin having a fluorene skeleton obtained by reacting fluorene epoxy (meth) acrylate with a polyvalent carboxylic acid or an anhydride thereof.

  However, the photosensitive resin composition containing a carboxyl group-containing resin having a bisphenolfluorene skeleton has low photosensitivity, and thus the efficiency of curing the photosensitive resin composition to form a layer was low.

Japanese Patent No. 4508929

  An object of the present invention is to provide a photosensitive resin composition having high photosensitivity and excellent developability even when the photosensitive resin composition contains a carboxyl group-containing resin having a bisphenolfluorene skeleton, A dry film which is a dried product of the photosensitive resin composition, a printed wiring board including 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 It is providing the printed wiring board provided.

A photosensitive resin composition according to one embodiment of the present invention includes a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, a photopolymerization initiator ( C) and an epoxy compound (D), wherein the carboxyl group-containing resin (A) is a reaction product of the epoxy compound (a1) and the unsaturated group-containing carboxylic acid (a2), Containing a carboxyl group-containing resin (A1) which is a reaction product with an acid anhydride, the epoxy compound (a1) has a bisphenolfluorene skeleton represented by the following formula (1), and in the following formula (1): R _{1 to} R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or halogen;

The photopolymerization initiator (C) contains an oxime ester photopolymerization initiator (C1) having a partial structure (S2) represented by the following formula (8). In the following formula (8), R ₉ is A hydrogen atom, R ₉ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group, and the hydrocarbon group having 1 to 20 carbon atoms includes a hydroxyl group, an ether group, a carbonyl group, and The aromatic hydrocarbon group may have at least one substituent selected from the group consisting of halogen, and the aromatic hydrocarbon group is at least one substituent selected from the group consisting of a hydroxyl group, an ether group, a carbonyl group, and a halogen May have a group,
R ₁₀ is a hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group, and the hydrocarbon group having 1 to 20 carbon atoms is selected from the group consisting of a hydroxyl group, an ether group, a carbonyl group, and a halogen. The aromatic hydrocarbon group may have at least one substituent selected from the group consisting of a hydroxyl group, an ether group, a carbonyl group, and a halogen. Often,

The amount of the oxime ester photopolymerization initiator (C1) relative to the total amount of the photopolymerization initiator (C) is in the range of 0.05 to 60% by mass.
It is characterized by that.

  The dry film which concerns on 1 aspect of this invention is a dried material of the said photosensitive resin composition.

  The printed wiring board which concerns on 1 aspect of this invention is equipped with the interlayer insulation layer containing the hardened | cured material of the said photosensitive resin composition.

  The printed wiring board which concerns on 1 aspect of this invention is equipped with the soldering resist layer containing the hardened | cured material of the said photosensitive resin composition.

  According to one embodiment of the present invention, even if the photosensitive resin composition contains a carboxyl group-containing resin having a bisphenolfluorene skeleton, the photosensitive resin can have high photosensitivity and excellent developability. Composition, dry film which is a dried product of this photosensitive resin composition, printed wiring board comprising a solder resist layer containing a cured product of this photosensitive resin composition, and an interlayer comprising a cured product of this photosensitive resin composition A printed wiring board provided with an insulating layer is obtained.

1A to 1E are cross-sectional views illustrating steps of manufacturing a multilayer printed wiring board according to an embodiment of the present invention.

  Hereinafter, an embodiment of the present invention will be described. In the following description, “(meth) acryl” means at least one of “acryl” and “methacryl”. For example, (meth) acrylate means at least one of acrylate and methacrylate.

  The photosensitive resin composition according to this embodiment includes a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, and a photopolymerization initiator (C). And an epoxy compound (D).

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

This carboxyl group-containing resin (A1) is represented by, for example, the following formula (1), and in formula (1), R _{1 to} R ₈ are each independently hydrogen, a bisphenol having 1 to 5 carbon atoms or halogen. It is a reaction product of an acid anhydride and an intermediate that is a reaction product of an epoxy compound (a1) having a fluorene skeleton and an ethylenically unsaturated group-containing carboxylic acid (a2). The carboxyl group-containing resin (A1) was obtained by reacting an epoxy compound (a1) having a bisphenolfluorene skeleton represented by the following formula (1) with an ethylenically unsaturated group-containing carboxylic acid (a2). It is synthesized by reacting an intermediate with an acid anhydride.

In formula (1), R _{1 to} R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or halogen. That is, each of R _{1 to} R ₈ in Formula (1) may be hydrogen, but may be an alkyl group having 1 to 5 carbon atoms or a halogen. Even if the hydrogen in the aromatic ring is substituted with a low molecular weight alkyl group or a halogen, the physical properties of the carboxyl group-containing resin (A1) are not adversely affected, but the carboxyl group-containing resin (A1) is included by being substituted. This is because the heat resistance or flame retardancy of the cured product of the photosensitive resin composition may be improved.

  The amount of the oxime ester photopolymerization initiator (C1) relative to the total amount of the photopolymerization initiator (C) according to this embodiment is in the range of 0.05 to 60% by mass. Thereby, even if the photosensitive resin composition contains a bisphenolfluorene skeleton, the photosensitivity of the photosensitive resin composition is improved, and excellent developability is imparted to a cured product made of the photosensitive resin composition. Can do. The amount of (C1) is more preferably in the range of 0.1 to 50% by mass, further preferably in the range of 0.2 to 45% by mass, and in the range of 0.3 to 15% by mass. It is particularly preferred that

  In the photosensitive resin composition according to the present embodiment, the amount of the photopolymerization initiator (C) with respect to the carboxyl group-containing resin (A) is preferably in the range of 3 to 20% by mass. Furthermore, the amount of the oxime ester photopolymerization initiator (C1) relative to the carboxyl group-containing resin (A) is preferably in the range of 0.01 to 3% by mass. In this case, excellent resolution can be imparted to the cured product of the photosensitive resin composition.

  The oxime ester photopolymerization initiator (C1) has a partial structure (SC1) represented by the formula (8).

In formula (8), R < ₉ > is a hydrogen atom, a C1-C20 hydrocarbon group, or an aromatic hydrocarbon group. The hydrocarbon group having 1 to 20 carbon atoms may have at least one substituent selected from the group consisting of a hydroxyl group, an ether group, a carbonyl group, and a halogen, and the aromatic hydrocarbon group includes a hydroxyl group, It may have at least one substituent selected from the group consisting of an ether group, a carbonyl group, and a halogen.

In formula (8), R < ₁₀ > is a C1-C20 hydrocarbon group or an aromatic hydrocarbon group. The hydrocarbon group having 1 to 20 carbon atoms may have at least one substituent selected from the group consisting of a hydroxyl group, an ether group, a carbonyl group, and a halogen, and the aromatic hydrocarbon group includes a hydroxyl group, You may have at least 1 substituent selected from the group which consists of an ether group, a carbonyl group, and a halogen.

  The partial structure (SC1) generates active radicals with very high efficiency by photolysis. For this reason, high sensitivity of the photosensitive resin composition can be achieved when the photosensitive resin composition contains a photopolymerization initiator having a partial structure (SC1). Furthermore, the outstanding surface curability can be provided to the coating film formed from the photosensitive resin composition by containing the photoinitiator which has a partial structure (SC1).

  The oxime ester photopolymerization initiator (C1) preferably has an absorption band in a wavelength region longer than 350 nm. In this case, since the deep part sclerosis | hardenability of the coating film formed from the photosensitive resin composition can be improved, the high sensitivity of a coating film is possible. Therefore, the photosensitive resin composition is particularly suitable for uses such as a solder resist layer, a plating resist layer, an etching resist layer, and an interlayer insulating layer.

  In the present embodiment, the oxime ester photopolymerization initiator (C1) preferably also contains the compound (c1) represented by the formula (11). That is, it is also preferable that the photosensitive resin composition contains the compound (c1).

In formula (11), R ₁₇ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group. The hydrocarbon group having 1 to 12 carbon atoms may have at least one substituent selected from the group consisting of a hydroxyl group, an ether group, and a carbonyl group, and the aromatic hydrocarbon group includes a hydroxyl group, an ether group, , And at least one substituent selected from the group consisting of carbonyl groups.

R ₁₈ and R ₂₀ are each independently a hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group. The hydrocarbon group having 1 to 20 carbon atoms may have at least one substituent selected from the group consisting of a hydroxyl group, an ether group, a carbonyl group, and a halogen, and the aromatic hydrocarbon group includes a hydroxyl group, It may have at least one substituent selected from the group consisting of an ether group, a carbonyl group, and a halogen.

R ₁₉ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group. The hydrocarbon group having 1 to 20 carbon atoms may have at least one substituent selected from the group consisting of a hydroxyl group, an ether group, a carbonyl group, and a halogen, and the aromatic hydrocarbon group includes a hydroxyl group, It may have at least one substituent selected from the group consisting of an ether group, a carbonyl group, and a halogen.

  Compound (c1) has an absorption band with a large absorbance in the ultraviolet region of 300 to 400 nm. When this compound (c1) is irradiated with ultraviolet rays, the mobility is very high and active radicals are generated with high efficiency. For this reason, when the photosensitive resin composition contains the compound (c1), it is possible to further increase the sensitivity and improve the surface curability of the photosensitive resin composition.

  Examples of the oxime ester photopolymerization initiator (C1) include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (manufactured by BASF, product number Irgacure OXE 01), Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (manufactured by BASF, part number Irgacure OXE 02), manufactured by ADEKA And Adeka Atomers N-1919, Adeka Arcles NCI-831, and Adeka Arcles NCI-930.

  In this embodiment, in addition to the oxime ester photopolymerization initiator (C1), the photopolymerization initiator (C) is an aminoacetophenone photopolymerization initiator (C2), and an acylphosphine oxide photopolymerization initiator (C3). It is preferable to contain at least one of them. That is, it is preferable that the photosensitive resin composition contains at least one of an aminoacetophenone photopolymerization initiator (C2) and an acylphosphine oxide photopolymerization initiator (C3).

  In this case, higher photosensitivity can be imparted to the photosensitive resin composition. Moreover, when irradiating and hardening the ultraviolet-ray to the coating film formed from the photosensitive resin composition, it becomes possible to fully harden a coating film over the deep part from the surface. That is, deep curability can be imparted to the coating film formed from the photosensitive resin composition.

  The aminoacetophenone photopolymerization initiator (C2) has, for example, a partial structure (SC2) represented by the formula (9).

In the formula (9), R ₁₁ and R ₁₂ are each independently an alkyl group having 1 to 12 carbon atoms or an arylalkyl group. R ₁₃ and R ₁₄ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ₁₃ and R ₁₄ may be bonded via an ether bond so that R ₁₃ and R ₁₄ constitute one cyclic alkyl ether.

  Examples of the aminoacetophenone photopolymerization initiator (C2) include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4- Selected from the group consisting of morpholinophenyl) -butanone-1 and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone Containing at least one component.

  Since the partial structure (SC2) has an absorption band having a large absorbance in the ultraviolet region of 300 to 400 nm, the partial structure (SC2) has high reactivity to ultraviolet rays and generates radicals. In addition, a thermal cleavage reaction occurs after irradiation with ultraviolet rays, whereby new active radicals are generated. Therefore, the partial structure (SC2) has an excellent ability to initiate photopolymerization and can impart high deep curability to the coating film formed from the photosensitive resin composition.

  The aminoacetophenone photopolymerization initiator (C2) preferably has an absorption band in a wavelength region longer than 350 nm. In this case, higher deep part curability can be imparted to the coating film formed from the photosensitive resin composition.

  The acylphosphine oxide photopolymerization initiator (C3) has a partial structure (SC3) represented by, for example, the formula (10).

In the formula (10), R ₁₅ and R ₁₆ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, a halogen atom, or an alkyl group. Or an aryl group substituted with an alkoxy group. Further, either one of R ₁₅ and R ₁₆ may be an alkanoyl group having a hydrocarbon group having 1 to 20 carbon atoms.

  The partial structure (SC3) exhibits a photobleaching effect due to ultraviolet absorption. For this reason, the outstanding deep-part curability can be provided to the coating film formed from photosensitive resin.

  The acylphosphine oxide photopolymerization initiator (C3) preferably has an absorption band in a wavelength region longer than 400 nm. In this case, higher deep part curability can be imparted to the coating film formed from the photosensitive resin composition.

  When the photopolymerization initiator (C) contains an acyl phosphine oxide photopolymerization initiator (C3), the acyl phosphine oxide photopolymerization initiator (C3) hardly inhibits the electrical insulation of the cured product. For this reason, by curing the photosensitive resin composition by exposure, a cured product having excellent electrical insulation can be obtained. For example, the cured product includes a solder resist layer, a plating resist layer, an etching resist layer, and an interlayer insulating layer. It is suitable as. Accordingly, the photopolymerization initiator (C) particularly preferably contains an acyl phosphine oxide photopolymerization initiator (C3).

  Acylphosphine oxide-based photopolymerization initiator (C3) is monoacylphosphine oxide-based light such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4,6-trimethylbenzoyl-ethyl-phenyl-phosphinate, etc. Polymerization initiator, and bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl)- 4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2 , 4,4- Limethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide, (2,5,6-trimethyl) One or more components selected from the group consisting of bisacylphosphine oxide photopolymerization initiators such as benzoyl) -2,4,4-trimethylpentylphosphine oxide can be contained. In particular, the acylphosphine oxide photopolymerization initiator (C3) preferably contains 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the acylphosphine oxide photopolymerization initiator (C3) is 2,4,6. It is also preferred to contain only trimethylbenzoyl-diphenyl-phosphine oxide.

  The photopolymerization initiator (C) preferably further contains a bis (dialkylamino) benzophenone photopolymerization initiator (C4). In this case, when developing after partially exposing the coating film formed from the photosensitive resin composition, the resolution is particularly enhanced by suppressing the curing of the unexposed portion. For this reason, it becomes possible to form a very fine pattern with the hardened | cured material of the photosensitive resin composition. In particular, when an interlayer insulating layer of a multilayer printed wiring board is prepared from a photosensitive resin composition and a small-diameter hole for a through hole is provided in the interlayer insulating layer by a photolithography method (see FIG. 1), the small-diameter hole is formed. It becomes possible to form precisely and easily.

  The bis (dialkylamino) benzophenone-based photopolymerization initiator (C4) contains, for example, 4,4'-bis (diethylamino) benzophenone and 4,4'-bis (dimethylamino) benzophenone.

  The amount of bis (dialkylamino) benzophenone (C4) relative to the carboxyl group-containing resin (A) is preferably in the range of 0.01 to 3% by mass. When the amount of bis (diethylamino) benzophenone (C4) is 0.01% by mass or more, the resolution of the coating film formed from the photosensitive resin composition is particularly high. Further, when the amount of bis (diethylamino) benzophenone (C4) is 3% by mass or less, bis (dialkylamino) benzophenone (C4) hardly inhibits the electrical insulation of the cured product of the photosensitive resin composition. The amount of bis (dialkylamino) benzophenone (C4) is more preferably 0.03 to 2% by mass, and particularly preferably 0.05 to 1% by mass.

  The photopolymerization initiator (C) may further contain a hydroxyketone photopolymerization initiator (C5). Hydroxy ketone photopolymerization initiator (C5) is, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, phenylglyoxyc acid methyl ester, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy- 2-Methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one And 2-hydroxy-2-methyl-1-phenyl-propan-1-one.

  The photosensitive resin composition may further contain a known photopolymerization accelerator, sensitizer and the like. For example, the photosensitive resin composition includes benzoin and its alkyl ethers; acetophenones such as acetophenone and benzyldimethyl ketal; anthraquinones such as 2-methylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2- Thioxanthones such as isopropylthioxanthone, 4-isopropylthioxanthone and 2,4-diisopropylthioxanthone; benzophenones such as benzophenone and 4-benzoyl-4′-methyldiphenyl sulfide; xanthones such as 2,4-diisopropylxanthone; Α-hydroxyketones such as hydroxy-2-methyl-1-phenyl-propan-1-one; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone It can contain at least one component selected from the group consisting of compounds containing a nitrogen atom. The photosensitive resin composition is known together with a photopolymerization initiator (C), such as tertiary amines such as p-dimethylbenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and 2-dimethylaminoethylbenzoate. You may contain a photoinitiator, a sensitizer, etc. If necessary, 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. The photosensitive resin composition contains a photopolymerization initiator (C) and a coumarin derivative such as 7-diethylamino-4-methylcoumarin that is a sensitizer for laser exposure, a carbocyanine dye system, a xanthene dye system, and the like. May be.

  The carboxyl group-containing resin (A1) will be described more specifically. In order to synthesize the carboxyl group-containing resin (A1), first, at least a part of the epoxy group (see formula (2)) in the epoxy compound (a1) having a bisphenolfluorene skeleton represented by formula (1) and unsaturated An intermediate is synthesized by reacting the group-containing carboxylic acid (a2). The intermediate has a structure (S3) represented by the following formula (3) generated 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 generated by a ring-opening addition reaction between an epoxy group and an unsaturated group-containing carboxylic acid (a2) in the structure represented by the formula (3). In Formula (3), A is an unsaturated group-containing carboxylic acid residue.

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

  The acid anhydride may contain at least one of acid dianhydride (a3) and acid monoanhydride (a4). When the acid anhydride contains acid monoanhydride (a4), the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton represented by the formula (1) and a structure (S4) represented by the following formula (4). .

  The structure (S4) is generated by the reaction between the secondary hydroxyl group in the intermediate structure (S3) and the acid anhydride group in the acid monoanhydride (a4). In Formula (4), A is an unsaturated group-containing carboxylic acid residue, and B is an acid monoanhydride residue.

  When the acid anhydride contains the acid dianhydride (a3), the carboxyl group-containing resin (A1) includes a bisphenolfluorene skeleton represented by the formula (1) and a structure (S5) represented by the following formula (5). Have.

  The structure (S5) is generated by the reaction between two acid anhydride groups in the acid dianhydride (a3) and two secondary hydroxyl groups in the intermediate. That is, the structure (S5) is generated by crosslinking the two secondary hydroxyl groups with the acid dianhydride (a3). In addition, the case where two secondary hydroxyl groups present in one molecule of the intermediate are crosslinked and the case where two secondary hydroxyl groups present in each of the two molecules of the intermediate are crosslinked It is possible. When the two secondary hydroxyl groups present in the two molecules of the intermediate are cross-linked, the molecular weight increases. In Formula (5), A is an unsaturated group-containing carboxylic acid residue, and D is an acid dianhydride residue.

  A carboxyl group-containing resin (A1) can be obtained by reacting the secondary hydroxyl group in the intermediate with an acid anhydride. When the acid anhydride contains an acid dianhydride (a3) and an acid monoanhydride (a4), a part of the secondary hydroxyl group in the intermediate is reacted with the acid dianhydride (a3), Another part of the secondary hydroxyl groups in the intermediate is reacted with acid monoanhydride (a4). Thereby, carboxyl group-containing resin (A1) can be synthesized. In this case, the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton represented by the formula (1), a structure represented by the above formula (4), and a structure (S5) represented by the above formula (5).

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

  When some of the epoxy groups in the epoxy compound (a1) remain unreacted during the synthesis of the intermediate, the carboxyl group-containing resin (A1) may have a structure (S2), that is, an epoxy group. Further, when 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 acid dianhydride (a3), the structure (S2) in the carboxyl group-containing resin (A1) is optimized by optimizing the reaction conditions during the synthesis of the carboxyl group-containing resin (A1). And the structure (S6) can be reduced or almost eliminated.

  As described above, the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton represented by the formula (1), and has a structure (S4) when the acid anhydride contains an acid monoanhydride (a4). And when an acid anhydride contains an acid dianhydride (a3), it can have a structure (S5). Further, when the acid anhydride contains acid monoanhydride (a4), the carboxyl group-containing resin (A1) may have at least one of the structure (S2) and the structure (S3). Moreover, when an acid anhydride contains an acid dianhydride (a3), carboxyl group-containing resin (A1) may have at least 1 type in a structure (S2) and a structure (S6). Furthermore, when the acid anhydride contains acid monoanhydride (a4) and acid dianhydride (a3), the carboxyl group-containing resin (A1) has (S2) structure, structure (S3), structure ( And at least one of S6).

  When the epoxy compound (a1) itself has a secondary hydroxyl group, that is, for example, when n = 1 or more in the formula (7) described later, the carboxyl group-containing resin (A1) is an epoxy compound (a1). ) In which a secondary hydroxyl group and an acid anhydride react with each other.

  In addition, the structure of the above-mentioned carboxyl group-containing resin (A1) is reasonably inferred based on the common general technical knowledge, and the structure of the carboxyl group-containing resin (A1) cannot be identified by analysis. The reason 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)), it contains a carboxyl group depending on the number of secondary hydroxyl groups in the epoxy compound (a1). The structure of the resin (A1) is greatly changed. When the intermediate and the acid dianhydride (a3) react, as described above, two secondary hydroxyl groups present in one molecule of the intermediate are acid dianhydrides (a3). There may be a case where two secondary hydroxyl groups respectively present in two molecules of the intermediate are crosslinked with an acid dianhydride (a3). For this reason, the carboxyl group-containing resin (A1) finally obtained contains a plurality of molecules having different structures, and even when the carboxyl group-containing resin (A1) is analyzed, the structure cannot be identified.

  The carboxyl group-containing resin (A1) has photoreactivity by having an ethylenically unsaturated group derived from the unsaturated group-containing carboxylic acid (a2). For this reason, carboxyl group-containing resin (A1) can provide photosensitivity, specifically, ultraviolet curability, to the photosensitive resin composition. Further, the carboxyl group-containing resin (A1) has a carboxyl group derived from an acid anhydride, so that the photosensitive resin composition contains an alkaline aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide. Developability can be imparted. Furthermore, when the acid anhydride contains an acid dianhydride (a3), the carboxyl group-containing resin (A1) is crosslinked by the acid dianhydride (a3), so that the molecular weight is adjusted. For this reason, the carboxyl group-containing resin (A1) in which the acid value and the molecular weight are appropriately adjusted is obtained. When the acid anhydride contains acid dianhydride (a3) and acid dianhydride (a4), the amount of acid dianhydride (a3) and acid dianhydride (a4), and acid dianhydride (a3) The molecular weight and acid value of the carboxyl group-containing resin (A1) can be easily adjusted by controlling the amount of the acid monoanhydride (a4) relative to.

  The weight average molecular weight of the carboxyl group-containing resin (A1) is preferably in the range of 700 to 10,000. When the weight average molecular weight is 700 or more, tackiness of a film formed from the photosensitive resin composition can be further suppressed, and insulation reliability and plating resistance of the cured product can be further improved. Moreover, the developability by the alkaline aqueous solution of the photosensitive resin composition improves especially that a weight average molecular weight is 10,000 or less. The weight average molecular weight is more preferably in the range of 900 to 8000, and particularly preferably in the range of 1000 to 5000.

  The solid content acid value of the carboxyl group-containing resin (A1) is preferably in the range of 60 to 140 mgKOH / g. In this case, the developability of the photosensitive resin composition is particularly improved. The acid value is more preferably in the range of 80 to 135 mgKOH / g, and the acid value is more preferably in the 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. The molecular weight measurement by gel permeation chromatography can be performed, for example, under the following conditions.

GPC device: SHODEX SYSTEM 11, manufactured by Showa Denko KK
Column: 4 series of SHODEX KF-800P, KF-005, KF-003, KF-001,
Mobile phase: THF,
Flow rate: 1 ml / min
Column temperature: 45 ° C
Detector: RI,
Conversion: Polystyrene.

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

  The epoxy compound (a1) has a structure (S7) represented by the following formula (7), for example. N in Formula (7) is a number within the range of 0-20, for example. In order to appropriately control the molecular weight of the carboxyl group-containing resin (A1), the average of n is particularly preferably in the range of 0-1. If the average of n is in the range of 0 to 1, particularly when the acid anhydride contains acid dianhydride (a3), an excessive increase in molecular weight due to addition of acid dianhydride (a3) is likely to be suppressed. Become.

  The unsaturated group-containing carboxylic acid (a2) can contain, for example, a compound having only one ethylenically unsaturated group in one molecule. More specifically, the unsaturated group-containing carboxylic acid (a2) is, for example, acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≈2) monoacrylate, crotonic acid, cinnamic acid, 2-acryloyloxyethyl succinate. Acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl phthalic acid, 2-acryloyloxypropyl phthalic acid, 2-methacryloyloxypropyl phthalic acid, 2-acryloyloxyethyl maleic acid, 2-methacryloyloxyethyl maleic acid, β-carboxyethyl acrylate, 2-acryloyloxyethyl tetrahydrophthalic acid, 2-methacryloyloxyethyl tetrahydrophthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid And one or more compounds selected from the group consisting of 2-methacryloyloxyethyl hexahydrophthalic acid. Preferably, unsaturated group containing carboxylic acid (a2) contains acrylic acid.

  In reacting 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 group-containing carboxylic acid (a2) to a solvent solution of the epoxy compound (a1), and further adding a thermal polymerization inhibitor and a catalyst as necessary and stirring and mixing. An intermediate can be obtained by reacting this reactive solution at a temperature of preferably 60 to 150 ° C., particularly preferably 80 to 120 ° C., by a conventional method. Solvents include, for example, ketones such as methyl ethyl ketone and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene, and ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether It can contain at least one component selected from the group consisting of acetates such as acetate and dialkyl glycol ethers. The thermal polymerization inhibitor contains, for example, at least one of hydroquinone and hydroquinone monomethyl ether. The catalyst is selected from the group consisting of tertiary amines such as benzyldimethylamine and triethylamine, quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride, triphenylphosphine, and triphenylstibine. It can contain at least one component.

  It is particularly preferred that the catalyst contains 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 between the epoxy group and the unsaturated group-containing carboxylic acid (a2) in the epoxy compound (a1) is particularly accelerated, and the reaction rate (conversion) is 95% or more, 97% or more, or almost 100%. Rate). For this reason, the intermediate which has a structure shown in Formula (3) is obtained with a high yield. Moreover, generation | occurrence | production of the ion migration in the layer containing the hardened | cured material of the photosensitive resin composition is suppressed, and the insulation reliability of the layer containing hardened | cured material further improves.

  When the epoxy compound (a1) and the unsaturated group-containing carboxylic acid (a2) are reacted, the amount of the unsaturated group-containing carboxylic acid (a2) relative to 1 mol of the epoxy group of the epoxy compound (a1) is 0.8 to 1. It is preferably within a range of 2 moles. In this case, excellent photosensitivity and storage stability of the photosensitive resin composition can be obtained.

  It is also preferable to react the epoxy compound (a1) and the unsaturated group-containing carboxylic acid (a2) under air bubbling. In this case, the addition polymerization reaction of the unsaturated group can be suppressed, and the increase in the molecular weight of the intermediate and the gelation of the intermediate solution can be suppressed. Moreover, the excessive coloring of carboxyl group-containing resin (A1) which is a final product can be suppressed.

  The intermediate obtained in this way has a hydroxyl group produced by the reaction of the epoxy group in the epoxy compound (a1) and the carboxyl group in the unsaturated group-containing carboxylic acid (a2).

  The acid dianhydride (a3) is a compound having two acid anhydride groups. The acid dianhydride (a3) can contain an anhydride of tetracarboxylic acid. Acid dianhydride (a3) is, for example, 1,2,4,5-benzenetetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, methylcyclohexene tetracarboxylic dianhydride, tetracarboxylic dianhydride, Naphthalene-1,4,5,8-tetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride, glycerin bisanhydrotri Melitate monoacetate, ethylene glycol bisanhydro trimellitate, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro -2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione, 1,2,3,4-buta Tetracarboxylic dianhydride, and 3,3 ', may contain at least one compound selected from the group consisting of 4,4'-biphenyl tetracarboxylic acid dianhydride. In particular, the acid dianhydride (a3) preferably contains 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride. That is, it is preferable that D in Formula (5) and Formula (6) includes a 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride residue. In this case, while ensuring good developability of the photosensitive resin composition, it is possible to further suppress the tackiness of a film formed from the photosensitive resin composition and further improve the insulation reliability and plating resistance of the cured product. . The total amount of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is preferably in the range of 20 to 100 mol%, and preferably 40 to 100 mol%, based on the entire acid dianhydride (a3). Although it is more preferable to be within the range, it is not limited to this range.

  The acid monoanhydride (a4) is a compound having one acid anhydride group. The acid monoanhydride (a4) can contain an anhydride of a dicarboxylic acid. Examples of the acid monoanhydride (a4) include phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride, methylhexa Hydrophthalic anhydride, succinic anhydride, methyl succinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and One or more compounds selected from the group consisting of itaconic anhydride can be contained. In particular, it is preferable that the acid monoanhydride (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 a structure represented by the formula (4), and B in the formula (4) includes a 1,2,3,6-tetrahydrophthalic anhydride residue. In this case, while ensuring good developability of the photosensitive resin composition, it is possible to further suppress the tackiness of a film formed from the photosensitive resin composition and further improve the insulation reliability and plating resistance of the cured product. . It is preferable that 1,2,3,6-tetrahydrophthalic anhydride is in the range of 20 to 100 mol%, and in the range of 40 to 100 mol%, based on the entire acid monoanhydride (a4). Is more preferable, but not limited to this.

  In reacting the intermediate with the acid anhydride, a known method can be employed. For example, a reactive solution is obtained by adding an acid anhydride to the solvent solution of the intermediate, further adding a thermal polymerization inhibitor and a catalyst as necessary, and stirring and mixing. The carboxyl group-containing resin (A1) can be obtained by reacting this reactive solution at a temperature of preferably 60 to 150 ° C., particularly preferably 80 to 120 ° C., by a conventional method. As the solvent, catalyst and polymerization inhibitor, appropriate ones can be used, and the solvent, catalyst and polymerization inhibitor used in the synthesis of the intermediate can also be used as they are.

  It is particularly preferred that the catalyst contains triphenylphosphine. That is, it is preferable to react an 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 accelerated, and a reaction rate (conversion rate) of 90%, 95%, 97%, or almost 100% can be achieved. Is possible. For this reason, the carboxyl group-containing resin (A1) having at least one of the structure represented by the formula (4) and the structure represented by the formula (5) can be obtained with high yield. Moreover, generation | occurrence | production of the ion migration in the layer containing the hardened | cured material of the photosensitive resin composition is suppressed, and the insulation reliability of the layer containing hardened | cured material further improves.

  When the acid anhydride contains an acid dianhydride (a3) and an acid monoanhydride (a4), the amount of the acid dianhydride (a3) is 1 mol of the epoxy group of the epoxy compound (a1), It is preferably in the range of 0.05 to 0.24 mol. Moreover, it is preferable that the quantity of acid monoanhydride (a4) exists in the range of 0.3-0.7 mol with respect to 1 mol of epoxy groups of an epoxy compound (a1). In this case, the carboxyl group-containing resin (A1) in which the acid value and the molecular weight are appropriately adjusted can be easily obtained.

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

  The carboxyl group-containing resin (F) can contain, for example, a compound having a carboxyl group and not having photopolymerizability (hereinafter referred to as (F1) component). (F1) A component contains the polymer of the ethylenically unsaturated monomer containing the ethylenically unsaturated compound which has a carboxyl group, for example. The ethylenically unsaturated compound having a carboxyl group can contain compounds such as acrylic acid, methacrylic acid, and ω-carboxy-polycaprolactone (n≈2) monoacrylate. The ethylenically unsaturated compound having a carboxyl group can also contain a reaction product of pentaerythritol triacrylate, pentaerythritol trimethacrylate and the like with a dibasic acid anhydride. The ethylenically unsaturated monomer is 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, linear or branched aliphatic or alicyclic (provided that It may further contain an ethylenically unsaturated compound having no carboxyl group, such as (meth) acrylic acid ester (which may partially have an unsaturated bond in the ring).

  The carboxyl group-containing resin (F) may contain a compound having a carboxyl group and an ethylenically unsaturated group (hereinafter referred to as (F2) component). Moreover, carboxyl group-containing resin (F) may contain only the (F2) component. The component (F2) includes, for example, an intermediate that is a reaction product of an epoxy compound (g1) having two or more epoxy groups in one molecule and an ethylenically unsaturated compound (g2), a polyvalent carboxylic acid and its anhydride. A resin (referred to as a first resin (g)) that is a reaction product with at least one compound (g3) selected from the group of substances. For example, the first resin (g) is obtained by adding the compound (g3) to an intermediate obtained by reacting the epoxy group in the epoxy compound (g1) with the carboxyl group in the ethylenically unsaturated compound (g2). Can be obtained. The epoxy compound (g1) can contain an appropriate epoxy compound such as a cresol novolac epoxy compound, a phenol novolac epoxy compound, or a biphenyl novolac epoxy compound. In particular, the epoxy compound (g1) preferably contains at least one compound selected from the group of biphenyl novolac type epoxy compounds and cresol novolac type epoxy compounds. The epoxy compound (g1) may contain only a biphenyl novolac type epoxy compound or may contain only a cresol novolac type epoxy compound. In this case, since an aromatic ring is contained in the main chain of the epoxy compound (g1), the cured product of the photosensitive resin composition is hardly corroded by the oxidizing agent. The epoxy compound (g1) may contain a polymer of the ethylenically unsaturated compound (h). The ethylenically unsaturated compound (h) contains a compound (h1) having an epoxy group such as glycidyl (meth) acrylate, or further has no epoxy group such as 2- (meth) acryloyloxyethyl phthalate. Contains compound (h2). The ethylenically unsaturated compound (g2) preferably contains at least one of acrylic acid and methacrylic acid. The compound (g3) contains one or more compounds 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. . In particular, the compound (g3) preferably contains at least one polycarboxylic acid selected from the group of phthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid.

  The component (F2) is a resin (second resin) that 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. (I)) may be contained. The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group. The second resin (i) can be obtained by reacting an ethylenically unsaturated compound having an epoxy group with a part of the carboxyl group in the polymer. The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group. Examples of the ethylenically unsaturated compound having a carboxyl group include compounds such as acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≈2) monoacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate. Examples of the ethylenically unsaturated compound having no carboxyl group include 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, linear or branched aliphatic or oil It contains a compound such as a (meth) acrylic acid ester of a cyclic group (however, it 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 the carboxyl group-containing resin (A1) and the carboxyl group-containing resin (F). The carboxyl group-containing resin (A) preferably contains 30% by mass or more of the carboxyl group-containing resin (A1), more preferably 50% by mass or more, and still more preferably 100% by mass. In this case, the heat resistance and insulation reliability of the cured product of the photosensitive resin composition can be particularly improved. Moreover, the tack property of the film | membrane formed from the photosensitive resin composition can fully be suppressed. Furthermore, the developability by the alkaline aqueous solution of the photosensitive resin composition is securable.

  As described above, the photosensitive resin composition includes a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, and a photopolymerization initiator (C). And an epoxy compound (D).

  The unsaturated compound (B) can impart photocurability to the photosensitive resin composition. The unsaturated compound (B) is, for example, a monofunctional (meth) acrylate such as 2-hydroxyethyl (meth) acrylate; and diethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε-caprolactone modified pentaerythritol hexaacrylate, tricyclodecandi At least one compound selected from the group consisting of polyfunctional (meth) acrylates such as methanol di (meth) acrylate can be contained.

  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 an alkaline aqueous solution is particularly improved. Trifunctional compounds include, 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 It can contain at least one compound selected from the group consisting of tris- (2-acryloxyethyl) isocyanurate and ethoxylated glycerin tri (meth) acrylate.

  It is also preferred 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. Phosphorus-containing unsaturated compounds include, for example, 2-methacryloyloxyethyl acid phosphate (as specific examples, product number light ester P-1M and light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.), 2-acryloyloxyethyl acid phosphate Fate (as a specific example, product number light acrylate P-1A manufactured by Kyoeisha Chemical Co., Ltd.), diphenyl-2-methacryloyloxyethyl phosphate (as a specific example, product number MR-260 manufactured by Daihachi Industry Co., Ltd.), and Showa Polymer Co., Ltd. HFA series manufactured by the company (part number HFA-6003 which is an addition reaction product of dipentaerystol hexaacrylate and HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) as a specific example, And HFA-6007, caprolact No. HFA-3003, HFA-6127, etc., which are addition reaction products of styrene-modified dipentaerystol hexaacrylate and HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide)) One or more compounds selected from the group consisting of:

  The unsaturated compound (B) may contain a prepolymer. The prepolymer is at least one 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 oligo (meth) acrylate prepolymers These compounds can be contained. Oligo (meth) acrylate prepolymers include, for example, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate At least one component selected from the group consisting of:

  The epoxy compound (D) can impart thermosetting properties to the photosensitive resin composition. The epoxy compound (D) preferably contains a crystalline epoxy resin. In this case, the developability of the photosensitive resin composition can be improved. The epoxy compound (D) may further contain 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) -trione, hydroquinone type crystallinity Epoxy resin (specifically, product name YDC-1312 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), biphenyl type crystalline epoxy resin (specifically, product name YX-4000 manufactured by Mitsubishi Chemical Corporation), diphenyl ether type crystalline epoxy resin (specific example) As Nippon Steel & Sumikin Chemical Co., Ltd. product number YSLV-80DE), bisphenol type crystalline epoxy resin (specifically, Nippon Steel & Sumikin Chemical Co., Ltd. product name YSLV-80XY), tetrakisphenol ethane type crystalline epoxy resin (specific example Japan) Product number GTR-1800 manufactured by Kayaku Co., Ltd., bisphenolfluorene type crystallinity Preferably contains one or more components selected from the group consisting of (epoxy resin having a structure represented by the formula (7) as a specific example) epoxy resin.

  The crystalline epoxy resin preferably has two epoxy groups in one molecule.

  The crystalline epoxy resin preferably has an epoxy equivalent of 150 to 300 g / eq. This epoxy equivalent is the gram weight of a crystalline epoxy resin containing 1 gram equivalent of epoxy groups. The crystalline epoxy resin has a melting point. As melting | fusing point of crystalline epoxy resin, 70-180 degreeC is mentioned, for example.

  In particular, the epoxy compound (D) preferably contains a crystalline epoxy resin having a melting point of 110 ° C. or lower. In this case, the developability of the photosensitive resin composition with an alkaline aqueous solution is particularly improved. Crystalline epoxy resins having a melting point of 110 ° C. or less include, for example, biphenyl type epoxy resin (specifically, product number YX-4000 manufactured by Mitsubishi Chemical Corporation), biphenyl ether type epoxy resin (specifically, product number YSLV manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) -80DE), and a bisphenol-type epoxy resin (specifically, Nippon Steel & Sumikin Chemicals product number YSLV-80XY), a bisphenolfluorene-type crystalline epoxy resin (specifically, an epoxy resin having the structure (S7)). At least one component.

  The amorphous epoxy resin is, for example, a phenol novolac type epoxy resin (specifically, product number EPICLON N-775 manufactured by DIC Corporation), or a cresol novolac type epoxy resin (specific example, product number EPICLON N-695 manufactured by DIC Corporation). Bisphenol A novolac type epoxy resin (specifically, product number EPICLON N-865 manufactured by DIC Corporation), bisphenol A type epoxy resin (specifically, product number jER1001 manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (specific example) As product number jER4004P manufactured by Mitsubishi Chemical Corporation), bisphenol S type epoxy resin (specifically, product number EPICLON EXA-1514 manufactured by DIC Corporation), bisphenol AD type epoxy resin, biphenyl novolak type Poxy resin (part number NC-3000 manufactured by Nippon Kayaku Co., Ltd.), hydrogenated bisphenol A type epoxy resin (part number ST-4000D manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), naphthalene type epoxy resin (particular example) DIC Corporation product numbers EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770), tertiary butyl catechol type epoxy resin (specifically, product number EPICLON HP-820 manufactured by DIC Corporation), dicyclopentadiene type Epoxy resin (part number EPICLON HP-7200 manufactured by DIC as a specific example), adamantane type epoxy resin (part number ADAMANATE X-E-201 manufactured by Idemitsu Kosan Co., Ltd.), special bifunctional type epoxy resin (specific example , Mitsubishi Chemical Corporation part numbers YL7175-500 and YL7175-1000; DIC Corporation part numbers EPICLON TSR-960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA-4850, EPICLON EXA-4816, EPICLON EXA-4822, and EPICLON EXA-9726; NS -156), rubber-like core-shell polymer-modified bisphenol F-type epoxy resin (as a specific example, product number MX-136 manufactured by Kaneka Corporation), and rubber particles It is preferable to contain one or more components selected from the group consisting of bisphenol F-type epoxy resins (as a specific example, product number Kane Ace MX-130 manufactured by Kaneka Corporation).

  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 (specifically, product numbers EPICLON EXA-9726 and EPICLON EXA-9710 manufactured by DIC Corporation), and product number Epototo FX-305 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Is mentioned.

  The photosensitive resin composition may contain melamine. The photosensitive resin composition may contain a component (E) containing at least one of melamine and a melamine derivative. In this case, the adhesion between the cured product of the photosensitive resin composition and a metal such as copper is increased. For this reason, the photosensitive resin composition is particularly suitable as an insulating material for a printed wiring board. Moreover, the plating resistance of the cured product of the photosensitive resin composition, that is, the whitening resistance during the electroless nickel / gold plating process is improved.

  Melamine is 2,4,6-triamino-1,3,5-triazine and is generally available from commercially available compounds. The melamine derivative may be a compound having one triazine ring and an amino group in one molecule. Examples of melamine derivatives include guanamine; acetoguanamine; benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl-4,6. -S-triazine derivatives such as diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid adduct; and melamine such as melamine-tetrahydrophthalate A reaction product with an acid anhydride is mentioned. Specific examples of the melamine derivative include Shikoku Kasei Kogyo Co., Ltd. product name VD-1, product name VD-2, and product name VD-3.

  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 can contain at least one material selected from the group consisting of, for example, barium sulfate, crystalline silica, nano silica, carbon nanotube, talc, bentonite, aluminum hydroxide, magnesium hydroxide, and titanium oxide. You may whiten the photosensitive resin composition and its hardened | cured material by making an inorganic filler contain white materials, such as a titanium oxide and a zinc oxide. Although the ratio of the inorganic filler in the photosensitive resin composition is appropriately set, the amount of the inorganic filler relative to the carboxyl group-containing resin (A) is preferably in the range of 0 to 300% by mass.

  The photosensitive resin composition may contain an organic filler. In this case, adhesion, flexibility, or thixotropy can be imparted to the film formed from the photosensitive resin composition. As the organic filler, for example, at least one material selected from the group consisting of rubber particles, acrylic resin particles, and cellulose particles can be contained. The organic filler may be a core-shell type. The organic filler may have a reactive group such as a carboxyl group, an amino group, an epoxy group, a vinyl group, or a hydroxyl group. Although the ratio of the organic filler in the photosensitive resin composition is appropriately set, the amount of the organic filler with respect to the carboxyl group-containing resin (A) is preferably in the range of 0 to 300% by mass.

  The photosensitive resin composition according to the present embodiment may contain an organic solvent. The organic solvent is used for the purpose of liquefaction or varnishing of the photosensitive resin composition, viscosity adjustment, application property adjustment, film formation property adjustment, and the like.

  Organic solvents include, for example, linear, branched, secondary or polyhydric 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 aromatic mixed solvents such as Swazol series (manufactured by Maruzen Petrochemical Co., Ltd.) and Solvesso series (manufactured by Exxon Chemical Co.); cellosolves such as cellosolve and butylcellosolve; Tolls; propylene glycol alkyl ethers such as propylene glycol methyl ether; polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; ethyl acetate, butyl acetate, cellosolve acetate, carb It can contain, as well as one or more compounds selected from the group consisting of dialkyl glycol ethers; Lumpur acid esters such as acetate.

  The amount of the component in the photosensitive resin composition is appropriately adjusted so that the photosensitive resin composition has photocurability and can be developed with an alkaline solution.

  The carboxyl group-containing resin (A) is preferably in the range of 5 to 85% by mass, more preferably in the range of 10 to 75% by mass, and more preferably in the range of 30 to 60% with respect to the solid content of the photosensitive resin composition. If it is in the range of mass%, it is still more preferable.

  The unsaturated compound (B) is preferably in the range of 1 to 50% by mass, more preferably in the range of 10 to 45% by mass with respect to the carboxyl group-containing resin (A), and more preferably 21 to 40% by mass. If it is in the range, it is more preferable.

  Regarding the amount of the epoxy compound (D), the total equivalent of the epoxy groups contained in the epoxy compound (D) is 0.7 to 2.5 with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A). Is preferably in the range of 0.7 to 2.3, more preferably in the range of 0.7 to 2.0. Moreover, it is preferable that the sum total of the equivalent of the epoxy group contained in crystalline epoxy resin exists in the range of 0.1-2.0 with respect to 1 equivalent of carboxyl groups contained in carboxyl group-containing resin (A), A range of 0.2 to 1.9 is more preferable, and a range of 0.3 to 1.5 is more preferable.

  When the photosensitive resin composition contains an organic solvent, the amount of the organic solvent is determined so that the organic solvent is volatilized quickly when the coating film formed from the photosensitive resin composition is dried, that is, the organic solvent is dried. It is preferable to adjust so as not to remain in the film. In particular, the organic solvent is preferably in the range of 0 to 99.5% by mass and more preferably in the range of 15 to 60% by mass with respect to the entire photosensitive resin composition. In addition, since the suitable ratio of an organic solvent changes with application methods etc., it is preferable that a ratio is suitably adjusted according to the application method.

  In addition, solid content is a total amount of all components remove | excluding volatile components, such as a solvent, from the photosensitive resin composition.

  Unless it deviates from the main point of this invention, the photosensitive resin composition may further contain components other than the said component.

  The photosensitive resin composition is composed of tolylene diisocyanate, morpholine diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate blocked isocyanates blocked with caprolactam, oxime, malonic acid ester, etc .; melamine resin, n-butylated melamine Resins, isobutylated melamine resins, butylated urea resins, butylated melamine urea cocondensation resins, benzoguanamine-based cocondensation resins, and other amino resins; various other thermosetting resins; ultraviolet curable epoxy (meth) acrylates; bisphenol A Resin obtained by adding (meth) acrylic acid to epoxy resin such as epoxy type, phenol novolac type, cresol novolac type, alicyclic type; and diallyl phthalate resin, phenoxy resin, urethane resin, fluorine resin It may contain one or more resins that are selected from the group consisting of a polymer compound.

  The photosensitive resin composition may contain a curing agent for curing the epoxy compound (D). Examples of the curing agent include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2- Imidazole derivatives such as cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4 Amine compounds such as methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic hydrazide and sebacic acid hydrazide; phosphorus compounds such as triphenylphosphine; acid anhydrides; phenols; mercaptans; Oni It may contain one or more components selected from the group consisting of unsalted. Examples of commercially available products of these components include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Co., Ltd., U-CAT3503N, U manufactured by San Apro Co., Ltd. -CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof).

  The photosensitive resin composition may contain an adhesion-imparting agent other than melamine. Examples of the adhesion-imparting agent include guanamine, acetoguanamine, benzoguanamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, and 2-vinyl-4. , 6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, and the like.

  Photosensitive resin composition includes curing accelerator; colorant; copolymer such as silicone and acrylate; leveling agent; adhesion imparting agent such as silane coupling agent; thixotropic agent; polymerization inhibitor; antihalation agent; One or more components selected from the group consisting of: an antifoaming agent, an antioxidant, a surfactant, and a polymer dispersant.

  The content of the amine compound in the photosensitive resin composition is preferably as small as possible. In this case, the electrical insulation of the layer made of a cured product of the photosensitive resin composition is unlikely to be impaired. In particular, the amine compound is preferably 6% by mass or less, more preferably 4% by mass or less, based on the carboxyl group-containing resin (A).

  The raw material of the photosensitive resin composition as described above is blended, and the photosensitive resin composition can be prepared by kneading by a known kneading method using, for example, a three roll, ball mill, sand mill or the like. In the case where the raw material of the photosensitive resin composition contains a liquid component, a low viscosity component, etc., the part of the raw material excluding the liquid component, the low viscosity component, etc. is first kneaded, and the resulting mixture is The photosensitive resin composition may be prepared by adding and mixing a liquid component, a component having a low viscosity, and the like.

  In consideration of storage stability and the like, the first agent may be prepared by mixing a part of the components of the photosensitive resin composition, and the second agent may be prepared by mixing the rest 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), a part of the organic solvent, and the thermosetting component among the components of the photosensitive resin composition. You may prepare a 2nd agent by mixing and disperse | distributing the remainder among the components of a composition. In this case, it is possible to prepare a mixed solution by mixing the necessary amount of the first agent and the second agent in a timely manner and curing the mixed solution to obtain a cured product.

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

  When the photosensitive resin composition according to the present embodiment is formed into a film having a thickness of 25 μm, it is preferable that the film can be developed with an aqueous sodium carbonate solution. In this case, since a sufficiently thick electrically insulating layer can be produced from the photosensitive resin composition by photolithography, the photosensitive resin composition is used as an interlayer insulating layer or solder resist in a printed wiring board. Widely applicable for producing layers and the like. Of course, it is also possible to produce an electrically insulating layer having a thickness of less than 25 μm from the photosensitive resin composition.

It can be confirmed by the following method that the film can be developed with an aqueous sodium carbonate solution. A wet paint film is formed by applying the photosensitive resin composition on a suitable substrate, and this wet paint film is heated at 80 ° C. for 40 minutes to form a film having a thickness of 25 μm. In a state where a negative mask having an exposed portion that transmits ultraviolet rays and a non-exposed portion that blocks ultraviolet rays is directly applied to the coating, the coating is irradiated with ultraviolet rays through the negative mask under the condition of 500 mJ / cm ² . A 1% Na ₂ CO ₃ aqueous solution at 30 ° C. is sprayed for 90 seconds at an injection pressure of 0.2 MPa on the film after exposure, 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 determined that development is possible when a portion corresponding to the non-exposed part of the film is removed and no residue is observed.

  Below, an example of the method of manufacturing a printed wiring board provided with the interlayer insulation layer formed from the photosensitive resin composition by this embodiment is demonstrated with reference to FIG. 1A to FIG. 1E. In this method, 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 includes, for example, at least one insulating layer 2 and at least one conductor wiring 3. The conductor wiring 3 provided on one surface of the core material 1 is hereinafter referred to as a first conductor wiring 3. As shown to FIG. 1B, the film | membrane 4 is formed from the photosensitive resin composition on the surface in which the 1st conductor wiring 3 of the core material 1 is provided. Examples of the method for forming the film 4 include a coating method and a dry film method.

  In the coating method, for example, a photosensitive resin composition is coated on the core material 1 to form a wet coating film. The method for applying the photosensitive resin composition is selected from the group consisting of known methods such as dipping, spraying, spin coating, roll coating, curtain coating, and screen printing. Subsequently, in order to volatilize the organic solvent in the photosensitive resin composition, the wet coating film is dried at a temperature in the range of 60 to 120 ° C., for example, and the coating film 4 can be obtained.

  In the dry film method, a photosensitive resin composition is first applied on a suitable support made of polyester or the like, and then dried to form a dry film that is a dried product of the photosensitive resin composition on the support. . Thereby, the dry film with a support provided with a dry film and the support body which supports a dry film is obtained. In this dry film with a support, the dry film is laminated on the core material 1, then pressure is applied to the dry film and the core material 1, and then the support is peeled off from the dry film, whereby the dry film is cored on the support. Transfer onto material 1. Thereby, the coating 4 made of a dry film is provided on the core material 1.

  The coating 4 is exposed to light and partially cured as shown in FIG. 1C. For this purpose, for example, a negative mask is applied to the film 4 and then the film 4 is irradiated with ultraviolet rays through the negative mask. The negative mask includes an exposure part that transmits ultraviolet light and a non-exposure part that blocks ultraviolet light, and the non-exposure part is provided at a position that matches the position of the through hole 10. The negative mask is 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 ultrahigh-pressure mercury lamp, a xenon lamp, and a metal halide lamp.

  As an exposure method, a method other than a method using a negative mask may be employed. For example, the film 4 may be exposed by a direct drawing method in which only the portion of the film 4 to be exposed is irradiated with ultraviolet rays emitted from a light source. The light source applied to the direct drawing method is, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, g line (436 nm), h line (405 nm), i line (365 nm), and g line, h line and i line. It is selected from the group consisting of two or more kinds of combinations.

  In the dry film method, after the dry film in the dry film with the support is stacked on the core material 1, the support 4 is allowed to pass through and the ultraviolet ray is irradiated onto the coating 4 made of the dry film without peeling off the support. Then, the coating 4 may be exposed to light, and then the support may be peeled off from the coating 4 before the development treatment.

  Subsequently, the coating 4 is developed to remove the unexposed portion 5 of the coating 4 shown in FIG. 1C, whereby the hole 6 is formed at the position where the through hole 10 is formed as shown in FIG. 1D. Is provided. In the development process, an appropriate developer according to the composition of the photosensitive resin composition can be used. The developer 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 is, for example, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethyl ammonium hydroxide and water. It contains at least one component selected from the group consisting of lithium oxide. 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 developer is preferably an alkaline aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide, and particularly preferably an aqueous sodium carbonate solution. In this case, it is possible to improve the work environment and reduce the burden of waste disposal.

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

  If necessary, the coating 4 may be further irradiated with ultraviolet rays before or after heating. In this case, photocuring of the film 4 can be further advanced.

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

  Further, before the hole plating 9 as shown in FIG. 1E is provided, the entire inner surface of the hole 6 and a part of the outer surface of the interlayer insulating layer 7 can be roughened. In this manner, the adhesion between the core material 1 and the hole plating 9 can be improved by roughening a part of the outer surface of the interlayer insulating layer 7 and the inner side surface of the hole 6.

  In roughening a part of the outer surface of the interlayer insulating layer 7 and the entire inner surface of the hole 6, the same procedure as a general desmear process using a commercially available desmear swelling liquid and desmear liquid can be performed. However, the present invention is not limited to this, and a method of imparting a rough surface to a cured product such as plasma treatment, UV treatment, or ozone treatment can be appropriately employed.

  When the hole plating 9 is provided, the initial wiring can be formed by subjecting a part of the roughened outer surface and the inner side surface of the hole 6 to electroless metal plating. Thereafter, the hole plating 9 can be formed by depositing a metal in the electrolyte plating solution on the initial wiring by electrolytic metal plating.

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

  First, a core material is prepared. 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 surface of the core material where the conductor wiring is provided. Examples of the method for forming the film include a coating method and a dry film method. As the coating method and the dry film method, the same method as that for forming the interlayer insulating layer can be employed. The film is partially photocured by exposure. The exposure method can be the same as the method for forming the interlayer insulating layer. Subsequently, the film is subjected to a development process to remove the unexposed part of the film, whereby the exposed part of the film remains on the core material. Subsequently, the coating on the core material is heated and cured. The developing method and the heating method can be the same as the method for forming the interlayer insulating layer. If necessary, the film may be further irradiated with ultraviolet rays before or after heating. In this case, photocuring of the film can be further advanced.

  By the above, the solderless resist layer which consists of hardened | cured material of the photosensitive resin composition is provided on a core material. Thereby, a printed wiring board provided with the core material provided with an insulating layer and the conductor wiring on it, and the soldering resist layer which partially covers the surface in which the conductor wiring in a core material is provided is obtained.

  Hereinafter, the present invention will be specifically described by way of examples.

(1) Synthesis of carboxyl group-containing resin (1-1) Synthesis examples A-1 to A-8
In a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube, and a stirrer, the components shown in the “first reaction” column of Table 1 are added, and these are stirred under air bubbling. A mixture was prepared. While stirring this mixture in the flask under air bubbling, the mixture was heated at the reaction temperature and reaction time shown in the “Reaction Conditions” column. This prepared an intermediate solution.

  Subsequently, the components shown in the “second reaction” column of Table 1 were added to the intermediate solution in the flask, and the reaction temperature and reaction time shown in the “reaction condition (1)” column while stirring under air bubbling. And heated. Then, it heated at the reaction temperature and reaction time which are shown in the "reaction condition (2)" column, stirring under air bubbling. This obtained a 65 mass% solution of carboxyl group-containing resin. The weight average molecular weight and acid value of the carboxyl group-containing resin are as shown in Table 1. The molar ratio between the components is also shown in Table 1.

In addition, the detail of the component shown in the (a1) column of Table 1 is as follows.
Epoxy compound 1: A bisphenolfluorene type epoxy compound having an epoxy equivalent of 250 g / eq, represented by the formula (7), wherein R _{1 to} R ₈ in the formula (7) are all hydrogen.
Epoxy compound 2: epoxy equivalent 279 g represented by the formula (7), wherein R ₁ and R ₅ in the formula (7) are all methyl groups, and R _{2 to} R ₄ and R _{6 to} R ₈ are all hydrogen / Eq bisphenolfluorene type epoxy compound.

(1-2) Synthesis Example B-1
In a four-necked flask equipped with a reflux condenser, thermometer, glass tube for nitrogen substituent, and stirrer, 75 parts by weight of methacrylic acid, 85 parts by weight of methyl methacrylate, 20 parts by weight of styrene, 20 parts by weight of butyl methacrylate, 430 parts by mass of propylene glycol monomethyl ether and 5 parts by mass of azobisisobutyronitrile were added. The liquid in the four-necked flask was heated at 75 ° C. for 5 hours under a nitrogen stream to advance the polymerization reaction, thereby obtaining a copolymer solution having a concentration of 32%.

  To this copolymer solution, 0.1 part by mass of hydroquinone, 50 parts by mass of glycidyl methacrylate, and 0.8 parts by mass of dimethylbenzylamine were added, and the addition reaction was allowed to proceed by heating at 80 ° C. for 24 hours. This obtained the 37% solution of carboxyl group-containing resin (B-1). The weight average molecular weight of the carboxyl group-containing resin (B-1) was 31790, and the solid content acid value was 120 mgKOH / g.

(1-3) Synthesis Example B-2
In a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube, and a stirrer, a biphenyl novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product number NC-3000-H, epoxy equivalent 288 g / eq) 288 Part by mass, 155 parts by mass of diethylene glycol monoethyl ether acetate, 0.2 parts by mass of methylhydroquinone, 72 parts by mass of acrylic acid, and 3 parts by mass of triphenylphosphine are added, and these are stirred under air bubbling. To prepare a mixture. The mixture was heated at 115 ° C. for 12 hours with stirring under air bubbling in the flask. This prepared an intermediate solution.

  Subsequently, 91.2 parts by mass of 1,2,3,6-tetrahydrophthalic anhydride and 90 parts by mass of diethylene glycol monoethyl ether acetate were added to the intermediate solution in the flask and stirred under air bubbling. However, it heated at 90 degreeC for 4 hours. This obtained the 65 mass% solution of carboxyl group-containing resin (B-2). The weight average molecular weight of the carboxyl group-containing resin (B-2) was 8120, and the acid value was 76 mgKOH / g.

(2) Preparation of photosensitive resin composition After kneading a part of the components shown in Table 2 and Table 3 below with three rolls, all the components shown in Table 2 and Table 3 below are flasked. The photosensitive resin composition was obtained by stirring and mixing in the inside. The details of the components shown in Tables 2 and 3 are as follows.
Unsaturated compound: trimethylolpropane triacrylate.
Photopolymerization initiator A: 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], manufactured by BASF, product number Irgacure OXE 01.
Photopolymerization initiator B: Etanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), manufactured by BASF, product number Irgacure OXE 02.
Photopolymerization initiator C: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, manufactured by BASF, product number Irgacure 907.
Photopolymerization initiator D: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, manufactured by BASF, product number Irgacure 369E.
Photopolymerization initiator E: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF, product number Irgacure TPO.
Photopolymerization initiator F: bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide, manufactured by BASF, product number Irgacure 819.
Photopolymerization initiator G: 4,4′-bis (diethylamino) benzophenone.
Photopolymerization initiator H: 1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF, product number Irgacure 184.
Photopolymerization initiator I: 2-hydroxy-2-methyl-1-phenyl-propan-1-one, manufactured by BASF, product number Irgacure 1173.
Crystalline epoxy resin A: Biphenyl type crystalline epoxy resin (product name YX-4000 manufactured by Mitsubishi Chemical Corporation, melting point 105 ° C., epoxy equivalent 187 g / eq).
Crystalline epoxy resin B: Bisphenol type crystalline epoxy resin (product name YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., melting point 75 to 85 ° C., 192 g / eq).
Epoxy resin solution C: a solution in which a long-chain carbon chain-containing bisphenol A type epoxy resin (manufactured by DIC, product number EPICLON EXA-4816, liquid resin, epoxy equivalent 410 g / eq) is dissolved in diethylene glycol monoethyl ether acetate at a solid content of 90%. (The epoxy equivalent in terms of solid content of 90% is 455.56 g / eq).
Melamine: manufactured by Nissan Chemical Industries, Ltd., fine melamine; dispersed in the photosensitive resin composition with an average particle size of 8 μm.
Organic filler dispersion solution: Crosslinked rubber (NBR) having an average primary particle size of 0.07 μm, manufactured by JSR Corporation, part number XER-91-MEK dispersion zone 15% solution, acid value 10.0 mgKOH / g.
Antioxidant: A hindered phenol antioxidant, manufactured by BASF, product number IRGANOX 1010.
Antifoaming agent: manufactured by Shin-Etsu Silicone Co., Ltd., product number KS-66.
Silane coupling agent: 3-glycidoxypropyltrimethoxysilane.
Surfactant: manufactured by DIC, product number MegaFuck F-477.
-Rheology control agent: Product number BYK-430 manufactured by Big Chemie Japan Co., Ltd.
Solvent: diethylene glycol monoethyl ether acetate.

(3) Preparation of test piece When using the photosensitive resin composition of each Example and comparative example except Example 17, the test piece was produced as follows.

A glass epoxy copper clad laminate (FR-4 type) provided with a copper foil having a thickness of 17.5 μm was prepared. A comb-shaped electrode having a line width / space width of 50 μm / 50 μm was formed as a conductor wiring on this glass epoxy copper clad laminate by a subtractive method, thereby obtaining a core material. A wet paint film was formed by applying the photosensitive resin composition to the front surface of the core material by screen printing. This wet coating film was heated at 80 ° C. for 40 minutes and preliminarily dried to form a film having a thickness of 25 μm. In a state where a negative mask having a non-exposed portion including a circular shape of 50 μm was applied to this film, the film was irradiated with ultraviolet rays through the negative mask under the condition of 100 mJ / cm ² . The exposed film was developed. In the development process, a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed onto the film for 90 seconds at a spray pressure of 0.2 MPa. Thereby, the layer which consists of hardened | cured material of the photosensitive resin composition was formed on the core material. As a result, a test piece was obtained.

In the case of using the photosensitive resin composition of Comparative Example 1, obtained in addition to the condition of the exposure amount 100 mJ / cm ^2, even in the condition of the exposure amount 400 mJ / cm ^2, the test piece in the same manner as described above It was. In the table, the evaluation in the case of the exposure amount of 100 mJ / cm ² is shown on the left side, and the evaluation in the case of the exposure amount of 400 mJ / cm ² is shown on the right side.

  Moreover, in the comparative example 2, the film | membrane is peeled partly by image development processing also in the exposed location, and the evaluation of (4-3)-(4-7) is not performed.

  When using the photosensitive resin composition of Example 17, the test piece was obtained as follows. The photosensitive resin composition was coated on a polyethylene phthalate film with an applicator and then dried by heating at 95 ° C. for 25 minutes to form a dry film having a thickness of 25 μm on the film.

  A glass epoxy copper clad laminate (FR-4 type) provided with a copper foil having a thickness of 17.5 μm was prepared. A comb-shaped electrode having a line width / space width of 50 μm / 50 μm was formed as a conductor wiring on this glass epoxy copper clad laminate by a subtractive method, thereby obtaining a core material. A dry film was laminated by heating with a vacuum laminator over the entire surface of the core material. The conditions for heat lamination are 0.5 MPa, 80 ° C., and 1 minute. As a result, a 25 μm-thick film made of a dry film was formed on the core material. The film was exposed, developed and irradiated with ultraviolet light under the same conditions as described above. In addition, the film made from a polyethylene terephthalate was peeled from the dry film (coating) after exposure and before development. This formed the layer which consists of hardened | cured material of the photosensitive resin composition on a printed wiring board (core material). As a result, a test piece was obtained.

  In addition, since Example 17 is a dry film type, (4-1) and (4-2) are not evaluated. In Example 17, development was possible without problems in the development process.

(4) Test evaluation (4-1) Tackiness For each of Examples and Comparative Examples except Example 17, the degree of adhesiveness of the film when removing the negative mask from the film after exposure of the film during test piece production was as follows. Evaluation was performed as shown in FIG.
A: Resistance is not felt when removing the negative mask from the film, and no sticking marks are observed on the film after the negative mask is removed.
B: Resistance was felt when the negative mask was removed from the film, and sticking marks were observed on the film after the negative mask was removed.
C: It was difficult to remove the negative mask from the film, and the film was damaged when the negative mask was forcibly removed.

  In addition, about the comparative example 5 whose tackiness evaluation is C, the evaluation of (4-3)-(4-8) is not performed.

(4-2) Developability About each Example and Comparative Example except Example 17, the wet paint film was formed by apply | coating the photosensitive resin composition to the whole surface of the printed wiring board by the screen printing method. This wet coating film was heated at 80 ° C. for 40 minutes or 60 minutes to form a film having a thickness of 25 μm. This film was developed without exposure. In the development processing, a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed for 90 seconds at a spray pressure of 0.2 MPa, and then pure was sprayed for 90 seconds at a spray pressure of 0.2 MPa. The printed wiring board after the treatment was observed, and the result was evaluated as follows.
A: The film was completely removed regardless of whether the heating time of the wet coating film was 40 minutes or 60 minutes.
B: When the heating time of the wet coating film was 40 minutes, all the coating film was removed, but at 60 minutes, a part of the coating film remained on the printed wiring board.
C: A part of the film remained on the printed wiring board regardless of whether the heating time of the wet coating film was 40 minutes or 60 minutes.

(4-3) Resolution The hole formed in the layer which consists of hardened | cured material in the test piece of each Example and a comparative example was observed, and the result was evaluated as follows.
A: The diameter of the bottom of the hole is 40 μm or more.
B: The diameter of the bottom of the hole is 25 μm or more and less than 40 μm.
C: The diameter of the bottom of the hole is less than 25 μm, or no clear hole is formed.

(4-4) Plating resistance After forming a nickel plating layer using a commercially available electroless nickel plating bath on the layer made of the cured product in the test pieces of the examples and comparative examples, a commercially available electroless material is used. A gold plating layer was formed using a gold plating bath. Thereby, the metal layer which consists of a nickel plating layer and a gold plating layer was formed on the layer which consists of hardened | cured material. The layer and metal layer which consisted of hardened | cured material were observed visually. Moreover, the cellophane adhesive tape peeling test was done with respect to the metal layer. The results were evaluated as follows.
A: No abnormality was observed in the appearance of the layer made of the cured product and the metal layer, and the metal layer was not peeled by the cellophane adhesive tape peel test.
B: Although discoloration was recognized in the layer which consists of hardened | cured material, peeling of the metal layer by the cellophane adhesive tape peeling test did not arise.
C: Lifting of the layer made of the cured product was observed, and the metal layer was peeled off by the cellophane adhesive tape peeling test.

(4-5) Insulation between lines While applying a bias voltage of DC 30 V to the conductor wiring (comb electrode) in the test pieces of the examples and comparative examples, the printed wiring board was placed at 121 ° C. and 97% R.D. H. The test environment was exposed for 180 hours. The electrical resistance value between the comb-type electrodes of the cured product layer in this test environment was constantly measured, and the result was evaluated according to the following evaluation criteria.
A: The electric resistance value was constantly maintained at 10 ⁶ Ω or more from the start of the test until 180 hours passed.
B: The electric resistance value was always maintained at 10 ⁶ Ω or more until 130 hours passed from the start of the test, but the electric resistance value became less than 10 ⁶ Ω before 180 hours passed from the start of the test.
C: The electrical resistance value was less than 10 ⁶ Ω before 130 hours passed from the start of the test.

(4-6) Interlayer insulation The conductive tape was affixed on the layer which consists of hardened | cured material in the test piece of each Example and a comparative example. While applying a bias voltage of DC 100 V to the conductive tape, the test piece was placed at 121 ° C. and 97% R.D. H. The test environment was exposed for 100 hours. The electrical resistance value between the conductive wiring of the layer made of the cured product and the conductive tape in this test environment was constantly measured, and the result was evaluated according to the following evaluation criteria.
A: The electric resistance value was constantly maintained at 10 ⁶ Ω or more until 100 hours passed from the start of the test.
B: The electric resistance value was always maintained at 10 ⁶ Ω or more until 80 hours passed from the start of the test, but the electric resistance value became less than 10 ⁶ Ω before 100 hours passed from the start of the test.
C: The electric resistance value was less than 10 ⁶ Ω before 80 hours passed from the start of the test.

(4-7) PCT (pressure cooker test)
The test pieces of each Example and Comparative Example were allowed to stand in an environment of 121 ° C. and 100% RH for 120 hours, and then the appearance of the cured layer was evaluated according to the following evaluation criteria.
A: No abnormality was found 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 partial swelling occurred.

(4-8) UV curing
For each example and comparative example, the exposure test mask “Step Tablet PHOTEC 21-stage” manufactured by Hitachi Chemical Co., Ltd. was applied at the time of exposure and adhered under reduced pressure, and the process up to the development step was performed under the same conditions as the preparation of the test piece. gave. For the exposure, a reduced pressure contact type double-side exposure machine “ORC HMW680GW” manufactured by Oak Manufacturing Co., Ltd. was used. As an index of deep UV curable property, the number of glossy steps among the remaining step steps after the development processing was determined and evaluated according to the following evaluation criteria.
A: The number of gloss steps was 2 or more.
B: The number of gloss steps was 1.
C: There was no glossy step number in the remaining step steps.

Claims (9)

A photosensitive resin composition comprising:
A carboxyl group-containing resin (A);
An unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule;
A photopolymerization initiator (C);
An epoxy compound (D);
Containing
The carboxyl group-containing resin (A) is a carboxyl group-containing resin (A1) that is a reaction product of an intermediate that 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) has a bisphenolfluorene skeleton represented by the following formula (1). In the following formula (1), R _{1 to} R ₈ are each independently hydrogen, alkyl having 1 to 5 carbon atoms. A group, or halogen,

The photopolymerization initiator (C) contains an oxime ester photopolymerization initiator (C1) having a partial structure (S2) represented by the following formula (8),
In the following formula (8), R ₉ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group, and the hydrocarbon group having 1 to 20 carbon atoms is a hydroxyl group, an ether group, The aromatic hydrocarbon group may have at least one substituent selected from the group consisting of a carbonyl group and halogen, and the aromatic hydrocarbon group is selected from the group consisting of a hydroxyl group, an ether group, a carbonyl group, and a halogen May have at least one substituent,
R ₁₀ is a hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group, and the hydrocarbon group having 1 to 20 carbon atoms is selected from the group consisting of a hydroxyl group, an ether group, a carbonyl group, and a halogen. The aromatic hydrocarbon group may have at least one substituent selected from the group consisting of a hydroxyl group, an ether group, a carbonyl group, and a halogen. Often,

The amount of the oxime ester photopolymerization initiator (C1) relative to the total amount of the photopolymerization initiator (C) is in the range of 0.05 to 60% by mass.
Photosensitive resin composition. The amount of the photopolymerization initiator (C) relative to the carboxyl group-containing resin (A) is in the range of 3 to 20% by mass,
The amount of the oxime ester photopolymerization initiator (C1) relative to the carboxyl group-containing resin (A) is in the range of 0.01 to 3% by mass.
The photosensitive resin composition according to claim 1. The photopolymerization initiator (C) contains at least one of an aminoacetophenone photopolymerization initiator (C2) and an acylphosphine oxide photopolymerization initiator (C3).
The photosensitive resin composition of Claim 1 or 2. The photopolymerization initiator (C) contains a bis (dialkylamino) benzophenone photopolymerization initiator (C4).
The photosensitive resin composition as described in any one of Claims 1 thru | or 3. The amount of the bis (dialkylamino) benzophenone photopolymerization initiator (C4) relative to the carboxyl group-containing resin (A) is in the range of 0.1 to 3% by mass.
The photosensitive resin composition of Claim 4. The oxime ester photopolymerization initiator (C1) contains a compound (c1) represented by the following formula (11),
In the following formula (11), R ₁₇ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group, and the hydrocarbon group having 1 to 12 carbon atoms is a hydroxyl group, The aromatic hydrocarbon group may have at least one substituent selected from the group consisting of an ether group and a carbonyl group, and the aromatic hydrocarbon group is at least selected from the group consisting of a hydroxyl group, an ether group, and a carbonyl group May have one substituent,
R ₁₈ and R ₂₀ are each independently a hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group, and the hydrocarbon group having 1 to 20 carbon atoms is a hydroxyl group, an ether group, or a carbonyl group. And at least one substituent selected from the group consisting of halogen, and the aromatic hydrocarbon group is at least one selected from the group consisting of a hydroxyl group, an ether group, a carbonyl group, and a halogen. May have two substituents,
R ₁₉ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group, and the hydrocarbon group having 1 to 20 carbon atoms includes a hydroxyl group, an ether group, a carbonyl group, and a halogen. It may have at least one substituent selected from the group, and the aromatic hydrocarbon group has at least one substituent selected from the group consisting of a hydroxyl group, an ether group, a carbonyl group, and a halogen. You may,

The photosensitive resin composition as described in any one of Claims 1 thru | or 5. It is a dried product of the photosensitive resin composition according to any one of claims 1 to 6.
Dry film. An interlayer insulating layer containing a cured product of the photosensitive resin composition according to any one of claims 1 to 6,
Printed wiring board. A solder resist layer including a cured product of the photosensitive resin composition according to any one of claims 1 to 6,
Printed wiring board.

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