JP6542435B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a coating material, for example, a photosensitive resin composition suitable for a coating material for coating a conductor circuit pattern formed on a substrate such as a printed wiring board, a cured product obtained by curing the same, and the cured product It relates to a coated printed wiring board.

  Printed wiring boards such as flexible printed wiring boards and rigid wiring boards are used to form a conductor circuit pattern on a substrate and to mount electronic components on the soldering lands of that pattern by soldering. Circuit portions other than the above are covered with an insulating protective film (for example, a solder resist film). Thereby, when soldering an electronic component to a printed wiring board, while preventing that a solder adheres to an unnecessary part, it prevents that a circuit conductor is directly exposed to air and is corroded by oxidation or humidity. Do.

  In addition, the conductor forming the conductor circuit pattern is designed to be thicker (35 μm or more, for example, 50 to 100 μm) than the conventional general-purpose thickness (approximately 10 to 25 μm) according to the use conditions and the like. is there. When a protective film such as a solder resist film is formed on a printed wiring board having a thick conductor circuit, the film thickness of the insulating protective film needs to be correspondingly thick (for example, 60 to 110 μm). It is necessary to apply a thick (for example, 70 to 150 .mu.m thick) resin composition.

  Therefore, a printed wiring board has been proposed in which the photocurable solder resist layer has a laminated structure including a lower layer solder resist and an upper layer solder resist (Patent Document 1).

  However, when the photosensitive resin composition, which is a raw material of the insulating protective film, is thickly coated as in Patent Document 1, it is difficult for the ultraviolet rays to reach at the deep portion of the coating film at the time of ultraviolet exposure due to the thickness of the coating film. However, the sensitivity of the coating film (in particular, the sensitivity near the bottom of the coating film) is not sufficient, and there is a problem that high resolution (high dimensional accuracy) or a good line shape may not be obtained.

  Moreover, a photosensitive resin composition may be coated on a printed wiring board by a spray coating method from the viewpoint of workability and productivity. However, when the photosensitive resin composition is thickly coated as described above by the spray coating method, there is a problem that a sagging occurs in the coating film or a problem that a good coating film appearance can not be obtained.

JP, 2010-129575, A

  In view of the above circumstances, it is an object of the present invention to have excellent sensitivity even in the case of a photosensitive resin composition thickly applied using a spray coating method, to prevent sagging, to be excellent in appearance, and high resolution It is an object of the present invention to provide a photosensitive resin composition capable of forming a cured coating film having properties (high dimensional accuracy) and insulating properties, and a wiring board such as a printed wiring board having a photocured film of the photosensitive resin composition.

An embodiment of the present invention is a radically polymerizable unsaturated monocarboxylic acid oxidized epoxy which is a reaction product of a multifunctional epoxy resin having two or more epoxy groups in one molecule (A) and a radically polymerizable unsaturated monocarboxylic acid Glycidyl having a radically polymerizable unsaturated group and an epoxy group at the carboxyl group of a polybasic acid-modified radically polymerizable unsaturated monocarboxylic acid oxidized epoxy resin which is a compound in which a polybasic acid or its anhydride is reacted with a hydroxyl group of resin A carboxyl group-containing photosensitive resin, which is a reaction product of a compound, (B) a photopolymerization initiator, (C) a reactive diluent, (D) an epoxy compound, and (E) a general formula (I) )
^{[R 1 R 2 R 3 R} 4 -N] + X - (I)
(Wherein, R ¹ , R ² , R ³ and R ⁴ are each independently a saturated aliphatic hydrocarbon group having 1 to 25 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 25 carbon atoms, or a substituent Or an aromatic hydrocarbon group which may have at least one of R ¹ , R ² , R ³ and R ⁴ is an aromatic hydrocarbon group which may have a substituent ), X represents a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine.) Bentonite treated with a quaternary ammonium salt, (F) hydrophobic silica, and (F) G) Color pigments other than phthalocyanine greens, and the (F) hydrophobic silica is 5.0 parts by mass to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A). It is a photosensitive resin composition contained.

  In the above embodiment, the carboxyl group-containing photosensitive resin of the component (A) further has a radically polymerizable unsaturated group and an epoxy group in the carboxyl group of the polybasic acid-modified radically polymerizable unsaturated monocarboxylic acid oxidized epoxy resin. Since the glycidyl compound has a reacted chemical structure, it has characteristics of improved photosensitivity. Moreover, "the carboxyl group-containing photosensitive resin 100 mass parts" means the mass part of solid content of a carboxyl group-containing photosensitive resin.

  An embodiment of the present invention is a photosensitive resin composition in which the color pigment other than the (G) phthalocyanine green type is at least one compound selected from the group consisting of phthalocyanine blue type and anthraquinone type.

The aspect of this invention is the photosensitive resin composition whose ^{one of} said R < ¹ >, R < ² >, R < ³ >, R < ⁴ > is an aromatic hydrocarbon group which may have a substituent.

  In the aspect of the present invention, the bentonite treated with the quaternary ammonium salt of the component (E) is 5.0 parts by mass to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A). It is a photosensitive resin composition contained.

  In the embodiment of the present invention, the (F) hydrophobic silica is contained in an amount of 6.5 parts by mass to 13.5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A). The photosensitive resin composition in which the bentonite treated with the quaternary ammonium salt of component) is contained in an amount of 8.0 parts by mass to 18 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A). is there.

  In the embodiment of the present invention, the weight of bentonite treated with the quaternary ammonium salt of the component (E): the weight of the hydrophobic silica (F) is in the range of 1.0: 0.30 to 3.0. It is a photosensitive resin composition.

  An embodiment of the present invention is the photosensitive resin composition wherein the (F) hydrophobic silica is a silica modified with an alkylsilyl group.

  An embodiment of the present invention is a photosensitive resin composition wherein the quaternary ammonium salt is a stearyl benzyldimethyl ammonium salt.

  An embodiment of the present invention is a photosensitive resin composition further comprising poly (oxyethylene) tridecyl ether phosphate.

  An aspect of the present invention is a photocured product of the photosensitive resin composition.

  An aspect of the present invention is a wiring board having a photocured film of the photosensitive resin composition.

  According to the aspect of the present invention, as the carboxyl group-containing photosensitive resin, the carboxyl group-containing photosensitive resin of the component (A) having the above-described property of improved photosensitivity is used, and further, the quaternary of the component (E) Ammonium salt-treated bentonite, 5.0 parts by mass to 20 parts by mass of (F) hydrophobic silica, and (G) phthalocyanine green based on 100 parts by mass of the carboxyl group-containing photosensitive resin of component (A) Even if it is a photosensitive resin composition thickly applied using a spray coating method by containing other color pigments, it has excellent sensitivity, can prevent sagging, is excellent in appearance, and has high resolution. A photosensitive resin composition capable of forming a cured coating film having imageability (high dimensional accuracy) and insulating properties can be obtained.

  According to the aspect of the present invention, since the color pigment other than phthalocyanine green is at least one color pigment selected from the group consisting of phthalocyanine blue and anthraquinone, excellent coating appearance and insulation properties can be obtained. While obtaining, it is possible to obtain better resolution (dimensional accuracy).

According to the aspect of the present invention, the insulating property is further improved by ^one of R ¹ , R ² , R ³ and R ^{4 being} an aromatic hydrocarbon group which may have a substituent. Can.

  According to the aspect of the present invention, the bentonite treated with the quaternary ammonium salt of the component (E) is 5.0 parts by mass to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A). Even when the photosensitive resin composition is thickly applied by the spray coating method, the insulating property is further improved without impairing the sensitivity, the prevention of sagging, the appearance of the coating film, and the resolution by being contained. Can.

  According to the embodiment of the present invention, 5.5 parts by mass to 13.5 parts by mass of hydrophobic silica is contained with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A), (E) By containing 8.0 parts by mass to 18 parts by mass of bentonite treated with the quaternary ammonium salt of the component, excellent sensitivity can be obtained even in the case of a photosensitive resin composition thickly applied by a spray coating method. It is possible to improve the prevention of sagging, the appearance of the coating film, the insulation properties and the resolution with good balance without any damage.

  According to an embodiment of the present invention, the mass of bentonite treated with the quaternary ammonium salt of the component (E): the mass of the hydrophobic silica (F) is in the range of 1.0: 0.30 to 3.0. As a result, even in the case of a photosensitive resin composition applied thickly by a spray coating method, sagging can be reliably prevented, and coating film appearance, insulation properties and resolution can be more reliably improved.

  According to the aspect of the present invention, the (F) hydrophobic silica is modified with an alkylsilyl group, so that even when the photosensitive resin composition is thickly coated by the spray coating method, it is more reliably coated. It is possible to prevent film sagging.

  According to the aspect of the present invention, when the quaternary ammonium salt is a stearyl benzyldimethyl ammonium salt, further superior insulating properties can be obtained.

  According to the aspect of the present invention, by further containing poly (oxyethylene) tridecyl ether phosphate, a cured coating film excellent in alkali developability can be obtained.

Next, the photosensitive resin composition of the present invention will be described below. The photosensitive resin composition of the present invention is a radically polymerizable unsaturated resin which is the reaction product of a polyfunctional epoxy resin having two or more epoxy groups in one molecule of (A) and a radically polymerizable unsaturated monocarboxylic acid. A radically polymerizable unsaturated group and an epoxy group at a carboxyl group of a polybasic acid-modified radically polymerizable unsaturated monocarboxylic acid oxidized epoxy resin which is a compound in which a polybasic acid or an anhydride thereof is reacted with a hydroxyl group of a monocarboxylic oxidized epoxy resin. A carboxyl group-containing photosensitive resin which is a reaction product of a glycidyl compound having a component (B), a photopolymerization initiator (B), a reactive diluent (C), an epoxy compound (D), and General formula (I)
^{[R 1 R 2 R 3 R} 4 -N] + X - (I)
(Wherein, R ¹ , R ² , R ³ and R ⁴ are each independently a saturated aliphatic hydrocarbon group having 1 to 25 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 25 carbon atoms, or a substituent Or an aromatic hydrocarbon group which may have at least one of R ¹ , R ² , R ³ and R ⁴ is an aromatic hydrocarbon group which may have a substituent ), X represents a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine.) Bentonite treated with a quaternary ammonium salt, (F) hydrophobic silica, and (F) G) Color pigments other than phthalocyanine greens, and the (F) hydrophobic silica is 5.0 parts by mass to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A). Part is included.

The carboxyl group-containing photosensitive resin of the component (A) The carboxyl group-containing photosensitive resin of the component (A) is an acrylic resin in at least a part of the epoxy group of the polyfunctional epoxy resin having two or more epoxy groups in one molecule. A radically polymerizable unsaturated monocarboxylic acid such as epoxy (meth) acrylate by reacting a radically polymerizable unsaturated monocarboxylic acid such as acid or methacrylic acid (hereinafter sometimes referred to as "(meth) acrylic acid") An epoxy resin is obtained, and a polybasic acid or its anhydride is reacted with a hydroxyl group of the radically polymerizable unsaturated monocarboxylic acid oxidized epoxy resin thus produced, and a polybasic acid-modified radical polymerizable property such as polybasic acid-modified epoxy (meth) acrylate Polybasic acid modified radically polymerizable unsaturated monocarboxylic oxidized epoxy resin obtained by obtaining unsaturated monocarboxylic oxidized epoxy resin It is a resin in which a glycidyl compound having one or more radically polymerizable unsaturated groups and an epoxy group is reacted with a part of carboxyl groups.

  The carboxyl group-containing photosensitive resin of the component (A) to be blended into the photosensitive resin composition of the present invention is to react a glycidyl compound with the carboxyl group of the polybasic acid-modified radically polymerizable unsaturated monocarboxylic acid oxidized epoxy resin Furthermore, since a radically polymerizable unsaturated group is introduced into the side chain of the polybasic acid-modified radically polymerizable unsaturated monocarboxylic acid oxidized epoxy resin, the polybasic acid-modified radically polymerizable unsaturated monocarboxylic acid oxidized resin and In comparison, it has excellent photosensitive properties.

  Therefore, a thick (for example, 60 to 110 μm thick) insulating protective film is formed on a printed wiring board designed to be thick (35 μm or more, for example, 50 to 100 μm thick) conductors forming the conductor circuit pattern. Even if the photosensitive resin composition is thickly applied (for example, 70 to 150 μm thick) to form the film, the sensitivity of the coating film (particularly, the sensitivity in the vicinity of the bottom of the coating film) is excellent. It is possible to obtain a cured coating film having good properties and good line shape.

  As the polyfunctional epoxy resin, any epoxy resin having two or more functional groups can be used. Although the epoxy equivalent of a polyfunctional epoxy resin is not specifically limited, 3000 or less is preferable, 2000 or less is more preferable, 1000 or less is more preferable, and 100-500 are especially preferable. The structure of the multifunctional epoxy resin is not particularly limited. For example, rubber modified epoxy resin such as biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, silicone modified epoxy resin, ε-caprolactone modified epoxy resin Phenol novolac type epoxy resin such as bisphenol A type, bisphenol F type, bisphenol AD type, cresol novolac type epoxy resin such as о-cresol novolac type, bisphenol A novolac type epoxy resin, cycloaliphatic polyfunctional epoxy resin, glycidyl Ester type multifunctional epoxy resin, glycidyl amine type multifunctional epoxy resin, heterocyclic multifunctional epoxy resin, bisphenol modified novolac type epoxy resin, multifunctional modified novolac type epoxy resin, The condensation-type epoxy resin etc. of phenols and the aromatic aldehyde which has phenolic hydroxyl group etc. can be mentioned. Further, those resins into which a halogen atom such as Br or Cl is introduced may be used. These polyfunctional epoxy resins may be used alone or in combination of two or more.

  The radically polymerizable unsaturated monocarboxylic acid is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid. Acrylic acid and methacrylic acid are preferable. These radically polymerizable unsaturated monocarboxylic acids may be used alone or in combination of two or more.

  The reaction method of a polyfunctional epoxy resin and a radically polymerizable unsaturated monocarboxylic acid is not particularly limited, and a known method can be used. For example, a polyfunctional epoxy resin and a radically polymerizable unsaturated monocarboxylic acid can be used. The reaction can be carried out by heating in a suitable diluent.

  The polybasic acid or polybasic acid anhydride is for reacting with the hydroxyl group formed by the reaction of the polyfunctional epoxy resin and the radically polymerizable unsaturated monocarboxylic acid to introduce a free carboxyl group into the resin. is there. The polybasic acid or its anhydride is not particularly limited, and either saturated or unsaturated one may be used. Examples of polybasic acids include succinic acid, maleic acid, adipic acid, citric acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid Ethyl tetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydro Phthalic acid, endo methylene tetrahydro phthalic acid, methyl endo methylene tetrahydro phthalic acid, trimellitic acid, pyromellitic acid, diglycolic acid and the like can be mentioned, and as polybasic acid anhydrides, these anhydrides can be mentioned. These compounds may be used alone or in combination of two or more.

  The glycidyl compound having one or more radically polymerizable unsaturated groups and an epoxy group is not particularly limited. For example, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, pentaerythritol triacrylate monoglycidyl ether, pentaerythritol trimethacrylate acrylate Glycidyl ether etc. are mentioned. In addition, you may have multiple glycidyl groups in 1 molecule. The compounds having one or more radically polymerizable unsaturated groups and epoxy groups may be used alone or in combination of two or more.

  The acid value of the carboxyl group-containing photosensitive resin of the component (A) is not particularly limited, but the lower limit thereof is preferably 30 mg KOH / g, particularly preferably 40 mg KOH / g, from the viewpoint of reliable alkali development. On the other hand, the upper limit value of the acid value is preferably 200 mg KOH / g from the viewpoint of dissolution prevention of the exposed part by the alkali developer, and particularly preferably 150 mg KOH / g from the viewpoint of maintaining the moisture resistance of the cured product and the excellent insulation properties.

  Further, the mass average molecular weight of the carboxyl group-containing photosensitive resin of the component (A) is not particularly limited, but for example, the lower limit thereof is preferably 3,000 from the viewpoint of the toughness and the touch dryness of the cured coating film. Is particularly preferred. On the other hand, the upper limit value of the mass average molecular weight is preferably 200,000, particularly preferably 50,000, from the viewpoint of smooth alkali developability.

(B) Photopolymerization initiator The photopolymerization initiator is not particularly limited as long as it is generally used, and any of them can be used. Specifically, for example, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime), phenylbis (2,4,5) 6-trimethyl benzoyl) phosphine oxide, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2, 2-dimethoxy-2-phenylacetophenone, 2 , 2-Diethoxy-2-phenylacetophenone, 2-methyl-4 '-(methylthio) -2-morpholinopropiophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl Keto , 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethyl Anthraquinone, 2-tert-butyl anthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal And p-dimethylaminobenzoic acid ethyl ester and the like. These may be used alone or in combination of two or more.

  The content of the photopolymerization initiator is not particularly limited, and preferably 5 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (solid content, the same applies hereinafter) of the component (A).

(C) Reactive Diluent The reactive diluent is, for example, a photopolymerizable monomer, and a compound having at least one, preferably at least two polymerizable double bonds per molecule per molecule. The reactive diluent is used to sufficiently cure the photosensitive resin composition to obtain a cured product having acid resistance, heat resistance, alkali resistance and the like.

  The reactive diluent is not particularly limited as long as it is the above-mentioned compound, and examples thereof include mono (meth) acrylate monomers and polyfunctional (meth) acrylate monomers having two or more functions. Specifically, for example, 2-hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 1,4 -Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid Neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, Fluorinated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate ) Acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylates, caprolactone modified dipentaerythritol hexa (meth) acrylates, urethane (meth) acrylates, etc. That. These may be used alone or in combination of two or more.

  The content of the reactive diluent is not particularly limited, and for example, 2.0 to 200 parts by mass is preferable and 10 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A). Particularly preferred.

(D) Epoxy Compound The epoxy compound is for increasing the crosslink density of the cured product to obtain a cured product having sufficient strength, and an epoxy resin can be mentioned, for example. Examples of the epoxy resin include biphenyl type epoxy resin, bisphenol A type epoxy resin, novolac type epoxy resin (phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, p-tert-butylphenol novolac type epoxy resin, etc.), bisphenol Bisphenol F type epoxy resin or bisphenol S type epoxy resin obtained by reacting epichlorohydrin with F or bisphenol S, and further an alicyclic epoxy resin having cyclohexene oxide group, tricyclodecane oxide group, cyclopentene oxide group, etc., tris ( Triglycidyl isocyanine having a triazine ring such as 2,3-epoxypropyl) isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate Over DOO, dicyclopentadiene type epoxy resins, adamantane type epoxy resins and the like. These compounds may be used alone or in combination of two or more.

  The content of the epoxy compound is not particularly limited, and for example, 10 to 200 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A) from the viewpoint of obtaining a coating film having sufficient strength after curing. Is preferable, and 20 to 100 parts by mass is particularly preferable.

Bentonite treated with quaternary ammonium salt of component (E) A spray coating method is prepared by blending bentonite treated with quaternary ammonium salt of component (E) together with hydrophobic silica (F) described later. Even with a photosensitive resin composition applied to a large thickness, it is possible to prevent sagging, to form a cured coating film having excellent coating film appearance and resolution, and further to provide excellent insulating properties to a cured product. be able to.

The bentonite treated with the quaternary ammonium salt of the component (E) has the following general formula (I)
^{[R 1 R 2 R 3 R} 4 -N] + X - (I)
(Wherein, R ¹ , R ² , R ³ and R ⁴ are each independently a saturated aliphatic hydrocarbon group having 1 to 25 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 25 carbon atoms, or a substituent Or an aromatic hydrocarbon group which may have at least one of R ¹ , R ² , R ³ and R ⁴ is an aromatic hydrocarbon group which may have a substituent X) is an organic bentonite treated with a quaternary ammonium salt represented by) which represents a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine.

Each of R ¹ , R ² , R ³ and R ⁴ of the quaternary ammonium salt is a saturated aliphatic hydrocarbon group having 1 to 25 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 25 carbon atoms, or a substituent Or an aromatic hydrocarbon group which may have at least one of R ¹ , R ² , R ³ and R ^{4 is} an aromatic hydrocarbon group which may have a substituent, The quaternary ammonium salt is not particularly limited as long as it is a quaternary ammonium salt having an aromatic hydrocarbon group, but the number of the aromatic hydrocarbon group which may have a substituent has an insulating property without impairing high resolution. From the point of further improvement, one (i.e., the sum of the saturated aliphatic hydrocarbon group having 1 to 25 carbon atoms and the unsaturated aliphatic hydrocarbon group having 2 to 25 carbon atoms is preferably 3). Moreover, as an aromatic hydrocarbon group, the group derived from a single ring and several rings is mentioned. As an aromatic hydrocarbon group, a benzyl group, a phenyl group, and a naphthyl group are preferable, and a benzyl group and a phenyl group are especially preferable. As a substituent of the aromatic hydrocarbon group which may have a substituent, C1-C5 alkyl groups, such as a methyl group and an ethyl group, can be mentioned, for example.

  In addition, even in the case of thick coating by a spray coating method, aliphatic hydrocarbon groups are used in that a cured coating film having more excellent coating film appearance, resolution and insulating properties is formed while surely preventing sagging. Are preferably quaternary ammonium salts having a saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms and a saturated aliphatic hydrocarbon group having 7 to 22 carbon atoms, and a saturated aliphatic hydrocarbon group having 1 to 2 carbon atoms And quaternary ammonium salts having a saturated aliphatic hydrocarbon group having 14 to 20 carbon atoms are particularly preferred.

  Specific examples of the above-mentioned quaternary ammonium salts include stearyl benzyldimethyl ammonium salts such as stearyl benzyl dimethyl ammonium, palmityl benzyl dimethyl ammonium salts such as palmityl benzyl dimethyl ammonium chloride, and myristyl benzyl such as myristyl benzyl dimethyl ammonium chloride Dimethyl ammonium salt, dodecyl benzyl dimethyl ammonium salt such as dodecyl benzyl dimethyl ammonium chloride, hexyl benzyl dimethyl ammonium salt such as hexyl benzyl dimethyl ammonium chloride, benzyl benzyl dimethyl ammonium salt such as benzyl benzyl dimethyl ammonium chloride, phenyltripropyl ammonium chloride Examples include phenyl tripropyl ammonium chloride and the like. Among these, stearyl benzyldimethyl ammonium salt is preferable in terms of obtaining excellent resolution and insulation properties.

  The content of the bentonite treated with the quaternary ammonium salt of the component (E) is not particularly limited. For example, the lower limit thereof is 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A). Even when thickly applied by the spray coating method, 5.0 parts by mass is preferable from the viewpoint of surely preventing sagging and further improving the insulation properties without impairing the excellent coating film appearance and resolution, and copper foil Particularly, 8.0 parts by mass is preferable in terms of improving the covering property near the conductor. The upper limit thereof is 20 parts by mass from the viewpoint of reliably maintaining the excellent appearance of the cured coating while facilitating spray coating with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A). Is preferred, and 18 parts by weight is particularly preferred.

(F) Hydrophobic silica The photosensitive resin composition thickly applied by the spray coating method by blending the hydrophobic silica with the bentonite treated with the quaternary ammonium salt of the component (E) described above. Even if it is an object, it is possible to prevent sagging without impairing the resolution and the insulating properties, and to provide an excellent coating film appearance.

  The hydrophobic silica is, for example, silica obtained by hydrophobizing the surface of a hydrophilic silica having a silanol group with a hydrophobic compound, and is a spherical or substantially spherical fine particle. As hydrophobic silica, for example, the surface of fine powder silica such as fumed silica or silica airgel obtained by the flame hydrolysis method of silicon tetrachloride, an organosilicon compound such as a silane compound or a siloxane compound which is a hydrophobic compound And those treated to be hydrophobic. Examples of the organic silicon compound which is the hydrophobic compound include methacryloxysilane, methylchlorosilane, dimethyldichlorosilane, hexamethyldisilazane, dimethylsiloxane, trimethoxyoctylsilane, methacrylsilane, acrylsilane and the like. Among them, even a photosensitive resin composition applied thickly by a spray coating method, it is possible to prevent dripping of the coating film more surely and obtain an excellent appearance of a cured coating film. Hydrophobic silicas whose surface is modified are preferred.

The primary particle diameter of the hydrophobic silica is not particularly limited, but is preferably 3 to 100 nm, particularly preferably 5 to 50 nm, from the viewpoint of dispersibility. Also, the BET specific surface area of the hydrophobic silica is not particularly limited, but for example, 50 to 500 m ² / g is preferable.

  The content of the hydrophobic silica is 5.0 parts by mass to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A). When the photosensitive resin composition of the present invention is thickly applied by the spray coating method, the amount of sagging is sufficiently less than 5.0 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A). When it exceeds 20 mass parts, it may not be able to prevent and the appearance of the outstanding cured coating film may not be obtained by the spray coating method. The content of the hydrophobic silica is not particularly limited as long as it is in the range of 5.0 parts by mass to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A). Even when thick coating is applied by spray coating to 100 parts by mass of the carboxyl group-containing photosensitive resin of component A), 5.5 parts by mass is preferable from the viewpoint of reliably preventing sagging, and sagging is reliably prevented. On the other hand, 6.5 parts by mass is particularly preferable in terms of obtaining a more excellent coating film appearance. In addition, the upper limit value of the content of hydrophobic silica provides a more excellent coating appearance even when thickly applied by spray coating to 100 parts by mass of the carboxyl group-containing photosensitive resin of component (A). From the point of view, 13.5 parts by mass is preferable.

  Moreover, even if it is the photosensitive resin composition thickly apply | coated by the spray coating method, it prevents dripping and improves a coating film appearance, insulation property, and resolution with sufficient balance, without impairing the outstanding sensitivity. (F) The hydrophobic silica is contained in an amount of 5.5 parts by mass to 13.5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A). Preferably, 8.0 parts by mass to 18 parts by mass of bentonite treated with a quaternary ammonium salt is contained.

  The ratio of the weight of the bentonite treated with the quaternary ammonium salt of the component (E) to the weight of the hydrophobic silica is not particularly limited, but the weight of the bentonite treated with the quaternary ammonium salt of the component (E): Even if the photosensitive resin composition is applied thick by the spray coating method, the mass of the hydrophobic silica is to prevent dripping and to improve the coating appearance, the insulation properties and the resolution in a well-balanced manner. 1.0: 0.30 to 3.0 is preferable, and 1.0: 0.50 to 2.5 is more preferable, from the viewpoint of improving the coating film appearance, the insulating property and the resolution with good balance. 1.0: 0.80 to 1.5 are particularly preferred.

(G) Color pigments other than phthalocyanine greens By blending color pigments other than phthalocyanine greens, that is, by not blending phthalocyanine greens, even if thick coating is applied by the spray coating method The photosensitive resin composition can be colored while improving resolution while preventing the prevention and the appearance of the coating. Further, it is possible to obtain more excellent insulating properties and resolution by blending a coloring pigment other than phthalocyanine green with the bentonite treated with the quaternary ammonium salt of the component (E) described above.

  The type of color pigment is not particularly limited as long as it is a color pigment other than phthalocyanine green type, for example, titanium oxide which is a white colorant, inorganic pigment such as carbon black which is a black colorant, blue color such as phthalocyanine blue type And organic pigments such as yellow colorants such as anthraquinones. These may be used alone or in combination of two or more.

  Among these, phthalocyanine blue and anthraquinone are preferable in that they can obtain better insulation properties and resolution in a well-balanced manner. When using phthalocyanine blue and anthraquinone in combination, the content (mass) of anthraquinone is at least the content (mass) of phthalocyanine blue, that is, the content (mass) of anthraquinone from the viewpoint of further improving the resolution. It is preferable that the value of the content (mass) of phthalocyanine / blue is 1.0 or more, and from the viewpoint of obtaining excellent sensitivity while further improving the resolution, the content (mass) of anthraquinone / containment of phthalocyanine blue The amount (mass) value of more than 1.0 is particularly preferably 5.0 or less.

  The content of color pigments other than phthalocyanine greens is not particularly limited. For example, from the viewpoint of the balance between the coloring properties and the sensitivity, 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A). 1-30 mass parts is preferable, 0.2-15 mass parts is more preferable, 0.5-5.0 mass parts is especially preferable.

  In the photosensitive resin composition of the present invention, in addition to the above components (A) to (G), if necessary, various components, for example, various additives, non-reactive diluents such as organic solvents, fillers Etc. can be blended.

  As various additives, for example, silicone type, hydrocarbon type and acrylic type antifoaming agent, dispersant, coupling type such as silane type, titanate type and alumina type, boron trifluoride-amine complex, dicyandiamide ( DICY) and its derivatives, organic acid hydrazide, diaminomaleonitrile (DAMN) and its derivatives, guanamine and its derivatives, melamine and its derivatives, amine imides (AI) and latent curing agents such as polyamines, acetyl acenate Zn and acetyl ace Metal salts of acetylacetone such as sodium chloride, enamines, tin octylate, quaternary sulfonium salts, imidazoles such as triphenylphosphine and 2-mercaptobenzimidazole, imidazolium salts, thermosetting accelerators such as triethanolamine borate, etc. The It can gel.

  The filler contributes to increasing the physical strength of the coating of the photosensitive resin composition, and examples thereof include talc, barium sulfate, silica, alumina, aluminum hydroxide and mica.

  The non-reactive diluent is for controlling the drying property and coating viscosity of the photosensitive resin composition, and examples thereof include an organic solvent. Organic solvents include, for example, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether Glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene Glycol monomethyl ether acetate and the above Esters such as esters of calls ethers; ethanol, can be mentioned propanol, ethylene glycol, and alcohols such as propylene glycol.

  Although the manufacturing method of the above-mentioned photosensitive resin composition is not limited to a specific method, For example, after mix | blending said each component by a predetermined | prescribed ratio, it can be mixed and disperse | distributed with a triple roll at room temperature. Moreover, you may pre-mix with a stirrer before the said mixing dispersion | distribution as needed.

  Next, an example of usage of the photosensitive resin composition of the present invention will be described. Here, a method of applying the photosensitive resin composition of the present invention as an insulating protective film (for example, a solder resist film or the like) of a printed wiring board will be described as an example.

  For example, the photosensitive resin composition of the present invention obtained as described above is a substrate having a circuit pattern formed by etching a copper foil (for example, a thickness of 50 μm or more of a copper foil as a conductor) When a desired thickness, for example, a DRY film thickness of 60 μm or more, is applied on the wiring board by spray coating (spray coater method), a wet film thickness of 70 μm or more is applied to form a coating film. Next, when the non-reactive diluent such as an organic solvent is contained in the photosensitive resin composition, the temperature is about 60 to 80 ° C. for 15 to 60 minutes in order to volatilize the non-reactive diluent. Pre-drying with some heating is performed to form a tack-free coating.

  Next, a negative film (photomask) having a pattern in which the light-transmitting property other than the lands of the circuit pattern is adhered onto the pre-dried coating, and ultraviolet light (for example, wavelength 300 to 400 nm) Irradiate. Then, the coating film is developed by removing the non-exposed area corresponding to the land with a dilute alkaline aqueous solution. A spray method, a shower method, etc. are used for the image development method, and 0.5-5 mass% sodium carbonate aqueous solution is mentioned as a dilute alkali aqueous solution to be used, for example. Then, by performing post curing for 20 to 80 minutes with a hot air circulating dryer at 130 to 170 ° C., a target insulating protective film such as a solder resist film can be formed on the printed wiring board.

  In addition, even if it replaces with spray coating (spray coater method) as a coating method, even if it uses other well-known coating methods, such as screen printing, a bar coater, an applicator, a blade coater, a knife coater, a roll coater, a gravure coater, etc. Good.

  EXAMPLES Next, examples of the present invention will be described, but the present invention is not limited to these examples as long as the purpose of the present invention is not exceeded.

Examples 1 to 8 and Comparative Examples 1 to 7
Each component shown in the following Tables 1 and 2 is blended at a ratio shown in the following Tables 1 and 2, mixed and dispersed at room temperature using a three-roll, in Examples 1 to 8 and Comparative Examples 1 to 7 The photosensitive resin composition to be used was prepared. And the prepared photosensitive resin composition was coated as follows, and the test piece was produced. The numbers in Tables 1 and 2 below indicate parts by mass. Moreover, the blank in Tables 1 and 2 below means no blending.

  In addition, the detail about each component in Table 1, 2 is as follows.

(A) Carboxyl group-containing photosensitive resin of component (A) To 250 parts by mass of carbitol acetate, 220 parts by mass of cresol novolac epoxy resin (manufactured by Sumitomo Chemical Co., Ltd., ESCN-220, epoxy equivalent 220) and 72 parts by mass of acrylic acid Were reacted under reflux to obtain cresol novolac epoxy acrylate. Next, 138.6 parts by mass of hexahydrophthalic anhydride is added to the obtained cresol novolac type epoxy acrylate, reacted under reflux until the acid value reaches a theoretical value, and then 56.8 parts by mass of glycidyl methacrylate is added, It was further reacted to obtain a synthetic resin (A-1) of the carboxyl group-containing photosensitive resin of the component (A) having a solid content of 65% by mass.

(B) Photopolymerization initiator, Irgacure 907: BASF Japan Ltd.
・ KAYACURE DETX: Nippon Kayaku Co., Ltd.
(C) Reactive Diluent · DPHA: Toagosei Co., Ltd.
(D) Epoxy Compound Epicoat 828, YX-4000 K: Mitsubishi Chemical Corporation

Bentonite Thixogel VZ treated with quaternary ammonium salt of component (E): united catalysts (F) Hydrophobic silica · Aerosil R 974: Surface modified with dimethylsilyl group, Nippon Aerosil Co., Ltd.
(G) Color pigments other than phthalocyanine greens · Chromophthal yellow AGR: Ciba Specialty Chemicals Co., Ltd.
・ Lionol blue FG-7351: Toyo Color Co., Ltd.

Filler · Barium sulfate B-34: Sakai Chemical Industry Co., Ltd.
・ FH105: Fuji Talc Co., Ltd.

Various additives, melamine: Nissan Chemical Industries, Ltd.
・ DICY-7: Japan Epoxy Resins Co., Ltd.
・ Ange MB: Kawaguchi Chemical Industry Co., Ltd.
Disperbyk-103 (main component: copolymer having a group having an affinity for filler), BYK-410 (main component: modified urea), Disperbyk-102 (main component: poly (oxyethylene) tridecyl ether phosphoric acid Salt, acid value 101 mg KOH / g): Big Chemie Japan Co., Ltd.
Non-reactive Diluent, PMA: Sanyo Chemical Industries, Ltd.

(A) Carboxyl group-containing photosensitive resin other than the component · Lipoxy SP-4621: Showa Denko KK
Bentonite Thixogel VP treated with quaternary ammonium salt other than the component (E): colored pigment other than the united catalyst (G) component Fastening green: DIC hydrophilic silica Aerosil # 380: Nippon Aerosil Co., Ltd.

Test piece production process board: Printed wiring board (glass epoxy board "FR-4", board thickness 1.6 mm, conductor (Cu foil) thickness 18 to 90 μm)
Substrate surface treatment: Buffing coating: Spray coating Coating conditions: Discharge amount (110 cc / min), conveyor speed (2.3 m / min), disc rotation number (30000 rpm), applied voltage (-35 KV)
Wet film thickness: 100 to 110 μm
Pre-drying: 80 ° C., 20 minutes exposure: 300 mJ / cm ² (main wavelength 365 nm, Oak Corporation “HMW-680 GW”) on a photosensitive resin composition
Alkali development: 1% by mass Na ₂ CO ₃ aqueous solution, liquid temperature 30 ° C., spray pressure 0.2 MPa, development time 60 seconds Post cure: 150 ° C., 60 minutes

The evaluation items are as follows.
(1) Thixo ratio After dilution with a solvent (propylene glycol monomethyl ether) so as to reach 60 to 65 seconds (25 ° C.) with Iwata cup, using a viscometer RVT type manufactured by Brookfield, spindle rotation number 5 rpm The BF viscosity (η5) of the photosensitive resin composition at a temperature of 25 ° C. and the BF viscosity (η50) of the photosensitive resin composition at a temperature of 25 ° C. at a spindle rotational speed of 50 rpm were respectively measured. Then, the thixo ratio (η5 // 50) was calculated from these measured values.

(2) Dareability With respect to the substrate after the preliminary drying performed in the test piece preparation step, the coating film of the photosensitive resin composition was visually evaluated based on the following criteria.
:: No dripping of the coating film in a thin wire pattern portion of 90 μm in conductor thickness ○: There is a dripping of coating film in a thin wire pattern portion of 90 μm in conductor thickness, no dripping of coating film in a thin wire pattern portion of 60 μm in conductor thickness There is sag of the coating film in the thin line pattern portion with a conductor thickness of 60 μm, but no dripping of the coating film in the thin line pattern portion of the conductor thickness 35 μm x: There is sag of the coating film in the thin line pattern portion of the conductor thickness 35 μm (conductor thickness of 18 μm No drips on the thin line pattern of

(3) Sensitivity In the test piece preparation step, a step tablet for sensitivity measurement (Kodak 21 stage) is placed on the coating of the substrate after predrying at 80 ° C. for 20 minutes, and the main wavelength is passed through the step tablet. The irradiation light quantity of ultraviolet rays of 365 nm is measured using an integrated actinometer ("UV-351", manufactured by OK Co., Ltd.), and 300 mJ / cm ² irradiation is used as a test piece, and 1 mass% After developing for 60 seconds at a spray pressure of 2.0 Kg / cm ² using a Na ₂ CO ₃ aqueous solution, the unremoved part of the exposed part is recorded by a number (step number) and evaluated according to the following criteria did.
○: 10 steps or more Δ: 8 to 9 steps ×: 7 steps or less

(4) Spray coatability (coating film appearance)
The appearance of the coated film surface after the preliminary drying in the test piece preparation process was visually observed and evaluated according to the following criteria.
:: no bubbles, no skin, and good leveling performance ○: some skin with wrinkles, or slightly thin covering near Cu foil △: some skin with wrinkles, some loss of coating surface Yes: There is skin of Yuzu, or spray coating is not possible

(5) Insulating Properties A cured coating was produced according to the above test piece production process on a comb-shaped conductor pattern having a conductor thickness of 18 μm and L / S: 100 μm / 100 μm. Next, DC 30 V was applied to the obtained substrate under an environment where the temperature in the tank was kept at 121 ° C. and the humidity in the tank was kept at 97%, and was introduced for 96 hours. Thereafter, the insulation resistance was measured by applying DC 50 V, and evaluated according to the following criteria.
◎: resistance 10 [Omega ¹¹ or more ○: less than the resistance value resistance 10 [Omega ⁹ or 10 [Omega ¹¹ △: × less than the resistance value of 10 [Omega ⁸ or more resistance 10 [Omega ^9: less than the resistance value of 10 [Omega ⁸

(6) Resolution (dimension accuracy)
The line width of the exposed portion of the photosensitive resin composition formed on a Cu foil via a photomask (line width 100 μm) was measured by an optical microscope and evaluated according to the following criteria in accordance with the test piece preparation step. .
:: line width 105 μm or less ○: line width 105 μm or more 110 μm △: line width 110 μm or more 115 μm or less ×: line width 115 μm or more

(7) Developability (Alkali developability)
The time required for developing (at 30 ° C., using a 1% by mass sodium carbonate developer) at a spray pressure of 0.2 MPa is taken as a break point, for the coating film after the preliminary drying in the test piece preparation step, The time was measured and evaluated according to the following criteria.
:: Breakpoint less than 20 seconds ○: Breakpoint greater than or equal to 20 seconds less than 30 seconds △: Breakpoint greater than or equal to 30 seconds less than 60 seconds ×: Breakpoint greater than or equal to 60 seconds

  The results of the above evaluation are shown in Tables 1 and 2 above.

  As shown in Table 1 above, carboxyl which is a reaction product of a glycidyl compound having a radically polymerizable unsaturated group and an epoxy group reacted with a carboxyl group of a polybasic acid-modified radically polymerizable unsaturated monocarboxylic acid oxidized epoxy resin Stearyl chloride corresponding to the quaternary ammonium salt represented by the above general formula (I) in the synthetic resin (A-1) corresponding to the group-containing photosensitive resin (carboxyl group-containing photosensitive resin of the component (A)) About 6.0 parts by weight per 100 parts by weight of the bentonite treated with the quaternary ammonium salt of the component (E), which is a bentonite treated with benzyldimethylammonium, and the carboxyl group-containing photosensitive resin of the component (A) In Examples 1 to 8 in which part to about 18 parts by mass of (F) hydrophobic silica and (G) a coloring pigment other than phthalocyanine green are blended Even if the photosensitive resin composition is thickly applied with a wet film thickness of 100 to 110 μm by a spray coating method to a conductor pattern having a thickness of 18 to 90 μm, it has excellent sensitivity and can prevent sagging, that is, An excellent drip resistance was obtained, and a cured film having an excellent appearance could be formed. Furthermore, in Examples 1 to 8, a cured coating film excellent in insulation properties, resolution (dimension accuracy) and alkali developability could be obtained. In particular, in Example 8 in which Disperbyk-102 (poly (oxyethylene) tridecyl ether phosphate) was used as a dispersant, a cured coating film excellent in alkali developability could be obtained.

  Moreover, from Examples 1 to 8, the weight of bentonite treated with the quaternary ammonium salt of the component (E): the weight of the (F) hydrophobic silica is in the range of 1.0: 0.30 to 3.0. Even if the photosensitive resin composition is thickly coated with a wet film thickness of 100 to 110 μm by the spray coating method to the conductor pattern of 18 to 90 μm thick, it has excellent sensitivity and It was possible to obtain a cured coating film which can be prevented and which is also excellent in coating film appearance, insulation properties and resolution (dimension accuracy).

  In addition, with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A), about 6.0 parts by mass to about 13 parts by mass of the hydrophobic silica (E) is a quaternary ammonium salt of the component (E) In Examples 1 to 5 and 8 in which about 9.0 parts by mass to about 18 parts by mass of the treated bentonite is blended, the photosensitive resin composition is applied with a thick wet film thickness of 100 to 110 μm by the spray coating method. Even if there was, it was possible to prevent sagging even for a 60 μm thick conductor pattern without impairing the excellent sensitivity, and also to improve the coating film appearance, insulation properties and resolution in a well-balanced manner.

  Further, from Examples 1, 3 to 8 and Example 2, when the blending amount of anthraquinone is larger than that of phthalocyanine blue, or the blending amount of anthraquinone is equivalent to the blending amount of phthalocyanine blue, the resolution is further increased. Improved.

On the other hand, as shown in Table 2 above, in Comparative Examples 1, 5 and 6 in which color pigments other than the component (G), that is, phthalocyanine green color pigments are blended, resolution (dimension accuracy) is obtained. It was not done. Further, in Comparative Examples 2 and 5 in which the bentonite treated with the quaternary ammonium salt of the component (E) was not blended, excellent insulation properties were obtained with a resistance value of 10 Ω ⁸ or more and a resistance value of 10 Ω less than ⁹ No spray coatability was obtained. In Comparative Examples 2 and 7 in which the glycidyl methacrylate skeleton was not introduced into the carboxyl group-containing photosensitive resin, the sensitivity was not obtained.

(F) In Comparative Example 3 in which hydrophilic silica was blended instead of hydrophobic silica, drip resistance and spray coatability were not obtained. Moreover, spray coating property was not obtained in the comparative example 4 in which (F) hydrophobic silica is contained about 27 mass parts with respect to 100 mass parts of carboxyl group-containing photosensitive resins of (A) component. Further, (E) in place of the quaternary ammonium salt-treated bentonite components, in Comparative Example 6 bentonite treated with distearyldimethylammonium chloride is blended, the resistance value of 10 [Omega ⁸ or more resistance 10 [Omega ^{When it was} less than ⁹ , excellent insulation properties were not obtained.

  In the present invention, even a photosensitive resin composition that is thickly applied using a spray coating method has excellent sensitivity, can prevent dripping, has excellent appearance, and has high resolution (high dimensional accuracy). Because a cured coating film having insulating properties can be formed, for example, it is highly useful in the field of providing an insulating protective film such as a solder resist film on a printed wiring board having a thick conductor pattern.

Claims (11)

(A) In the hydroxyl group of a radically polymerizable unsaturated monocarboxylic acid oxidized epoxy resin which is a reaction product of a polyfunctional epoxy resin having two or more epoxy groups in one molecule and a radically polymerizable unsaturated monocarboxylic acid, A reaction product of a glycidyl compound having a radically polymerizable unsaturated group and an epoxy group reacted with a carboxyl group of a polybasic acid-modified radically polymerizable unsaturated monocarboxylic acid oxidized epoxy resin which is a compound in which a basic acid or its anhydride has reacted. A carboxyl group-containing photosensitive resin which is
(B) a photopolymerization initiator,
(C) a reactive diluent,
(D) an epoxy compound,
(E) the following general formula (I)
^{[R 1 R 2 R 3 R} 4 -N] + X - (I)
(Wherein, R ¹ , R ² , R ³ and R ⁴ are each independently a saturated aliphatic hydrocarbon group having 1 to 25 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 25 carbon atoms, or a substituent Or an aromatic hydrocarbon group which may have at least one of R ¹ , R ² , R ³ and R ⁴ is an aromatic hydrocarbon group which may have a substituent ), X represents a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine))
And bentonite treated with a quaternary ammonium salt represented by
(F) hydrophobic silica,
(G) Color pigments other than phthalocyanine greens,
Contains
The photosensitive resin composition which the said (F) hydrophobic silica contains 5.0 mass parts-20 mass parts with respect to 100 mass parts of carboxyl group-containing photosensitive resins of the said (A) component.   The photosensitive resin composition according to claim 1, wherein the color pigment other than (G) phthalocyanine green is at least one compound selected from the group consisting of phthalocyanine blue and anthraquinone. The photosensitive resin composition according to claim 1 or 2, wherein ^one of R ¹ , R ² , R ³ and R ⁴ is an aromatic hydrocarbon group which may have a substituent.   The bentonite treated with the quaternary ammonium salt of the component (E) is contained in an amount of 5.0 parts by mass to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A). 3. The photosensitive resin composition according to any one of to 3.   The (F) hydrophobic silica is contained in an amount of 5.5 parts by mass to 13.5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A), and the fourth grade of the component (E) The bentonite treated with an ammonium salt is contained in an amount of 8.0 parts by mass to 18 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin of the component (A). Photosensitive resin composition.   The mass of bentonite treated with the quaternary ammonium salt of the component (E): the mass of the hydrophobic silica (F) is in the range of 1.0: 0.30 to 3.0. The photosensitive resin composition according to any one of the above.   The photosensitive resin composition according to any one of claims 1 to 6, wherein the (F) hydrophobic silica is a silica modified with an alkylsilyl group.   The photosensitive resin composition according to any one of claims 1 to 7, wherein the quaternary ammonium salt is a stearyl benzyldimethyl ammonium salt.   The photosensitive resin composition according to any one of claims 1 to 8, further comprising poly (oxyethylene) tridecyl ether phosphate.   The photocured material of the photosensitive resin composition according to any one of claims 1 to 9.   A wiring board having a photocured film of the photosensitive resin composition according to any one of claims 1 to 9.