JP6481251B2 - Photosensitive resin composition and photosensitive element - Google Patents

Description

  The present invention relates to a photosensitive resin composition and a photosensitive element using the same.

  With the reduction in size and weight of various electronic devices, photosensitive resin compositions are used to form fine patterns in the production of printed wiring boards, semiconductor package substrates, flexible wiring boards, and the like.

  As a solder resist used for a printed wiring board, for example, a liquid photosensitive resin composition is used. As the liquid photosensitive resin composition, for example, a two-component type photosensitive resin in which a thermosetting epoxy resin and a photosensitive prepolymer containing a carboxylic acid group for imparting alkali developability are separately provided. A resin composition is mentioned. As the photosensitive prepolymer, an alkali developable photosensitive prepolymer which is obtained by adding acrylic acid to a cresol novolak type epoxy resin and then acid-modifying with an acid anhydride or the like is widely used (for example, see Patent Document 1). .

  In the two-component photosensitive resin composition, the reaction between the epoxy resin and the carboxylic acid group of the photosensitive prepolymer proceeds even at room temperature, so that the storage stability after mixing the two components (also referred to as “pot life”). ) A few hours to a day. Therefore, use conditions are limited, for example, the two liquids must be mixed immediately before using the photosensitive resin composition. In recent years, in order to solve the problem of such limitations, a one-part type photosensitive resin composition having improved storage stability by using a block type isocyanate compound instead of an epoxy resin as a thermosetting agent. A thing is proposed (for example, refer to patent documents 2).

  On the other hand, from the viewpoint of uniformly forming the photosensitive layer using the photosensitive resin composition at a desired thickness or improving the handleability, a dry film type photosensitive resin composition is used for a solder resist. It is strongly desired. By using a dry film type photosensitive resin composition, effects such as simplification of the process of forming a solder resist and reduction of the amount of solvent discharged during the formation of the solder resist can be obtained in addition to the above characteristics. Conventionally, as a dry film type photosensitive resin composition for a solder resist, for example, a polymer having a carboxyl group, a photopolymerizable compound, a photopolymerization initiator and a photosensitive film containing a bismaleimide compound, maleic anhydride Proposed is a photosensitive film containing a copolymer obtained by reacting 0.1 to 1.2 equivalents of a primary amine compound with respect to the anhydride group of the copolymer, a polymerizable compound and a photopolymerization initiator. (For example, see Patent Documents 3 and 4).

  Furthermore, when a semiconductor package is mounted, the components constituting the semiconductor package, in particular, the semiconductor chip and the solder resist have different coefficients of thermal expansion. Therefore, when the semiconductor package is heated and cooled, there is a gap between the semiconductor chip and the solder resist. In this case, thermal stress is generated and defects such as a short circuit occur between the wirings. Therefore, in order to make it difficult for thermal stress to occur, the photosensitive resin composition for solder resist is required to have a thermal expansion coefficient close to that of the semiconductor chip, that is, to lower the thermal expansion coefficient. ing.

  In order to achieve a low thermal expansion coefficient of the photosensitive resin composition, for example, it has been proposed to add a filler. In particular, silica having the same thermal expansion coefficient as that of a semiconductor chip has been favorably used. For example, crushed silica or fused silica. On the other hand, as described above, cresol novolac type epoxy resins are widely used for solder resists and have poor affinity with silica which is an inorganic substance. For this reason, there is a drawback that the filler settles in a varnish state or the filler slides down after the solder resist is cured. Furthermore, hydroxyl groups remain on the silica surface, which is one of the causes of aggregation and deterioration of insulation reliability.

JP-A 61-243869 JP 2001-305726 A JP 2004-287267 A JP 2005-316431 A

  The present invention relates to a photosensitive resin composition which is excellent in stability in a varnish state and has a coating film-forming property and hardly causes the filler to slide down, and a photosensitive element which is a dry film type photosensitive solder resist capable of alkali development. The purpose is to provide.

The inventors include (a) a resin having an ethylenically unsaturated group and a carboxyl group, (b) a photopolymerizable monomer having an ethylenically unsaturated group, (c) a photopolymerization initiator, and (d) It discovered that the photosensitive resin composition containing the silica by which the surface was coupling-processed using the thermosetting agent and the (e) coupling agent, and the photosensitive film using the same can achieve the said subject. .
That is, the present invention provides [1] (a) a resin having an ethylenically unsaturated group and a carboxyl group, (b) a photopolymerizable monomer having an ethylenically unsaturated group, (c) a photopolymerization initiator, It is related with the photosensitive resin composition containing the silica by which the surface was coupling-processed using (d) thermosetting agent and (e) coupling agent.
In the present invention, [2] the coupling agent is at least one selected from the group consisting of titanate coupling agents, silane coupling agents, aluminate coupling agents, and zirconate coupling agents. The present invention relates to the photosensitive resin composition according to [1].
Moreover, this invention is [3] The said coupling agent is 1 or more types chosen from the group which consists of an epoxy silane compound, an aminosilane compound, an acrylic silane compound, a thiol silane compound, a ureido silane compound, and an isocyanate silane compound. It relates to the photosensitive resin composition according to [1] or [2].
Furthermore, the present invention provides a photosensitive resin composition layer comprising the [4] support and the photosensitive resin composition according to any one of the above [1] to [3] formed on the support. And a photosensitive element.

  INDUSTRIAL APPLICABILITY According to the present invention, a photosensitive resin composition that is excellent in stability in a varnish state and has a good coating film formation property and hardly causes the filler to slide down, and a photosensitive film that becomes a dry film type photosensitive solder resist capable of alkali development. A sex element is provided.

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

  The photosensitive resin composition of the present invention comprises (a) a resin having an ethylenically unsaturated group and a carboxyl group, (b) a photopolymerizable monomer having an ethylenically unsaturated group, (c) a photopolymerization initiator, (D) It contains silica whose surface is subjected to a coupling treatment using a thermosetting agent and (e) a coupling agent.

  The main feature of the present invention is that the component (e) uses silica whose surface is subjected to a coupling treatment using a coupling agent. Each of these components will be described.

<(A) component>
The resin having an ethylenically unsaturated group and a carboxyl group as the component (a) of the present invention is a photo radical reactive resin having at least one ethylenically unsaturated group and a carboxyl group in the molecule, Specific examples include acid-modified epoxy acrylate and urethane-modified epoxy acrylate.
As the acid-modified epoxy acrylate, for example, an addition reaction product obtained by adding a saturated or unsaturated polybasic acid anhydride (a3) to an esterified product of an epoxy compound (a1) and an unsaturated monocarboxylic acid (a2) can be used. . These can be obtained by a two-step reaction. In the first reaction (hereinafter referred to as “first reaction” for convenience), the epoxy compound (a1) and the unsaturated monocarboxylic acid (a2) react. In the next reaction (hereinafter referred to as “second reaction” for convenience), the esterified product produced in the first reaction reacts with the saturated or unsaturated polybasic acid anhydride (a3).

  Although there is no restriction | limiting in particular as said epoxy compound (a1), For example, a bisphenol type epoxy compound, a novolak type epoxy compound, a biphenyl type epoxy compound, and a polyfunctional epoxy compound are mentioned.

  As the bisphenol type epoxy compound, those obtained by reacting bisphenol A type, bisphenol F type and epichlorohydrin are suitable. Specifically, GY-260, GY-255, XB-2615 manufactured by Ciba Geigy Corp., Bisphenol A type such as Epicoat 828, 1007, 807 manufactured by Japan Epoxy Resin Co., Ltd., bisphenol F type, hydrogenated bisphenol A type, amino group Containing, alicyclic or polybutadiene modified epoxy compounds are preferably used.

  As the novolak type epoxy compound, those obtained by reacting novolaks obtained by reacting phenol, cresol, halogenated phenol and alkylphenols with formaldehyde in the presence of an acidic catalyst and epichlorohydrin are suitable.

  Examples of the novolak type epoxy compound include YDCN-701, 704, YDPN-638, 602 manufactured by Tohto Kasei Co., Ltd., DEN-431, 439 manufactured by Dow Chemical Company, EPN-1299 manufactured by Ciba Geigy Co., and N manufactured by DIC Corporation. -730, 770, 865, 665, 673, VH-4150, 4240, Nippon Kayaku Co., Ltd. EOCN-120, BREN are mentioned.

  Examples of other epoxy compounds include salicylaldehyde-phenol or cresol type epoxy compounds (Nippon Kayaku Co., Ltd., EPPN502H, FAE2500, etc.), DIC Corporation Epicron 840, 860, 3050, Dow Chemical Company-made DER-330, 337, 361, Daicel Chemical Industries, Ltd. Celoxide 2021, Mitsubishi Gas Chemical Co., Ltd. TETRAD-X, C, Nippon Soda Co., Ltd. EPB-13, 27 can also be used. These may be used alone or in combination of two or more, and a mixture or a block copolymer may be used.

  Examples of the unsaturated monocarboxylic acid (a2) include (meth) acrylic acid, crotonic acid, cinnamic acid, and saturated or unsaturated polybasic acid anhydrides and (meth) acrylates having one hydroxyl group in one molecule. Or the reaction material of the half-ester compound of a saturated or unsaturated dibasic acid and an unsaturated monoglycidyl compound is mentioned. Examples of the reactant include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and tris (hydroxyethyl) isocyanurate. Examples thereof include reactants obtained by reacting di (meth) acrylate, glycidyl (meth) acrylate and the like in an equimolar ratio by a conventional method. These unsaturated monocarboxylic acids can be used alone or in combination. Among these, acrylic acid is preferable.

  Examples of the saturated or unsaturated polybasic acid anhydride (a3) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride Methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride, trimellitic anhydride, and the like.

  In the first reaction, a hydroxyl group is generated by an addition reaction between the epoxy group of the epoxy compound (a1) and the carboxyl group of the unsaturated monocarboxylic acid (a2). In the first reaction, the ratio of the epoxy compound (a1) to the unsaturated monocarboxylic acid (a2) is such that the unsaturated monocarboxylic acid (a2) is 0.001 equivalent to 1 equivalent of the epoxy group of the epoxy compound (a1). The ratio is preferably 7 to 1.05 equivalent, and more preferably 0.8 to 1.0 equivalent.

  The epoxy compound (a1) and the unsaturated monocarboxylic acid (a2) can be reacted by dissolving in an organic solvent. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatic carbonization such as octane and decane Petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha can be used.

  In the first reaction, it is preferable to use a catalyst in order to accelerate the reaction. Examples of the catalyst that can be used include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, and triphenylphosphine. It is preferable that the usage-amount of a catalyst shall be 0.1-10 mass parts with respect to a total of 100 mass parts of an epoxy compound (a1) and unsaturated monocarboxylic acid (a2).

  In the first reaction, in order to prevent polymerization between the epoxy compounds (a1) or between the unsaturated monocarboxylic acids (a2) or between the epoxy compound (a1) and the unsaturated monocarboxylic acid (a2), a polymerization inhibitor is used. It is preferable to use it. As the polymerization inhibitor, for example, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like can be used. It is preferable that the usage-amount of a polymerization inhibitor shall be 0.01-1 mass part with respect to a total of 100 mass parts of an epoxy compound (a1) and unsaturated monocarboxylic acid (a2). 60-150 degreeC is preferable and, as for the reaction temperature of a 1st reaction, 80-120 degreeC is more preferable.

  In the first reaction, an unsaturated monocarboxylic acid (a2) and a polybasic acid anhydride such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, etc., if necessary Can be used in combination.

  In the second reaction, when the hydroxyl group formed in the first reaction and the hydroxyl group originally present in the epoxy compound (a1) undergo a half-ester reaction with the acid anhydride group of the saturated or unsaturated polybasic acid anhydride (a3). Inferred. Here, 0.1 to 1.0 equivalent of polybasic acid anhydride (a3) can be reacted with 1 equivalent of hydroxyl group in the resin obtained by the first reaction. By adjusting the amount of the polybasic acid anhydride (a3) within this range, the acid value of the component (a) can be adjusted.

  The component (a) that can be used in the present invention is commercially available as CCR-1218H, CCR-1159H, CCR-1222H, PCR-1050, TCR-1335H, ZAR-1035, ZAR-2001H, ZFR-1185, and ZCR-1569H. (Nippon Kayaku Co., Ltd., trade name), UE-EXP-2810, UE-EXP-2827, UE-EXP-3073 (above, DIC Corporation, trade name) and the like are available.

  Moreover, urethane-modified epoxy acrylate can be used for resin which has the ethylenically unsaturated group and carboxyl group which are (a) component used by this invention. Urethane-modified epoxy acrylate contains an epoxy acrylate compound having an ethylenically unsaturated group and two or more hydroxyl groups (hereinafter referred to as “raw material epoxy acrylate”), a diisocyanate compound (hereinafter referred to as “raw material diisocyanate”), and a carboxyl group. It is preferable to use this polyurethane compound, which is obtained by reacting a diol compound (hereinafter referred to as “raw material diol”).

  Examples of the raw material epoxy acrylate include compounds obtained by reacting (meth) acrylic acid with an epoxy compound such as a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a novolac type epoxy compound, or an epoxy compound having a fluorene skeleton. Can be mentioned.

  As said raw material diisocyanate, if it is a compound which has two isocyanate groups, it can apply without a restriction | limiting in particular. Such compounds include, for example, phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tridenic diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, arylene sulfone. Examples include ether diisocyanate, allyl cyanide diisocyanate, N-acyl diisocyanate, trimethylhexamethylene diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, and norbornane-diisocyanate methyl. These can be used individually by 1 type or in combination of 2 or more types.

  The raw material diol is a compound having two hydroxyl groups in the molecule and a carboxyl group. Examples of the hydroxyl group include alcoholic hydroxyl groups and phenolic hydroxyl groups. From the viewpoint of improving the developability of the photosensitive resin composition with an alkaline aqueous solution, the hydroxyl group is preferably an alcoholic hydroxyl group. Examples of such raw material diols include dimethylolpropionic acid and dimethylolbutanoic acid.

  As said polyurethane compound, the compound which has a structural unit represented by following General formula (1) is mentioned, for example.

Here, in the general formula (1), R ¹⁰ represents a hydrogen atom or a methyl group, R ¹⁷ represents a residue of a raw material epoxy acrylate, R ¹⁸ represents a residue of a raw material diisocyanate, and R ¹⁹ represents 1 carbon atom. Represents an alkyl group of ~ 5. In addition, a residue means the structure of the part remove | excluding the functional group used for the coupling | bonding from the raw material component. Specifically, as R ¹⁷ , for example, bis (4-oxyphenyl) -methane, 2,2-bis (4-oxyphenyl) -propane, 2,2-bis (4-oxyphenyl) -1, Examples thereof include bisphenol A-type skeletons such as 1,1,3,3,3-hexafluoropropane and bisphenol F-type skeletons, novolak skeletons, fluorene skeletons, and the like. Examples of R ¹⁸ include phenylene, tolylene, xylylene, tetramethylxylylene, and the like. Lene, diphenylmethylene, hexamethylene, trimethylhexamethylene, dicyclohexylmethylene, isophorone and the like. The alkyl group having 1 to 5 carbon atoms for R ^19, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, amyl group.

  A plurality of groups in general formula (1) may be the same or different. Moreover, when the terminal of the polyurethane compound is a hydroxyl group, the hydroxyl group may be treated with a saturated or unsaturated polybasic acid anhydride.

  Further, in the general formula (1), the structural unit derived from the raw material epoxy acrylate and the structural unit derived from the raw material diol are alternately polymerized via the structural unit derived from the raw material diisocyanate. However, a structure in which a structural unit derived from a raw material epoxy acrylate and a structural unit derived from a raw material diol are polymerized in a block manner via a structural unit derived from a raw material diisocyanate may be used.

As the component (a), among the compounds represented by the general formula (1), it is preferable that the hard segment part of the raw material epoxy acrylate that is one of the main skeletons of polyurethane, that is, R ¹⁷ has a bisphenol A structure. Such a compound is commercially available as UXE-3011, UXE-3012, UXE-3024 (manufactured by Nippon Kayaku Co., Ltd.) and the like. These can be used alone or in combination of two or more.

  The resin having a carboxyl group as component (a) preferably has an acid value of 20 to 180 mgKOH / g, more preferably 30 to 150 mgKOH / g, and further preferably 40 to 120 mgKOH / g. preferable. Thereby, the developability with the alkaline aqueous solution of the photosensitive resin composition becomes good, and an excellent resolution can be obtained.

Here, the acid value can be measured by the following method. First, after precisely weighing 1.000 g of a solution containing a resin whose acid value is to be measured, 30 g of acetone is added to this resin solution to dissolve it. Next, an appropriate amount of an indicator, phenolphthalein, is added to the solution and titrated with a 0.1N KOH ethanol solution. And an acid value is computed by following Formula.
A = 10 × V · f × 56.1 / (Wp × I)
In the formula, A represents the acid value (mgKOH / g), V represents the titration amount (mL) of 0.1N KOH ethanol solution, f represents the factor of 0.1N KOH ethanol solution, and Wp represents the measurement. The resin solution mass (g) was shown, and I represents the ratio (mass%) of the non-volatile content of the measured resin solution.

  The weight average molecular weight of the resin as component (a) is preferably 3000 to 30000, more preferably 5000 to 20000, and particularly preferably 7000 to 15000 from the viewpoint of coating properties. .

  In addition, a weight average molecular weight (Mw) can be calculated | required from the standard polystyrene conversion value by a gel permeation chromatography (GPC).

  The component (b) of the present invention is a photopolymerizable monomer having an ethylenically unsaturated group.

  Examples of such compounds include bisphenol A-based (meth) acrylate compounds, compounds obtained by reacting polyhydric alcohols with α, β-unsaturated carboxylic acids, and glycidyl group-containing compounds with α, β-unsaturated carboxylic acids. Examples thereof include a compound obtained by reacting an acid, and a urethane monomer or urethane oligomer such as a (meth) acrylate compound having a urethane bond in the molecule. Besides these, nonylphenoxy polyoxyethylene acrylate, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloyloxy Examples thereof include phthalic acid compounds such as alkyl-o-phthalate, (meth) acrylic acid alkyl esters, EO-modified nonylphenyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.

  The component (b) preferably contains a bisphenol A (meth) acrylate compound from the viewpoint of improving alkali developability. Examples of bisphenol A-based (meth) acrylate compounds include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy). ) Phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane. It is done. You may use these individually or in combination of 2 or more types.

  The component (b) more preferably contains 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane from the viewpoint of improving sensitivity and resolution. Examples of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy nonaethoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ( (Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxyhexa) Decaethoxy) phenyl) propane. You may use these individually or in combination of 2 or more types.

  Among the above compounds, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is a trade name “FA-321M” manufactured by Hitachi Chemical Co., Ltd. or a trade name “BPE” manufactured by Shin-Nakamura Chemical Co., Ltd. -500 "and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is commercially available under the trade name" BPE-1300 "manufactured by Shin-Nakamura Chemical Co., Ltd. Is available.

  Examples of 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic) Xinonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) propane 2,2-bis (4-((meth) acryloxydodecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl) propane and 2,2-bis (4-((meth)) Acryloxyhexadecapropoxy) phenyl) propane. These may be used alone or in combination of two or more.

  Examples of 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane, Examples include 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane. These can be used alone or in combination of two or more.

  The component (b) preferably contains a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid from the viewpoint of improving the balance of adhesion, resolution and electric corrosion resistance. Examples of the compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups. Polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO / PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) A Chlorate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO-modified glyceryl tri (meth) acrylate, PO-modified glyceryl tri (meth) acrylate and EO. PO-modified glyceryl tri (meth) acrylate is exemplified. These may be used alone or in combination of two or more.

  Among the above compounds, dipentaerythritol hexaacrylate is commercially available under the trade name “KAYARAD-DPHA” manufactured by Toagosei Co., Ltd., and trimethylolpropane triethoxytriacrylate is sold under the trade name “SR-454” manufactured by Nippon Kayaku Co., Ltd. Are available.

“EO” refers to “ethylene oxide”, and “PO” refers to “propylene oxide”. Further, “EO modified” means having a block structure of ethylene oxide units (—CH ₂ —CH ₂ —O—), and “PO modified” means propylene oxide units (—CH ₂ —CH ₂ —CH _2). -O-) or isopropylene oxide units _{(-CH 2 -CH (CH 3)} -O -, - CH (CH 3) means having a block structure of -CH 2 -O-).

  Examples of the compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid include trimethylolpropane triglycidyl ether tri (meth) acrylate and 2,2-bis (4- (meth) acryloxy- 2-hydroxy-propyloxy) phenyl. These can be used alone or in combination of two or more. Examples of the α, β-unsaturated carboxylic acid for obtaining these compounds include (meth) acrylic acid.

  Examples of urethane monomers include (meth) acrylic monomers having an OH group at the β-position and diisocyanate compounds such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. And tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, and EO or PO-modified urethane di (meth) acrylate. These can be used alone or in combination of two or more.

  Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, and 2-hydroxyethyl. (Meth) acrylate is mentioned. These can be used alone or in combination of two or more.

(C) Component: Photopolymerization Initiator The photopolymerization initiator (c) used in the present invention is not particularly limited as long as it matches the light wavelength of the exposure machine used, and a known one is used. be able to. Specifically, for example, benzophenone, N, N′-tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl- 1- [4- (methylthio) phenyl] -2-morpholino-propanone-1,4,4'-bis (dimethylamino) benzophenone (Michler ketone), 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4 Aromatic ketones such as' -dimethylaminobenzophenone, quinones such as alkylanthraquinone and phenanthrenequinone, benzoin compounds such as benzoin and alkylbenzoin, benzoin ether compounds such as benzoin alkyl ether and benzoin phenyl ether, and benzyl such as benzyldimethyl ketal Guidance 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluoro Phenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer , 2,4,5-triarylimidazole dimer such as 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, N-phenylglycine, N-phenylglycine derivative, 9- Acridine derivatives such as phenylacridine, oxy such as 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)] Esters, coumarin compounds such as 7-diethylamino-4-methylcoumarin, thioxanthone compounds such as 2,4-diethylthioxanthone, acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. These may be used alone or in combination of two or more.

  From the viewpoint of making the resist shape better, it is preferable to use a phosphine oxide photopolymerization initiator. Examples of such compounds include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide as monoacylphosphine oxide, and bis (2,4,6-trimethylbenzoyl) as bisacylphosphine oxide. -Phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. These are commercially available as DAROCURE-TPO and IRGACURE-819 (both are trade names, manufactured by Ciba Japan).

  Moreover, it is preferable to further contain the compound which has an acridine ring or the compound which has an oxime ester from a viewpoint of improving a sensitivity more, and these can also be used together. Examples of the compound having an acridine ring include 9-phenylacridine, 9-aminoacridine, 9-pentylaminoacridine, 1,2-bis (9-acridinyl) ethane, and 1,3-bis (9-acridinyl) propane. 1,4-bis (9-acridinyl) butane, 1,5-bis (9-acridinyl) pentane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, , 8-bis (9-acridinyl) octane, 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12 -Bis (9-acridinyl) alkanes such as bis (9-acridinyl) dodecane, 9-phenylacridine, 9-pyridylacridyl 9-pyrazinylacridine, 9-monopentylaminoacridine, 1,3-bis (9-acridinyl) -2-oxapropane, 1,3-bis (9-acridinyl) -2-thiapropane, 1,5- Examples include bis (9-acridinyl) -3-thiapentane, and among these, 1,7-bis (9-acridinyl) heptane is more preferable. 1,7-bis (9-acridinyl) heptane is commercially available as N-1717 (manufactured by ADEKA Corporation, trade name). Examples of the compound having the oxime ester include (2- (acetyloxyiminomethyl) thioxanthen-9-one), (1,2-octanedione, 1- [4- (phenylthio)-, 2- (o -Benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime)). Examples of commercially available products include IRGACURE-OXE01 and IRGACURE-OXE02 (both manufactured by BASF).

Examples of the thermosetting agent (d) include epoxy compounds, oxetane compounds, benzoxazine compounds, oxazoline compounds, cyclic carbonate compounds, blocked isocyanates, or melamine derivatives.
Examples of the epoxy compound include bisphenol A type epoxy resins such as bisphenol A diglycidyl ether, bisphenol F type epoxy resins such as bisphenol F diglycidyl ether, bisphenol S type epoxy resins such as bisphenol S diglycidyl ether, and biphenol diglycidyl ether. Biphenol type epoxy resins such as bixylenol type diglycidyl ether, hydrogenated bisphenol A type epoxy resins such as hydrogenated bisphenol A glycidyl ether, and dibasic acid-modified diglycidyl ether type epoxy resins thereof Etc. These may be used alone or in combination of two or more. Commercially available compounds can be used as these compounds. For example, examples of bisphenol A diglycidyl ether include Epicoat 828, Epicoat 1001, and Epicoat 1002 (all are trade names manufactured by Japan Epoxy Resin Co., Ltd.). Examples of bisphenol F diglycidyl ether include Epicoat 807 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), and examples of bisphenol S diglycidyl ether include EBPS-200 (trade name, manufactured by Nippon Kayaku Co., Ltd.) and Epicron. EXA-1514 (manufactured by DIC Corporation, trade name) and the like. Examples of the biphenol diglycidyl ether include YL-6121 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.). Examples of the bixylenol diglycidyl ether include YX-4000 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.). Etc. Furthermore, examples of the hydrogenated bisphenol A glycidyl ether include ST-2004 and ST-2007 (both manufactured by Tohto Kasei Co., Ltd., trade names), and the dibasic acid-modified diglycidyl ether type epoxy resin described above. ST-5100 and ST-5080 (both manufactured by Tohto Kasei Co., Ltd., trade names) and the like can be mentioned.

  Examples of the oxetane compound include all compounds having two or more oxetane rings in one molecule, such as 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3- Oxetanyl) methoxy] methyl} benzene, 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester, and the like. . Specific examples include the Aron Oxetane series manufactured by Toa Gosei Co., Ltd. and the Etanacol Oxetane series manufactured by Ube Industries, Ltd. When an oxetane compound is used, a curing catalyst such as triphenylphosphine may be used because of low reactivity.

  In addition, benzoxazine compounds, oxazoline compounds, and cyclic carbonate compounds may be used as the thermosetting agent that undergoes ring-opening polymerization in the same manner as epoxy compounds and oxetane compounds and generates less outgas.

  (D) The block type isocyanate as the thermosetting agent is inactive at room temperature (25 ° C.), but when heated, the blocking agent reversibly dissociates and regenerates the isocyanate group. Isocyanurate type, biuret type and adduct type are exemplified, but isocyanurate type is preferable from the viewpoint of adhesion. These may be used alone or in combination of two or more. Examples of the blocking agent include at least one compound selected from diketones, oximes, phenols, alkanols, and caprolactams. Specific examples include methyl ethyl ketone oxime and ε-caprolactam. Block type isocyanate is easily available as a commercial product, for example, Sumidur BL-3175, Desmodur TPLS-2957, TPLS-2062, TPLS-2957, TPLS-2078, BL4165, TPLS2117, BL1100, BL1265, Desmotherm 2170. , Desmotherm 2265 (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate 2512, Coronate 2513, Coronate 2520 (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.), B-830, B-815, B-846, B-870, B -874, B-882 (trade name of Mitsui Takeda Chemical Co., Ltd.) and the like. The dissociation temperature of the blocking agent is preferably 120 to 200 ° C.

  In particular, when insulation is required, it is desirable that the structure includes an isocyanuric skeleton or an aromatic ring such as a benzene ring. Examples of such a block type isocyanate include Sumijoule BL-3175, Sumijoule BL-4265, and B-870.

  The melamine derivative is an initial condensate obtained by reacting an aldehyde with an amino group-containing compound such as melamine, urea, benzoguanamine, etc., for example, trimethylol melamine resin, tetramethylol melamine resin, hexamethylol melamine resin, hexamethoxymethyl Melamine resins such as melamine resin, hexabutoxymethyl melamine resin, N, N′-dimethylol urea resin, Cymel 300, Cymel 301, Cymel 303, Cymel 325, Cymel 350, etc. (trade names of Melamine Resins manufactured by Mitsui Toatsu Simel Co., Ltd.) Melanin resins such as Melan 523, Melan 623, Melan 2000 (trade name of melamine resin manufactured by Hitachi Chemical Co., Ltd.), urea resins such as Melan 18 (trade name of urea resin manufactured by Hitachi Chemical Co., Ltd.), and benzoguanami such as Melan 362A Such as resin (trade name of Hitachi Chemical Co., Ltd. benzoguanamine resin), and the like. A particularly preferred amino resin includes hexamethoxymethyl melamine resin.

  (D) When the thermosetting agent is a blocked isocyanate or a melamine derivative, in the present invention, the added amount in the resin composition is the above-mentioned blocked with respect to 100 parts by mass of the solid content of the photosensitive resin composition. The amount of isocyanate and melamine derivative is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less. By setting it as 20 mass parts or less, generation | occurrence | production of the outgas at the time of thermosetting can be suppressed.

  In the present invention, the component (e) is silica whose surface is subjected to a coupling treatment using a coupling agent. If the silica surface is not subjected to a coupling treatment, the affinity with the resin matrix is poor, and the silica tends to settle or aggregate, so that the filler tends to slide off the resin matrix.

  Examples of the coupling agent include silane coupling agents, titanate coupling agents, aluminate coupling agent systems, and zirconate coupling agents. These can be used alone or in combination of two or more.

Examples of the silane coupling agent include epoxy silane compounds, amino silane compounds, acrylic silane compounds (vinyl silane compounds), thiol silane compounds, ureido silane compounds, and isocyanate silane compounds.
As epoxy silane compounds, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane , 3-glycidoxypropyltriethoxysilane and the like.
As aminosilane compounds, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltri Ethoxysilane, 4-aminobutylmethyldimethoxysilane, 4-aminobutylmethyldiethoxysilane, N- (3-trimethoxysilylethyl) ethylenediamine, N- (3-triethoxysilylethyl) ethylenediamine, N- (3-methyl Dimethoxysilylethyl) ethylenediamine, N- (3-methyldiethoxysilylethyl) ethylenediamine, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimee Xysilane, 3- (2-aminoethylamino) propylmethyldimethoxysilane, 3- (2-aminoethylamino) propylmethyldiethoxysilane, 3- [2- (2-aminoethylamino) ethylamino] propyltrimethoxysilane 3- [2- (2-aminoethylamino) ethylamino] propyltriethoxysilane, 3- [2- (2-aminoethylamino) ethylamino] propylmethyldimethoxysilane, 3- [2- (2-amino) And ethylamino) ethylamino] propylmethyldiethoxysilane.
As an acrylic silane compound (vinylsilane compound), vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, γ- (methacryloxypropyl) trimethoxysilane, p-styryltrimethoxysilane, Examples include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.
Examples of the thiol silane compound include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldimexisilane.
Examples of the ureidosilane compound include 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropylmethyldimethoxysilane, and 3-ureidopropylmethyldiethoxysilane.
Examples of the isocyanate silane compound include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, and 3-isocyanatepropylmethyldiethoxysilane.
Other sulfide group-containing silane coupling agents include bis (triethoxysilylpropyl) tetrasulfide, bis (trimethoxysilylpropyl) tetrasulfide, bis (methyldimethoxysilylpropyl) tetrasulfide, and bis (methyldiethoxysilylpropyl). ) Tetrasulfide and the like.

  Examples of the titanate coupling agent include amine, phosphorous acid, pyrophosphoric acid, and carboxylic acid. Specifically, isopropyl tristearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl / aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphate) titanate, isopropyl tridodecylbenzene sulfonyl titanate, Isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetra (1,1-diallyloxymethyl-1-butyl) bis- (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) ethylene titanate , Isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl RESTIR diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, dicumyl phenyloxy acetate titanate, etc. diisostearoyl ethylene titanate.

  Examples of the aluminate coupling agent include acetoalkoxy aluminum diisopropylate, aluminum diisopropoxy monoethyl acetoacetate, aluminum trisethyl acetoacetate, and aluminum trisacetylacetonate.

  Examples of the zirconate coupling agent include zirconium tetrakisacetylacetonate, zirconium dibutoxybisacetylacetonate, zirconium tetrakisethylacetoacetate, diconium tributoxymonoethylacetoacetate, zirconium tributoxyacetylacetonate and the like.

  From the viewpoint that the coupling agent further improves the effects of the present invention, at least one selected from the group consisting of epoxy silane compounds, amino silane compounds, acrylic silane compounds, thiol silane compounds, ureido silane compounds, and isocyanate silane compounds is present. Preferably, at least one selected from the group consisting of an epoxy silane compound, an amino silane compound, an acrylic silane compound, and a thiol silane compound is more preferable, and at least one selected from the group consisting of an epoxy silane compound, an amino silane compound, and an acryl silane compound. Further preferred. Examples of these coupling agents include epoxy silanes such as γ-glycidoxypropyltriethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, aminopropyltriethoxysilane, and ureidopropyltriethoxy. Examples thereof include aminosilanes such as silane and N-phenylaminopropyltrimethoxysilane, hydrophobic silane compounds such as phenyltrimethoxysilane, methyltrimethoxysilane, and octadecyltrimethoxysilane, and mercaptosilane.

  The blending amount of the coupling agent is not particularly limited, but is usually 0.05 to 10% by mass with respect to silica. If it is less than 0.05% by mass, it is difficult to obtain the intended effect, and if it exceeds 10% by mass, the effect reaches saturation and becomes economically disadvantageous, and the fluidity of the composition is impaired. The method of blending these coupling agents is not particularly limited. For example, a method of drying after immersing the filler in a coupling agent solution (aqueous solution, organic solvent solution, water / organic solvent mixed solution), or various For example, a method of mixing and mixing a coupling agent and silica with a mixer may be used.

  In addition to the above-described components (a) to (e), the photosensitive resin composition of the present invention may further include other components according to desired properties.

  Moreover, in this invention, it is preferable to use (g) inorganic fillers other than a silica as needed in order to improve characteristics, such as adhesiveness and hardness. For example, inorganic fillers such as barium sulfate, barium titanate, talc, clay, calcined kaolin, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder can be used. The amount used is preferably 0 to 70% by mass.

  Moreover, in this invention, it is desirable to use (h) dilution solvent as needed. Examples of the diluent include aliphatic alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, n-pentanol and hexanol, hydrocarbons such as benzyl alcohol and cyclohexane, diacetone alcohol, Aliphatic ketones such as 3-methoxy-1-butanol, acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, methyl hexyl ketone, ethyl butyl ketone, dibutyl ketone, ethylene glycol, diethylene glycol, tri Ethylene glycol, tetraethylene glycol, propylene glycol, ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol monoacetate, pro Ethylene glycol alkyl ethers such as lenglycol diacetate, propylene glycol monoethyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate And its acetate, diethylene glycol monoalkyl ether and its acetate diethylene glycol dialkyl ether, triethylene glycol alkyl ether, propylene glycol alkyl ether and its acetate, dipropylene glycol alkyl ether, and toluene, petroleum ether, petroleum naphtha, Hydrogenated petroleum naphtha Or petroleum solvents such as solvent naphtha, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, etc. Acid esters, amines, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dioxane, tetrahydrofuran, cyclohexanone, γ-butyrolactone, 3- Solvents such as hydroxy-2-butanone, 4-hydroxy-2-pentanone and 6-hydroxy-2-hexanone can be used alone or in combination of two or more.

  When the photosensitive resin composition is required to be in close contact with a metal such as copper, as an adhesion improver, melamine, dicyandiamide, triazine compound and derivatives thereof, imidazole, thiazole, triazole, silane coupling agent Etc. can be contained. Specifically, for example, melamine, acetoguanamine, benzoguanamine, melamine-phenol-formalin resin, dicyandiamide, ethyldiamino-s-triazine, 2,4-diamino-s-triazine, 2,4-diamino-6-xylyl- Examples include s-triazine, trade names “2MZ-AZINE”, “2E4MZ-AZINE”, “C11Z-AZINE”, and “2MA-OK” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Also, if necessary, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, phenothiazine, thixotropic agents such as benton, montmorillonite, aerosil, amide wax, silicone, fluorine, polymer An antifoaming agent such as a leveling agent can be used.

  Content of each component in the photosensitive resin composition is 30 to 80 parts by mass of component (a) and 20 to 70 parts by mass of component (b) with respect to 100 parts by mass in total of components (a) and (b). It is preferable to become a part. Furthermore, it is more preferable that component (a) is blended in an amount of 40 to 75 parts by mass and component (b) in an amount of 25 to 60 parts by mass. Moreover, it is preferable that the component (c) is blended in an amount of 0.1 to 30 parts by mass, preferably 0.1 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass. The component (d) is preferably 3 to 50 parts by mass, and more preferably 5 to 40 parts by mass. Component (e) is preferably 1 to 100 parts by mass, and more preferably 10 to 70 parts by mass.

  When the diluent used in the present invention is applied to a support and used as a photosensitive element, 20 to 70% of the total mass is contained in the varnish before coating. Then, after making into a film, in order to volatilize in the drying process at the time of film preparation, it shall be 3% or less.

Next, the photosensitive element of the present invention will be described.
The photosensitive element of this invention is equipped with a support body and the photosensitive resin composition layer containing the photosensitive resin composition of this invention formed on this support body. On the photosensitive resin composition layer, you may further provide the protective film which coat | covers this photosensitive resin composition layer.

  The photosensitive resin composition layer is prepared by dissolving the photosensitive resin composition of the present invention in the above solvent or mixed solvent to obtain a solution having a solid content of about 30 to 80% by mass, and then applying the solution onto a support. It is preferable to form. Although the thickness of the photosensitive resin composition layer varies depending on the use, it is preferably 5 to 200 μm and more preferably 15 to 60 μm in thickness after drying after removing the solvent by heating and / or hot air blowing. . If this thickness is less than 5 μm, it tends to be difficult to apply industrially, and if it exceeds 200 μm, the above-mentioned effects produced by the present invention tend to be reduced, and in particular, physical properties and resolution tend to decrease.

  Examples of the support provided in the photosensitive element include a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene.

  The thickness of the support is preferably 5 to 100 μm, and more preferably 10 to 30 μm. If the thickness is less than 5 μm, the support tends to be broken when the support is peeled off before development, and if it exceeds 100 μm, the resolution and flexibility tend to decrease.

  The photosensitive element consisting of two layers of the support and the photosensitive resin composition layer as described above or the photosensitive element consisting of three layers of the support, the photosensitive resin composition layer and the protective film is stored, for example, as it is. Alternatively, the protective film may be interposed and wound around the core in a roll shape and stored.

  The method for forming a resist pattern using the photosensitive resin composition or photosensitive element of the present invention is, firstly, from a known screen printing, application by a roll coater or the like, or from the photosensitive element described above as necessary. A photosensitive resin composition layer is laminated on a substrate on which a resist is to be formed by a process of removing the protective film and attaching it by lamination or the like. Next, an actinic ray is irradiated to a predetermined portion of the photosensitive resin composition layer through a mask pattern, and an exposure process is performed in which the photosensitive resin composition layer in the irradiated portion is photocured. The photosensitive resin composition layer other than the irradiated part is removed by the next development step. In addition, the board | substrate which forms a resist points out a printed wiring board, a board | substrate for semiconductor packages, and a flexible wiring board.

As the light source of actinic light, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp that emits ultraviolet rays effectively is used. Moreover, what emits visible light effectively, such as a photographic flood light bulb and a solar lamp, is also used.
Further, direct drawing direct laser exposure may be used. An excellent pattern can be formed by using the photopolymerization initiator of component (c) corresponding to each laser light source and exposure method.

  In the development process, an alkaline developer such as a dilute solution of sodium carbonate (1 to 5% by mass aqueous solution) at 20 to 50 ° C. is used as the developer, and known spraying, rocking immersion, brushing, scraping, etc. Develop by the method of.

After the development step, it is preferable to perform ultraviolet irradiation or heating with a high-pressure mercury lamp for the purpose of improving solder heat resistance, chemical resistance, and the like. When irradiating with ultraviolet rays, the irradiation amount can be adjusted as necessary. For example, irradiation can be performed with an irradiation amount of 0.2 to 10 J / cm ² . Moreover, when heating a resist pattern, it is preferable to carry out for 15 to 90 minutes in the range of 100-170 degreeC. Furthermore, ultraviolet irradiation and heating can be performed at the same time, and after either one is performed, the other can be performed. When performing ultraviolet irradiation and heating simultaneously, it is more preferable to heat to 60 to 150 ° C. from the viewpoint of effectively imparting solder heat resistance, chemical resistance and the like.

  This photosensitive resin composition layer also serves as a protective film for wiring after soldering to the substrate, has good lamination temperature stability, excellent resolution, excellent flatness, crack resistance, HAST resistance, Since it has gold plating properties, it is effective as a solder resist for printed wiring boards, semiconductor package substrates, and flexible wiring boards.

  The substrate provided with the resist pattern in this manner is then mounted with a semiconductor element or the like (for example, wire bonding or solder connection) and then mounted on an electronic device such as a personal computer.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

(Preparation of photosensitive resin composition solution)
The photosensitive resin composition solution was obtained by mixing each component shown in Table 1 with the compounding quantity (part by mass) shown in the same table. The following were used for each component shown in Table 1.

<(A) component; resin having an ethylenically unsaturated group and a carboxyl group>
“UXE-3024”: urethane-modified epoxy acrylate (trade name, manufactured by Nippon Kayaku Co., Ltd.)
“UE-EXP-2827”: acid-modified cresol novolac epoxy acrylate (manufactured by DIC Corporation, trade name)

<(B) component; photopolymerizable monomer having an ethylenically unsaturated group>
“FA-321M”: 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (trade name, manufactured by Hitachi Chemical Co., Ltd.)
“UX-5002D-M20”: Tricyclodecane structure-containing urethane acrylate (trade name, manufactured by Nippon Kayaku Co., Ltd.)

<(C) component; photopolymerization initiator>
“IRGACURE-907”: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name, manufactured by BASF)
“KATACURE-DETX-S”: 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd., trade name)
“DAROCURE-TPO”: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name, manufactured by BASF)
“IRGACURE-OXE02”: Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name, manufactured by BASF)

<(D) component; thermosetting agent>
“NC-3000H”: biphenyl aralkyl novolac type epoxy resin (trade name, manufactured by Nippon Kayaku Co., Ltd.)
“BL-3175”: Block type isocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., trade name)

<Component (e): Silica whose surface has been coupled with a coupling agent>
“Silica-A”: silica having an average particle size of 500 nm coupled with an aminosilane compound (manufactured by Admatechs Co., Ltd.)
“Silica-B”: silica having an average particle size of 500 nm coupled with an acrylic silane compound (manufactured by Admatechs)
“Silica-C”: silica having an average particle diameter of 500 nm coupled with an epoxysilane compound (manufactured by Admatechs)
“Silica-D”: Silica having an average particle diameter of 500 nm not subjected to coupling treatment (manufactured by Admatechs Co., Ltd.)
The average particle size is determined by measuring the particles dispersed in the solvent using a laser diffraction / scattering microtrack particle size distribution meter (trade name “MT3000”, manufactured by Nikkiso Co., Ltd.). Cumulative particle diameter at 50% (volume basis) (also referred to as “D50”).

<Other ingredients>
“Variace B-30”: Barium sulfate “Variace B-30” (manufactured by Sakai Chemical Industry Co., Ltd., trade name), barium sulfate dispersion dicyandiamide prepared by the following method: dicyandiamide (Wako Pure Chemical Industries, Ltd.) )

  (B) 20 parts by mass (solid content) of the component, 40 parts by mass of the barium sulfate, and 40 parts by mass of methyl ethyl ketone were mixed with Starmill LMZ (manufactured by Ashizawa Finetech Co., Ltd.) using zirconia beads having a diameter of 1.0 mm. Dispersion was carried out at 12 m / s for 3 hours to obtain a barium sulfate dispersion. Barium sulfate was added to the photosensitive resin composition by blending the dispersion prepared above.

  To the photosensitive resin composition solutions of Examples and Comparative Examples, methyl ethyl ketone was added as a diluent so that the solid content of the resin composition solution was 60% by mass.

＊：表１中の配合量は固形分（質量部）での数値を示す。

*: The compounding amount in Table 1 indicates a numerical value in solid content (parts by mass).

(Production of photosensitive element)
Next, the photosensitive resin composition solution obtained above is applied on a 16 μm-thick polyethylene terephthalate film (G2-16, manufactured by Teijin Ltd., trade name) as a support so that the thickness is uniform. Was used to form a layer of the photosensitive resin composition solution, which was dried at 100 ° C. for 10 minutes using a hot air convection dryer. The film thickness after drying of the photosensitive resin composition layer was 20 μm.

  Subsequently, on the surface of the photosensitive resin composition layer opposite to the side in contact with the support, a polyethylene film (NF-15, manufactured by Tamapoly Co., Ltd., trade name) is bonded as a protective film, and is photosensitive. Got the element.

(Characteristic evaluation of photosensitive element)
Each of the following tests was performed using the photosensitive resin composition solutions (varnishes) of Examples 1 to 7 and Comparative Examples 1 to 3 and the photosensitive element, respectively, and stability, coating properties, and resolution in the varnish state. Property, sliding property, adhesion, and PCT were evaluated. The obtained results are shown in Table 2.

(Evaluation of stability in varnish state (varnish stability))
The obtained photosensitive resin composition solution (varnish) was placed in a transparent container and allowed to stand at room temperature (25 ° C.) for 3 days, and then the stability in the varnish state was visually confirmed and evaluated according to the following criteria.
"A": Aggregation of filler cannot be observed on the varnish surface, bottom, or entire surface. "B": Aggregation of filler can be observed on the varnish surface, bottom, or entire surface.

(Evaluation of coating properties)
The appearance of the obtained photosensitive element was observed, the coating property was visually confirmed, and the evaluation was made according to the following criteria.
“A”: Color unevenness, streaks or repellency defects cannot be observed on the coating film appearance “B”: Color unevenness, streaks or repellency defects can be observed on the coating film appearance

(Resolution evaluation)
The copper surface of a printed wiring board substrate (E-679, manufactured by Hitachi Chemical Co., Ltd., trade name) obtained by laminating a 12 μm thick copper foil on a glass epoxy substrate was polished with an abrasive brush, washed with water, and dried. The polyethylene film of the photosensitive element is peeled off by using a vacuum pressurizing laminator (MVLP-500, trade name, manufactured by Meiki Seisakusho Co., Ltd.) on the printed wiring board substrate, and the pressure is 0.4 MPa and the press heat is applied. Lamination was performed at a plate temperature of 80 ° C., a vacuum drawing time of 20 seconds, a lamination press time of 30 seconds, and an atmospheric pressure of 4 kPa or less, and a photosensitive resin composition layer was laminated to obtain a laminate for evaluation.

  A photo tool having a diameter of 10 μm in a range of via opening diameter = X μm (X = 30 to 200) is adhered as a negative on the evaluation laminate, and an EXM-1201 type exposure machine manufactured by Oak Manufacturing Co., Ltd. is used. Thus, exposure was performed with an energy amount such that the number of remaining step steps after development of the 41-step step tablet was 16.0. Next, after standing at 25 ° C. for 1 hour, the polyethylene terephthalate as a support on the laminate is peeled off, and spray development is performed for 60 seconds with a 1 mass% sodium carbonate aqueous solution at 30 ° C. to remove unexposed portions. Then, a resist pattern was formed.

  The formed resist pattern was observed using a stereomicroscope at a magnification of 4 times, and the minimum via opening diameter formed was evaluated as resolution.

(Sliding properties of silica)
The via opening side wall obtained in the above-described resolution evaluation was observed using a scanning electron microscope (SEM) (manufactured by Hitachi High-Technologies Corporation, trade name “SU-1500”) at a magnification of 1000 times, Silica slipping was evaluated according to the following criteria. Observations were made with 10 random fields of view. In addition, the observation visual field when it expanded by 1000 time using the said SEM was made into 1 visual field.
“A”: The filler sliding down cannot be observed on the via opening side wall. “B”: The filler sliding down can be observed on the via opening side wall.

(Evaluation of adhesion)
Using the EXM-1201 type exposure machine manufactured by Oak Manufacturing Co., Ltd., the entire surface of the evaluation laminate was exposed with an energy amount such that the number of remaining step stages after development of the 41-step tablet was 16.0. Next, after standing at 25 ° C. for 1 hour, the polyethylene terephthalate as a support on the laminate was peeled off, and spray development was performed for 60 seconds with a 1 mass% sodium carbonate aqueous solution at 30 ° C. A pattern was formed. Subsequently, using an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd., the ultraviolet rays were irradiated with an energy amount of 1 J / cm ² , and further subjected to a heat treatment at 160 ° C. for 60 minutes, thereby evaluating the adhesiveness formed with the solder resist. A laminate substrate was obtained.

The obtained board | substrate was cut using the cross-cut method, the cut board | substrate was confirmed visually, and the following criteria evaluated.
"A": Can not observe peeling on the grid "B": Can observe peeling on the grid

(PCT evaluation)
A pressure cooker test (PCT, 2 atm (2026 hPa), 121 ° C., 100% RH, 96 hours) is performed using the substrate cut by the cross-cut method on the adhesion evaluation substrate, and the substrate is visually observed. It confirmed and evaluated by the following criteria.
“A”: Cannot observe defects such as swelling and peeling on the grid. “B”: Can observe defects such as swelling and peeling on the grid.

  According to the present invention, a photosensitive resin composition excellent in stability in a varnish state and excellent in coating film formability, not sufficiently causing the filler to slide down, and having excellent moisture resistance, and a photosensitive element obtained therefrom. Can be provided.

Claims (2)

(A) a resin having an ethylenically unsaturated group and a carboxyl group, (b) a photopolymerizable monomer having an ethylenically unsaturated group, (c) a phosphine oxide photopolymerization initiator, and (d) a thermosetting agent. And (e) containing a silica whose surface is coupled using a coupling agent,
A photosensitive resin composition in which the coupling agent is an aminosilane compound (however, bisphenol F type epoxy acrylate having acid anhydride modification, dipentaerythritol hexaacrylate, and bis (2,4,6-trimethylbenzoyl)) -Phenylphosphine oxide, dicyclopentadiene type epoxy resin, liquid naphthalene type epoxy resin, spherical fused silica surface-treated with a phenylaminosilane coupling agent, 2-phenyl-4-methylimidazole, A photosensitive resin composition containing 4-diethylthioxanthone is excluded.) .   A photosensitive element provided with a support body and the photosensitive resin composition layer containing the photosensitive resin composition of Claim 1 formed on this support body.