Photosensitive resin composition, and dry film, printed wiring board and method for manufacturing printed wiring board using the composition

Abstract

To provide a photosensitive resin composition having excellent adhesion strength with plated copper and showing excellent resolution and adhesiveness to a substrate made of a silicon raw material such as a silicon wafer and to a chip component, and a dry film, a printed wiring board and a method for manufacturing a printed wiring board using the above composition.SOLUTION: The photosensitive resin composition comprises (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a silane compound, in which the content of the (D) inorganic filler is 20 to 60 mass% based on a total solid content of the photosensitive resin composition. A dry film, a printed wiring board and a method for manufacturing a printed wiring board using the above composition are also disclosed.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a photosensitive resin composition, and a method for producing a dry film, a semiconductor device, and a printed wiring board using the same. [Background technology]

[0002] In recent years, the increasing performance of electronic devices (smaller size, lighter weight, and more functionality) has led to the increasing integration of semiconductor components such as LSIs and chips. This has led to a rapid shift in the form of semiconductor components, with more pins and smaller size. Furthermore, as the integration of semiconductor components increases, the semiconductor elements, semiconductor packages, printed wiring boards, flexible wiring boards, and other components that make up semiconductor components are becoming increasingly dense and precise. As a result, component-embedded substrates with embedded chips and chip capacitors are being considered. Surface protection films or interlayer insulating films used in semiconductor components are required to be able to form via opening patterns for interlayer connections, and to adhere not only to substrate materials and copper patterns (conductor patterns) but also to chip components.

[0003] A build-up method is a conventional method for manufacturing printed wiring boards. In this build-up method, an insulating resin film is first laminated onto an inner layer circuit board (a substrate having a first conductor pattern), cured by heating to form an interlayer insulating film, and then via holes are formed by laser processing. Next, the interlayer insulating film is roughened and smeared by alkaline permanganate treatment or the like, and then electroless copper plating is performed to form via holes that enable interlayer connection with a second conductor pattern (see, for example, Patent Document 1).

[0004] In recent years, the increasing density of conductor patterns has led to a demand for high resolution in surface protection films, and photosensitive resin compositions that can be patterned by photolithography have come into widespread use. Among these, alkali-developable photosensitive resin compositions that can be developed with a weak alkaline aqueous solution such as an aqueous sodium carbonate solution have become mainstream from the viewpoints of preserving the working environment and the global environment. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 7-304931 Summary of the Invention [Problem to be solved by the invention]

[0006] On the other hand, conventional laser processing to form via holes using a build-up method requires forming each via individually, which can be time-consuming when a large number of vias are required for high density. Therefore, photolithography has been considered as a method for forming a surface protection film that can simultaneously form a large number of vias. However, the adhesive strength between the surface protection film and electroless-plated copper is not sufficient.

[0007] Therefore, the problem that the present disclosure aims to solve is to provide a photosensitive resin composition that has excellent adhesive strength with plated copper, excellent resolution, and excellent adhesion to silicon substrates such as silicon wafers and chip components, as well as a dry film, a printed wiring board, and a method for manufacturing a printed wiring board that use the same (hereinafter, these may be referred to as "photosensitive resin composition, etc."). [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above-mentioned problems and have found that the problems can be solved by the following invention: That is, the present disclosure provides the following photosensitive resin composition, a dry film using the same, a printed wiring board, and a method for producing a printed wiring board.

[0009] [1] A photosensitive resin composition comprising (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a silane compound, wherein the content of the inorganic filler (D) is 10 to 80 mass% based on the total amount of solids in the photosensitive resin composition. [2] A dry film having a carrier film and a photosensitive layer using the photosensitive resin composition described in [1] above. [3] A printed wiring board having at least one of a surface protective film and an interlayer insulating film formed from the photosensitive resin composition according to [1] above. [4] A method for producing a printed wiring board, comprising the steps of providing a photosensitive layer on a substrate using the photosensitive resin composition described in [1] above or the dry film described in [2] above, forming a resin pattern using the photosensitive layer, and curing the resin pattern to form at least one of a surface protective film and an interlayer insulating film, in that order. [Effects of the Invention]

[0010] According to the present disclosure, it is possible to provide a photosensitive resin composition that has excellent adhesive strength with plated copper, excellent resolution, and excellent adhesion to silicon substrates such as silicon wafers and chip components, as well as a dry film, a printed wiring board, and a method for manufacturing a printed wiring board that use the same. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic diagram showing one embodiment of a process for producing a multilayer printed wiring board using a cured product of the photosensitive resin composition of the present embodiment as at least one of a surface protective film and an interlayer insulating film. DETAILED DESCRIPTION OF THE INVENTION

[0012] [Photosensitive resin composition] The photosensitive resin composition according to an embodiment of the present disclosure (hereinafter, sometimes simply referred to as this embodiment) contains (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a silane compound, and the content of the inorganic filler (D) is 10 to 80 mass% based on the total solid content of the photosensitive resin composition. In this specification, these components may be simply referred to as component (A), component (B), component (C), etc. In this specification, the term "solid content" refers to the non-volatile content of the photosensitive resin composition excluding volatile substances such as water and solvents. It refers to the components that remain without volatilization when the resin composition is dried, and also includes liquid, starch syrup-like, and wax-like components at room temperature around 25°C. Each component will be explained below.

[0013] <(A) Acid-modified vinyl group-containing epoxy resin> The photosensitive resin composition of this embodiment contains an acid-modified vinyl group-containing epoxy resin as component (A). Component (A) is a compound obtained by modifying an epoxy resin with a vinyl group-containing organic acid, such as an epoxy resin obtained by reacting a resin obtained by reacting an epoxy resin with a vinyl group-containing monocarboxylic acid with a saturated or unsaturated group-containing polybasic acid anhydride.

[0014] Examples of component (A) include an acid-modified vinyl-group-containing epoxy resin (A1) (hereinafter sometimes referred to as component (A1)) made using a bisphenol novolac epoxy resin (a1) (hereinafter sometimes referred to as component (a1)) and an acid-modified vinyl-group-containing epoxy resin (A2) (hereinafter sometimes referred to as component (A2)) made using an epoxy resin (a2) (hereinafter sometimes referred to as component (a2)) other than the epoxy resin (a1). These may be used alone or in combination. Furthermore, from the viewpoint of improving adhesive strength in particular, component (A) may contain at least one component (A1) made using component (a1) and at least one component (A2) made using component (a2).

[0015] (Epoxy resin (a1)) From the viewpoints of enabling alkaline development and improving resolution and adhesion strength, it is preferable that the component (A) contains a component (A1) obtained using the component (a1). From the same viewpoints, the component (a1) is preferably one selected from bisphenol novolac epoxy resins having a structural unit represented by the following general formula (I) or (II), and more preferably a bisphenol novolac epoxy resin having a structural unit represented by the following general formula (II).

[0016] [Epoxy resin having a structural unit represented by general formula (I)] One preferred embodiment of the component (a1) is an epoxy resin having a structural unit represented by the following general formula (I):

[0017] [ka]

[0018] In general formula (I), R 11 represents a hydrogen atom or a methyl group, and Y 1 Each of R independently represents a hydrogen atom or a glycidyl group. 11 may be the same or different, and Y 1 At least one of these groups represents a glycidyl group.

[0019] R 11 is preferably a hydrogen atom from the viewpoint of improving resolution and adhesive strength. 1 is preferably a glycidyl group.

[0020] The number of structural units in the epoxy resin (a1) having a structural unit represented by general formula (I) is 1 or more and can be appropriately selected from 10 to 100, 15 to 80, or 15 to 70. When the number of structural units is within the above range, the resolution and adhesive strength are improved. Here, the number of structural units of the structural unit is an integer value in a single molecule, and is a rational number that is an average value in an aggregate of multiple types of molecules. The same applies to the number of structural units of the structural unit hereinafter.

[0021] [Epoxy resin having a structural unit represented by general formula (II)] One preferred embodiment of the component (a1) is an epoxy resin having a structural unit represented by the following general formula (II):

[0022] [ka]

[0023] In general formula (II), R 12 represents a hydrogen atom or a methyl group, and Y 2 Each of R independently represents a hydrogen atom or a glycidyl group. 12 may be the same or different, and Y 2 At least one of these groups represents a glycidyl group.

[0024] R 12 is preferably a hydrogen atom from the viewpoint of improving resolution and adhesive strength. From a similar perspective, Y 2 is preferably a glycidyl group.

[0025] The number of structural units in the component (A2) having the structural unit represented by general formula (II) is 1 or more, and may be appropriately selected from 10 to 100, 15 to 80, or 15 to 70. When the number of structural units is within the above range, adhesive strength, heat resistance, and electrical insulation properties are improved.

[0026] In general formula (II), R 12 is a hydrogen atom, and Y2 The glycidyl group is available as the EXA-7376 series (manufactured by DIC Corporation), and R 12 is a methyl group, and Y 2 Those having a glycidyl group are commercially available as the EPON SU8 series (trade name, manufactured by Mitsubishi Chemical Corporation).

[0027] (Epoxy resin (a2)) There are no particular restrictions on the component (a2) as long as it is an epoxy resin different from the component (a1). From the viewpoint of improving adhesive strength and resolution, the component (a2) may be a novolac-type epoxy resin, and may, for example, be one having a structural unit represented by the following general formula (III):

[0028] From the viewpoint of improving resolution in particular, it is preferable to use the component (a2) in combination with a bisphenol novolac epoxy resin containing a structural unit represented by the general formula (I) or (II) among the components (a1).

[0029] [Epoxy resin having a structural unit represented by general formula (III)] The component (a2) is preferably a novolac epoxy resin having a structural unit represented by the following general formula (III). An example of a novolac epoxy resin having such a structural unit is a novolac epoxy resin represented by the following general formula (III').

[0030] [ka]

[0031] In the general formulas (III) and (III'), R 13 represents a hydrogen atom or a methyl group, and Y 3 represents a hydrogen atom or a glycidyl group. In general formula (III'), n1 is a number of 1 or more, and a plurality of R 13 and Y 3 may be the same or different, and Y 3 At least one of these groups represents a glycidyl group.

[0032] R 13 is preferably a hydrogen atom from the viewpoint of improving resolution. Y 3 represents a hydrogen atom in the general formula (III'). 3 and a glycidyl group, Y 3 The molar ratio of Y to Y may be appropriately selected from the range of 0 / 100 to 30 / 70 or 0 / 100 to 10 / 90 from the viewpoint of improving resolution. 3 At least one of the groups is a glycidyl group.

[0033] n1 is a number of 1 or more, and may be appropriately selected from 10 to 200, 30 to 150, or 30 to 100. When n1 is within the above range, a resist shape with improved linearity of the resist pattern contour can be formed, and adhesive strength, heat resistance, and electrical insulation properties are improved.

[0034] Examples of the novolac epoxy resin represented by general formula (III') include phenol novolac epoxy resin and cresol novolac epoxy resin. These novolac epoxy resins can be obtained, for example, by reacting a phenol novolac resin or a cresol novolac resin with epichlorohydrin using a known method.

[0035] To promote the reaction between hydroxyl groups and epichlorohydrin, the reaction is preferably carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide, or dimethylsulfoxide in the presence of an alkali metal hydroxide at a reaction temperature of 50 to 120° C. When the reaction temperature is within the above range, the reaction is less likely to slow down, and side reactions can be further suppressed.

[0036] Examples of the phenol novolac epoxy resin or cresol novolac epoxy resin represented by general formula (III') include YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, YDPN-602 (all of which are trade names manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), DEN-431, DEN-439 (all of which are trade names manufactured by The Dow Chemical Company), EOCN-120, EOCN-1 Commercially available examples include EOCN-02S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027, and BREN (all of which are trade names manufactured by Nippon Kayaku Co., Ltd.), EPN-1138, EPN-1235, and EPN-1299 (all of which are trade names manufactured by BASF), and N-730, N-770, N-865, N-665, N-673, VH-4150, and VH-4240 (all of which are trade names manufactured by DIC Corporation).

[0037] The component (a2) may be at least one selected from the novolac epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, and triphenolmethane epoxy resin.

[0038] [Epoxy resin having a structural unit represented by general formula (IV)] The bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferably at least one selected from bisphenol A type epoxy resins and bisphenol F type epoxy resins having a structural unit represented by the following general formula (IV). Examples of epoxy resins having such a structural unit include bisphenol A type epoxy resins and bisphenol F type epoxy resins represented by the following general formula (IV'), with bisphenol F type epoxy resins being preferred.

[0039] [ka]

[0040] In the general formulas (IV) and (IV'), R 14represents a hydrogen atom or a methyl group, and Y 4 represents a hydrogen atom or a glycidyl group. 14 In general formula (IV'), n2 represents a number of 1 or more, and when n2 is 2 or more, a plurality of Y 4 may be the same or different, and at least one Y 4 is a glycidyl group.

[0041] R 14 is preferably a hydrogen atom, from the viewpoint of making it difficult for undercuts and chipping of the upper part of the resist to occur and improving the linearity and resolution of the resist pattern contour. From a similar perspective, Y 4 is preferably a glycidyl group.

[0042] n2 is a number of 1 or more, and may be appropriately selected from 10 to 100, 10 to 80, or 15 to 60. When n2 is within the above range, a resist shape with improved linearity of the resist pattern contour can be formed, and adhesion to a copper substrate, heat resistance, and electrical insulation properties are improved.

[0043] Represented by general formula (IV), Y 4 The bisphenol A type epoxy resin or bisphenol F type epoxy resin in which Y is a glycidyl group is represented by, for example, the general formula (IV), 4 is a hydrogen atom, the hydroxyl group (-OY 4 ) with epichlorohydrin.

[0044] To promote the reaction between hydroxyl groups and epichlorohydrin, the reaction is preferably carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide, or dimethylsulfoxide in the presence of an alkali metal hydroxide at a reaction temperature of 50 to 120° C. When the reaction temperature is within the above range, the reaction is less likely to slow down, and side reactions can be further suppressed.

[0045] Commercially available examples of the bisphenol A epoxy resin or bisphenol F epoxy resin represented by general formula (IV') include Epicoat 807, 815, 825, 827, 828, 834, 1001, 1004, 1007, and 1009 (all of which are trade names manufactured by Mitsubishi Chemical Corporation), DER-330, DER-301, and DER-361 (all of which are trade names manufactured by The Dow Chemical Company), YD-8125, YDF-170, YDF-175S, YDF-2001, YDF-2004, and YDF-8170 (all of which are trade names manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).

[0046] [Epoxy resin having a structural unit represented by general formula (V)] The triphenolmethane type epoxy resin of the component (a2) is preferably a triphenolmethane type epoxy resin having a structural unit represented by the following general formula (V). A preferred example of a triphenolmethane type epoxy resin having such a structural unit is a triphenolmethane type epoxy resin represented by the following general formula (V').

[0047] [ka] In formulas (V) and (V'), Y 5 represents a hydrogen atom or a glycidyl group, and a plurality of Y 5 may be the same or different, and at least one Y 5 is a glycidyl group. In general formula (V'), n3 is a number of 1 or more.

[0048] Y 5 is a hydrogen atom Y 5 and a glycidyl group, Y 5 The molar ratio of Y to Y may be appropriately selected from the range of 0 / 100 to 30 / 70 in order to prevent undercutting and loss of the upper part of the resist and to improve the linearity and resolution of the resist pattern contour. 5 At least one of the groups is a glycidyl group. n3 is a number of 1 or more, and may be appropriately selected from 10 to 100, 15 to 80, or 15 to 70. When n3 is within the above range, a resist shape with improved linearity of the resist pattern contour can be formed, and adhesion to a copper substrate, heat resistance, and electrical insulation properties are improved.

[0049] As the triphenolmethane type epoxy resin represented by the general formula (V'), for example, FAE-2500, EPPN-501H, EPPN-502H (all of which are trade names manufactured by Nippon Kayaku Co., Ltd.) and the like are commercially available.

[0050] From the viewpoint of improving resolution, the components (A1) and (A2) are preferably resins obtained by reacting the components (a1) and (a2) (hereinafter sometimes referred to as "component (a)") with a vinyl group-containing monocarboxylic acid (b) (hereinafter sometimes referred to as component (b)), to obtain resins (A1') and (A2') (hereinafter sometimes collectively referred to as "component (A')"), with a saturated or unsaturated group-containing polybasic acid anhydride (c) (hereinafter sometimes referred to as component (c)).

[0051] [Vinyl group-containing monocarboxylic acid (b)] Preferred examples of component (b) include acrylic acid, acrylic acid dimers, methacrylic acid, acrylic acid derivatives such as β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, and α-cyanocinnamic acid, half-ester compounds which are reaction products of hydroxyl group-containing acrylates and dibasic acid anhydrides, and half-ester compounds which are reaction products of vinyl group-containing monoglycidyl ethers or vinyl group-containing monoglycidyl esters and dibasic acid anhydrides.

[0052] The half-ester compound can be obtained, for example, by reacting a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether, or a vinyl group-containing monoglycidyl ester with a dibasic acid anhydride in an equimolar ratio. These components (b) can be used alone or in combination.

[0053] Examples of the hydroxyl group-containing acrylate, vinyl group-containing monoglycidyl ether, and vinyl group-containing monoglycidyl ester used in the synthesis of the above-mentioned half-ester compound, which is an example of component (b), include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, pentaerythritol pentamethacrylate, glycidyl acrylate, and glycidyl methacrylate.

[0054] The dibasic acid anhydride used in the synthesis of the above-mentioned half ester compound may be one containing a saturated group or one containing an unsaturated group. Specific examples of the dibasic acid anhydride include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride.

[0055] In the reaction between the above components (a) and (b), the ratio of component (b) may be 0.6 to 1.05 equivalents or 0.8 to 1.0 equivalents per equivalent of epoxy group in component (a). By reacting at such a ratio, photopolymerization is improved, i.e., photosensitivity is increased, resulting in improved resolution.

[0056] The components (a) and (b) can be reacted by dissolving them in an organic solvent. Preferred examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, 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 hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

[0057] Furthermore, it is preferable to use a catalyst to promote the reaction between component (a) and component (b), such as triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, or triphenylphosphine. The amount of catalyst used may be appropriately selected from 0.01 to 10 parts by mass, 0.05 to 2 parts by mass, or 0.1 to 1 part by mass relative to 100 parts by mass of the total of components (a) and (b). When used in the above amount, the reaction between components (a) and (b) is promoted.

[0058] In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor, such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, or pyrogallol. The amount of the polymerization inhibitor used may be appropriately selected from 0.01 to 1 part by mass, 0.02 to 0.8 parts by mass, or 0.04 to 0.5 parts by mass relative to 100 parts by mass of the total of the components (a) and (b) from the viewpoint of improving the storage stability of the composition.

[0059] The reaction temperature between the components (a) and (b) may be appropriately selected from 60 to 150°C, 80 to 120°C, or 90 to 110°C from the viewpoint of productivity.

[0060] In this way, it is presumed that component (A'), which is obtained by reacting component (a) with component (b), has a hydroxyl group formed by a ring-opening addition reaction between the epoxy group of component (a) and the carboxyl group of component (b). It is presumed that by further reacting the component (A') obtained above with the component (c) containing a saturated or unsaturated group, the hydroxyl groups of component (A') (including the hydroxyl groups originally present in component (a)) and the acid anhydride groups of component (c) are semi-esterified to form an acid-modified vinyl group-containing epoxy resin.

[0061] [Polybasic acid anhydride (c)] As the component (c), those containing a saturated group or those containing an unsaturated group can be used. Specific examples of the component (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride. Among these, tetrahydrophthalic anhydride is preferred from the viewpoint of obtaining a photosensitive resin composition capable of forming a pattern with excellent resolution.

[0062] In the reaction between component (A') and component (c), for example, the acid value of the acid-modified vinyl group-containing epoxy resin can be adjusted by reacting 0.1 to 1.0 equivalents of component (c) with 1 equivalent of hydroxyl groups in component (A').

[0063] The acid value of component (A) may be 30 to 150 mgKOH / g, 40 to 120 mgKOH / g, or 50 to 100 mgKOH / g. When the acid value is 30 mgKOH / g or more, the solubility of the photosensitive resin composition in a dilute alkaline solution is excellent, and when it is 150 mgKOH / g or less, the electrical properties of the cured film are improved.

[0064] The reaction temperature between the component (A') and the component (c) may be appropriately selected from 50 to 150°C, 60 to 120°C, or 70 to 100°C from the viewpoint of productivity.

[0065] If necessary, component (a) may also contain, for example, a hydrogenated bisphenol A epoxy resin. Furthermore, component (A) may also contain, for example, a styrene-maleic acid resin such as a hydroxyethyl (meth)acrylate-modified styrene-maleic anhydride copolymer.

[0066] (Molecular weight of component (A)) The weight-average molecular weight of component (A) may be 3,000 to 30,000, 4,000 to 25,000, or 5,000 to 18,000. Within these ranges, adhesive strength, heat resistance, and electrical insulation are improved. Here, the weight-average molecular weight is a polyethylene-equivalent weight-average molecular weight measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. More specifically, for example, the weight-average molecular weight can be determined by measuring using the GPC measurement device and measurement conditions described below, and converting the value using a calibration curve of standard polystyrene. The calibration curve is also prepared using a five-sample set of standard polystyrenes ("PStQuick MP-H" and "PStQuick B," manufactured by Tosoh Corporation). (GPC measurement device) GPC equipment: High-speed GPC equipment "HCL-8320GPC", detector is differential refractometer or UV, manufactured by Tosoh Corporation Column: TSKgel SuperMultipore HZ-H column (column length: 15 cm, column inner diameter: 4.6 mm), manufactured by Tosoh Corporation (Measurement conditions) Solvent: tetrahydrofuran (THF) Measurement temperature: 40℃ Flow rate: 0.35ml / min Sample concentration: 10mg / THF5ml Injection volume: 20μl

[0067] (Content of component (A)) The content of the component (A) may be appropriately selected from 5 to 60 mass%, 10 to 50 mass%, or 15 to 40 mass%, based on the total solid content of the photosensitive resin composition, from the viewpoint of improving heat resistance, electrical properties, and chemical resistance.

[0068] (Total content of components (A1) and (A2) in component (A)) When component (A1) and component (A2) are used in combination as component (A), the total content of components (A1) and (A2) in component (A) may be appropriately selected from the ranges of 80 to 100 mass%, 90 to 100 mass%, 95 to 100 mass%, or 100 mass% from the viewpoint of improving resolution and heat resistance. When either component (A1) or component (A2) is used alone, the total content may also be appropriately selected from the above ranges.

[0069] (mass ratio of component (A1) to component (A2)) When the component (A) is a combination of the component (A1) and the component (A2), the mass ratio (A1 / A2) may be appropriately selected from within the range of 30 / 70 to 90 / 10, 40 / 60 to 80 / 20, or 50 / 50 to 80 / 20 from the viewpoint of improving resolution and heat resistance.

[0070] <(B) Photopolymerizable compound> The component (B) is not particularly limited as long as it is a photopolymerizable or photocrosslinkable compound, and preferred examples thereof include compounds having a functional group exhibiting photopolymerizability, such as a vinyl group, allyl group, propargyl group, butenyl group, ethynyl group, phenylethynyl group, maleimide group, nadimide group, or (meth)acryloyl group, which has an ethylenically unsaturated bond.

[0071] As the component (B), from the viewpoint of photosensitivity, a compound having a molecular weight of 1000 or less is preferred, and examples thereof include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; glycol mono- or di(meth)acrylates such as ethylene glycol, methoxytetraethylene glycol, and polyethylene glycol; (meth)acrylamides such as N,N-dimethyl (meth)acrylamide and N-methylol (meth)acrylamide; aminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate; hexanediol, trimethylolpropane, and pentaerythritol. Preferred examples of the (B) component include polyhydric (meth)acrylates of polyhydric alcohols such as ditrimethylolpropane, dipentaerythritol, and tris-hydroxyethyl isocyanurate, or their ethylene oxide or propylene oxide adducts; (meth)acrylates of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth)acrylate and polyethoxydi(meth)acrylate of bisphenol A; (meth)acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and melamine (meth)acrylate. These (B) components can be used alone or in combination. From the viewpoint of improving sensitivity, the ink may contain polyhydric (meth)acrylates of the above polyhydric alcohols or their ethylene oxide or propylene oxide adducts.

[0072] Furthermore, in order to increase the crosslink density upon photocuring and improve heat resistance and electrical reliability, a compound having three or more ethylenically unsaturated bonds in the molecule can be selected as component (B). Examples of such compounds include the polyvalent (meth)acrylates, and dipentaerythritol tri(meth)acrylate can be selected from the viewpoint of improving sensitivity.

[0073] ((B) Component Content) The content of component (B) may be appropriately selected from 2 to 50 mass%, 3 to 20 mass%, or 3 to 10 mass%, based on the total solid content in the photosensitive resin composition. When the content of component (B) is 2 mass% or more, photosensitivity is improved and exposed areas tend to be less susceptible to elution during development, while when it is 50 mass% or less, heat resistance is improved.

[0074] <(C) Photopolymerization initiator> The component (C) used in this embodiment is not particularly limited as long as it can polymerize the component (B), and can be appropriately selected from commonly used photopolymerization initiators. Examples of component (C) include benzoins such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methyl Acetophenones such as [thio)phenyl]-2-morpholino-1-propanone and N,N-dimethylaminoacetophenone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone thioxanthones such as acetophenone dimethyl ketal, benzil dimethyl ketal, and other ketals; benzophenones such as benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, Michler's ketone, and 4-benzoyl-4'-methyldiphenyl sulfide; acridines such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; 2,4,6-trimethylbenzophenone; oxime esters such as 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime), and 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime]. These component (C) can be used alone or in combination of two or more.

[0075] Among these, from the viewpoint of improving the curing property of the bottom portion by photobleaching, it is possible to appropriately select from the above-mentioned acylphosphine oxides, and from the viewpoint of being less likely to volatilize and to be less likely to be generated as outgassing, it is possible to appropriately select from the above-mentioned acetophenones.

[0076] ((C) Component Content) The content of component (C) may be appropriately selected from 0.2 to 15 mass%, 0.4 to 5 mass%, or 0.6 to 1 mass%, based on the total solid content of the photosensitive resin composition. If the content of component (C) is 0.2 mass% or more, the exposed area tends to be less likely to dissolve during development, and if it is 15.0 mass% or less, heat resistance is improved.

[0077] In addition to the component (C) described above, (C') photopolymerization initiation aids such as tertiary amines such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine can also be used alone or in combination.

[0078] <(D) Inorganic filler> The photosensitive resin composition of this embodiment contains component (D) mainly for the purpose of further improving various properties such as adhesive strength and coating hardness. Examples of component (D) include silica (SiO2), alumina (Al2O3), titania (TiO2), tantalum oxide (Ta2O5), zirconia (ZrO2), silicon nitride (Si3N4), barium titanate (BaO·TiO2), barium carbonate (BaCO3), magnesium carbonate (MgCO3), aluminum hydroxide (Al(OH)3), magnesium hydroxide (Mg(OH)2), lead titanate (PbO·TiO2), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga2O3), spinel (MgO·Al2O3), magnesium hydroxide (Mg(OH)2), lead zirconate ... zirconate titanate (PLZT), gallium oxide (Ga2O3), spinel (MgO·Al2O3), magnesium hydroxide (Mg(OH)2), lead zirconate titanate (PbO·TiO2), lead zirconate titanate (PZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zirconate titanate (PLZT), lead zircon Examples of inorganic fillers that can be used include zirconia (Y2O3·ZrO2), zirconia silicate (BaO·8SiO2), boron nitride (BN), calcium carbonate (CaCO3), barium sulfate (BaSO4), calcium sulfate (CaSO4), zinc oxide (ZnO), magnesium titanate (MgO·TiO2), hydrotalcite, mica, calcined kaolin, and carbon (C). These inorganic fillers can be used alone or in combination.

[0079] The average particle size of component (D) may be appropriately selected from 0.01 to 5 μm, 0.1 to 3 μm, or 0.1 to 2 μm from the viewpoint of resolution. Here, the average particle size of component (D) refers to the average particle size of the inorganic filler dispersed in the photosensitive resin composition, and is a value obtained by measuring as follows. First, the photosensitive resin composition is diluted (or dissolved) 1000 times with methyl ethyl ketone, and then particles dispersed in the solvent are measured using a submicron particle analyzer (manufactured by Beckman Coulter, Inc., product name: N5) in accordance with the international standard ISO 13321 at a refractive index of 1.38. The particle size at 50% cumulative (volume basis) in the particle size distribution is defined as the average particle size. Furthermore, component (D) contained in the photosensitive layer or cured film of the photosensitive resin composition provided on the carrier film can also be measured using the submicron particle analyzer after diluting (or dissolving) the composition 1000 times (volume ratio) with a solvent as described above.

[0080] Among the components (D), silica may be included from the viewpoint of improving heat resistance, barium sulfate may be included from the viewpoint of improving heat resistance and adhesive strength, or a combination of silica and barium sulfate may be included. Furthermore, the inorganic filler may be appropriately selected from those whose surface has been previously treated with alumina or an organic silane compound from the viewpoint of improving the dispersibility of the inorganic filler in the resin composition by preventing aggregation.

[0081] The elemental composition of aluminum on the surface of an inorganic filler that has been surface-treated with alumina or an organosilane compound may be appropriately selected from 0.5 to 10 atomic %, 1 to 5 atomic %, or 1.5 to 3.5 atomic %. The elemental composition of silicon on the surface of the inorganic filler may be appropriately selected from 0.5 to 10 atomic %, 1 to 5 atomic %, or 1.5 to 3.5 atomic %. The elemental composition of carbon on the surface of the inorganic filler may be appropriately selected from 10 to 30 atomic %, 15 to 25 atomic %, or 18 to 23 atomic %. These elemental compositions can be measured using XPS.

[0082] An example of an inorganic filler that has been surface-treated with alumina or an organic silane compound is barium sulfate that has been surface-treated with alumina or an organic silane compound, which is commercially available as NanoFine BFN40DC (trade name, manufactured by Nippon Solvay K.K.).

[0083] ((D) Component Content) The content of component (D) is 10 to 80 mass% based on the total solid content of the photosensitive resin composition. The content of component (D) may be appropriately selected from 12 to 70 mass%, 15 to 65 mass%, or 18 to 60 mass%. When the content of component (D) is within the above range, the strength, heat resistance, resolution, etc. of the cured product of the photosensitive resin composition can be improved.

[0084] When silica is used as component (D), the content of silica may be appropriately selected from 5 to 60 mass%, 10 to 55 mass%, or 15 to 50 mass%, based on the total solid content of the photosensitive resin composition. When barium sulfate is used as component (D), the content of barium sulfate may be appropriately selected from 5 to 30 mass%, 5 to 25 mass%, or 10 to 20 mass%, based on the total solid content of the photosensitive resin composition. When the contents of silica and barium sulfate are within the above ranges, a low coefficient of thermal expansion, solder heat resistance, and adhesive strength can be improved.

[0085] <(E)> Silane compounds The component (E) may be at least one organic silane compound selected from alkylsilanes, alkoxysilanes, vinylsilanes, epoxysilanes, aminosilanes, acrylsilanes, methacrylsilanes, mercaptosilanes, sulfidesilanes, isocyanatesilanes, sulfursilanes, styrylsilanes, and alkylchlorosilanes.

[0086] More specific examples of component (E) include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecylmethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, 3-phenylaminopropyltrimethoxysilane, Examples of silane compounds include silane compounds such as acetoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, bis(3-(triethoxysilyl)propyl)disulfide, bis(3-(triethoxysilyl)propyl)tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, and N-(1,3-dimethylbutylidene)-3-aminopropyltriethoxysilane.

[0087] Component (E) preferably has a functional group capable of reacting with component (A). Examples of functional groups capable of reacting with component (A) include epoxy groups, amino groups, mercapto groups, and isocyanate groups. Among these, epoxy groups can be selected from the viewpoint of improving the stability of the photosensitive resin composition, and glycidyl ether groups can be selected from the viewpoint of improving resolution, and an epoxysilane having at least one glycidyl ether group can be selected.

[0088] (Content of component (E)) The content of component (E) may be appropriately selected from 0.5 to 30 mass % or 1 to 10 mass % based on the total solid content of the photosensitive resin composition. When the content of component (E) is within the above range, it is possible to improve adhesion to chip components such as silicon wafers while maintaining resolution.

[0089] <(F) Pigment> The photosensitive resin composition of this embodiment may further contain component (F) depending on the desired color to improve the appearance by concealing the conductor pattern, etc. As component (F), a colorant that produces the desired color may be appropriately selected and used, and preferred examples include known colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black.

[0090] ((F) Component Content) The content of the component (F) may be appropriately selected from 0.01 to 5 mass%, 0.03 to 3 mass%, or 0.05 to 2 mass%, based on the total amount of solids in the photosensitive resin composition, from the viewpoints of making the production equipment easier to identify and further concealing the conductive pattern.

[0091] <(G) Hardener> The photosensitive resin composition of this embodiment may further contain a component (G). Examples of the component (G) include a compound that cures by itself with heat, ultraviolet light, or the like, or a compound that cures by reacting with a carboxyl group or a hydroxyl group of the acid-modified vinyl group-containing epoxy resin (A) with heat, ultraviolet light, or the like. Use of the component (G) can further improve heat resistance, adhesive strength, chemical resistance, and the like.

[0092] Examples of the component (G) include thermosetting compounds such as epoxy compounds, melamine compounds, urea compounds, oxazoline compounds, and blocked isocyanates. Examples of epoxy compounds include bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol A epoxy resins, brominated bisphenol A epoxy resins, novolac epoxy resins, bisphenol S epoxy resins, biphenyl epoxy resins, heterocyclic epoxy resins such as triglycidyl isocyanurate, and bixylenol epoxy resins. Examples of melamine compounds include triaminotriazine, hexamethoxymelamine, and hexabutoxylated melamine. Examples of urea compounds include dimethylol urea.

[0093] From the viewpoint of further improving heat resistance, the component (G) preferably contains at least one selected from an epoxy compound (epoxy resin) and a blocked isocyanate.

[0094] The blocked isocyanate is an addition reaction product of a polyisocyanate compound and an isocyanate blocking agent. Examples of the polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, bis(isocyanatomethyl)cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate, as well as adducts, biuret compounds, and isocyanurates thereof.

[0095] ((G) Component Content) The component (G) may be used alone or in combination of two or more. When the curing agent (G) is used, its content may be appropriately selected from 2 to 40 mass%, 3 to 30 mass%, or 5 to 20 mass%, based on the total solid content of the photosensitive resin composition. By keeping the content of the component (G) within the above range, it is possible to further improve the heat resistance of the cured film formed while maintaining good developability.

[0096] <(H) Elastomer> The photosensitive resin composition of this embodiment may further contain component (H). Component (H) is particularly suitable when the photosensitive resin composition of this embodiment is used for a semiconductor package substrate. Adding component (H) to the photosensitive resin composition of this embodiment can suppress a decrease in flexibility and adhesive strength caused by strain (internal stress) inside the cured product due to cure shrinkage of component (A). In other words, the flexibility, adhesive strength, etc. of the cured film formed from the photosensitive resin composition can be improved.

[0097] Examples of component (H) include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, and silicone-based elastomers. These elastomers are composed of a hard segment component and a soft segment component, with the former generally contributing to heat resistance and strength, and the latter contributing to flexibility and toughness.

[0098] Examples of styrene-based elastomers include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene-butylene-styrene block copolymers, and styrene-ethylene-propylene-styrene block copolymers.

[0099] Olefin elastomers are copolymers of α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-hexene, and 4-methylpentene. Specific examples include ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), copolymers of α-olefins with non-conjugated dienes having 2 to 20 carbon atoms, such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidenenorbornene, butadiene, and isoprene, and carboxy-modified NBR obtained by copolymerizing butadiene-acrylonitrile copolymer with methacrylic acid. More specific examples include ethylene-α-olefin copolymer rubber, ethylene-α-olefin-non-conjugated diene copolymer rubber, propylene-α-olefin copolymer rubber, and butene-α-olefin copolymer rubber. More specifically, examples of usable materials include Milastomer (manufactured by Mitsui Chemicals, Inc.), EXACT (manufactured by Exxon Chemical), ENGAGE (manufactured by Dow Chemical), hydrogenated styrene-butadiene rubber "DYNABON HSBR" (manufactured by JSR Corporation), butadiene-acrylonitrile copolymer "NBR series" (manufactured by JSR Corporation), butadiene-acrylonitrile copolymer "XER series" (manufactured by JSR Corporation) modified with carboxyl groups at both ends, and epoxidized polybutadiene BF-1000 (manufactured by Nippon Soda Co., Ltd.), PB-4700, and PB-3600 (manufactured by Daicel Corporation) which are partially epoxidized polybutadiene.

[0100] Examples of polyester elastomers include those obtained by polycondensation of dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof.

[0101] Specific examples of dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, aromatic dicarboxylic acids in which hydrogen atoms in the aromatic nuclei are substituted with methyl groups, ethyl groups, phenyl groups, etc., aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid, and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These compounds can be used alone or in combination of two or more.

[0102] Specific examples of the diol compound include aliphatic diols and alicyclic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, 1,4-cyclohexanediol, etc. These compounds can be used alone or in combination of two or more.

[0103] In addition to the elastomers mentioned above, rubber-modified epoxy resins can also be used as elastomers. Rubber-modified epoxy resins can be obtained, for example, by modifying some or all of the epoxy groups of the bisphenol F epoxy resin, bisphenol A epoxy resin, salicylaldehyde epoxy resin, phenol novolac epoxy resin, or cresol novolac epoxy resin with a butadiene-acrylonitrile rubber modified at both ends with carboxylic acid, an amino-modified silicone rubber, or the like. Among these elastomers, butadiene-acrylonitrile copolymers modified at both ends with carboxyl groups and hydroxyl-containing polyester elastomers such as Espel (Hitachi Chemical Co., Ltd., Espel 1108, 1612, and 1620) are preferred in terms of shear adhesive strength. Furthermore, elastomers that are liquid at room temperature are particularly preferred.

[0104] (Content of component (H)) When component (H) is used, its content may be appropriately selected from 1 to 20 parts by mass, 2 to 15 parts by mass, or 3 to 10 parts by mass per 100 parts by mass of component (A) (solid content). By adjusting the content within the above range, it is possible to further improve thermal shock resistance and adhesive strength while maintaining good developability. Furthermore, when used on a thin-film substrate, it is possible to reduce warpage of the thin-film substrate.

[0105] <(I) Epoxy resin curing agent> Component (I) may also be added to the photosensitive resin composition of this embodiment for the purpose of further improving various properties such as heat resistance, adhesive strength, and chemical resistance. Examples of such component (I) include imidazole derivatives such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, and polybasic hydrazides; organic acid salts or epoxy adducts thereof; amine complexes of boron trifluoride; and triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, and 2,4-diamino-6-xylyl-S-triazine.

[0106] ((I) Content of Component) The component (I) can be used alone or in combination of two or more types. When the component (I) is used, the content thereof may be appropriately selected from 0.01 to 20 mass%, 0.1 to 10 mass%, or 0.1 to 3 mass%, based on the total solid content of the photosensitive resin composition, from the viewpoint of further suppressing the effect on the photosensitive properties.

[0107] <(J)Thermoplastic resin> The photosensitive resin composition of this embodiment may further contain component (J) to improve the flexibility of the cured film. Examples of component (J) include acrylic resins and urethane resins.

[0108] (Content of component (J)) The component (J) can be used alone or in combination of two or more types. When the component (J) is used, its content may be appropriately selected from 1 to 30 mass % or 5 to 20 mass % based on the total solid content of the photosensitive resin composition from the viewpoint of improving the flexibility of the cured film.

[0109] <Diluent> A diluent can be used in the photosensitive resin composition of this embodiment, if necessary. Examples of the diluent include organic solvents. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, 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 hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These diluents can be used alone or in combination.

[0110] The amount of diluent used may be appropriately selected from amounts such that the total solid content in the photosensitive resin composition is 50 to 90 mass%, 60 to 80 mass%, or 65 to 75 mass%. That is, when a diluent is used, the content of the diluent in the photosensitive resin composition may be appropriately selected from 10 to 50 mass%, 20 to 40 mass%, or 25 to 35 mass%. By setting the amount of diluent used within the above range, the coatability of the photosensitive resin composition is improved, and it becomes possible to form a more precise pattern.

[0111] <Other additives> The photosensitive resin composition of this embodiment may contain, as needed, various known and commonly used additives such as polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol, thickeners such as bentone and montmorillonite, silicone-based, fluorine-based, and vinyl resin-based antifoaming agents, and silane coupling agents.Furthermore, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, and phosphate compounds of phosphorus-based compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters may be used.

[0112] The photosensitive resin composition of the present embodiment can be obtained by uniformly kneading and mixing the ingredients using a roll mill, a bead mill, or the like.

[0113] [Dry film] The dry film of this embodiment includes a carrier film and a photosensitive layer using the photosensitive resin composition of this embodiment. The thickness of the photosensitive layer may be appropriately selected from 10 to 50 μm, 15 to 40 μm, or 20 to 30 μm.

[0114] The dry film of the present embodiment can be produced, for example, by applying the photosensitive resin composition of the present embodiment onto a carrier film by a known method such as reverse roll coating, gravure roll coating, comma coating, or curtain coating, and drying the composition to form a photosensitive layer. Examples of the carrier film include polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polyolefins such as polypropylene and polyethylene. The thickness of the carrier film may be appropriately selected from the range of 5 to 100 μm. In addition, the dry film of this embodiment may have a protective layer laminated on the surface of the photosensitive layer opposite to the surface that contacts the carrier film. For example, a polymer film such as polyethylene or polypropylene may be used as the protective layer. Furthermore, the same polymer film as the above-mentioned carrier film may be used, or a different polymer film may be used. The coating film can be dried using hot air drying or a dryer using far-infrared rays or near-infrared rays, and the drying temperature can be appropriately selected from 60 to 120° C., 70 to 110° C., or 80 to 100° C. The drying time can be appropriately selected from 1 to 60 minutes, 2 to 30 minutes, or 5 to 20 minutes.

[0115] [Printed wiring board] The printed wiring board of this embodiment includes at least one of a surface protective film and an interlayer insulating film formed from the photosensitive resin composition of this embodiment. The printed wiring board of this embodiment includes at least one of a surface protective film and an interlayer insulating film formed from the photosensitive resin composition of this embodiment, and therefore has a pattern that has excellent adhesive strength with plated copper, excellent heat resistance, a low coefficient of thermal expansion, excellent resolution, and excellent adhesion to chip components. Furthermore, this pattern has excellent formation stability for the size of the hole diameter and the spacing pitch between the holes, which have become smaller with the recent miniaturization and high performance of electronic devices.

[0116] [Printed wiring board manufacturing method] The method for producing a printed wiring board of this embodiment includes, in order, a step of providing a photosensitive layer on a substrate using the photosensitive resin composition of this embodiment or the dry film of this embodiment, a step of forming a resin pattern using the photosensitive layer, and a step of curing the resin pattern to form at least one of a surface protective film and an interlayer insulating film. Specifically, for example, it can be produced as follows. First, a photosensitive resin composition is applied to a metal-clad laminate substrate such as a copper-clad laminate by a method such as screen printing, spraying, roll coating, curtain coating, or electrostatic coating to a film thickness appropriately selected from 10 to 200 μm, 15 to 150 μm, 20 to 100 μm, or 23 to 50 μm, and then the coating film is dried at 60 to 110°C, or the dry film of this embodiment from which the protective layer has been peeled off is thermally laminated onto the substrate using a laminator, thereby providing a photosensitive layer on the substrate. Next, a negative film is brought into direct contact with the photosensitive layer (or in a non-contact state via a transparent film such as a carrier film), and actinic light is irradiated at 10 to 2,000 mJ / cm 2 2 , 100-1,500mJ / cm 2 , or 300 to 1,000 mJ / cm 2 The pattern is then formed by dissolving and removing the unexposed areas with a dilute alkaline aqueous solution (development). Examples of actinic light that can be used include electron beams, ultraviolet rays, and X-rays, with ultraviolet rays being preferred. Examples of light sources that can be used include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and halogen lamps. Next, the exposed portion of the photosensitive layer is sufficiently cured by at least one of post-exposure (ultraviolet light exposure) and post-heating to form at least one of a surface protective film and an interlayer insulating film. The exposure dose for post-exposure is 100 to 5,000 mJ / cm 2 , 500-2,000mJ / cm 2 , or 700 to 1,500 J / cm 2 It may be selected appropriately from the above. The heating temperature for post-heating may be appropriately selected from 100 to 200°C, 120 to 180°C, or 135 to 165°C. The heating time for post-heating may be appropriately selected from 5 minutes to 12 hours, 10 minutes to 6 hours, or 30 minutes to 2 hours. Thereafter, a conductor pattern is formed by etching to produce a printed wiring board.

[0117] Multilayer printed wiring boards can also be manufactured using the photosensitive resin composition of this embodiment or the dry film of this embodiment. FIG. 1 is a schematic diagram showing one embodiment of a manufacturing process for a multilayer printed wiring board using a cured product of the photosensitive resin composition of this embodiment as at least one of a surface protective film and an interlayer insulating film. The multilayer printed wiring board 100A shown in FIG. 1(f) comprises a substrate having a conductor pattern 102 on its surface, a plurality of conductor patterns 107 arranged in layers, an interlayer insulating film 103 between each layer, and the conductor patterns 102 of each layer are connected by the conductor pattern 107 provided in the interlayer insulating film 103 and the opening 104. A surface protective film 108 is provided on the surface, and at least one of the surface protective film 108 and the interlayer insulating film 103 is formed using the photosensitive resin composition of this embodiment or the dry film of this embodiment. The multilayer printed wiring board 100A can be obtained, for example, by laminating a copper clad laminate, an interlayer insulating material, a metal foil, or the like, and appropriately forming a conductor pattern by etching or a semi-additive method. A method for manufacturing multilayer printed wiring board 100A will now be briefly described with reference to FIG.

[0118] First, an interlayer insulating layer 103 is formed on both surfaces of a copper clad laminate 101 having conductive patterns 102 on both surfaces (see FIG. 1(a)). The interlayer insulating layer 103 is formed by the method described in the printed wiring board manufacturing method, i.e., by applying the photosensitive resin composition of this embodiment or by thermally laminating the dry film of this embodiment using a laminator to form a photosensitive layer, exposing and curing the photosensitive layer using a negative film except for areas that need to be electrically connected to the outside (conductive patterns on other layers), and then removing the unexposed areas (see FIG. 1(b)). This interlayer insulating layer 103 is a film having an opening 104. Here, smears (residues) present around the opening 104 can be removed by desmearing.

[0119] Next, the conductor pattern 107 is formed. The conductor pattern 107 can be formed by a semi-additive method, for example, by forming a thin metal layer (seed layer), forming a resin pattern (plating resist), forming the conductor pattern 107 by electrolytic plating, removing the resin pattern, and then removing the seed layer by etching. Specifically, a seed layer 105 is formed by electroless plating on the interlayer insulating film 103 and on the conductor pattern 102 in the opening 104 (see FIG. 1(c)). This seed layer 105 can be formed of plated copper by electroless copper plating, for example. A photosensitive layer is formed on the seed layer 105 using a semi-additive photosensitive resin composition, and predetermined portions of the photosensitive layer are exposed to light using a negative film, followed by development to form a resin pattern 106 having a predetermined pattern (see FIG. 1(d)). Next, a conductor pattern 107 is formed by electroplating in the portion of the seed layer 105 where the resin pattern 106 is not formed, the resin pattern 106 is removed with a stripping solution, and the seed layer 105 is removed by etching (see FIG. 1(e)). The steps of FIGS. 1(b) to 1(e) are repeated to form conductor patterns 107 corresponding to the desired number of layers, and a surface protection film (permanent mask resist) 108 formed from a cured product of the photosensitive resin composition according to this embodiment is formed on the outermost surface, thereby producing a multilayer printed wiring board 100A (see FIG. 1(f)). Here, the photosensitive resin composition according to this embodiment, for example, can be used as the semi-additive photosensitive resin composition.

[0120] In the multilayer printed wiring board 100A obtained in this manner, semiconductor elements can be mounted at corresponding locations, ensuring electrical connections.

[0121] The printed wiring board according to this embodiment uses the photosensitive resin composition according to this embodiment for at least one of the surface protective film and the interlayer insulating film, and therefore enjoys the advantages of the photosensitive resin composition, namely, excellent adhesive strength with plated copper, excellent resolution, and adhesion to chip components. Furthermore, with the trend toward miniaturization and high performance of electronic devices, there is a marked trend toward higher density by narrowing the pitch of conductor patterns in semiconductor chips. To address this trend, the mainstream semiconductor packaging method is the flip-chip connection method, which joins a semiconductor chip to a substrate using solder bumps. However, this method has traditionally presented the following problems: This flip-chip connection method is a semiconductor mounting method using a reflow process in which solder balls are placed between a substrate and a semiconductor chip and then heated to melt and bond them together. Therefore, during solder reflow, the substrate itself is exposed to a high-temperature environment, and thermal contraction of the substrate generates large stresses in the solder balls connecting the substrate and the semiconductor, which can lead to poor connection of the conductor pattern and cracks in the surface protective film or underfill. Furthermore, exposure of the substrate to a high-temperature environment can cause thermal expansion of the resin composition forming the surface protective film or other film on the substrate, resulting in large stresses at the connection interface and poor connection. The photosensitive resin composition according to this embodiment has excellent adhesive strength with plated copper, excellent resolution, and adhesion to chip components, as well as excellent heat resistance and a low coefficient of thermal expansion, and therefore has sufficient performance to solve these problems. Therefore, the printed wiring board according to this embodiment is high-quality and less susceptible to poor connection of the conductor pattern and cracks in the surface protective film or other film. [Example]

[0122] The objects and advantages of the present embodiment will be explained in more detail below based on examples and comparative examples, but the present embodiment is not limited to the following examples.

[0123] (Synthesis Example 1: Synthesis of Acid-Modified Vinyl Group-Containing Epoxy Resin (A1)) Bisphenol F novolac epoxy resin (a) (EXA-7376, manufactured by DIC Corporation, in the general formula (II), Y2 is a glycidyl group, R 12 350 parts by weight of bisphenol F novolac epoxy resin (containing a structural unit in which (a) is a hydrogen atom), 70 parts by weight of acrylic acid (b), 0.5 parts by weight of methylhydroquinone, and 120 parts by weight of carbitol acetate were charged and heated to 90°C with stirring to react and completely dissolve the mixture. Next, the resulting solution was cooled to 60°C, 2 parts by weight of triphenylphosphine was added, and the mixture was heated to 100°C and reacted until the acid value of the solution reached 1 mgKOH / g. 98 parts by weight of tetrahydrophthalic anhydride (THPAC) (c) and 850 parts by weight of carbitol acetate were added to the reacted solution, heated to 80°C, and reacted for 6 hours. The mixture was then cooled to room temperature to obtain a THPAC-modified bisphenol F novolac epoxy acrylate (epoxy resin (1)) as component (A1) with a solids concentration of 73% by weight.

[0124] (Examples 1 to 6, Comparative Examples 1 to 5) A photosensitive resin composition was prepared by blending components according to the formulation shown in Table 1 and kneading them in a three-roll mill. Carbitol acetate was added so that the solid content concentration became 60% by mass, and a photosensitive resin composition was obtained.

[0125] [Table 1]

[0126] Details of each material in Table 1 are as follows: The epoxy resin (1) is the acid-modified vinyl group-containing epoxy resin (A1) obtained in Synthesis Example 1. The epoxy resin (2) is a compound represented by the general formula (III), 13 is a hydrogen atom, Y 3 The epoxy resin (A2) is an acid-modified vinyl group-containing epoxy resin (weight average molecular weight: 3300, acid value: 42.4 mg / KOH) obtained by acrylate-modifying the glycidyl groups of a glycidyl group-containing novolac epoxy resin ("UE-EXP-3165", product name, manufactured by DIC Corporation) and modifying the hydroxyl groups with tetrahydrophthalic anhydride (THPAC). Aronix M402: Dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd.) Irgacure 819: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (BASF, trade name) Irgacure 907: 2-methyl-[4-(methylthio)phenyl]morpholino-1-propanone (BASF, trade name) SC2050-LNF: Silica particles (manufactured by Admatechs Co., Ltd., product name, average particle size: 0.5 μm) ASA: Barium sulfate particles (product name, manufactured by Nippon Solvay Co., Ltd., average particle size: 1.0 μm) KBM-403: 3-glycidoxypropyltrimethoxysilane (product name, manufactured by Shin-Etsu Silicone Co., Ltd.) X-12-984S: Multifunctional epoxy silane (product name, manufactured by Shin-Etsu Silicone Co., Ltd.) Phthalocyanine pigments: Phthalocyanine pigments (manufactured by Sanyo Dye Co., Ltd.) YSLV-80XY: Tetramethylbisphenol F type epoxy resin (Nippon Steel Sumikin Chemical Co., Ltd., product name) RE-306: Novolac-type multifunctional epoxy resin (product name, manufactured by Nippon Kayaku Co., Ltd.) PB-3600: Epoxidized polybutadiene (manufactured by Daicel Corporation, product name) SP1108: Polyester resin (Espel 1108, manufactured by Hitachi Chemical Co., Ltd.) Melamine: Nissan Chemical Industries, Ltd.

[0127] Next, the photosensitive resin composition obtained above was used to carry out various evaluations under the conditions shown below. The evaluation results are shown in Table 2.

[0128] [Dry film preparation] A 16 μm-thick polyethylene terephthalate film (G2-16, Teijin Limited, product name) was used as a carrier film, and the photosensitive resin compositions of the Examples and Comparative Examples were uniformly coated onto the carrier film so that the film thickness after drying was 25 μm, and then dried at 75° C. for 30 minutes using a hot air convection dryer to form a photosensitive layer. Subsequently, a polyethylene film (NF-15, Tamapoly Corporation, product name) (protective layer) was attached to the surface of the photosensitive layer opposite the side in contact with the carrier film to produce a dry film.

[0129] [Resolution Evaluation] The protective layer of the dry film prepared above was peeled off and the film was laminated onto a 1.0 mm thick copper-clad laminate substrate (MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.) using a continuous press vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd., product number) under specified lamination conditions (pressure: 0.4 MPa, press hot plate temperature: 80°C, vacuum time: 40 seconds, lamination press time: 20 seconds, air pressure: 4 kPa or less) to obtain a laminate with a photosensitive layer. Next, an i-line exposure system (UX-2240SM-XJ-01, manufactured by Ushio Inc., product number) was used to expose the vias to 100 to 500 mJ / cm through a negative mask having via patterns of predetermined sizes (opening diameter sizes: 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, and 200 μmφ). 2 in the range of 50 mJ / cm 2 After that, the film was exposed to light while changing the temperature by 1.765 × 10 for a time equivalent to twice the shortest development time (the shortest time required for the unexposed portion of the photosensitive layer to be removed) at 30°C in a 1% by mass aqueous sodium carbonate solution. 5 The unexposed areas were then developed by spray development at a pressure of 2000 mJ / cm 2 using an ultraviolet exposure device. 2 and heated at 170° C. for 1 hour to prepare a test piece having a via pattern of a predetermined size on a copper-clad laminate substrate containing the cured product of the photosensitive resin composition. The test pieces were observed using a metallurgical microscope and evaluated according to the following criteria. The evaluation results are shown in Table 2. A: The minimum diameter of the opening was 50 μm or less. B: The minimum diameter of the opening was more than 50 μm and less than 100 μm. C: The minimum diameter of the opening exceeded 100 μm.

[0130] [Evaluation of adhesive strength with plated copper] A laminate having the photosensitive layer prepared in the above [Evaluation of resolution] was prepared, and the laminate was exposed to 500 mJ / cm using an i-line exposure device (UX-2240SM-XJ-01, manufactured by Ushio Inc., product number). 2 Then, the entire surface was exposed to 2000 mJ / cm using an ultraviolet exposure device. 2 The substrate was exposed to an exposure dose of 1000 ppm and heated at 170°C for 1 hour to obtain a copper-clad laminate substrate having a cured film of the photosensitive resin composition. To chemically roughen the cured film, a swelling solution (aqueous solution of diethylene glycol monobutyl ether: 200 ml / L, sodium hydroxide: 5 g / L) was prepared, heated to 70°C, and the substrate was immersed for 10 minutes. Next, a roughening solution (aqueous solution of potassium permanganate: 60 g / L, sodium hydroxide: 40 g / L) was prepared, heated to 70°C, and the substrate was immersed for 15 minutes. Subsequently, a neutralizing solution (aqueous solution of tin chloride (SnCl): 30 g / L, hydrogen chloride: 300 ml / L) was prepared, heated to 40°C, and the substrate was immersed for 5 minutes to reduce the potassium permanganate and chemically roughen the cured film. The specimens were then immersed in an electroless plating catalyst containing lead chloride (PdCl2) (Activator Neogant 834, Atotech Japan, Inc.) heated to 35°C for 5 minutes, then immersed in an electroless copper plating solution (Printoganth MSK-DK, Atotech Japan, Inc.) at room temperature for 15 minutes, followed by copper sulfate electroplating. The specimens were then annealed at 180°C for 60 minutes to form a 35 μm-thick conductor layer, yielding test specimens. A 10 mm wide, 50 mm long region was formed on the conductor layer by treatment with a sulfuric acid / hydrogen peroxide etching solution. One end of this region was peeled off 10 mm from the interface between the conductor layer (copper layer) and the cured resin film. The peeled resin film was then gripped with a gripper and pulled in the thickness direction (perpendicular to the specimen) at room temperature at a pulling rate of 50 mm / min, and the peel load (peel strength) was measured. The evaluation results are shown in Table 2. In this specification, room temperature refers to 25°C.

[0131] [Adhesion evaluation] A laminate having a photosensitive layer was obtained in the same manner as described in [Evaluation of resolution], except that the copper-clad laminate substrate was replaced with a 6-inch silicon wafer (manufactured by Electronics and Materials Corporation). The laminate was exposed to 500 mJ / cm using an i-line exposure device (UX-2240SM-XJ-01, manufactured by Ushio Inc.). 2 Then, the entire surface was exposed to 2000 mJ / cm using an ultraviolet exposure device. 2 The wafer was exposed to an exposure dose of 1000 ppm and heated at 170°C for 1 hour to obtain a silicon wafer having a cured film of the photosensitive resin composition. An aluminum stud (adhesive diameter: 2.7 mm, P / N 901106, PhotoTechnica Corporation, product name) with an epoxy adhesive was then placed vertically on the cured film, and the film was heated in an oven at 150°C for 1 hour to obtain a test piece. The stud on the test piece was fixed to the chuck of a thin film adhesion strength measuring device (PhotoTechnica Corporation), and a force was applied perpendicular to the cured film. The subsequent condition was evaluated according to the following criteria. The evaluation results are shown in Table 2. A: The epoxy adhesive failed cohesively. B: Peeling occurred at the interface between the cured film and the silicon wafer.

[0132] [Measurement of thermal expansion coefficient and glass transition temperature] The dry film prepared above was exposed to 500 mJ / cm using an i-line exposure device (UX-2240SM-XJ-01, manufactured by Ushio Inc.). 2 After leaving it to stand at room temperature (25°C) for 1 hour, the polyethylene film was peeled off and the film was spray-developed with a 1% by mass aqueous solution of sodium carbonate at 30°C. After that, a UV irradiation device (manufactured by Oak Manufacturing Co., Ltd.) was used to expose the entire surface to 2 J / cm 2 The sample was then irradiated with ultraviolet light for 10 seconds, and then heated for 60 minutes at 170° C. Then, a piece 3 mm wide and 30 mm long was cut using a cutter knife, and the polyethylene terephthalate film (carrier film) was peeled off to obtain a cured product for evaluation of the thermal expansion coefficient. The thermal expansion coefficient was measured in tension mode using a TMA instrument (SS6000, Seiko Instruments Inc., product number). The tensile load was 5 g, the span (distance between chucks) was 15 mm, and the heating rate was 10°C / min. First, the test specimen was mounted in the instrument and heated from room temperature (25°C) to 160°C and left for 15 minutes. It was then cooled to -60°C and measured again at a heating rate of 10°C / min from -60°C to 250°C, from which the thermal expansion coefficient and glass transition temperature were calculated. The thermal expansion coefficient and glass transition temperature are shown in Table 2.

[0133] [Table 2]

[0134] From Table 2, it was confirmed that the photosensitive resin compositions of this embodiment of Examples 1 to 6 exhibit excellent performance in terms of resolution, adhesive strength, and adhesion, and are particularly suitable for use as surface protection films in printed wiring boards, interlayer insulating films, and surface protection films in contact with silicon materials. In contrast, the resin compositions of Comparative Examples 1 to 5 did not achieve sufficient effects in terms of resolution, adhesive strength, or adhesion. Furthermore, from the results of the thermal expansion coefficient and glass transition point, it was also confirmed that the photosensitive resin composition of this embodiment has excellent heat resistance and a low thermal expansion coefficient. [Explanation of symbols]

[0135] 100A. Multilayer printed wiring board 102. Conductor Pattern 103. Interlayer insulating film 104. Opening 105. Seed layer 106. Resin Pattern 107. Conductor Pattern 108.Surface protective film

Claims

1. The photosensitive film has a carrier film, a photosensitive layer using a photosensitive resin composition, and a protective layer, the photosensitive resin composition contains (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a silane compound, the content of the inorganic filler (D) being 10 to 80 mass% based on the total amount of solids in the photosensitive resin composition, the (C) photopolymerization initiator contains at least one selected from acetophenones and acylphosphine oxides, the (D) inorganic filler contains silica having an average particle size of 0.1 to 3 μm as measured by the following average particle size measurement method, and the (E) silane compound is at least one selected from alkylsilane, alkoxysilane, vinylsilane, epoxysilane, aminosilane, acrylsilane, methacrylsilane, mercaptosilane, sulfidesilane, isocyanatesilane, sulfursilane, styrylsilane, and alkylchlorosilane, excluding compositions containing a nitroxyl compound; The protective layer is provided on the surface of the photosensitive layer opposite to the surface in contact with the carrier film. Dry film. (Method for measuring average particle size) The photosensitive resin composition is diluted or dissolved 1000 times with methyl ethyl ketone, and then particles dispersed in the solvent are measured using a submicron particle analyzer in accordance with the international standard ISO 13321 at a refractive index of 1.38, and the particle diameter at an integrated value of 50% (volume basis) in the particle size distribution is taken as the average particle diameter.

2. 2. The dry film according to claim 1, wherein the photosensitive layer has a thickness of 10 to 50 μm.

3. 3. The dry film according to claim 1, wherein the carrier film is a film of a polymer selected from polyester and polyolefin.

4. The dry film according to any one of claims 1 to 3, wherein the thickness of the carrier film is 5 to 100 µm.

5. 5. The dry film according to claim 1, wherein the protective layer is a film of a polymer selected from polyester and polyolefin.

6. 6. The dry film according to claim 1, wherein the protective layer has a thickness of 5 to 100 μm.

7. The dry film according to any one of claims 1 to 6, wherein the component (A) contains at least one acid-modified vinyl group-containing epoxy resin (A1) made using a bisphenol novolac epoxy resin (a1), and at least one acid-modified vinyl group-containing epoxy resin (A2) made using an epoxy resin (a2) different from the epoxy resin (a1).

8. The dry film according to claim 7, wherein the epoxy resin (a2) is at least one selected from the group consisting of novolac-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and triphenolmethane-type epoxy resins.

9. The acid-modified vinyl group-containing epoxy resins (A1) and (A2) are resins obtained by reacting the epoxy resins (a1) and (a2) with a vinyl group-containing monocarboxylic acid (b) to form resins (A1') and (A2'), respectively, and then reacting a saturated or unsaturated group-containing polybasic acid anhydride (c).

10. The bisphenol novolac type epoxy resin (a1) has a structural unit represented by the following general formula (I) or a structural unit represented by the following general formula (II): The dry film according to any one of claims 7 to 9. 【Chemical 1】 [In formula (I), R １１ represents a hydrogen atom or a methyl group, and Y １ Each of R independently represents a hydrogen atom or a glycidyl group. １１ may be the same or different, and Y １ At least one of the groups represents a glycidyl group. 【Chemistry 2】 [In formula (II), R １２ represents a hydrogen atom or a methyl group, and Y ２ Each of R independently represents a hydrogen atom or a glycidyl group. １２ may be the same or different, and Y ２ At least one of the groups represents a glycidyl group.

11. The bisphenol novolac epoxy resin (a1) has a structural unit represented by the general formula (I), and the epoxy resin (a2) is a novolac epoxy resin containing a structural unit represented by the following general formula (III): 【Chemistry 3】 [In formula (III), R １３ represents a hydrogen atom or a methyl group, and Y ３ represents a hydrogen atom or a glycidyl group.

12. 12. The dry film according to any one of items 1 to 11, wherein the photopolymerizable compound (B) includes a compound having three or more ethylenically unsaturated bonds in the molecule.

13. The dry film according to any one of claims 1 to 12, wherein the contents of the (A) acid-modified vinyl group-containing epoxy resin, (B) photopolymerizable compound, (C) photopolymerization initiator, (D) inorganic filler, and (E) silane compound are 5 to 60 mass%, 0.2 to 15 mass%, 0.1 to 10 mass%, 20 to 60 mass%, and 0.5 to 30 mass%, respectively, based on the total solid content in the photosensitive resin composition.

14. The dry film according to any one of claims 1 to 13, further comprising (F) a pigment.

15. The dry film according to any one of claims 1 to 14, wherein the photopolymerization initiator (C) comprises an acetophenone and an acylphosphine oxide.

16. A method for manufacturing a printed wiring board, comprising the steps of: providing a photosensitive layer using the dry film according to any one of claims 1 to 15; forming a resin pattern using the photosensitive layer; and curing the resin pattern to form at least one of a surface protective film and an interlayer insulating film.

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