JP2022103237A - Photosensitive resin composition, and dry film, printed wiring board and method for manufacturing printed wiring board using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: 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

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present disclosure relates to a photosensitive resin composition, a dry film using the same, a semiconductor device, and a method for manufacturing a printed wiring board.

In recent years, with the increase in performance (miniaturization, weight reduction, and multifunctionality) of electronic devices, the integration of semiconductor parts such as LSIs and chips has been increasing. Along with this, the form of semiconductor parts is rapidly changing to multiple pins and miniaturization. In addition, with the increasing integration of semiconductor parts, the density and definition of semiconductor elements, semiconductor packages, printed wiring boards, flexible wiring boards, etc. that make up semiconductor parts are increasing, and chips, chip capacitors, etc. are used as substrates. A board with built-in components embedded inside is being studied. As the surface protective film or interlayer insulating film used for semiconductor parts, it is required that a via opening pattern for interlayer connection can be formed, and that it can be adhered not only to a substrate material and a copper pattern (conductor pattern) but also to a chip component. Has been done.

As a method for manufacturing a printed wiring board, a build-up method can be mentioned as a method conventionally adopted. In this build-up method, an insulating resin film is first laminated on an inner circuit board (a base material having a first conductor pattern), cured by heating, an interlayer insulating film is formed, and then a via hole is formed by laser processing. do. Next, the interlayer insulating film is roughened and smeared by an alkaline permanganic acid treatment or the like, and then electroless copper plating is performed to form a second conductor pattern and a via hole that enables interlayer connection. (See, for example, Patent Document 1).

In recent years, as the density of conductor patterns has increased, high resolution has been required for surface protective films, and photosensitive resin compositions that can form patterns by a photolithography method have been actively used. Among them, alkali-developable photosensitive resin compositions that can be developed with a weak alkaline aqueous solution such as an aqueous sodium carbonate solution have become the mainstream from the viewpoint of work environment conservation and global environment conservation.

Japanese Unexamined Patent Publication No. 7-304931

On the other hand, the formation of via holes in the build-up method by conventional laser processing requires the formation of each via one by one, and it takes a lot of time when it is necessary to provide a large number of vias by increasing the density. There's a problem. Therefore, as a method capable of forming a large number of vias at once, the formation of a surface protective film by a photolithography method has been studied. However, it cannot be said that sufficient adhesive strength between the surface protective film and electroless plated copper is obtained.

Therefore, the problem to be solved by the present disclosure is a photosensitive resin composition having excellent adhesive strength with plated copper, excellent resolution, and excellent adhesion to a substrate of a silicon material such as a silicon wafer and chip components. It is an object of the present invention to provide an article, a dry film using the same, a printed wiring board, and a method for manufacturing the printed wiring board (hereinafter, may be referred to as "photosensitive resin composition or the like").

As a result of diligent research to solve the above-mentioned problems, the present inventors have found that the following inventions can solve the problems. 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 manufacturing the printed wiring board.

[1] 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. A photosensitive resin composition having an inorganic filler content of 10 to 80% by 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 according to the above [1].
[3] The photosensitive property according to the above [1] on a printed wiring board [4] substrate provided with at least one of a surface protective film and an interlayer insulating film formed by the photosensitive resin composition according to the above [1]. A step of providing a photosensitive layer using the resin composition or the dry film according to the above [2], a step of forming a resin pattern using the photosensitive layer, and a step of curing the resin pattern to provide a surface protective film and interlayer insulation. A method for manufacturing a printed wiring board, which comprises, in order, a step of forming at least one of the films.

According to the present disclosure, a photosensitive resin composition having excellent adhesive strength with plated copper, excellent resolution, a substrate of a silicon material such as a silicon wafer, and excellent adhesion to chip parts is used. A method for manufacturing a dry film, a printed wiring board, and a printed wiring board can be provided.

It is a schematic diagram which shows one aspect of the manufacturing process of the multilayer printed wiring board which uses the cured product of the photosensitive resin composition of this embodiment as at least one of a surface protective film and an interlayer insulating film.

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

<(A) Acid-modified vinyl group-containing epoxy resin>
The photosensitive resin composition of the present embodiment contains an acid-modified vinyl group-containing epoxy resin as the component (A). The component (A) is a compound obtained by modifying an epoxy resin with a vinyl group-containing organic acid, for example, a resin obtained by reacting an epoxy resin with a vinyl group-containing monocarboxylic acid, and a saturated group- or unsaturated group-containing polybasic acid. Epoxy resin obtained by reacting an anhydride can be mentioned.

The component (A) may be referred to as, for example, a bisphenol novolak type epoxy resin (a1) (hereinafter, referred to as a component (a1)) from the viewpoint of being capable of alkaline development and improving resolution and adhesive strength. ), An acid-modified vinyl group-containing epoxy resin (A1) (hereinafter, may be referred to as a component (A1)), and an epoxy resin (a2) other than the epoxy resin (a1) (hereinafter, a component (a2)). The acid-modified vinyl group-containing epoxy resin (A2) (hereinafter, may be referred to as (A2) component) and the like using (may be referred to as (A2) component) and the like can be mentioned, and these may be used alone or in combination of two or more. Can be used. Further, particularly from the viewpoint of improving the adhesion strength, the component (A) is composed of at least one (A1) component using the (a1) component and at least one (A2) component using the (a2) component. And may be contained.

(Epoxy resin (a1))
As the component (A), it is preferable to contain the component (A1) using the component (a1) from the viewpoint of being capable of alkaline development and improving resolution and adhesion strength. From the same viewpoint as this, as the component (a1), one selected from the bisphenol novolak type epoxy resin having the structural unit represented by the following general formula (I) or (II) is preferable, and the following general formula (II) is preferable. ), A bisphenol novolak type epoxy resin having a structural unit represented by) is more preferable.

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

In the general formula (I), R ¹¹ represents a hydrogen atom or a methyl group, and Y ¹ independently represents a hydrogen atom or a glycidyl group. The plurality of R ^11s may be the same or different, and at least one of Y ¹ represents a glycidyl group.

R ¹¹ is preferably a hydrogen atom from the viewpoint of improving the resolution and the adhesive strength. Further, from the same viewpoint as this, Y ¹ is preferably a glycidyl group.

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

[Epoxy resin having a structural unit represented by the general formula (II)]
Further, one of the preferred embodiments of the component (a1) is an epoxy resin having a structural unit represented by the following general formula (II).

In the general formula (II), R ¹² represents a hydrogen atom or a methyl group, and Y ² independently represents a hydrogen atom or a glycidyl group. The plurality of R ^12s may be the same or different, and at least one of Y ² represents a glycidyl group.

R ¹² is preferably a hydrogen atom from the viewpoint of improving resolution and adhesive strength.
Further, from the same viewpoint as this, Y ² is preferably a glycidyl group.

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

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

(Epoxy resin (a2))
The component (a2) is not particularly limited as long as it is an epoxy resin different from the component (a1), but may be a novolak type epoxy resin from the viewpoint of improving the adhesive strength and the resolution, for example, the following. It may have a structural unit represented by the general formula (III).

The component (a2) is used in combination with the bisphenol novolak type epoxy resin containing the structural unit represented by the general formula (I) or (II) among the components (a1), particularly from the viewpoint of improving the resolution. Is preferable.

[Epoxy resin having a structural unit represented by the general formula (III)]
As the component (a2), a novolak type epoxy resin having a structural unit represented by the following general formula (III) is preferably mentioned, and the novolak type epoxy resin having such a structural unit is, for example, the following general formula (a2). The novolak type epoxy resin represented by III') can be mentioned.

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. Further, in the general formula (III'), n ₁ is a number of 1 or more, and a plurality of R ¹³ and Y ³ may be the same or different, and at least one of Y ³ represents a glycidyl group.

R ¹³ is preferably a hydrogen atom from the viewpoint of improving the resolution.
In the general formula (III'), Y ³ has a molar ratio of Y ³ which is a hydrogen atom and Y ³ which is a glycidyl group of 0/100 to 30/70 or 0/100 to 30/70 from the viewpoint of improving resolution. It may be appropriately selected from 0/100 to 10/90. As can be seen from this molar ratio, at ^least one of Y3 is a glycidyl group.

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

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

In order to promote the reaction between the hydroxyl group and epichlorohydrin, it is preferable to carry out the reaction at a reaction temperature of 50 to 120 ° C. in the presence of an alkali metal hydroxide in a polar organic solvent such as dimethylformamide, dimethylacetamide or dimethyl sulfoxide. When the reaction temperature is within the above range, the reaction is less likely to be slowed down and side reactions can be further suppressed.

Examples of the phenol novolac type epoxy resin or cresol novolac type epoxy resin represented by the general formula (III') include YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638. YDPN-602 (above, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., trade name), DEN-431, DEN-439 (above, manufactured by Dow Chemical Co., Ltd., trade name), EOCN-120, EOCN-102S, EOCN-103S , EOCN-1012S, EOCN-1012, EOCN-1025, EOCN-1027, BREN (above, manufactured by Nippon Kayaku Co., Ltd., trade name), EPN-1138, EPN-1235, EPN-1299 (above, manufactured by BASF). , Product name), N-730, N-770, N-865, N-665, N-673, VH-4150, VH-4240 (all manufactured by DIC Co., Ltd., product name), etc. are commercially available. It is possible.

Further, the component (a2) may be at least one selected from the above-mentioned novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and triphenol methane type epoxy resin.

[Epoxy resin having a structural unit represented by the general formula (IV)]
As the bisphenol A type epoxy resin and the bisphenol F type epoxy resin, for example, at least one selected from the bisphenol A type epoxy resin having a structural unit represented by the following general formula (IV) and the bisphenol F type epoxy resin is preferable. Examples of the epoxy resin having such a structural unit include bisphenol A type epoxy resin represented by the following general formula (IV') or bisphenol F type epoxy resin, and bisphenol F type epoxy resin is preferable.

In the general formulas (IV) and (IV'), R ¹⁴ represents a hydrogen atom or a methyl group, and Y ⁴ represents a hydrogen atom or a glycidyl group. Further, the plurality of R ^14s existing may be the same or different. Further, in the general formula (IV'), n ₂ indicates a number of 1 or more, and when n ₂ is 2 or more, a plurality of Y ^4s may be the same or different, and at least one Y ⁴ is a glycidyl group. be.

Hydrogen atom is preferable for R ¹⁴ from the viewpoint that undercut and chipping of the upper part of the resist are less likely to occur and the linearity and resolution of the resist pattern contour are improved.
Further, from the same viewpoint as this, ^Y4 is preferably a glycidyl group.

n ₂ indicates a number of 1 or more, and may be appropriately selected from 10 to 100, 10 to 80, or 15 to 60. When n ₂ is within the above range, a resist shape having improved linearity of the contour of the resist pattern can be formed, and adhesion to a copper substrate, heat resistance, and electrical insulation are improved.

The bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by the general formula (IV) in which Y ⁴ is a glycidyl group is represented by, for example, the general formula (IV) and Y ⁴ is a hydrogen atom. It can be obtained by reacting a hydroxyl group (-OY ⁴ ) of an epoxy resin or a bisphenol F type epoxy resin with epichlorohydrin.

In order to promote the reaction between the hydroxyl group and epichlorohydrin, it is preferable to carry out the reaction at a reaction temperature of 50 to 120 ° C. in the presence of an alkali metal hydroxide in a polar organic solvent such as dimethylformamide, dimethylacetamide or dimethyl sulfoxide. When the reaction temperature is within the above range, the reaction is less likely to be slowed down and side reactions can be further suppressed.

Examples of the bisphenol A type epoxy resin or the bisphenol F type epoxy resin represented by the general formula (IV') include Epicoat 807, 815, 825, 827, 828, 834, 1001, 1004, 1007 and 1009 (hereinafter, Mitsubishi). Chemical Co., Ltd., trade name), DER-330, DER-301, DER-361 (above, Dow Chemical Corporation, trade name), YD-8125, YDF-170, YDF-170, YDF-175S , YDF-2001, YDF-2004, YDF-8170 (all manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation, trade name) and the like are commercially available.

[Epoxy resin having a structural unit represented by the general formula (V)]
As the triphenol methane type epoxy resin of the component (a2), a triphenol methane type epoxy resin having a structural unit represented by the following general formula (V) is preferably mentioned, and a triphenol methane type having such a structural unit is preferable. As the epoxy resin, for example, a triphenol methane type epoxy resin represented by the following general formula (V') is preferably mentioned.

式（Ｖ）及び（Ｖ’）中、Ｙ^５は水素原子又はグリシジル基を示し、複数のＹ^５は同一でも異なっていてもよく、少なくとも一つのＹ^５はグリシジル基である。また、一般式（Ｖ’）中、ｎ_３は１以上の数を示す。

In formulas (V) and (V'), Y ⁵ represents a hydrogen atom or a glycidyl group, and a plurality of Y ^5s may be the same or different, and at least one Y ⁵ is a glycidyl group. Further, in the general formula (V'), n ₃ indicates a number of 1 or more.

The viewpoint of Y ^{5 is that the molar ratio of Y 5 which} is a hydrogen atom and Y ⁵ which is a glycidyl group is less likely to cause undercut and chipping of the upper part of the resist, and the linearity and resolution of the contour of the resist pattern are improved. Therefore, it may be appropriately selected from 0/100 to 30/70. As can be seen from this molar ratio, at ^least one of Y5 is a glycidyl group.
n ₃ indicates a number of 1 or more, and may be appropriately selected from 10 to 100, 15 to 80, or 15 to 70. When n ₃ is within the above range, a resist shape having improved linearity of the contour of the resist pattern can be formed, and adhesion to a copper substrate, heat resistance, and electrical insulation are improved.

As the triphenol methane type epoxy resin represented by the general formula (V'), for example, FAE-2500, EPPN-501H, EPPN-502H (all manufactured by Nippon Kayaku Co., Ltd., trade name) and the like are commercially available. It is available at.

The component (A1) and the component (A2) contain a component (a1) and a component (a2) (hereinafter, may be referred to as "component (a)") and a vinyl group from the viewpoint of improving the resolution. Resins (A1') and (A2') obtained by reacting with a monocarboxylic acid (b) (hereinafter, may be referred to as a component (b)) (hereinafter, collectively referred to as a "component (A')". In some cases, it is preferable that the resin is obtained by reacting a saturated or unsaturated group-containing polycarboxylic acid anhydride (c) (hereinafter, may be referred to as a component (c)).

[Vinyl group-containing monocarboxylic acid (b)]
As the component (b), for example, acrylic acid, a dimer of acrylic acid, methacrylic acid, β-flufurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α-cyanoesteric acid and other acrylic acids. Semi-ester compound which is a reaction product of derivative, hydroxyl group-containing acrylate and dibasic acid anhydride, vinyl group-containing monoglycidyl ether or semi-ester which is reaction product of vinyl group-containing monoglycidyl ester and dibasic acid anhydride Compounds and the like are preferably mentioned.

The semi-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 of two or more.

Examples of the hydroxyl group-containing acrylate, vinyl group-containing monoglycidyl ether, and vinyl group-containing monoglycidyl ester used for synthesizing the semiester compound which is an example of the component (b) include hydroxyethyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl acrylate. , Hydroxypropyl Methacrylate, Hydroxybutyl Acrylate, Hydroxybutyl Methacrylate, Polyethylene Glycol Monoacrylate, Polyethylene Glycol Monomethacrylate, Trimethylol Propane Diacrylate, Trimethylol Propane Dimethacrylate, Pentaerythritol Triacrylate, Pentaerythritol Trimethacrylate, Dipentaerythritol Examples thereof include pentaacrylate, pentaerythritol pentamethacrylate, glycidyl acrylate, and glycidyl methacrylate.

Examples of the dibasic acid anhydride used for the synthesis of the semi-ester compound include those containing a saturated group and those 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, and methylhexahydrophthalic anhydride. Acids, ethylhexahydrophthalic anhydride, phthalic anhydride and the like can be mentioned.

In the reaction between the component (a) and the component (b), the component (b) may be reacted at a ratio of 0.6 to 1.05 equivalent to 1 equivalent of the epoxy group of the component (a). , 0.8 to 1.0 equivalent may be reacted. By reacting at such a ratio, the photopolymerizability is improved, that is, the photosensitivity is increased, so that the resolution is improved.

The component (a) and the component (b) can be dissolved in an organic solvent and reacted.
Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether and dipropylene. Glycol ethers such as 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. ; Petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrocarbon petroleum naphtha, and solvent naphtha are preferably mentioned.

Further, it is preferable to use a catalyst to promote the reaction between the component (a) and the component (b). Examples of the catalyst include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine and the like.
The amount of the catalyst used is 0.01 to 10 parts by mass, 0.05 to 2 parts by mass, or 0.1 to 1 part by mass with respect to a total of 100 parts by mass of the component (a) and the component (b). It may be selected appropriately from. When the above amount is used, the reaction between the component (a) and the component (b) is promoted.

Further, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like.
From the viewpoint of improving the storage stability of the composition, the amount of the polymerization inhibitor used is 0.01 to 1 part by mass, 0.02 with respect to 100 parts by mass in total of the component (a) and the component (b). It may be appropriately selected from ~ 0.8 parts by mass or 0.04 to 0.5 parts by mass.

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

As described above, the component (A') formed by reacting the component (a) and the component (b) is formed by a ring-opening addition reaction between the epoxy group of the component (a) and the carboxyl group of the component (b). It is presumed that it has a hydroxyl group.
By further reacting the component (A') obtained above with the component (c) containing a saturated or unsaturated group, the hydroxyl group of the component (A') (the hydroxyl group originally present in the component (a) can also be obtained. It is presumed that the acid anhydride group of the component (including) and (c) are semi-esterified to form an acid-modified vinyl group-containing epoxy resin.

[Polybasic acid anhydride (c)]
As the component (c), one containing a saturated group and one 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, and methylhexahydrophthalic anhydride. , Ethylhexahydrophthalic anhydride, phthalic anhydride and the like. Among these, tetrahydrophthalic anhydride is preferable from the viewpoint of obtaining a photosensitive resin composition capable of forming a pattern having excellent resolution.

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

The acid value of the 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 the acid value is 150 mgKOH / g or less, the electrical characteristics of the cured film are improved.

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.

Further, if necessary, for example, a hydrogenated bisphenol A type epoxy resin may be partially used in combination as the component (a). Further, as the component (A), a styrene-maleic acid-based resin such as a hydroxyethyl (meth) acrylate-modified product of a styrene-maleic anhydride copolymer can be partially used in combination.

(Molecular weight of component (A))
The weight average molecular weight of the component (A) may be 3,000 to 30,000, 4,000 to 25,000, or 5,000 to 18,000. Within the above range, the 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 a gel permeation chromatography (GPC) method using tetrahydrofuran as a solvent. More specifically, for example, a value measured by the following GPC measuring device and measurement conditions and converted using a standard polystyrene calibration curve can be used as the weight average molecular weight. In addition, a 5-sample set (“PStQuick MP-H” and “PStQuick B”, manufactured by Tosoh Corporation) is used as the standard polystyrene for preparing the calibration curve.
(GPC measuring device)
GPC device: High-speed GPC device "HCL-8320GPC", detector is differential refractometer or UV, manufactured by Tosoh Corporation Column: Column TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), Tosoh Made by Co., Ltd. (Measurement conditions)
Solvent: Tetrahydrofuran (THF)
Measurement temperature: 40 ° C
Flow rate: 0.35 ml / min Sample concentration: 10 mg / THF 5 ml
Injection amount: 20 μl

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

(Total content of (A1) component and (A2) component in (A) component)
When the component (A1) and the component (A2) are used in combination as the component (A), the total content of the component (A1) and the component (A2) in the component (A) is resolution and heat resistance. From the viewpoint of improving the above, it may be appropriately selected from the range of 80 to 100% by mass, 90 to 100% by mass, 95 to 100% by mass, or 100% by mass. Further, when either the component (A1) or the component (A2) is used alone, it may be appropriately selected from the above range.

(Mass ratio of (A1) component and (A2) component)
When the component (A1) and the component (A2) are used in combination as the component (A), the mass ratio (A1 / A2) is 30/70 to 90 / from the viewpoint of improving resolution and heat resistance. It may be appropriately selected from 10, 40/60 to 80/20, or 50/50 to 80/20.

<(B) Photopolymerizable compound>
The component (B) is not particularly limited as long as it is a photopolymerizable compound or a photocrosslinkable compound. , Phenylethynyl group, maleimide group, nadiimide group, (meth) acryloyl group and other compounds having a functional group having an ethylenically unsaturated bond are preferably mentioned.

As the component (B), a compound having a molecular weight of 1000 or less is preferable from the viewpoint of photosensitivity, and hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferable. Mono or di (meth) acrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol; (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide; N , Aminoalkyl (meth) acrylates such as N-dimethylaminoethyl (meth) acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris-hydroxyethyl isocyanurate or Polyvalent (meth) acrylates of these ethylene oxide or propylene oxide adducts; (meth) acrylates of phenolic phenols such as phenoxyethyl (meth) acrylates and polyethoxydi (meth) acrylates of bisphenol A. Kind; (meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; melamine (meth) acrylates and the like are preferably mentioned. These components (B) can be used alone or in combination of two or more.
From the viewpoint of improving the sensitivity, the polyhydric alcohol or the polyvalent (meth) acrylates of these ethylene oxides or propylene oxide adducts may be contained.

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

(Contents of (B) component)
The content of the component (B) may be appropriately selected from 2 to 50% by mass, 3 to 20% by mass, or 3 to 10% by mass based on the total solid content in the photosensitive resin composition. When the content of the component (B) is 2% by mass or more, the light sensitivity is improved and the exposed portion tends to be difficult to elute during development, and when it is 50% by mass or less, the heat resistance is improved.

<(C) Photopolymerization Initiator>
The component (C) used in the present embodiment is not particularly limited as long as the component (B) can be polymerized, and can be appropriately selected from commonly used photopolymerization initiators.
Examples of the 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-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2- Acetophenones such as morpholino-1-propanone and N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone and the like. Anthracinones; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; acetophenone dimethylketal, benzyldimethylketal and other ketals; benzophenone, methylbenzophenone , 4,4'-Dichlorobenzophenone, 4,4'-bis (diethylamino) benzophenone, Michler's ketone, 4-benzoyl-4'-methyldiphenylsulfide and other benzophenones; 9-phenylaclydin, 1,7-bis (9, Acrydins such as 9'-acrydinyl) heptane; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- ( O-benzoyloxime), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone 1- (O-acetyloxime), 1-phenyl-1,2-propanedione -2- [O- (ethoxycarbonyl) oxime] and other oxime esters, and the like can be mentioned. These (C) components may be used alone or in combination of two or more.

Above all, from the viewpoint of improving the curability of the bottom by photobleaching, it may be appropriately selected from the above acylphosphine oxides, and it is difficult to volatilize and it is difficult to generate outgas, so it should be appropriately selected from the above acetophenones. Just do it.

(Contents of component (C))
The content of the component (C) is appropriately selected from 0.2 to 15% by mass, 0.4 to 5% by mass, or 0.6 to 1% by mass based on the total solid content of the photosensitive resin composition. do it. When the content of the component (C) is 0.2% by mass or more, the exposed portion tends to be difficult to elute during development, and when it is 15.0% by mass or less, the heat resistance is improved.

In addition to the above component (C), N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like are available. (C') photopolymerization initiators such as tertiary amines can also be used alone or in combination of two or more.

<(D) Inorganic filler>
The photosensitive resin composition of the present embodiment contains the component (D) mainly for the purpose of further improving various properties such as adhesive strength and coating film hardness.
Examples of the component (D) include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TIO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), and silicon nitride (Si ₃ N). ₄ ), barium titanate (BaO · TiO ₂ ), barium carbonate (BaCO ₃ ), magnesium carbonate (MgCO ₃ ), aluminum hydroxide (Al (OH) ₃ ), magnesium hydroxide (Mg (OH) ₂ ), titanium Lead Acid Acid (PbO · TiO ₂ ), Lead Tyrconate Titanium (PZT), Lead Lantern Tirconate Titanium (PLZT), Gallium Oxide (Ga ₂ O ₃ ), Spinel (MgO · Al ₂ O ₃ ), Murite (3Al) _2O 3.2SiO ₂ ), Cordierite (2MgO ・ 2Al 2O ₃ /5SiO ₂ ), Talk (3MgO ・_{4SiO 2}・_H2O ), Aluminum Titanium _{( TIO2}・_Al2O3 ) _, Itria Zirconia (Y ₂ O ₃ · ZrO ₂ ), barium silicate (BaO · 8SiO ₂ ), boron nitride (BN), calcium carbonate (CaCO ₃ ), barium sulfate (BaSO ₄ ), calcium sulfate (CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO · TiO ₂ ), hydrotalcite, mica, calcined kaolin, carbon (C) and the like can be used. These inorganic fillers can be used alone or in combination of two or more.

The average particle size of the 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 the component (D) is the average particle size of the inorganic filler in a state of being 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 compliant with the international standard ISO13321 using a submicron particle analyzer (manufactured by Beckman Coulter, Inc., trade name: N5). Then, the particles dispersed in the solvent are measured at a refractive index of 1.38, and the particle size at the integrated value of 50% (volume basis) in the particle size distribution is taken as the average particle size. Further, the component (D) contained in the photosensitive layer or the cured film of the photosensitive resin composition provided on the carrier film is also diluted (or dissolved) 1000 times (volume ratio) with a solvent as described above. After that, it can be measured by using the above-mentioned submicron particle analyzer.

Among the components (D), silica may be contained from the viewpoint of improving heat resistance, barium sulfate may be contained from the viewpoint of improving heat resistance and adhesive strength, or a combination of silica and barium sulfate may be contained. .. Further, the inorganic filler may be appropriately selected from the viewpoint of improving the dispersibility of the inorganic filler in the resin composition by the aggregation preventing effect, and the inorganic filler is surface-treated with alumina or an organic silane compound in advance.

The elemental composition of aluminum on the surface of the inorganic filler surface-treated with alumina or an organic silane compound is appropriately from 0.5 to 10 atomic%, 1 to 5 atomic%, or 1.5 to 3.5 atomic%. You can select it. 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.

As the inorganic filler surface-treated with an aluminana or an organic silane-based compound, for example, barium sulfate surface-treated with an aluminana or an organic silane-based compound can be used as NanoFine BFN40DC (trade name, manufactured by Nippon Solvay Corporation). It is commercially available.

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

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

<(E)> Silane compound (E) components include alkylsilane, alkoxysilane, vinylsilane, epoxysilane, aminosilane, acrylicsilane, methacrylsilane, mercaptosilane, sulfidesilane, isocyanatesilane, sulfersilane, styrylsilane, and alkylchlorosilane. Included are at least one organic silane compound selected from.

More specifically, the component (E) includes, for example, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, and the like. 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, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycid Xypropylmethyldiethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Triisopropoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl Examples thereof include silane compounds such as dimethoxysilane, 3-mercaptopropyltriethoxysilane, and N- (1,3-dimethylbutylidene) -3-aminopropyltriethoxysilane.

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

(Contents of (E) component)
The content of the component (E) may be appropriately selected from 0.5 to 30% by mass or 1 to 10% by mass based on the total solid content of the photosensitive resin composition. When the content of the component (E) is within the above range, the adhesion to chip parts such as silicon wafers can be improved while maintaining the resolution.

<(F) Pigment>
The photosensitive resin composition of the present embodiment may further contain the component (F) depending on the desired color in order to improve the appearance such as hiding the conductor pattern. As the component (F), a colorant that develops a desired color may be appropriately selected and used. For example, phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal violet, titanium oxide, carbon black, etc. Known colorants such as naphthalene black are preferably mentioned.

(Contents of (F) component)
The content of the component (F) is 0.01 to 5% by mass, 0, based on the total amount of solid content in the photosensitive resin composition, from the viewpoint of making it easier to identify the manufacturing apparatus and hiding the conductor pattern. It may be appropriately selected from 3.03 to 3% by mass or 0.05 to 2% by mass.

<(G) Hardener>
The photosensitive resin composition of the present embodiment may further contain the component (G). As the component (G), a compound that itself cures with heat, ultraviolet rays, etc., or a compound that cures by reacting with a carboxy group or a hydroxyl group of (A) an acid-modified vinyl group-containing epoxy resin with heat, ultraviolet rays, etc. Can be mentioned. By using the component (G), heat resistance, adhesive strength, chemical resistance and the like can be further improved.

Examples of the component (G) include thermosetting compounds such as epoxy compounds, melamine compounds, urea compounds, oxazoline compounds, and block-type isocyanates.
Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, novolak type epoxy resin, bisphenol S type epoxy resin, and biphenyl type epoxy resin. , Triglycidyl isocyanurate and other heterocyclic epoxy resins, bixilenol type epoxy resins and the like. Examples of the melamine compound include triaminotriazine, hexamethoxymelamine, hexabutoxydylated melamine and the like. In addition, examples of the urea compound include dimethylol urea and the like.

The component (G) preferably contains at least one selected from an epoxy compound (epoxy resin) and a block-type isocyanate from the viewpoint of further improving heat resistance.

As the block-type isocyanate, an addition reaction product of a polyisocyanate compound and an isocyanate blocking agent is used. Examples of the polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, phenylenedi isocyanate, naphthylene diisocyanate, bis (isocyanatemethyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate and the like. Polyisocyanate compounds of the above, and adducts, burettes, isocyanurates and the like thereof.

(Contents of component (G))
The component (G) may be used alone or in combination of two or more. (G) When a curing agent is used, the content thereof should be appropriately selected from 2 to 40% by mass, 3 to 30% by mass, or 5 to 20% by mass based on the total solid content of the photosensitive resin composition. Just do it. By keeping the content of the component (G) within the above range, the heat resistance of the formed cured film can be further improved while maintaining good developability.

<(H) Elastomer>
The photosensitive resin composition of the present embodiment may further contain the component (H). The component (H) can be suitably used particularly when the photosensitive resin composition of the present embodiment is used for a semiconductor package substrate. By adding the component (H) to the photosensitive resin composition of the present embodiment, the flexibility and the adhesive strength are lowered due to the strain (internal stress) inside the cured product due to the curing shrinkage of the component (A). Can be suppressed. That is, it is possible to improve the flexibility, adhesive strength, etc. of the cured film formed by the photosensitive resin composition.

Examples of the 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, and the former generally contributes to heat resistance and strength, and the latter contributes to flexibility and toughness.

Examples of the styrene-based elastomer include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer and the like.

The olefin-based elastomer is a copolymer of α-olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, and 4-methyl-pentene. Specific examples thereof include ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidenenorbornene, butadiene, and the like. Examples thereof include a non-conjugated diene having 2 to 20 carbon atoms such as isoprene and an α-olefin copolymer, and a carboxy-modified NBR obtained by copolymerizing a butadiene-acrylonitrile copolymer with methacrylic acid. More specifically, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-non-conjugated diene copolymer rubber, propylene-α-olefin copolymer rubber, butene-α-olefin copolymer rubber Can be mentioned. More specifically, Mirastoma (manufactured by Mitsui Chemicals Co., Ltd.), EXACT (manufactured by Exxon Chemical Co., Ltd.), ENGAGE (manufactured by Dow Chemical Co., Ltd.), hydrogenated styrene-butadiene rubber "DYNABON HSBR" (manufactured by JSR Co., Ltd.), butadiene- Acrylonitrile copolymer "NBR series" (manufactured by JSR Co., Ltd.), or double-ended carboxyl group-modified butadiene-acrylonitrile copolymer "XER series" (manufactured by JSR Co., Ltd.), epoxy partially epoxidized with polybutadiene BF-1000 (manufactured by Nippon Soda Co., Ltd.), PB-4700, PB-3600 (manufactured by Daicel Co., Ltd.) and the like can be used.

Examples of the polyester-based elastomer include those obtained by polycondensing a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof.

Specific examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which the hydrogen atom of these aromatic nuclei is substituted with a methyl group, an ethyl group, a phenyl group, or the like. Examples thereof include 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.

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

In addition to the above-mentioned elastomer, a rubber-modified epoxy resin can also be used as the elastomer. The rubber-modified epoxy resin contains, for example, a part or all of the epoxy groups of the above-mentioned bisphenol F type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. It is obtained by modifying with a terminal carboxylic acid-modified butadiene-acrylonitrile rubber, a terminal amino-modified silicone rubber, or the like. Among these elastomers, in terms of shear adhesive strength, both-terminal carboxyl group-modified butadiene-acrylonitrile copolymer and Esper, which is a polyester-based elastomer having a hydroxyl group (Esper 1108, 1612, 1620, manufactured by Hitachi Chemical Co., Ltd.) Etc. are preferable. Elastomers that are liquid at room temperature are particularly preferred.

(Contents of component (H))
When the component (H) is used, the content thereof is appropriately selected from 1 to 20 parts by mass, 2 to 15 parts by mass, or 3 to 10 parts by mass with respect to 100 parts by mass of the component (A) component (solid content). do it. Within the above range, thermal impact resistance and adhesive strength can be further improved while maintaining good developability. Further, when used for a thin film substrate, the warp property of the thin film substrate can be reduced.

<(I) Epoxy resin curing agent>
The component (I) can also be added to the photosensitive resin composition of the present embodiment for the purpose of further improving various properties such as heat resistance, adhesive strength, and chemical resistance.
Examples of such the component (I) include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methyl-5. Imidazole derivatives such as hydroxymethylimidazole; guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulphon, dicyandiamide, urea, urea derivatives, melamine and polybase hydrazide. These organic acid salts or epoxyadducts; amine complexes of boron trifluoride; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xysilyl-S-triazine, etc. Examples thereof include triazine derivatives.

(Contents of (I) component)
The component (I) can be used alone or in combination of a plurality of types, and when the component (I) is used, the content thereof is a photosensitive resin composition from the viewpoint of further suppressing the influence on the photosensitive characteristics. It may be appropriately selected from 0.01 to 20% by mass, 0.1 to 10% by mass, or 0.1 to 3% by mass based on the total solid content of.

<(J) Thermoplastic resin>
The component (J) can also be added to the photosensitive resin composition of the present embodiment for the purpose of further improving the flexibility of the cured film. Examples of the component (J) include acrylic resin and urethane resin.

(Contents of (J) component)
The component (J) can be used alone or in combination of a plurality of types, and when the component (J) is used, the content thereof is a photosensitive resin composition from the viewpoint of improving the flexibility of the cured film. It may be appropriately selected from 1 to 30% by mass or 5 to 20% by mass based on the total amount of the solid content of.

<Diluent>
A diluent can be used in the photosensitive resin composition of the present embodiment, if necessary. As the diluent, for example, an organic solvent or the like can be used. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether and dipropylene. Glycol ethers such as 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. ; Petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrocarbon petroleum naphtha, and solvent naphtha can be mentioned. Diluents can be used alone or in combination of two or more.

The amount of the diluent to be used may be appropriately selected from an amount such that the total solid content in the photosensitive resin composition is 50 to 90% by mass, 60 to 80% by mass, or 65 to 75% by 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% by mass, 20 to 40% by mass, or 25 to 35% by mass. By setting the amount of the diluent to be used within the above range, the coatability of the photosensitive resin composition is improved, and a higher-definition pattern can be formed.

<Other additives>
The photosensitive resin composition of the present embodiment may contain, if necessary, a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, a thickener such as Benton, montmorillonite, silicone-based, fluorine-based, and the like. Various known and commonly used additives such as vinyl resin-based defoaming agents and silane coupling agents can be used. Further, flame retardant agents such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphate compounds of phosphorus-based compounds, aromatic condensed phosphoric acid esters, and halogen-containing condensed phosphoric acid esters can be used.

The photosensitive resin composition of the present embodiment can be obtained by uniformly kneading and mixing the compounding components with a roll mill, a bead mill or the like.

[Dry film]
The dry film of the present embodiment has a carrier film and a photosensitive layer using the photosensitive resin composition of the present 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.

The dry film of the present embodiment is obtained by applying and drying the photosensitive resin composition of the present embodiment on a carrier film by a known method such as a reverse roll coat, a gravure roll coat, a comma coat, and a curtain coat. , A photosensitive layer can be formed and manufactured.
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. Further, in the dry film of the present embodiment, the protective layer can be laminated on the surface of the photosensitive layer opposite to the surface in contact with the carrier film. As the protective layer, for example, a polymer film such as polyethylene or polypropylene may be used. Further, 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 by hot air drying, far infrared rays, or a dryer using near infrared rays, and the drying temperature is from 60 to 120 ° C., 70 to 110 ° C., or 80 to 100 ° C. It may be selected as appropriate. The drying time may be appropriately selected from 1 to 60 minutes, 2 to 30 minutes, or 5 to 20 minutes.

[Printed wiring board]
The printed wiring board of the present embodiment includes at least one of a surface protective film and an interlayer insulating film formed by the photosensitive resin composition of the present embodiment.
Since the printed wiring board of the present embodiment includes at least one of the surface protective film and the interlayer insulating film formed from the photosensitive resin composition of the present embodiment, it has excellent adhesive strength with plated copper and excellent heat resistance. It has properties, a low coefficient of thermal expansion, and a pattern with excellent resolution and adhesion to chip components. In addition, this pattern is excellent in the size of the miniaturized hole diameter and the formation stability of the interval pitch between holes due to the recent miniaturization and higher performance of electronic devices.

[Manufacturing method of printed wiring board]
The method for manufacturing a printed wiring board of the present embodiment is a step of providing a photosensitive layer on a substrate using the photosensitive resin composition of the present embodiment or the dry film of the present embodiment, and a resin pattern is formed using the photosensitive layer. It has a step of forming and a step of curing the resin pattern to form at least one of a surface protective film and an interlayer insulating film in order.
Specifically, for example, it can be manufactured as follows.
First, on a metal-clad laminated substrate such as a copper-clad laminate, a screen printing method, a spray method, a roll coating method, a curtain coating method, an electrostatic coating method, etc. are used to obtain 10 to 200 μm, 15 to 150 μm, and 20 to 100 μm. Alternatively, the dry film of the present embodiment is coated with the photosensitive resin composition having a film thickness appropriately selected from 23 to 50 μm, and then the coating film is dried at 60 to 110 ° C., or the protective layer is peeled off. A photosensitive layer is provided on the substrate by thermally laminating on the substrate using a laminator.
Next, the negative film is brought into direct contact with the photosensitive layer (or non-contact via a transparent film such as a carrier film), and the active light is emitted from 10 to 2,000 mJ / cm ² , 100 to 1,500 mJ / cm. ² Or, irradiation is performed with an exposure amount appropriately selected from 300 to 1,000 mJ / cm ² , and then the unexposed portion is dissolved and removed (developed) with a dilute alkaline aqueous solution to form a pattern. Examples of the active light used include electron beams, ultraviolet rays, X-rays and the like, and ultraviolet rays are preferable. Further, as the light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a halogen lamp, or the like can be used.
Next, the exposed portion of the photosensitive layer is sufficiently cured by at least one of post-exposure (ultraviolet exposure) and post-heating treatment to form at least one of the surface protective film and the interlayer insulating film.
The exposure amount for the post-exposure may be appropriately selected from 100 to 5,000 mJ / cm ² , 500 to 2,000 mJ / cm ² , or 700 to 1,500 J / cm ² .
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.
After that, a conductor pattern is formed by etching, and a printed wiring board is produced.

Further, the photosensitive resin composition of the present embodiment or the dry film of the present embodiment can be used to manufacture a multilayer printed wiring board. FIG. 1 is a schematic view showing an aspect of a manufacturing process of 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. The multilayer printed wiring board 100A shown in FIG. 1 (f) has a plurality of conductor patterns 107 in a layered manner on a substrate having a conductor pattern 102 on its surface, and has an interlayer insulating film 103 between each layer. The conductor pattern 102 is connected by a conductor pattern 107 provided in the interlayer insulating film 103 and the opening 104, and a surface protective film 108 is provided on the surface thereof. At least one is formed by using the photosensitive resin composition of the present embodiment or the dry film of the present embodiment. The multilayer printed wiring board 100A is 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 an etching method or a semi-additive method. Hereinafter, a method for manufacturing the multilayer printed wiring board 100A will be briefly described with reference to FIG.

First, an interlayer insulating layer 103 is formed on both surfaces of a copper-clad laminate 101 having a conductor pattern 102 on both surfaces (see FIG. 1A). The interlayer insulating film 103 is photosensitive by the method described in the method for manufacturing a printed wiring board, that is, by applying the photosensitive resin composition of the present embodiment or thermally laminating the dry film of the present embodiment using a laminator. A layer is formed, and a negative film is used for the photosensitive layer to expose and cure a region other than a portion that needs to be electrically connected to the outside (conductor pattern of another layer) to further expose an unexposed portion. It is formed by removal (see FIG. 1 (b)). The interlayer insulating film 103 is a film having an opening 104. Here, the smear (residue) existing around the opening 104 may be removed by desmear treatment.

Next, the conductor pattern 107 is formed. For example, the conductor pattern 107 forms a thin metal layer (seed layer), forms a resin pattern (plating resist), and then forms the conductor pattern 107 by an electrolytic plating method. It can be formed by a semi-additive method in which the resin pattern is removed and the seed layer is removed by etching. Specifically, the seed layer 105 is formed on the interlayer insulating film 103 and on the conductor pattern 102 at the opening 104 by an electroless plating method (see FIG. 1 (c)). The seed layer 105 can be formed of plated copper, for example, by electroless copper plating. A photosensitive layer is formed on the seed layer 105 using a semi-additive photosensitive resin composition, a negative film is used for the photosensitive layer, a predetermined portion is exposed and developed, and a resin having a predetermined pattern is formed. The pattern 106 is formed (see FIG. 1 (d)). Next, a conductor pattern 107 is formed in a portion of the seed layer 105 where the resin pattern 106 is not formed by an electrolytic plating method, the resin pattern 106 is removed by a stripping solution, and the seed layer 105 is removed by etching (FIG. FIG. 1 (e)). The work of FIGS. 1 (b) to 1 (e) is repeated to form a conductor pattern 107 according to a desired number of layers, and a cured product of the photosensitive resin composition according to the present embodiment is formed on the outermost surface. A surface protective film (permanent mask resist) 108 can be formed to produce a multilayer printed wiring board 100A (see FIG. 1 (f)). Here, as the semi-additive photosensitive resin composition, for example, the photosensitive resin composition according to the present embodiment can be used.

In the multilayer printed wiring board 100A thus obtained, a semiconductor element is mounted at a corresponding portion, and it is possible to secure an electrical connection.

Since the printed wiring board according to the present embodiment uses the photosensitive resin composition according to the present embodiment for at least one of the surface protective film and the interlayer insulating film, the feature of the photosensitive resin composition, that is, You will enjoy excellent adhesive strength with plated copper, excellent resolution, and adhesion with chip parts. In addition, with the trend toward miniaturization and higher performance of electronic devices, there is a remarkable tendency for semiconductor chips to have higher densities due to narrower pitches of conductor patterns. The flip-chip connection method for joining to a substrate has become the mainstream, but there have been some problems as described below in the past.
This flip-chip connection method is a semiconductor mounting method by a reflow method in which solder balls are arranged between a substrate and a semiconductor chip and the whole is heated and melt-bonded. Therefore, the substrate itself is exposed to a high temperature environment during solder reflow, and due to the thermal shrinkage of the substrate, a large stress is generated in the solder balls connecting the substrate and the semiconductor, resulting in poor connection of the conductor pattern, cracking in the surface protective film or underfill ( It may cause cracks). Further, when the substrate is exposed to a high temperature environment, a large stress is generated at the connection interface due to the thermal expansion of the resin composition forming the surface protective film or the like provided on the substrate, which may cause a connection failure. The photosensitive resin composition according to the present embodiment has excellent heat resistance and low thermal expansion rate in addition to excellent adhesive strength with plated copper, excellent resolution, and adhesion to chip parts. , It has sufficient performance to solve these problems. Therefore, the printed wiring board according to the present embodiment has high quality, in which poor connection of the conductor pattern, cracking of the surface protective film, etc. are unlikely to occur.

Hereinafter, the purpose and advantages of this embodiment will be described more specifically based on Examples and Comparative Examples, but the present embodiment is not limited to the following examples.

(Synthesis Example 1; Synthesis of Acid-Modified Vinyl Group-Containing Epoxy Resin (A1))
Bisphenol F novolak type epoxy resin (a) (EXA-7376, manufactured by DIC Co., Ltd., in general formula (II), bisphenol F novolak type epoxy containing a structural unit in which Y ² is a glycidyl group and R ¹² is a hydrogen atom. Resin) 350 parts by mass, acrylic acid (b) 70 parts by mass, methylhydroquinone 0.5 parts by mass, carbitol acetate 120 parts by mass, heated to 90 ° C. and stirred to react, and the mixture is completely dissolved. did. Next, the obtained solution was cooled to 60 ° C., 2 parts by mass 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. To the solution after the reaction, 98 parts by mass of tetrahydrophthalic anhydride (THPAC) (c) and 850 parts by mass of carbitol acetate were added, and the mixture was heated to 80 ° C. and reacted for 6 hours. Then, the mixture was cooled to room temperature to obtain a THPAC-modified bisphenol F novolak type epoxy acrylate (epoxy resin (1)) as a component (A1) having a solid content concentration of 73% by mass.

(Examples 1 to 6, Comparative Examples 1 to 5)
The compositions were blended according to the blending composition shown in Table 1 and kneaded with a three-roll mill to prepare a photosensitive resin composition. Carbitol acetate was added so that the solid content concentration became 60% by mass to obtain a photosensitive resin composition.

The 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 novolak type epoxy resin (“UE-EXP-3165”, manufactured by DIC Co., Ltd., trade name) in which R ¹³ is a hydrogen atom and Y ³ is a glycidyl group in the general formula (III). An acid-modified vinyl group-containing epoxy resin (A2) (weight average molecular weight: 3300, acid value: 42.4 mg / KOH) in which a glycidyl group is acrylated and a hydroxyl group is modified with tetrahydrophthalic anhydride (THPAC).
-Aronix M402: Dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., trade name)
-Irgacure 819: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by BASF, trade name)
-Irgacure 907: 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (manufactured by BASF, trade name)
SC2050-LNF: Silica particles (manufactured by Admatex Co., Ltd., trade name, average particle size: 0.5 μm)
-ASA: Barium sulfate particles (manufactured by Nippon Solvay Co., Ltd., trade name, average particle size: 1.0 μm)
KBM-403: 3-glycidoxypropyltrimethoxysilane (manufactured by Shinetsu Silicone Co., Ltd., trade name)
X-12-984S: Polyfunctional epoxysilane (manufactured by Shinetsu Silicone Co., Ltd., trade name)
・ Phthalocyanine pigment: Phthalocyanine pigment (manufactured by Sanyo Pigment Co., Ltd.)
-YSLV-80XY: Tetramethylbisphenol F type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name)
RE-306: Novolac type polyfunctional epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name)
-PB-3600: Epoxidized polybutadiene (manufactured by Daicel Corporation, trade name)
-SP1108: Polyester resin (Esper 1108, manufactured by Hitachi Kasei Co., Ltd.)
・ Melamine: Made by Nissan Chemical Industries, Ltd.

Next, using the photosensitive resin composition obtained above, each evaluation was performed under the conditions shown below. The evaluation results are shown in Table 2.

[Making a dry film]
A 16 μm-thick polyethylene terephthalate film (G2-16, manufactured by Teijin Limited, trade name) is used as a carrier film, and the photosensitive resin compositions of Examples and Comparative Examples are placed on the carrier film to have a thickness after drying. The film was uniformly applied to a thickness of 25 μm and dried at 75 ° C. for 30 minutes using a hot air convection dryer to form a photosensitive layer. Subsequently, a polyethylene film (NF-15, manufactured by Tamapoli Co., Ltd., trade name) (protective layer) is attached to the surface of the photosensitive layer on the side opposite to the side in contact with the carrier film, and the dry film is attached. Made.

[Evaluation of resolution]
A continuous press type vacuum laminator (MVLP-500, Using a product number manufactured by Meiki Seisakusho Co., Ltd., under predetermined laminating conditions (crimping pressure: 0.4 MPa, press hot plate temperature: 80 ° C, evacuation time: 40 seconds, laminating press time: 20 seconds, atmospheric pressure: (4 kPa or less) Laminating was performed to obtain a laminated body having a photosensitive layer.
Next, a negative mask having a via pattern of a predetermined size (opening diameter size: 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, and 200 μmφ) is provided. Then, using an i-line exposure apparatus (UX-2240SM-XJ-01, manufactured by Ushio Co., Ltd., product number), exposure was performed in the range of 100 to 500 mJ / cm ² while changing by 50 mJ / cm ² . Then, spray with a 1 mass% sodium carbonate aqueous solution at a pressure of ^1.765 × 105 Pa, which is equivalent to twice the shortest development time at 30 ° C. (the shortest time for removing the unexposed portion of the photosensitive layer). It was developed and the unexposed portion was melt-developed. Next, it is exposed to an exposure amount of 2000 mJ / cm ² using an ultraviolet exposure device, heated at 170 ° C. for 1 hour, and a cured product of the photosensitive resin composition is formed on a copper-clad laminated substrate with a via pattern of a predetermined size. A test piece having was prepared.
The above test piece was 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 exceeded 50 μm and was 100 μm or less.
C: The minimum diameter of the opening exceeded 100 μm.

[Evaluation of adhesive strength with plated copper]
A laminate having a photosensitive layer prepared in the above [evaluation of resolution] was prepared, and the laminate was used with an i-line exposure apparatus (UX-2240SM-XJ-01, manufactured by Ushio, Inc., product number) at 500 mJ /. The entire surface was exposed at cm ² , then exposed at an exposure amount of 2000 mJ / cm ² using an ultraviolet exposure apparatus, and heated at 170 ° C. for 1 hour to obtain a copper-clad laminated substrate having a cured film of a photosensitive resin composition. .. In order to chemically roughen the cured film, a swelling solution (an aqueous solution of diethylene glycol monobutyl ether: 200 ml / L and sodium hydroxide: 5 g / L) was prepared, heated to 70 ° C., and immersed for 10 minutes. Next, a roughened solution (an aqueous solution of potassium permanganate: 60 g / L and sodium hydroxide: 40 g / L) was prepared, heated to 70 ° C., and immersed for 15 minutes. Subsequently, an aqueous solution of a neutralizing solution (tin chloride (SnCl ₂ ): 30 g / L, hydrogen chloride: 300 ml / L) was prepared, heated to 40 ° C. and immersed for 5 minutes to reduce potassium permanganate. The cured film was chemically roughened.
Next, a catalyst for electrolytic plating containing lead chloride (PdCl ₂ ) (Activator Neogant 834, manufactured by Atotech Japan Co., Ltd., trade name) was heated to 35 ° C. and immersed for 5 minutes to be immersed in electrolytic copper. It was immersed in a plating solution for plating (Print Gantt MSK-DK, manufactured by Atotech Japan Co., Ltd., trade name) at room temperature for 15 minutes, and further subjected to copper sulfate electrolytic plating. Then, the annealing treatment was performed at 180 ° C. for 60 minutes to form a conductor layer having a thickness of 35 μm, and a test piece was obtained. A region having a width of 10 mm and a length of 50 mm was formed on the conductor layer by treatment with a sulfuric acid-based etching solution, and one end of this region was peeled off by 10 mm at the interface between the conductor layer (copper layer) and the cured resin film. Next, the peeled resin film was pinched with a grasping tool, and the tensile speed was 50 mm / min in the thickness direction (vertical direction) of the test piece, and the load (peeling strength) when peeled at room temperature was measured. The evaluation results are shown in Table 2. Here, in the present specification, room temperature means 25 ° C.

[Evaluation of adhesion]
A laminate having a photosensitive layer was obtained by the same method as described in [Evaluation of resolution] except that the copper-clad laminated substrate was replaced with a 6-inch silicon wafer (manufactured by Electronics End Materials Corporation). .. The laminate was fully exposed at 500 mJ / cm ² using an i-line exposure apparatus (UX-2240SM-XJ-01, manufactured by Ushio, Inc., product number), and then 2000 mJ / cm ² using an ultraviolet exposure apparatus. It was exposed to an exposure amount and heated at 170 ° C. for 1 hour to obtain a silicon wafer having a cured film of a photosensitive resin composition. After that, an Al stud with an epoxy adhesive (adhesive part diameter: 2.7 mm, P / N901106, manufactured by Phototechnica Co., Ltd., trade name) was placed vertically on the cured film, and placed in an oven at 150 ° C., 1 A test piece was obtained by heat treatment for an hour. The stud on the test piece was fixed to a chuck of a thin film adhesion strength measuring device (manufactured by Phototechnica Co., Ltd.), a force was applied perpendicularly to the cured film, and the subsequent state was evaluated according to the following criteria. The evaluation results are shown in Table 2.
A: The epoxy adhesive coagulated and fractured.
B: Peeled off at the interface between the cured film and the silicon wafer.

[Measurement of coefficient of thermal expansion and glass transition point]
The dry film produced above was exposed to the entire surface at 500 mJ / cm ² using an i-line exposure device (UX-2240SM-XJ-01, manufactured by Ushio Co., Ltd., product number), and allowed to stand at room temperature (25 ° C.) for 1 hour. After that, the polyethylene film was peeled off and spray-developed with a 1% by mass sodium carbonate aqueous solution at 30 ° C. Then, ultraviolet irradiation of 2 J / cm ² was performed using an ultraviolet irradiation device (manufactured by ORC Manufacturing Co., Ltd.), and further heat treatment was performed at 170 ° C. for 60 minutes. Then, after cutting into a width of 3 mm and a length of 30 mm with a cutter knife, the polyethylene terephthalate film (carrier film) was peeled off to obtain a cured product for evaluation of the coefficient of thermal expansion.
The coefficient of thermal expansion in the tensile mode was measured using a TMA device (SS6000, manufactured by Seiko Instruments Co., Ltd., product number). The tensile load is 5 g, the span (distance between chucks) is 15 mm, and the heating rate is 10 ° C./min. First, the test piece was attached to the device, heated from room temperature (25 ° C.) to 160 ° C., and left for 15 minutes. After that, the mixture was cooled to −60 ° C. and measured from −60 ° C. to 250 ° C. under the condition of a heating rate of 10 ° C./min to calculate the coefficient of thermal expansion and the glass transition point. Table 2 shows the coefficient of thermal expansion and the glass transition point.

From Table 2, the photosensitive resin compositions of the present embodiments of Examples 1 to 6 show excellent performance in resolution, adhesive strength, and adhesion, and in particular, the surface protective film and the interlayer in the printed wiring board. It was confirmed that the composition can be suitably used as an insulating film, a surface protective film in contact with a silicon material, and the like. On the other hand, the resin compositions of Comparative Examples 1 to 5 did not have sufficient effects in terms of resolution, adhesive strength, and adhesiveness. From the results of the coefficient of thermal expansion and the glass transition point, it was also confirmed that the photosensitive resin composition of the present embodiment has excellent heat resistance and a low coefficient of thermal expansion.

100A. Multi-layer 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 (12)

It 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 is 10 to 80% by mass based on the total amount of solids in the photosensitive resin composition.
The (B) photopolymerizable compound contains a compound having three or more ethylenically unsaturated bonds in the molecule.
The (C) photopolymerization initiator contains at least one selected from acetophenones and acylphosphine oxides.
The (E) silane compound is at least one selected from alkylsilane, alkoxysilane, vinylsilane, epoxysilane, aminosilane, acrylicsilane, methacrylicsilane, mercaptosilane, sulfidesilane, isocyanatesilane, sulfasilane, styrylsilane, and alkylchlorosilane. be,
Photosensitive resin composition. An epoxy resin (A1) containing at least one acid-modified vinyl group whose component (A) is a bisphenol novolak type epoxy resin (a1), and an epoxy resin (a2) different from the epoxy resin (a1). The photosensitive resin composition according to claim 1, which contains at least one acid-modified vinyl group-containing epoxy resin (A2) to be used. The photosensitive resin composition according to claim 2, wherein the epoxy resin (a2) is at least one selected from a novolak type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a triphenol methane type epoxy resin. thing. The acid-modified vinyl group-containing epoxy resin (A1) and (A2) is a resin (A1') obtained by reacting the epoxy resins (a1) and (a2) with a vinyl group-containing monocarboxylic acid (b), respectively. The photosensitive resin composition according to claim 2 or 3, which is a resin obtained by reacting (A2') with a saturated or unsaturated group-containing polybasic acid anhydride (c). Any of claims 2 to 4, wherein the bisphenol novolak 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 photosensitive resin composition according to item 1.

[In formula (I), R ¹¹ represents a hydrogen atom or a methyl group, and Y ¹ independently represents a hydrogen atom or a glycidyl group. The plurality of R ^11s may be the same or different, and at least one of Y ¹ represents a glycidyl group. ]

[In formula (II), R ¹² represents a hydrogen atom or a methyl group, and Y ² independently represents a hydrogen atom or a glycidyl group. The plurality of R ^12s may be the same or different, and at least one of Y ² represents a glycidyl group. ] The bisphenol novolak type epoxy resin (a1) has a structural unit represented by the general formula (I), and the epoxy resin (a2) has a structural unit represented by the following general formula (III). The photosensitive resin composition according to any one of claims 2 to 5, which is a novolak type epoxy resin contained.

[In formula (III), R ¹³ represents a hydrogen atom or a methyl group, and Y ³ represents a hydrogen atom or a glycidyl group. ] The content of the (A) acid-modified vinyl group-containing epoxy resin, (B) photopolymerizable compound, (C) photopolymerization initiator, (D) inorganic filler, and (E) silane compound is the photosensitive resin composition. Claim 1 is 5 to 60% by mass, 0.2 to 15% by mass, 0.1 to 10% by mass, 20 to 60% by mass, and 0.5 to 30% by mass, respectively, based on the total amount of solid content in the medium. The photosensitive resin composition according to any one of 6 to 6. The photosensitive resin composition according to any one of claims 1 to 7, further comprising (F) a pigment. The photosensitive resin composition according to any one of claims 1 to 8, wherein the (C) photopolymerization initiator contains acetophenones and acylphosphine oxides. A dry film having a carrier film and a photosensitive layer using the photosensitive resin composition according to any one of claims 1 to 9. A printed wiring board comprising at least one of a surface protective film and an interlayer insulating film formed by the photosensitive resin composition according to any one of claims 1 to 9. A step of providing a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 9 or the dry film according to claim 10, and forming a resin pattern using the photosensitive layer. A method for manufacturing a printed wiring board, which comprises, in order, a step of curing the resin pattern to form at least one of a surface protective film and an interlayer insulating film.

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