JP7284205B2 - Photosensitive resin composition, dry film using the same, printed wiring board, and method for producing printed wiring board - Google Patents

Description

TECHNICAL FIELD 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.

2. Description of the Related Art In recent years, semiconductor components such as LSIs and chips have been highly integrated as electronic devices have become more sophisticated (smaller, lighter, and multifunctional). Along with this, the form of semiconductor components is rapidly changing toward multi-pin and miniaturization. In addition, along with the high integration of semiconductor parts, the semiconductor elements, semiconductor packages, printed wiring boards, flexible wiring boards, etc. that make up the semiconductor parts are becoming higher density and higher definition. Substrates with built-in components are being considered. The surface protective film or interlayer insulating film used for semiconductor parts is required to be able to form a via opening pattern for interlayer connection, and to be able to adhere not only to substrate materials and copper patterns (conductor patterns) but also to chip parts. It is

As a method for manufacturing a printed wiring board, a build-up method can be mentioned as a conventional method. In this build-up method, first, an insulating resin film is laminated on the inner layer circuit board (base material having the first conductor pattern), cured by heating to form an interlayer insulating film, and then via holes are formed by laser processing. do. Next, the interlayer insulating film is subjected to roughening treatment and smear treatment by alkali permanganate 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 Patent Document 1, for example).

In recent years, with the increasing density of conductor patterns, surface protective films are required to have high resolution, and photosensitive resin compositions that can be patterned by photolithography have been widely used. Among them, an alkali-developable photosensitive resin composition that can be developed with a weakly alkaline aqueous solution such as an aqueous sodium carbonate solution has become mainstream from the viewpoint of working environment conservation and global environment conservation.

JP-A-7-304931

On the other hand, the formation of via holes in the build-up method using conventional laser processing requires that each via be formed one by one. 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 photolithography has been studied. However, it cannot be said that sufficient adhesive strength is obtained between the surface protective film and the electroless plated copper.

Therefore, the problem to be solved by the present disclosure is a photosensitive resin composition that has excellent adhesive strength with plated copper, excellent resolution, silicon material substrates such as silicon wafers, and excellent adhesion to chip parts. The object of the present invention is to provide a product, a dry film using the same, a printed wiring board, and a method for manufacturing a printed wiring board (hereinafter sometimes referred to as "photosensitive resin composition, etc.").

The present inventors have made intensive studies to solve the above problems, and as a result, have found that the problems can be solved by the following inventions. 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.

[1] (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 containing (D) A photosensitive resin composition having an inorganic filler content of 10 to 80% by mass based on the total solid content in the photosensitive resin composition.
[2] A dry film comprising a carrier film and a photosensitive layer using the photosensitive resin composition described in [1] above.
[3] Printed wiring board comprising at least one of a surface protective film and an interlayer insulating film formed from the photosensitive resin composition described in [1] above [4] Photosensitivity according to [1] above on a substrate A step of providing a photosensitive layer using the resin composition or the dry film described in [2] above, a step of forming a resin pattern using the photosensitive layer, and curing the resin pattern to form a surface protective film and interlayer insulation A method of manufacturing a printed wiring board, comprising, in order, the steps 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, excellent adhesion to silicon material substrates such as silicon wafers, and chip parts, and using it A dry film, a printed wiring board, and a method for manufacturing a printed wiring board can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows one aspect|mode of the manufacturing process of the multilayer printed wiring board which uses the hardened|cured material of the photosensitive resin composition of this embodiment as at least one of a surface protective film and an interlayer insulation film.

[Photosensitive resin composition]
A photosensitive resin composition according to an embodiment of the present disclosure (hereinafter sometimes simply referred to as this embodiment) comprises (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerizable compound, (C ) contains 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. In this specification, these components may be simply referred to as (A) component, (B) component, (C) component, and the like. As used herein, the term “solid content” refers to non-volatile content excluding volatile substances such as water and solvents contained in the photosensitive resin composition, and when the resin composition is dried, It also includes those that are liquid, syrup-like, and wax-like at room temperature around 25°C.
Each component is explained 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 component (A). 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 and a vinyl group-containing monocarboxylic acid with a saturated or unsaturated group-containing polybasic acid. Epoxy resins obtained by reacting anhydrides can be mentioned.

Component (A) is, for example, a bisphenol novolac type epoxy resin (a1) (hereinafter sometimes referred to as component (a1)) from the viewpoint of enabling alkali development and improving resolution and adhesive strength. ) using an acid-modified vinyl group-containing epoxy resin (A1) (hereinafter sometimes referred to as the (A1) component), an epoxy resin (a2) other than the epoxy resin (a1) (hereinafter, the (a2) component (hereinafter sometimes referred to as the (A2) component) using an acid-modified vinyl group-containing epoxy resin (A2) (hereinafter sometimes referred to as the (A2) component). can be used In particular, from the viewpoint of improving the adhesion strength, the (A) component includes at least one (A1) component using the (a1) component and at least one (A2) component using the (a2) component. and may contain.

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

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

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

From the viewpoint of improving resolution and adhesive strength, R ¹¹ is preferably a hydrogen atom. From the same point of view, ^Y1 is preferably a glycidyl group.

The number of structural units in the epoxy resin (a1) having a structural unit represented by general formula (I) is 1 or more, and is 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, resolution and adhesive strength are improved. Here, the number of structural units of a structural unit represents an integer value for a single molecule, and represents a rational number, which is an average value, for an aggregate of multiple types of molecules. Hereinafter, the number of structural units of the structural units is the same.

[Epoxy Resin Having Structural Unit Represented by Formula (II)]
Moreover, one of preferred embodiments of the component (a1) is an epoxy resin having a structural unit represented by the following general formula (II).

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

From the viewpoint of improving resolution and adhesive strength, R ¹² is preferably a hydrogen atom.
From the same point of view, ^Y2 is preferably a glycidyl group.

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

In general formula (II), those in which R ¹² is a hydrogen atom and Y ² is a glycidyl group are referred to as EXA-7376 series (manufactured by DIC Corporation, trade name), and R ¹² is a methyl group, Those in which ^Y2 is a glycidyl group are commercially available as the EPON SU8 series (manufactured by Mitsubishi Chemical Corporation, trade name).

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

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

[Epoxy Resin Having Structural Unit Represented by Formula (III)]
Component (a2) is preferably a novolak type epoxy resin having a structural unit represented by the following general formula (III). As a novolac type epoxy resin having such a structural unit, for example, the following general formula ( III') includes a novolac type epoxy resin.

In general formulas (III) and (III'), ^R13 represents a hydrogen atom or a methyl group, and ^Y3 represents a hydrogen atom or a glycidyl group. Further, in general formula (III'), n ₁ is a number of 1 or more, 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.

From the viewpoint of improving resolution, R ¹³ is preferably a hydrogen atom.
In the general formula (III′), the molar ratio of Y ³ that is a hydrogen atom and ^{Y 3 that} is a glycidyl group is 0/100 to 30/70 from the viewpoint of improving resolution, or 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.

_n1 is a number of 1 or more, and may be appropriately selected from 10-200, 30-150, or 30-100. 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 are improved.

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

In order to accelerate the reaction between hydroxyl groups and epichlorohydrin, the reaction is preferably carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, etc. 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.

Examples of the phenol novolak type epoxy resin or cresol novolak type epoxy resin represented by the general formula (III′) include YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, YDPN-602 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name), DEN-431, DEN-439 (manufactured by Dow Chemical Co., Ltd., trade name), EOCN-120, EOCN-102S, EOCN-103S , EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027, BREN (manufactured by Nippon Kayaku Co., Ltd., trade name), EPN-1138, EPN-1235, EPN-1299 (manufactured by BASF) , trade names), N-730, N-770, N-865, N-665, N-673, VH-4150, VH-4240 (manufactured by DIC Corporation, trade names), etc. are commercially available. It is possible.

The component (a2) may be at least one selected from the above novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and triphenolmethane type epoxy resins.

[Epoxy Resin Having Structural Unit Represented by Formula (IV)]
As the bisphenol A type epoxy resin and the bisphenol F type epoxy resin, for example, 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) is preferable. Examples of epoxy resins having such a structural unit include bisphenol A epoxy resins and bisphenol F epoxy resins represented by the following general formula (IV'), with bisphenol F epoxy resins being preferred.

In 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. Moreover, multiple R ¹⁴ may be the same or different. In general formula (IV′), n ₂ represents a number of 1 or more, and when n ₂ 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. be.

R ¹⁴ is preferably a hydrogen atom from the viewpoint of less occurrence of undercuts and voids in the upper portion of the resist, and from the viewpoint of improving the linearity of the contour of the resist pattern and the resolution.
From the same point of view, ^Y4 is preferably a glycidyl group.

_n2 represents a number of 1 or more, and may be appropriately selected from 10-100, 10-80, or 15-60. When _n2 is within the above range, a resist shape with improved linearity of the resist pattern contour can be formed, and adhesion to the copper substrate, heat resistance, and electrical insulation are improved.

A bisphenol A type epoxy resin or a bisphenol F type epoxy resin represented by the general formula (IV) in which ^Y4 is a glycidyl group is, for example, a bisphenol A type epoxy resin represented by the general formula (IV) in which ^Y4 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 accelerate the reaction between hydroxyl groups and epichlorohydrin, the reaction is preferably carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, etc. 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.

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

[Epoxy Resin Having Structural Unit Represented by Formula (V)]
As the triphenolmethane-type epoxy resin as the component (a2), a triphenolmethane-type epoxy resin having a structural unit represented by the following general formula (V) is preferable. As the epoxy resin, for example, a triphenolmethane type epoxy resin represented by the following general formula (V') is preferably used.

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, multiple Y ⁵ may be the same or different, and at least one Y ⁵ is a glycidyl group. Further, in general formula (V'), _n3 represents a number of 1 or more.

Y ⁵ is the molar ratio of Y ⁵ , which is a hydrogen atom and Y ⁵ , which is a glycidyl group, so that undercuts and missing parts of the upper part of the resist are less likely to occur, and the linearity and resolution of the resist pattern contour are improved. from 0/100 to 30/70. As can be seen from this molar ratio, at least one of ^Y5 is a glycidyl group.
_n3 represents a number of 1 or more, and may be appropriately selected from 10-100, 15-80, or 15-70. 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 are improved.

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

The (A1) component and the (A2) component are, from the viewpoint of improving resolution, the (a1) component and the (a2) component (hereinafter sometimes referred to as "(a) component") and a vinyl group-containing Resins (A1′) and (A2′) obtained by reacting monocarboxylic acid (b) (hereinafter sometimes referred to as component (b)) (hereinafter collectively referred to as “(A′) component”) ) with saturated or unsaturated group-containing polybasic acid anhydride (c) (hereinafter sometimes referred to as component (c)).

[Vinyl group-containing monocarboxylic acid (b)]
Component (b) includes, for example, acrylic acid, dimers of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, and α-cyanocinnamic acid. Derivatives, half-ester compounds that are reaction products of hydroxyl group-containing acrylates and dibasic acid anhydrides, vinyl group-containing monoglycidyl ethers or half esters that are reaction products of vinyl group-containing monoglycidyl esters and dibasic acid anhydrides Compounds and the like are preferably exemplified.

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 (b) components can be used individually or in combination of multiple types.

Examples of hydroxyl group-containing acrylates, vinyl group-containing monoglycidyl ethers, and vinyl group-containing monoglycidyl esters used for synthesizing the above half-ester compounds, which are examples of component (b), include hydroxyethyl acrylate, hydroxyethyl methacrylate, and 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, glycidyl methacrylate and the like.

Dibasic acid anhydrides used in the synthesis of the above half-ester compounds include those containing saturated groups and those containing unsaturated groups. Specific examples of dibasic acid anhydrides include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. acid, ethylhexahydrophthalic anhydride, itaconic anhydride, and the like.

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

The components (a) and (b) can be dissolved in an organic solvent and reacted.
Examples of organic solvents 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, 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 solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha;

Furthermore, it is preferable to use a catalyst in order to accelerate the reaction between components (a) and (b). Examples of catalysts include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine and the like.
The amount of 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 100 parts by mass of components (a) and (b) in total. can be selected as appropriate. The amount used promotes the reaction between the components (a) and (b).

Moreover, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction. Polymerization inhibitors include, for example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol.
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 parts per 100 parts by mass of the components (a) and (b). 0.8 parts by mass, or 0.04 to 0.5 parts by mass.

The reaction temperature of 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.

Thus, component (A'), which is obtained by reacting component (a) and component (b), is 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 it has a hydroxyl group that is
By further reacting the (A') component obtained above with the (c) component containing a saturated or unsaturated group, the hydroxyl groups of the (A') component (the hydroxyl groups originally present in the (a) component containing) and the acid anhydride group of component (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 or one containing an unsaturated group can be used. Specific examples of component (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 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.

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

The acid value of component (A) may be 30-150 mgKOH/g, 40-120 mgKOH/g, or 50-100 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.

The reaction temperature of component (A') and 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.

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

(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 the above range, 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, the weight-average molecular weight can be obtained by measuring with the following GPC measurement apparatus and measurement conditions and converting using a standard polystyrene calibration curve. A calibration curve is prepared using a set of 5 samples (“PStQuick MP-H” and “PStQuick B” manufactured by Tosoh Corporation) as standard polystyrene.
(GPC measuring device)
GPC apparatus: high-speed GPC apparatus "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 Co., Ltd. (measurement conditions)
Solvent: Tetrahydrofuran (THF)
Measurement temperature: 40°C
Flow rate: 0.35 ml/min Sample concentration: 10 mg/THF5 ml
Injection volume: 20 μl

(Content of component (A))
From the viewpoint of improving heat resistance, electrical properties and chemical resistance, the content of component (A) is 5 to 60% by mass, 10 to 50% by mass, or , 15 to 40% by mass.

(Total content of component (A1) and component (A2) in component (A))
When using a combination of the (A1) component and the (A2) component as the component (A), the total content of the (A1) component and the (A2) component in the (A) component is the resolution and heat resistance. From the viewpoint of improving, 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. Moreover, when either the (A1) component or the (A2) component 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>
Component (B) is not particularly limited as long as it is a photopolymerizable compound or a photocrosslinkable compound. , a phenylethynyl group, a maleimide group, a nadimide group, a (meth)acryloyl group, and other functional groups having an ethylenically unsaturated bond are preferred.

From the viewpoint of photosensitivity, the component (B) is preferably a compound having a molecular weight of 1000 or less, for example, hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. ; Ethylene glycol, methoxytetraethylene glycol, glycol mono- or di(meth)acrylates such as polyethylene glycol; N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide and other (meth)acrylamides; N , N-dimethylaminoethyl (meth)acrylate and other aminoalkyl (meth)acrylates; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris-hydroxyethyl isocyanurate and other polyhydric alcohols or Polyvalent (meth)acrylates of these 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, triglycidyl isocyanurate; and melamine (meth)acrylate. These (B) components can be used individually or in combination of multiple types.
From the viewpoint of improving sensitivity, the above polyhydric alcohols or polyhydric (meth)acrylates of ethylene oxide or propylene oxide adducts thereof may also be included.

In addition, 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 compounds include the above polyvalent (meth)acrylates, and from the viewpoint of improving sensitivity, dipentaerythritol tri(meth)acrylate can be selected.

(Content of component (B))
The content of 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 photosensitivity is improved and the exposed portion tends to be less eluted during development, and when the content is 50% by mass or less, the heat resistance is improved.

<(C) Photoinitiator>
The component (C) used in the present 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; -dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 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 thioxanthone such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, methylbenzophenone , 4,4′-dichlorobenzophenone, 4,4′-bis(diethylamino)benzophenone, Michler’s ketone, benzophenones such as 4-benzoyl-4′-methyldiphenylsulfide; 9-phenylacridine, 1,7-bis(9, 9′-acridinyl)heptane and other acridines; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and other acylphosphine oxides; 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-( O-benzoyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime), 1-phenyl-1,2-propanedione -2-[O-(ethoxycarbonyl)oxime] and other oxime esters, and the like. These (C) components can be used individually by 1 type or in combination of 2 or more types.

Among them, from the viewpoint of improving the curability of the bottom portion by photobleaching, it may be appropriately selected from the above acylphosphine oxides, and from the point of being less likely to volatilize and less likely to generate outgas, it may be appropriately selected from the above acetophenones. Just do it.

(Content of component (C))
The content of 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 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), there may be added three compounds such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine. The (C') photopolymerization initiation aids such as class amines may be used alone or in combination.

<(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.
Component (D) includes, for example, silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), 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 oxide ( _PbO.TiO2 ), lead zirconate titanate (PZT), lead lanthanum zirconate titanate ( _PLZT ), gallium oxide ( _Ga2O3 ), spinel ( _{MgO.Al2O3 )} , mullite (3Al _{2O3.2SiO2 )} , cordierite ( _{2MgO.2Al2O3 / 5SiO2} ), talc _{( 3MgO.4SiO2.H2O} ) _, aluminum titanate ( _TiO2.Al2O3 ), yttria _{- containing} Zirconia ( _Y2O3.ZrO2 ), Barium Silicate ( _BaO.8SiO2 ), _Boron Nitride (BN ₎ , Calcium Carbonate ( _CaCO3 ), Barium Sulfate ( _BaSO4 ), Calcium Sulfate ( _CaSO4 ), 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 individually or in combination of multiple types.

The average particle diameter of component (D) may be appropriately selected from the viewpoint of resolution from 0.01 to 5 μm, 0.1 to 3 μm, or 0.1 to 2 μm. Here, the average particle size of the component (D) is the average particle size of the inorganic filler dispersed in the photosensitive resin composition, and is a value obtained by measuring as follows. First, after diluting (or dissolving) the photosensitive resin composition 1000-fold with methyl ethyl ketone, a submicron particle analyzer (manufactured by Beckman Coulter, Inc., trade name: N5) was used to measure according to the international standard ISO13321. Then, the particles dispersed in the solvent are measured at a refractive index of 1.38, and the particle diameter at 50% (volume basis) of the integrated value in the particle size distribution is defined as the average particle diameter. Further, the component (D) contained in the photosensitive layer provided on the carrier film or the cured film of the photosensitive resin composition is also diluted (or dissolved) to 1000 times (volume ratio) using a solvent as described above. After that, it can be measured by using the submicron particle analyzer described above.

Among component (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, and silica and barium sulfate may be combined. . Moreover, from the viewpoint of improving the dispersibility of the inorganic filler in the resin composition due to the anti-aggregation effect, the inorganic filler may be appropriately selected from those previously surface-treated with alumina or an organic silane compound.

The elemental composition of aluminum on the surface of the inorganic filler surface-treated with alumina or an organic silane compound is appropriately selected from 0.5 to 10 atomic %, 1 to 5 atomic %, or 1.5 to 3.5 atomic %. You can choose. Also, 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 %. Also, 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 alumina or an organic silane compound, for example, barium sulfate surface-treated with alumina or an organic silane compound is NanoFine BFN40DC (manufactured by Solvay Japan Co., Ltd., trade name). commercially available.

(Content of component (D))
The content of component (D) is 10 to 80% by mass based on the total solid content of the photosensitive resin composition. Also, the content of 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, etc. of the photosensitive resin composition can be improved.

When silica is used as component (D), the content of silica is 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 can be selected as appropriate. Further, 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 30% by mass, based on the total solid content of the photosensitive resin composition. It may be appropriately selected from 20% by mass. When the content of silica and barium sulfate is within the above ranges, a low coefficient of thermal expansion, solder heat resistance, and adhesive strength can be improved.

<(E)> Silane compound Component (E) includes alkylsilanes, alkoxysilanes, vinylsilanes, epoxysilanes, aminosilanes, acrylsilanes, methacrylsilanes, mercaptosilanes, sulfidesilanes, isocyanatesilanes, sulfursilanes, styrylsilanes, and alkylchlorosilanes. at least one organic silane compound selected from

Component (E) more specifically includes, for example, 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, 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 include silane compounds such as dimethoxysilane, 3-mercaptopropyltriethoxysilane, N-(1,3-dimethylbutylidene)-3-aminopropyltriethoxysilane.

Component (E) preferably has a functional group capable of reacting with component (A). (A) Component and a reactive functional group 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 resolution, and an epoxysilane having at least one glycidyl ether group is selected. can.

(Content of component (E))
The content of 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, it is possible to improve the adhesion to chip parts such as silicon wafers 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 concealing the conductor pattern. As component (F), a coloring agent that develops a desired color may be appropriately selected and used. Examples include phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal violet, titanium oxide, carbon black, Known colorants such as naphthalene black are preferred.

(Content of component (F))
The content of component (F) is 0.01 to 5% by mass, based on the total solid content in the photosensitive resin composition, from the viewpoint of making it easier to identify the manufacturing equipment and more concealing the conductor pattern. 0.03 to 3% by mass, or 0.05 to 2% by mass.

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

Examples of 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 type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol S type epoxy resin, and biphenyl type epoxy resin. , heterocyclic epoxy resins such as triglycidyl isocyanurate, and bixylenol type epoxy resins. Melamine compounds include, for example, triaminotriazine, hexamethoxymelamine, hexabutoxylated melamine, and the like. Urea compounds include, for example, dimethylol urea.

From the viewpoint of further improving heat resistance, the component (G) preferably contains at least one selected from epoxy compounds (epoxy resins) and blocked isocyanates.

As the blocked 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, phenylene diisocyanate, naphthylene diisocyanate, bis(isocyanatomethyl)cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, and the like. polyisocyanate compounds, and their adducts, burettes and isocyanurates.

(Content of component (G))
(G) A component is used individually or in combination of multiple types. (G) When a curing agent is used, its content is 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 setting the content of the component (G) within the above range, it is possible to further improve the heat resistance of the formed cured film while maintaining good developability.

<(H) Elastomer>
The photosensitive resin composition of the present embodiment may further contain component (H). 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 (H) component to the photosensitive resin composition of the present embodiment, the flexibility and adhesive strength are reduced due to the distortion (internal stress) inside the cured product due to the cure shrinkage of the (A) component. can be suppressed. That is, it is possible to improve the flexibility, adhesive strength, etc. of the cured film formed from the photosensitive resin composition.

Component (H) includes, for example, styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, and silicone-based elastomers. These elastomers consist of a hard segment component and a soft segment component, the former generally contributing to heat resistance and strength, and the latter contributing to flexibility and toughness.

Styrenic elastomers include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene-butylene-styrene block copolymers, styrene-ethylene-propylene-styrene block copolymers, and the like.

Olefin elastomers are copolymers of α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene. Specific examples include ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidenenorbornene, butadiene, Carboxy-modified NBR obtained by copolymerizing a non-conjugated diene having 2 to 20 carbon atoms such as isoprene with an α-olefin copolymer, and a butadiene-acrylonitrile copolymer with methacrylic acid. More specifically, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-nonconjugated diene copolymer rubber, propylene-α-olefin copolymer rubber, and butene-α-olefin copolymer rubber mentioned. More specifically, Milastoma (manufactured by Mitsui Chemicals), EXACT (manufactured by Exxon Chemicals), ENGAGE (manufactured by Dow Chemicals), hydrogenated styrene-butadiene rubber "DYNABON HSBR" (manufactured by JSR Corporation), butadiene- Acrylonitrile copolymer "NBR series" (manufactured by JSR Corporation), or both terminal carboxyl group-modified butadiene-acrylonitrile copolymer "XER series" (manufactured by JSR Corporation), epoxy obtained by partially epoxidizing polybutadiene Polybutadiene BF-1000 (manufactured by Nippon Soda Co., Ltd.), PB-4700, PB-3600 (manufactured by Daicel Co., Ltd.) and the like can be used.

Polyester-based elastomers include those obtained by polycondensation of dicarboxylic acids or derivatives thereof and diol compounds or derivatives thereof.

Specific examples of dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid, and aromatic dicarboxylic acids in which the hydrogen atoms of these 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 are included. These compounds can be used individually or in combination of 2 or more types.

Specific examples of diol compounds 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 diols. These compounds can be used individually or in combination of 2 or more types.

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

(Content of component (H))
When component (H) is used, its content 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 component (A) (solid content). do it. By setting the content within the above range, it is possible to further improve the thermal shock resistance and adhesive strength while maintaining good developability. Moreover, when used for a thin film substrate, the warpage of the thin film substrate can be reduced.

<(I) Epoxy resin curing agent>
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 component (I) include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl-5- Imidazole derivatives such as 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; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine Examples include triazine derivatives.

(Content of component (I))
Component (I) can be used alone or in combination of multiple types, and when component (I) is used, the content thereof should be adjusted from the viewpoint of further suppressing the effect on the photosensitive properties of the photosensitive resin composition. 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>
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 component (J) include acrylic resins and urethane resins.

(Content of component (J))
Component (J) can be used alone or in combination of multiple types. When component (J) is used, the content thereof is determined from the viewpoint of improving the flexibility of the cured film. Based on the total solid content of , it may be appropriately selected from 1 to 30% by mass, or 5 to 20% by mass.

<Diluent>
A diluent can be used for the photosensitive resin composition of this embodiment as needed. As a diluent, for example, an organic solvent or the like can be used. Examples of organic solvents 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, 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 solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; A diluent can use these individually or in combination of multiple types.

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 usage amount of the diluent within the above range, the applicability of the photosensitive resin composition is improved, making it possible to form a higher definition pattern.

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

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

[Dry film]
The dry film of this embodiment has 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.

The dry film of the present embodiment can be obtained, for example, by coating and drying the photosensitive resin composition of the present embodiment on a carrier film by a known method such as reverse roll coating, gravure roll coating, comma coating, or curtain coating. , can be manufactured by forming a photosensitive layer.
Examples of carrier films 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, in the dry film of the present embodiment, a 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. Also, the same polymer film as the carrier film described above may be used, or a different polymer film may be used.
For drying the coating film, hot air drying, far infrared rays, or a dryer using near infrared rays can be used. It can be selected as appropriate. Moreover, 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 comprises at least one of a surface protective film and an interlayer insulating film formed from 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 a low coefficient of thermal expansion, excellent resolution, and a pattern with excellent adhesion to chip parts. In addition, this pattern is excellent in formation stability of the size of the hole diameter and the interval pitch between the holes, which have been miniaturized due to the recent miniaturization and high performance of electronic devices.

[Method for manufacturing printed wiring board]
The method for producing a printed wiring board of the present embodiment includes a step of providing a photosensitive layer using the photosensitive resin composition of the present embodiment or a dry film of the present embodiment on a substrate, and 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 manufactured as follows.
First, on a metal-clad laminate substrate such as a copper-clad laminate, by a method such as a screen printing method, a spray method, a roll coating method, a curtain coating method, or an electrostatic coating method, 10 to 200 μm, 15 to 150 μm, 20 to 100 μm Alternatively, the photosensitive resin composition is applied to a film thickness appropriately selected from 23 to 50 μm, and then the coating film is dried at 60 to 110 ° C., or the dry film of the present embodiment with the protective layer peeled off. A photosensitive layer is provided on the substrate by thermal lamination on the substrate using a laminator.
Next, a negative film is brought into direct contact with the photosensitive layer (or non-contact via a transparent film such as a carrier film), and actinic light is applied at 10 to 2,000 mJ/cm ² , 100 to 1,500 mJ/cm 2 . ² , or an exposure dose appropriately selected from 300 to 1,000 mJ/cm ² , and then the unexposed area is dissolved and removed (developed) with a dilute alkaline aqueous solution to form a pattern. Actinic light to be used includes electron beams, ultraviolet rays, X-rays, etc., and ultraviolet rays are preferred. Moreover, as a 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 hardened by at least one of post-exposure (ultraviolet exposure) and post-heating to form at least one of a surface protective film and an interlayer insulating film.
The exposure amount of 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.
Thereafter, a conductor pattern is formed by etching to produce a printed wiring board.

A multilayer printed wiring board can also be produced using the photosensitive resin composition of the present embodiment or the dry film of the present embodiment. FIG. 1 is a schematic diagram showing one aspect of the 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. A multilayer printed wiring board 100A shown in FIG. The conductor pattern 102 is connected to the interlayer insulating film 103 by a conductor pattern 107 provided in the opening 104, and a surface protective film 108 is provided on the surface thereof. At least one of them is formed 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, etc., and appropriately forming a conductor pattern by an etching method or a semi-additive method. A method for manufacturing multilayer printed wiring board 100A will be briefly described below with reference to FIG.

First, an interlayer insulating layer 103 is formed on both surfaces of a copper-clad laminate 101 having conductor patterns 102 on both surfaces (see FIG. 1(a)). The interlayer insulating film 103 is formed by the method described in the printed wiring board manufacturing method, 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, a negative film is used for the photosensitive layer, and areas other than those required to be electrically connected to the outside (conductor patterns of other layers) are exposed, cured, and the unexposed areas are removed. It is formed by removing (see FIG. 1(b)). This 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 processing.

Next, the conductor pattern 107 is formed. For example, the conductor pattern 107 is formed by forming a thin metal layer (seed layer), forming a resin pattern (plating resist), and then electroplating to form the conductor pattern 107, 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, 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. 1C). This seed layer 105 can be formed of plated copper, for example by electroless copper plating. On the seed layer 105, a photosensitive layer is formed using a semi-additive photosensitive resin composition, a negative film is used for the photosensitive layer, and predetermined portions are exposed and developed to form a resin having a predetermined pattern. A pattern 106 is formed (see FIG. 1(d)). Next, a conductor pattern 107 is formed by electroplating on a portion of the seed layer 105 where the resin pattern 106 is not formed, the resin pattern 106 is removed by a peeling solution, and the seed layer 105 is removed by etching (Fig. 1(e)). 1B to 1E are repeated to form a conductor pattern 107 corresponding to the desired number of layers, and the outermost surface is formed with a cured product of the photosensitive resin composition according to the present embodiment. A surface protection film (permanent mask resist) 108 is formed, and a multilayer printed wiring board 100A can be produced (see FIG. 1(f)). Here, for example, the photosensitive resin composition according to the present embodiment can be used as the semi-additive photosensitive resin composition.

In multilayer printed wiring board 100A obtained in this way, semiconductor elements are mounted at corresponding locations, and electrical connection can be ensured.

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 features 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, along with the trend toward smaller size and higher performance of electronic equipment, there is a remarkable trend toward higher density due to the narrower pitch of conductor patterns in semiconductor chips. A flip-chip connection method for bonding to a substrate has become mainstream, but there have been some problems in the past, such as those described below.
This flip chip connection method is a semiconductor mounting method based on a reflow method in which solder balls are placed between a substrate and a semiconductor chip and the whole is heated to melt and bond. As a result, the substrate itself is exposed to a high-temperature environment during solder reflow, and the thermal shrinkage of the substrate generates a large amount of stress in the solder balls that connect the substrate and the semiconductor, resulting in poor connection of the conductor pattern, cracks in the surface protective film or underfill ( cracks) may occur. In addition, when the substrate is exposed to a high-temperature environment, thermal expansion of the resin composition forming the surface protective film, etc. provided on the substrate generates a large stress at the connection interface, which may cause connection failure. The photosensitive resin composition according to the present embodiment has excellent adhesive strength with plated copper, excellent resolution, and adhesion with chip components, as well as excellent heat resistance and a low coefficient of thermal expansion. , 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 and cracking of the surface protective film are unlikely to occur.

EXAMPLES The purpose and advantages of the present embodiment will be described in more detail below 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 Corporation, bisphenol F novolac type epoxy containing a structural unit in which ^Y2 is a glycidyl group and ^R12 is a hydrogen atom in the general formula (II) 350 parts by mass of resin), 70 parts by mass of acrylic acid (b), 0.5 parts by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate are charged, heated to 90° C. and stirred to react to completely dissolve the mixture. bottom. Next, the obtained solution was cooled to 60° C., 2 parts by mass of triphenylphosphine was added, heated to 100° C., and reacted until the acid value of the solution reached 1 mgKOH/g. 98 parts by mass of tetrahydrophthalic anhydride (THPAC) (c) and 850 parts by mass of carbitol acetate were added to the solution after the reaction, heated to 80° C., and reacted for 6 hours. Thereafter, the mixture was cooled to room temperature to obtain a THPAC-modified bisphenol F novolac type epoxy acrylate (epoxy resin (1)) as the component (A1) having a solid content of 73% by mass.

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

Details of each material in Table 1 are as follows.
- Epoxy resin (1) is the acid-modified vinyl group-containing epoxy resin (A1) obtained in Synthesis Example 1.
・ Epoxy resin (2) is a novolac type epoxy resin (“UE-EXP-3165”, manufactured by DIC Corporation, trade name) in which R ¹³ is a hydrogen atom and Y ³ is a glycidyl group in general formula (III). It is an acid-modified vinyl group-containing epoxy resin (A2) (weight average molecular weight: 3300, acid value: 42.4 mg/KOH) in which glycidyl groups are acrylated and hydroxyl groups are 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 Admatechs Co., Ltd., trade name, average particle size: 0.5 μm)
・ ASA: barium sulfate particles (manufactured by Solvay Japan Co., Ltd., trade name, average particle size: 1.0 μm)
・ KBM-403: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name)
・X-12-984S: Polyfunctional epoxysilane (manufactured by Shin-Etsu 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 Co., Ltd., trade name)
・ SP1108: Polyester resin (Espel 1108, manufactured by Hitachi Chemical Co., Ltd.)
・Melamine: manufactured by Nissan Chemical Industries, Ltd.

Next, each evaluation was performed on the conditions shown below using the photosensitive resin composition obtained above. Table 2 shows the evaluation results.

[Preparation of dry film]
A 16 μm thick polyethylene terephthalate film (G2-16, manufactured by Teijin Limited, trade name) was used as a carrier film, and the photosensitive resin compositions of Examples and Comparative Examples were applied onto the carrier film so that the film thickness after drying was It was applied uniformly 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 Tamapoly Co., Ltd., trade name) (protective layer) is attached to the surface of the photosensitive layer opposite to the side in contact with the carrier film, and a dry film is attached. made.

[Resolution evaluation]
While peeling off the protective layer of the dry film prepared above, a continuous press vacuum laminator (MVLP-500, ( (manufactured by Meiki Seisakusho Co., Ltd., product number) under predetermined lamination conditions (crimping pressure: 0.4 MPa, press hot plate temperature: 80 ° C., evacuation time: 40 seconds, lamination press time: 20 seconds, atmospheric pressure: 4 kPa or less) to obtain a laminate having a photosensitive layer.
Next, 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) was prepared. Using an i-ray exposure device (UX-2240SM-XJ-01, manufactured by Ushio Inc., product number), the film was exposed to light in the range of 100 to 500 mJ/cm ² by increments of 50 mJ/cm ² . Thereafter, a 1% by weight sodium carbonate aqueous solution was sprayed at 30° C. for a time corresponding to twice the shortest development time (shortest time for removing the unexposed portion of the photosensitive layer) at a pressure of 1.765×10 ⁵ Pa. After development, the unexposed area was developed by dissolution. Next, using an ultraviolet exposure device, the exposure dose was 2000 mJ/cm ² , followed by heating at 170° C. for 1 hour. A test piece having
The test piece was observed using a metallurgical microscope and evaluated according to the following criteria. Table 2 shows the evaluation results.
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 the photosensitive layer prepared in [Evaluation of Resolution] above was prepared, and the laminate was exposed to 500 mJ/min using an i-line exposure apparatus (UX-2240SM-XJ-01, manufactured by Ushio Inc., product number). cm ² , followed by exposure with an ultraviolet exposure device at an exposure amount of 2000 mJ/cm ² and heating at 170° C. for 1 hour to obtain a copper clad laminate having a cured film of a photosensitive resin composition. . In order to chemically roughen the cured film, a swelling liquid (diethylene glycol monobutyl ether: 200 ml/L, sodium hydroxide: 5 g/L aqueous solution) was prepared, heated to 70° C. and immersed for 10 minutes. Next, a roughening solution (potassium permanganate: 60 g/L, sodium hydroxide: 40 g/L aqueous solution) was prepared, heated to 70° C., and immersed for 15 minutes. Subsequently, an aqueous solution of 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. to chemically roughen the cured film.
Next, an electroless plating catalyst (Activator Neogant 834, manufactured by Atotech Japan Co., Ltd., trade name) containing lead chloride (PdCl ₂ ) was heated to 35° C. and immersed for 5 minutes to obtain electroless copper. It was immersed in a plating solution for plating (Printgant MSK-DK, manufactured by Atotech Japan Co., Ltd., trade name) at room temperature for 15 minutes, and then subjected to copper sulfate electroplating. Annealing treatment was then performed at 180° C. for 60 minutes to form a conductor layer with a thickness of 35 μm to obtain a test piece. 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-peroxide-based etchant, 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 gripped with a gripper, and the load (peel strength) when peeled off at room temperature at a speed of 50 mm/min in the thickness direction (perpendicular direction) of the test piece was measured. Table 2 shows the evaluation results. Here, in this specification, room temperature indicates 25°C.

[Evaluation of adhesion]
A laminate having a photosensitive layer was obtained in the same manner as described in [Evaluation of Resolution] except that the copper-clad laminate was replaced with a 6-inch silicon wafer (manufactured by Electronics End Materials Corporation). . The laminate was exposed entirely to 500 mJ/cm ² using an i-ray exposure device (UX-2240SM-XJ-01, manufactured by Ushio Inc., product number), and then exposed to 2000 mJ/cm ² using an ultraviolet exposure device. It was exposed to light and heated at 170° C. for 1 hour to obtain a silicon wafer having a cured film of the photosensitive resin composition. After that, an aluminum stud with an epoxy adhesive (adhesion part diameter: 2.7 mm, P/N 901106, manufactured by Phototechnica, trade name) was placed vertically on the cured film, and heated in an oven at 150°C for 1 hour. A time heat treatment was performed to obtain a test piece. A stud on the test piece was fixed to a chuck of a thin film adhesion strength measuring device (manufactured by Photo Technica Co., Ltd.), a force was applied perpendicularly to the cured film, and the state after that was evaluated according to the following criteria. Table 2 shows the evaluation results.
A: Cohesive failure occurred in the epoxy adhesive.
B: Peeling occurred at the interface between the cured film and the silicon wafer.

[Measurement of thermal expansion coefficient and glass transition point]
The dry film prepared above was exposed entirely to 500 mJ/cm ² using an i-ray exposure device (UX-2240SM-XJ-01, manufactured by Ushio Inc., product number), and allowed to stand at room temperature (25°C) for 1 hour. After that, the polyethylene film was peeled off, and the film was developed with a 1% by mass sodium carbonate aqueous solution at 30°C by spraying. After that, an ultraviolet irradiation device (manufactured by Oak Manufacturing Co., Ltd.) was used to irradiate ultraviolet rays at 2 J/cm ² , followed by heat treatment at 170° C. for 60 minutes. Next, after cutting out with a cutter knife to a width of 3 mm and a length of 30 mm, the polyethylene terephthalate film (carrier film) was peeled off to obtain a cured product for thermal expansion coefficient evaluation.
A TMA device (SS6000, manufactured by Seiko Instruments Inc., product number) was used to measure the coefficient of thermal expansion in a tensile mode. 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 apparatus, heated from room temperature (25° C.) to 160° C., and left for 15 minutes. Then, it was cooled to -60°C, and measured from -60°C to 250°C at 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 this embodiment of Examples 1 to 6 show excellent performance in terms of resolution, adhesive strength, and adhesion. 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 exhibit sufficient effects in terms of any one of resolution, adhesive strength and adhesion. It was also confirmed from the results of the coefficient of thermal expansion and the glass transition point that the photosensitive resin composition of this embodiment has excellent heat resistance and a low coefficient of thermal expansion.

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 protection film

Claims (16)

(A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an inorganic filler, (E) a silane compound and (I) an epoxy resin curing agent, The content of the inorganic filler (D) is 18 to 60% by mass based on the total solid content in the photosensitive resin composition, and the photopolymerization initiator (C) is selected from acetophenones and acylphosphine oxides. wherein the (D) inorganic filler contains silica, and the (E) silane compound contains alkylsilane, alkoxysilane, vinylsilane, epoxysilane, aminosilane, acrylicsilane, methacrylsilane, mercaptosilane, sulfidesilane , and A photosensitive resin composition comprising at least one selected from lufursilane, styrylsilane, and alkylchlorosilane. The component (A) comprises at least one acid-modified vinyl group-containing epoxy resin (A1) obtained by using a bisphenol novolac type epoxy resin (a1) and an epoxy resin (a2) different from the epoxy resin (a1). 2. The photosensitive resin composition according to claim 1, which contains at least one acid-modified vinyl group-containing epoxy resin (A2) used. 3. The photosensitive resin composition according to claim 2, wherein the epoxy resin (a2) is at least one selected from novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and triphenolmethane type epoxy resins. thing. The acid-modified vinyl group-containing epoxy resins (A1) and (A2) are resins (A1′) obtained by reacting the epoxy resins (a1) and (a2), respectively, with the vinyl group-containing monocarboxylic acid (b). 4. The photosensitive resin composition according to claim 2, which is a resin obtained by reacting (A2') with a saturated or unsaturated group-containing polybasic acid anhydride (c). Any one 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). 1. The photosensitive resin composition according to claim 1.

[In formula (I), R ¹¹ represents a hydrogen atom or a methyl group, and each Y ¹ independently represents a hydrogen atom or a glycidyl group. Plural R ¹¹ 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 each Y ² independently represents a hydrogen atom or a glycidyl group. Plural R ¹² 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). 6. The photosensitive resin composition according to any one of claims 2 to 5, which is a novolac type epoxy resin.

[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 photosensitive resin composition according to any one of claims 1 to 6, wherein the (B) photopolymerizable compound contains a compound having three or more ethylenically unsaturated bonds in the molecule. Contents of (A) acid-modified vinyl group-containing epoxy resin, (B) photopolymerizable compound, (C) photopolymerization initiator, (D) inorganic filler, (E) silane compound and (I) epoxy resin curing agent However, based on the total solid content in the photosensitive resin composition, each 5 to 60% by mass, 0.2 to 15% by mass, 0.1 to 10% by mass, 20 to 60% by mass, 0.5 to 30% by mass %, and 0.1 to 3% by mass, the photosensitive resin composition according to any one of claims 1 to 7. The photosensitive resin composition according to any one of claims 1 to 8, wherein (I) the epoxy resin curing agent contains melamine. The photosensitive resin composition according to any one of claims 1 to 9, further comprising (F) a pigment. The photosensitive resin composition according to any one of claims 1 to 10, further comprising (G) a curing agent. 12. The photosensitive resin composition according to claim 11, wherein the (G) curing agent contains an epoxy compound. 13. The photosensitive resin composition according to claim 12, wherein the epoxy compound is at least one selected from bisphenol F type epoxy resins and novolac type epoxy resins. A dry film comprising a carrier film and a photosensitive layer using the photosensitive resin composition according to any one of claims 1 to 13. A printed wiring board comprising at least one of a surface protective film and an interlayer insulating film formed from the photosensitive resin composition according to any one of claims 1 to 13. A step of providing a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 13 or the dry film according to claim 14, and 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.

Images