JP2022149899A - Photosensitive resin composition - Google Patents

Abstract

To provide a photosensitive resin composition enabling the production of a cured product that enables the formation of a via hole having a small diameter and suppresses the occurrence of an undercut.SOLUTION: A photosensitive resin composition contains (A-1) a resin having an ethylenically unsaturated group and a carboxyl group having a weight average molecular weight of 6,000 or less, (A-2) a resin containing an ethylenically unsaturated group and a carboxyl group having a weight average molecular weight larger than that of the component (A-1) by 2,000 or more, and (B) a photopolymerization initiator, wherein the molecular weight of the component (B) is 400 or more.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive resin composition. Furthermore, it relates to a support-attached photosensitive film, a printed wiring board, and a semiconductor device obtained by using the photosensitive resin composition.

A printed wiring board is sometimes provided with a solder resist as a permanent protective film to prevent solder from adhering to areas where solder is not required and to prevent corrosion of the circuit board. As a solder resist, for example, a photosensitive resin composition as described in Patent Document 1 is generally used.

JP 2014-115672 A

In recent years, along with the miniaturization and thinning of printed wiring boards, formation of small-diameter via holes is required.

However, the smaller the diameter of the via hole to be formed, the more likely the undercut will occur. Undercut is a phenomenon in which the contour shape of the via does not become the desired shape on the bottom side of the via, and the diameter expands. The diameter of the bottom corresponding to the bottom of the via hole is larger than the diameter of the top of the via hole.

An object of the present invention is to provide a photosensitive resin composition capable of forming via holes with a small diameter and capable of obtaining a cured product in which the occurrence of undercuts is suppressed; a support obtained using the photosensitive resin composition An object of the present invention is to provide a photosensitive film, a printed wiring board, and a semiconductor device.

As a result of intensive studies by the present inventors, a combination of two or more resins containing an ethylenically unsaturated group and a carboxyl group having different weight average molecular weights and a photopolymerization initiator having a molecular weight of 400 or more resulted in a small diameter The present inventors have found that it is possible to form a via hole and that a cured product in which the occurrence of undercuts is suppressed can be obtained, and have completed the present invention.

（式（Ｂ－１）中、Ｒ^１は活性光線吸収基を表し、Ｒ^２はそれぞれ独立に２価の炭化水素基を表す。ｎは１～１０の整数を表す。＊は結合手を表す。）
［７］ ソルダーレジスト形成用である、［１］～［６］のいずれかに記載の感光性樹脂組成物。
［８］ 支持体と、該支持体上に設けられた、［１］～［７］のいずれかに記載の感光性樹脂組成物を含む感光性樹脂組成物層と、を有する支持体付き感光性フィルム。
［９］ ［１］～［７］のいずれかに記載の感光性樹脂組成物の硬化物により形成された絶縁層を含むプリント配線板。
［１０］ 絶縁層が、層間絶縁材、及びソルダーレジストのいずれかである、［９］に記載のプリント配線板。
［１１］ ［９］又は［１０］に記載のプリント配線板を含む、半導体装置。 That is, the present invention includes the following contents.
[1] (A-1) a resin containing an ethylenically unsaturated group and a carboxyl group having a weight average molecular weight of 6000 or less,
(A-2) a resin containing an ethylenically unsaturated group and a carboxyl group having a weight average molecular weight 2000 or more greater than that of component (A-1), and (B) a photopolymerization initiator,
A photosensitive resin composition in which the component (B) has a molecular weight of 400 or more.
[2] The photosensitive resin composition according to [1], further comprising (C) an inorganic filler.
[3] The photosensitive resin composition according to [2], wherein the content of component (C) is 1% by mass or more based on 100% by mass of non-volatile components in the photosensitive resin composition.
[4] Components (A-1) and (A-2) have any one of a cresol novolak skeleton, bisphenol A skeleton, bisphenol F skeleton, biphenyl skeleton, and naphthol aralkyl skeleton [1] to [3] The photosensitive resin composition according to any one of .
[5] The photosensitive resin composition according to any one of [1] to [4], wherein the component (A-1) and the component (A-2) contain an epoxy (meth)acrylate containing an acid-modified cresol novolak skeleton. .
[6] The photosensitive resin composition according to any one of [1] to [5], wherein component (B) has a structural unit represented by the following formula (B-1).

(In formula (B-1), R ¹ represents an actinic ray absorbing group, R ² each independently represents a divalent hydrocarbon group, n represents an integer of 1 to 10, * represents a bond, .)
[7] The photosensitive resin composition according to any one of [1] to [6], which is for solder resist formation.
[8] A photosensitive material with a support, comprising a support and a photosensitive resin composition layer containing the photosensitive resin composition according to any one of [1] to [7] provided on the support. sex film.
[9] A printed wiring board comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of [1] to [7].
[10] The printed wiring board according to [9], wherein the insulating layer is either an interlayer insulating material or a solder resist.
[11] A semiconductor device including the printed wiring board according to [9] or [10].

According to the present invention, a photosensitive resin composition capable of forming a small-diameter via hole and capable of obtaining a cured product in which the occurrence of undercutting is suppressed; a support obtained using the photosensitive resin composition; A photosensitive film, a printed wiring board, and a semiconductor device can be provided.

The photosensitive resin composition, the photosensitive film with support, the printed wiring board, and the semiconductor device of the present invention are described in detail below.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention comprises (A-1) a resin containing an ethylenically unsaturated group and a carboxyl group having a weight average molecular weight of 6000 or less, and (A-2) 2000 or more from the component (A-1) It contains a resin containing an ethylenically unsaturated group and a carboxyl group having a large weight average molecular weight, and (B) a photopolymerization initiator, and the molecular weight of component (B) is 400 or more.

In the present invention, in addition to the components (A-1) and (A-2) having different weight-average molecular weights, a combination of the component (B) having a predetermined molecular weight makes it possible to form small-diameter via holes. , it is possible to obtain a cured product in which the occurrence of undercuts is suppressed. Moreover, in the present invention, it is also possible to obtain a cured product that is generally excellent in peel strength with the conductor layer, glass transition temperature (Tg), average coefficient of linear thermal expansion (CTE), and surface shape.

The photosensitive resin composition further optionally contains (C) an inorganic filler, (D) an epoxy resin, (E) a reactive diluent, (F) a solvent, and (G) other additives. may contain components of In this specification, the components (A-1) and (A-2) are sometimes collectively referred to as "(A) a resin containing an ethylenically unsaturated group and a carboxyl group". Each component contained in the photosensitive resin composition will be described in detail below.

<(A) Resin Containing Ethylenically Unsaturated Group and Carboxyl Group>
The photosensitive resin composition includes (A-1) a resin containing an ethylenically unsaturated group and a carboxyl group having a weight average molecular weight of 6000 or less, and (A-2) a weight that is 2000 or more greater than the component (A-1). It contains a resin containing an ethylenically unsaturated group with an average molecular weight and a carboxyl group. By using the component (A-1) and the component (A-2) together, it is possible to form via holes with a small diameter and obtain a cured product in which the generation of undercuts is suppressed.

The weight-average molecular weight of component (A-1) is 6000 or less, preferably 5500 or less, from the viewpoint of obtaining a cured product in which small-diameter via holes can be formed and undercuts are suppressed. is preferably 1000 or more, more preferably 1500 or more. The weight average molecular weight of component (A-1) is the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

The weight average molecular weight of component (A-2) is 2000 or more, preferably 2500 or more, higher than that of component (A-1). The upper limit is preferably 20,000 or less, more preferably 17,000 or less, and even more preferably 15,000 or less. The weight average molecular weight of component (A-2) can be measured by the same method as for the weight average molecular weight of component (A-1).

The specific weight average molecular weight of component (A-2) varies depending on the weight average molecular weight of component (A-1) used in combination, but is preferably 3000 or more, more preferably 3500 or more, and still more preferably 4000 or more. It is preferably 20,000 or less, more preferably 17,000 or less, and even more preferably 15,000 or less.

The ethylenically unsaturated groups in components (A-1) and (A-2) have a carbon-carbon double bond, such as vinyl, allyl, propargyl, butenyl, ethynyl, and phenylethynyl. group, maleimide group, nadimide group, and (meth)acryloyl group, and from the viewpoint of reactivity of photoradical polymerization, (meth)acryloyl group is preferred. A "(meth)acryloyl group" includes a methacryloyl group, an acryloyl group, and combinations thereof. Since the (A-1) component and the (A-2) component contain an ethylenically unsaturated group, photoradical polymerization is possible. The number of ethylenically unsaturated groups per molecule of components (A-1) and (A-2) may be one or two or more. Further, when component (A-1) and component (A-2) contain two or more ethylenically unsaturated groups per molecule, those ethylenically unsaturated groups may be the same or different. .

In addition, since the (A-1) component and the (A-2) component contain carboxyl groups, the photosensitive resin composition containing the (A-1) component and the (A-2) component is an alkaline solution (for example, 1% by mass sodium carbonate aqueous solution as an alkaline developer). The number of carboxyl groups per molecule of components (A-1) and (A-2) may be one or two or more.

The components (A-1) and (A-2) are compounds having different weight average molecular weights, having an ethylenically unsaturated group and a carboxyl group, and capable of photoradical polymerization and alkali development. Although there is no particular limitation, resins having both a carboxyl group and two or more ethylenically unsaturated groups in one molecule are preferred.

One aspect of the resin containing an ethylenically unsaturated group and a carboxyl group includes an acid-modified unsaturated epoxy ester resin obtained by reacting an epoxy compound with an unsaturated carboxylic acid and further with an acid anhydride. Specifically, an unsaturated epoxy ester resin is obtained by reacting an epoxy compound with an unsaturated carboxylic acid, and an acid-modified unsaturated epoxy ester resin can be obtained by reacting the unsaturated epoxy ester resin with an acid anhydride.

As the epoxy compound, any compound having an epoxy group in the molecule can be used. For example, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin. , bisphenol S-type epoxy resin, modified bisphenol F-type epoxy resin obtained by reacting epichlorohydrin with bisphenol F-type epoxy resin to modify it to be trifunctional or higher; bisphenol-type epoxy resin; biphenol-type epoxy resin, tetramethylbiphenol type Novolac epoxy resins such as phenol novolak epoxy resins, cresol novolac epoxy resins, bisphenol A novolac epoxy resins, and alkylphenol novolac epoxy resins; bisphenol AF epoxy resins, and perfluoroalkyl epoxy resins Fluorine-containing epoxy resins such as resins; naphthalene type epoxy resin, dihydroxynaphthalene type epoxy resin, polyhydroxy binaphthalene type epoxy resin, naphthol type epoxy resin, naphthol aralkyl type epoxy resin, binaphthol type epoxy resin, naphthylene ether type epoxy resin naphthol Epoxy resins having a naphthalene skeleton (naphthalene skeleton-containing epoxy resins), such as novolac-type epoxy resins, naphthalene-type epoxy resins obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes; bixylenol-type epoxy resins; dicyclopentadiene-type epoxy resins trisphenol type epoxy resin; tert-butyl-catechol type epoxy resin; epoxy resin containing condensed ring skeleton such as anthracene type epoxy resin; glycidylamine type epoxy resin; glycidyl ester type epoxy resin; biphenyl type epoxy resin; Aliphatic epoxy resin; epoxy resin having a butadiene structure; alicyclic epoxy resin; heterocyclic epoxy resin; spiro ring-containing epoxy resin; cyclohexanedimethanol type epoxy resin; trimethylol type epoxy resin; Glycidyl group-containing acrylic resins such as polyglycidyl (meth)acrylate, copolymers of glycidyl methacrylate and acrylic acid ester; fluorene type epoxy resins; halogenated epoxy resins and the like.

From the viewpoint of reducing the average coefficient of linear thermal expansion, the epoxy compound is preferably an epoxy resin containing an aromatic skeleton. Here, the aromatic skeleton is a concept including polycyclic aromatics and aromatic heterocycles. Among them, any one of cresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, and naphthol aralkyl type epoxy resin is preferable. As a result, from the viewpoint of further reducing the average coefficient of linear thermal expansion of the cured product of the resin composition, cresol novolak type epoxy resins, biphenyl type epoxy resins, and naphthol aralkyl type epoxy resins are more preferable, and cresol novolac type epoxy resins are more preferable. More preferred.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, cinnamic acid and crotonic acid, and these may be used alone or in combination of two or more. Among them, acrylic acid and methacrylic acid are preferable from the viewpoint of improving the photocurability of the photosensitive resin composition. In this specification, the epoxy ester resin that is the reaction product of the above epoxy compound and (meth)acrylic acid may be referred to as "epoxy (meth)acrylate", where the epoxy group of the epoxy compound is It is substantially extinguished by the reaction with (meth)acrylic acid. "(Meth)acrylate" refers to methacrylate and acrylate. Acrylic acid and methacrylic acid are sometimes collectively referred to as "(meth)acrylic acid".

Examples of acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid di Anhydrides, etc., may be mentioned, and any one of these may be used alone, or two or more thereof may be used in combination. Among these, succinic anhydride and tetrahydrophthalic anhydride are preferred from the viewpoint of improving the resolution and insulation reliability of the cured product, and tetrahydrophthalic anhydride is more preferred.

In obtaining the acid-modified unsaturated epoxy ester resins of the components (A-1) and (A-2), the unsaturated carboxylic acid and the epoxy resin are reacted in the presence of a catalyst to obtain the unsaturated epoxy ester resin, An unsaturated epoxy ester resin and an acid anhydride may be reacted. Moreover, you may use a solvent and a polymerization inhibitor as needed.

The acid-modified unsaturated epoxy ester resin in components (A-1) and (A-2) may have any one of a cresol novolak skeleton, bisphenol A skeleton, bisphenol F skeleton, biphenyl skeleton, and naphthol aralkyl skeleton. preferable. Acid-modified epoxy (meth)acrylates are preferred as the acid-modified unsaturated epoxy ester resins in the components (A-1) and (A-2). The “epoxy” in the acid-modified unsaturated epoxy ester resin represents a structure derived from the epoxy compound described above. For example, "acid-modified bisphenol-type epoxy (meth)acrylate" is an acid-modified unsaturated epoxy ester resin obtained by using a bisphenol-type epoxy resin as an epoxy compound and using (meth)acrylic acid as an unsaturated carboxylic acid. point to The preferred range of acid-modified epoxy (meth)acrylates is derived from the preferred range of epoxy compounds. That is, from the viewpoint of lowering the average coefficient of linear thermal expansion of the cured product of the resin composition, the acid-modified unsaturated epoxy ester resin includes an acid-modified cresol novolac skeleton-containing epoxy (meth)acrylate and an acid-modified bisphenol A skeleton-containing epoxy (meth)acrylate. ) acrylate, acid-modified bisphenol F skeleton-containing epoxy (meth) acrylate, biphenyl skeleton-containing epoxy (meth) acrylate, naphthol aralkyl skeleton-containing epoxy (meth) acrylate, acid-modified cresol novolak skeleton-containing epoxy (meth) acrylate, biphenyl skeleton Epoxy (meth)acrylates containing epoxy (meth)acrylates and naphthol aralkyl skeleton-containing epoxy (meth)acrylates are more preferable, and epoxy (meth)acrylates containing acid-modified cresol novolak skeletons are even more preferable. Acid-modified cresol novolak skeleton-containing epoxy (meth)acrylate is a compound obtained by reacting an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride with a reaction product of a cresol novolac-type epoxy resin and (meth)acrylate. is. Acid-modified bisphenol A skeleton-containing epoxy (meth)acrylate is a compound obtained by reacting a reaction product of bisphenol A type epoxy resin and (meth)acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. is. Acid-modified bisphenol F skeleton-containing epoxy (meth)acrylate is a compound obtained by reacting a reaction product of bisphenol F type epoxy resin and (meth)acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. is. Acid-modified biphenyl skeleton-containing epoxy (meth)acrylate is a compound obtained by reacting a reaction product of biphenyl-type epoxy resin and (meth)acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. . Acid-modified naphthol aralkyl skeleton-containing epoxy (meth) acrylate is a compound obtained by reacting a reaction product of naphthol aralkyl epoxy resin and (meth) acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. is.

A commercially available product can be used as the acid-modified unsaturated epoxy ester resin in the component (A). Specific examples of the acid-modified unsaturated epoxy ester resin as the component (A-1) include "CCR-1373H" (cresol novolac type epoxy acrylate) and "ZCR-8001H" (acid-modified biphenyl type epoxy acrylate) manufactured by Nippon Kayaku Co., Ltd. epoxy acrylate), "ZCR-1569H" (acid-modified biphenyl-type epoxy acrylate: reaction product of biphenyl-type epoxy resin, acrylic acid, and acid anhydride). These may be used individually by 1 type, and may be used in combination of 2 or more type.

Specific examples of the acid-modified unsaturated epoxy ester resin as the component (A-2) include "CCR-1171H" (cresol novolac type epoxy acrylate) and "ZCR-1797H" (acid-modified biphenyl type epoxy acrylate) manufactured by Nippon Kayaku Co., Ltd. epoxy acrylate), Nippon Kayaku's "ZAR-2000" (a reaction product of bisphenol A type epoxy resin, acrylic acid, and succinic anhydride), "ZFR-1491H", "ZFR-1533H" (bisphenol F type epoxy resin, acrylic acid, and reaction product of tetrahydrophthalic anhydride), "PR-300CP" manufactured by Showa Denko Co., Ltd. (reaction product of cresol novolak type epoxy resin, acrylic acid, and acid anhydride), manufactured by Nippon Kayaku Co., Ltd. "CCR-1179" (cresol novolac F-type epoxy acrylate) and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The acid value of component (A-1) and component (A-2) is preferably 0.1 mgKOH/g or more from the viewpoint of improving the alkali developability of the photosensitive resin composition. More preferably 0.5 mgKOH/g or more, more preferably 1 mgKOH/g or more, 10 mgKOH/g or more, 20 mgKOH/g or more, 30 mgKOH/g or more, 40 mgKOH/g or more, 50 mgKOH/g or more. On the other hand, the acid value is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, from the viewpoint of suppressing the elution of the fine pattern of the cured product by development and improving the insulation reliability. It is preferably 100 mgKOH/g or less, and more preferably 100 mgKOH/g or less. Here, the acid value is the residual acid value of the carboxyl groups present in the component (A), and the acid value can be measured by the following method. First, about 1 g of the resin solution to be measured is accurately weighed, and then 30 g of acetone is added to the resin solution to uniformly dissolve the resin solution. Next, an appropriate amount of phenolphthalein as an indicator is added to the solution, and titration is performed using a 0.1N aqueous ethanol solution. Then, the acid value is calculated by the following formula.
Formula: A = 10 x (Vf-BL) x F x 56.11 / (Wp x I)

In the above formula, A represents the acid value (mgKOH / g), Vf is the titration amount of KOH (mL), BL is the blank, F is the factor (potency), and Wp is the measured resin solution mass (g). and I represents the non-volatile content (% by mass) of the measured resin solution.

In the production of components (A-1) and (A-2), from the viewpoint of improving storage stability, the number of moles of epoxy groups in the epoxy resin and the total number of carboxyl groups of the unsaturated carboxylic acid and the acid anhydride is preferably in the range of 1:0.8 to 1.3, more preferably in the range of 1:0.9 to 1.2.

The total content of the component (A-1) and the component (A-2) is 10% by mass when the non-volatile component of the photosensitive resin composition is 100% by mass from the viewpoint of improving the alkali developability. % or more, more preferably 20 mass % or more, and even more preferably 25 mass % or more. From the viewpoint of improving heat resistance, the upper limit is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less. In the present invention, the content of each component in the photosensitive resin composition is a value when the non-volatile component in the photosensitive resin composition is 100% by mass, unless otherwise specified.

From the viewpoint of improving alkali developability, the content of component (A-1) is preferably 5% by mass or more when the non-volatile component of the photosensitive resin composition is 100% by mass, and 8% by mass. It is more preferable that the content be 10% by mass or more, and more preferably 10% by mass or more. From the viewpoint of improving heat resistance, the upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

From the viewpoint of improving alkali developability, the content of component (A-2) is preferably 5% by mass or more when the non-volatile component of the photosensitive resin composition is 100% by mass, and 8% by mass. It is more preferable that the content be 10% by mass or more, and more preferably 10% by mass or more. From the viewpoint of improving heat resistance, the upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

When the non-volatile component of the photosensitive resin composition is 100% by mass, the content of component (A-1) is defined as a1 (% by mass), and the content of component (A-2) is defined as a2 (% by mass). When, from the viewpoint of improving resolution, a1/a2 is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, preferably 10 or less, more preferably 8 or less, more preferably 5 or less.

<(B) Photoinitiator>
The photosensitive resin composition contains (B) a photopolymerization initiator as the (B) component. Component (B) has a molecular weight of 400 or more. By including the component (B) in the photosensitive resin composition, it is possible to suppress the occurrence of undercuts and obtain a cured product having excellent peel strength even if the arithmetic mean roughness (Ra) is small.

The molecular weight of the component (B) is 400 or more, preferably 500 or more, from the viewpoint of suppressing the occurrence of undercuts and obtaining a cured product having excellent peel strength even if the arithmetic average roughness (Ra) is small. It is preferably 600 or more and 700 or more. Although the upper limit is not particularly limited, it is preferably 3,000 or less, more preferably 2,500 or less, and still more preferably 2,000 or less.

（式（Ｂ－１）中、Ｒ^１は活性光線吸収基を表し、Ｒ^２はそれぞれ独立に２価の炭化水素基を表す。ｎは１～１０の整数を表す。＊は結合手を表す。） As the component (B), a compound that has a molecular weight of 400 or more, has a group that absorbs actinic rays such as ultraviolet rays, and can be efficiently photocured can be used. Such a component (B) is preferably, for example, a compound containing a structural unit represented by formula (B-1).

(In formula (B-1), R ¹ represents an actinic ray absorbing group, R ² each independently represents a divalent hydrocarbon group, n represents an integer of 1 to 10, * represents a bond, .)

R ¹ represents an actinic ray absorbing group. The actinic ray absorbing group is a group capable of absorbing actinic rays such as ultraviolet rays. The actinic ray-absorbing group may be any functional group capable of absorbing actinic rays. , a group having a xanthone skeleton, a group having an acetophenone skeleton, a group having a benzoin skeleton, a group having a thioxanthone skeleton, a group having a benzoate skeleton, and the like.

Specific examples of actinic ray absorbing groups include the following groups (i) to (vii). Among them, any one of (i) and (ii) is preferable as the actinic ray absorbing group. In the formula, * represents a bond.

Each ^R2 independently represents a divalent hydrocarbon group. The divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group, and from the viewpoint of significantly obtaining the effects of the present invention, a divalent aliphatic hydrocarbon group is preferable.

The divalent aliphatic hydrocarbon group is preferably a divalent saturated aliphatic hydrocarbon group, such as an alkylene group or an alkenylene group, with an alkylene group being more preferred. The alkylene group may be linear, branched or cyclic, preferably linear. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 3 carbon atoms. is more preferred. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a cyclohexylene group and the like, and a methylene group is preferred. The alkenylene group may be linear, branched or cyclic, preferably linear. The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and even more preferably an alkenylene group having 2 to 5 carbon atoms.

An arylene group, a heteroarylene group, etc. are mentioned as a bivalent aromatic hydrocarbon group. As the arylene group and heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferable, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferable.

A divalent hydrocarbon group may have a substituent. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, arylalkyl groups, silyl groups, acyl groups, acyloxy groups, carboxy groups, sulfo groups, cyano groups, nitro groups, hydroxy groups, mercapto groups, An oxo group and the like can be mentioned.

n represents an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and even more preferably an integer of 1 to 3.

（一般式（Ｂ－２）中、Ｒ^１１はそれぞれ独立に活性光線吸収基を表し、Ｒ^１２はそれぞれ独立に２価の炭化水素基を表し、Ｒ^１３はｍ価の炭化水素基を表す。ｎ１は１～１０の整数を表し、ｍは１～４の整数を表す。
一般式（Ｂ－３）中、Ｒ^２１、Ｒ^２３はそれぞれ独立に活性光線吸収基を表し、Ｒ^２２はそれぞれ独立に２価の炭化水素基を表す。ｎ２は１～１０の整数を表す。） Component (B) preferably contains either a compound represented by the following general formula (B-2) or a compound represented by the following general formula (B-3).

(In general formula (B-2), each R ¹¹ independently represents an actinic ray absorbing group, each R ¹² independently represents a divalent hydrocarbon group, and each R ¹³ represents an m-valent hydrocarbon group. n1 represents an integer of 1-10, and m represents an integer of 1-4.
In general formula (B-3), R ²¹ and R ²³ each independently represent an actinic ray absorbing group, and R ²² each independently represents a divalent hydrocarbon group. n2 represents an integer of 1-10. )

Each R ¹¹ independently represents an actinic ray absorbing group, which is the same as the actinic ray absorbing group represented by R ¹ in formula (B-1).

Each R ¹² independently represents a divalent hydrocarbon group and is the same as the divalent hydrocarbon group represented by R ² in formula (B-1).

^R13 represents an m-valent hydrocarbon group. The m-valent hydrocarbon group includes an m-valent aliphatic hydrocarbon group and an m-valent aromatic hydrocarbon group, preferably an m-valent aliphatic hydrocarbon group. For example, when m is 3, an alkynylene group is preferred. Specific examples of the group represented by R ¹³ include those shown below. In the formula, "*" represents a bond.

n1 represents an integer of 1 to 10 and is the same as n in formula (B-1).

m represents an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 3.

R ²¹ and R ²³ each independently represent an actinic ray absorbing group and are the same as the actinic ray absorbing group represented by R ¹ in formula (B-1).

Each R ²² independently represents a divalent hydrocarbon group and is the same as the divalent hydrocarbon group represented by R ² in formula (B-1).

(B) A commercial item can be used for a component. Examples of commercially available products include "Omnipol 910" and "Omnipol TP" manufactured by IGM.

The content of the component (B) is such that the occurrence of undercuts is suppressed, and the non-volatile component of the photosensitive resin composition is 100% from the viewpoint of obtaining a cured product having excellent peel strength even if the arithmetic mean roughness (Ra) is small. When expressed as % by mass, the content is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more. From the viewpoint of improving heat resistance, the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

<(C) Inorganic filler>
The photosensitive resin composition may further contain (C) an inorganic filler as an optional component. By containing the component (C), a cured product having a low average coefficient of linear thermal expansion can be obtained. (C) component may be used individually by 1 type, and may be used in combination of 2 or more types.

(C) The material of the inorganic filler is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate , titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica and barium sulfate are preferred, and silica is particularly preferred. As silica, spherical silica is preferable. (C) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types.

(C) The average particle diameter of the inorganic filler is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less, 2 μm or less, 1 μm or less, or 0 μm or less, from the viewpoint of obtaining a cured product having a low average linear thermal expansion coefficient. 0.7 μm or less. The lower limit of the average particle diameter is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, and still more preferably 0.07 μm or more, 0.1 μm or more, or 0.2 μm or more. be.

The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering particle size distribution analyzer, and the median diameter thereof can be used as the average particle size for measurement. As the measurement sample, one obtained by ultrasonically dispersing an inorganic filler in water can be preferably used. As the laser diffraction scattering type particle size distribution analyzer, Horiba's "LA-500", Shimadzu Corporation's "SALD-2200" and the like can be used.

(C) The specific surface area of the inorganic filler is preferably 1 m ² /g or more, more preferably 3 m ² /g or more, and particularly preferably 5 m ² /g or more, from the viewpoint of obtaining a cured product having a low average linear thermal expansion coefficient. is. Although there is no particular upper limit, it is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method and calculating the specific surface area using the BET multipoint method. .

(C) Inorganic fillers include vinylsilane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, from the viewpoint of improving moisture resistance and dispersibility. It is preferably treated with one or more surface treatment agents such as alkoxysilane compounds, organosilazane compounds and titanate coupling agents. Examples of commercially available surface treatment agents include "KBM-1003" (vinyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "KBM-803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE-903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM-103" (phenyltrimethoxysilane), Shin-Etsu Chemical "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Kogyo Co., Ltd. and the like can be mentioned.

(C) An inorganic filler can use a commercial item. Commercial products include, for example, Admatechs "SC2050", "SC4050", "SO-C4", "SO-C2", "SO-C1", "Admafine", Denki Kagaku Kogyo "SFP series" ”, Nippon Steel & Sumikin Materials Co., Ltd. “SP (H) Series”, Sakai Chemical Industry Co., Ltd. “Sciqas Series”, Nippon Shokubai Co., Ltd. “Seahoster Series”, Nippon Steel & Sumikin Materials Co., Ltd. “AZ Series”, “AX series”, “B series” and “BF series” manufactured by Sakai Chemical Industry Co., Ltd., and the like.

(C) The content of the inorganic filler is preferably 1% by mass or more, when the non-volatile component in the photosensitive resin composition is 100% by mass, from the viewpoint of obtaining a cured product having a low average coefficient of linear thermal expansion. It is preferably 3% by mass or more, more preferably 5% by mass or more, 10% by mass or more, 20% by mass or more, and 30% by mass or more. From the viewpoint of obtaining excellent developability by suppressing light reflection during exposure, the upper limit is, for example, preferably 65% by mass or less, more preferably 60% by mass or less, further preferably 55% by mass or less, and 50% by mass or less. , 40% by mass or less.

<(D) Epoxy resin>
The photosensitive resin composition may further contain (D) an epoxy resin as an optional component. By including the component (D), the insulation reliability of the cured product of the photosensitive resin composition can be improved. However, the (D) component here does not include (A) an epoxy resin containing an ethylenically unsaturated group and a carboxyl group. Component (D) may be used singly or in combination of two or more.

Component (D) includes, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin. resins, naphthol novolak-type epoxy resins, phenol novolak-type epoxy resins, tert-butyl-catechol-type epoxy resins, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, glycidylamine-type epoxy resins, glycidyl ester-type epoxy resins, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedioxy Methanol-type epoxy resin, naphthylene ether-type epoxy resin, trimethylol-type epoxy resin, tetraphenylethane-type epoxy resin, tetraglycidyldiaminodiphenylmethane-type epoxy resin, and the like. Among them, the component (D) is preferably a biphenyl type epoxy resin. Epoxy resins may be used singly or in combination of two or more.

The resin composition preferably contains, as component (D), an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of obtaining the desired effect of the present invention remarkably, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass with respect to 100% by mass of the non-volatile components of the component (D). Above, more preferably 60% by mass or more, particularly preferably 70% by mass or more.

Epoxy resins include liquid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “liquid epoxy resins”) and solid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “solid epoxy resins”). ). As component (D), the resin composition may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. However, from the viewpoint of significantly obtaining the desired effect of the present invention, it is preferable to contain only solid epoxy resin.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin, and more preferably biphenyl type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP -7200H" (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" ( Naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "ESN485" manufactured by Nippon Steel Chemical & Materials " (naphthol novolac type epoxy resin); Mitsubishi Chemical Corporation "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin); Mitsubishi Chemical Corporation "YX4000HK" (bixylenol type epoxy resin); Mitsubishi Chemical "YX8800" (anthracene type epoxy resin) manufactured by the company; "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation. . These may be used individually by 1 type, and may be used in combination of 2 or more types.

A liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.

Examples of liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolak type epoxy resin, ester skeleton. An alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferred. As the glycidylamine type epoxy resin, a tetraglycidyldiaminodiphenylmethane type epoxy resin is preferable.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC; 828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical Corporation "jER807", "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical Corporation "jER152" (phenol novolac type epoxy resin); Mitsubishi Chemical Corporation "630", "630LSD" (glycidylamine type epoxy resin); Nippon Steel Chemical & Materials "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX Co., Ltd. "EX-721" (glycidyl ester type epoxy resin); "Celoxide 2021P" manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); "PB-3600" manufactured by Daicel (epoxy resin having a butadiene structure) Nippon Steel Chemical & Materials "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin); Sumitomo Chemical Co., Ltd. "ELM-434L", (glycidylamine type epoxy resin); Sumitomo Chemical "ELM-434VL" (tetraglycidyldiaminodiphenylmethane type epoxy resin) manufactured by ADEKA; "EP-3980S" (bifunctional glycidylamine type epoxy resin) manufactured by ADEKA; "EP-3950L" (trifunctional glycidyl amine type epoxy resin); Nissan Chemical Co., Ltd. "TEPIC-VL" (isocyanuric ring type epoxy resin); Sumitomo Chemical Co., Ltd. "ELM-100H" (N-[2-methyl-4-(oxiranylmethoxy) phenyl]-N-(oxiranylmethyl)oxiranemethanamine) and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

When a combination of a liquid epoxy resin and a solid epoxy resin is used as component (D), the ratio by mass (liquid epoxy resin: solid epoxy resin) is preferably 1:0.01 to 1:0. 20, more preferably 1:0.1 to 1:10, particularly preferably 1:0.5 to 1:5. The desired effect of the present invention can be remarkably obtained by setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range. Furthermore, it usually provides moderate tackiness when used in the form of a supported photosensitive film. In addition, when used in the form of a support-attached photosensitive film, sufficient flexibility is usually obtained to improve handleability. Furthermore, usually, a cured product having sufficient breaking strength can be obtained.

The epoxy equivalent of component (D) is preferably 50 g/eq. ~5000g/eq. , more preferably 50 g/eq. ~3000g/eq. , more preferably 80 g/eq. ~2000g/eq. , even more preferably 110 g/eq. ~1000g/eq. is. Within this range, the crosslink density of the cured product of the resin composition layer is sufficient, and an insulating layer with a small surface roughness can be obtained. Epoxy equivalent weight is the weight of an epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of component (D) is preferably 100 to 5,000, more preferably 200 to 3,000, and still more preferably 250 to 1,500 from the viewpoint of significantly obtaining the desired effects of the present invention. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, the content of component (D) is preferably 1% by mass or more, or more when the non-volatile component in the resin composition is 100% by mass. It is preferably 5% by mass or more, more preferably 10% by mass or more. The upper limit of the epoxy resin content is preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

<(E) Reactive diluent>
The photosensitive resin composition may further contain (E) a reactive diluent as an optional component. However, components corresponding to components (A), (B) and (D) are not included in component (E). Photoreactivity can be improved by including the component (E) in the photosensitive resin composition. Component (E) can be, for example, a photosensitive (meth)acrylate compound that is liquid, solid or semi-solid at room temperature and has one or more (meth)acryloyl groups in one molecule. Room temperature represents about 25°C. (E) component may be used individually by 1 type, and may be used in combination of 2 or more types.

Representative photosensitive (meth)acrylate compounds include, for example, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate, and glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol. Mono- or diacrylates, acrylamides such as N,N-dimethylacrylamide and N-methylol acrylamide, aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate, trimethylolpropane, pentaerythritol and dipentaerythritol polyhydric acrylates of ethylene oxide, propylene oxide or ε-caprolactone adducts thereof, phenols such as phenoxy acrylate and phenoxyethyl acrylate, or acrylates such as ethylene oxide or propylene oxide adducts thereof, trimethylolpropane Examples include epoxy acrylates derived from glycidyl ethers such as triglycidyl ether, modified epoxy acrylates, melamine acrylates, and/or methacrylates corresponding to the above acrylates. Among these, polyvalent acrylates or polyvalent methacrylates are preferable. For example, trivalent acrylates or methacrylates include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane EO-added tri(meth)acrylate, glycerin PO-added tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetrafurfuryl alcohol oligo(meth)acrylate, ethyl carbitol oligo(meth)acrylate, 1,4-butanediol Oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate ) acrylates, N,N,N′,N′-tetrakis(β-hydroxyethyl)ethyldiamine (meth)acrylic acid esters, and trivalent or higher acrylates or methacrylates include tri(2- (Meth)acryloyloxyethyl)phosphate, tri(2-(meth)acryloyloxypropyl)phosphate, tri(3-(meth)acryloyloxypropyl)phosphate, tri(3-(meth)acryloyl-2-hydroxyloxypropyl) Phosphate, di(3-(meth)acryloyl-2-hydroxyloxypropyl)(2-(meth)acryloyloxyethyl)phosphate, (3-(meth)acryloyl-2-hydroxyloxypropyl)di(2-(meth) Phosphoric acid triester (meth)acrylates such as acryloyloxyethyl)phosphate may be mentioned. Any one of these photosensitive (meth)acrylate compounds may be used alone, or two or more thereof may be used in combination. "EO" refers to ethylene oxide;

(E) A commercially available product can be used as the reaction diluent. Examples of commercially available products include "DPHA" manufactured by Nippon Kayaku Co., Ltd., and "EBECRYL3708" manufactured by Daicel Ornex.

(E) The content of the component is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, and 20% by mass or less , 10% by mass or less.

<(F) Organic solvent>
The photosensitive resin composition may further contain (F) an organic solvent as an optional component. The varnish viscosity can be adjusted by including the component (F). (F) Examples of organic solvents include ketones such as methyl ethyl ketone (MEK) and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, and propylene. Glycol ethers such as glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether Esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate and ethyl diglycol acetate , octane, and decane; and petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These are used individually by 1 type or in combination of 2 or more types. When using an organic solvent, the content can be appropriately adjusted from the viewpoint of coating properties of the photosensitive resin composition.

<(G) Other Additives>
The photosensitive resin composition may further contain (G) other additives to the extent that the object of the present invention is not impaired. (G) Other additives include, for example, thermoplastic resins, organic fillers, fine particles such as melamine and organic bentonite, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, Colorants such as naphthalene black, polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol and pyrogallol, thickeners such as bentone and montmorillonite, silicone-based, fluorine-based, and vinyl resin-based defoaming agents, Flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus compounds, aromatic condensed phosphate esters, halogen-containing condensed phosphate esters, phenolic curing agents, heat such as cyanate ester curing agents Various additives such as curable resins can be added.

The photosensitive resin composition is prepared by mixing the above (A) to (B) components as essential components, and appropriately mixing the above (C) to (G) components as optional components. A resin varnish can be produced by kneading or stirring with a kneading means such as a ball mill, bead mill or sand mill, or a stirring means such as a super mixer, planetary mixer or high-speed rotating mixer.

<Physical properties and uses of the photosensitive resin composition>
Since the photosensitive resin composition contains the components (A-1) and (A-2), it exhibits excellent resolution. Specifically, when a via hole is formed by exposing and developing the photosensitive resin composition, the minimum opening diameter (minimum via diameter) of the via hole that can be formed without causing residue and peeling can be reduced. The minimum opening diameter is preferably 60 μm or less, more preferably less than 50 μm. Although the lower limit is not particularly limited, it can be, for example, 1 μm or more. The minimum aperture diameter can be measured according to the method described in Examples below.

Since the photosensitive resin composition contains the components (A-1) and (A-2), it exhibits excellent resolution. Specifically, when a via hole is formed by exposing and developing a photosensitive resin composition, a via hole in which the occurrence of undercutting is suppressed can be formed. It is possible to form a via hole having a shape with a small or no difference in . Specifically, the top radius (μm) and the bottom radius (μm) of the cross section of a via hole with an opening diameter of 50 μm are measured by SEM. Find the difference between the top radius and the bottom radius (top radius - bottom radius). The result is preferably less than 3 μm, more preferably no undercut (0 μm). The evaluation of undercut can be measured according to the method described in Examples below.

After photocuring the photosensitive resin composition, the cured product obtained by heat curing at 180° C. for 30 minutes can increase the peel strength (adhesion) between the conductor layer formed by plating. Therefore, when an insulating layer and a solder resist are formed from this cured product, an insulating layer having high peel strength between itself and the plating conductor layer can be obtained. The peel strength may preferably be 0.30 kgf/cm or more. The upper limit of the peel strength is not particularly limited, but can be, for example, 10.0 kgf/cm or less. The peel strength can be measured according to the method described in the examples below.

The roughened surface after roughening the surface of the cured product obtained by photocuring the photosensitive resin composition and further heat-curing at 180 ° C. for 30 minutes usually exhibits the characteristic that the arithmetic average roughness (Ra) is low. . Thus, said cured product provides an insulating layer with a low arithmetic mean roughness. The arithmetic mean roughness is preferably 400 nm or less, more preferably 200 nm or less, still more preferably less than 200 nm. On the other hand, the lower limit of the arithmetic mean roughness can be 1 nm or more. Evaluation of the arithmetic mean roughness can be measured according to the method described in Examples below.

A cured product obtained by photocuring the photosensitive resin composition and then thermally curing the composition at 170° C. for 1 hour usually exhibits a high glass transition temperature (Tg). That is, an insulating layer and a solder resist having a high glass transition temperature are obtained. The glass transition temperature is preferably above 150°C. Although the upper limit is not particularly limited, it may be 350° C. or less. The glass transition temperature (Tg) can be measured according to the method described in Examples below.

A cured product obtained by photocuring the photosensitive resin composition and then thermally curing the composition at 170° C. for 1 hour usually exhibits a low average coefficient of linear thermal expansion (CTE). That is, an insulating layer and a solder resist having a low average linear thermal expansion coefficient are obtained. The average coefficient of linear thermal expansion is preferably 70 ppm or less, more preferably 50 ppm or less, and even more preferably less than 50 ppm. Although the lower limit is not particularly limited, it may be 10 ppm or more. The average linear thermal expansion coefficient can be measured according to the method described in Examples below.

Applications of the photosensitive resin composition of the present invention are not particularly limited, but include photosensitive films with supports, insulating resin sheets such as prepreg, circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underlays, etc. - It can be used in a wide range of applications that require a photosensitive resin composition, such as filling materials, die bonding materials, semiconductor sealing materials, hole-filling resins, and part-embedding resins. Among them, a photosensitive resin composition for an insulating layer of a printed wiring board (a printed wiring board having a cured product of a photosensitive resin composition as an insulating layer), a photosensitive resin composition for an interlayer insulating layer (a photosensitive resin composition Printed wiring board with a cured product as an interlayer insulating layer (interlayer insulating material)), photosensitive resin composition for plating (printed wiring board in which plating is formed on the cured product of the photosensitive resin composition), and solder resist (printed wiring board using a cured product of the photosensitive resin composition as a solder resist).

[Photosensitive film with support]
The photosensitive resin composition of the present invention can be suitably used in the form of a support-attached photosensitive film in which a photosensitive resin composition layer is formed on a support. That is, the support-attached photosensitive film includes a support and a photosensitive resin composition layer formed of the photosensitive resin composition of the present invention provided on the support.

Examples of the support include polyethylene terephthalate film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, triacetyl acetate film and the like, and polyethylene terephthalate film is particularly preferred.

Commercially available supports include, for example, product names “Alphan MA-410” and “E-200C” manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and product name “PS-25” manufactured by Teijin Limited. Polyethylene terephthalate films such as the PS series, etc., but not limited to these. In order to facilitate removal of the photosensitive resin composition layer, these supports are preferably coated with a release agent such as a silicone coating agent on the surface. The thickness of the support is preferably in the range of 5 μm to 50 μm, more preferably in the range of 10 μm to 25 μm. By setting the thickness to 5 μm or more, it is possible to suppress breakage of the support when the support is peeled off before development. Resolution can be improved. Also preferred are supports with low fisheyes. Here, fisheye refers to foreign substances, undissolved substances, oxidized substances, etc. of the material being incorporated into the film when the film is produced by heat-melting the material, kneading, extruding, biaxial stretching, casting, etc. It is a thing.

In order to reduce light scattering during exposure by actinic rays such as ultraviolet rays, the support preferably has excellent transparency. Specifically, the support preferably has a turbidity (haze standardized by JIS-K6714) of 0.1 to 5, which is an index of transparency. Furthermore, the photosensitive resin composition layer may be protected with a protective film.

By protecting the photosensitive resin composition layer side of the support-attached photosensitive film with a protective film, it is possible to prevent dust from adhering to the surface of the photosensitive resin composition layer and scratches on the surface of the photosensitive resin composition layer. As the protective film, a film made of the same material as the support can be used. Although the thickness of the protective film is not particularly limited, it is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, even more preferably in the range of 10 μm to 30 μm. When the thickness is 1 μm or more, the handleability of the protective film can be improved, and when the thickness is 40 μm or less, the cost tends to be improved. The protective film preferably has a lower adhesive strength between the photosensitive resin composition layer and the protective film than the adhesive strength between the photosensitive resin composition layer and the support.

A support-attached photosensitive film can be produced, for example, by preparing a resin varnish by dissolving the photosensitive resin composition of the present invention in an organic solvent, applying the resin varnish on a support, and removing the organic solvent by heating or blowing with hot air. can be produced by drying to form a photosensitive resin composition layer. Specifically, first, after completely removing bubbles in the photosensitive resin composition by a vacuum defoaming method or the like, the photosensitive resin composition is applied onto a support, and the solvent is removed in a hot air oven or a far-infrared oven. A support-attached photosensitive film can be produced by removing, drying, and optionally laminating a protective film on the obtained photosensitive resin composition layer. Specific drying conditions vary depending on the curability of the photosensitive resin composition and the amount of organic solvent in the resin varnish. can be dried for 3 to 13 minutes. The amount of residual organic solvent in the photosensitive resin composition layer is preferably 5% by mass or less with respect to the total amount of the photosensitive resin composition layer from the viewpoint of preventing diffusion of the organic solvent in subsequent steps. It is more preferable to make it 2% by mass or less. A person skilled in the art can appropriately set suitable drying conditions by simple experiments. The thickness of the photosensitive resin composition layer is preferably in the range of 5 μm to 500 μm from the viewpoint of improving handleability and suppressing deterioration of sensitivity and resolution inside the photosensitive resin composition layer. , more preferably 10 μm to 200 μm, more preferably 15 μm to 150 μm, even more preferably 20 μm to 100 μm, and most preferably 20 μm to 60 μm.

The coating method of the photosensitive resin composition includes, for example, gravure coating, micro gravure coating, reverse coating, kiss reverse coating, die coating, slot die, lip coating, comma coating, blade coating, A roll coating method, a knife coating method, a curtain coating method, a chamber gravure coating method, a slot orifice method, a spray coating method, a dip coating method, and the like can be mentioned.

The photosensitive resin composition may be applied in several times, may be applied in one time, or may be applied by combining a plurality of different methods. Among them, the die coating method is preferable because of its excellent uniform coatability. Also, in order to avoid contamination by foreign substances, it is preferable to perform the coating process in an environment such as a clean room where foreign substances are less likely to occur.

[Printed wiring board]
The printed wiring board of the present invention includes an insulating layer formed from a cured product of the photosensitive resin composition of the present invention. The insulating layer is preferably used as a solder resist.

Specifically, the printed wiring board of the present invention can be produced using the support-attached photosensitive film described above. A case where the insulating layer is a solder resist will be described below.

<Lamination and drying process>
The photosensitive resin composition layer side of the support-attached photosensitive film is laminated on a circuit board and dried to form a photosensitive resin composition layer on the circuit board.

Examples of circuit substrates include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. Here, the term "circuit board" refers to a board having a patterned conductor layer (circuit) formed on one side or both sides of the board as described above. In addition, in a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, a substrate in which one or both sides of the outermost layer of the multilayer printed wiring board is a patterned conductor layer (circuit) is also included here. included in the circuit board. The surface of the conductor layer may be roughened in advance by blackening treatment, copper etching, or the like.

As one embodiment of the lamination step, the photosensitive resin composition layer side is laminated on one side or both sides of the circuit board using a vacuum laminator. In the lamination step, if the photosensitive film with a support has a protective film, after removing the protective film, preheat the photosensitive film with a support and the circuit board as necessary to obtain a photosensitive resin composition. The material layer is press-bonded to the circuit board while being pressurized and heated. In the support-attached photosensitive film, a method of laminating on a circuit board under reduced pressure by a vacuum lamination method is preferably used.

The conditions of the lamination step are not particularly limited, but for example, the pressure bonding temperature (laminating temperature) is preferably 70° C. to 140° C., and the pressure bonding pressure is preferably 1 kgf/cm ² to 11 kgf/cm ² (9. 8×10 ⁴ N/m ² to 107.9×10 ⁴ N/m ² ), the pressure bonding time is preferably 5 seconds to 300 seconds, and the air pressure is 20 mmHg (26.7 hPa) or less. is preferred. Moreover, the lamination process may be of a batch type or a continuous type using rolls. A vacuum lamination method can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nikko Materials, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a roll-type dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC. be able to. Thus, a photosensitive film with a support is formed on the circuit board.

Instead of laminating a photosensitive film with a support, the photosensitive resin composition is directly coated on the circuit board in a resin varnish state, and the organic solvent is dried to form a photosensitive resin composition layer on the circuit board. may be formed. As a coating method, screen printing is generally used for full surface printing, but any other coating method may be used as long as it can be applied uniformly. For example, spray coating method, hot melt coating method, bar coating method, applicator method, blade coating method, knife coating method, air knife coating method, curtain flow coating method, roll coating method, gravure coating method, offset printing method, dip coating method. , brushing, or any other conventional application method can be used. After coating, drying is performed in a hot air oven, a far infrared oven, or the like, if necessary. The drying conditions are preferably 80° C. to 120° C. for 3 minutes to 13 minutes.

<Exposure process>
After the photosensitive resin composition layer is provided on the circuit board by the above steps, then, through the mask pattern, a predetermined portion of the photosensitive resin composition layer is irradiated with actinic rays, and the photosensitive resin composition in the irradiated portion An exposure step is performed to photoharden the layer. Actinic rays include, for example, ultraviolet rays, visible rays, electron beams, X-rays, and the like, and ultraviolet rays are particularly preferred. The dose of ultraviolet rays is about 10 mJ/cm ² to 1000 mJ/cm ² . The exposure method includes a contact exposure method in which a mask pattern is brought into close contact with a printed wiring board and a non-contact exposure method in which a parallel light beam is used for exposure without close contact. Either method may be used. Further, when a support exists on the photosensitive resin composition layer, exposure may be performed from above the support, or exposure may be performed after peeling off the support.

Since the solder resist uses the photosensitive resin composition of the present invention, it has excellent developability (resolution). Therefore, as the exposure pattern in the mask pattern, for example, the ratio (L/S) of the circuit width (line; L) and the width (space; S) between the circuits is 100 μm/100 μm or less (that is, the wiring pitch is 200 μm or less). , L/S = 80 µm/80 µm or less (wiring pitch 160 µm or less), L/S = 70 µm/70 µm or less (wiring pitch 140 µm or less), L/S = 60 µm/60 µm or less (wiring pitch 120 µm or less) can be used. is. It should be noted that the pitch need not be the same throughout the circuit board.

<Development process>
After the exposure step, if there is a support on the photosensitive resin composition layer, the support is removed, and then wet development or dry development is performed to remove the non-photocured portion (unexposed portion). Then, a pattern can be formed by developing.

In the case of the wet development, a safe and stable developing solution with good operability such as an alkaline aqueous solution, an aqueous developer, an organic solvent, etc. is used as the developing solution. As a developing method, known methods such as spraying, rocking immersion, brushing, scraping, and the like are appropriately employed.

Examples of the alkaline aqueous solution used as the developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; and sodium phosphate. , alkali metal phosphates such as potassium phosphate, aqueous solutions of alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, and aqueous solutions of organic bases containing no metal ions such as tetraalkylammonium hydroxide, An aqueous solution of tetramethylammonium hydroxide (TMAH) is preferable because it does not contain metal ions and does not affect the semiconductor chip.

Surfactants, antifoaming agents and the like can be added to these alkaline aqueous solutions in order to improve the developing effect. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8-12, more preferably in the range of 9-11. Further, the base concentration of the alkaline aqueous solution is preferably 0.1% by mass to 10% by mass. The temperature of the alkaline aqueous solution can be appropriately selected according to the developability of the photosensitive resin composition layer, but is preferably 20°C to 50°C.

Organic solvents used as developers include, for example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol. It is monobutyl ether.

The concentration of such an organic solvent is preferably 2% by mass to 90% by mass with respect to the total amount of the developer. Moreover, the temperature of such an organic solvent can be adjusted according to the developability. Furthermore, such organic solvents can be used alone or in combination of two or more. Organic solvent-based developers used alone include, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

In pattern formation, if necessary, two or more of the above-described developing methods may be used in combination. Development methods include a dip method, a battle method, a spray method, a high-pressure spray method, brushing, slapping, etc. The high-pressure spray method is suitable for improving resolution. When the spray method is employed, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

<Thermal curing (post-baking) process>
After the development process is completed, a heat curing (post-baking) process is performed to form a solder resist. Examples of the post-baking process include an ultraviolet irradiation process using a high-pressure mercury lamp, a heating process using a clean oven, and the like. In the case of irradiating with ultraviolet rays, the irradiation amount can be adjusted as necessary, for example, irradiation can be performed at an irradiation amount of about 0.05 J/cm ² to 10 J/cm ² . The heating conditions may be appropriately selected according to the type and content of the resin component in the photosensitive resin composition, preferably 150° C. to 220° C. for 20 minutes to 180 minutes, more preferably It is selected in the range of 160° C. to 200° C. for 30 minutes to 120 minutes.

<Other processes>
After forming the solder resist, the printed wiring board may further include a drilling step and a desmear step. These steps may be carried out according to various methods known to those skilled in the art for use in manufacturing printed wiring boards.

After forming the solder resist, if desired, the solder resist formed on the circuit board is subjected to a drilling step to form via holes and through holes. The drilling step can be carried out by a known method such as drilling, laser, plasma, or a combination of these methods if necessary, but a drilling step using a laser such as a carbon dioxide gas laser or a YAG laser is preferred.

A desmear process is a process of desmearing. Resin residue (smear) generally adheres to the inside of the opening formed in the drilling process. Since such smears cause electrical connection failures, processing for removing smears (desmear processing) is performed in this step.

Desmearing may be performed by dry desmearing, wet desmearing, or a combination thereof.

Dry desmearing includes, for example, desmearing using plasma. Desmearing using plasma can be performed using a commercially available plasma desmearing device. Among commercially available plasma desmear treatment apparatuses, suitable examples for use in manufacturing printed wiring boards include a microwave plasma apparatus manufactured by Nissin Co., Ltd., and an atmospheric pressure plasma etching apparatus manufactured by Sekisui Chemical Co., Ltd., and the like.

Examples of wet desmear treatment include desmear treatment using an oxidizing agent solution. When the desmear treatment is performed using the oxidant solution, it is preferable to perform the swelling treatment with the swelling liquid, the oxidation treatment with the oxidant solution, and the neutralization treatment with the neutralization solution in this order. Examples of the swelling liquid include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment is preferably carried out by immersing the substrate having via holes and the like formed therein in a swelling liquid heated to 60° C. to 80° C. for 5 to 10 minutes. As the oxidizing agent solution, an aqueous alkaline permanganate solution is preferable. For example, a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be mentioned. The oxidation treatment with the oxidizing agent solution is preferably carried out by immersing the substrate after the swelling treatment in the oxidizing agent solution heated to 60° C. to 80° C. for 10 minutes to 30 minutes. Examples of commercially available alkaline permanganate aqueous solutions include "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan. The neutralization treatment with the neutralizing solution is preferably carried out by immersing the substrate after the oxidation treatment in the neutralizing solution at 30° C. to 50° C. for 3 to 10 minutes. As the neutralizing liquid, an acidic aqueous solution is preferable, and commercially available products include, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan.

When the dry desmear treatment and the wet desmear treatment are performed in combination, the dry desmear treatment may be performed first, or the wet desmear treatment may be performed first.

When the insulating layer is used as an interlayer insulating layer, it can be carried out in the same manner as in the case of the solder resist, and after the thermosetting process, the drilling process, the desmear process, and the plating process may be carried out.

A plating process is a process of forming a conductor layer on an insulating layer. The conductor layer may be formed by combining electroless plating and electrolytic plating, or by forming a plating resist having a pattern opposite to that of the conductor layer and forming the conductor layer only by electroless plating. As a method for subsequent pattern formation, for example, a subtractive method, a semi-additive method, or the like known to those skilled in the art can be used.

[Semiconductor device]
A semiconductor device of the present invention includes a printed wiring board. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. A "conducting part" is a "part where an electric signal is transmitted on a printed wiring board", and the place may be a surface or an embedded part. Also, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting the semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively. Examples include a mounting method using a buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, "a mounting method using a build-up layer without bumps (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected." is.

EXAMPLES The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. A weight average molecular weight is a weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography method.

<Synthesis Example 1: Synthesis of naphthol aralkyl-type epoxy acrylate (1000)>
Epoxy equivalent is 325g/eq. 325 parts of an epoxy resin (“ESN-475V”, manufactured by Nippon Steel Chemical & Materials Co., Ltd.) having a naphthol aralkyl skeleton of is placed in a flask equipped with a gas inlet tube, a stirrer, a condenser tube and a thermometer, and carbitol acetate 340 parts were added and dissolved by heating, and 0.46 parts of hydroquinone and 1 part of triphenylphosphine were added. This mixture was heated to 95 to 105° C., 72 parts of acrylic acid was gradually added dropwise, and the mixture was reacted for 16 hours. The reaction product was cooled to 80-90° C., 80 parts of tetrahydrophthalic anhydride was added, reacted for 8 hours, and cooled. The amount of solvent was adjusted to obtain a resin solution (non-volatile content: 70%, hereinafter abbreviated as “naphthol aralkyl type epoxy acrylate (1000)”) having a solid acid value of 60 mgKOH/g. The weight average molecular weight of the naphthol aralkyl type epoxy acrylate (1000) was 1000.

<Examples 1 to 13, Comparative Examples 1 to 9>
A resin varnish was prepared by blending each component in the blending ratio shown in the table below and using a high-speed rotating mixer.

Next, as a support, a PET film (“Lumirror T6AM” manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C., “release type PET") was prepared. The prepared resin varnish is uniformly applied to the release PET with a die coater so that the thickness of the photosensitive resin composition layer after drying becomes 25 μm, and dried at 80° C. to 110° C. for 6 minutes. A support-attached photosensitive film having a photosensitive resin composition layer on the release PET was obtained.

<Measurement of glass transition temperature and average coefficient of linear thermal expansion>
(Preparation of cured product A for evaluation)
The photosensitive resin composition layers of the support-attached photosensitive films obtained in Examples and Comparative Examples were irradiated with ultraviolet rays at 2 J/cm ² and further heat-treated at 170° C. for 1 hour to obtain cured products. . After that, the support was peeled off to obtain a cured product A for evaluation.

(Measurement of glass transition temperature (Tg))
The cured product A for evaluation was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and a dynamic viscoelasticity measuring device (EXSTAR6000, manufactured by SII Nanotechnology) was used to perform thermomechanical analysis by a tensile load method. rice field. After mounting the test piece on the apparatus, the measurement was performed under the measurement conditions of a load of 200 mN and a heating rate of 2° C./min. The obtained tan δ peak top was calculated as the glass transition temperature (° C.) and evaluated according to the following criteria.
◯: Glass transition temperature is 150° C. or higher.
x: The glass transition temperature is less than 150°C.

(Measurement of average linear thermal expansion coefficient)
The cured product A for evaluation was cut into a test piece having a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer (Thermo Plus, TMA8310 manufactured by Rigaku Corporation). After mounting the test piece on the apparatus, the measurement was performed twice continuously under the measurement conditions of a load of 1 g and a temperature increase rate of 5° C./min. The average coefficient of linear thermal expansion (ppm) from 25° C. to 150° C. in the second measurement was calculated and evaluated according to the following criteria.
◯: Average coefficient of linear thermal expansion is less than 50 ppm.
Δ: The average coefficient of linear thermal expansion is 50 ppm or more and 70 ppm or less.
x: The average coefficient of linear thermal expansion exceeds 70 ppm.

<Preparation of laminate A for evaluation>
The copper layer of a glass epoxy substrate (copper clad laminate) on which a circuit is formed by patterning a copper layer with a thickness of 18 μm is treated with a surface treatment agent (CZ8100, manufactured by MEC Co., Ltd.) containing an organic acid to roughen it. changed. Next, the photosensitive resin composition layer of the support-attached photosensitive film obtained in Examples and Comparative Examples is placed in contact with the surface of the copper circuit, and a vacuum laminator (VP160, manufactured by Nikko Materials Co., Ltd.) is used. A laminate for evaluation A was prepared by laminating the copper-clad laminate, the photosensitive resin composition layer, and the support in this order. The crimping conditions were as follows: evacuation time of 30 seconds, crimping temperature of 80° C., crimping pressure of 0.7 MPa, and pressurization time of 30 seconds. After producing the laminate A for evaluation, it was allowed to stand at room temperature (25° C.) for 30 minutes or longer.

<Evaluation of resolution>
(1) Exposure, development, and curing process of photosensitive resin composition layer Using a pattern forming apparatus using a 41-stage step tablet and a round hole pattern from the support of the evaluation laminate A, exposure was performed with ultraviolet light. . As an exposure pattern, a quartz glass mask was used for drawing circular holes with openings of 40 μm/50 μm/60 μm/70 μm/80 μm/90 μm/100 μm. After standing at room temperature for 30 minutes, the laminate A for evaluation was peeled off from the support. The entire surface of the photosensitive resin composition layer on the evaluation laminated plate A was developed by spraying a 1% by mass sodium carbonate aqueous solution at 30° C. as a developer at a spray pressure of 0.2 MPa for 1 minute. After the spray development, ultraviolet irradiation was performed at 2 J/cm ² and heat treatment was performed at 170° C. for 1 hour to cure the photosensitive resin composition layer.

(2) Evaluation of resolution The exposure energy amount at which the number of steps of remaining gloss of the 41-step tablet becomes 8 was defined as the sensitivity of the photosensitive resin composition. The round holes patterned in the evaluation laminate A exposed at this sensitivity were observed with an SEM (magnification: 1000), and the minimum via hole diameter without residue and peeling was observed and evaluated according to the following criteria.
◯: The minimum via hole diameter is less than 50 μm.
Δ: The minimum via hole diameter is 50 μm or more and 60 μm or less.
x: There are no via holes with a minimum via hole diameter of 60 μm or less.

Regarding the observation of the undercut, a via hole with a diameter of 50 μm was observed by SEM (magnification: 1000). The top radius (μm) and the bottom radius (μm) of the cross section of the via hole with an opening diameter of 50 μm are measured by SEM, and the difference between the bottom radius and the top radius (bottom radius−top ) was obtained, and the obtained value was regarded as an undercut, and was evaluated according to the following criteria.
A: No undercut.
◯: Undercut is less than 3 μm.
Δ: Undercut is 3 μm or more and 6 μm or less.
x: Undercut is larger than 6 μm. Alternatively, a via hole with a diameter of 50 μm is not opened.

<Evaluation of roughness and peel strength>
(1) Exposure, development, and curing process of photosensitive resin composition layer Using a pattern forming apparatus from the support of laminate A for evaluation, the exposure energy is such that the number of steps of the 41-step tablet with residual gloss is 8 steps. UV exposure was performed. A quartz glass mask without an exposure pattern was used. After standing at room temperature for 30 minutes, the laminate A for evaluation was peeled off from the support. The entire surface of the photosensitive resin composition layer on the evaluation laminated plate A was developed by spraying a 1% by mass sodium carbonate aqueous solution at 30° C. as a developer at a spray pressure of 0.2 MPa for 1 minute. After the spray development, ultraviolet irradiation was performed at 2 J/cm ² and heat treatment was performed at 170° C. for 1 hour to cure the photosensitive resin composition layer.

(2) Roughening treatment The evaluation laminate A is immersed in a swelling liquid, Swelling Dip Securigand P containing diethylene glycol monobutyl ether manufactured by Atotech Japan Co., Ltd., at 60°C for 10 minutes, and then used as a roughening liquid. , Atotech Japan's Concentrate Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) immersed for 10 minutes at 80 ° C. Finally, as a neutralizing solution, Atotech Japan's Reduction Shore It was immersed in Thin Securigant P at 40° C. for 5 minutes. Laminate A for evaluation after this roughening treatment was used as Sample A.

(3) Plating Formation by Semi-Additive Method To form a circuit on the insulating layer surface, sample A was immersed in an electroless plating solution containing PdCl ₂ and then in an electroless copper plating solution. After annealing by heating at 150° C. for 30 minutes, an etching resist was formed, and after pattern formation by etching, copper sulfate electroplating was performed to form a conductor layer with a thickness of 25 μm. Annealing was then performed at 180° C. for 60 minutes. This sample A was designated as sample B.

(4) Measurement of arithmetic average roughness (Ra) For sample A, a non-contact surface roughness meter (WYKO NT3300 manufactured by Bcoinstruments) was used in VSI mode with a 50x lens to obtain a measurement range of 121 µm × 92 µm. Arithmetic mean roughness (Ra) was obtained from the numerical values obtained. Then, an average value of 10 points was calculated to obtain a measured value, and evaluation was made according to the following criteria.
◯: Arithmetic mean roughness is less than 200 μm.
Δ: Arithmetic mean roughness of 200 μm to 400 μm.
x: The arithmetic mean roughness is larger than 400 µm.

(5) Measurement of peeling strength (peel strength) of plated conductor layer In the conductor layer of sample B, a cut of 10 mm in width and 100 mm in length is made, one end of this is peeled off and a gripping tool (TSE) (manufactured by Autocom Co., Ltd., AC-50C-SL), and measured the load (kgf / cm) when peeling off 35 mm in the vertical direction at a speed of 50 mm / min at room temperature. was evaluated according to the criteria of
◯: Peel strength is 0.3 kgf/cm or more.
x: The peel strength is less than 0.3 kgf/cm.

・ＯｍｎｉｐｏｌＴＰ：下記構造で表される化合物（ＩＧＭ社製、分子量は９００以上）式中、ａ、ｂ、ｃはそれぞれ１～１０の整数を表す。

・Ｏｍｎｉｒａｄ３７９ＥＧ：（ＩＧＭ社製、分子量３８０．５）

・ＯｍｎｉｒａｄＴＰＯ：（ＩＧＭ社製、分子量３４８）

・ＮＣ３０００Ｈ：ビフェニル型エポキシ樹脂（日本化薬社製、エポキシ当量２７１ｇ／ｅｑ．）
・ＳＯ－Ｃ２：無機充填材（球状シリカ、アドマテックス社製、平均粒径０．５μｍ、比表面積６ｍ^２／ｇ）
・ＤＰＨＡ：ジペンタエリスリトールヘキサアクリレート（日本化薬社製）
・ＥＤＧ－Ａｃ：エチルジグリコールアセテート
・ＭＥＫ：メチルエチルケトン Abbreviations in the table are as follows.
・CCR-1171H: cresol novolac type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH/g, solid content concentration about 60%, weight average molecular weight 7500)
・CCR-1373H: cresol novolac epoxy acrylate (manufactured by Nippon Kayaku, acid value 99 mgKOH/g, solid content concentration about 60%, weight average molecular weight 2800)
・ ZCR-1797H: Biphenyl type epoxy acrylate (Nippon Kayaku Co., Ltd., acid value 99 mgKOH / g, solid content concentration about 60%, weight average molecular weight 6500)
・ ZCR-8001H: Biphenyl type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 109 mgKOH / g, solid content concentration about 60%, weight average molecular weight 3700)
・CCR-1224H: cresol novolac type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH/g, solid content concentration about 60%, weight average molecular weight 8700)
- Naphthol aralkyl type (1000): Naphthol aralkyl type epoxy acrylate (1000) synthesized in Synthesis Example 1
· Omnipol 910: a compound represented by the following structure (manufactured by IGM, molecular weight of 850 or more). In the formula, d represents an integer of 1-10.

· Omnipol TP: a compound represented by the following structure (manufactured by IGM, molecular weight of 900 or more).

· Omnirad 379EG: (manufactured by IGM, molecular weight 380.5)

・Omnirad TPO: (manufactured by IGM, molecular weight 348)

· NC3000H: biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 271 g / eq.)
・SO-C2: Inorganic filler (spherical silica, manufactured by Admatechs, average particle size 0.5 μm, specific surface area 6 m ² /g)
・ DPHA: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
・EDG-Ac: ethyl diglycol acetate ・MEK: methyl ethyl ketone

In each example, it has been confirmed that the same results as those of the above examples are obtained even if the components (C) to (F) are not contained, although there is a difference in degree.

Claims (11)

(A-1) a resin containing an ethylenically unsaturated group and a carboxyl group having a weight average molecular weight of 6000 or less;
(A-2) a resin containing an ethylenically unsaturated group and a carboxyl group having a weight average molecular weight 2000 or more greater than that of component (A-1), and (B) a photopolymerization initiator,
A photosensitive resin composition in which the component (B) has a molecular weight of 400 or more. 2. The photosensitive resin composition according to claim 1, further comprising (C) an inorganic filler. 3. The photosensitive resin composition according to claim 2, wherein the content of component (C) is 1% by mass or more based on 100% by mass of non-volatile components in the photosensitive resin composition. 4. Any one of claims 1 to 3, wherein component (A-1) and component (A-2) have any one of a cresol novolak skeleton, bisphenol A skeleton, bisphenol F skeleton, biphenyl skeleton, and naphtholaralkyl skeleton. The photosensitive resin composition according to . The photosensitive resin composition according to any one of claims 1 to 4, wherein the component (A-1) and the component (A-2) contain an acid-modified cresol novolak skeleton-containing epoxy (meth)acrylate. The photosensitive resin composition according to any one of claims 1 to 5, wherein component (B) has a structural unit represented by the following formula (B-1).

(In formula (B-1), R ¹ represents an actinic ray absorbing group, R ² each independently represents a divalent hydrocarbon group, n represents an integer of 1 to 10, * represents a bond, .) The photosensitive resin composition according to any one of claims 1 to 6, which is for solder resist formation. A photosensitive film with a support, comprising a support and a photosensitive resin composition layer containing the photosensitive resin composition according to any one of claims 1 to 7 provided on the support. A printed wiring board comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of claims 1 to 7. 10. The printed wiring board according to claim 9, wherein the insulating layer is one of an interlayer insulating material and a solder resist. A semiconductor device comprising the printed wiring board according to claim 9 or 10.