TW202248252A - Photosensitive resin composition - Google Patents

Abstract

The present invention addresses the problem of providing a photosensitive resin composition and the like capable of obtaining a cured product in which a via hole having a small diameter can be formed and the occurrence of undercutting can be suppressed. The photosensitive resin composition contains (A-1) a resin containing an ethylenically unsaturated group and a carboxyl group and having a weight-average molecular weight of 6000 or less, (A-2) a resin containing an ethylenically unsaturated group and a carboxyl group and having a weight-average molecular weight greater than that of the component (A-1) by 2000 or more, and (B) a photopolymerization initiator, and the component (B) has a molecular weight of 400 or more.

Description

Photosensitive resin composition

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

In printed wiring boards, a solder resist may be provided as a permanent protective film for suppressing corrosion of a circuit board while suppressing solder adhesion to portions not requiring solder. As a solder resist, generally, the photosensitive resin composition as described in patent document 1 is used, for example.

[Prior Art Literature] [Patent Document] Patent Document 1: Japanese Patent Laid-Open No. 2014-115672

The problem to be solved by the invention

In recent years, along with miniaturization and thinning of printed wiring boards, it is required to form small-diameter via holes (via holes).

However, the smaller the diameter of the formed via hole, the more prone to undercut. Undercut refers to a phenomenon in which the outline of the via hole does not form the desired shape at the bottom side of the via hole, but becomes an enlarged diameter shape. In the via hole where the undercut occurs, there is an uppermost part corresponding to the opening of the via hole. A shape with a larger diameter than the diameter of the bottom of the via hole equivalent to the bottom.

The object of the present invention is to provide a photosensitive resin composition capable of forming a small-diameter via hole and to obtain a cured product that suppresses the occurrence of undercut; Wiring boards and semiconductor devices.

means of solving problems As a result of intensive studies by the inventors of the present invention, it has been found that by combining two or more resins containing ethylenically unsaturated groups and carboxyl groups with different weight average molecular weights, and further using a photopolymerization initiator with a molecular weight of 400 or more, it is possible to obtain The present invention has been completed by forming a small-diameter via hole and a cured product that suppresses the occurrence of undercut.

That is, the present invention includes the following content, [1] A photosensitive resin composition comprising: (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 2,000 or more larger than that of the component (A-1), and (B) a photopolymerization initiator, and (B) The molecular weight of a component is 400 or more.

[2] The photosensitive resin composition according to [1], which further contains (C) an inorganic filler.

[3] The photosensitive resin composition according to [2], wherein the content of the component (C) is 1% by mass or more when the non-volatile components in the photosensitive resin composition are 100% by mass.

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the components (A-1) and (A-2) have a cresol novolac skeleton, a bisphenol A skeleton, a bisphenol A Any of a phenol F skeleton, a biphenyl skeleton, and a naphthol aralkyl skeleton.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the components (A-1) and (A-2) contain epoxy resins containing an acid-modified cresol novolac skeleton. base (meth)acrylate.

(式(B-1)中，R ¹表示活性光線吸收基，R ²分別獨立地表示2價烴基；n表示1~10的整數；*表示鍵結位)。 [6] The photosensitive resin composition according to any one of [1] to [5], wherein the component (B) has a structural unit represented by the following formula (B-1),

(In the formula (B-1), R ¹ represents an active light-absorbing group, and R ² independently represent a divalent hydrocarbon group; n represents an integer of 1 to 10; * represents a bonding position).

[7] The photosensitive resin composition according to any one of [1] to [6], which is used to form a solder resist.

[8] A photosensitive film with a support, which has a support, and a photosensitive resin composition comprising the photosensitive resin composition according to any one of [1] to [7] provided on the support Floor.

[9] A printed wiring board including an insulating layer formed of 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 any one of an interlayer insulating material and a solder resist.

[11] A semiconductor device including the printed wiring board according to [9] or [10].

[Invention effect] According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a small-diameter via hole and to obtain a cured product capable of suppressing the occurrence of undercut; a photosensitive film with a support obtained by using the photosensitive resin composition, and a printed wiring boards and semiconductor devices.

Hereinafter, the photosensitive resin composition of this invention, the photosensitive film with a support body, a printed wiring board, and a semiconductor device are demonstrated in detail.

[Photosensitive resin composition] The photosensitive resin composition of the present invention contains (A-1) a resin containing an ethylenically unsaturated group and a carboxyl group with a weight average molecular weight of 6000 or less, and (A-2) has a weight 2000 or more greater than that of the component (A-1). Resin containing an ethylenically unsaturated group and a carboxyl group of an average molecular weight, and (B) a photopolymerization initiator, and the molecular weight of (B) component is 400 or more.

In the present invention, in addition to components (A-1) and (A-2) having different weight-average molecular weights, by using component (B) having a predetermined molecular weight in combination, via holes capable of forming small diameters can be obtained, Hardened product that suppresses occurrence of undercut. In addition, in the present invention, usually, a cured product having excellent peel strength from the conductor layer, glass transition temperature (Tg), average linear thermal expansion coefficient (CTE) and surface shape can be obtained.

The photosensitive resin composition may further include optional components such as (C) inorganic filler, (D) epoxy resin, (E) reactive diluent, (F) solvent, and (G) other additives as needed. In this specification, (A-1) component and (A-2) component may be collectively referred to as "(A) resin containing an ethylenically unsaturated group and a carboxyl group." Hereinafter, each component contained in a photosensitive resin composition is demonstrated in detail.

＜(A) Resins containing ethylenically unsaturated groups and carboxyl groups＞ The photosensitive resin composition contains (A-1) a resin containing an ethylenically unsaturated group and a carboxyl group with a weight average molecular weight of 6000 or less, and (A-2) a resin having a weight average molecular weight 2000 or more larger than that of the component (A-1). Resin containing ethylenically unsaturated groups and carboxyl groups. By using (A-1) component and (A-2) component together, the hardened|cured material which can form the via hole of a small diameter and suppress generation|occurrence|production of an undercut can be obtained.

The weight average molecular weight of the component (A-1) is 6,000 or less, preferably 5,500 or less, and the lower limit is preferably 1,000 from the viewpoint of obtaining a cured product capable of forming small-diameter via holes and suppressing the occurrence of undercuts. Above, more preferably above 1500. (A-1) The weight average molecular weight of a component is the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) method.

The weight average molecular weight of the component (A-2) is greater than the weight average molecular weight of the component (A-1) by 2000 or more, preferably 2500 or more. The upper limit is preferably 20,000 or less, more preferably 17,000 or less, further preferably 15,000 or less. (A-2) The weight average molecular weight of a component can be measured by the method similar to the weight average molecular weight of (A-1) component.

Although the specific weight-average molecular weight of the component (A-2) varies depending on the weight-average molecular weight of the component (A-1) used in combination, it is preferably 3,000 or more, more preferably 3,500 or more, and still more preferably 3,500 or more. 4000 or more, preferably 20000 or less, more preferably 17000 or less, further preferably 15000 or less.

The ethylenically unsaturated groups in the components (A-1) and (A-2) have a carbon-carbon double bond, and examples thereof include vinyl, allyl, propargyl, butenyl, ethynyl, benzene Ethynyl, maleimide, nadimide (nadimide) and (meth)acryl, preferably (meth)acryl from the viewpoint of photoradical polymerization reactivity Acyl group. "(Meth)acryl" includes methacryl, acryl, and combinations thereof. Since (A-1) component and (A-2) component contain an ethylenically unsaturated group, photoradical polymerization is possible. (A-1) The number of ethylenically unsaturated groups per 1 molecule of a component and (A-2) component may be 1, and may be 2 or more. Moreover, when (A-1) component and (A-2) component contain 2 or more ethylenically unsaturated groups per 1 molecule, these ethylenically unsaturated groups may be the same or different.

In addition, (A-1) component and (A-2) component contain a carboxyl group, so the photosensitive resin composition containing (A-1) component and (A-2) component is resistant to alkaline solution (for example, as alkaline developing solution) 1 mass % sodium carbonate aqueous solution) shows solubility. (A-1) The number of carboxyl groups per 1 molecule of a component and (A-2) component may be 1, and may be 2 or more.

The components (A-1) and (A-2) are not particularly limited as long as they are compounds having different weight average molecular weights, having an ethylenically unsaturated group and a carboxyl group, capable of photoradical polymerization, and capable of alkali development at the same time. Preferably, it is a resin having both a carboxyl group and two or more ethylenically unsaturated groups in one molecule.

An example 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 reacting an acid anhydride. Specifically, an unsaturated epoxy ester resin can be obtained by reacting an epoxy compound with an unsaturated carboxylic acid, and an acid-modified unsaturated epoxy ester resin can be obtained by reacting an 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 A type epoxy resin, hydrogenated bisphenol A type epoxy resin, Bisphenol-type epoxy resins such as phenol F-type epoxy resins, bisphenol-S-type epoxy resins, and modified bisphenol-F-type epoxy resins modified by reacting bisphenol-F-type epoxy resins with epichlorohydrin to have more than three functions Oxygen resin; biphenol type epoxy resin, tetramethyl biphenol type and other biphenol type epoxy resin; phenol novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol A type novolak type epoxy resin resin, alkylphenol novolac epoxy resin and other novolac epoxy resins; bisphenol AF epoxy resins and perfluoroalkyl epoxy resins and other fluorine-containing epoxy resins; naphthalene epoxy resins, Hydroxynaphthalene type epoxy resin, polyhydroxy binaphthalene type epoxy resin, naphthol type epoxy resin, naphthol aralkyl type epoxy resin, binaphthol type epoxy resin, naphthol type epoxy resin naphthol novolac Varnish-type epoxy resins, naphthalene-type epoxy resins obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes, and other epoxy resins with a naphthalene skeleton (epoxy resins containing a naphthalene skeleton); bixylenol-type epoxy resins Resin; dicyclopentadiene type epoxy resin; triphenol type epoxy resin; tertiary butyl-catechol type epoxy resin; anthracene type epoxy resin and other epoxy resins containing condensation ring skeleton; glycidol amine type epoxy resin; glycidyl ester type epoxy resin; biphenyl type epoxy resin; linear aliphatic epoxy resin; epoxy resin with butadiene structure; alicyclic epoxy resin; heterocyclic Epoxy resins containing spiro rings; Cyclohexanedimethanol type epoxy resins; Trimethylol type epoxy resins; Tetraphenylethane type epoxy resins; Polyglycidyl (meth)acrylate Acrylic resins containing glycidyl groups, such as copolymers of glycidyl methacrylate and acrylate, etc.; fennel-type epoxy resins; halogenated epoxy resins, etc.

The epoxy compound is preferably an aromatic skeleton-containing epoxy resin from the viewpoint of reducing the average linear thermal expansion coefficient. Here, the aromatic skeleton is a concept that also includes 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 especially preferred. From the standpoint of increasing the rigidity of the molecules and suppressing the movement of the molecules, as a result, the average linear thermal expansion coefficient of the cured product of the resin composition is further reduced, cresol novolak type epoxy resins and biphenyl type epoxy resins are more preferable. The resin is a naphthol aralkyl type epoxy resin, more preferably a cresol novolak type epoxy resin.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid and the like, and these may be used alone or in combination of two or more. Among them, acrylic acid and methacrylic acid are particularly preferable from the viewpoint of improving the photocurability of the photosensitive resin composition. In addition, in this specification, the epoxy ester resin which is the reactant of the above-mentioned epoxy compound and (meth)acrylic acid may be referred to as "epoxy (meth)acrylate", and here the epoxy compound The epoxy group is substantially eliminated by the reaction with (meth)acrylic acid. "(Meth)acrylate" means methacrylate and acrylate. Sometimes acrylic acid and methacrylic acid are 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, and pyromellitic anhydride. , benzophenone tetracarboxylic dianhydride and the like may be used alone or in combination of two or more. Among these, succinic anhydride and tetrahydrophthalic anhydride are preferable, and tetrahydrophthalic anhydride is more preferable from the viewpoint of improving the resolution and insulation reliability of the cured product.

When obtaining the acid-modified unsaturated epoxy ester resin in the components (A-1) and (A-2), the unsaturated carboxylic acid can be reacted with the epoxy resin in the presence of a catalyst to obtain the unsaturated epoxy ester After the resin, the unsaturated epoxy ester resin is reacted with an anhydride. Moreover, a solvent and a polymerization inhibitor can be used as needed.

As the acid-modified unsaturated epoxy ester resin in the components (A-1) and (A-2), it is preferable to have a cresol novolac skeleton, a bisphenol A skeleton, a bisphenol F skeleton, a biphenyl skeleton, and a naphthalene Any of the phenol aralkyl skeletons. Moreover, acid-modified epoxy (meth)acrylate is preferable as an acid-modified unsaturated epoxy ester resin in (A-1) component and (A-2) component. The "epoxy" in the acid-modified unsaturated epoxy ester resin means a structure derived from the above-mentioned epoxy compound. For example, "acid-modified bisphenol-type epoxy (meth)acrylate" refers to an acid-modified non-acrylic acid obtained by using a bisphenol-type epoxy resin as an epoxy compound and (meth)acrylic acid as an unsaturated carboxylic acid. Saturated epoxy ester resin. The preferred range of acid-modified epoxy (meth)acrylate is derived from the preferred range of epoxy compounds. That is, the acid-modified unsaturated epoxy ester resin is preferably an epoxy-based (meth)acrylic acid-modified cresol novolak skeleton from the viewpoint of reducing the average linear thermal expansion coefficient of the cured product of the resin composition. Ester, epoxy (meth)acrylate containing acid-modified bisphenol A skeleton, epoxy (meth)acrylate containing acid-modified bisphenol F skeleton, epoxy (meth)acrylate containing biphenyl skeleton base) acrylate, epoxy (meth)acrylate containing naphthol aralkyl skeleton, more preferably epoxy (meth)acrylate containing acid modified cresol novolac skeleton, biphenyl skeleton Epoxy (meth)acrylates, epoxy (meth)acrylates containing naphthol aralkyl skeletons, more preferably epoxy (meth)acrylic acid-modified cresol novolac skeletons Acrylate. Epoxy (meth)acrylate containing acid-modified cresol novolac skeleton is the reactant of cresol novolak type epoxy resin and (meth)acrylate and then reacted with succinic anhydride or tetrahydrophthalic anhydride Compounds obtained by reacting with acid anhydrides. Epoxy (meth)acrylate containing acid-modified bisphenol A skeleton refers to the reaction of bisphenol A epoxy resin and (meth)acrylate with succinic anhydride or tetrahydrophthalic anhydride, etc. Compounds obtained by the reaction of acid anhydrides. Epoxy (meth)acrylate containing acid-modified bisphenol F skeleton refers to the reaction of bisphenol F epoxy resin and (meth)acrylate with succinic anhydride or tetrahydrophthalic anhydride, etc. Compounds obtained by the reaction of acid anhydrides. Epoxy (meth)acrylate containing acid-modified biphenyl skeleton refers to reacting the reactant of biphenyl epoxy resin and (meth)acrylate with acid anhydrides such as succinic anhydride or tetrahydrophthalic anhydride the obtained compound. The epoxy group (meth) acrylate containing acid modified naphthol aralkyl skeleton refers to the reactant of naphthol aralkyl type epoxy resin and (meth) acrylate with succinic anhydride or tetrahydro phthalate A compound obtained by reacting an acid anhydride such as diformic anhydride.

A commercial item can be used for the acid-modified unsaturated epoxy ester resin in such (A) component. Specific examples of the acid-modified unsaturated epoxy ester resin used as the component (A-1) include "CCR-1373H" (cresol novolak type epoxy acrylate) manufactured by Nippon Kayaku Co., Ltd., "ZCR-8001H" (acid-modified biphenyl epoxy acrylate), "ZCR-1569H" (acid modified biphenyl epoxy acrylate): reactants of biphenyl epoxy resin, acrylic acid and anhydride )Wait. These may be used alone or in combination of two or more.

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

The acid values of the components (A-1) and (A-2) are preferably 0.1 mgKOH/g or more, more preferably 0.5 mgKOH from the viewpoint of improving the alkali developability of the photosensitive resin composition. /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, still more preferably 100 mgKOH/g or less, from the viewpoint of suppressing the dissolution of the fine pattern of the cured product due to development and improving insulation reliability. below g. Here, an acid value means the residual acid value of the carboxyl group which exists in (A) component, and an acid value can be measured by the following method. First, after accurately weighing and measuring about 1 g of the resin solution, 30 g of acetone was added to the resin solution to uniformly dissolve the resin solution. Next, an appropriate amount of phenolphthalein as an indicator was added to the solution, and titration was performed using a 0.1 N ethanol aqueous solution. And, the acid value was calculated by the following formula.

Formula: A=10×(Vf-BL)×F×56.11/(Wp×I) Furthermore, in the above formula, A represents the acid value (mgKOH/g), Vf represents the titration (mL) of KOH, BL represents a blank, F represents a factor (power value), and Wp represents the determination of the resin solution quality (g ), I represents the ratio (mass %) of measuring the non-volatile components of the resin solution.

(A-1) In the manufacture of components and (A-2) components, from the viewpoint of improving storage stability, the number of moles of epoxy groups in epoxy resins and the total carboxyl groups of unsaturated carboxylic acids and acid anhydrides The molar ratio 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 (A-1) component and (A-2) component is from the viewpoint of improving alkali developability, when the non-volatile content of the photosensitive resin composition is 100% by mass, the content is preferably set to 10 mass % or more, More preferably, it is 20 mass % or more, More preferably, it is 25 mass % or more. The upper limit is preferably at most 50 mass %, more preferably at most 45 mass %, further preferably at most 40 mass %, from the viewpoint of improving heat resistance. In addition, in the present invention, unless otherwise specified, the content of each component in the photosensitive resin composition is a value when the non-volatile components in the photosensitive resin composition are 100% by mass.

(A-1) From the viewpoint of improving alkali developability, the content of the component is preferably 5% by mass or more, more preferably 8% by mass, based on 100% by mass of the non-volatile components of the photosensitive resin composition. Mass % or more, More preferably, it is 10 mass % or more. The upper limit is preferably at most 40 mass %, more preferably at most 35 mass %, and still more preferably at most 30 mass %, from the viewpoint of improving heat resistance.

(A-2) From the viewpoint of improving the alkali developability, the content of the component is preferably 5% by mass or more, more preferably 8% by mass, based on 100% by mass of the non-volatile components of the photosensitive resin composition. Mass % or more, More preferably, it is 10 mass % or more. The upper limit is preferably at most 40 mass %, more preferably at most 35 mass %, further preferably at most 30 mass %, from the viewpoint of improving heat resistance.

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

＜(B) Photopolymerization initiator＞ The photosensitive resin composition contains (B) photoinitiator as (B) component. (B) The molecular weight of a component is 400 or more. By containing (B) component in a photosensitive resin composition, generation|occurrence|production of an undercut can be suppressed, and even if an arithmetic average roughness (Ra) is small, the hardened|cured material which is excellent in peeling strength can be obtained.

The molecular weight of the component (B) is 400 or more, preferably 500 or more, more preferably More than 600, more than 700. The upper limit is not particularly limited, but is preferably 3000 or less, more preferably 2500 or less, further preferably 2000 or less.

As (B) component, the compound which has a molecular weight of 400 or more, has a group which absorbs active rays, such as an ultraviolet-ray, and can be photocured efficiently can be used. As such (B) component, the compound containing the structural unit represented by formula (B-1), for example is preferable.

(式(B-1)中，R ¹表示活性光線吸收基，R ²分別獨立地表示2價烴基；n表示1~10的整數；*表示鍵結位)。

(In the formula (B-1), R ¹ represents an active light-absorbing group, and R ² independently represent a divalent hydrocarbon group; n represents an integer of 1 to 10; * represents a bonding position).

R ¹ represents an active ray absorbing group. The active ray absorbing group refers to a group capable of absorbing active rays such as ultraviolet rays. As the active light absorbing group, as long as it is a functional group capable of absorbing active light, for example, a group having an aminoketone skeleton, a group having an anthraquinone skeleton, a group having a thioxanthone skeleton, a group having a ketal skeleton, etc. , a group having a benzophenone skeleton, 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 Wait.

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

R ²分別獨立地表示2價烴基。作為2價烴基，可以舉出2價脂肪族烴基、2價芳香族烴基，從顯著得到本發明的效果的觀點而言，較佳為2價脂肪族烴基。

R ² each independently represent a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group, and a divalent aliphatic hydrocarbon group is preferred from the viewpoint of remarkably obtaining the effects of the present invention.

As a divalent aliphatic hydrocarbon group, a divalent saturated aliphatic hydrocarbon group is preferable, and an alkylene group, an alkenylene group, etc. are mentioned, and an alkylene group is more preferable. The alkylene group may be linear, branched, or cyclic, and is 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, further preferably an alkylene group having 1 to 5 carbon atoms, or carbon An alkylene group with 1 to 3 atoms. As such an alkylene group, a methylene group, an ethylidene group, a propylidene group, a butylene group, a pentylene group, a hexylene group, a cyclohexylene group etc. are mentioned, for example, A methylene group is preferable. The alkenylene group may be linear, branched, or cyclic, and is 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 still more preferably an alkenylene group having 2 to 5 carbon atoms.

Examples of the divalent aromatic hydrocarbon group include an arylylene group, a heteroarylylene group, and the like. The arylylene group or heteroarylylene group is preferably an arylylene group or a heteroarylylene group having 6 to 20 carbon atoms, more preferably an arylylene group or a heteroarylylene group having 6 to 10 carbon atoms.

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, carboxyl groups, sulfo groups, cyano groups, nitro groups, hydroxyl groups, Mercapto, side oxygen, etc.

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

(B) It is preferable that a component contains either of the compound represented by the following general formula (B-2) and the compound represented by the following general formula (B-3).

(通式(B-2)中，R ¹¹分別獨立地表示活性光線吸收基，R ¹²分別獨立地表示2價烴基，R ¹³表示m價烴基；n1表示1~10的整數，m表示1~4的整數； 通式(B-3)中，R ²¹、R ²³分別獨立地表示活性光線吸收基，R ²²分別獨立地表示2價烴基；n2表示1~10的整數)。

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

R ¹¹ each independently represent an active ray absorbing group, and are the same as the active ray absorbing group represented by R ¹ in formula (B-1).

R ¹² each independently represent a divalent hydrocarbon group, and are the same as the divalent hydrocarbon group represented by R ² in formula (B-1).

R ¹³ represents an m-valent hydrocarbon group. Examples of the m-valent hydrocarbon group include 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, preferably an alkynylene group. Specific examples of the group represented by ^R13 include, for example, the groups shown below. In the formula, "*" represents a bonding position.

n1表示1~10的整數，與式(B-1)中的n相同。

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

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

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

R ²² each independently represent a divalent hydrocarbon group, and are 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. As a commercial item, "Omnipol 910" and "Omnipol TP" etc. by the IGM company are mentioned, for example.

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

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

(C) The material of the inorganic filler is not particularly limited, and examples thereof include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, and hydrotalcite. , diaspore, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, titanic acid Magnesium, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc. Among them, silicon dioxide and barium sulfate are preferable, and silicon dioxide is particularly preferable. Moreover, as silica, spherical silica is preferable. (C) The inorganic filler may be used alone or in combination of two or more.

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

The average particle size of the inorganic filler can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler was prepared on a volume basis with a laser diffraction and scattering particle size distribution measuring device, and the median diameter was used as the average particle size for measurement. As a measurement sample, one obtained by dispersing an inorganic filler in water by ultrasonic waves can be preferably used. As a laser diffraction-scattering type particle size distribution measuring device, "LA-500" by Horiba Corporation, "SALD-2200" by Shimadzu Corporation, etc. can be used.

(C) The specific surface area of the inorganic filler is preferably at least 1 m ² /g, more preferably at least 3 m ² /g, particularly preferably at least 5 m ² /g from the viewpoint of obtaining a cured product with a low average linear thermal expansion coefficient. above. The upper limit is not particularly limited, but 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 was obtained by adsorbing nitrogen gas on the surface of the sample 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 filler From the viewpoint of improving moisture resistance and dispersibility, vinyl silane coupling agents, amino silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, One or more surface treatment agents such as silane-based coupling agents, alkoxysilane compounds, organic silazane compounds, and titanate-based coupling agents. Commercially available surface treatment agents include, for example, Shin-Etsu Chemical Co., Ltd. "KBM-1003" (vinyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-403" (3-glycidyloxy Propyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE-903" (3-aminopropyltriethoxy 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 Co., Ltd. "KBM-4803" (long-chain epoxy-type silane coupling agent), etc.

(C) A commercial item can be used for an inorganic filler. Examples of commercially available products include "SC2050", "SC4050", "SO-C4", "SO-C2", "SO-C1", "Admafine" manufactured by Admatechs, "SFP series" manufactured by Denki Kagaku Kogyo Co., Ltd. ”, “SP(H) Series” manufactured by Nippon Steel & Sumikin Materials Co., Ltd., “Sciqas Series” manufactured by Sakai Chemical Industry Co., Ltd., “Seahostar Series” manufactured by Nippon Shokubai Co., Ltd., “AZ Series” manufactured by Nippon Steel & Sumikin Materials Co., Ltd., "AX series", "B series" manufactured by Sakai Chemical Industry Co., Ltd., "BF series", etc.

(C) The content of the inorganic filler is preferably 1% by mass or more, based on 100% by mass of the non-volatile components in the photosensitive resin composition, from the viewpoint of obtaining a cured product with a low average linear thermal expansion coefficient. More preferably, it is 3 mass % or more, More preferably, it is 5 mass % or more, 10 mass % or more, 20 mass % or more, and 30 mass % or more. From the viewpoint of suppressing light reflection during exposure and obtaining excellent developability, 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, 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 containing (D)component, the insulation reliability of the hardened|cured material of a photosensitive resin composition can be improved. However, (D) component here does not include (A) the epoxy resin containing an ethylenically unsaturated group and a carboxyl group. (D) A component may be used individually by 1 type, and may use it in combination of 2 or more types.

Examples of the component (D) include bixylenol epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, and bisphenol AF epoxy resins. , dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolac type epoxy resin, tertiary butyl-catechol type epoxy resin, naphthalene Type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin Resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane epoxy resin, Cyclohexanedimethanol type epoxy resin, naphthalene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, tetraglycidyl diaminodiphenylmethane type epoxy resin resin etc. Among these, as (D) component, biphenyl type epoxy resin is preferable. The epoxy resins may be used alone or in combination of two or more.

It is preferable that a resin composition contains the epoxy resin which has 2 or more epoxy groups in 1 molecule as (D)component. From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50 with respect to 100% by mass of the non-volatile components of the component (D). Mass % or more, More preferably, it is 60 mass % or more, Especially preferably, it is 70 mass % or more.

Among epoxy resins, there are epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resin") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as as "solid epoxy resin"). The resin composition may contain only liquid epoxy resin as component (D), may only contain solid epoxy resin, and may also contain liquid epoxy resin and solid epoxy resin in combination. From the viewpoint of desired effect, it is preferable to include only solid epoxy resin.

The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, more preferably an aromatic solid having three or more epoxy groups in one molecule shaped epoxy resin.

As the solid epoxy resin, bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, and dicyclopentadiene-type epoxy resins are preferable. Resin, triphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin Resin, tetraphenylethane type epoxy resin, more preferably biphenyl type epoxy resin.

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

As a liquid epoxy resin, what has two or more epoxy groups in 1 molecule is preferable.

As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, shrink Glycerylamine type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type Epoxy resins, and epoxy resins with a butadiene structure. As the glycidylamine-type epoxy resin, tetraglycidyldiaminodiphenylmethane-type epoxy resin is preferable.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", " 825", "Epicoat 828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac resin) manufactured by Mitsubishi Chemical Corporation varnish type epoxy resin); "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (bisphenol A type epoxy resin and Bisphenol F-type epoxy resin mixture); Nagase ChemteX company's "EX-721" (glycidyl ester type epoxy resin); Daicel company's "Celloxide 2021P" (alicyclic ring with ester skeleton epoxy resin); "PB-3600" (epoxy resin with a butadiene structure) manufactured by Daicel; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidyl cyclohexane type epoxy resin); Sumitomo Chemical Co., Ltd. "ELM-434L", (glycidyl amine type epoxy resin); Sumitomo Chemical Co., Ltd. "ELM-434VL", (tetraglycidyl diamine Diphenylmethane type epoxy resin); ADEKA company's "EP-3980S" (bifunctional glycidylamine type epoxy resin); ADEKA company's "EP-3950L" (trifunctional glycidylamine type epoxy resin) resin); Nissan Chemical Co., Ltd. "TEPIC-VL" (isocyanuric acid cyclic epoxy resin); Sumitomo Chemical Co., Ltd. "ELM-100H" (N-[2-methyl-4-(oxirane Alkylmethoxy)phenyl]-N-(oxiranylmethyl)oxiranemethanamine) and the like. These may be used alone or in combination of two or more.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (D), the molar ratio (liquid epoxy resin:solid epoxy resin) is preferably 1:0.01 by mass ratio. ~1:20, more preferably 1:0.1~1:10, especially preferably 1:0.5~1:5. By making the quantity ratio of a liquid epoxy resin and a solid epoxy resin into the said range, the desired effect of this invention can be acquired remarkably. Furthermore, when used in the form of the photosensitive film with a support normally, moderate adhesiveness is acquired. Moreover, when using normally in the form of the photosensitive film with a support, sufficient flexibility is acquired and handling property improves. Furthermore, a cured product having sufficient breaking strength can usually be obtained.

(D) The epoxy equivalent of the component is preferably 50 g/eq.~5000 g/eq., more preferably 50 g/eq.~3000 g/eq., further preferably 80 g/eq.~2000 g/eq., Further more preferably, it is 110g/eq.~1000g/eq. By setting it as this range, the crosslinking density of the hardened|cured material of a resin composition layer becomes sufficient, and the insulating layer with small surface roughness can be obtained. The epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured in accordance with JIS K7236.

(D) The weight average molecular weight (Mw) of a component is 100-5000 from a viewpoint of remarkably obtaining the desired effect of this invention, More preferably, it is 200-3000, More preferably, it is 250-1500. The weight average molecular weight of resin can be measured as the value of polystyrene conversion by the gel permeation chromatography (GPC) method.

The content of the component (D) is preferably at least 1% by mass, more Preferably, it is 5 mass % or more, More preferably, it is 10 mass % or more. The upper limit of the content of the epoxy resin is preferably at most 25% by mass, more preferably at most 20% by mass, particularly preferably at most 15% by mass, from the viewpoint of remarkably obtaining the desired effect of the present invention.

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

Typical photosensitive (meth)acrylate compounds include, for example, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate, ethylene glycol, methoxytetraethylene Diol, polyethylene glycol, propylene glycol and other diol mono- or diacrylates, N,N-dimethylacrylamide, N-methylolacrylamide and other acrylamides, acrylic acid N,N- Amino alkyl acrylates such as dimethylaminoethyl ester, polyhydric alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol, or additions of ethylene oxide, propylene oxide, or ε-caprolactone Polyacrylic acid esters, phenoxy acrylate, phenoxy ethyl acrylate and other phenols, or acrylates such as ethylene oxide or propylene oxide adducts, trimethylolpropane three Epoxy acrylates derived from glycidyl ethers such as glycidyl ether, modified epoxy acrylates, melamine acrylates, and/or methacrylates corresponding to the above-mentioned acrylates, etc. Among these, polyvalent acrylates or polymethacrylates are preferred, and examples of trivalent acrylates or methacrylates include trimethylolpropane tri(meth)acrylate, Pentaerythritol tri(meth)acrylate, trimethylolpropane EO addition tri(meth)acrylate, glycerol PO addition 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 base) acrylate, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate Esters, (meth)acrylates of N,N,N',N'-tetrakis(β-hydroxyethyl)ethylenediamine, etc., as acrylates or methacrylates of trivalence or more, include Tris(2-(meth)acryloxyethyl)phosphate, Tris(2-(meth)acryloxypropyl)phosphate, Tris(3-(meth)acryloxypropyl)phosphate oxypropyl) ester, tris(3-(meth)acryl-2-hydroxyloxypropyl) phosphate, bis(3-(meth)acryl-2-hydroxyloxypropyl) phosphate )(2-(meth)acryloxyethyl)ester, (3-(meth)acryl-2-hydroxyloxypropyl)bis(2-(meth)acryloxypropyl)phosphate Phosphate triester (meth)acrylate such as ethyl ethyl) ester. These photosensitive (meth)acrylate compounds may be used alone or in combination of two or more. "EO" means ethylene oxide.

(E) A commercially available product can be used for a reactive diluent. As a commercial item, "DPHA" by Nippon Kayaku Co., Ltd., "EBECRYL3708" by Daicel Allnex, etc. are mentioned, for example.

The content of component (E) is preferably 1% when the non-volatile components in the photosensitive resin composition are 100% by mass, from the viewpoint of promoting photocuring and suppressing stickiness when it is made into a cured product. Mass % or more, more preferably 3 mass % or more, more preferably 5 mass % or more, preferably 40 mass % or less, more preferably 35 mass % or less, further preferably 30 mass % or less, 20 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. By containing (F)component, the viscosity of a varnish can be adjusted. (F) Organic solvents include, for example, ketones such as methyl ethyl ketone (MEK) and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, etc. agent, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers, ethyl acetate Esters, butyl acetate, butyl cellosolve acetate, carbitol acetate, ethyl diethylene glycol acetate and other esters, octane, decane and other aliphatic hydrocarbons, petroleum ether, naphtha , Hydrogenated naphtha, solvent naphtha and other petroleum-based solvents. These can be used individually by 1 type, or in combination of 2 or more types. The content in the case of using an organic solvent can be appropriately adjusted from the viewpoint of coatability of the photosensitive resin composition.

＜(G)Other additives＞ The photosensitive resin composition may further contain (G) other additives to such an extent that the object of the present invention is not hindered. As (G) other additives, for example, thermoplastic resins, organic fillers, fine particles such as melamine and organic bentonite, phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene Colorants such as black, polymerization inhibitors such as hydroquinone, phenothiazine, methyl hydroquinone, hydroquinone monomethyl ether, catechol, gallicol, organic clay, montmorillonite and other thickeners, silicon Ketone-based, fluorine-based, vinyl resin-based defoamers, brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus-based compounds, aromatic condensed phosphates, halogen-containing condensed phosphates, etc. Various additives such as thermosetting resins such as combustion agents, phenolic hardeners, and cyanate hardeners.

The photosensitive resin composition mixes the above-mentioned (A)~(B) components as essential components, and appropriately mixes the above-mentioned (C)~(G) components as optional components. In addition, it can be prepared by three-roll mill, ball mill, The resin varnish is produced by kneading or stirring by kneading means such as a bead mill or a sand mill, or by a stirring means such as a super mixer, a planetary mixer, or a high-speed rotary mixer.

<Physical properties and uses of photosensitive resin composition> Since the photosensitive resin composition contains (A-1) component and (A-2) component, it shows the characteristic excellent in resolution. Specifically, when a via hole is formed by exposing and developing a photosensitive resin composition, the minimum opening diameter (minimum via hole diameter) of a formable via hole can be reduced without causing residue or peeling. The minimum opening diameter is preferably 60 μm or less, more preferably less than 50 μm. The lower limit is not particularly limited, and it can be set to 1 μm or more. The measurement of the minimum opening diameter can be performed according to the method described in Examples described later.

Since the photosensitive resin composition contains (A-1) component and (A-2) component, it shows the characteristic excellent in resolution. Specifically, when a via hole is formed by exposing and developing a photosensitive resin composition, it is possible to form a via hole in which the occurrence of undercuts is suppressed. Specifically, the difference between the radius of the uppermost portion and the radius of the bottom can be formed. Small, or indistinguishable shape vias. Specifically, the radius (μm) of the uppermost part and the radius (μm) of the bottom of the cross section of the via hole having an opening diameter of 50 μm were measured by SEM. Find the difference between the uppermost radius and the bottom radius (uppermost radius - bottom radius). As a result, it 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 described later.

After photocuring the photosensitive resin composition, the cured product that is thermally cured at 180° C. for 30 minutes can improve the peel strength (adhesion) with the conductor layer formed by plating. Therefore, when an insulating layer and a solder resist are formed from this hardened|cured material, the insulating layer with high peeling strength with a plated 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, and may be, for example, 10.0 kgf/cm or less. The peel strength can be measured according to the method described in the Examples described later.

The roughened surface obtained by photocuring the photosensitive resin composition and then thermally curing the cured product at 180° C. for 30 minutes is generally characterized by a low arithmetic mean roughness (Ra). Therefore, the aforementioned cured product obtains an insulating layer having a low arithmetic mean roughness. The arithmetic mean roughness is preferably at most 400 nm, more preferably at most 200 nm, further preferably at most 200 nm. On the other hand, the lower limit of the arithmetic mean roughness may be 1 nm or more. Evaluation of the arithmetic mean roughness can be measured according to the method described in the Examples described later.

After photocuring the photosensitive resin composition, a cured product that is thermally cured at 170° C. for 1 hour usually has 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 greater than 150°C. The upper limit is not particularly limited, and may be 350° C. or lower. The measurement of glass transition temperature (Tg) can be measured by the method described in the Example mentioned later.

After photocuring the photosensitive resin composition, a cured product that is thermally cured at 170° C. for 1 hour usually exhibits a low average coefficient of thermal expansion (CTE). That is, an insulating layer and a solder resist having a low average linear thermal expansion coefficient are obtained. The average linear thermal expansion rate is preferably at most 70 ppm, more preferably at most 50 ppm, further preferably at most 50 ppm. The lower limit is not particularly limited, and may be 10 ppm or more. The average linear thermal expansion coefficient can be measured according to the method described in the examples described later.

The application of the photosensitive resin composition of the present invention is not particularly limited, and it can be used for photosensitive films with supports, insulating resin sheets such as prepregs, circuit boards (for laminated boards, multilayer printed wiring boards, etc.), resistors, etc. A wide range of applications requiring photosensitive resin compositions, such as fluxes, underfill materials, die bonding materials, semiconductor sealing materials, hole filling resins, and component embedding resins. Among them, photosensitive resin compositions for insulating layers of printed wiring boards (printed wiring boards in which a cured product of the photosensitive resin composition is used as an insulating layer), photosensitive resin compositions for interlayer insulating layers (containing The cured product of the photosensitive resin composition is used as an interlayer insulating layer (interlayer insulating material) for printed wiring boards), the photosensitive resin composition for plating formation (the printed wiring board in which plating is formed on the cured product of the photosensitive resin composition ), and a photosensitive resin composition for solder resist (a 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 photosensitive film with a support in which a photosensitive resin composition layer is formed on a support. That is, the photosensitive film with a support 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, etc. , particularly preferably a polyethylene terephthalate film.

Commercially available supports include, for example, product names "Alphan MA-410" and "E-200C" manufactured by Oji Paper Co., Ltd., polypropylene films such as those manufactured by Shin-Etsu Film Co., Ltd., and product names "PS-25" manufactured by Teijin Corporation. ” and other PS series and other polyethylene terephthalate films, etc., but not limited to these. These supports may be coated with a release agent such as a silicone coating agent on the surface in order to facilitate the removal of the photosensitive resin composition layer. 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, the support can be suppressed from cracking when the support is peeled off before development, and by setting the thickness to 50 μm or less, the resolution at the time of exposure from the support can be improved. Moreover, it is preferable that it is a low fisheye support body. Here, fish eyes mean that foreign matter, undissolved matter, oxidative deterioration, etc. of the material enter the film when the film is produced by thermal melting, kneading, extrusion, biaxial stretching, casting, etc. of the material.

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

By protecting the photosensitive resin composition layer side of the photosensitive film with a support with a protective film, it is possible to prevent adhesion of dirt and the like or scratches on the surface of the photosensitive resin composition layer. As the protective film, a film made of the same material as the above-mentioned support can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and even more preferably in the range of 10 μm to 30 μm. By setting the thickness to 1 μm or more, the handleability of the protective film can be improved, and by setting it to 40 μm or less, there is a tendency that the cheapness becomes better. Furthermore, the protective film preferably has smaller adhesive force between the photosensitive resin composition layer and the protective film than the adhesive force between the photosensitive resin composition layer and the support.

The photosensitive film with a support can be formed by, for example, preparing a resin varnish obtained by dissolving the photosensitive resin composition of the present invention in an organic solvent, coating the resin varnish on a support, and applying heat or hot air. The organic solvent is dried to form a photosensitive resin composition layer, thereby producing. Specifically, first, after the bubbles in the photosensitive resin composition are completely removed by a vacuum defoaming method, etc., the photosensitive resin composition is coated on a support, and the solvent is removed by a hot air furnace or a far-infrared furnace, After drying, if necessary, a protective film is laminated on the obtained photosensitive resin composition layer to manufacture a photosensitive film with a support. The specific drying conditions vary depending on the curability of the photosensitive resin composition and the amount of organic solvent in the resin varnish. In a resin varnish containing 30% by mass to 60% by mass of organic solvent, it can be dried at 80°C to 120°C. 3 minutes to 13 minutes to dry. 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, more preferably Make it 2 mass % or less. Those skilled in the art can properly set suitable drying conditions through simple experiments. The thickness of the photosensitive resin composition layer is preferably in the range of 5 μm to 500 μm, more preferably 10 μm to 200 μm, from the viewpoint of improving handleability and suppressing reduction in sensitivity and resolution inside the photosensitive resin composition layer. The range of 15 μm to 150 μm is further preferred, the range of 20 μm to 100 μm is further more preferred, and the range of 20 μm to 60 μm is particularly preferred.

Examples of coating methods for the photosensitive resin composition include gravure coating, micro-gravure coating, reverse coating, kiss reverse coating, die coating, and slot die coating. method, lip coating method, notch wheel coating method, blade coating method, roll coating method, blade coating method, curtain coating method, chamber gravure coating method, slit hole (slot orifice) method, spray coating method, dip coating method, etc.

The photosensitive resin composition can be applied multiple times, or can be applied at one time, and can also be applied in combination of various methods. Among them, a die coating method excellent in uniform coating property is preferable. In addition, in order to avoid contamination of foreign matter, etc., it is preferable to carry out the coating step in an environment where foreign matter is rarely generated, such as a clean room.

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

In detail, the printed wiring board of this invention can be manufactured using the said photosensitive film with a support body. Hereinafter, a case where the insulating layer is a solder resist will be described.

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

Examples of the circuit board include glass epoxy boards, metal boards, polyester boards, polyimide boards, BT resin boards, and thermosetting polyphenylene ether boards. Furthermore, the circuit board here refers to a substrate on which a patterned conductor layer (circuit) is formed on one or both sides of the above-mentioned substrate. In addition, in a multilayer printed wiring board obtained by laminating conductor layers and insulating layers alternately, substrates in which one or both surfaces of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits) are also included here. In the so-called circuit substrate. Furthermore, 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 or both surfaces of the circuit board using a vacuum laminator. In the lamination step, when the photosensitive film with a support has a protective film, after removing the protective film, the photosensitive film with a support and the circuit board are preheated as necessary to dry the photosensitive resin composition layer. Pressing and bonding to the circuit board while applying pressure and heating. For the photosensitive film with a support, the method of laminating on a circuit board under reduced pressure by this vacuum lamination method is suitably used.

The conditions of the lamination step are not particularly limited. For example, the crimping temperature (lamination temperature) is preferably set at 70°C to 140°C, and the crimping pressure is preferably set at 1kgf/cm ² to 11kgf/cm ² (9.8× 10 ⁴ N/m ² to 107.9×10 ⁴ N/m ² ), the crimping time is preferably 5 seconds to 300 seconds, and the air pressure is preferably 20 mmHg (26.7 hPa) or less, and the lamination is performed under reduced pressure. Furthermore, the lamination step may be batch or continuous using rolls. The vacuum lamination method can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum applicator made by Nikko Materials Co., Ltd., a vacuum pressurized laminator made by Meiji Seisakusho Co., Ltd., a roll-type dry coater made by Hitachi Industries, and a vacuum laminator made by Hitachi AIC Co., Ltd. are mentioned. Laminating machines etc. In this manner, the photosensitive film with a support is formed on the circuit board.

Instead of laminating the photosensitive film with a support, the photosensitive resin composition may be directly coated on the circuit board in the state of resin varnish, and the organic solvent may be dried to form a photosensitive resin composition layer on the circuit board. As a coating method, in general, full-surface printing by a screen printing method is often used, but other than that, any method may be used as long as it is a coating method that enables uniform coating. 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 coating method, roll coating method, gravure Coating methods, lithographic printing methods, dip coating methods, brush coating methods, and other common coating methods can be used. After coating, it is dried in a hot air oven, a far infrared oven, or the like as necessary. The drying condition is preferably at 80°C~120°C for 3 minutes to 13 minutes.

<Exposure step> After the photosensitive resin composition layer is provided on the circuit board through the above steps, then, a predetermined part of the photosensitive resin composition layer is irradiated with active light by using a mask pattern, and the irradiated part is irradiated. The exposure step of photohardening of the photosensitive resin composition layer. Examples of active rays include ultraviolet rays, visible rays, electron beams, X-rays, and the like, and ultraviolet rays are particularly preferred. The irradiation amount of ultraviolet rays is about 10mJ/cm ² -1000mJ/cm ² . Among the exposure methods, there are contact exposure methods in which a mask pattern is brought into close contact with a printed wiring board, and non-contact exposure methods in which exposure is performed using parallel rays without contact, and both can be used. Moreover, when a support exists on a photosensitive resin composition layer, it may expose from a support, and may expose after peeling a support.

Since the photosensitive resin composition of this invention is used for a soldering resist, it is excellent in developability (resolution). Therefore, as the exposure pattern in the mask pattern, for example, the ratio (L/S) of the circuit width (line; L) to the width between circuits (space; S) is 100 μm/100 μm or less (that is, the wiring pitch is 200 μm below), L/S=80μm/80μm or below (wiring pitch below 160μm), L/S=70μm/70μm or below (wiring pitch below 140μm), L/S=60μm/60μm or below (wiring pitch below 120μm) . Also, the pitch need not be the same across the entirety of the circuit substrate.

＜Development step＞ After the exposure step, if there is a support body on the photosensitive resin composition layer, after removing the support body, wet or dry development is used to remove and develop the non-photohardened part (unexposed part), thereby enabling form a pattern.

In the case of the above-mentioned wet development, a safe and stable developer with good workability, such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, is used as the developing solution. Among them, the developing step using an alkaline aqueous solution is particularly preferable. Moreover, well-known methods, such as spraying, shaking dipping, brushing, and scraping, are employ|adopted suitably as a developing method.

Examples of the alkaline aqueous solution used as a developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; sodium phosphate; phosphoric acid; Aqueous solutions of alkali metal phosphates such as potassium, sodium pyrophosphate, and potassium pyrophosphate; aqueous solutions of organic bases such as tetraalkylammonium hydroxide that do not contain metal ions, which do not contain metal ions and are not harmful to semiconductor wafers In terms of influence, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferable.

In these alkaline aqueous solutions, in order to improve the developing effect, a surfactant, an antifoaming agent, etc. may be added to the developing solution. 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. In addition, the alkali concentration of the alkaline aqueous solution is preferably set to 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, and is preferably set at 20°C to 50°C.

The organic solvent used as a developer is, for example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group with 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether.

The concentration of such an organic solvent is preferably 2% by mass to 90% by mass relative to the total amount of the developer. In addition, the temperature of such an organic solvent can be adjusted according to developability. Furthermore, such an organic solvent can be used individually or in combination of 2 or more types. Examples of organic solvent-based developers used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl Isobutyl ketone, gamma-butyrolactone.

In pattern formation, if necessary, two or more of the above-mentioned developing methods may be used in combination. The developing method includes dipping method, liquid filling method, spraying method, high-pressure spraying method, brushing, scraping, etc., and the high-pressure spraying method is suitable for improving the resolution. The spray pressure in the case of using a spray method is preferably 0.05 MPa to 0.3 MPa.

<Thermosetting (post-baking) step> After the above-mentioned development step is completed, a thermosetting (post-baking) step is performed to form a solder resist. As a post-baking process, the heating process using a clean oven etc. are mentioned. The heating conditions may be appropriately selected according to the type and content of the resin components in the photosensitive resin composition, preferably at 150°C to 220°C for 20 minutes to 180 minutes, more preferably at 160°C to 200°C Select from the range of 30 minutes to 120 minutes. This step may be an ultraviolet irradiation step using a high-pressure mercury lamp. In the case of irradiating ultraviolet rays, the irradiation amount can be adjusted as necessary, for example, it can be irradiated at an irradiation amount of about 0.05 J/cm ² to 10 J/cm ² .

＜Other steps＞ After forming the solder resist, the printed wiring board may further include a hole-opening step and a smear-removing step. These steps can be implemented according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards.

After forming the solder resist, if desired, the solder resist formed on the circuit board is subjected to a hole-opening step to form via holes and through-holes. The drilling step can be performed by well-known methods such as drill, laser, plasma, etc., and these methods can be combined as needed, and the drilling step using lasers such as carbon dioxide laser and YAG laser is preferred.

The desmearing step is a step of performing desmearing treatment. In general, resin residue (smear) adheres to the inside of the opening formed in the drilling step. Since the smear becomes a cause of poor electrical connection, a process for removing smear (smear removal process) is performed in this step.

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

As a dry desmear process, the desmear process using plasma etc. are mentioned, for example. The desmear treatment using plasma can be performed using a commercially available plasma desmear treatment apparatus. Among commercially available plasma desmearing equipment, examples suitable for the production of printed wiring boards include microwave plasma equipment manufactured by Nissin Co., Ltd., and atmospheric pressure plasma etching equipment manufactured by Sekisui Chemical Industry Co., Ltd. .

As a wet desmear process, the desmear process using an oxidizing agent solution etc. are mentioned, for example. When performing desmearing treatment using an oxidizing agent solution, it is preferable to perform swelling treatment using a swelling solution, oxidation treatment using an oxidizing solution, and neutralization treatment using a neutralizing solution in this order. As a swelling liquid, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan Co., Ltd., etc. are mentioned, for example. The swelling treatment is preferably performed by immersing the substrate on which via holes and the like are formed in a swelling liquid heated to 60° C. to 80° C. for 5 minutes to 10 minutes. The oxidizing agent solution is preferably an aqueous alkaline permanganic acid solution, and examples include solutions in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide. The oxidation treatment using the oxidizing agent solution can be performed by immersing the swelled substrate in the oxidizing agent solution heated to 60° C. to 80° C. for 10 minutes to 30 minutes. As a commercial item of alkaline permanganic acid aqueous solution, for example, "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd., "Dosing Solution Securiganth P", etc. The neutralization treatment using a neutralizing solution is preferably carried out by immersing the oxidized substrate in a neutralizing solution at 30° C. to 50° C. for 3 minutes to 10 minutes. As a neutralizing solution, it is more It is preferably an acidic aqueous solution, and as a commercial product, for example, Atotech Japan Co., Ltd. product "Reduction Solution Securiganth P".

In the case of performing dry desmear treatment and wet desmear treatment in combination, dry desmear treatment may be performed first, or wet desmear treatment may be performed first.

When an insulating layer is used as an interlayer insulating layer, it can be performed similarly to the case of a solder resist, and after a thermosetting process, a drilling process, a desmear process, and a plating process can be performed.

The plating step is a step of forming a conductor layer on the insulating layer. The conductor layer can be formed by combining electroless plating and electrolytic plating. In addition, it is also possible to form a plating resist with a pattern opposite to that of the conductor layer, and form the conductor layer only by electroless plating. As a subsequent pattern forming method, for example, a subtractive method, a semi-additive method, or the like known to those skilled in the art can be used.

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

Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as locomotives, automobiles, trains, ships, and aircraft).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor wafer) at a conductive portion of a printed wiring board. The "conduction part" refers to "the part where electrical signals are transmitted in the printed wiring board", and the part may be a surface or a buried part. In addition, the semiconductor wafer is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The mounting method of the semiconductor wafer when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor wafer functions effectively. Specifically, a wire bonding mounting method, a flip chip mounting method, and a bumpless build-up ( BBUL), the mounting method using anisotropic conductive film (ACF), the mounting method using non-conductive film (NCF), etc. Here, "a mounting method using a bumpless build-up layer (BBUL)" means "a mounting method in which a semiconductor chip is directly buried in a recess of a printed wiring board, and the semiconductor chip is connected to wiring on the printed wiring board." [Example]

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to these examples. In addition, in the following description, "part" and "%" which show an amount refer to "part by mass" and "% by mass", respectively, unless otherwise specified. The weight average molecular weight is a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography.

<Synthesis Example 1: Synthesis of Naphthol Aralkyl Type Epoxy Acrylate (1000)> 325 parts of epoxy resin ("ESN-475V", manufactured by Nippon Steel Chemical & Materials Co., Ltd.) having a naphthol aralkyl skeleton with an epoxy equivalent of 325g/eq. 340 parts of carbitol acetate were added to the flask of the thermometer, heated and dissolved, and 0.46 parts of hydroquinone and 1 part of triphenylphosphine were added. The mixture was heated to 95-105° C., 72 parts of acrylic acid was slowly added dropwise, and reacted for 16 hours. The reaction product was cooled to 80 to 90° C., 80 parts of tetrahydrophthalic anhydride was added, reacted for 8 hours, and cooled. Adjust the amount of solvent to obtain the resin solution (70% of non-volatile content, hereinafter referred to as "naphthol aralkyl type epoxy acrylate (1000)" or "naphthol aralkyl) of the acid value of solid matter 60mgKOH/g type (1000)"). The weight average molecular weight of naphthol aralkyl type epoxy acrylate (1000) was 1000.

<Examples 1-13, Comparative Examples 1-9> The components were blended at the blending ratio shown in the table below, and a resin varnish was prepared using a high-speed rotary mixer.

Next, as a support, a PET film (manufactured by Toray Corporation, "Lumirror T6AM", thickness 38 μm, Softening point 130°C, "release PET"). The prepared resin varnish was uniformly coated on the release PET with a die coater so that the thickness of the dried photosensitive resin composition layer reached 25 μm, and dried at 80° C. to 110° C. for 6 minutes. In this way, a photosensitive film with a support having a photosensitive resin composition layer on the release PET was obtained.

<Measurement of Glass Transition Temperature and Average Linear Thermal Expansion Coefficient> (Preparation of Hardened Product A for Evaluation) The photosensitive resin composition layer of the photosensitive film with support obtained in Examples and Comparative Examples was subjected to 2 J/cm ² Ultraviolet ray irradiation was performed, and heat treatment was further performed at 170° C. for 1 hour to obtain a cured product. Thereafter, the support was peeled off to obtain a cured product A for evaluation.

(Measurement of glass transition temperature (Tg)) The hardened 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 was subjected to thermomechanical analysis by a tensile weight method using a dynamic viscoelasticity measuring device (EXSTAR6000, manufactured by SII Nanotechnology). After attaching the test piece to the aforementioned device, it was measured under the measurement conditions of a load of 200 mN and a temperature increase rate of 2° C./min. The peak top of the obtained tan δ was calculated as the glass transition temperature (° C.), and evaluated according to the following criteria.

◯: The glass transition temperature is 150° C. or higher.

×: The glass transition temperature is lower 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 weight method using a thermomechanical analysis device (manufactured by Rigaku, Thermo Plus, TMA8310). After attaching the test piece to the aforementioned apparatus, the measurement conditions were continuously measured twice under the measurement conditions of a load of 1 g and a temperature increase rate of 5° C./min. The average linear coefficient of thermal expansion (ppm) from 25° C. to 150° C. in the second measurement was calculated, and evaluated according to the following criteria.

◯: The average linear thermal expansion rate is less than 50 ppm.

Δ: The average linear thermal expansion rate is not less than 50 ppm and not more than 70 ppm.

X: The average linear thermal expansion rate is more than 70 ppm.

<Preparation of laminate A for evaluation> The copper layer of the glass epoxy substrate (copper-clad laminate) on which the circuit obtained by patterning the copper layer with a thickness of 18 μm was formed was treated with a surface treatment agent (CZ8100, manufactured by MEC Corporation) containing an organic acid. Implement roughening. Next, the photosensitive resin composition layer of the photosensitive film with a support obtained in Examples and Comparative Examples was arranged so that the surface of the copper circuit was in contact, and laminated using a vacuum laminator (manufactured by Nikko Materials, VP160). , A laminate A for evaluation in which the copper-clad laminate, the photosensitive resin composition layer, and the support were laminated in this order was produced. The crimping conditions were evacuation time of 30 seconds, crimping temperature of 80° C., crimping pressure of 0.7 MPa, and pressurization time of 30 seconds. After preparing the laminated body A for evaluation, it left still at room temperature (25 degreeC) for 30 minutes or more.

<Evaluation of resolution> (1) Exposure, development, and hardening steps of the photosensitive resin composition layer. From the support of the evaluation laminate A, use a 41-stage step exposure meter and a hole pattern. The device is formed and exposed to ultraviolet light. The exposure pattern uses a quartz glass mask that draws circular holes with openings: 40 μm/50 μm/60 μm/70 μm/80 μm/90 μm/100 μm. After leaving still at room temperature for 30 minutes, the support body was peeled off from the laminated board A for evaluation. On the entire surface of the photosensitive resin composition layer on the evaluation laminate A, a 30° C. 1 mass % sodium carbonate aqueous solution was spray-developed for 1 minute at a spray pressure of 0.2 MPa as a developer. After the spray development, 2 J/cm ² of ultraviolet rays were irradiated, and heat treatment was further performed at 170° C. for 1 hour to harden the photosensitive resin composition layer.

(2) Evaluation of resolution The exposure energy at which the number of gloss remaining steps of the 41-segment step exposure meter reaches 8 is recorded as the sensitivity of the photosensitive resin composition. The evaluation laminate A exposed at this sensitivity observed the patterned circular holes with SEM (magnification 1000 times), observed the minimum via hole diameter without residue or peeling, and evaluated according to the following criteria.

○: The minimum via hole diameter is less than 50 μm.

Δ: The minimum via hole diameter is not less than 50 μm and not more than 60 μm.

×: There is no minimum via hole diameter of 60 μm or less.

In addition, regarding the observation of the undercut, a via hole having a via hole diameter of 50 μm was observed with a SEM (magnification: 1000 times). The radius (μm) at the top and the radius (μm) at the bottom of the cross-section of a via hole with an opening diameter of 50 μm were measured by SEM, and the difference between the radius at the bottom and the radius at the top (radius at the bottom - the radius at the bottom) was obtained. Radius of the upper part), the obtained value was regarded as an undercut, and evaluated according to the following criteria.

◎: No undercut.

○: The undercut is less than 3 μm.

Δ: The undercut is 3 μm or more and 6 μm or less.

X: The undercut is larger than 6 μm. Or a via hole with a via hole diameter of 50 μm is not opened.

<Evaluation of roughness and peel strength> (1) Exposure, development, and curing steps of the photosensitive resin composition layer. Using a patterning device on the support of the evaluation laminate A, the gloss of the surface was exposed in 41 stages. Ultraviolet exposure is carried out with the exposure energy of 8 stages remaining. The quartz glass mask uses a mask with no exposure pattern. After leaving still at room temperature for 30 minutes, the support body was peeled off from the laminated board A for evaluation. On the entire surface of the photosensitive resin composition layer on the evaluation laminate A, a 30° C. 1 mass % sodium carbonate aqueous solution was spray-developed for 1 minute at a spray pressure of 0.2 MPa as a developer. After the spray development, 2 J/cm ² of ultraviolet rays were irradiated, and heat treatment was further performed at 170° C. for 1 hour to harden the photosensitive resin composition layer.

(2) Roughening treatment The laminate A for evaluation was immersed in Swelling Dip Securiganth P containing diethylene glycol monobutyl ether as a swelling solution at 60°C for 10 minutes, followed by roughening. solution, in Concentrate Compact P (KMnO ₄ : 60g/L, NaOH: 40g/L aqueous solution) manufactured by Atotech Japan Co., Ltd. Immerse in Securiganth P for 5 minutes at 40 °C. The laminated board A for evaluation after this roughening process was made into the sample A.

(3) Plating Formation by Semi-Additive Process In order to form a circuit on the surface of the insulating layer, the sample A was immersed in an electroless plating solution containing PdCl ₂ , and then immersed in an electroless copper plating solution. After annealing by heating at 150° C. for 30 minutes, a corrosion resist was formed, patterned by etching, and copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 25 μm. Next, an annealing treatment was performed at 180° C. for 60 minutes. This sample A was made into sample B.

(4) Determination of arithmetic mean roughness (Ra) For sample A, a non-contact surface roughness meter (Veeco WYKO NT3300 manufactured by Instruments Co., Ltd., with a VSI mode and a 50x lens, the measurement range was set to 121 μm×92 μm, and the arithmetic mean roughness (Ra) was obtained from the obtained value. And by obtaining the average value of each 10 points, it evaluated according to the following reference|standard as a measured value.

◯: Arithmetic mean roughness is less than 200 μm.

Δ: Arithmetic mean roughness is 200 μm or more and 400 μm or less.

X: The arithmetic average roughness is more than 400 μm.

(5) Measurement of the peel strength (peel strength) of the plated conductor layer On the conductor layer of sample B, a slit of a portion with a width of 10 mm and a length of 100 mm was introduced, and the end was peeled off, clamped with a jig (manufactured by TSE Corporation, Autocom type testing machine, AC-50C-SL), and at room temperature, The load (kgf/cm) at the time of peeling 35 mm in the vertical direction at the speed of 50 mm/min was measured, and it evaluated by the following reference|standard.

○The peel strength is 0.3 kgf/cm or more.

×: Peel strength is less than 0.3 kgf/cm.

Abbreviations in the tables are as follows.

・CCR-1373H: Cresol novolak type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH/g, solid content concentration about 60%, weight average molecular weight 2800) ・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) ・Naphthol aralkyl type (1000): naphthol aralkyl type epoxy acrylate (1000) synthesized in Synthesis Example 1 ・CCR-1171H: Cresol novolak 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-1224H: Cresol novolak type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH/g, solid content concentration about 60%, weight average molecular weight 8700) ・ZCR-1797H: Biphenyl type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH/g, solid content concentration about 60%, weight average molecular weight 6500) ・Omnipol 910: A compound (manufactured by IGM Corporation, molecular weight 850 or more) represented by the following structure. In the formula, d represents an integer of 1 to 10.

・Omnipol TP：下述結構所示的化合物(IGM公司製、分子量為900以上)式中，a、b、c分別表示1~10的整數。

・Omnipol TP: A compound (manufactured by IGM Corporation, molecular weight 900 or more) represented by the following structure. In the formula, a, b, and c each represent an integer of 1 to 10.

・Omnirad379EG：(IGM公司製、分子量380.5)。

・Omnirad379EG: (manufactured by IGM Corporation, molecular weight: 380.5).

・Omnirad TPO：(IGM公司製、分子量348)。

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

・SO-C2：無機填充材料(球狀二氧化矽、Admatechs公司製、平均粒徑0.5μm、比表面積6m ²/g) ・NC3000H：聯苯型環氧樹脂(日本化藥公司製、環氧當量271g/eq.) ・DPHA：二季戊四醇六丙烯酸酯(日本化藥公司製) ・EDG-Ac：乙基二乙二醇乙酸酯 ・MEK：甲基乙基酮。

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

In each example, even when (C)-(F) component etc. were not contained, although there were differences in degree, it confirmed that the same result as the above-mentioned example was attributed.

Claims (11)

A photosensitive resin composition, which contains: (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 2,000 or more greater than that of the component (A-1), and (B) a photopolymerization initiator; and (B) The molecular weight of a component is 400 or more. The photosensitive resin composition according to Claim 1, further comprising (C) an inorganic filler. The photosensitive resin composition according to claim 2, wherein the content of the component (C) is 1% by mass or more when the non-volatile components in the photosensitive resin composition are 100% by mass. Such as the photosensitive resin composition of claim 1, wherein, (A-1) component and (A-2) component have cresol novolac skeleton, bisphenol A skeleton, bisphenol F skeleton, biphenyl skeleton and naphthol aromatic Any of the alkyl skeletons. The photosensitive resin composition according to Claim 1, wherein the components (A-1) and (A-2) contain epoxy (meth)acrylates containing an acid-modified cresol novolak skeleton. The photosensitive resin composition according to claim 1, wherein component (B) has a structural unit represented by the following formula (B-1);

In the formula (B-1), R ¹ represents an active ray absorbing group, and R ² independently represent a divalent hydrocarbon group; n represents an integer of 1 to 10; * represents a bonding position. The photosensitive resin composition according to claim 1, which is used to form a solder resist. A photosensitive film with a support, which has a support and a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 7 disposed on the support. A printed wiring board including an insulating layer formed of a cured product of the photosensitive resin composition according to any one of claims 1 to 7. The printed wiring board according to claim 9, wherein the insulating layer is any one of an interlayer insulating material and a solder resist. A semiconductor device comprising the printed wiring board according to claim 9 or 10.