TW202115137A - Photosensitive resin composition capable of obtaining a cured product excellent in flexibility and insulation properties and excellent in resolution - Google Patents

Abstract

The object of the present invention is to provide a photosensitive resin composition capable of obtaining a cured product excellent in flexibility and insulation properties and having an excellent resolution. The solution of the present invention is a photosensitive resin composition containing (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an epoxy resin, (C) a photopolymerizable monomer and (D) a photopolymerization initiator. Any one of the components (A), (B) and (C) contains an alkylene oxide chain. A parameter X represented by the formula (1) is 4 or more but 25 or less.

Description

Photosensitive resin composition

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

In the printed wiring board, a solder resist layer is provided as a permanent protective film for inhibiting the adhesion of solder to the part where the solder is not needed and for inhibiting corrosion of the circuit board. As the solder resist layer, a photosensitive resin composition as described in Patent Document 1, for example, is generally used. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2014-115672 A

[The problem to be solved by the invention]

The photosensitive resin composition for the solder resist layer generally requires resolution, insulation, etc. In recent years, with the miniaturization of electronic devices, etc., space saving has become necessary, and therefore, the flexibility (bendability) of the printed wiring board is required. Flexibility is also required for the solder resist layer used in this printed wiring board.

However, the inventors of the present invention have worked hard as a result of research and found that when the flexibility is to be improved, the insulation of the solder resist will deteriorate. In the photosensitive resin composition for the solder resist, there is a difference between the flexibility and the insulation. There is a relationship of choice.

The subject of the present invention is to provide a photosensitive resin composition that can obtain a cured product with excellent flexibility and insulation and excellent resolution; and to provide a photosensitive film and a support body obtained by using the photosensitive resin composition Photosensitive films, printed wiring boards and semiconductor devices. [Means to solve the problem]

As a result of intensive research, the inventors found that the photosensitive resin composition contains an ethylenically unsaturated group and a carboxyl group-containing resin, epoxy resin, and photopolymerizable monomer containing an oxyalkylene group. (alkylene oxide) chain, and the alkylene oxide chain satisfies the predetermined relationship, and the flexibility and insulation are improved, thereby achieving the completion of the present invention.

式(1)中，M_AO 係，當包含氧化伸烷基鏈之成分為共聚物時表示下述式(2)所示之值，或當包含氧化伸烷基鏈之成分不是共聚物時表示((A)~(C)成分中所含之各化合物的氧化伸烷基鏈的分子量)/((A)~(C)成分中所含之各化合物的分子量)；N表示於(A)~(C)成分所含之全部化合物的固體成分含量(質量份)，n表示(A)~(C)成分中所含之各化合物的固體成分含量(質量份)，

式(2)中，A_AO 表示包含氧化伸烷基鏈之各單體的氧化伸烷基鏈的分子量，A表示包含氧化伸烷基鏈之各單體的分子量，B_AO 表示包含氧化伸烷基鏈之各單體的莫耳數，B表示共聚物中所含之全單體的合計莫耳數。 [2] 如[1]記載之感光性樹脂組成物，其進而包含(E)無機填充材。 [3] 如[1]或[2]記載之感光性樹脂組成物，其中氧化伸烷基鏈包含於(B)成分及(C)成分之任一者。 [4] 如[1]~[3]中任一項記載之感光性樹脂組成物，其中(A)成分包含酸改質不飽和環氧酯樹脂。 [5] 如[1]~[4]中任一項記載之感光性樹脂組成物，其中(A)成分包含酸改質環氧(甲基)丙烯酸酯。 [6] 如[1]~[5]中任一項記載之感光性樹脂組成物，其中(A)成分包含酸改質含萘骨架之環氧(甲基)丙烯酸酯及酸改質含雙酚骨架之環氧(甲基)丙烯酸酯之任一者。 [7] 如[6]記載之感光性樹脂組成物，其中酸改質含雙酚骨架之環氧(甲基)丙烯酸酯具有雙酚A骨架及雙酚F骨架之任一者。 [8] 如[1]~[7]中任一項記載之感光性樹脂組成物，其中(B)成分具有聯苯骨架。 [9] 如[1]~[8]中任一項記載之感光性樹脂組成物，其中(D)成分包含肟酯系光聚合起始劑。 [10] 一種感光性薄膜，其含有如[1]~[9]中任一項記載之感光性樹脂組成物。 [11] 一種附支持體之感光性薄膜，其具有支持體、與設置於該支持體上之包含如[1]~[9]中任一項記載之感光性樹脂組成物的感光性樹脂組成物層。 [12] 一種印刷配線板，其包含由如[1]~[9]中任一項記載之感光性樹脂組成物的硬化物所形成的絕緣層。 [13] 如[12]記載之印刷配線板，其中絕緣層為阻焊層。 [14] 一種半導體裝置，其包含如[12]或[13]記載之印刷配線板。 [發明之效果]That is, the present invention includes the following contents. [1] A photosensitive resin composition comprising: (A) a resin containing ethylenically unsaturated groups and carboxyl groups, (B) epoxy resins, (C) photopolymerizable monomers, and (D) photopolymerizable monomers Starting agent: Any one of (A) component, (B) component and (C) component contains an oxyalkylene chain, and the parameter X represented by the following formula (1) is 4 or more and 25 or less,

In formula (1), M _AO series, when the component containing the oxyalkylene chain is a copolymer, it means the value shown in the following formula (2), or when the component containing the oxyalkylene chain is not a copolymer, it means (Molecular weight of the oxyalkylene chain of each compound contained in components (A)~(C))/(Molecular weight of each compound contained in components (A)~(C)); N is expressed in (A) ~(C) The solid content (parts by mass) of all the compounds contained in the component, n represents the solid content (parts by mass) of each compound contained in the (A)~(C) components,

In formula (2), A _AO represents the molecular weight of the oxyalkylene chain of each monomer containing the oxyalkylene chain, A represents the molecular weight of each monomer containing the oxyalkylene chain, and B _AO represents the molecular weight of each monomer containing the oxyalkylene chain. The number of moles of each monomer in the base chain, and B represents the total number of moles of all monomers contained in the copolymer. [2] The photosensitive resin composition as described in [1], which further contains (E) an inorganic filler. [3] The photosensitive resin composition according to [1] or [2], in which the oxyalkylene chain is contained in either of the (B) component and (C) component. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the component (A) contains an acid-modified unsaturated epoxy ester resin. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the component (A) contains an acid-modified epoxy (meth)acrylate. [6] The photosensitive resin composition as described in any one of [1] to [5], wherein the component (A) contains an acid-modified epoxy (meth)acrylate containing a naphthalene skeleton and an acid-modified epoxy (meth)acrylate containing a double Any of phenolic epoxy (meth)acrylates. [7] The photosensitive resin composition according to [6], wherein the acid-modified bisphenol skeleton-containing epoxy (meth)acrylate has either a bisphenol A skeleton or a bisphenol F skeleton. [8] The photosensitive resin composition according to any one of [1] to [7], wherein the component (B) has a biphenyl skeleton. [9] The photosensitive resin composition according to any one of [1] to [8], wherein the component (D) contains an oxime ester-based photopolymerization initiator. [10] A photosensitive film containing the photosensitive resin composition as described in any one of [1] to [9]. [11] A photosensitive film with a support, which has a support, and a photosensitive resin composition including the photosensitive resin composition described in any one of [1] to [9] provided on the support物层。 The material layer. [12] A printed wiring board comprising an insulating layer formed of a cured product of the photosensitive resin composition as described in any one of [1] to [9]. [13] The printed wiring board as described in [12], wherein the insulating layer is a solder resist layer. [14] A semiconductor device comprising the printed wiring board as described in [12] or [13]. [Effects of Invention]

According to the present invention, it is possible to provide a photosensitive resin composition that can obtain a cured product with excellent flexibility and insulation properties and has excellent resolution; and provide a photosensitive film and a support body obtained by using the photosensitive resin composition Photosensitive films, printed wiring boards and semiconductor devices.

Hereinafter, the photosensitive resin composition, photosensitive film, photosensitive film with support, printed wiring board, and semiconductor device of the present invention will be described in detail.

式(1)中，M_AO 係，當包含氧化伸烷基鏈之成分為共聚物時表示下述式(2)所示之值，或當包含氧化伸烷基鏈之成分不是共聚物時表示((A)~(C)成分中所含之各化合物的氧化伸烷基鏈的分子量)/((A)~(C)成分中所含之各化合物的分子量)。N表示於(A)~(C)成分所含之全部化合物的固體成分含量(質量份)，n表示(A)~(C)成分中所含之各化合物的固體成分含量(質量份)。

式(2)中，A_AO 表示包含氧化伸烷基鏈之各單體的氧化伸烷基鏈的分子量，A表示包含氧化伸烷基鏈之各單體的分子量，B_AO 表示包含氧化伸烷基鏈之各單體的莫耳數，B表示共聚物中所含之全單體的合計莫耳數。[Photosensitive resin composition] The photosensitive resin composition of the present invention contains (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an epoxy resin, (C) a photopolymerizable monomer, and (D) a light A polymerization initiator in which an oxyalkylene chain is contained in any of the (A) component, (B) component, and (C) component, and the parameter X represented by the following formula (1) is 4 or more 25 the following.

In formula (1), M _AO series, when the component containing the oxyalkylene chain is a copolymer, it means the value shown in the following formula (2), or when the component containing the oxyalkylene chain is not a copolymer, it means (Molecular weight of the oxyalkylene chain of each compound contained in components (A) to (C))/(Molecular weight of each compound contained in components (A) to (C)). N represents the solid content (parts by mass) of all the compounds contained in the components (A) to (C), and n represents the solid content (parts by mass) of each compound contained in the components (A) to (C).

In formula (2), A _AO represents the molecular weight of the oxyalkylene chain of each monomer containing the oxyalkylene chain, A represents the molecular weight of each monomer containing the oxyalkylene chain, and B _AO represents the molecular weight of each monomer containing the oxyalkylene chain. The number of moles of each monomer in the base chain, and B represents the total number of moles of all monomers contained in the copolymer.

In the present invention, the oxyalkylene chain contained in any one of the (A) component, (B) component, and (C) component is adjusted with respect to all the components (A) to (C) of the curable resin It can provide a cured product with excellent flexibility and insulation, and a photosensitive resin composition with excellent resolution. In addition, a cured product with excellent adhesion is usually also obtained. The inventors of the present invention found that if the photosensitive resin composition is hydrophilic, the flexibility becomes excellent, but the insulation is poor. Therefore, we focused on the content of the oxyalkylene chain that is related to polymerization and has a hydrophobic structure in the components (A) to (C). As a result, with respect to the total components (A) to (C), the oxidation extension contained in any one of the (A) component, (B) component, and (C) component is adjusted so as to satisfy the above formula (1). The content of the alkyl chain can improve the flexibility of the photosensitive resin composition and improve both flexibility and insulation. In addition, it is considered that the adhesion is also improved by the hydrophobic structure of the oxidized alkylene chain.

式(a)中，R分別獨立地表示可具有取代基之伸烷基，q表示1~100之整數。The oxyalkylene chain has a structure represented by the following formula (a).

In formula (a), R each independently represents an alkylene group which may have a substituent, and q represents an integer of 1-100.

R represents an alkylene group which may have a substituent. 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, and even more preferably an alkylene group having 1 to 5, 1 to 4, or 1 carbon atoms. 3 of the alkylene group. Specific examples of alkylene include methylene, ethylene, propylene, isopropyl, n-butyl, pentylene, hexylene, and the like.

The alkylene group may have a substituent. As a substituent, a C1-C3 alkyl group, a halogen atom, etc. are mentioned. The substituent system may be contained singly, or may be contained in combination of two or more kinds.

q represents an integer from 1 to 100, preferably an integer from 1 to 50, more preferably an integer from 1 to 10, and still more preferably an integer from 1 to 5.

Examples of the oxyalkylene chain include methylene oxide, ethylene oxide (EO), propylene oxide (PO), and isopropyl oxide ( isopropylene oxide), butylene oxide (BO), etc.

The oxyalkylene chain is preferably contained in the component (A), is preferably contained in the component (B), and is preferably contained in the component (C). In addition, the oxyalkylene chain is preferably contained in the (A) component and (B) component, is preferably contained in the (A) component and (C) component, and is preferably contained in the (B) component and (C) component. It is preferably contained in (A) ~ (C) ingredients. Among them, the oxyalkylene chain is more preferably contained in the (B) component and (C) component.

The components (A) to (C) may have one type of oxyalkylene chain or plural kinds of oxyalkylene chains in one molecule.

The photosensitive resin composition may further contain arbitrary components combined with (A) to (D) components. Examples of optional components include (E) inorganic fillers, (F) solvents, and (G) other additives. Hereinafter, each component contained in the photosensitive resin composition will be described in detail.

＜(A) Resin containing ethylenically unsaturated group and carboxyl group＞ The photosensitive resin composition contains a resin containing an ethylenically unsaturated group and a carboxyl group as the component (A). By containing the component (A) in the photosensitive resin composition, the developability can be improved.

Examples of ethylenically unsaturated groups include vinyl groups, allyl groups, propynyl groups, butenyl groups, ethynyl groups, phenylethynyl groups, maleimino groups, nadic acid imino groups, (methyl ) An acryloyl group, and from the viewpoint of the reactivity of photoradical polymerization, a (meth)acryloyl group is preferred. "(Meth)acryloyl" refers to methacryloyl and acryloyl.

(A) The component has an ethylenically unsaturated group and a carboxyl group. With this structure, the component (A) can undergo photoradical polymerization and can undergo alkali development. As this (A) component, the resin which has both a carboxyl group and 2 or more ethylenic unsaturated groups in 1 molecule is preferable, for example.

As an aspect of the resin containing an ethylenically unsaturated group and a carboxyl group, the unsaturated epoxy ester resin etc. which make an unsaturated carboxylic acid react with an epoxy compound, and further react with an acid anhydride, etc. are mentioned. Specifically, by reacting an unsaturated carboxylic acid with an epoxy compound to obtain an unsaturated epoxy ester resin, and reacting the unsaturated epoxy ester resin with an acid anhydride, an acid-modified unsaturated epoxy ester resin can be obtained. Any one of the epoxy compound, unsaturated carboxylic acid, and acid anhydride may have an oxyalkylene chain.

The epoxy compound can be used as long as it has an epoxy group in the molecule. Examples include epoxy group-containing copolymers, bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, and bisphenols. F-type epoxy resin, hydrogenated bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, epichlorohydrin and bisphenol F-type epoxy resin are reacted to be modified into modified bisphenol F with more than three functions Bisphenol type epoxy resin such as type epoxy resin; Biphenol type epoxy resin such as biphenol type epoxy resin and tetramethyl biphenol type; Phenol novolak type epoxy resin, cresol novolak type epoxy Resin, bisphenol A novolak type epoxy resin, alkylphenol novolak type epoxy resin, etc. novolac type epoxy resin; bisphenol AF type epoxy resin and perfluoroalkyl type epoxy resin, etc. Fluorine epoxy resin; naphthalene type epoxy resin, dihydroxy naphthalene type epoxy resin, polyhydroxy binaphthyl type epoxy resin, naphthol type epoxy resin, binaphthol type epoxy resin, naphthyl ether type ring Oxygen resin naphthol novolac type epoxy resin, naphthalene type epoxy resin obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes, etc. have naphthalene skeleton epoxy resin (naphthalene skeleton-containing epoxy resin); Xylenol type epoxy resin; dicyclopentadiene type epoxy resin; triphenol type epoxy resin; tertiary butyl-catechol type epoxy resin; anthracene type epoxy resin containing condensed ring skeleton Epoxy resin; glycidyl 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 resin; Epoxy resin containing spiro ring; Cyclohexane dimethanol type epoxy resin; Trimethylol type epoxy resin; Tetraphenyl ethane type epoxy resin; Poly(methyl) ) Glycidyl acrylate, copolymer of glycidyl methacrylate and acrylate, etc.; glycidyl group-containing acrylic resin; cyanotype epoxy resin; halogenated epoxy resin, etc.

From the viewpoint of reducing the average linear thermal expansion rate, the epoxy compound is preferably an epoxy group-containing copolymer or an aromatic skeleton-containing epoxy resin. Here, the aromatic skeleton system also includes the concepts of polycyclic aromatics and aromatic heterocycles. The epoxy compound is preferably an epoxy resin containing a naphthalene skeleton; an epoxy resin containing a condensed ring skeleton; a biphenyl type epoxy resin; a bisphenol type such as bisphenol F type epoxy resin and bisphenol A type epoxy resin Epoxy resin; cresol novolac type epoxy resin; glycidyl ester type epoxy resin.

The epoxy group-containing copolymer can be obtained by polymerizing an epoxy group-containing monomer and optionally any monomer. Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 2-methyl-3,4-cyclic (meth)acrylate. Epoxy group-containing (meth)acrylate monomers such as oxycyclohexyl ester and allyl glycidyl ether are preferably glycidyl (meth)acrylate. The epoxy-containing single system can be used alone, or two or more of them can be mixed for use.

As an arbitrary monomer, for example, styrene, (meth)acrylic acid, methyl (meth)acrylate, ethyl methacrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, N-Butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, (meth)acrylic acid N-heptyl ester, n-octyl (meth)acrylate, 2-ethylhexyl methacrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, ( Tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth) ) 4-tert-butylcyclohexyl acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, benzyl (meth)acrylate, acrylamide, N,N-dimethyl (Meth)acrylamide, (meth)acrylonitrile, 3-(meth)acrylonitrile propyl trimethoxysilane, (meth)acrylic acid N,N-dimethylaminoethyl, (meth)acrylonitrile Base) glycidyl acrylate, styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate Ester, 4-hydroxy-n-butyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-n-butyl (meth)acrylate, 3-hydroxy-n-butyl (meth)acrylate Esters, 1,4-cyclohexanedimethanol mono(meth)acrylate, glycerol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, Modification of 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, lactone with hydroxyl at the end (Meth)acrylate, 1-adamantyl (meth)acrylate, etc., preferably n-butyl (meth)acrylate. Any single system may be used alone, or two or more of them may be mixed and used. "(Meth)acrylic acid" refers to acrylic acid and methacrylic acid. "(Meth)acrylate" refers to acrylate and methacrylate.

As the epoxy resin containing a naphthalene skeleton, a dihydroxynaphthalene type epoxy resin, a polyhydroxybinaphthalene type epoxy resin, and a naphthalene type epoxy resin obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes are preferable. Examples of dihydroxynaphthalene-type epoxy resins include 1,3-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyloxynaphthalene, 1,6-diglycidoxynaphthalene, Glycidyloxynaphthalene, 2,3-diglycidyloxynaphthalene, 2,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene, etc. Examples of polyhydroxy binaphthyl epoxy resins include 1,1'-bis(2-glycidyloxy)naphthyl, 1-(2,7-diglycidyloxy)-1'-(2' -Glycidyloxy)binaphthyl, 1,1'-bis(2,7-diglycidyloxy)naphthyl, etc. Examples of naphthalene-type epoxy resins obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes include 1,1'-bis(2,7-diglycidoxynaphthyl)methane, 1-(2, 7-Diglycidoxynaphthyl)-1'-(2'-glycidoxynaphthyl)methane, 1,1'-bis(2-glycidoxynaphthyl)methane.

As an unsaturated carboxylic acid, acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, glycidyl methacrylate, glycidyl acrylate, etc. are mentioned, for example, These may be used individually by 1 type, and may use 2 or more types together. Among them, acrylic acid and methacrylic acid are preferable from the viewpoint of improving the photocurability of the photosensitive resin composition. In addition, in this specification, the epoxy ester resin of the reaction product of the above-mentioned epoxy compound and (meth)acrylic acid may be described as "epoxy (meth)acrylate", where the epoxy of the epoxy compound The radical is substantially eliminated by the reaction with (meth)acrylic acid.

Examples of acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzhydryl Ketotetracarboxylic dianhydride, etc., can be used alone or in combination of two or more. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferable in terms of improving the resolution and insulation reliability of the cured product.

When obtaining acid-modified unsaturated epoxy ester resins, catalysts, solvents, polymerization inhibitors, etc. can also be used as needed.

The acid-modified unsaturated epoxy ester resin is preferably acid-modified epoxy (meth)acrylate, and more preferably contains acid-modified epoxy (meth)acrylate containing naphthalene skeleton and acid-modified epoxy (meth)acrylate. Any of epoxy (meth)acrylates of bisphenol skeleton. The "epoxy" in the acid-modified unsaturated epoxy ester resin means the structure derived from the above-mentioned epoxy compound. For example, "acid-modified bisphenol-type epoxy (meth)acrylate" refers to acid-modification obtained by using bisphenol-type epoxy resin as the epoxy compound and (meth)acrylic acid as the unsaturated carboxylic acid Unsaturated epoxy ester resin.

The acid-modified unsaturated epoxy ester resin is preferably a (meth)acrylic polymer having a glass transition temperature of -20°C or less. The (meth)acrylic polymer refers to a polymer containing a structural unit having a structure formed by polymerizing a (meth)acrylic monomer. Examples of such (meth)acrylic polymers include polymers obtained by polymerizing (meth)acrylic monomers, or (meth)acrylic monomers and copolymers that can be copolymerized with (meth)acrylic monomers. The monomer is copolymerized to form a polymer.

Examples of (meth)acrylic polymers having a glass transition temperature of -20°C or less include reacting (meth)acrylic acid with an epoxy-containing copolymer, and further modifying the acid formed by the reaction with acid anhydride. Saturated epoxy (meth)acrylic copolymer, etc. In detail, an unsaturated epoxy (meth)acrylic copolymer is obtained by reacting (meth)acrylic acid with an epoxy-containing copolymer, and the unsaturated epoxy (meth)acrylic copolymer is combined with The acid anhydride is reacted to obtain an acid-modified unsaturated epoxy (meth)acrylic copolymer.

As a preferable aspect of the (meth)acrylic polymer having a glass transition temperature of -20°C or less, the following compound is obtained by polymerizing an epoxy-containing monomer and an optional monomer. Epoxy copolymer, (meth)acrylic acid, and acid anhydride are reacted to form a compound, wherein the epoxy group-containing monomer is glycidyl methacrylate, any monomer is butyl acrylate, and the acid anhydride is tetra Hydrogen phthalic anhydride.

Such an acid-modified unsaturated epoxy ester resin can be commercially available. As a specific example, "ZAR-2000" manufactured by Nippon Kayaku Co., Ltd. (a reactant of bisphenol A epoxy resin, acrylic acid, and succinic anhydride) can be used. , "ZFR-1491H", "ZFR-1533H" (reactants of bisphenol F type epoxy resin, acrylic acid and tetrahydrophthalic anhydride (acid-modified epoxy acrylate containing bisphenol F type skeleton)) , Showa Denko Corporation "PR-300CP" (cresol novolac type epoxy resin, acrylic acid and acid anhydride reactants), etc. These can be used individually by 1 type, and can also be used in combination of 2 or more types.

As other aspects of resins containing ethylenically unsaturated groups and carboxyl groups, (meth)acrylic resins having structural units obtained by polymerizing (meth)acrylic acid, and epoxy resins containing ethylenically unsaturated groups may be mentioned. An unsaturated modified (meth)acrylic resin in which the compound reacts to introduce an ethylenically unsaturated group. Examples of epoxy compounds containing ethylenically unsaturated groups include glycidyl methacrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth)acrylate. Ester etc. Furthermore, it is also possible to make an acid anhydride react with the hydroxyl group generated when the unsaturated group is introduced. As the acid anhydride, the same as the above-mentioned acid anhydride can be used, and the preferred range is also the same.

As such unsaturated modified (meth)acrylic resin, commercially available products can be used. Specific examples include "SPC-1000" and "SPC-3000" manufactured by Showa Denko Corporation and "Cyclomer" manufactured by Daicel-allnex. P(ACA)Z-250", "Cyclomer P(ACA)Z-251", "Cyclomer P(ACA)Z-254", "Cyclomer P(ACA)Z-300", "Cyclomer P(ACA)Z- 320" and so on.

(A) The weight average molecular weight of the component is preferably 1,000 or more, more preferably 1,500 or more, and still more preferably 2,000 or more from the viewpoint of film formability. From the viewpoint of developability, the upper limit is preferably 50,000 or less, more preferably 30,000 or less, and still more preferably 25,000 or less. The weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by the gel permeation chromatography (GPC) method.

(A) The acid value of the component. From the viewpoint of improving the alkali developability of the photosensitive resin composition, the acid value is preferably 0.1 mgKOH/g or more, more preferably 0.5 mgKOH/g or more, and still more preferably 1 mgKOH/ g above. On the other hand, from the viewpoint of suppressing the elution of the fine pattern of the cured product due to development and improving the insulation reliability, the acid value is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, and still more preferably 100 mgKOH/ g or less. Here, the acid value refers to the remaining acid value of the carboxyl group present in the component (A), and the acid value can be measured by the following method. First, after weighing approximately 1 g of the resin solution for measurement, 30 g of acetone is added to the resin solution to uniformly dissolve the resin solution. Next, an appropriate amount of phenolphthalein as an indicator was added to the solution, and a 0.1N KOH aqueous solution was used for titration. Next, the acid value was calculated by the following formula.

In addition, in the above formula, A(b) represents the acid value (mgKOH/g), Vf represents the titer of KOH (mL), Wp represents the mass of the measured resin solution (g), and I represents the ratio of non-volatile components in the measured resin solution (quality%).

In the manufacture of component (A), from the viewpoint of improving storage stability, the molar number of epoxy groups of the epoxy resin is preferably 1 compared with the molar number of the total carboxyl groups of the unsaturated carboxylic acid and acid anhydride. : The range of 0.8~1.3, more preferably the range of 1:0.9~1.2.

Wm表示構成(A)成分之各單體的含量(質量%)，Tgm表示構成(A)成分之各單體的玻璃轉移溫度(K)。(A) The glass transition temperature (Tg) of the component, from the viewpoint of improving flexibility, is preferably -300°C or higher, more preferably -200°C or higher, still more preferably -80°C or higher, and preferably- 20°C or less, more preferably -23°C or less, still more preferably -25°C or less. Here, the glass transition temperature of (A) component refers to the theoretical glass transition temperature of the main chain of (A) component, and this theoretical glass transition temperature can be calculated by the formula of FOX shown below. The glass transition temperature determined by the formula of FOX is almost the same as the glass transition temperature measured by differential scanning calorimetry (TMA, DSC, DTA), so it is also possible to measure (A) component by differential scanning calorimetry The glass transition temperature of the main chain.

Wm represents the content (mass %) of each monomer constituting the (A) component, and Tgm represents the glass transition temperature (K) of each monomer constituting the (A) component.

(A) From the viewpoint of improving alkali developability, when the non-volatile content in the photosensitive resin composition is 100% by mass, the component (A) is preferably 3% by mass or more, more preferably 5% by mass or more, It is still more preferably 10% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less from the viewpoint of improving heat resistance or average linear expansion. In addition, in the present invention, the content of each component in the photosensitive resin composition is a value when the non-volatile component in the photosensitive resin composition is 100% by mass, unless otherwise clearly indicated.

＜(B) Epoxy resin＞ The photosensitive resin composition contains an epoxy resin as the (B) component. By including (B) component, insulation reliability can be improved. However, here, the (B) component does not include an epoxy resin containing an ethylenically unsaturated group and a carboxyl group.

As the (B) component, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, Dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tertiary butyl-catechol type epoxy resin, naphthalene type ring Oxygen resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear Aliphatic epoxy resin, aliphatic epoxy resin containing alkylene oxide chain, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring , Cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane type epoxy resin, etc. Among them, the (B) epoxy resin is preferably a biphenyl type epoxy resin and a linear aliphatic epoxy resin, and more preferably a biphenyl type epoxy resin. (B) Epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types. As the aliphatic epoxy resin containing an oxyalkylene chain, for example, a linear aliphatic epoxy resin containing an oxyalkylene chain, a branched aliphatic epoxy resin containing an oxyalkylene chain, and an oxidized alkylene chain-containing aliphatic epoxy resin Cyclic aliphatic epoxy resin of alkylene chain, etc.

The photosensitive resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the (B) 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 per molecule is preferably 50 relative to 100% by mass of the non-volatile content of the component (B) Mass% or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more.

(B) In the component, there are epoxy resins that are liquid at a temperature of 20°C (hereinafter also referred to as "liquid epoxy resins"), and epoxy resins that are solid at a temperature of 20°C (also referred to as " Solid epoxy resin"). The resin composition system may contain only a liquid epoxy resin as the (B) component, may contain only a solid epoxy resin, and may contain a liquid epoxy resin and a solid epoxy resin in combination.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in a molecule, and more preferably an aromatic solid ring having 3 or more epoxy groups in a molecule Oxy resin.

The solid epoxy resin is preferably a dixylenol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, and a dicyclopentadiene type epoxy resin. 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, tetraphenylethane type epoxy resin, more preferably naphthalene type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolak type epoxy resin) made by DIC; "N-695" (cresol novolak type epoxy resin) made by DIC; "HP-7200" and "HP- 7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-" manufactured by DIC Corporation G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (triphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolak type manufactured by Nippon Kayaku Co., Ltd.) Epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl epoxy resin) manufactured by Nippon Kayaku Co.; "ESN475V" (naphthol epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Resin); "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co.; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical "YX4000HK" (dixylenol type epoxy resin) manufactured by the company; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Corporation; Mitsubishi Chemical "YL7760" (bisphenol AF type epoxy resin) manufactured by the company; "YL7800" manufactured by Mitsubishi Chemical Corporation (茀 type epoxy resin); "jER1010" manufactured by Mitsubishi Chemical Corporation (solid bisphenol A epoxy resin); Mitsubishi "JER1031S" (Hydroxyphenylethane type epoxy resin) manufactured by Chemical Company, etc. These can be used alone in one type, or in combination of two or more types.

As a liquid epoxy resin, the liquid epoxy resin which has 2 or more epoxy groups in 1 molecule is preferable.

The liquid epoxy resin is preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, and glycidol Amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidyl amine type epoxy resin , And epoxy resin with butadiene structure, more preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "jER828EL", "825" manufactured by Mitsubishi Chemical Corporation, "Epikote828EL" (bisphenol A epoxy resin); "jER807" and "1750" (bisphenol F epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolak epoxy resin) manufactured by Mitsubishi Chemical Corporation ; "630" and "630LSD" manufactured by Mitsubishi Chemical Corporation (glycidylamine epoxy resin); "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Corporation (mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) Product); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Kasei; "EX-821", "EX-920" (linear fat containing oxidized alkylene chain) manufactured by Nagase Kasei Group epoxy resin); "CELLOXIDE 2021P" manufactured by Daicel (alicyclic epoxy resin with ester skeleton); "PB-3600" manufactured by Daicel (epoxy resin with butadiene structure); Nippon Steel & Sumikin "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane epoxy resin), etc. manufactured by Chemical Corporation. These can be used individually by 1 type, and can also be used in combination of 2 or more types.

When using a combination of a liquid epoxy resin and a solid epoxy resin as the component (B), the ratio of these amounts (liquid epoxy resin: solid epoxy resin) is based on a mass ratio, and is preferably 1:1~1:20, more preferably 1:1.5~1:15, particularly preferably 1:2~1:10. When the ratio of the liquid epoxy resin to the solid epoxy resin is within this range, the desired effect of the present invention can be significantly obtained.

(B) The epoxy equivalent of the component is preferably 50g/eq.~5000g/eq., more preferably 50g/eq.~3000g/eq., still more preferably 80g/eq.~2000g/eq., further More preferably, it is 110g/eq.~1000g/eq. With this range, the crosslink density of the cured product of the resin composition layer can be made sufficient, and an insulating layer with a small surface roughness can be obtained. The epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of epoxy. The epoxy equivalent can be measured in accordance with JIS K7236.

(B) The weight average molecular weight (Mw) of the component is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500 from the viewpoint of remarkably obtaining the desired effect of the present invention. The weight average molecular weight of the resin can be measured by the value of polystyrene conversion by the gel permeation chromatography (GPC) method.

(B) The content of the component, from the viewpoint of obtaining an insulating layer exhibiting good tensile mechanical strength and insulation reliability, when the non-volatile content in the resin composition is 100% by mass, it is preferably 1 mass % Or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more. (C) The upper limit of the content of the component is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less from the viewpoint of remarkably obtaining the desired effect of the present invention.

＜(C) Photopolymerizable monomer＞ The photosensitive resin composition contains a photopolymerizable monomer as the (C) component. However, (A) component and (B) component are not included in (C) component. By containing the (C) photopolymerizable monomer in the photosensitive resin composition, the photoreactivity can be improved. As the (C) component, for example, a photosensitive (meth)acrylate compound having one or more (meth)acrylic groups in one molecule, which is liquid, solid, or semisolid at room temperature, can be used. The so-called room temperature means about 25°C.

As the photosensitive (meth)acrylate compound, for example, hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; ethylene glycol, methoxytetraethylene glycol Mono- or di-(meth)acrylates such as diols such as, polyethylene glycol and propylene glycol; acrylamides such as N,N-dimethyl acrylamide and N-methylol acrylamide; acrylic acid N,N-Dimethylaminoethyl (meth)acrylate aminoalkyl esters; trimethylolpropane, pentaerythritol, dipentaerythritol, etc. polyols or such ethylene oxide and propylene oxide Or polyvalent (meth)acrylates of adducts of ε-caprolactone; phenols such as phenoxy acrylate and phenoxyethyl acrylate, or adducts of ethylene oxide or propylene oxide, etc. (Meth)acrylates; epoxy acrylates derived from glycidyl ether such as trimethylolpropane triglycidyl ether, modified epoxy acrylates, melamine acrylates, and/or corresponding The methacrylates of the above-mentioned acrylates, etc. The term (meth)acrylate refers to acrylate and methacrylate.

Among these, preferred are diols such as mono- or di(meth)acrylates, phenols such as phenoxy acrylate, phenoxy ethyl acrylate, or their ethylene oxide or propylene oxide adducts (Meth)acrylates and polyvalent (meth)acrylates.

As the mono- or di(meth)acrylates of diols, polytetramethylene glycol diacrylate etc. are mentioned, for example.

Examples of phenols such as phenoxy acrylate and phenoxy ethyl acrylate, or (meth)acrylates such as ethylene oxide or propylene oxide adducts, include EO modified bisphenol A acrylic acid. Ester etc.

As the polyvalent (meth)acrylates, for example, trivalent acrylates or methacrylates are preferred, and as trivalent acrylates or methacrylates, 1.9-nonanediol two Acrylate, 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, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, N,N,N',N'-(β-hydroxyethyl)ethyl diamine (meth)acrylate, etc., as acrylates with a valence of more than 3 or The methacrylates include tris(2-(meth)acryloyloxyethyl) phosphate, tris(2-(meth)acryloyloxypropyl) phosphate, tris(3-(methyl) Yl)acryloyloxypropyl) phosphate, tris(3-(meth)acryloyl-2-hydroxyoxypropyl)phosphate, bis(3-(meth)acryloyl-2-hydroxyl Oxypropyl) (2-(meth)acryloyloxyethyl) phosphate, (3-(meth)acryloyl-2-hydroxyoxypropyl)bis(2-(meth)propene Phosphoric triester (meth)acrylate such as oxyethyl phosphate. Any of these photosensitive (meth)acrylate compounds may be used alone or in combination of two or more kinds.

(C) A commercially available product can be used for the photopolymerizable monomer. Examples of commercially available products include "DPHA" manufactured by Nippon Kayaku Co., Ltd., "EBECRYL3708" manufactured by Daicel-allnex Co., Ltd., "R-551" manufactured by Nippon Kayaku Co., Ltd., and "A-PTMG-65" manufactured by Shin Nakamura Chemical Industry Co., Ltd. , "1.9ND" made by Jiaoyingsha Chemical Company, etc.

As the content of the (C) photopolymerizable monomer, from the viewpoint of promoting photocuring, when the total solid content of the photosensitive resin composition is 100% by mass, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, more preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less.

＜(D)Photopolymerization initiator＞ The photosensitive resin composition contains a photopolymerization initiator as the (D) component. By containing the (D) photopolymerization initiator in the photosensitive resin composition, the photosensitive resin composition can be photocured efficiently. These can be used individually by 1 type, and can also be used in combination of 2 or more types.

(D) Any compound can be used as the photopolymerization initiator, for example, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide), 2,4,6-trimethyl Phosphine oxide-based photopolymerization initiators such as benzyl-diphenyl-phosphine oxide; 1,2-octanedione, 1-4-(phenylthio)-2-(O-benzene) Methyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyl oxime ) And other oxime ester-based photopolymerization initiators; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino) )-2-[(4-Methylphenyl)methyl]-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio) ) Phenyl]-2-morpholinopropan-1-one and other α-amino benzophenone photopolymerization initiators; benzophenone, methyl benzophenone, benzoic acid , Benzoyl ethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzyl ) Phosphine oxide, ethyl-(2,4,6-trimethylbenzyl)phenylphosphonite, 4,4'-bis(diethylamino)benzophenone, 1- Hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]- 2-hydroxy-2-methyl-1-propan-1-one, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide; sulfonate-based photopolymerization initiator, etc. These may be used individually by 1 type, and may use 2 or more types together. Among them, from the viewpoint of photocuring the photosensitive resin composition more efficiently, any one of an phosphine oxide-based photopolymerization initiator and an oxime ester-based photopolymerization initiator is preferred , More preferably an oxime ester-based photopolymerization initiator.

(D) Specific examples of the photopolymerization initiator include "Omnirad907", "Omnirad369", "Omnirad379", "Omnirad819", "OmniradTPO", "IrgacureOXE-01" and "IrgacureOXE- 02", "IrgacureTPO", "Irgacure819", ADEKA "N-1919", "NCI-831", etc.

In addition, the photosensitive resin composition system can be combined with (D) a photopolymerization initiator to contain N,N-dimethylaminobenzoic acid ethyl ester and N,N-dimethyl as a photopolymerization initiator Tertiary amines such as isoamyl aminobenzoic acid, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, etc., and may also contain pyrazolines, anthracenes, and fragrances. Photosensitizers such as legumes, oxyalionones, and thioxanthones. These may be used individually by any 1 type, and may use 2 or more types together.

As the content of the (D) photopolymerization initiator, from the viewpoint of sufficiently photocuring the photosensitive resin composition and improving insulation reliability, when the non-volatile content of the photosensitive resin composition is set to 100% by mass In this case, it is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and still more preferably 0.01% by mass or more. On the other hand, from the viewpoint of suppressing the decrease in resolution due to excessively high sensitivity, the upper limit is preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less. Moreover, when the photosensitive resin composition contains a photopolymerization initiation assistant, the total content of (D) the photopolymerization initiator and the photopolymerization initiation assistant is preferably within the above-mentioned range.

＜(E) Inorganic fillers＞ In addition to the above-mentioned components, the photosensitive resin composition may further contain an inorganic filler as the (E) component as an optional component.

(E) As the material of the inorganic filler, an inorganic compound is used. Examples of materials for inorganic fillers include silica, alumina, glass, cordierite, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, 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, magnesium titanate, 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 magnesium hydroxide are preferred, and magnesium hydroxide is particularly preferred. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, as the silica, spherical silica is preferred. (F) The inorganic filler system may be used alone or in combination of two or more types.

Examples of commercially available products of (E) component include "UFP-20" and "UFP-30" manufactured by Denka; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Advanced Materials Co., Ltd.; and Admatechs "SC2050", "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", "SO-C1"; Tokuyama Corporation " "Sylfil NSS-3N", "Sylfil NSS-4N", "Sylfil NSS-5N"; "EP4-A" manufactured by Kamijima Chemical Co., Ltd., etc.

(E) The specific surface area of the component is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, and particularly ^{preferably 3 m 2} /g or more. The upper limit is not particularly limited, but it is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area is based on the BET method, using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech), adsorbing nitrogen on the surface of the sample, and calculating the specific surface area using the BET multipoint method.

(E) The average particle diameter of the component, from the viewpoint of remarkably obtaining the desired effect of the present invention, is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and preferably 5 μm or less , More preferably 2 μm or less, still more preferably 1 μm or less.

The average particle size of the (E) component can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, by using a laser diffraction scattering particle size distribution measuring device, the particle size distribution of the inorganic filler can be produced on a volume basis, and the median diameter can be measured as the average particle size. For the measurement sample, 100 mg of inorganic filler and 10 g of methyl ethyl ketone can be weighed into a sample bottle and dispersed by ultrasonic for 10 minutes. For the sample to be measured, a laser diffraction particle size distribution measuring device is used, and the wavelength of the light source used is set to blue and red, and the volume-based particle size distribution of the (E) component is measured by the flow cell method. From the obtained particle size Distribution, the average particle size is calculated as the median diameter. As a laser diffraction type particle size distribution measuring device, for example, "LA-960" manufactured by Horiba Manufacturing Co., Ltd. can be cited.

(E) From the viewpoint of improving moisture resistance and dispersibility, the component (E) is preferably treated with a surface treatment agent. Examples of surface treatment agents include vinyl silane coupling agents, (meth)acrylic coupling agents, fluorine-containing silane coupling agents, amino silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents Mixtures, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. Among them, from the viewpoint of remarkably obtaining the effects of the present invention, vinyl silane coupling agents, (meth)acrylic coupling agents, and aminosilane coupling agents are preferred. Moreover, the surface treatment agent system may be used individually by 1 type, and may be used in combination of 2 or more types arbitrarily.

Commercial products of the surface treatment agent include, for example, "KBM1003" (vinyl triethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM503" (3-methacryloxypropyl triethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Ethoxysilane), "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Industrial company "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy Type silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

The degree of surface treatment using the surface treatment agent is preferably set within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface treated with 0.2 parts by mass to 5 parts by mass of the surface treatment agent, preferably 0.2 parts by mass to 3 parts by mass for surface treatment, and 0.3 parts by mass to 2 parts by mass It is better to perform surface treatment on one portion.

The degree of surface treatment using the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and even more preferably 0.2 mg from the viewpoint of improving the dispersibility of the inorganic filler /m ² or more. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity in the film form, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and still more preferably 0.5 mg /m ² or less.

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the carbon content per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd. can be used.

(E) The content of the component, from the viewpoint of remarkably obtaining the effect of the present invention, when the non-volatile content in the photosensitive resin composition is 100% by mass, it is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70 Mass% or less, 60% by mass or less, 50% by mass or less, and 40% by mass or less.

＜(F) Solvent＞ In addition to the above-mentioned components, the photosensitive resin composition may further contain (F) a solvent as an optional component. The viscosity of the varnish can be adjusted by containing (F) solvent. As the (F) solvent, an organic solvent can be exemplified.

(F) Solvents include, for example, ketones such as ethyl methyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, butyl cellosolve, methyl Glycol ethers such as base carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc.; ethyl acetate, Butyl acetate, butyl cellosolve acetate, carbitol acetate, ethyl diethylene glycol acetate and other esters; aliphatic hydrocarbons such as octane and decane; petroleum ether, naphtha, hydrogenated Petroleum solvents such as naphtha and solvent naphtha. These can be used individually by 1 type or in combination of 2 or more types. From the viewpoint of the coatability of the resin composition, the content when the solvent is used can be appropriately adjusted.

＜(G) Other additives＞ The photosensitive resin composition may further contain (G) other additives to the extent that it does not interfere with the purpose of the present invention. (G) Other additives include thermoplastic resins, organic fillers, fine particles of melamine, organic bentonite, etc., phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc. Coloring agents such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, gallic phenol, etc. polymerization inhibitors, bentonite, montmorillonite, etc. Anti-foaming agents based on fluorine, fluorine and vinyl resins, brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus compounds, aromatic condensed phosphates, halogen-containing condensed phosphates, etc. Various additives such as flame retardants, phenolic hardeners, cyanate ester hardeners and other thermosetting resins.

The photosensitive resin composition can be prepared by mixing the above-mentioned components (A) to (D) as essential components, and appropriately mixing the above-mentioned components (E) to (G) as optional components, and, if necessary, passing through a three-roller, ball mill, It is manufactured by mixing or mixing the mixing means such as bead mills and sand mills or the mixing means such as super mixers and planetary mixers.

式(1)中，M_AO 係，當包含氧化伸烷基鏈之成分為共聚物時表示下述式(2)所示之值。又，M_AO 係，當包含氧化伸烷基鏈之成分不是共聚物時表示((A)~(C)成分中所含之各化合物的氧化伸烷基鏈的分子量)/((A)~(C)成分中所含之各化合物的分子量)。因 此，當包含氧化伸烷基鏈之成分不是共聚物時，M_AO 表示該等各成分中佔有之氧化伸烷基鏈之質量比率。N表示於(A)~(C)成分所含之全部化合物的固體成分含量(質量份)，n表示(A)~(C)成分中所含之各化合物的固體成分含量(質量份)。因此，X係，分別對於樹脂組成物中之全部(A)~(C)成分計算出M_AO 與n之積，求取據此所得之所有積的和，將該和除以N，並以百分率表示之值。

式(2)中，A_AO 表示包含氧化伸烷基鏈之各單體的氧化伸烷基鏈的分子量，A表示包含氧化伸烷基鏈之各單體的分子量，B_AO 表示包含氧化伸烷基鏈之各單體的莫耳數，B表示共聚物中所含之全單體的合計莫耳數。<Physical properties and use of photosensitive resin composition> The photosensitive resin composition contains an oxyalkylene chain in any of the (A) component, (B) component, and (C) component. At this time, the parameter X represented by the following formula (1) is 4 or more and 25 or less. By satisfying the formula (1), a cured product excellent in flexibility and insulation can be obtained.

In the formula (1), the M _AO system represents the value shown in the following formula (2) when the component including the oxyalkylene chain is a copolymer. In addition, M _AO system, when the component containing the oxyalkylene chain is not a copolymer, it means (the molecular weight of the oxyalkylene chain of each compound contained in the components (A)~(C))/((A)~ (C) The molecular weight of each compound contained in the component). Therefore, when the component containing the oxyalkylene chain is not a copolymer, M _AO represents the mass ratio of the oxyalkylene chain occupied by each component. N represents the solid content (parts by mass) of all the compounds contained in the components (A) to (C), and n represents the solid content (parts by mass) of each compound contained in the components (A) to (C). _{Therefore, for the X system, calculate the product of M AO} and n for all the components (A) ~ (C) in the resin composition, find the sum of all the products obtained therefrom, divide the sum by N, and use The value expressed as a percentage.

In formula (2), A _AO represents the molecular weight of the oxyalkylene chain of each monomer containing the oxyalkylene chain, A represents the molecular weight of each monomer containing the oxyalkylene chain, and B _AO represents the molecular weight of each monomer containing the oxyalkylene chain. The number of moles of each monomer in the base chain, and B represents the total number of moles of all monomers contained in the copolymer.

The term "copolymer" refers to a polymer obtained by polymerizing 2 or more monomers and having a weight average molecular weight of 10,000 or more. The copolymer may be any of random copolymerization, block copolymerization, alternating copolymerization, and graft copolymerization.

The copolymer has the state of random copolymerization as described above, and it may be difficult to calculate the value of _{M AO based on the molecular weight.} Since copolymers generally have an additive system, when it is difficult to calculate _{the value of M AO} based on the molecular weight, formula (2) can be used to calculate M _AO . The molecular weight of each unit of the oxyalkylene chain is obtained _{by A AO} /A in formula (2), _{and further, by multiplying by B AO} /B in formula (2) that contains the oxyalkylene chain The molar ratio of the monomers can be used to calculate the value _{of M AO in the copolymer.} The "monomer" described in the definition in formula (2) means a compound corresponding to the monomer unit contained in the copolymer. The so-called "monomer unit" refers to a partial structure in a copolymer formed by polymerizing a certain compound.

X in the formula (1) is 25 or less, preferably 23 or less, more preferably 20 or less, and still more preferably, from the viewpoint of obtaining a cured product with excellent flexibility and insulation and improving resolution, Below 18. The lower limit of X in the formula (1) is 4 or more, preferably 5 or more, and more preferably 6 or more from the viewpoint of remarkably obtaining the effect of the present invention.

The cured product obtained by light-curing the photosensitive resin composition of the present invention exhibits excellent resolution characteristics. Therefore, when a round hole (through hole) with an opening diameter of 100 μm is formed by the hardened material, the formation of residues at the bottom of the round hole can be suppressed. The evaluation of the residue at the bottom of the via can be performed according to the method described in the below-mentioned "Evaluation of the residue at the bottom of the via".

The cured product obtained by light-curing the photosensitive resin composition of the present invention exhibits excellent flexibility. A specific example of the measurement of the flexibility is to use a photosensitive film obtained by fully exposing, developing, and heating the photosensitive resin composition layer, and evaluate the flexibility in accordance with JIS P8115 using an MIT flexural fatigue tester. At this time, the average number of bending times is usually 100 times or more, preferably 300 times or more. The details of the evaluation of the flexibility can be measured according to the method described in the below-mentioned Examples.

The cured product formed by light-curing the photosensitive resin composition of the present invention exhibits excellent insulating properties. A specific example of insulation evaluation is to expose, develop, and heat a photosensitive resin film from a comb-shaped wiring pattern. Weld copper wires as electrodes on both sides of the comb pattern, apply a predetermined voltage, and measure the resistance values at 7 locations after 500 hours. In this case, the resistance value is preferably 10 ⁸ Ω or more. The details of the insulation evaluation can be measured in accordance with the method described in the examples described later.

The cured product obtained by light-curing the photosensitive resin composition of the present invention usually exhibits excellent adhesive strength with copper foil. As a specific example of the evaluation of adhesion strength, a photosensitive resin composition layer bonded with a glass epoxy substrate is bonded to a rolled copper foil, and the entire surface is exposed, developed, and heated. For the peeling of copper, a tensile testing machine ("AC-50C-SL" manufactured by TSE Corporation) in accordance with Japanese Industrial Standards (JIS C6481) was used to peel the copper foil. At this time, the adhesion strength to the copper foil is usually 0.5 kgf or more. The details of the evaluation of the adhesion strength can be measured in accordance with the method described in the examples described later.

The use of the photosensitive resin composition of the present invention is not particularly limited, and it can be used for photosensitive films, photosensitive films with support, prepregs, and other insulating resin films, circuit boards (for laminates, multilayer printed wiring boards) Applications, etc.), solder resists, underfill materials, die-bonding materials, semiconductor sealing materials, filling resins, parts embedding resins, etc., which use photosensitive resin compositions as necessary applications in a wide range. Among them, the photosensitive resin composition for the insulating layer of the printed wiring board (printed wiring board in which the cured product of the photosensitive resin composition is used as the insulating layer), the photosensitive resin composition for the interlayer insulating layer (the photosensitive resin composition The cured product of the resin composition is used as a printed wiring board with an interlayer insulating layer), a photosensitive resin composition for plating formation (a printed wiring board where a plating is formed on the cured product of the photosensitive resin composition), and a solder resist layer Photosensitive resin composition (printed wiring board in which the cured product of the photosensitive resin composition is used as a solder resist layer).

[Photosensitive film] The photosensitive resin composition system of the present invention can be used as a photosensitive film by coating it on a support substrate in a resin varnish state and drying the organic solvent to form a photosensitive resin composition layer. In addition, a photosensitive film previously formed on a support may be laminated on a support substrate and used. The photosensitive film can be laminated on various supporting substrates. As the supporting substrate, substrates such as glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates can be mainly cited.

[Photosensitive film with support] The photosensitive resin composition system of the present invention can be suitably used in the form of a photosensitive film with a support formed by forming a photosensitive resin composition layer 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.

As the support, for example, a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a polyvinyl alcohol film, a triacetate film, etc. can be cited, especially Polyethylene terephthalate film is preferred.

Examples of commercially available supports include Oji Paper Co.’s product names "ALPHAN MA-410" and "E-200C", Shin-Etsu Film Co., Ltd. and other polypropylene films, and Teijin Co., Ltd. product names "PS-25". PS series and other polyethylene terephthalate films, etc., but not limited to these. In order to facilitate the removal of the photosensitive resin composition layer, the support may be coated with a release agent such as a silicone coating agent on the surface. The thickness of the support is preferably in the range of 5 μm to 50 μm, more preferably in the range of 10 μm to 25 μm. By setting the thickness to 5 μm or more, the support can be prevented from breaking when the support is peeled off before development, and by setting the thickness to 50 μm or less, the resolution during exposure from the support can be improved. In addition, it is preferably a support with low fish eyes. The term “fisheye” here refers to a material that is mixed with foreign matter, undissolved matter, oxidized and deteriorated material, etc., when the material is thermally melted and the film is manufactured by kneading, extrusion, biaxial stretching, casting, etc.

In addition, in order to reduce light scattering during exposure by active energy rays such as ultraviolet rays, the support is preferably one having excellent transparency. Specifically, the support is preferably one having a haze (haze standardized in JIS-K6714) of 0.1 to 5 as an index of transparency. Furthermore, the photosensitive resin composition layer can 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, adhesion or damage to the surface of the photosensitive resin composition layer, such as dirt, can be prevented. 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 still more preferably in the range of 10 μm to 30 μm. By setting the thickness to 1 μm or more, the location of the protective film can be improved, and by setting it to 40 μm or less, there is a tendency for the low cost to improve. In addition, for the protective film system, it is preferable that the adhesive force between the photosensitive resin composition layer and the protective film is smaller than the adhesive force between the photosensitive resin composition layer and the support.

The photosensitive film with a support of the present invention can be prepared by, for example, a resin varnish prepared by dissolving the photosensitive resin composition of the present invention in an organic solvent according to a method known to those having ordinary knowledge in the field of the present invention. It is manufactured by coating this resin varnish on the support and drying the organic solvent by heating or blowing with hot air to form a photosensitive resin composition layer. Specifically, first, after the bubbles in the photosensitive resin composition are completely removed by a vacuum degassing method or the like, the photosensitive resin composition is coated on a support, and the solvent is removed by a hot air oven or a far-infrared oven to make it After drying, if necessary, a protective film is laminated on the obtained photosensitive resin composition layer, whereby a photosensitive film with a support can be manufactured. The specific drying conditions vary depending on the curability of the photosensitive resin composition or the amount of organic solvent in the resin varnish, but for resin varnishes containing 30% to 60% by mass of organic solvents, the temperature can be at 80°C to 120°C Dry for 3 minutes to 13 minutes. The amount of residual organic solvent in the photosensitive resin composition layer is preferably set to 5% by mass or less with respect to the total amount of the photosensitive resin composition layer from the viewpoint of preventing the diffusion of the organic solvent in the steps described later. More preferably, it is set to 2% by mass or less. Those with ordinary knowledge in the field of the present invention can appropriately set better drying conditions through simple experiments. The thickness of the photosensitive resin composition layer is preferably set to be in the range of 5μm~500μm, more preferably set to 10μm~ from the viewpoint of improving handleability and suppressing the decrease in sensitivity and resolution inside the photosensitive resin composition layer. The range of 200μm is more preferably set to the range of 15μm~150μm, still more preferably the range of 20μm~100μm, particularly preferably the range of 20μm~60μm.

As the coating method of the photosensitive resin composition, for example, a gravure coating method, a micro gravure coating method, a reverse coating method, a reverse kiss coating method, a die coating method, a slit die method, Lip coating method, chipped wheel coating method, knife coating method, roll coating method, blade coating method, curtain coating method, chamber gravure coating method, slit orifice method, spray Coating method, dip coating method, etc. The photosensitive resin composition may be divided into several times and applied, or may be applied once, or may be applied in combination with a plurality of different methods. Among them, a die coating method with excellent uniform coating properties is preferred. In addition, in order to avoid mixing of foreign materials, etc., it is preferable to perform the coating step in an environment where the generation of foreign materials such as a clean room is less.

[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 layer.

Specifically, the printed wiring board of the present invention can be manufactured using the above-mentioned photosensitive film or photosensitive film with a support. Hereinafter, the case where the insulating layer is a solder resist layer will be described.

＜Coating and drying steps＞ The photosensitive resin composition is directly coated on the circuit board in the resin varnish state, and the organic solvent is dried to form a photosensitive film on the circuit board.

As the circuit board, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, etc. may be mentioned. In addition, the circuit substrate herein 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 formed by alternately laminating a conductor layer and an insulating layer, the outermost layer of the multilayer printed wiring board has one or both sides becoming a patterned conductor layer (circuit) substrate, which is also included here The so-called circuit board. In addition, the surface of the conductor layer may be roughened in advance by blackening treatment, copper etching, or the like.

As a coating method, in general, full-scale printing by screen printing is mostly used, but other coating methods that can be uniformly coated can also be used by any means. For example, spray coating method, hot melt coating method, bar coating method, coater method, knife coating method, blade coating method, air knife coating method, curtain flow coating method, Roll coating method, gravure coating method, offset printing method, dip coating method, brush coating method, and other common coating methods can all be used. After coating, it can be dried in a hot air oven or a far-infrared oven if necessary. The drying conditions are preferably set at 80°C to 120°C for 3 minutes to 13 minutes. In this way, a photosensitive film can be formed on the circuit board.

＜Laminating step＞ Moreover, in the case of using a photosensitive film with a support, a vacuum laminator is used to laminate the photosensitive resin composition layer side on one or both sides of the circuit board. In the laminating step, when the photosensitive film with support has a protective film, after removing the protective film, if necessary, the photosensitive film with support and the circuit board are preheated, while pressing and heating the photosensitive resin The composition layer is crimped to the circuit substrate. The photosensitive film with support is suitable for laminating to the circuit board under reduced pressure by the vacuum laminating method.

The conditions of the lamination step are not particularly limited, but for example, the crimping temperature (laminating temperature) is preferably set to 70°C to 140°C, and the crimping pressure is preferably set to 1kgf/cm ² to 11kgf/cm ² ( 9.8×10 ⁴ N/m ² ~107.9×10 ⁴ N/m ² ), the crimping time is preferably set to 5 seconds to 300 seconds, and the air pressure is set to 20mmHg (26.7hPa) or less under reduced pressure. Together is better. In addition, the lamination step may be a batch type or a continuous type using rolls. The vacuum lamination method can be carried out using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, vacuum applicators manufactured by Nikko-Materials, vacuum pressurized laminators manufactured by Meike Manufacturing Co., Ltd., roll-type dry coaters manufactured by Hitachi Industries, and vacuum manufactured by Hitachi AIC. Laminator, etc. In this way, a photosensitive film can be formed on the circuit board.

<Exposure step> After the photosensitive film is placed on the circuit board through the coating and drying step, or the lamination step, a mask pattern is then performed to irradiate a predetermined part of the photosensitive resin composition layer with active light to make The exposure step of photocuring the photosensitive resin composition layer of the irradiated part. As active rays, for example, ultraviolet rays, visible rays, electron beams, X-rays, etc. can be cited, and ultraviolet rays are particularly preferred. The amount of ultraviolet radiation is about 10mJ/cm ² ~1000mJ/cm ² . The exposure method includes a contact exposure method in which a mask pattern is adhered to a printed wiring board, and a non-contact exposure method in which exposure is performed using parallel light without adhesion, and either one can be used. In addition, when a support exists on the photosensitive resin composition layer, exposure may be performed from the support, or exposure may be performed after the support is peeled off.

Since the solder resist layer uses the photosensitive resin composition of this invention, it is excellent in 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 (space; S) between the circuits is 100μm/100μm or less (that is, the wiring pitch is 200μm L/S=80μm/80μm or less (wiring pitch 160μm or less), L/S=70μm/70μm or less (wiring pitch 140μm or less), L/S=60μm/60μm or less (wiring pitch 120μm or less). In addition, the pitch does not need to be the same across the entire circuit board.

<Development step> After the exposure step, when the support is present on the photosensitive resin composition layer, the support is removed, and then the uncured part (unexposed part) is removed by wet development or dry development to develop a pattern, thereby forming a pattern.

In the above-mentioned wet development, as the developer, a safe, stable, and easy-to-operate developer such as an alkaline aqueous solution, an aqueous developer, an organic solvent, etc. can be used. Among them, a development step by an alkaline aqueous solution is preferred. In addition, as the development method, conventional methods such as spraying, shaking dipping, brushing, and blade coating can be suitably used.

The alkaline aqueous solution used as the developer includes, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, carbonates or bicarbonates such as sodium carbonate, sodium bicarbonate, sodium phosphate, and phosphoric acid. Alkali metal phosphates such as potassium, sodium pyrophosphate, potassium pyrophosphate and other alkali metal pyrophosphate aqueous solutions, or tetraalkylammonium hydroxide and other organic alkali aqueous solutions that do not contain metal ions, never contain metal ions, From the viewpoint of not affecting the semiconductor wafer, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred.

To these alkaline aqueous solutions, in order to enhance the development effect, surfactants, defoamers, etc. can be added to the developer. The pH of the above-mentioned 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 to 20°C to 50°C.

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

The concentration of the organic solvent is preferably 2% by mass to 90% by mass relative to the total amount of the developer. In addition, the temperature of the organic solvent can be adjusted according to the developability. Moreover, such an organic solvent system can be used individually or in combination of 2 or more types. As an organic solvent-based developer used alone, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl iso Butanone, γ-butyrolactone.

For pattern formation, if necessary, two or more of the above-mentioned development methods can be used in combination. The development methods include dipping, paddle stirring, spraying, high-pressure spraying, brushing, slapping, etc. The high-pressure spraying method is preferred because it can increase the resolution. The spray pressure when using the spray method is preferably 0.05 MPa to 0.3 MPa.

<Thermal hardening (post-baking) step> After the above-mentioned development step is completed, a thermal hardening (post-baking) step is performed to form a solder resist layer. As the post-baking step, an ultraviolet irradiation step using a high-pressure mercury lamp or a heating step using a clean oven can be cited. When irradiating ultraviolet rays, the irradiation amount can be adjusted as needed, for example, the irradiation amount can be about 0.05 J/cm ² to 10 J/cm ² . In addition, the heating conditions may be appropriately selected according to the type and content of the resin component in the photosensitive resin composition, but it is preferably in the range of 20 minutes to 180 minutes at 150°C to 220°C, and more preferably 160 Choose from the range of 30 minutes to 120 minutes at ℃~200℃.

＜Other steps＞ After the solder resist layer is formed on the printed wiring board, it may further include a hole opening step and a desmear step. These steps can be implemented according to various methods known to those having ordinary knowledge in the field of the present invention for the manufacture of printed wiring boards.

After the solder resist layer is formed, the solder resist layer formed on the circuit substrate is opened as desired to form via holes and through holes. The hole-opening step can be performed by conventional methods such as drills, lasers, plasmas, etc., or a combination of these methods as necessary, but it is preferable to use lasers such as carbon dioxide lasers, YAG lasers, etc. The opening step.

The step of removing scum is the step of removing scum. Generally speaking, resin residue (smear) adheres to the inside of the opening formed in the hole-opening step. Such scum will become the cause of poor electrical connection, so the process of removing scum (desmear treatment) is implemented in this step.

The desmear treatment can be implemented by dry desmear treatment, wet desmear treatment or a combination of these.

As a dry desmear treatment, for example, a desmear treatment using plasma can be mentioned. The desmearing treatment using plasma can be implemented using a commercially available plasma desmearing treatment device. Among commercially available plasma desmear processing devices, examples of suitable applications for manufacturing printed wiring boards include a microwave plasma device manufactured by Nissin Corporation, an atmospheric pressure plasma etching device manufactured by Sekisui Chemical Co., Ltd., and the like.

Examples of the wet desmear treatment include desmear treatment using an oxidizing agent solution. When using oxidant solution for desmear treatment, it is better to sequentially perform swelling treatment with swelling solution, oxidation treatment with oxidant solution, and neutralization treatment with neutralization solution. As the swelling liquid, for example, "Swelling Dip" manufactured by Atotech Japan Securiganth P", "Swelling Dip Securiganth SBU", etc. The swelling treatment is preferably performed by immersing the substrate on which the vias are formed in a swelling solution heated to 60°C to 80°C for 5 minutes to 10 minutes. The oxidizing agent solution is preferably an alkaline permanganic acid aqueous solution. For example, a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide is mentioned. The oxidation treatment using an oxidizing agent solution is preferably performed by immersing the swelled substrate in an oxidizing agent solution heated to 60°C to 80°C for 10 minutes to 30 minutes. Examples of commercially available products of the alkaline permanganic acid aqueous solution include "Concentrate Compact CP" manufactured by Atotech Japan, "Dosing Solution Securiganth P", and the like. The neutralization treatment with a neutralization solution is preferably performed by immersing the substrate after oxidation treatment in a neutralization solution at 30°C to 50°C for 3 minutes to 10 minutes. The neutralizing liquid is preferably an acidic aqueous solution, and as a commercially available product, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan can be cited.

When combined dry desmear treatment and wet desmear treatment, the dry desmear treatment may be implemented first, or the wet desmear treatment may be implemented first.

When the insulating layer is used as an interlayer insulating layer, it can also be carried out in the same manner as in the case of the solder resist layer. After the thermal hardening step, an opening step, a desmear step, and a plating step can be performed.

The plating step is a step of forming a conductor layer on the insulating layer. The conductive layer can be formed by combining electroless plating and electrolytic plating, and it is also possible to form a plating resist with a pattern opposite to that of the conductive layer, and form the conductive layer by only electroless plating. As a method of pattern formation thereafter, for example, a subtractive method, a semi-additive method, etc., which are well-known to those with ordinary knowledge in the field of the invention, can be used.

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

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

The semiconductor device of the present invention can be manufactured by mounting parts (semiconductor chips) on the conductive parts of the printed wiring board. "Conducting part" refers to "the part of the printed wiring board that transmits electrical signals", and its position can be either the surface or the embedded part. In addition, if the semiconductor wafer is an electronic circuit element using a semiconductor as a material, it is not particularly limited.

The mounting method of the semiconductor wafer during the manufacture of the semiconductor device of the present invention is not particularly limited as long as the semiconductor wafer can effectively perform its functions. Specifically, it includes wire bonding mounting methods, flip-chip mounting methods, and bumpless mounting methods. Layer (BBUL) installation method, anisotropic conductive film (ACF) installation method, non-conductive film (NCF) installation method, etc. Here, the "mounting method using bumpless build-up (BBUL)" refers to the "mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board". [Example]

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to these examples. In addition, in the following description, the "parts" and "%" that indicate the amount mean "parts by mass" and "% by mass", respectively, as long as they are not clearly stated otherwise.

(Synthesis example 1: Synthesis of resin (A-1)) Into a 4-necked flask, 60.8 parts (0.26 mol) of bisphenol A, 43.4 parts (0.11 mol) of bisphenol A epoxy compound (YD8125, manufactured by Nippon Steel Chemical Co., Ltd.), polyethylene glycol diglycidyl ether were fed (EX861, manufactured by Nagase Chemical Co., Ltd.) 145.8 parts (0.13 mol), 1.25 parts of triphenylphosphine as a catalyst, 1.25 parts of N,N-dimethylbenzylamine, and 250 parts of toluene as a solvent, under nitrogen flow, The temperature was raised to 110°C while stirring, and the reaction was carried out for 8 hours to obtain a hydroxyl-containing resin. Next, 49.8 parts (0.48 mol) of succinic anhydride (RIKACID SA, manufactured by New Japan Rika Co., Ltd.) as an acid anhydride was added, and the reaction was carried out as it was at 110°C for 4 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, 41.1 parts (0.29 mol) of glycidyl methacrylate (GMA, manufactured by NOF Corporation) and 0.17 parts of hydroquinone as a polymerization inhibitor were added while stirring, and the reaction was carried out at 80°C for 8 hours. After the completion of the reaction, 26.0 parts (0.25 mol) of RIKACID SA (manufactured by New Japan Chemical Co., Ltd.: succinic anhydride) as an acid anhydride was added, and the reaction was carried out directly at 80°C for 4 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Methyl ethyl ketone was added to this solution to adjust so that the solid content became 50%. The weight average molecular weight of the obtained resin (A-1) was 20,000, and the acid value of the resin solid content was 70 mgKOH/g.

Resin (A-1) is a copolymer. _{Therefore, M AO} in formula (1) can be obtained by formula (2). Specifically, it is obtained in the following way. The monomer with an oxyalkylene chain is polyethylene glycol diglycidyl ether (EX861). Since the molecular weight of EX861 is 1098, A in formula (2) is 1098. In addition, since the molecular weight of the oxidized alkylene chain is 968, A _AO in formula (2) is 968. Resin (A-1) is a copolymer of bisphenol A, bisphenol A epoxy compound, polyethylene glycol diglycidyl ether, succinic anhydride and glycidyl methacrylate. Since the monomer containing the oxyalkylene chain is polyethylene glycol diglycidyl ether, the B _AO in formula (2) is 0.13. In addition, B in formula (2) is 0.26+0.11+0.13+0.48+0.29+0.25=1.52. Therefore, the formula (2) is (968/1098)×(0.13/1.52)≒0.08.

(Synthesis Example 2: Synthesis of Polymer 1) In a 4-necked flask, add 510 g of propylene glycol monomethyl ether acetate, 50 g of methyl methacrylate, 90 g of butyl methacrylate, 60 g of hydroxyethyl methacrylate, and 2 g of azobisisobutyronitrile, while blowing in Heat at 80°C for 6 hours under nitrogen. The weight average molecular weight of the obtained polymer 1 was 40,000.

(Preparation of resin varnish) The resin material is prepared as shown in the following preparation table, and a high-speed rotating mixer is used to obtain a resin varnish.

The abbreviations in the table are as follows. ･(A-1): The resin (A-1) synthesized in Synthesis Example 1, a methyl ethyl ketone solution with 50% solid content, M _AO ×100=8 ･ZFR-1491H: containing bis-F skeleton Acid-modified epoxy acrylate, manufactured by Nippon Kayaku Corporation, EDGAc (Ethyl Diethylene Glycol Acetate) cut, solid content 70%, M _AO ×100=0 ･ZAR-2000: Contains bis-A The acid-modified epoxy acrylate of the skeleton, manufactured by Nippon Kayaku Co., EDGAc fraction, solid content 70%, M _AO ×100=0 ･EX-821: polyethylene glycol diglycidyl ether, n=4, epoxy Base equivalent 185g/eq., manufactured by Nagase Kasei Co., M _AO ×100=58 ･EX-920: Polypropylene glycol diglycidyl ether, n=3, epoxy equivalent 176g/eq., manufactured by Nagase Kasei Co., Ltd.) M _AO ×100=57 ･NC3000H: Biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent is about 272g/eq.), M _AO ×100=0 ･R-551: EO modified bisphenol A Type acrylate, manufactured by Nippon Kayaku Co., Ltd., M _AO ×100=34 ･A-PTMG-65: Polytetramethylene glycol #650 diacrylate, manufactured by Shinnakamura Chemical Industry Co., Ltd., M _AO ×100=83 ･ 1.9ND-A: 1.9-nonanediol diacrylate, manufactured by Kyoei Chemical Co., Ltd., M _AO ×100=0 ･NCI-831: oxime ester-based photopolymerization initiator, manufactured by ADEKA, ･EP4-A: Magnesium hydroxide treated with aminosilane (manufactured by Kamishima Chemical Co., Ltd.) ･MEK: methyl ethyl ketone, manufactured by Junsei Chemical Co., Ltd.･Polymer 1: Polymer 1 synthesized in Synthesis Example 2, propylene glycol with 25% solid content Monomethyl ether acetate solution, M _AO ×100=8

A-PTMG-65的分子量為774。又，氧化伸烷基鏈的分子量為648(72×9=648)。因此，M_AO 為648/774≒0.83。"A-PTMG-65" manufactured by Shinnakamura Chemical Industry Co., Ltd. has the following structural formula. Since A-PTMG-65 is not a copolymer, M _{AO can be} obtained by formula (1).

The molecular weight of A-PTMG-65 is 774. In addition, the molecular weight of the oxyalkylene chain is 648 (72×9=648). Therefore, M _AO is 648/774≒0.83.

The X system in the formula (1) of Example 1 was obtained as follows.

(Production of photosensitive film with support) Prepare a PET film (“Lumirror T6AM” manufactured by Toray Co., Ltd., thickness 38μm, softening point 130°C, “release PET”) that has been demolded with an alkyd resin-based mold release agent (“AL-5” manufactured by Lintec). Support body. Using a die coater, the prepared resin varnish is uniformly coated on the release PET so that the thickness of the photosensitive resin composition layer after drying becomes 25μm, and the coating is obtained by drying at 80°C to 120°C. The photosensitive film of the support.

(Formation of laminate for evaluation) For the copper layer of the glass epoxy substrate (copper-clad laminate) formed by patterning a copper layer with a thickness of 18 μm, a surface treatment agent containing an organic acid (CZ8100 , MEC Corporation). Next, the photosensitive resin composition layer of the photosensitive film with a support obtained in the Examples and Comparative Examples was placed in contact with the surface of the copper layer, and a vacuum laminator (manufactured by Nikko-Materials, VP160) was used. Laminating is performed to form a laminate in which the copper clad laminate, the photosensitive resin composition layer, and the support are laminated in this order. The crimping conditions were set to vacuum time of 30 seconds, crimping temperature of 80°C, crimping pressure of 0.7 MPa, and pressurizing time of 30 seconds. The laminate was left at room temperature for more than 30 minutes, and the support of the laminate was exposed to ultraviolet rays using a circular hole pattern and a pattern forming device. The exposure pattern is drawn with openings: 50μm/60μm/ 70μm/80μm/90μm/100μm round holes (through holes), L/S (line/space): 50μm/50μm, 60μm/60μm, 70μm/70μm, 80μm/ 80μm, 90μm/90μm, 100μm/100μm line and space, 1cm×2cm square quartz glass mask. After standing at room temperature for 30 minutes, the support was peeled off from the aforementioned laminate. On the entire surface of the insulating layer on the laminate, a 1% by mass sodium carbonate aqueous solution at 30°C as a developing solution was spray-developed for 2 minutes at a spray pressure of 0.2 MPa. After spray development, 1J/cm ² of ultraviolet ray was irradiated, and further heat treatment was performed at 180°C for 30 minutes to form an insulating layer with openings on the laminate. This was used as a laminate for evaluation.

＜Evaluation of residue on the bottom of vias＞ In the round holes of 100 μm formed in the evaluation laminate, evaluation was performed based on the following criteria. ○: No residue. ×: A residue is observed, or the film is peeled off, or the resin is partially dissolved.

＜Evaluation of Flexibility＞ The photosensitive resin composition layer of the photosensitive film with a support obtained in the Examples and Comparative Examples was subjected to full exposure, development, and heat treatment. The conditions of exposure, development, and heat treatment were the same as the formation conditions of the evaluation laminate. The support was peeled off to obtain a cured film. The cured product film was cut into 15 mm×110 mm, and the bending properties were evaluated using an MIT bending fatigue tester (manufactured by Toyo Seiki Co., Ltd.). The test was performed in accordance with JIS P8115, and the tension was 500g, the test speed: 175 times/min, the bending angle: 135°, and the bending jig R: 0.38mm. Count the number of bends until breaking, and evaluate the average of the number of bends of 3 times based on the following criteria. ◎: 300 times or more ○: 100 times or more but less than 300 times ×: less than 100 times

＜Evaluation of copper adhesion＞ Prepare rolled copper foil (made by JX Nikkei Nippon Steel Co., BHY-22B-T, thickness 18μm) washed and dried with 10% sulfuric acid. The photosensitive film with a support is attached to the glossy surface of the rolled copper foil, and the entire surface is exposed, developed, and heated to obtain a substrate. The conditions of exposure, development, and heat treatment were set to be the same as the evaluation of flexibility. The insulating layer side of the obtained substrate was joined to the glass epoxy substrate, and the peel strength of the copper foil was measured using a tensile tester (manufactured by TSE Corporation, "AC-50C-SL") in accordance with the Japanese Industrial Standards (JIS C6481). It is evaluated based on the following benchmarks. ○: Adhesive strength is 0.5kgf or more ×: The adhesion strength is less than 0.5kgf

<Evaluation of insulation (HHBT)> From the support of the photosensitive film with the support, the comb-shaped wiring pattern of L (wiring width)/S (space)=20μm/20μm is used to perform full exposure with ultraviolet rays. Development and heat treatment. The conditions of overall exposure, development, and heat treatment were set to be the same as the formation conditions of the evaluation laminate. Weld copper wires as electrodes on both sides of the comb-shaped wiring pattern, apply a voltage of 50V at 85℃ and 85%RH, measure the resistance value (Ω) after 500 hours, and calculate the average value from the resistance values at 7 locations, and The evaluation is based on the following benchmarks. ○: The average value of the resistance value is 10 ⁸ Ω or more ×: The average value of the resistance value is less than 10 ⁸ Ω

From the results of the above table, it can be seen that if the photosensitive resin composition of the present invention is used, developability, bendability, adhesion, and insulation become good. Regarding Comparative Example 3, although an acrylic polymer having an oxyalkylene chain (Polymer 1) was used, it was judged that since Polymer 1 is a thermoplastic resin and is not included in the hardening system, the desired result cannot be obtained.

It was confirmed in each Example that even when the (E) component and (F) component are not contained, there is a difference in degree, but it can be attributed to the same result as the above-mentioned example.

Claims (14)

A photosensitive resin composition comprising: (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an epoxy resin, (C) a photopolymerizable monomer, and (D) a photopolymerization initiator; Any one of (A) component, (B) component, and (C) component contains an alkylene oxide chain, and the parameter X represented by the following formula (1) is 4 or more and 25 or less,

In formula (1), M _AO series, when the component containing the oxyalkylene chain is a copolymer, it means the value shown in the following formula (2), or when the component containing the oxyalkylene chain is not a copolymer, it means (Molecular weight of the oxyalkylene chain of each compound contained in components (A)~(C))/(Molecular weight of each compound contained in components (A)~(C)); N is expressed in (A) ~(C) The solid content (parts by mass) of all the compounds contained in the component, n represents the solid content (parts by mass) of each compound contained in the (A)~(C) components,

In formula (2), A _AO represents the molecular weight of the oxyalkylene chain of each monomer containing the oxyalkylene chain, A represents the molecular weight of each monomer containing the oxyalkylene chain, and B _AO represents the molecular weight of each monomer containing the oxyalkylene chain. The number of moles of each monomer in the base chain, and B represents the total number of moles of all monomers contained in the copolymer. The photosensitive resin composition of claim 1, which further contains (E) an inorganic filler. The photosensitive resin composition according to claim 1, wherein the oxyalkylene chain is contained in any one of the (B) component and (C) component. The photosensitive resin composition according to claim 1, wherein the component (A) contains an acid-modified unsaturated epoxy ester resin. The photosensitive resin composition of claim 1, wherein the component (A) contains acid-modified epoxy (meth)acrylate. Such as the photosensitive resin composition of claim 1, wherein the component (A) includes an acid-modified epoxy (meth)acrylate containing a naphthalene skeleton and an acid-modified epoxy (meth)acrylate containing a bisphenol skeleton Either. The photosensitive resin composition according to claim 6, wherein the acid-modified epoxy (meth)acrylate containing a bisphenol skeleton has any one of a bisphenol A skeleton and a bisphenol F skeleton. The photosensitive resin composition of claim 1, wherein the component (B) has a biphenyl skeleton. The photosensitive resin composition of claim 1, wherein the component (D) contains an oxime ester-based photopolymerization initiator. A photosensitive film containing the photosensitive resin composition according to any one of claims 1-9. A photosensitive film with a support body, which has a support body and a photosensitive resin composition layer including the photosensitive resin composition according to any one of claims 1 to 9 provided on the support body. A printed wiring board comprising an insulating layer formed of a cured product of the photosensitive resin composition according to any one of claims 1 to 9. Such as the printed wiring board of claim 12, wherein the insulating layer is a solder resist layer. A semiconductor device including the printed wiring board as claimed in claim 12.