Photosensitive resin composition

Abstract

The present invention provides a photosensitive resin composition and the like which can provide a cured product having excellent flexibility and insulation, and excellent resolution. The present invention is 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, wherein any of the (A) component, the (B) component, and the (C) component contains an alkylene oxide chain, and a parameter X represented by the following formula (1) is 4 or more and 25 or less.

Description

Technical Field

[0001] This invention relates to photosensitive resin compositions. It also relates to photosensitive films obtained using these compositions, photosensitive films with supports, printed wiring boards, and semiconductor devices. Background Technology

[0002] In printed wiring boards, a solder resist layer is sometimes provided as a permanent protective film to prevent solder from adhering to areas where solder is not needed and to inhibit corrosion of the circuit board. As a solder resist layer, a photosensitive resin composition, such as that described in Patent Document 1, is generally used.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2014-115672. Summary of the Invention

[0006] The technical problem that the invention aims to solve

[0007] The photosensitive resin composition used in solder mask layers is generally required to have high resolution and good insulation properties. In recent years, with the miniaturization of electronic devices and the need for further space saving, printed circuit boards (PCBs) require flexibility. The solder mask layer used in these PCBs also requires flexibility.

[0008] However, after careful investigation, the inventors found that if the flexibility is increased, the insulation of the solder resist layer may deteriorate. In the photosensitive resin composition used for the solder resist layer, there is a trade-off between flexibility and insulation.

[0009] The objective of this invention is to provide: a photosensitive resin composition that yields a cured product with excellent flexibility and insulation and excellent resolution; a photosensitive film obtained from the photosensitive resin composition; a photosensitive film with a support; a printed wiring board; and a semiconductor device.

[0010] Technical solutions adopted to solve technical problems

[0011] The inventors conducted careful research and discovered that by including oxidized olefin chains in any component of the photosensitive resin composition containing olefinic unsaturated groups and carboxyl groups, epoxy resin, and photopolymerizable monomers, and ensuring that the oxidized olefin chains satisfy a specified relationship, both flexibility and insulation are improved, thus completing the present invention.

[0012] That is, the present invention includes the following:

[0013] [1] A photosensitive resin composition comprising the following components (A) to (D),

[0014] (A) Resins containing olefinic unsaturated groups and carboxyl groups,

[0015] (B) Epoxy resin,

[0016] (C) Photopolymerizable monomers, and

[0017] (D) Photopolymerization initiator,

[0018] Among them, any component of component (A), component (B) and component (C) contains an oxidized olefin chain, and the parameter X represented by the following formula (1) is 4 or more and 25 or less;

[0019] [Mathematical Expression 1]

[0020]

[0021] In equation (1),

[0022] M AO When the component containing oxidized olefin chains is a copolymer, the value is expressed as shown in the following formula (2), or when the component containing oxidized olefin chains is not a copolymer, the value is expressed as (molecular weight of the oxidized olefin chains of each compound contained in components (A) to (C)) / (molecular weight of each compound contained in components (A) to (C)).

[0023] N represents the solid content (parts by mass) of all compounds contained in components (A) to (C).

[0024] n represents the solid content (parts by mass) of each compound contained in components (A) to (C);

[0025] [Mathematical Expression 2]

[0026]

[0027] In equation (2),

[0028] A AO This indicates the molecular weight of the olefin oxide chain in each monomer containing the olefin oxide chain.

[0029] A represents the molecular weight of each monomer containing the oxidized olefin chain.

[0030] B AO This indicates the molar number of each monomer containing the oxidized olefin chain.

[0031] B represents the total number of moles of all monomers contained in the copolymer;

[0032] [2] The photosensitive resin composition according to [1] further comprises (E) an inorganic filler material;

[0033] [3] The photosensitive resin composition according to [1] or [2], wherein the oxidized olefin chain is included in any of the components (B) and (C);

[0034] [4] The photosensitive resin composition according to any one of [1] to [3], wherein component (A) comprises an acid-modified unsaturated epoxy ester resin;

[0035] [5] The photosensitive resin composition according to any one of [1] to [4], wherein component (A) comprises acid-modified epoxy (meth)acrylate;

[0036] [6] The photosensitive resin composition according to any one of [1] to [5], wherein component (A) comprises: any one of an acid-modified epoxy (meth)acrylate containing a naphthalene skeleton and an acid-modified epoxy (meth)acrylate containing a bisphenol skeleton;

[0037] [7] The photosensitive resin composition according to [6], wherein the acid-modified epoxy (meth)acrylate containing a bisphenol backbone has either a bisphenol A backbone or a bisphenol F backbone;

[0038] [8] The photosensitive resin composition according to any one of [1] to [7], wherein component (B) has a biphenyl skeleton;

[0039] [9] The photosensitive resin composition according to any one of [1] to [8], wherein component (D) comprises an oxime ester photopolymerization initiator;

[0040]

[10] A photosensitive film comprising any one of the photosensitive resin compositions described in [1] to [9];

[0041]

[11] A photosensitive film with a support, comprising: a support, and a photosensitive resin composition layer comprising any one of [1] to [9] disposed on the support;

[0042]

[12] A printed wiring board comprising an insulating layer formed by curing a photosensitive resin composition according to any one of [1] to [9];

[0043]

[13] The printed wiring board according to

[12] , wherein the insulating layer is a solder resist layer;

[0044]

[14] A semiconductor device comprising the printed wiring board described in

[12] or

[13] .

[0045] The effects of the invention

[0046] If the present invention is adopted, it is possible to provide: a photosensitive resin composition that yields a cured product with excellent flexibility and insulation and excellent resolution, a photosensitive film obtained from the photosensitive resin composition, a photosensitive film with a support, a printed wiring board, and a semiconductor device. Detailed Implementation

[0047] 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 below.

[0048] [Photosensitive Resin Composition]

[0049] The photosensitive resin composition of the present invention is a photosensitive resin composition comprising (A) a resin containing an olefinic unsaturated group and a carboxyl group, (B) an epoxy resin, (C) a photopolymerizable monomer, and (D) a photopolymerization initiator, wherein any component (A), (B) and (C) contains an oxidized olefin chain, and the parameter X represented by the following formula (1) is 4 or more and 25 or less.

[0050] [Mathematical Expression 3]

[0051]

[0052] In equation (1), M AO When the component containing oxidized olefin chains is a copolymer, the value is expressed as shown in formula (2) below; or when the component containing oxidized olefin chains is not a copolymer, the value is expressed as (molecular weight of the oxidized olefin chains 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 compounds contained in components (A) to (C). n represents the solid content (parts by mass) of each compound contained in components (A) to (C).

[0053] [Mathematical Expression 4]

[0054]

[0055] In equation (2), A AO A represents the molecular weight of the olefin chain in each monomer containing the olefin chain, and B represents the molecular weight of the olefin chain in each monomer containing the olefin chain. AO B represents the molar number of each monomer containing the oxidized olefin chain, and B represents the total molar number of all monomers contained in the copolymer.

[0056] In this invention, by adjusting the content of oxidized olefin chains in any component of (A), (B), and (C) relative to the overall components (A) to (C) as curable resins, a photosensitive resin composition with excellent flexibility, insulation, and resolution can be provided. Furthermore, a cured product with excellent adhesion is also generally obtained. The inventors have discovered that if the photosensitive resin composition is hydrophilic, it exhibits excellent flexibility but poor insulation. Therefore, they focused on the content of oxidized olefin chains with hydrophobic structures participating in polymerization in components (A) to (C). As a result, if the content of oxidized olefin chains in any component of (A), (B), and (C) is adjusted relative to the overall components (A) to (C) to satisfy the above formula (1), the flexibility of the photosensitive resin composition increases, thereby improving both flexibility and insulation. Furthermore, it is believed that the adhesion is also improved by utilizing the hydrophobic structure of the oxidized olefin chains.

[0057] An oxidized olefin chain refers to a structure represented by the following formula (a);

[0058] [Chemical Formula 1]

[0059]

[0060] In formula (a), R independently represents an alkylene group with optional substituents, and q represents an integer from 1 to 100.

[0061] R represents an alkylene group optionally having a substituent. Preferably, the alkylene group has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 5, 1 to 4, or 1 to 3 carbon atoms. Examples of specific alkylene groups include methylene, ethylene, propylene, isopropylene, n-butylene, pentylene, and hexylene.

[0062] Alkyl groups may have substituents. Examples of substituents include alkyl groups with 1 to 3 carbon atoms, halogen atoms, etc. Substituents may be present alone or in combination of two or more.

[0063] q represents an integer from 1 to 100, preferably an integer from 1 to 50, more preferably an integer from 1 to 10, and even more preferably an integer from 1 to 5.

[0064] Examples of oxidized olefin chains include methylene oxide, ethylene oxide (EO), propylene oxide (PO), isopropylene oxide, and butene oxide (BO).

[0065] The oxidized olefin chain is preferably included in component (A), preferably in component (B), and preferably in component (C). Furthermore, the oxidized olefin chain is preferably included in components (A) and (B), preferably in components (A) and (C), preferably in components (B) and (C), and preferably in components (A) to (C). Among these, the oxidized olefin chain is more preferably included in components (B) and (C).

[0066] Components (A) to (C) may have one type of oxidized olefin chain or multiple types of oxidized olefin chains in one molecule.

[0067] The photosensitive resin composition may further include any components in combination with components (A) to (D). Examples of such components include (E) inorganic fillers, (F) solvents, and (G) other additives. The components contained in the photosensitive resin composition will be described in detail below.

[0068] <(A) Resins containing olefinic unsaturated groups and carboxyl groups>

[0069] The photosensitive resin composition includes, as component (A), a resin containing olefinic unsaturated groups and carboxyl groups. By including component (A) in the photosensitive resin composition, the developability can be improved.

[0070] Examples of olefinic unsaturated groups include vinyl, allyl, propargyl, butenyl, ethynyl, phenylethynyl, maleimide, nadiimide, and (meth)acryloyl. From the viewpoint of the reactivity of photoradical polymerization, (meth)acryloyl is preferred. "(meth)acryloyl" refers to both methacryloyl and acryloyl groups.

[0071] Component (A) has an olefinic unsaturated group and a carboxyl group. Because of this structure, component (A) can achieve not only photoradical polymerization but also alkaline development. Preferably, as component (A), a resin having, for example, a carboxyl group and two or more olefinic unsaturated groups simultaneously in one molecule is preferred.

[0072] Examples of resins containing olefinic unsaturated groups and carboxyl groups include acid-modified unsaturated epoxy ester resins, obtained by reacting unsaturated carboxylic acids with epoxy compounds, and subsequently with acid anhydrides. Specifically, an unsaturated epoxy ester resin is obtained by reacting an unsaturated carboxylic acid with an epoxy compound, and then an acid-modified unsaturated epoxy ester resin is obtained by reacting the unsaturated epoxy ester resin with an acid anhydride. One of the epoxy compound, the unsaturated carboxylic acid, and the acid anhydride may have an oxidized olefin chain.

[0073] As epoxy compounds, any compound containing an epoxy group within its molecule can be used. Examples include: epoxy-containing copolymers, bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol F type epoxy resins, bisphenol S type epoxy resins, and modified bisphenol F type epoxy resins modified by reacting epichlorohydrin with bisphenol F type epoxy resin to achieve trifunctionality or higher, etc.; biphenol type epoxy resins, tetramethyl... Biphenol-type epoxy resins, including biphenol type; phenolic varnish-type epoxy resins, cresol phenolic varnish-type epoxy resins, bisphenol A type phenolic varnish-type epoxy resins, alkylphenol phenolic varnish-type epoxy resins, and other phenolic varnish-type epoxy resins (novolac); bisphenol AF type epoxy resins and perfluoroalkyl type epoxy resins, and other fluorinated epoxy resins; naphthalene-type epoxy resins, dihydroxynaphthalene-type epoxy resins, polyhydroxybinaphthyl-type epoxy resins, naphthol-type epoxy resins, and binaphthol-type epoxy resins. Epoxy resins, including naphthylene ether type epoxy resins, naphthol phenolic varnish type epoxy resins, and naphthalene-type epoxy resins obtained through the condensation reaction of polyhydroxynaphthalene with aldehydes (epoxy resins containing a naphthalene skeleton); bixylenol type epoxy resins; dicyclopentadiene type epoxy resins; triphenol type epoxy resins; tert-butylcatechol type epoxy resins; anthracene type epoxy resins; glycidylamine type epoxy resins; and glycidyl ester type epoxy resins. Biphenyl-type epoxy resins; linear aliphatic epoxy resins; epoxy resins with butadiene structures; alicyclic epoxy resins; heterocyclic epoxy resins; spirocyclic epoxy resins; cyclohexanediol-type epoxy resins; trimethylol epoxy resins; tetraphenylethane-type epoxy resins; (meth)acrylate polyglycidyl acrylate, copolymers of glycidyl methacrylate and acrylates, and other acrylic resins containing glycidyl groups; fluorene-type epoxy resins; halogenated epoxy resins, etc.

[0074] From the viewpoint of reducing the average coefficient of linear thermal expansion, epoxy compounds are preferably copolymers containing epoxy groups or epoxy resins containing an aromatic backbone. Here, the aromatic backbone includes both polycyclic aromatic hydrocarbons and aromatic heterocycles. Preferred epoxy compounds include epoxy resins containing a naphthalene backbone; epoxy resins containing a fused-ring backbone; biphenyl-type epoxy resins; bisphenol-type epoxy resins such as bisphenol F and bisphenol A; cresol-phenolic varnish-type epoxy resins; and glycidyl ester-type epoxy resins.

[0075] Epoxy-containing copolymers can be obtained by polymerizing an epoxy-containing monomer and any monomers used as needed. Examples of epoxy-containing monomers include glycidyl methacrylate, 3,4-epoxybutyl methacrylate, 2-methyl-3,4-epoxycyclohexyl methacrylate, allyl glycidyl ether, and other epoxy-containing (meth)acrylate monomers, with glycidyl methacrylate being preferred. One epoxy-containing monomer can be used alone, or two or more can be used in combination.

[0076] Examples of any monomer include: styrene, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, dodecyl (meth)acrylate, dodecyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, benzyl (meth)acrylate, acrylamide, N,N-dimethyl(meth)acrylamide, (methyl) Acrylonitrile, 3-(meth)acryloylpropyltrimethoxysilane, N,N-dimethylaminoethyl methacrylate, glycidyl methacrylate, styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 1,4-cyclohexanediol mono(meth)acrylate, glyceryl mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, lactone-modified (meth)acrylate with hydroxyl groups at the end, 1-adamantyl methacrylate, etc., preferably n-butyl methacrylate. Any monomer can be used alone or in combination with two or more. "(Meth)acrylic acid" refers to acrylic acid and methacrylic acid. "(Meth)acrylate" refers to acrylates and methacrylates.

[0077] As epoxy resins containing a naphthalene skeleton, dihydroxynaphthalene-type epoxy resins, polyhydroxynaphthalene-type epoxy resins, and naphthalene-type epoxy resins obtained by the condensation reaction of polyhydroxynaphthalene with aldehydes are preferred. Examples of dihydroxynaphthalene-type epoxy resins include: 1,3-diepoxypropoxynaphthalene, 1,4-diepoxypropoxynaphthalene, 1,5-diepoxypropoxynaphthalene, 1,6-diepoxypropoxynaphthalene, 2,3-diepoxypropoxynaphthalene, 2,6-diepoxypropoxynaphthalene, and 2,7-diepoxypropoxynaphthalene. Examples of polyhydroxynaphthalene-type epoxy resins include: 1,1'-bi(2-epoxypropoxy)naphthalene, 1-(2,7-diepoxypropoxy)-1'-(2'-epoxypropoxy)naphthalene, and 1,1'-bi(2,7-diepoxypropoxy)naphthalene. Examples of naphthalene-type epoxy resins obtained by the condensation reaction of polyhydroxynaphthalene with aldehydes include 1,1'-bis(2,7-diepoxypropoxynaphthyl)methane, 1-(2,7-diepoxypropoxynaphthyl)-1'-(2'-epoxypropoxynaphthyl)methane, and 1,1'-bis(2-epoxypropoxynaphthyl)methane.

[0078] Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, cinnamic acid, butenoic acid, glycidyl methacrylate, and glycidyl acrylate. These carboxylic acids can be used alone or in combination of two or more. From the viewpoint of improving the photocurability of the photosensitive resin composition, acrylic acid and methacrylic acid are preferred. It should be noted that in this specification, the epoxy ester resin described above as a reaction product of an epoxy compound and (meth)acrylic acid is sometimes referred to as "epoxy (meth)acrylate," where the epoxy groups of the epoxy compound are substantially eliminated through the reaction with (meth)acrylic acid.

[0079] Examples of acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic dianhydride. These anhydrides can be used alone or in combination of two or more. From the perspective of improving the resolution and insulation reliability of the cured product, succinic anhydride and tetrahydrophthalic anhydride are preferred.

[0080] When obtaining acid-modified unsaturated epoxy ester resin, catalysts, solvents, and polymerization inhibitors can be used as needed.

[0081] As an acid-modified unsaturated epoxy ester resin, an acid-modified epoxy (meth)acrylate is preferred, more preferably an acid-modified epoxy (meth)acrylate containing a naphthalene backbone or an acid-modified epoxy (meth)acrylate containing a bisphenol backbone. The term "epoxy" in acid-modified unsaturated epoxy ester resin refers to a structure derived from the aforementioned epoxy compound. For example, "bisphenol-type acid-modified epoxy (meth)acrylate" refers to an acid-modified unsaturated epoxy ester resin obtained by using a bisphenol-type epoxy resin as the epoxy compound and (meth)acrylate as the unsaturated carboxylic acid.

[0082] The acid-modified unsaturated epoxy ester resin is preferably a (meth)acrylic polymer with a glass transition temperature below -20°C. A (meth)acrylic polymer refers to a polymer containing structural units having a structure formed by polymerizing (meth)acrylic monomers. Examples of such (meth)acrylic polymers include polymers formed by polymerizing (meth)acrylic monomers, or polymers formed by copolymerizing (meth)acrylic monomers and monomers that can copolymerize with those (meth)acrylic monomers.

[0083] Examples of (meth)acrylic acid polymers with a glass transition temperature below -20°C include acid-modified unsaturated epoxy (meth)acrylic acid copolymers obtained by reacting (meth)acrylic acid with an epoxy-containing copolymer and then with an acid anhydride. Specifically, unsaturated epoxy (meth)acrylic acid copolymers are obtained by reacting (meth)acrylic acid with an epoxy-containing copolymer, and acid-modified unsaturated epoxy (meth)acrylic acid copolymers are obtained by reacting the unsaturated epoxy (meth)acrylic acid copolymer with an acid anhydride.

[0084] The preferred form of (meth)acrylic acid polymers with a glass transition temperature below -20°C is a compound obtained by reacting an epoxy-containing copolymer obtained by polymerizing an epoxy-containing monomer and any monomer, (meth)acrylic acid, and an acid anhydride, wherein the epoxy-containing monomer is glycidyl methacrylate, the arbitrary monomer is butyl acrylate, and the acid anhydride is tetrahydrophthalic anhydride.

[0085] Such acid-modified unsaturated epoxy ester resins can be commercially available. Specific examples include: "ZAR-2000" (a reaction product of bisphenol A type epoxy resin, acrylic acid, and succinic anhydride), "ZFR-1491H," and "ZFR-1533H" (a reaction product of bisphenol F type epoxy resin, acrylic acid, and tetrahydrophthalic anhydride (an acid-modified epoxy acrylate containing a bisphenol F type backbone)) manufactured by Nippon Kayaku Co., Ltd., and "PR-300CP" (a reaction product of cresol phenolic varnish type epoxy resin, acrylic acid, and acid anhydride) manufactured by Showa Denko Co., Ltd. These resins can be used alone or in combination of two or more.

[0086] Another form of resin containing olefinic unsaturated groups and carboxyl groups can be exemplified by unsaturated modified (meth)acrylic resins obtained by reacting an epoxy compound containing olefinic unsaturated groups with a (meth)acrylic resin having structural units obtained by polymerizing (meth)acrylic acid. Examples of epoxy compounds containing olefinic unsaturated groups include glycidyl methacrylate, 4-hydroxybutyl methacrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl methacrylate. Furthermore, an anhydride can be reacted with the hydroxyl groups generated when the unsaturated groups are introduced. The same compounds as those described above can be used as the anhydride, and the preferred range is also the same.

[0087] Such unsaturated modified (meth)acrylic resins can be commercially available. Specific examples include: "SPC-1000" and "SPC-3000" manufactured by Showa Denko Corporation, and "CYCLOMER P(ACA)Z-250", "CYCLOMER P(ACA)Z-251", "CYCLOMER P(ACA)Z-254", "CYCLOMER P(ACA)Z-300", and "CYCLOMER P(ACA)Z-320" manufactured by Daicel-Allnex Corporation.

[0088] From the viewpoint of film-forming properties, the weight-average molecular weight of component (A) is preferably 1000 or more, more preferably 1500 or more, and even more preferably 2000 or more. As an upper limit, from the viewpoint of developability, it is preferably 50000 or less, more preferably 30000 or less, and even more preferably 25000 or less. The weight-average molecular weight is the weight-average molecular weight converted from polystyrene as determined by gel permeation chromatography (GPC).

[0089] Regarding the acid value of component (A), from the viewpoint of improving the alkaline developability of the photosensitive resin composition, an acid value of 0.1 mg KOH / g or higher is preferred, more preferably 0.5 mg KOH / g or higher, and even more preferably 1 mg KOH / g or higher. On the other hand, from the viewpoint of suppressing the washing away of fine patterns in the cured product due to development and improving insulation reliability, an acid value of 150 mg KOH / g or lower is preferred, more preferably 120 mg KOH / g or lower, and even more preferably 100 mg KOH / g or lower. Here, the acid value refers to the residual acid value of the carboxyl groups present in component (A), and the acid value can be determined by the following method. First, after accurately weighing about 1 g of the test resin solution, 30 g of acetone is added to the resin solution to dissolve it uniformly. Next, an appropriate amount of phenolphthalein as an indicator is added to the solution, and titration is performed with a 0.1 N KOH aqueous solution. Then, the acid value is calculated using the following formula.

[0090] Formula: A(b)=10×Vf×56.1 / (Wp×I)

[0091] It should be noted that in the above formula, A(b) represents the acid value (mgKOH / g), Vf represents the titration amount of KOH (mL), Wp represents the mass of the resin solution to be determined (g), and I represents the proportion of non-volatile components in the resin solution to be determined (mass%).

[0092] (A) In the manufacture of the component, from the viewpoint of improving storage stability, the ratio of "the number of moles of epoxy groups in the epoxy resin" to "the total number of moles of carboxyl groups in the unsaturated carboxylic acid and anhydride" is preferably in the range of 1:0.8 to 1.3, and more preferably in the range of 1:0.9 to 1.2.

[0093] From the viewpoint of improving flexibility, the glass transition temperature (Tg) of component (A) is preferably -300°C or higher, more preferably -200°C or higher, even more preferably -80°C or higher, preferably -20°C or lower, more preferably -23°C or lower, and even more preferably -25°C or lower. Here, the glass transition temperature of component (A) refers to the theoretical glass transition temperature of the main chain of component (A), which can be calculated using the FOX formula shown below. The glass transition temperature obtained by the FOX formula is essentially consistent with the glass transition temperature measured by differential scanning calorimetry (TMA, DSC, DTA), so the glass transition temperature of the main chain of component (A) can also be determined by differential scanning calorimetry; 1 / Tg=(W1 / Tg1)+(W2 / Tg2)+…+(Wm / Tgm)

[0094] W1 + W2 + ... + Wm = 1

[0095] Wm represents the content (mass%) of each monomer constituting component (A), and Tgm represents the glass transition temperature (K) of each monomer constituting component (A).

[0096] From the viewpoint of improving alkaline developability, when the non-volatile component in the photosensitive resin composition is set to 100% by mass, the content of component (A) is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. From the viewpoint of improving heat resistance and average coefficient of linear expansion, the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. It should be noted that, unless otherwise specified, the content of each component in the photosensitive resin composition in this invention refers to the value when the non-volatile component in the photosensitive resin composition is set to 100% by mass.

[0097] <(B) Epoxy Resin>

[0098] The photosensitive resin composition contains epoxy resin as component (B). The inclusion of component (B) improves insulation reliability. However, component (B) as described herein does not include epoxy resins containing olefinic unsaturated groups and carboxyl groups.

[0099] As component (B), examples include: 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 phenolic varnish type epoxy resin, phenol phenolic varnish type epoxy resin, tert-butylcatechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, and glycidylamine type epoxy resin. The epoxy resins include aliphatic, glycidyl ester type, cresol phenolic varnish type, biphenyl type, linear aliphatic epoxy resin, aliphatic epoxy resin containing oxidized olefin chains, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spirocyclic epoxy resin, cyclohexane type, cyclohexanediol type, naphthyl ether type, tris(hydroxymethyl) type, and tetraphenylethane type epoxy resin. Among these, biphenyl type epoxy resin and linear aliphatic epoxy resin are preferred as (B) epoxy resin, and biphenyl type epoxy resin is more preferred. One type of (B) epoxy resin may be used alone, or two or more types may be used in combination. Examples of aliphatic epoxy resins containing oxidized olefin chains include linear aliphatic epoxy resins containing oxidized olefin chains, branched aliphatic epoxy resins containing oxidized olefin chains, and cyclic aliphatic epoxy resins containing oxidized olefin chains.

[0100] In the photosensitive resin composition, it is preferable that component (B) comprises an epoxy resin having two or more epoxy groups per molecule. From the viewpoint of significantly obtaining the desired effect of the present invention, the proportion of epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the non-volatile component of component (B) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0101] Component (B) includes an epoxy resin that is liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at 20°C (hereinafter sometimes referred to as "solid epoxy resin"). The resin composition may contain only liquid epoxy resin, only solid epoxy resin, or a combination of both.

[0102] As a solid epoxy resin, a solid epoxy resin having three or more epoxy groups per molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups per molecule is more preferred.

[0103] As a solid epoxy resin, the preferred types are xylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol-phenolic varnish-type epoxy resin, dicyclopentadiene-type epoxy resin, triphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, and tetraphenylethane-type epoxy resin, with naphthalene-type epoxy resin being more preferred.

[0104] Specific examples of solid epoxy resins include: DIC Corporation's "HP4032H" (naphthalene-type epoxy resin); DIC Corporation's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); DIC Corporation's "N-690" (cresol phenolic varnish type epoxy resin); DIC Corporation's "N-695" (cresol phenolic varnish type epoxy resin); and DIC Corporation's "HP-7200," "HP-7200HH," and "HP-72..." 00H (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", and "HP6000" (naphthyl ether type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (triphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol phenolic varnish type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; and "NC3000H" manufactured by Nippon Kayaku Co., Ltd. "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; "ESN485" (naphthol phenolic varnish type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. The following are epoxy resins manufactured by Mitsubishi Chemical Corporation: YX8800 (anthracene-type epoxy resin); PG-100 and CG-500 manufactured by Osaka Gas Chemical Co., Ltd.; YL7760 (bisphenol AF type epoxy resin); YL7800 (fluorene type epoxy resin); jER1010 (solid bisphenol A type epoxy resin); and jER1031S (tetrahydroxyphenyl ethane type epoxy resin). These can be used individually or in combination.

[0105] As a liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0106] The preferred liquid epoxy resins are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenolic varnish type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanediol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin with butadiene structure, with bisphenol A type epoxy resin and bisphenol F type epoxy resin being more preferred.

[0107] Specific examples of liquid epoxy resins include: DIC Corporation's "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin); Mitsubishi Chemical Corporation's "828US", "jER828EL", "825", and "EPIKOTE 828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical Corporation's "jER807" and "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical Corporation's "jER152" (phenolic varnish type epoxy resin); Mitsubishi Chemical Corporation's "630" and "630LSD" (glycidylamine type epoxy resin); Nippon Steel & Sumitomo Metal Chemicals Co., Ltd.'s "ZX1059" (a mixture of bisphenol A and bisphenol F type epoxy resins); Nagase... ChemteX Corporation's "EX-721" (glycidyl ester type epoxy resin); Nagase ChemteX Corporation's "EX-821" and "EX-920" (linear aliphatic epoxy resins containing oxidized olefin chains); Daicel Corporation's "CELLOXIDE 2021P" (alicyclic epoxy resin with an ester skeleton); Daicel Corporation's "PB-3600" (epoxy resin with a butadiene structure); Nippon Steel & Sumitomo Chemical Co., Ltd.'s "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin), etc. These can be used individually or in combination of two or more.

[0108] When liquid epoxy resin and solid epoxy resin are used as components (B), their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:1 to 1:20, more preferably 1:1.5 to 1:15, and particularly preferably 1:2 to 1:10. By keeping the mass ratio of liquid epoxy resin to solid epoxy resin within the aforementioned range, the desired effects of the present invention can be significantly obtained.

[0109] (B) The epoxy equivalent of component B is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., even more preferably 80 g / eq. to 2000 g / eq., and still more preferably 110 g / eq. to 1000 g / eq. By ensuring that it falls within this range, the crosslinking density of the cured resin composition layer becomes sufficient, resulting in an insulating layer with low surface roughness. The epoxy equivalent is the mass of epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be determined according to JIS K7236.

[0110] From the viewpoint of significantly achieving the desired effects of the present invention, the weight-average molecular weight (Mw) of component (B) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. The weight-average molecular weight of the resin can be determined by gel permeation chromatography (GPC) as a value converted from polystyrene.

[0111] From the viewpoint of obtaining an insulating layer exhibiting good tensile mechanical strength and insulation reliability, when the non-volatile component in the resin composition is set to 100% by mass, the content of component (B) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more. From the viewpoint of significantly obtaining the desired effects of the present invention, the upper limit of the content of component (B) is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less.

[0112] <(C) Photopolymerizable monomers>

[0113] The photosensitive resin composition contains a photopolymerizable monomer as component (C). However, component (C) does not include components (A) and (B). By including the photopolymerizable monomer (C) in the photosensitive resin composition, photoreactivity can be improved. As component (C), a photosensitive (meth)acrylate compound having one or more (meth)acryloyl groups in one molecule, which is liquid, solid, or semi-solid at room temperature, can be used. Room temperature refers to approximately 25°C.

[0114] Examples of photosensitive (meth)acrylate compounds include, for example, hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; mono- or di(meth)acrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; acrylamides such as N,N-dimethylacrylamide and N-hydroxymethylacrylamide; aminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl acrylate; and trimethylolpropane, pentaerythritol, etc. Poly(meth)acrylates, such as dipentaerythritol and other polyols or their adducts of ethylene oxide, propylene oxide, or ε-caprolactone; phenols, such as phenoxyacrylates and phenoxyethylacrylates, or their adducts of ethylene oxide or propylene oxide, etc.; epoxy acrylates, modified epoxy acrylates, melamine acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether, and / or methacrylates corresponding to the aforementioned acrylic acids, etc. (Meth)acrylates refer to acrylates and methacrylates.

[0115] Among them, preferred are mono- or di(meth)acrylates of diols, phenols such as phenoxyacrylates and phenoxyethylacrylates, or (meth)acrylates such as their ethylene oxide or propylene oxide adducts, and poly(meth)acrylates.

[0116] Examples of mono- or di(meth)acrylates that are diols include, for example, polytetramethylene glycol diacrylate.

[0117] Examples of methacrylates include phenols such as phenoxy acrylates and phenoxy ethyl acrylates, or their ethylene oxide or propylene oxide adducts, such as EO-modified bisphenol A type acrylates.

[0118] As poly(meth)acrylates, ternary acrylates or methacrylates are preferred. Examples of ternary acrylates or methacrylates include 1,9-nonanediol diacrylate, 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, and tetramethylolmethane tetra(meth)acrylate. Acrylates, dipentaerythritol hexa(meth)acrylates, N,N,N',N'-tetra(β-hydroxyethyl)ethylenediamine (meth)acrylates, etc., as ternary or higher-order acrylates or methacrylates, include tris(2-(meth)acryloyloxyethyl) phosphate, tris(2-(meth)acryloyloxypropyl) phosphate, tris(3-(meth)acryloyloxypropyl) phosphate, tris(3-(meth)acryloyl-2-hydroxyoxypropyl) phosphate, di(3-(meth)acryloyl-2-hydroxyoxypropyl)(2-(meth)acryloyloxyethyl) phosphate, (3-(meth)acryloyl-2-hydroxyoxypropyl)di(2-(meth)acryloyloxyethyl) phosphate, and other phosphate triesters (meth)acrylates. These photosensitive (meth)acrylate compounds can be used alone or in combination of two or more.

[0119] (C) Commercially available monomers can be used for photopolymerization. Examples of commercially available monomers include "DPHA" manufactured by Nippon Kayaku Co., Ltd., "EBECRYL 3708" manufactured by Daicel-Zhenxin Co., Ltd., "R-551" manufactured by Nippon Kayaku Co., Ltd., "A-PTMG-65" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and "1.9ND" manufactured by Kyoeisha Chemical Co., Ltd.

[0120] As for the content of (C) photopolymerizable monomer, from the viewpoint of promoting photocuring, when the total solid content of the photosensitive resin composition is set to 100% by mass, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 1.5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0121] <(D) Photopolymerization Initiator>

[0122] The photosensitive resin composition contains a photopolymerization initiator as component (D). By including the photopolymerization initiator (D) in the photosensitive resin composition, the photosensitive resin composition can be effectively photocured. One of these initiators can be used alone, or two or more can be used in combination.

[0123] (D) The photopolymerization initiator can be any compound, including, for example: acylphosphine oxide photoinitiators such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; oxime ester photoinitiators such as 1-[4-(phenylthio)-1,2-octanedione 2-(O-benzoyl oxime) and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-acetone 1-(O-acetyl oxime); 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-[4-(4-morpholinyl)phenyl]-1-butanone, and 2-methyl-1-[4-(methylthio)]-[[4-methylphenyl]-[[4-(4-morpholinyl)phenyl]-1-butanone]-[[4-(methylthio]-[[4-methylphenyl ... α-aminoalkylbenzene ketone photopolymerization initiators such as [phenyl]-2-morpholino-1-propanone; benzophenone, methyl benzophenone, o-benzoylbenzoic acid, benzoyl ethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthraphenone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl 2,4,6-trimethylbenzoyl)phenylphosphine acid, 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-propane-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; sulfonium salt photopolymerization initiators, etc. These photopolymerization initiators can be used alone or in combination of two or more. From the viewpoint of enabling more effective photocuring of the photosensitive resin composition, either an acylphosphine oxide photopolymerization initiator or an oxime ester photopolymerization initiator is preferred, and an oxime ester photopolymerization initiator is more preferred.

[0124] Specific examples of (D) photopolymerization initiators include "Omnirad 907", "Omnirad 369", "Omnirad 379", "Omnirad 819", and "Omnirad TPO" manufactured by IGM Corporation; "Irgacure OXE-01", "Irgacure OXE-02", "Irgacure TPO", and "Irgacure 819" manufactured by BASF Corporation; and "N-1919" and "NCI-831" manufactured by ADEKA Corporation.

[0125] Furthermore, the photosensitive resin composition may also include (D) photopolymerization initiators as photopolymerization initiation aids, such as tertiary amines like ethyl N,N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine, as well as photosensitizers like pyrazolines, anthracene derivatives, coumarins, xanthones, and thioxanthones. These compounds may be used individually or in combination of two or more.

[0126] Regarding the content of the (D) photopolymerization initiator, from the viewpoint of ensuring sufficient photocuring of the photosensitive resin composition and improving insulation reliability, when the non-volatile component of the photosensitive resin composition is set to 100% by mass, it is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more. On the other hand, from the viewpoint of suppressing resolution degradation due to oversensitivity, the upper limit is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less. It should be noted that when the photosensitive resin composition contains a photopolymerization initiation aid, the total content of the (D) photopolymerization initiator and the photopolymerization initiation aid is preferably within the above-mentioned range.

[0127] <(E) Inorganic Filler Materials>

[0128] In addition to the components mentioned above, the photosensitive resin composition may also contain inorganic filler materials as component (E) as an optional component.

[0129] As the inorganic filler material (E), an inorganic compound is used. Examples of inorganic filler materials include: silicon dioxide, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconium phosphate, and zirconium phosphotungstenate, etc. Among these, silicon dioxide and magnesium hydroxide are preferred, and magnesium hydroxide is particularly preferred. As silicon dioxide, amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, hollow silicon dioxide, etc. are examples. Furthermore, as silicon dioxide, spherical silicon dioxide is preferred. (F) One type of inorganic filler material may be used alone, or two or more types may be used in combination.

[0130] Commercially available products that are components (E) include, for example: "UFP-20" and "UFP-30" manufactured by DENKA Corporation; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd.; "SC2050", "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs Co., Ltd.; "SILFIL NSS-3N", "SILFIL NSS-4N", and "SILFIL NSS-5N" manufactured by Tokuyama Co., Ltd.; and "EP4-A" manufactured by Kamishima Chemical Co., Ltd.

[0131] The specific surface area of ​​component (E) is preferably 1 m². 2 / g or more, preferably 2m 2 / g or more, especially preferably 3m 2 / g or more. There is no particular limit to the upper limit, but 60m is preferred. 2 / g or less, 50m 2 / g or less or 40m 2 / g or less. The specific surface area can be obtained by using a specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH Corporation) to adsorb nitrogen onto the sample surface and then calculating the specific surface area using the BET multi-point method.

[0132] From the viewpoint of significantly achieving the desired effect of the present invention, the average particle size of component (E) is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less.

[0133] The average particle size of component (E) can be determined by laser diffraction scattering based on the Mie scattering theory. Specifically, a laser diffraction particle size distribution measuring device can be used to prepare the particle size distribution of the inorganic filler material on a volume basis, and the median particle size can be used as the average particle size for measurement. The sample for testing can be obtained by weighing 100 mg of inorganic filler material and 10 g of methyl ethyl ketone into a tube and dispersing it ultrasonically for 10 minutes. For the sample for testing, a laser diffraction particle size distribution measuring device can be used, with the light source wavelength set to blue and red, to measure the volume-based particle size distribution of component (E) in a flow cell mode, and the average particle size can be calculated based on the obtained particle size distribution as the median particle size. Examples of laser diffraction particle size distribution measuring devices include the "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

[0134] From the viewpoint of improving moisture resistance and dispersibility, component (E) is preferably treated with a surface treatment agent. Examples of surface treatment agents include vinyl silane coupling agents, (meth)acrylic acid coupling agents, fluorinated silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. Among these, from the viewpoint of significantly achieving the effects of the present invention, vinyl silane coupling agents, (meth)acrylic acid coupling agents, and aminosilane coupling agents are preferred. Furthermore, a single surface treatment agent may be used alone, or two or more may be used in any combination.

[0135] Commercially available surface treatment agents include, for example: KBM1003 (vinyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd.; KBM503 (3-methacryloyloxypropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd.; KBM403 (3-epoxypropoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd.; KBM803 (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd.; and KBE903 (3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Products manufactured by Shin-Etsu Chemical Co., Ltd. include: N-phenyl-3-aminopropyltrimethoxysilane, SZ-31 (hexamethyldisilazane), KBM103 (phenyltrimethoxysilane), KBM-4803 (long-chain epoxy silane coupling agent), and KBM-7103 (3,3,3-trifluoropropyltrimethoxysilane).

[0136] From the viewpoint of improving the dispersibility of inorganic filler materials, the degree of surface treatment by surface treatment agent is preferably controlled within a specified range. Specifically, 100 parts by weight of inorganic filler material is preferably surface treated with 0.2 parts by weight to 5 parts by weight of surface treatment agent, more preferably with 0.2 parts by weight to 3 parts by weight of surface treatment agent, and even more preferably with 0.3 parts by weight to 2 parts by weight of surface treatment agent.

[0137] The degree of surface treatment by the surface treatment agent can be evaluated by the carbon content per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m². 2 The above, more preferably 0.1 mg / m 2 The above is further preferred to be 0.2 mg / m³. 2That's all. On the other hand, from the viewpoint of suppressing the increase in melt viscosity and melt viscosity under film morphology of the resin varnish, 1 mg / m³ is preferred. 2 The following is more preferably 0.8 mg / m³ 2 The following is a further preferred value: 0.5 mg / m³ 2 the following.

[0138] The carbon content per unit surface area of ​​inorganic filler materials can be determined after cleaning the surface-treated inorganic filler material with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, sufficient MEK is added as a solvent to the surface-treated inorganic filler material, and the mixture is ultrasonically cleaned at 25°C for 5 minutes. After removing the supernatant and drying the solid components, the carbon content per unit surface area of ​​the inorganic filler material can be determined using a carbon analyzer. A suitable carbon analyzer is the "EMIA-320V" manufactured by Horiba Corporation.

[0139] From the viewpoint of achieving significant effects of the present invention, when the non-volatile component in the photosensitive resin composition is set to 100% by mass, the content of component (E) is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less.

[0140] <(F) Solvent>

[0141] In addition to the components mentioned above, the photosensitive resin composition may further include solvent (F) as an optional component. By including solvent (F), the viscosity of the varnish can be adjusted. Organic solvents are examples of solvent (F).

[0142] Examples of solvents used as (F) include: ketones such as methyl ethyl ketone and cyclohexanone; aromatics such as toluene, xylene, and tetramethylbenzene; glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, and diethylene glycol monoethyl ether acetate; aliphatic hydrocarbons such as octane and decane; and petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha. One of these solvents may be used alone, or two or more may be used in combination. The amount of solvent used can be adjusted appropriately from the perspective of the coatability of the resin composition.

[0143] <(G) Other Additives>

[0144] The photosensitive resin composition may further contain (G) other additives to a degree that does not impair the purpose of the present invention. As (G) other additives, various additives may be added, such as: thermoplastic resins, organic fillers, melamine, organobentonite particles, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, carbon black, naphthalene black, etc.; polymerization inhibitors such as hydroquinone, phenothiazine, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc.; thickeners such as bentonite, montmorillonite, etc.; defoamers such as organosilicon, fluorine, and vinyl resins; brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus compounds, aromatic condensed phosphates, halogenated condensed phosphates, etc.; flame retardants such as phenolic curing agents, cyanate ester curing agents, etc., and various additives for thermosetting resins.

[0145] The photosensitive resin composition can be prepared by mixing the above-mentioned components (A) to (D) as essential components, appropriately mixing the above-mentioned components (E) to (G) as optional components, and mixing (blending) or stirring with mixing equipment such as a three-roll mill, ball mill, bead mill, sand mill, or a stirring device such as a super mixer or planetary mixer as needed.

[0146] <Properties and Uses of Photosensitive Resin Compositions>

[0147] The photosensitive resin composition contains oxidized olefin chains in any of components (A), (B), and (C). In this case, the parameter X, expressed by formula (1) below, is 4 or more and 25 or less. By satisfying formula (1), a cured product with excellent flexibility and insulation can be obtained;

[0148] [Mathematical Expression 5]

[0149]

[0150] In equation (1), M AO When the component containing oxidized olefin chains is a copolymer, the value is expressed as shown in formula (2) below. Furthermore, M... AO When the component containing oxidized olefin chains is not a copolymer, M represents (the molecular weight of the oxidized olefin chains of each compound contained in components (A) to (C)) / (the molecular weight of each compound contained in components (A) to (C)). Therefore, when the component containing oxidized olefin chains is not a copolymer, M AO This indicates the mass percentage of oxidized olefin chains in each of these components. N represents the solid content (parts by mass) of all compounds contained in components (A) to (C), and n represents the solid content (parts by mass) of each compound contained in components (A) to (C). Therefore, X is the M calculated separately for all components (A) to (C) in the resin composition. AOThe product of n, summing all such products, dividing the sum by N and expressing the value as a percentage;

[0151] [Mathematical Expression 6]

[0152]

[0153] In equation (2), A AO A represents the molecular weight of the olefin chain in each monomer containing the olefin chain, and B represents the molecular weight of the olefin chain in each monomer containing the olefin chain. AO B represents the molar number of each monomer containing the oxidized olefin chain, and B represents the total molar number of all monomers contained in the copolymer.

[0154] The term "copolymer" refers to a polymer obtained by polymerization of two or more monomers, and is a polymer with a weight-average molecular weight of 10,000 or more. Copolymers can be any of the following: random copolymers, block copolymers, alternating copolymers, and graft copolymers.

[0155] As mentioned above, copolymers can exist in forms such as random copolymerization, making it sometimes difficult to calculate M from molecular weight. AO The value of M. For copolymers, additivity usually holds, so it is difficult to calculate M from molecular weight alone. AO Given the value of M, equation (2) can be used to calculate M. AO Through A in equation (2) AO / A, calculate the average molecular weight per unit of the oxidized olefin chain, and then multiply it by B in equation (2). AO / B represents the molar proportion of monomers containing oxidized olefin chains, from which M in the copolymer can be calculated. AO The value of . The "monomer" in the definition in equation (2) refers to the compound that is equivalent to the monomer unit contained in the copolymer. "Monomer unit" refers to a part of the structure in the copolymer formed by polymerizing a certain compound.

[0156] From the viewpoint of obtaining a cured product with excellent flexibility and insulation and improving resolution, X in formula (1) is 25 or less, preferably 23 or less, more preferably 20 or less, and even more preferably 18 or less. From the viewpoint of significantly obtaining the effects of the present invention, the lower limit of X in formula (1) is 4 or more, preferably 5 or more, and more preferably 6 or more.

[0157] The cured product obtained by photocuring the photosensitive resin composition of the present invention exhibits excellent resolution. Therefore, when a circular hole (through hole) with an opening diameter of 100 μm is formed in the cured product, the formation of residue at the bottom of the circular hole can be suppressed. The evaluation of residue at the bottom of the through hole can be performed according to the method described in "Evaluation of Residue at the Bottom of Through Hole" described later.

[0158] The cured product obtained by photocuring the photosensitive resin composition of the present invention exhibits excellent bending properties. As a specific example of bending property testing, a photosensitive film on which the photosensitive resin composition layer has undergone full-surface exposure, development, and heat treatment was used, and the bending property was evaluated using an MIT flexural fatigue tester according to JIS P8115. In this case, the average number of bends is typically 100 or more, preferably 300 or more. The bending property evaluation can be specifically performed according to the method described in the examples below.

[0159] The cured product obtained by photocuring the photosensitive resin composition of the present invention exhibits excellent insulating properties. As a specific example of insulation evaluation, a photosensitive resin film is exposed, developed, and heat-treated on a comb-shaped wiring pattern. Copper wires are soldered as electrodes on both sides of the comb-shaped pattern, a predetermined voltage is applied, and the resistance values ​​at seven locations are measured after 500 hours. At this time, a resistance value of 10 is preferred. 8 Ω or higher. The insulation performance can be specifically evaluated according to the methods described in the examples below.

[0160] The cured product obtained by photocuring the photosensitive resin composition of the present invention typically exhibits excellent adhesion strength to copper foil. As a specific example for evaluating adhesion strength, a layer of photosensitive resin composition with a glass epoxy resin substrate bonded to it is bonded to rolled copper foil, and subjected to full-surface exposure, development, and heat treatment. Regarding copper peeling, the copper foil is peeled using a tensile testing machine (TSE Corporation "AC-50C-SL") based on Japanese Industrial Standard (JIS C6481). At this time, the adhesion strength to the copper foil is typically 0.5 kgf or higher. The adhesion strength can be specifically evaluated according to the methods described in the examples below.

[0161] The applications of the photosensitive resin composition of the present invention are not particularly limited, and it can be widely used in photosensitive films, photosensitive films with supports, insulating resin films such as prepregs, circuit boards (for laminates, multilayer printed wiring boards, etc.), solder resist layers (solder resist), underfill materials, chip bonding materials, semiconductor sealing materials, through-hole filling resins, component embedding resins, and other applications requiring photosensitive resin compositions. Suitable applications include: photosensitive resin compositions for insulating layers of printed wiring boards (printed wiring boards where the cured product of the photosensitive resin composition serves as the insulating layer), photosensitive resin compositions for interlayer insulating layers (printed wiring boards where the cured product of the photosensitive resin composition serves as the interlayer insulating layer), photosensitive resin compositions for plating formation (printed wiring boards where a plating layer is formed on the cured product of the photosensitive resin composition), and photosensitive resin compositions for solder resist layers (printed wiring boards where the cured product of the photosensitive resin composition serves as the solder resist layer).

[0162] [Photosensitive film]

[0163] Regarding the photosensitive resin composition of the present invention, a photosensitive film can be formed by coating a support substrate in the form of a resin varnish and drying it with an organic solvent. Alternatively, a photosensitive film pre-formed on a support can be laminated onto the support substrate for use. The photosensitive film can be laminated onto various support substrates. Examples of support substrates include glass epoxy boards, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates.

[0164] [Photosensitive film with support]

[0165] The photosensitive resin composition of the present invention can be suitably used in the form of a photosensitive film with a support on which a photosensitive resin composition layer is formed. That is, the photosensitive film with a support includes a support and a photosensitive resin composition layer formed with the photosensitive resin composition of the present invention disposed on the support.

[0166] Examples of supports include polyethylene terephthalate films, polyethylene naphthalate films, polypropylene films, polyethylene films, polyvinyl alcohol films, triacetyl acetate films, etc., with polyethylene terephthalate films being particularly preferred.

[0167] Commercially available supports include, for example, polypropylene films manufactured by Oji Paper Co., Ltd. (product names "ALPHAN MA-410" and "E-200C"), polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and polyethylene terephthalate films such as the PS series (product name "PS-25") manufactured by Teijin Co., Ltd., but are not limited to these examples. For these supports, a release agent such as a silicone coating agent can be coated on the surface to facilitate the removal of the photosensitive resin composition layer. The thickness of the support is preferably in the range of 5 μm to 50 μm, more preferably in the range of 10 μm to 25 μm. By making the thickness 5 μm or more, the cracking of the support can be suppressed during support peeling before development; by making the thickness 50 μm or less, the resolution during exposure from the support can be improved. Furthermore, a support with low white point (fish eye) is preferred. Here, white spots refer to defects formed when foreign matter, undissolved substances, oxidized deterioration products, etc., enter the membrane during the manufacturing process of a membrane by hot melting of materials and mixing, extrusion, biaxial stretching, casting, etc.

[0168] Furthermore, to reduce light scattering during exposure using active energy rays such as ultraviolet light, the support is preferably made of a material with excellent transparency. Specifically, the support is preferably made of a material with a turbidity (haze standardized according to JIS-K6714) of 0.1 to 5, which is an indicator of transparency. Furthermore, the photosensitive resin composition layer can also be protected with a protective film.

[0169] By protecting the photosensitive resin composition layer of the photosensitive film with the support with a protective film, it is possible to prevent debris or other contaminants from adhering to the surface of the photosensitive resin composition layer or causing damage. The protective film can be made of the same material as the support described above. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and even more preferably in the range of 10 μm to 30 μm. A thickness of 1 μm or more improves the processability of the protective film; a thickness of 40 μm or less tends to improve economic efficiency (low cost). It should be noted that, for the protective film, it is preferable that the adhesion between the photosensitive resin composition layer and the protective film is smaller than the adhesion between the photosensitive resin composition layer and the support.

[0170] The photosensitive film with a support of the present invention can be manufactured by methods known to those skilled in the art. For example, a resin varnish obtained by dissolving the photosensitive resin composition of the present invention in an organic solvent can be prepared, the resin varnish can be coated onto a support, and the organic solvent can be dried by heating or hot air blowing to form a photosensitive resin composition layer. Specifically, firstly, after completely removing bubbles from the photosensitive resin composition by vacuum degassing or the like, the photosensitive resin composition is coated onto a support, the solvent is removed by a hot air furnace or far-infrared furnace, and it is dried. Then, a protective film is laminated onto the resulting photosensitive resin composition layer as needed, thereby manufacturing a photosensitive film with a support. The specific drying conditions vary depending on the curability of the photosensitive resin composition and the amount of organic solvent in the resin varnish. For a resin varnish containing 30% to 60% by mass of organic solvent, it can be dried at 80°C to 120°C for 3 to 13 minutes. From the viewpoint of preventing the diffusion of organic solvents in subsequent processes, the amount of residual organic solvent in the photosensitive resin composition layer is preferably 5% by mass or less, more preferably 2% by mass or less, relative to the total amount of the photosensitive resin composition layer. Those skilled in the art can appropriately set suitable drying conditions through simple experiments. From the viewpoint of improving processability and suppressing the decrease in sensitivity and resolution within the photosensitive resin composition layer, the thickness of the photosensitive resin composition layer is preferably in the range of 5 μm to 500 μm, more preferably in the range of 10 μm to 200 μm, further preferably in the range of 15 μm to 150 μm, even more preferably in the range of 20 μm to 100 μm, and particularly preferably in the range of 20 μm to 60 μm.

[0171] Examples of coating methods for photosensitive resin compositions include: gravure coating, micro-gravure coating, reverse coating, kiss reverse coating, die coating, slot die coating, lip coating, comma coating, blade coating, roller coating, knife coating, curtain coating, chamber gravure coating, slot orifice coating, spraying, and dip coating. The photosensitive resin composition can be coated in multiple coats, in a single coat, or in combination of different methods. Die coating, which provides excellent coating uniformity, is preferred. Furthermore, to avoid foreign matter contamination, the coating process is preferably performed in an environment with minimal foreign matter generation, such as a cleanroom.

[0172] Printed wiring board

[0173] The printed wiring board of the present invention comprises an insulating layer formed by curing the photosensitive resin composition of the present invention. This insulating layer is preferably used as a solder resist layer.

[0174] In detail, the printed wiring board of the present invention can be manufactured using the above-described photosensitive film or a photosensitive film with a support. Hereinafter, the case where the insulating layer is a solder resist layer will be described.

[0175] <Coating and Drying Process>

[0176] A photosensitive film is formed on a circuit board by directly applying a photosensitive resin composition in the form of a resin varnish and allowing the organic solvent to dry.

[0177] Examples of circuit boards include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. It should be noted that, here, a circuit board refers to a substrate on one or both sides of the substrate described above where a patterned conductor layer (circuit) is formed. Furthermore, in multilayer printed wiring boards (PCBs) formed by alternating layers of conductor and insulating layers, the substrate on one or both sides of the outermost layer of the PCB is also included within the scope of the circuit board discussed here. It should be noted that the surface of the conductor layer may be pre-roughened through blackening treatment, copper etching, or similar processes.

[0178] As for the coating method, full-page printing based on screen printing is generally used, but any other means can be used as long as it can achieve uniform coating. For example, spray coating, hot melt coating, rod coating, squeegee coating, blade coating, air knife coating, curtain flow coating, roller coating, gravure coating, offset printing, dip coating, brush coating, and other common coating methods can all be used. After coating, drying is performed using a hot air oven or far-infrared oven as needed. The preferred drying conditions are 80℃~120℃ for 3 to 13 minutes. This process forms a photosensitive film on the circuit board.

[0179] <Lamination Process>

[0180] On the other hand, when using a photosensitive film with a support, the photosensitive resin composition layer is laminated to one or both sides of the circuit board using a vacuum laminator. During the lamination process, if the photosensitive film with the support has a protective film, after removing the protective film, the photosensitive film with the support and the circuit board are preheated as needed, and the photosensitive resin composition layer is pressed onto the circuit board while being heated. For photosensitive films with a support, a vacuum lamination method is preferably used to laminate them to the circuit board under reduced pressure.

[0181] There are no particular limitations on the conditions for the lamination process. For example, preferred conditions are: the pressing temperature (lamination temperature) is preferably set to 70℃~140℃, and the pressing pressure is preferably set to 1kgf / cm. 2 ~11kgf / cm 2 (9.8×10 4 N / m 2 ~107.9×10 4 N / m 2 The lamination time is preferably set to 5 to 300 seconds, and lamination is performed under reduced pressure of 20 mmHg (26.7 hPa) or less. Furthermore, the lamination process can be batch-type or continuous using rollers. Vacuum lamination can be performed using commercially available vacuum laminators. Examples of commercially available vacuum laminators include: vacuum dressing machines manufactured by Nikko-Materials Co., Ltd., vacuum pressure laminators manufactured by Meiki Manufacturing Co., Ltd., roller dry coating machines manufactured by Hitachi Industries Co., Ltd., and vacuum laminators manufactured by Hitachi AIC Co., Ltd. This operation forms a photosensitive film on the circuit board.

[0182] <Exposure Process>

[0183] After a photosensitive film is applied to a circuit board through a coating and drying process or a lamination process, an exposure process is performed whereby a predetermined portion of the photosensitive resin composition layer is irradiated with active light through a mask pattern, causing the irradiated portion of the photosensitive resin composition layer to photocure. Examples of active light include ultraviolet light, visible light, electron beams, and X-rays, with ultraviolet light being particularly preferred. The irradiation dose of ultraviolet light is approximately 10 mJ / cm². 2 ~1000mJ / cm 2 Exposure methods include contact exposure, where the mask pattern is tightly adhered to the printed wiring board, and non-contact exposure, where parallel light is used for exposure in a loosely adhered state; either method can be used. Furthermore, if a support is present on the photosensitive resin composition layer, exposure can be performed from the support, or the support can be peeled off before exposure.

[0184] The solder mask layer uses the photosensitive resin composition of the present invention, thus exhibiting excellent resolution. Therefore, as the exposure pattern in the mask pattern, patterns with a circuit width (line width, L) to circuit spacing (line pitch, S) ratio (L / S) of 100 μm / 100 μm or less (i.e., wiring spacing 200 μm or less), L / S = 80 μm / 80 μm or less (wiring spacing 160 μm or less), L / S = 70 μm / 70 μm or less (wiring spacing 140 μm or less), and L / S = 60 μm / 60 μm or less (wiring spacing 120 μm or less) can be used. It should be noted that the spacing does not need to be uniform across the entire circuit board.

[0185] <Developing Process>

[0186] After the exposure process, if a support is present on the photosensitive resin composition layer, the uncured portion (unexposed portion) is removed by wet or dry development and then developed to form a pattern.

[0187] In the case of wet development described above, the developer can be a safe, stable, and easy-to-handle developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. Among these, the development step using an alkaline aqueous solution is preferred. Furthermore, as the development method, known methods such as spraying, shaking immersion, brushing, and scraping can be appropriately employed.

[0188] Examples of alkaline aqueous solutions used as developers include: aqueous solutions of alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; alkali metal phosphates such as sodium phosphate and potassium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; or aqueous solutions of organic bases that do not contain metal ions, such as tetraalkylammonium hydroxide. From the viewpoint that the absence of metal ions will not affect the semiconductor chip, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred.

[0189] To improve the developing effect of these alkaline aqueous solutions, surfactants, defoamers, etc., can be added to the developing solution. The pH of the alkaline aqueous solution is preferably in the range of 8 to 12, more preferably in the range of 9 to 11. Furthermore, the alkali concentration of the alkaline aqueous solution is preferably set to 0.1% 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.

[0190] Organic solvents used as developing solutions include, for example, acetone, ethyl acetate, alkoxyethanol having alkoxy groups having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.

[0191] The concentration of such organic solvent relative to the total amount of developer is preferably 2% to 90% by mass. Furthermore, the temperature of such organic solvent can be adjusted according to the developability. Moreover, such organic solvent can be used alone or in combination of two or more. Examples of organic solvent-based developers that can be used alone include, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

[0192] In pattern formation, two or more of the above-mentioned developing methods can be used simultaneously as needed. Developing methods include immersion, spin-dip, spraying, high-pressure spraying, brushing, and scraping, with high-pressure spraying being preferred due to its improved resolution. When using the spraying method, the preferred spray pressure is 0.05 MPa to 0.3 MPa.

[0193] <Thermosetting (Post-baking) Process>

[0194] After the above developing process is completed, a heat curing (post-baking) process is performed to form the solder resist layer. Examples of post-baking processes include ultraviolet irradiation using a high-pressure mercury lamp and heating using a clean oven. When using ultraviolet irradiation, the irradiation dose can be adjusted as needed, for example, to 0.05 J / cm². 2 ~10J / cm 2Irradiation is performed at approximately [amount missing]. Furthermore, the heating conditions can be appropriately selected based on the type and content of the resin components in the photosensitive resin composition, preferably within the range of 150°C to 220°C for 20 to 180 minutes, and more preferably within the range of 160°C to 200°C for 30 to 120 minutes.

[0195] <Other Processes>

[0196] For printed circuit boards, after the solder mask layer is formed, the process may include opening vias and desmearing. These processes can be carried out according to various methods known to those skilled in the art in the manufacture of printed circuit boards.

[0197] After the solder mask layer is formed, a hole-opening process is performed on the solder mask layer formed on the circuit board to form through holes or vias, as needed. The hole-opening process can be carried out by known methods such as drilling, laser, and plasma, and these methods can be combined as needed. Preferably, the hole-opening process uses lasers such as carbon dioxide lasers or YAG lasers.

[0198] The resin residue removal process is a procedure to remove resin residue. The openings formed during the drilling process typically have resin residue (resin residue) adhering to them. This residue can cause poor electrical connections; therefore, this process involves removing the resin residue (resin residue removal treatment).

[0199] Degumming can be removed by dry degumming, wet degumming, or a combination thereof.

[0200] As a dry method for removing adhesive residue, plasma-based methods can be cited as examples. Plasma-based adhesive residue removal can be performed using commercially available plasma adhesive residue removal equipment. Examples of commercially available plasma adhesive residue removal equipment suitable for printed circuit board manufacturing include microwave plasma equipment manufactured by NISSIN Corporation and atmospheric pressure plasma etching equipment manufactured by Sekisui Chemicals Co., Ltd.

[0201] Examples of wet descaling treatments include descaling treatment using an oxidizing agent solution. When using an oxidizing agent solution for descaling, it is preferable to sequentially perform a swelling treatment using a swelling solution, an oxidation treatment using an oxidizing agent solution, and a neutralization treatment using a neutralizing solution. Examples of swelling solutions include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by ATOTECH JAPAN Co., Ltd. The swelling treatment is preferably performed by immersing the substrate with through-holes or the like in a swelling solution heated to 60°C to 80°C for 5 to 10 minutes. An alkaline permanganate aqueous solution is preferred as the oxidizing agent solution; examples include solutions obtained by dissolving potassium permanganate or sodium permanganate in an aqueous sodium hydroxide solution. The oxidation treatment using an oxidizing agent solution is preferably performed by immersing the swollen substrate in an oxidizing agent solution heated to 60°C to 80°C for 10 to 30 minutes. Commercially available alkaline permanganate solutions include, for example, "Concentrate Compact CP" and "Dosingsolution Securiganth P" manufactured by Ammet Japan Co., Ltd. Neutralization treatment using a neutralizing solution is preferably performed by immersing the oxidized substrate in a neutralizing solution at 30°C to 50°C for 3 to 10 minutes. An acidic aqueous solution is preferred as the neutralizing solution; commercially available examples include "Reduction solution Securiganth P" manufactured by Ammet Japan Co., Ltd.

[0202] When combining dry and wet degumming treatments, either the dry or wet degumming treatment can be performed first.

[0203] When the insulating layer is used as an interlayer insulating layer, it can be done in the same way as the solder resist layer. The opening process, the descaling process, and the plating process can be performed after the thermosetting process.

[0204] The plating process is the process of forming a conductor layer on an insulating layer. For the conductor layer, electroless plating and electrolytic plating can be combined to form it. Alternatively, a resist layer with a pattern opposite to the conductor layer can be formed, and the conductor layer can be formed using only electroless plating. As for the subsequent patterning method, subtractive or semi-additive methods known to those skilled in the art can be used, for example.

[0205] [Semiconductor Devices]

[0206] 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.

[0207] As semiconductor devices, examples include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trams, ships, and aircraft).

[0208] The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. A "conductive portion" refers to a portion of the printed wiring board that conducts electrical signals; its location can be on the surface or embedded. Furthermore, the semiconductor chip is not particularly limited to any electrical circuit element made of semiconductor material.

[0209] Regarding the mounting method of the semiconductor chip when manufacturing the semiconductor device of the present invention, there is no particular limitation as long as the semiconductor chip can function effectively. Specific examples include wire bonding mounting methods, flip chip mounting methods, mounting methods using a solderless built-in layer (BBUL), mounting methods using anisotropic conductive film (ACF), and mounting methods using non-conductive film (NCF). Here, "mounting method using a solderless built-in layer (BBUL)" refers to "a mounting method in which the semiconductor chip is directly embedded in a recess of a printed wiring board, thereby connecting the semiconductor chip to the wiring on the printed wiring board."

[0210] Example

[0211] The present invention will now be specifically described through embodiments, but the present invention is not limited to these embodiments. It should be noted that, unless otherwise expressly stated, in the following description, "parts" and "%" refer to "parts by mass" and "% by mass," respectively.

[0212] (Synthesis Example 1: Synthesis of Resin (A-1))

[0213] 60.8 parts (0.26 mol) of bisphenol A, 43.4 parts (0.11 mol) of bisphenol A-type epoxy compound (YD8125, manufactured by Nippon Steel Chemical Co., Ltd.), 145.8 parts (0.13 mol) of polyethylene glycol diglycidyl ether (EX861, manufactured by Nagase ChemteX Co., Ltd.), 1.25 parts of triphenylphosphine as a catalyst, 1.25 parts of N,N-dimethylbenzylamine, and 250 parts of toluene as a solvent were added to a four-necked flask. The mixture was stirred and reacted at 110°C for 8 hours under a nitrogen atmosphere to obtain a hydroxyl-containing resin. Next, 49.8 parts (0.48 mol) of succinic anhydride (RIKACID SA, manufactured by Rika Co., Ltd.) was added as the anhydride, and the reaction was maintained at 110°C for 4 hours. After confirming the disappearance of the anhydride group absorption by FT-IR measurement, the mixture was cooled to room temperature. Next, while stirring, 41.1 parts (0.29 mol) of glycidyl methacrylate (GMA, manufactured by Nippon Oil Co., Ltd.) and 0.17 parts of hydroquinone as a polymerization inhibitor were added, and the reaction was carried out at 80°C for 8 hours. After the reaction was completed, 26.0 parts (0.25 mol) of RIKACID SA (manufactured by Shin Nippon Rikka Co., Ltd.: succinic anhydride) as an acid anhydride was added, and the reaction was maintained at 80°C for 4 hours. After confirming the disappearance of the anhydride group absorption by FT-IR measurement, the solution was cooled to room temperature. Methyl ethyl ketone was added to the solution to adjust the solid content to 50%. The resulting resin (A-1) had a weight-average molecular weight of 20,000 and an acid value of 70 mg KOH / g for the solid content of the resin.

[0214] Resin (A-1) is a copolymer. Therefore, M in equation (1) can be obtained from equation (2). AO Specifically, it is obtained as follows: the monomer with the oxidized olefin chain is polyethylene glycol diglycidyl ether (EX861). The molecular weight of EX861 is 1098, so A in formula (2) is 1098. In addition, the molecular weight of the oxidized olefin chain is 968, so A in formula (2) is 968. AO It is 968;

[0215] Resin (A-1) is a copolymer of bisphenol A, bisphenol A type epoxy compound, polyethylene glycol diglycidyl ether, succinic anhydride, and glycidyl methacrylate. The monomer containing the oxidized olefin chain is polyethylene glycol diglycidyl ether, therefore B in formula (2) AO The value is 0.13. Furthermore, B in equation (2) is 0.26 + 0.11 + 0.13 + 0.48 + 0.29 + 0.25 = 1.52;

[0216] Therefore, equation (2) is (968 / 1098)×(0.13 / 1.52)≈0.08.

[0217] (Synthesis Example 2: Synthesis of Polymer 1)

[0218] 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 were added to a four-necked flask. Nitrogen gas was introduced while the mixture was heated at 80 °C for 6 hours. The resulting polymer 1 had a weight-average molecular weight of 40,000.

[0219] (Preparation of resin varnish)

[0220] The resin materials were blended as shown in the following formulation table, and a resin varnish was obtained using a high-speed rotary mixer.

[0221] [Table 1]

[0222]

[0223] The abbreviations in the table are as follows:

[0224] • (A-1): The resin (A-1) synthesized in Synthesis Example 1, a 50% solids solution of methyl ethyl ketone, M AO ×100=8

[0225] ZFR-1491H: An acid-modified epoxy acrylate containing a bisphenol F (bis-F) backbone, manufactured by Nippon Kayaku Co., Ltd., formulated with EDGAc (diethylene glycol monoethyl ether acetate), 70% solids. AO ×100=0

[0226] ZAR-2000: An acid-modified epoxy acrylate containing a bisphenol A (bis-A) backbone, manufactured by Nippon Kayaku Co., Ltd., formulated with EDGAc, 70% solids, M AO ×100=0

[0227] EX-821: Polyethylene glycol diglycidyl ether, n=4, epoxy equivalent 185g / eq., manufactured by Nagase ChemteX Co., Ltd. AO ×100=58

[0228] EX-920: Polypropylene glycol diglycidyl ether, n=3, epoxy equivalent 176g / eq., manufactured by Nagase ChemteX Co., Ltd. AO ×100=57

[0229] NC3000H: Biphenyl-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent approximately 272 g / eq.), M AO ×100=0

[0230] R-551: EO-modified bisphenol A acrylate, manufactured by Nippon Kayaku Co., Ltd., M AO×100=34

[0231] • A-PTMG-65: Polytetramethylene glycol #650 diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., M AO ×100=83

[0232] ·1.9ND-A: 1,9-Nonanediol diacrylate, manufactured by Kyoei Chemical Co., Ltd., M AO ×100=0

[0233] • NCI-831: Oxime ester photopolymerization initiator, manufactured by ADEKA Corporation

[0234] •EP4-A: Magnesium hydroxide treated with aminosilane (manufactured by Kamishima Chemical Co., Ltd.)

[0235] MEK: Methyl ethyl ketone, manufactured by Pure Chemical Co., Ltd.

[0236] • Polymer 1: Polymer 1 synthesized in Synthesis Example 2, a 25% solids solution of propylene glycol monomethyl ether acetate, M AO ×100=8.

[0237] The "A-PTMG-65" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. has the following structural formula. A-PTMG-65 is not a copolymer, therefore M is obtained through formula (1). AO ;

[0238] [Chemical Formula 2]

[0239]

[0240] The molecular weight of A-PTMG-65 is 774. Furthermore, the molecular weight of the oxidized olefin chain is 648 (72 × 9 = 648). Therefore, M AO The value is approximately 648 / 774≈0.83.

[0241] X in equation (1) of Example 1 is obtained as follows;

[0242] X={(2.5÷55)×58}+{(7÷55)×34}+{(3÷55)×83}≈11.5.

[0243] (Fabrication of photosensitive film with support)

[0244] As a support, a PET film (Toray Industries, Inc.'s "LUMIRROR T6AM", thickness 38 μm, softening point 130°C, "release PET") that had been released using an alkyd resin release agent (Lintec Corporation's "AL-5") was prepared. Using a die-casting machine, the prepared resin varnish was uniformly coated onto the release PET to a thickness of 25 μm for the dried photosensitive resin composition layer, and dried at 80°C to 120°C, thereby obtaining a photosensitive film with a support.

[0245] (Evaluation of the formation of laminates)

[0246] The copper layer of a glass epoxy board (copper-clad laminate) with a circuit formed by patterning a copper layer with a thickness of 18 μm was roughened by treatment with a surface treatment agent containing organic acid (CZ8100, manufactured by MEC Corporation). Next, a photosensitive resin composition layer with a support, obtained through the examples and comparative examples, was deposited on the copper layer surface, and laminated using a vacuum laminator (Nikko-Materials Corporation, VP160) to form a laminate in which the copper-clad laminate, the photosensitive resin composition layer, and the support are sequentially stacked. The lamination conditions were set as follows: vacuum time 30 seconds, lamination temperature 80°C, lamination pressure 0.7 MPa, and lamination time 30 seconds. The laminate was left to stand at room temperature for at least 30 minutes, and a circular hole pattern was formed on the support of the laminate, which was then exposed to ultraviolet light using a patterning apparatus. Regarding the exposure pattern, a 1cm × 2cm rectangular quartz glass mask was used, depicting circular holes (through holes) with openings of 50μm / 60μm / 70μm / 80μm / 90μm / 100μm and line widths / spacings of 50μm / 50μm, 60μm / 60μm, 70μm / 70μm, 80μm / 80μm, 90μm / 90μm, and 100μm / 100μm. After standing at room temperature for 30 minutes, the support was peeled off from the laminate. The entire surface of the insulating layer on the laminate was spray-developed for 2 minutes using a 1% (w / w) sodium carbonate aqueous solution at 30°C as the developer at a spray pressure of 0.2MPa. After spray development, an 1J / cm² exposure was performed. 2 The laminate is subjected to ultraviolet irradiation and then heat treatment at 180°C for 30 minutes to form an insulating layer with openings. This laminate is used for evaluation.

[0247] <Evaluation of residue at the bottom of the through hole>

[0248] The 100 μm circular holes formed in the evaluation laminate were evaluated according to the following criteria;

[0249] ○: No residue;

[0250] ×: Residue was observed, or the membrane peeled off or partially dissolved.

[0251] <Evaluation of Bending Performance>

[0252] The photosensitive resin composition layer of the photosensitive film with support obtained in the Examples and Comparative Examples was subjected to full-sided exposure, development, and heat treatment. The exposure, development, and heat treatment conditions were the same as those for forming the laminate used for evaluation. The support was peeled off to obtain a cured film. The cured film was cut into 15mm × 110mm pieces, and its flexural properties were evaluated using an MIT flexural fatigue testing machine (manufactured by Toyo Seiki Co., Ltd.). The test was conducted according to JIS P8115, with the following conditions: tension: 500g, test speed: 175 times / minute, bending angle: 135°, and bending clamp radius: 0.38mm. The number of bends until breakage was counted, and the average of the three counts of bends (number of bends) was evaluated according to the following criteria.

[0253] ◎: More than 300 times

[0254] ○: More than 100 times but less than 300 times

[0255] ×: less than 100 times.

[0256] <Evaluation of Copper Seam Strength>

[0257] Rolled copper foil (manufactured by JX Nippon Minerals & Metals Co., Ltd., BHY-22B-T, 18 μm thick) that had been cleaned and dried with 10% sulfuric acid was prepared. A photosensitive film with a support was laminated onto the glossy side of the rolled copper foil, and the entire surface was exposed, developed, and heat-treated to obtain a substrate. The conditions for exposure, development, and heat treatment were the same as those for evaluating the bendability. The insulating layer side of the obtained substrate was bonded to a glass epoxy board, and the peel strength of the copper foil was measured using a tensile testing machine (manufactured by TSE Co., Ltd., "AC-50C-SL") based on Japanese Industrial Standard (JIS C6481). The evaluation was carried out according to the following criteria.

[0258] ○: Adhesion strength is above 0.5 kgf

[0259] ×: The seal strength is less than 0.5 kgf.

[0260] <Evaluation of Insulation Performance (HHBT)>

[0261] A comb-shaped wiring pattern with L (wiring width) / S (space) = 20 μm / 20 μm was used on the support of the photosensitive film with a support. The entire surface was exposed, developed, and heated using ultraviolet light. The conditions for exposure, development, and heating were the same as those for forming the evaluation laminate. Copper wires were soldered as electrodes on both sides of the comb-shaped wiring pattern. A voltage of 50 V was applied at 85°C and 85% RH. After 500 hours, the resistance value (Ω) was measured. The average value was calculated based on the resistance values ​​at 7 locations, and the evaluation was performed according to the following criteria.

[0262] ○: The average resistance value is 10. 8 Ω and above

[0263] ×: The average resistance value is less than 10. 8 Ω.

[0264] As can be seen from the results in the table above, when the photosensitive resin composition of the present invention is used, the developability, flexibility, adhesion, and insulation become good. Regarding Comparative Example 3, it is believed that although an acrylic polymer (polymer 1) with oxidized olefin chains was used, the desired effect could not be obtained because polymer 1 is a thermoplastic resin and was not included in the curing system.

[0265] It was confirmed that in each embodiment, even without components (E) and (F), although the degree of difference was different, the result was the same as that in the embodiments described above.

Claims

1. A photosensitive resin composition, which is a photosensitive resin composition comprising the following (A) to (D) components, (A) a resin containing an ethylenic unsaturated group and a carboxyl group, (B) an epoxy resin, (C) a photopolymerizable monomer, and (D) a photopolymerization initiator, wherein any of the (A) component, the (B) component, and the (C) component contains an alkylene oxide chain, and a parameter X represented by the following formula (1) is 4 or more and 25 or less; in formula (1), M AO In the case where the component containing an oxyalkylene chain is a copolymer, the value represented by the following formula (2) is represented, or in the case where the component containing an oxyalkylene chain is not a copolymer, the value of ((molecular weight of the oxyalkylene chain of each compound contained in the (A) to (C) components) / (molecular weight of each compound contained in the (A) to (C) components)) is represented. N represents, in terms of mass parts, a solid content amount of all the compounds contained in the (A) to (C) components, n represents, in terms of mass parts, a solid content amount of each of the compounds contained in the (A) to (C) components; in formula (2), A AO Mw represents the molecular weight of the oxyalkylene chain of each monomer comprising an oxyalkylene chain, A represents a molecular weight of each of the monomers containing the alkylene oxide chain, B AO represents the number of moles of each monomer comprising an oxyalkylene chain, B represents a total number of moles of all the monomers contained in the copolymer.

2. The photosensitive resin composition according to claim 1, wherein X in formula (1) is 18 or less.

3. The photosensitive resin composition according to claim 1, wherein X in formula (1) is 6 or more.

4. The photosensitive resin composition according to claim 1, wherein The content of the (A) component is 3 mass% or more when the nonvolatile component in the photosensitive resin composition is taken as 100 mass%.

5. The photosensitive resin composition according to claim 1, wherein The content of the (A) component is 10 mass% or more when the nonvolatile component in the photosensitive resin composition is taken as 100 mass%.

6. The photosensitive resin composition according to claim 1, wherein The content of the (A) component is 30 mass% or less when the nonvolatile component in the photosensitive resin composition is taken as 100 mass%.

7. The photosensitive resin composition according to claim 1, wherein The content of the (A) component is 20 mass% or less when the nonvolatile component in the photosensitive resin composition is taken as 100 mass%.

8. The photosensitive resin composition according to claim 1, wherein The content of the (B) component is 1 mass% or more when the nonvolatile component in the photosensitive resin composition is taken as 100 mass%.

9. The photosensitive resin composition according to claim 1, wherein The content of the (B) component is 3 mass% or more when the nonvolatile component in the photosensitive resin composition is taken as 100 mass%.

10. The photosensitive resin composition according to claim 1, wherein The content of the (B) component is 20 mass% or less when the nonvolatile component in the photosensitive resin composition is taken as 100 mass%.

11. The photosensitive resin composition according to claim 1, wherein The content of the (B) component is 10 mass% or less when the nonvolatile component in the photosensitive resin composition is taken as 100 mass%.

12. The photosensitive resin composition according to claim 1, wherein The content of the (C) component is 0.5 mass% or more when the nonvolatile component in the photosensitive resin composition is taken as 100 mass%.

13. The photosensitive resin composition according to claim 1, wherein The content of the (C) component is 1.5 mass% or more when the nonvolatile component in the photosensitive resin composition is taken as 100 mass%.

14. The photosensitive resin composition according to claim 1, wherein The content of the (C) component is 20 mass% or less when the nonvolatile component in the photosensitive resin composition is taken as 100 mass%.

15. The photosensitive resin composition according to claim 1, wherein The content of the (C) component is 10 mass% or less when the nonvolatile component in the photosensitive resin composition is taken as 100 mass%.

16. The photosensitive resin composition according to claim 1, wherein The content of the (D) component is 0.001 mass% or more when the nonvolatile component in the photosensitive resin composition is taken as 100 mass%.

17. The photosensitive resin composition according to claim 1, wherein The content of the (D) component is 0.01 mass% or more when the nonvolatile component in the photosensitive resin composition is taken as 100 mass%.

18. The photosensitive resin composition according to claim 1, wherein The content of the (D) component is 3 mass% or less when the nonvolatile component in the photosensitive resin composition is taken as 100 mass%.

19. The photosensitive resin composition according to claim 1, wherein The content of the (D) component is 0.5 mass% or less when the nonvolatile component in the photosensitive resin composition is taken as 100 mass%.

20. The photosensitive resin composition according to claim 1, further comprising (E) an inorganic filler.

21. The photosensitive resin composition according to claim 20, wherein The content of the (E) component is 10% by mass or more, based on 100% by mass of the nonvolatile components in the photosensitive resin composition.

22. The photosensitive resin composition according to claim 20, wherein The content of the (E) component is 25% by mass or more, based on 100% by mass of the nonvolatile components in the photosensitive resin composition.

23. The photosensitive resin composition according to claim 20, wherein The content of the (E) component is 90% by mass or less, based on 100% by mass of the nonvolatile components in the photosensitive resin composition.

24. The photosensitive resin composition according to claim 20, wherein The content of the (E) component is 70% by mass or less, based on 100% by mass of the nonvolatile components in the photosensitive resin composition.

25. The photosensitive resin composition according to claim 1, wherein The oxyalkylene chain is contained in any of the (B) component and the (C) component.

26. The photosensitive resin composition according to claim 1, wherein The (A) component contains an acid-modified unsaturated epoxy ester resin.

27. The photosensitive resin composition according to claim 1, wherein The (A) component contains an acid-modified epoxy (meth)acrylate.

28. The photosensitive resin composition according to claim 1, wherein The (A) component contains either an acid-modified epoxy (meth)acrylate containing a naphthalene skeleton or an acid-modified epoxy (meth)acrylate containing a bisphenol skeleton.

29. The photosensitive resin composition according to claim 28, wherein The acid-modified epoxy (meth)acrylate containing a bisphenol skeleton has either a bisphenol A skeleton or a bisphenol F skeleton.

30. The photosensitive resin composition according to claim 1, wherein The (B) component has a biphenyl skeleton.

31. The photosensitive resin composition according to claim 1, wherein The (D) component contains an oxime ester-based photopolymerization initiator.

32. A photosensitive film containing the photosensitive resin composition according to any one of claims 1 to 31.

33. A support-equipped photosensitive film having: a support, and a photosensitive resin composition layer containing the photosensitive resin composition according to any one of claims 1 to 31 disposed on the support.

34. A printed wiring board including an insulating layer formed using a cured product of the photosensitive resin composition according to any one of claims 1 to 31.

35. The printed wiring board of claim 34 wherein, The insulating layer is a solder resist layer.

36. A semiconductor device including the printed wiring board according to claim 34.

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