Photosensitive resin composition, photosensitive element, printed wiring board, and method for manufacturing printed wiring board

Abstract

To provide a photosensitive resin composition capable of forming a permanent resist having excellent TCT resistance and HAST resistance, a photosensitive element using the photosensitive resin composition, a printed wiring board, and a method for manufacturing a printed wiring board.SOLUTION: The present disclosure relates to a photosensitive resin composition for a permanent resist, the photosensitive resin composition containing (A) an acid-modified vinyl group-containing resin, (B) an elastomer, (C) a photopolymerization initiator, (D) a curing agent, and (E) an inorganic filler including a surface-treated filler.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a photosensitive resin composition for permanent resist, a photosensitive element, a printed wiring board, and a method for producing a printed wiring board. [Background technology]

[0002] As the performance of various electronic devices improves, semiconductor integration is becoming more and more advanced. Accordingly, various performance requirements are being placed on permanent resists (solder resists) formed on printed wiring boards, semiconductor package substrates, etc.

[0003] Known photosensitive resin compositions used to form permanent resists include, for example, photocurable resin compositions containing an acid-modified vinyl group-containing epoxy resin, an elastomer, a photopolymerization initiator, a diluent, and a curing agent as essential components (see Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 11-240930 Summary of the Invention [Problem to be solved by the invention]

[0005] As package substrates become smaller and more sophisticated, permanent resists are required to have improved thermal shock resistance (TCT resistance).In addition, as wiring pitches become narrower due to the high integration of semiconductor devices, permanent resists are required to have excellent resistance to highly accelerated stress tests (HAST resistance).

[0006] An object of the present disclosure is to provide a photosensitive resin composition capable of forming a permanent resist excellent in TCT resistance and HAST resistance, a photosensitive element using the photosensitive resin composition, a printed wiring board, and a method for producing a printed wiring board. [Means for solving the problem]

[0007] One aspect of the present disclosure relates to a photosensitive resin composition for permanent resist, comprising (A) an acid-modified vinyl group-containing resin, (B) an elastomer, (C) a photopolymerization initiator, (D) a curing agent, and (E) an inorganic filler, wherein the inorganic filler comprises a surface-treated filler.

[0008] Another aspect of the present disclosure relates to a photosensitive element comprising a support film and a photosensitive layer formed on the support film, the photosensitive layer containing the above-described photosensitive resin composition.

[0009] Another aspect of the present disclosure relates to a printed wiring board comprising a permanent resist containing a cured product of the above-described photosensitive resin composition.

[0010] Another aspect of the present disclosure relates to a method for producing a printed wiring board, comprising the steps of: forming a photosensitive layer on a substrate using the above-described photosensitive resin composition or photosensitive element; exposing and developing the photosensitive layer to form a resist pattern; and curing the resist pattern to form a permanent resist. [Effects of the Invention]

[0011] According to the present disclosure, it is possible to provide a photosensitive resin composition capable of forming a permanent resist excellent in TCT resistance and HAST resistance, a photosensitive element using the photosensitive resin composition, a printed wiring board, and a method for producing a printed wiring board. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is a cross-sectional view schematically illustrating a photosensitive element according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0013] The photosensitive resin composition according to the embodiment of the present disclosure, a photosensitive element using the photosensitive resin composition, a printed wiring board, and a method for producing a printed wiring board are listed below. [1] A photosensitive resin composition for a permanent resist, comprising: (A) an acid-modified vinyl group-containing resin; (B) an elastomer; (C) a photopolymerization initiator; (D) a curing agent; and (E) an inorganic filler, wherein the inorganic filler comprises a surface-treated filler. [2] The photosensitive resin composition according to [1] above, wherein the surface-treated filler has a photoreactive functional group or a thermally reactive functional group. [3] The photosensitive resin composition according to [1] or [2] above, wherein the surface-treated filler has at least one group selected from the group consisting of a (meth)acryloyl group, a vinyl group, an epoxy group, and a phenylamino group. [4] The photosensitive resin composition according to any one of the above [1] to [3], wherein the surface-treated filler is a surface-treated silica filler. [5] The photosensitive resin composition according to any one of the above [1] to [4], wherein the content of the surface-treated filler is 7 to 28 mass % based on the total solid content of the photosensitive resin composition. [6] The photosensitive resin composition according to the above [4] or [5], wherein the inorganic filler comprises the surface-treated silica filler and barium sulfate. [7] The photosensitive resin composition according to the above [6], wherein the surface-treated silica filler has a (meth)acryloyl group, an epoxy group, or a phenylamino group. [8] The photosensitive resin composition according to the above [6], wherein the surface-treated silica filler has a (meth)acryloyl group. [9] A photosensitive element comprising a support film and a photosensitive layer formed on the support film, wherein the photosensitive layer contains the photosensitive resin composition according to any one of [1] to [8] above.

[10] A printed wiring board comprising a permanent resist containing a cured product of the photosensitive resin composition according to any one of [1] to [8] above.

[11] A method for producing a printed wiring board, comprising the steps of: forming a photosensitive layer on a substrate using the photosensitive resin composition according to any one of [1] to [8] above or the photosensitive element according to [9] above; exposing and developing the photosensitive layer to form a resist pattern; and curing the resist pattern to form a permanent resist.

[0014] The present disclosure will be described in detail below. In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended function of the process is achieved. The term "layer" encompasses not only a structure that is formed over the entire surface when observed in a plan view, but also a structure that is formed only on a portion of the surface. A numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in this specification, the upper or lower limit of a numerical range of a certain stage may be replaced with the upper or lower limit of a numerical range of another stage. In numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples.

[0015] When referring to the amount of each component in a composition in this specification, if there are multiple substances corresponding to each component in the composition, the total amount of those multiple substances present in the composition is meant unless otherwise specified.

[0016] In this specification, "(meth)acrylate" means at least one of "acrylate" and its corresponding "methacrylate," and the same applies to other similar expressions such as (meth)acrylic acid and (meth)acryloyl. In this specification, "solid content" refers to the non-volatile content excluding volatile substances (water, solvent, etc.) contained in the photosensitive resin composition, and includes components that are liquid, syrup-like, or waxy at room temperature (around 25°C).

[0017] [Photosensitive resin composition] The photosensitive resin composition for permanent resist according to this embodiment contains (A) an acid-modified vinyl group-containing resin, (B) an elastomer, (C) a photopolymerization initiator, (D) a curing agent, and (E) an inorganic filler, and the inorganic filler includes a surface-treated filler. The photosensitive resin composition according to this embodiment is a negative-tone photosensitive resin composition, and a cured film of the photosensitive resin composition can be used as a permanent resist having excellent TCT resistance and HAST resistance. Each component used in the photosensitive resin composition according to this embodiment will be described in more detail below.

[0018] (Component (A): Acid-modified vinyl group-containing resin) The photosensitive resin composition according to this embodiment contains an acid-modified vinyl group-containing resin as component (A). The acid-modified vinyl group-containing resin is not particularly limited as long as it has a vinyl group, which is a photopolymerizable ethylenically unsaturated bond, and an alkali-soluble acidic group. Examples of the acidic group contained in the acid-modified vinyl group-containing resin include a carboxy group, a sulfo group, and a phenolic hydroxyl group. Among these, a carboxy group is preferred from the viewpoint of resolution.

[0019] Examples of acid-modified vinyl group-containing resins include acid-modified epoxy(meth)acrylates. Acid-modified epoxy(meth)acrylates are resins obtained by acid-modifying epoxy(meth)acrylates, which are reaction products of epoxy resins and organic acids having vinyl groups. Examples of acid-modified epoxy(meth)acrylates include addition reaction products obtained by adding saturated or unsaturated polybasic acid anhydrides (c) to esterified products obtained by reacting epoxy resins (a) with vinyl group-containing monocarboxylic acids (b).

[0020] Examples of the epoxy resin (a) include bisphenol novolac type epoxy resins, novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, triphenolmethane type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, and dicyclopentadiene type epoxy resins.

[0021] Examples of the vinyl group-containing monocarboxylic acid (b) include acrylic acid, acrylic acid dimers, methacrylic acid, acrylic acid derivatives such as β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, and α-cyanocinnamic acid, half-ester compounds which are reaction products of hydroxyl group-containing (meth)acrylates and dibasic acid anhydrides, and half-ester compounds which are reaction products of vinyl group-containing monoglycidyl ethers or vinyl group-containing monoglycidyl esters and dibasic acid anhydrides.

[0022] Examples of hydroxyl group-containing (meth)acrylates, vinyl group-containing monoglycidyl ethers, and vinyl group-containing monoglycidyl esters include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, pentaerythritol pentamethacrylate, glycidyl acrylate, and glycidyl methacrylate.

[0023] Examples of dibasic acid anhydrides include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride.

[0024] Examples of the saturated or unsaturated polybasic acid anhydride (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride. Among these, tetrahydrophthalic anhydride may be used from the viewpoint of obtaining a photosensitive resin composition capable of forming a pattern with excellent resolution.

[0025] The acid value of component (A) is not particularly limited. From the viewpoint of improving the solubility of the unexposed area in an alkaline aqueous solution, the acid value of component (A) may be 30 mgKOH / g or more, 40 mgKOH / g or more, or 50 mgKOH / g or more. From the viewpoint of improving the electrical properties of the cured film, the acid value of component (A) may be 150 mgKOH / g or less, 120 mgKOH / g or less, or 100 mgKOH / g or less.

[0026] The weight average molecular weight (Mw) of component (A) is not particularly limited. From the viewpoint of improving the adhesion of the cured film, Mw of component (A) may be 3,000 or more, 4,000 or more, or 5,000 or more. From the viewpoint of improving the resolution of the photosensitive layer, Mw of component (A) may be 30,000 or less, 25,000 or less, or 18,000 or less. Mw can be measured by gel permeation chromatography (GPC).

[0027] The content of the component (A) in the photosensitive resin composition may be 20 to 70 mass%, 25 to 60 mass%, 30 to 50 mass%, or 32 to 45 mass%, based on the total solid content of the photosensitive resin composition, from the viewpoint of improving the heat resistance, electrical properties, and chemical resistance of the permanent resist.

[0028] (Component (B): Elastomer) The photosensitive resin composition according to this embodiment contains an elastomer as component (B), which can suppress a decrease in flexibility and adhesive strength caused by strain (internal stress) inside the resin due to cure shrinkage of component (A).

[0029] Examples of component (B) include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, and silicone-based elastomers. These elastomers are composed of hard segment components that contribute to heat resistance and strength, and soft segment components that contribute to flexibility and toughness.

[0030] Examples of styrene-based elastomers include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene-butylene-styrene block copolymers, and styrene-ethylene-propylene-styrene block copolymers. In addition to styrene, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene can be used as components constituting styrene-based elastomers.

[0031] Examples of olefin-based elastomers include ethylene-propylene copolymers, ethylene-α-olefin copolymers, ethylene-α-olefin-non-conjugated diene copolymers, propylene-α-olefin copolymers, butene-α-olefin copolymers, ethylene-propylene-diene copolymers, copolymers of non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidenenorbornene, butadiene, and isoprene with α-olefins, and carboxylic acid-modified butadiene-acrylonitrile copolymers.

[0032] As the urethane-based elastomer, a compound composed of a hard segment made of a low molecular weight (short chain) diol and diisocyanate, and a soft segment made of a high molecular weight (long chain) diol and diisocyanate can be used.

[0033] Examples of short-chain diols include ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A. The number average molecular weight of the short-chain diol is preferably 48-500.

[0034] Examples of long-chain diols include polypropylene glycol, polytetramethylene oxide, poly(1,4-butylene adipate), poly(ethylene-1,4-butylene adipate), polycaprolactone, poly(1,6-hexylene carbonate), and poly(1,6-hexylene-neopentylene adipate). The number-average molecular weight of the long-chain diol is preferably 500 to 10,000.

[0035] As the polyester elastomer, a compound obtained by polycondensation of a dicarboxylic acid or a derivative thereof with a diol compound or a derivative thereof can be used.

[0036] Examples of dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid, and dodecanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The dicarboxylic acids can be used alone or in combination of two or more.

[0037] Examples of diol compounds include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,10-decanediol; alicyclic diols such as 1,4-cyclohexanediol; and aromatic diols such as bisphenol A, bis-(4-hydroxyphenyl)methane, bis-(4-hydroxy-3-methylphenyl)propane, and resorcinol.

[0038] Polyester elastomers can be multiblock copolymers that use aromatic polyesters (e.g., polybutylene terephthalate) as hard segment components and aliphatic polyesters (e.g., polytetramethylene glycol) as soft segment components. There are various grades of polyester elastomers that differ in the type, ratio, and molecular weight of the hard and soft segments.

[0039] Polyamide elastomers are broadly classified into two types: polyether block amides and polyether ester block amides, which use polyamides for the hard segments and polyethers or polyesters for the soft segments. Examples of polyamides include polyamide-6, polyamide-11, and polyamide-12. Examples of polyethers include polyoxyethylene glycol, polyoxypropylene glycol, and polytetramethylene glycol.

[0040] The acrylic elastomer may be a compound containing a structural unit based on a (meth)acrylic acid ester as a main component. Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxyethyl (meth)acrylate. The acrylic elastomer may be a compound obtained by copolymerizing a (meth)acrylic acid ester with acrylonitrile, or may be a compound obtained by further copolymerizing a monomer having a functional group that serves as a crosslinking point. Examples of monomers having a functional group include methyl methacrylate, glycidyl methacrylate, and allyl glycidyl ether.

[0041] Examples of acrylic elastomers include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, methyl methacrylate-butyl acrylate-methacrylic acid copolymer, and acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer. As the acrylic elastomer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer or methyl methacrylate-butyl acrylate-methacrylic acid copolymer is preferred, and methyl methacrylate-butyl acrylate-methacrylic acid copolymer is more preferred.

[0042] Silicone elastomers are compounds primarily composed of organopolysiloxane. Examples of organopolysiloxane include polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. Silicone elastomers may be compounds in which a portion of an organopolysiloxane is modified with a vinyl group, an alkoxy group, or the like.

[0043] From the viewpoint of improving the adhesion of the cured film, the component (B) may contain a carboxylic acid-modified butadiene-acrylonitrile copolymer or a polyester-based elastomer having a hydroxyl group.

[0044] The content of component (B) may be 2 to 50 parts by mass, 4 to 45 parts by mass, 6 to 40 parts by mass, or 10 to 35 parts by mass per 100 parts by mass of component (A). When the content of component (B) is within the above range, the elastic modulus of the cured film in the high temperature range decreases, and the unexposed areas become more easily eluted in a developer.

[0045] (Component (C): Photopolymerization initiator) The photopolymerization initiator as component (C) is not particularly limited as long as it can polymerize component (A). Component (C) may be used alone or in combination of two or more.

[0046] Examples of the component (C) include benzoin compounds such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane, N, Acetophenone compounds such as N-dimethylaminoacetophenone; anthraquinone compounds such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal. Benzophenone compounds such as benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, Michler's ketone, and 4-benzoyl-4'-methyldiphenyl sulfide; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, and 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer. imidazole compounds such as 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer, and 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer; acridine compounds such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide;Examples of suitable oxime ester compounds include 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime), and 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime]; and tertiary amine compounds such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine.

[0047] The content of component (C) in the photosensitive resin composition is not particularly limited, but may be 0.2 to 15 mass%, 0.5 to 10 mass%, or 1 to 5 mass%, based on the total solid content of the photosensitive resin composition.

[0048] (Component (D): hardener) The curing agent, component (D), can be a compound that cures by itself with heat, ultraviolet light, etc., or a compound that cures by reacting with the acidic group of component (A) with heat, ultraviolet light, etc. Use of component (D) can improve the heat resistance, adhesiveness, chemical resistance, etc. of the cured film (permanent resist) formed from the photosensitive resin composition.

[0049] Examples of the component (D) include thermosetting compounds such as epoxy compounds, melamine compounds, urea compounds, oxazoline compounds, blocked isocyanates, etc. The component (D) may be used alone or in combination of two or more.

[0050] Examples of epoxy compounds include bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol A epoxy resins, brominated bisphenol A epoxy resins, novolac epoxy resins, bisphenol S epoxy resins, biphenyl epoxy resins, naphthalene epoxy resins, dicyclo epoxy resins, hydantoin epoxy resins, triglycidyl isocyanurate, and bixylenol epoxy resins. Examples of melamine compounds include triaminotriazine, hexamethoxymelamine, and hexabutoxylated melamine. Examples of urea compounds include dimethylol urea.

[0051] The content of component (D) may be 2 to 30 mass%, 5 to 25 mass%, or 10 to 20 mass%, based on the total solid content of the photosensitive resin composition. By keeping the content of component (D) within the above range, it is possible to further improve the heat resistance of the formed cured film while maintaining good developability.

[0052] (Component (E): inorganic filler) The photosensitive resin composition according to this embodiment contains an inorganic filler, including a surface-treated filler, as component (E). The surface-treated filler can be obtained by treating the surface of the inorganic filler with a surface treatment agent such as an organic silane compound. Treating the surface of the inorganic filler improves the adhesive strength with component (A) at the filler interface, thereby improving the TCT resistance and HAST resistance of the cured film of the photosensitive resin composition. One type of surface-treated filler may be used alone, or two or more types may be used in combination.

[0053] Examples of inorganic fillers include silica, alumina, titania, tantalum oxide, zirconia, silicon nitride, gallium oxide, and boron nitride.

[0054] As the surface treatment agent, from the viewpoint of further improving TCT resistance, an organic silane compound such as an epoxy silane compound, an amino silane compound, a (meth)acrylic silane compound, or a vinyl silane compound may be used.

[0055] Examples of the organic silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, and arylsilane. and 3-isocyanatopropyltriethoxysilane, N-(1,3-dimethylbutylidene)-3-amino ...

[0056] The surface-treated filler preferably has a photoreactive functional group or a thermally reactive functional group. By using a surface-treated filler having a photoreactive functional group or a thermally reactive functional group, the adhesive strength between component (A) and component (E) can be increased.

[0057] Examples of photoreactive functional groups include (meth)acryloyl groups and vinyl groups. Examples of thermally reactive functional groups include epoxy groups, amino groups, phenylamino groups, isocyanate groups, and mercapto groups. The surface-treated filler according to this embodiment preferably has at least one group selected from the group consisting of (meth)acryloyl groups, vinyl groups, epoxy groups, and phenylamino groups.

[0058] From the viewpoint of improving dispersibility and adhesive strength, the surface-treated filler is preferably a filler surface-treated with silica, alumina, titania, or boron nitride, more preferably a filler surface-treated with silica, alumina, or boron nitride, and even more preferably a surface-treated silica filler. From the viewpoint of improving low expansion properties and heat resistance, component (E) preferably contains a surface-treated silica filler, more preferably a silica filler having at least one group selected from the group consisting of a (meth)acryloyl group, a vinyl group, an epoxy group, and a phenylamino group, even more preferably a surface-treated silica filler having a (meth)acryloyl group, an epoxy group, or a phenylamino group, and even more preferably a surface-treated silica filler having a (meth)acryloyl group.

[0059] The content of the surface-treated filler may be 5% by mass or more, 6% by mass or more, 7% by mass or more, 8% by mass or more, 9% by mass or more, or 10% by mass or more, based on the total solid content of the photosensitive resin composition, and may be 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 20% by mass or less, or 15% by mass or less. From the viewpoint of resolution and a low coefficient of thermal expansion, the content of the surface-treated filler may be 5 to 35% by mass, 6 to 30% by mass, 7 to 28% by mass, 8 to 25% by mass, 9 to 20% by mass, or 10 to 15% by mass, based on the total solid content of the photosensitive resin composition. When the content of the surface-treated filler is within the above range, it is possible to further improve the low coefficient of thermal expansion, heat resistance, insulation reliability, thermal shock resistance, resolution, film strength, and the like.

[0060] From the viewpoint of resolution, the average particle size of the surface-treated filler may be 0.01 μm or more, 0.1 μm or more, or 0.2 μm or more, and may be 5.0 μm or less, 4.0 μm or less, or 3.0 μm or less.

[0061] Component (E) may further contain an inorganic filler other than the above-mentioned surface-treated filler. Examples of inorganic fillers include barium titanate, barium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, lead titanate, lead zirconate titanate, lead lanthanum zirconate titanate, gallium oxide, spinel, mullite, cordierite, talc, aluminum titanate, yttria-containing zirconia, barium sulfate, barium silicate, calcium carbonate, calcium sulfate, zinc oxide, and magnesium titanate. The inorganic fillers may be surface-treated.

[0062] Component (E) may further contain barium sulfate from the viewpoint of improving resolution. Component (E) may contain a surface-treated silica filler and barium sulfate from the viewpoint of improving photosensitivity, and preferably contains a surface-treated silica filler having a (meth)acryloyl group, an epoxy group, or a phenylamino group and barium sulfate, and more preferably contains a surface-treated silica filler having a (meth)acryloyl group and barium sulfate. The barium sulfate may be surface-treated.

[0063] The content of barium sulfate may be 5 to 30 mass %, 10 to 25 mass %, 12 to 20 mass %, or 14 to 18 mass % based on the total solid content of the photosensitive resin composition.

[0064] ((F) component: photopolymerizable compound) The photosensitive resin composition according to this embodiment may further contain a photopolymerizable compound having no acidic group as component (F) from the viewpoint of improving sensitivity and resolution. The component (F) may be used alone or in combination of two or more.

[0065] Examples of the component (F) include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; mono- or di(meth)acrylates of glycols such as ethylene glycol, methoxytetraethylene glycol and polyethylene glycol; (meth)acrylamide compounds such as N,N-dimethyl (meth)acrylamide and N-methylol (meth)acrylamide; aminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, Examples of the polyhydric (meth)acrylate include polyhydric alcohols such as dipentaerythritol and tris-hydroxyethyl isocyanurate, or polyhydric (meth)acrylates of these ethylene oxide or propylene oxide adducts; (meth)acrylate compounds of ethylene oxide or propylene oxide adducts of phenolic compounds such as phenoxyethyl (meth)acrylate and polyethoxydi(meth)acrylate of bisphenol A; (meth)acrylate compounds of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; and melamine (meth)acrylate.

[0066] From the viewpoint of increasing the crosslink density upon photocuring and improving heat resistance and electrical insulation, component (F) may contain a photopolymerizable compound having three or more ethylenically unsaturated groups. Examples of photopolymerizable compounds having three or more ethylenically unsaturated groups include trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO,PO-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, and dipentaerythritol hexaacrylate.

[0067] (Component (G): Pigment) The photosensitive resin composition of this embodiment may further contain a pigment as component (G) from the viewpoint of improving the distinguishability or appearance of the production equipment. As component (G), a colorant that develops a desired color when concealing wiring, etc., can be used. Examples of component (G) include phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black.

[0068] From the viewpoint of further concealing the wiring, the content of the component (G) may be 0.1 to 10 mass %, 0.5 to 8 mass %, or 1 to 5 mass % based on the total amount of solids in the photosensitive resin composition.

[0069] (Other ingredients) The photosensitive resin composition according to this embodiment may further contain various additives as needed, such as polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol; thickeners such as bentone and montmorillonite; silicone-based, fluorine-based, and vinyl resin-based antifoaming agents; silane coupling agents; and flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphate compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters.

[0070] (solvent) The photosensitive resin composition according to this embodiment contains a solvent for dissolving and dispersing each component, which makes it easy to apply the composition onto a substrate and allows the formation of a coating film of uniform thickness.

[0071] Examples of solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons 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, and carbitol acetate; aliphatic hydrocarbons such as octane and decane; and petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These solvents may be used alone or in combination of two or more.

[0072] The amount of the solvent to be added is not particularly limited, but the ratio of the solvent in the photosensitive resin composition may be 10 to 50 mass %, 20 to 40 mass %, or 25 to 35 mass %.

[0073] The photosensitive resin composition of this embodiment can be prepared by uniformly mixing the above-mentioned components using a roll mill, a bead mill, or the like.

[0074] [Photosensitive element] The photosensitive element according to this embodiment includes a support film and a photosensitive layer containing the above-described photosensitive resin composition. Fig. 1 is a cross-sectional view schematically showing the photosensitive element according to this embodiment. As shown in Fig. 1, the photosensitive element 1 includes a support film 10 and a photosensitive layer 20 formed on the support film 10.

[0075] The photosensitive element 1 can be produced by applying the photosensitive resin composition according to this embodiment onto a support film 10 by a known method such as reverse roll coating, gravure roll coating, comma coating, or curtain coating, and then drying the coating to form a photosensitive layer 20.

[0076] Examples of the support film include polyester films such as polyethylene terephthalate and polybutylene terephthalate; and polyolefin films such as polypropylene and polyethylene. The thickness of the support film may be, for example, 5 to 100 μm. The thickness of the photosensitive layer may be, for example, 5 to 50 μm, 5 to 40 μm, or 10 to 30 μm. The surface roughness of the support film is not particularly limited, but the arithmetic mean roughness (Ra) may be 1000 nm or less, 500 nm or less, or 250 nm or less.

[0077] The coating film can be dried by hot air drying, far infrared drying, or near infrared drying. The drying temperature may be 60 to 120° C., 70 to 110° C., or 80 to 100° C. The drying time may be 1 to 60 minutes, 2 to 30 minutes, or 5 to 20 minutes.

[0078] The photosensitive element 1 may further include a protective film 30 on the photosensitive layer 20 to cover the photosensitive layer 20. The photosensitive element 1 may also have the protective film 30 laminated on the surface of the photosensitive layer 20 opposite to the surface that contacts the support film 10. The protective film 30 may be, for example, a polymer film such as polyethylene or polypropylene.

[0079] [Printed wiring board] The printed wiring board according to this embodiment includes a permanent resist containing a cured product of the photosensitive resin composition according to this embodiment, which can improve HAST resistance and TCT resistance.

[0080] The method for producing a printed wiring board according to this embodiment includes the steps of forming a photosensitive layer on a substrate using the above-described photosensitive resin composition or photosensitive element, exposing and developing the photosensitive layer to form a resist pattern, and curing the resist pattern to form a permanent resist. An example of each step will be described below.

[0081] First, a substrate such as a copper-clad laminate is prepared, and a photosensitive layer is formed on the substrate. The photosensitive layer may be formed by applying a photosensitive resin composition to the substrate and drying it. Examples of methods for applying the photosensitive resin composition include screen printing, spraying, roll coating, curtain coating, and electrostatic coating. The drying temperature may be 60 to 120°C, 70 to 110°C, or 80 to 100°C. The drying time may be 1 to 7 minutes, 1 to 6 minutes, or 2 to 5 minutes.

[0082] The photosensitive layer may be formed on the substrate by peeling off the protective film from the photosensitive element and laminating the photosensitive layer on the substrate. Examples of methods for laminating the photosensitive layer include thermal lamination using a laminator.

[0083] Next, a negative film is brought into contact with the photosensitive layer directly or via a support film, and the layer is exposed to actinic rays. Examples of actinic rays include electron beams, ultraviolet rays, and X-rays, with ultraviolet rays being preferred. Examples of light sources that can be used include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and halogen lamps. The exposure dose is 10 to 2000 mJ / cm. 2 , 100-1500mJ / cm 2 , or 300 to 1000 mJ / cm 2 may be.

[0084] After exposure, the unexposed areas are removed with a developer to form a resist pattern. Examples of the developing method include dipping and spraying. Examples of the developer that can be used include aqueous alkali solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, and tetramethylammonium hydroxide.

[0085] A patterned cured film (permanent resist) can be formed by subjecting the resist pattern to at least one of post-exposure and post-heating. The exposure dose of the post-exposure is 100 to 5000 mJ / cm. 2 , 500~2000mJ / cm 2 , or 700 to 1500 J / cm2 The heating temperature for post-heating may be 100 to 200° C., 120 to 180° C., or 135 to 165° C. The heating time for post-heating may be 5 minutes to 12 hours, 10 minutes to 6 hours, or 30 minutes to 2 hours.

[0086] The permanent resist according to this embodiment can be used as an interlayer insulating layer or a surface protective layer of a semiconductor element. A semiconductor element having an interlayer insulating layer or a surface protective layer formed from a cured film of the above-described photosensitive resin composition, and an electronic device including the semiconductor element, can be produced. The semiconductor element may be, for example, a memory, a package, or the like having a multilayer wiring structure, a rewiring structure, or the like. Examples of electronic devices include mobile phones, smartphones, tablet terminals, personal computers, and hard disk suspensions. By providing a patterned cured film formed from the photosensitive resin composition according to this embodiment, semiconductor elements and electronic devices with excellent reliability can be provided. [Example]

[0087] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0088] (Synthesis Example 1) 350 parts by weight of bisphenol F novolac epoxy resin (manufactured by DIC Corporation, trade name "EXA-7376"), 70 parts by weight of acrylic acid, 0.5 parts by weight of methylhydroquinone, and 120 parts by weight of carbitol acetate were mixed with stirring at 90°C. The mixture was cooled to 60°C, and 2 parts by weight of triphenylphosphine was added. The mixture was reacted at 100°C until the acid value of the solution reached 1 mgKOH / g or less. 98 parts by weight of tetrahydrophthalic anhydride and 85 parts by weight of carbitol acetate were added to the reaction mixture, which was then heated to 80°C and reacted for 6 hours. The reaction mixture was then cooled to room temperature (25°C) to obtain a solution of acid-modified epoxy acrylate (A-1) as component (A) (solids concentration: 73% by weight).

[0089] The following materials were prepared as components (B) to (G). B-1: Polyester elastomer having hydroxyl groups (manufactured by Showa Denko Materials Co., Ltd., product name "ESPEL 1612") B-2: Polyester elastomer having hydroxyl groups (manufactured by Showa Denko Materials Co., Ltd., product name "ESPEL 1620") B-3: Carboxylic acid-modified butadiene-acrylonitrile copolymer (manufactured by JSR Corporation, product name "XER-91") C-1: 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane (manufactured by IGM Resins BV, trade name "Omirad 907") C-2: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name "DETX-S") D-1: Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER 828") D-2: Melamine (Mitsui Chemicals, Inc.) E-1: Silica filler with methacryloyl groups (average particle size 0.5 μm) (manufactured by Admatechs Co., Ltd.) E-2: Silica filler with vinyl groups (average particle size 0.5 μm) (manufactured by Admatechs Co., Ltd.) E-3: Silica filler with epoxy groups (average particle size 0.5 μm) (manufactured by Admatechs Co., Ltd.) E-4: Silica filler with phenylamino groups (average particle size 0.5 μm) (manufactured by Admatechs Co., Ltd.) E-5: Untreated silica filler (average particle size 0.5 μm) (manufactured by Admatechs Co., Ltd., product name "SO-C2") E-6: Barium sulfate (average particle size 1.0 μm) (manufactured by Nippon Solvay Co., Ltd., product name "ASA") F-1: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "DPHA") G-1: Phthalocyanine Green

[0090] [Photosensitive resin composition] The components were blended in the amounts (parts by mass, solid content equivalent) shown in Table 1 or Table 2 and kneaded using a three-roll mill. Then, carbitol acetate was added so that the solid content concentration became 60% by mass, thereby preparing a photosensitive resin composition.

[0091] (light sensitivity) The photosensitive resin composition was applied to a copper-clad laminate using a 120-mesh Tetron screen and dried in a hot air circulation dryer at 80°C for 30 minutes to form a photosensitive layer with a thickness of approximately 30 μm. A 21-step step tablet (manufactured by Stoffer) was attached to the photosensitive layer, and the cumulative exposure dose was 500 mJ / cm. 2 Next, the film was irradiated with ultraviolet light at 1.8 kgf / cm for 60 seconds using a 1% by mass aqueous solution of sodium carbonate. 2 After development, the number of photosensitive layer steps remaining undeveloped was counted and evaluated according to the following criteria. A: The number of photosensitive layers that remained undeveloped was 8 or more. B: The number of photosensitive layers that remained undeveloped was 5 to 7. C: The number of photosensitive layers that remained undeveloped was 4 or less.

[0092] (TCT resistance) After development, the copper-clad laminate was heated at 150°C for 1 hour to produce a test plate with a permanent mask resist with an opening pattern formed on the copper-clad laminate. The test specimens were subjected to a temperature cycle test consisting of 30 minutes at -55°C and 30 minutes at 125°C. After 1500 and 2000 cycles, the test specimens were observed visually and with an optical microscope and evaluated according to the following criteria. A: No cracks were observed after 2000 cycles. B: No cracks were observed after 1500 cycles, but cracks were observed after 2000 cycles. C: Cracks were observed after 1500 cycles.

[0093] (HAST resistance) A printed wiring board substrate (manufactured by Showa Denko Materials Co., Ltd., product name "MCL-E-679") was prepared by laminating a 12 μm-thick copper foil to a glass epoxy substrate. The copper surface of the substrate was etched to form interdigital electrodes with a line / space of 28 μm / 32 μm. A photosensitive resin composition was applied to the copper-clad laminate using a 120-mesh Tetron screen and dried in a hot air circulation dryer at 80°C for 30 minutes to form a photosensitive layer with a thickness of approximately 30 μm. As described above, an evaluation substrate was prepared on which a cured film of the photosensitive element was formed. The evaluation substrate was exposed to a DC 5V voltage at 135°C and 85% RH for 200 hours, after which the resistance was measured and evaluated according to the following criteria. A: Resistance is 1 x 10 7 It was above Ω. B: Resistance is 1×10 6 Ω or more 1×10 7 It was less than Ω. C: Resistance is 1×10 6 It was less than Ω.

[0094] [Table 1]

[0095] [Table 2] [Explanation of symbols]

[0096] 1...photosensitive element, 10...support film, 20...photosensitive layer, 30...protective film.

Claims

1. (A) an acid-modified vinyl group-containing resin, (B) an elastomer, (C) a photopolymerization initiator, (D) a curing agent, and (E) an inorganic filler; The photosensitive resin composition for a permanent resist, wherein the inorganic filler comprises a surface-treated filler.

2. The photosensitive resin composition according to claim 1 , wherein the surface-treated filler has a photoreactive functional group or a thermally reactive functional group.

3. 2. The photosensitive resin composition according to claim 1, wherein the surface-treated filler has at least one group selected from the group consisting of a (meth)acryloyl group, a vinyl group, an epoxy group, and a phenylamino group.

4. The photosensitive resin composition according to claim 1 , wherein the surface-treated filler is a surface-treated silica filler.

5. 2. The photosensitive resin composition according to claim 1, wherein the content of the surface-treated filler is 7 to 28 mass % based on the total solid content of the photosensitive resin composition.

6. The photosensitive resin composition according to claim 4 , wherein the inorganic filler comprises the surface-treated silica filler and barium sulfate.

7. The photosensitive resin composition according to claim 6 , wherein the surface-treated silica filler has a (meth)acryloyl group, an epoxy group, or a phenylamino group.

8. The photosensitive resin composition according to claim 6 , wherein the surface-treated silica filler has a (meth)acryloyl group.

9. A support film and a photosensitive layer formed on the support film, A photosensitive element, wherein the photosensitive layer comprises the photosensitive resin composition according to any one of claims 1 to 8.

10. A printed wiring board comprising a permanent resist comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 8.

11. forming a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 8; exposing and developing the photosensitive layer to form a resist pattern; hardening the resist pattern to form a permanent resist; A method for manufacturing a printed wiring board, comprising:

12. forming a photosensitive layer on a substrate using the photosensitive element of claim 9; exposing and developing the photosensitive layer to form a resist pattern; hardening the resist pattern to form a permanent resist; A method for manufacturing a printed wiring board, comprising:

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