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WO2018179260A1 - Composition de résine photosensible, film durci à motif ainsi que procédé de fabrication de celui-ci, élément photosensible, et carte de circuit imprimé ainsi que procédé de fabrication de celle-ci - Google Patents

Composition de résine photosensible, film durci à motif ainsi que procédé de fabrication de celui-ci, élément photosensible, et carte de circuit imprimé ainsi que procédé de fabrication de celle-ci Download PDF

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Publication number
WO2018179260A1
WO2018179260A1 PCT/JP2017/013343 JP2017013343W WO2018179260A1 WO 2018179260 A1 WO2018179260 A1 WO 2018179260A1 JP 2017013343 W JP2017013343 W JP 2017013343W WO 2018179260 A1 WO2018179260 A1 WO 2018179260A1
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WIPO (PCT)
Prior art keywords
epoxy resin
resin composition
group
acid
photosensitive resin
Prior art date
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Ceased
Application number
PCT/JP2017/013343
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English (en)
Japanese (ja)
Inventor
真治 入澤
吉野　利純
田中　恵生
好章 布施
雄汰 代島
伸仁 古室
正幸 小島
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
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Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to PCT/JP2017/013343 priority Critical patent/WO2018179260A1/fr
Publication of WO2018179260A1 publication Critical patent/WO2018179260A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention relates to an alkali-developable photosensitive resin composition for a protective film of a printed wiring board, and more specifically, for a protective film of a printed wiring board used as a permanent mask resist in the resist field such as a substrate for a semiconductor package.
  • the present invention relates to a photosensitive resin composition.
  • a permanent mask resist (protective film) is formed on a printed wiring board.
  • a method for forming a pattern of a photosensitive resist a colored photosensitive resin composition is applied to a substrate, dried, and then cured by selectively irradiating with ultraviolet rays, and then only an uncured portion is developed with an alkaline solution or the like.
  • This permanent mask resist has a role of preventing the solder from adhering to unnecessary portions of the conductor layer of the printed wiring board in the process of flip chip mounting the semiconductor element on the printed wiring board via solder. Further, the permanent mask resist has a role of preventing corrosion of the conductor layer and maintaining electrical insulation between the conductor layers when the printed wiring board is used.
  • thermosetting resin paste is screen printed except for a rigid wiring board, an IC chip, an electronic component, or an LCD panel and a connection wiring pattern portion,
  • a permanent mask resist is formed by thermosetting (see, for example, Patent Document 1).
  • the warpage can be improved, and even if the curing conditions are strict to achieve high rigidity, the gap between the permanent mask resist and the substrate can be improved.
  • Photosensitive resin composition capable of preventing peeling, patterned cured film and method for producing the same, photosensitive element, printed wiring board comprising permanent mask resist formed using these, and method for producing printed wiring board The purpose is to provide.
  • this invention provides the following photosensitive resin composition, the pattern cured film using the same, its manufacturing method, a photosensitive element, a printed wiring board, and the manufacturing method of a printed wiring board.
  • [1] Contains (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerizable monomer having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a curing agent.
  • a photosensitive resin composition comprising: (D) the content of the inorganic filler is 30 to 60% by mass of the total solid content in the photosensitive resin composition; and (E) the content of the curing agent is (A) A photosensitive resin composition having 75 to 140 parts by mass per 100 parts by mass of the acid-modified vinyl group-containing epoxy resin.
  • two R 12 s each independently represent a hydrogen atom or a methyl group; two Y 2 s each independently represent a hydrogen atom or a glycidyl group; and two R 12 s are the same or different. Provided that at least one of Y 2 represents a glycidyl group.
  • two R 13 s each independently represent a hydrogen atom or a methyl group, two Y 3 s each independently represent a hydrogen atom or a glycidyl group, and the two R 13 s are the same or different. Provided that at least one of Y 3 represents a glycidyl group.
  • the (A) acid-modified vinyl group-containing epoxy resin has a novolak epoxy resin having a structural unit represented by the general formula (1), and a bisphenol having a structural unit represented by the general formula (2).
  • the photosensitive resin composition according to [2] which is a resin obtained by reacting a saturated or unsaturated group-containing polybasic acid anhydride (c) with a resin (A ′) obtained by reacting with a resin (A ′).
  • the curing agent contains a compound that cures by reacting with a carboxyl group and a hydroxyl group, and a compound that reacts and cures with a carboxyl group, a hydroxyl group, and a glycidyl group [1] to [3] ]
  • the photosensitive resin composition of any one of.
  • the curing agent contains an epoxy resin and a melamine compound, and the content of the epoxy resin in (E) the curing agent is 15 per 100 parts by mass of the (A) acid-modified vinyl group-containing epoxy resin.
  • a method for producing a cured pattern film comprising: a step of exposing to light, a step of removing an unexposed portion by development to obtain a pattern resin film, and a step of curing the pattern resin film.
  • a photosensitive element having a support and a photosensitive layer using the photosensitive resin composition according to any one of [1] to [8] on the support.
  • a printed wiring board comprising a permanent mask resist formed from the photosensitive resin composition according to any one of [1] to [8].
  • a step of forming a photosensitive layer on the substrate using the photosensitive resin composition according to any one of [1] to [8] or the photosensitive element according to [11], The manufacturing method of a printed wiring board which has the process of forming a resist pattern using a layer, and the process of hardening
  • the warpage can be improved, and the permanent mask resist and the substrate can be used even if the curing conditions are strict to achieve high rigidity.
  • a photosensitive resin composition capable of preventing peeling between the two, a pattern cured film and a method for producing the same, a photosensitive element, and a printed wiring board and a printed wiring board having a permanent mask resist formed using the photosensitive element A manufacturing method can be provided.
  • the photosensitive resin composition of the present invention comprises (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerizable monomer having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) It contains a curing agent (hereinafter simply referred to as (A) component, (B) component, (C) component, (D) component, (E) component, etc.)).
  • a curing agent hereinafter simply referred to as (A) component, (B) component, (C) component, (D) component, (E) component, etc.
  • the (A) acid-modified vinyl group-containing epoxy resin used in the present invention will be described.
  • the acid-modified vinyl group-containing epoxy resin is obtained by modifying an epoxy resin with a vinyl group-containing organic acid. For example, it is saturated with a resin obtained by reacting an epoxy resin with a vinyl group-containing monocarboxylic acid.
  • An epoxy resin obtained by reacting a group or unsaturated group-containing polybasic acid anhydride can be used.
  • the (A) acid-modified vinyl group-containing epoxy resin used in the present invention is a structural unit represented by the following general formula (1) from the viewpoint of being capable of alkali development and being excellent in resolution and adhesiveness.
  • a novolak-type epoxy resin for example, a novolak-type epoxy resin represented by the following general formula (1 ′)
  • a bisphenol novolac-type epoxy resin having a structural unit represented by the following general formula (2) and the following general formula Obtained by reacting at least one epoxy resin (a) selected from the group consisting of bisphenol novolac type epoxy resins having the structural unit represented by (3) with a vinyl group-containing monocarboxylic acid (b).
  • a resin (A ′′) obtained by reacting the resin (A ′) with a saturated or unsaturated group-containing polybasic acid anhydride (c) is preferable.
  • R 11 represents a hydrogen atom or a methyl group
  • Y 1 represents a hydrogen atom or a glycidyl group
  • the molar ratio of hydrogen atom to glycidyl group is 0/100 to 30/70.
  • n1 represents a number of 1 or more
  • a plurality of R 11 and Y 1 may be the same or different.
  • at least one Y 1 represents a glycidyl group.
  • the molar ratio of Y 1 as a hydrogen atom to Y 1 as a glycidyl group is 0/100 to 30/70, preferably 0/100 to 10/90.
  • the number of structural units of the structural unit in one molecule of the epoxy resin (a) having the structural unit represented by the general formula (1) and the number of structural units represented by n1 in the general formula (1 ′) are 1
  • the number is preferably 10 to 200, more preferably 30 to 150, still more preferably 30 to 100.
  • the number of structural units represents an integer value when the epoxy resin (a) is composed of a single kind of molecule, and a rational number that is an average value when the epoxy resin (a) is an aggregate of a plurality of kinds of molecules. .
  • two R 12 s each independently represent a hydrogen atom or a methyl group
  • two Y 2 s each independently represent a hydrogen atom or a glycidyl group.
  • Two R 12 may be the same or different
  • two Y 2 may be the same or different. However, at least one of Y 2 represents a glycidyl group.
  • the number of structural units of the structural unit in one molecule of the epoxy resin (a) having the structural unit represented by the general formula (2) is one or more, and adhesion to the copper substrate, heat resistance, and electricity From the viewpoint of improving the insulation, it is preferably 10 to 100, more preferably 15 to 80, and still more preferably 15 to 70.
  • two R 13 s each independently represent a hydrogen atom or a methyl group
  • two Y 3 s each independently represent a hydrogen atom or a glycidyl group.
  • Two R 13 may be the same or different
  • two Y 3 may be the same or different.
  • at least one of Y 3 represents a glycidyl group.
  • the number of structural units of the structural unit in one molecule of the epoxy resin (a) having the structural unit represented by the general formula (3) is one or more, and adhesion to a copper substrate, heat resistance and electricity From the viewpoint of improving the insulation, it is preferably 10 to 100, more preferably 15 to 80, and still more preferably 15 to 70.
  • Examples of the novolac type epoxy resin having the structural unit represented by the general formula (1) include a phenol novolac type epoxy resin and a cresol novolak type epoxy resin. These novolak-type epoxy resins can be obtained, for example, by reacting a phenol novolak resin, a cresol novolak resin and epichlorohydrin by a known method.
  • epoxy resin (a) from the viewpoint of having excellent process tolerance and improving solvent resistance, a novolak epoxy resin having a structural unit represented by the general formula (1), for example, the general formula (1) A novolac type epoxy resin represented by ′) is preferred.
  • Examples of the phenol novolak type epoxy resin or cresol novolak type epoxy resin represented by the general formula (1 ′) include YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, and YDPN.
  • the reaction is preferably carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide or dimethylsulfoxide in the presence of an alkali metal hydroxide at a reaction temperature of 50 to 120 ° C.
  • a polar organic solvent such as dimethylformamide, dimethylacetamide or dimethylsulfoxide
  • an alkali metal hydroxide at a reaction temperature of 50 to 120 ° C.
  • the epoxy resin (a) is represented by the general formula (2) and / or the general formula (3) from the viewpoint of further reducing the warpage of the thin film substrate and further improving the thermal shock resistance. It is preferable to use a bisphenol novolac type epoxy resin having a structural unit of
  • R 13 is a hydrogen atom and Y 3 is a glycidyl group as EXA-7376 series (trade name, manufactured by DIC Corporation), and R 13 is a methyl group.
  • Y 3 having a glycidyl group is commercially available as EPON SU8 series (trade name, manufactured by Japan Epoxy Resin Co., Ltd.).
  • vinyl group-containing monocarboxylic acid (b) examples include acrylic acid, a dimer of acrylic acid, methacrylic acid, ⁇ -furfurylacrylic acid, ⁇ -styrylacrylic acid, cinnamic acid, crotonic acid, ⁇ - Acrylic acid derivatives such as cyanocinnamic acid, half-ester compounds which are reaction products of hydroxyl group-containing acrylates and dibasic acid anhydrides, vinyl group-containing monoglycidyl ethers or vinyl group-containing monoglycidyl esters and dibasic acid anhydrides The half-ester compound which is a reaction product of is mentioned.
  • the vinyl group-containing monocarboxylic acid (b) can be used alone or in combination of two or more.
  • the half ester compound is obtained by reacting a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester with a dibasic acid anhydride in an equimolar ratio.
  • vinyl group-containing monocarboxylic acids (b) can be used singly or in combination of two or more.
  • Examples of the hydroxyl group-containing acrylate, vinyl group-containing monoglycidyl ether, and vinyl group-containing monoglycidyl ester used in the synthesis of the half ester compound as an example of the vinyl group-containing monocarboxylic acid (b) 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 tris Methacrylate, dipentaerythritol pentaacrylate, Pentaerythritol penta methacrylate, glycidyl acrylate, glycidyl methacrylate.
  • dibasic acid anhydride used for the synthesis of the half ester compound one containing a saturated group or one containing an unsaturated group can be used.
  • dibasic acid anhydrides include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride.
  • examples include acid, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.
  • the vinyl group-containing monocarboxylic acid (b) is preferably 0.8 relative to 1 equivalent of the epoxy group of the epoxy resin (a).
  • the reaction is preferably performed at a ratio of 5 to 1.05 equivalents, more preferably 0.6 to 1.05 equivalents, and more preferably at a ratio of 0.8 to 1.0 equivalents.
  • the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) can be reacted by dissolving in an organic solvent.
  • organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as 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 carbonization such as octane and decane
  • petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha,
  • a catalyst in order to promote the reaction.
  • the catalyst for example, triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, triphenylphosphine, and the like can be used.
  • the amount of the catalyst used is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b).
  • a polymerization inhibitor for the purpose of preventing polymerization during the reaction.
  • the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like.
  • the amount of the polymerization inhibitor used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass in total of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b).
  • the reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 120 ° C.
  • a vinyl group-containing monocarboxylic acid (b) and a phenolic compound such as p-hydroxyphenethyl alcohol, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic acid
  • a polybasic acid anhydride such as an anhydride can be used in combination.
  • the resin (A ′) obtained by reacting the epoxy resin (a) with the vinyl group-containing monocarboxylic acid (b) is a glycidyl group of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). It is presumed to have a hydroxyl group formed by an addition reaction with a carboxyl group.
  • the resin (A ′′) thus obtained the hydroxyl group of the resin (A ′) is synthesized.
  • it is an acid-modified vinyl group-containing epoxy resin in which the acid anhydride group of the polybasic acid anhydride (c) is half-esterified (including the hydroxyl group originally present in the epoxy resin (a)) Inferred.
  • polybasic acid anhydride (c) As the polybasic acid anhydride (c), one containing a saturated group or one containing an unsaturated group can be used.
  • Specific examples of the polybasic acid anhydride (c) include, for example, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, Examples include methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride.
  • a polybasic acid anhydride (c) can be used individually by 1 type or in combination of 2 or more types.
  • the polybasic acid anhydride (c) is 0.1 to 1.0 equivalent per 1 equivalent of the hydroxyl group in the resin (A ′). By reacting, the acid value of the acid-modified vinyl group-containing epoxy resin can be adjusted.
  • the acid value of the acid-modified vinyl group-containing epoxy resin is preferably 30 to 150 mgKOH / g, more preferably 40 to 120 mgKOH / g, and particularly preferably 50 to 100 mgKOH / g. If the acid value is less than 30 mg KOH / g, the solubility of the photosensitive resin composition in a dilute alkaline solution tends to be reduced, and if it exceeds 150 mg KOH / g, the electric properties of the cured film tend to be reduced.
  • the reaction temperature between the resin (A ′) and the polybasic acid anhydride (c) is preferably 60 to 120 ° C.
  • epoxy resin (a) for example, a hydrogenated bisphenol A type epoxy resin can be partially used together.
  • (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto
  • (meth) acrylate means acrylate and corresponding methacrylate
  • (meth) acryloyl group means acryloyl.
  • Group and its corresponding methacryloyl group, and (meth) acryloxy group means an acryloxy group and its corresponding methacryloxy group.
  • the weight average molecular weight of the component (A) acid-modified vinyl group-containing epoxy resin is preferably 3,000 to 30,000, more preferably 4 from the viewpoint of improving adhesion to a copper substrate, heat resistance and electrical insulation. 5,000 to 25,000, more preferably 5,000 to 18,000.
  • the weight average molecular weight is a polyethylene-converted weight average molecular weight measured by a gel permeation chromatography (GPC) method using tetrahydrofuran as a solvent. More specifically, for example, a value measured by the following GPC measurement apparatus and measurement conditions and converted using a standard polystyrene calibration curve can be used as the weight average molecular weight.
  • GPC gel permeation chromatography
  • the calibration curve is prepared by using five sample sets (“PStQuick MP-H” and “PStQuick B”, manufactured by Tosoh Corporation) as standard polystyrene.
  • GPC measuring device GPC apparatus: High-speed GPC apparatus “HCL-8320GPC”, detector is a differential refractometer or UV, manufactured by Tosoh Corporation Column: column TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), Tosoh Corporation Made by company (measurement conditions)
  • Solvent Tetrahydrofuran (THF) Measurement temperature: 40 ° C Flow rate: 0.35 ml / min Sample concentration: 10 mg / THF 5 ml Injection volume: 20 ⁇ l
  • the content of the (A) acid-modified vinyl group-containing epoxy resin is preferably 5 to 60% by mass based on the total solid content of the photosensitive resin composition. More preferably, it is ⁇ 50% by mass, and particularly preferably 15 ⁇ 40% by mass. When the content of the component (A) is within the above range, a coating film that is superior in heat resistance, electrical characteristics, and chemical resistance can be obtained.
  • Photopolymerizable compound having an ethylenically unsaturated bond As the photopolymerizable compound (B) having an ethylenically unsaturated bond used in the photosensitive resin composition of the present invention, a compound having a molecular weight of 1000 or less is preferable.
  • 2-hydroxyethyl (meth) acrylate, 2 -Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate, mono- or di (meth) acrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, N, N-dimethyl (meth) acrylamide, (Meth) acrylamides such as N-methylol (meth) acrylamide, aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, hexanediol, trimethylolpropane, pentaerythritol, dito Polyhydric alcohols such as methylolpropane, dipentaerythritol, tris-hydroxyethyl isocyanurate, or poly (meth) acrylates of these ethylene oxide or propylene oxide adducts,
  • ethylenically unsaturated bonds in one molecule in order to increase the crosslinking density by photocuring and improve heat resistance and electrical reliability.
  • examples of such a compound having an ethylenically unsaturated bond include dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.
  • These (B) compounds having an ethylenically unsaturated group are used singly or in combination of two or more.
  • the content of the photopolymerizable compound having an ethylenically unsaturated bond is preferably 2 to 50% by mass, more preferably 3 to 30% by mass, based on the total solid content in the photosensitive resin composition. More preferably, it is 3 to 20% by mass. If it is 2% by mass or more, the photosensitivity is low, so that the tendency of the exposed portion to elute during development can be suppressed, and if it is 50% by mass or less, a decrease in heat resistance can be suppressed.
  • Examples of the (C) photopolymerization initiator used in the photosensitive resin composition of the present invention include benzoins 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 Acetophenones such as -1- [4- (methylthio) phenyl] -2-morpholino-1-propanone and N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1 -Chloro
  • These (C) photoinitiators can be used individually by 1 type or in combination of 2 or more types. Further, Irgacure 819 having good curability at the bottom for photobleaching and Irgacure 369 which is less likely to be generated as outgas because it is less volatile.
  • C ′ such as tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like.
  • Photopolymerization initiation assistants can be used alone or in combination of two or more.
  • the content of the photopolymerization initiator (C) in the photosensitive resin composition of the present invention is preferably 0.2 to 20% by mass, more preferably 0.4%, based on the total solid content of the photosensitive resin composition. -15% by mass, more preferably 0.6-10% by mass. Further, when the content of (C) the photopolymerization initiator is 0.2% by mass or more, the exposed portion is hardly eluted during development, and when it is 20% by mass or less, a decrease in heat resistance can be suppressed.
  • Examples of the (D) inorganic filler used in the photosensitive resin composition of the present invention include silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), tantalum oxide (Ta 2 O 5 ), Zirconia (ZrO 2 ), silicon nitride (Si 3 N 4 ), barium titanate (BaO ⁇ TiO 2 ), barium carbonate (BaCO 3 ), magnesium carbonate, aluminum oxide, aluminum hydroxide, magnesium hydroxide, lead titanate ( PbO ⁇ TiO 2 ), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga 2 O 3 ), spinel (MgO ⁇ Al 2 O 3 ), mullite (3Al 2 O 3 ⁇ 2SiO 2), cordierite (2MgO ⁇ 2Al 2 O 3 / 5SiO 2), talc
  • the surface treatment was performed with a silane coupling agent as necessary.
  • a silane coupling agent generally available ones can be used, for example, alkyl silane, alkoxy silane, vinyl silane, epoxy silane, amino silane, acrylic silane, methacryl silane, mercapto silane, sulfide silane, isocyanate silane, Sulfur silane, styryl silane, alkylchlorosilane, and the like can be used.
  • Specific compound names include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyltrimethoxy.
  • Silane diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecylmethoxysilane, phenyltrimethoxysilane, diphenyldimethoxy Silane, triphenylsilanol, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, n-octyldi Tylchlorosilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl
  • silane coupling agent those that react with the carboxy group of the (A) acid-modified vinyl group-containing epoxy resin contained in the photosensitive resin composition are preferable.
  • epoxy silane, acrylic silane, methacryl Silane is preferred. Since these silane coupling agents strengthen the bond between silica and resin, they increase the strength of the film when used as a permanent mask resist and contribute to crack resistance and the like in a temperature cycle test. Further, mercaptosilane or isocyanate silane may be used.
  • B It is thought that it reacts with the ethylenically unsaturated group of the photopolymerizable monomer having an ethylenically unsaturated bond and exhibits the same effect as when the silane coupling agent is used.
  • silica fine particles from the viewpoint of improving the low expansion coefficient and heat resistance.
  • barium sulfate fine particles are used from the viewpoint of improving solder heat resistance, HAST property (insulation reliability), crack resistance (thermal shock resistance), and adhesion strength between the underfill material and the cured film after the PCT test. It is also preferable to do.
  • the said silica fine particle is surface-treated with an alumina and / or an organosilane type compound from a viewpoint which can improve the aggregation prevention effect.
  • the average particle diameter of the inorganic filler is preferably 0.01 to 1 ⁇ m, more preferably 0.1 to 1 ⁇ m from the viewpoint of practicality and resolution, and 0.3 to 0.7 ⁇ m. Most preferably it is. Further, (D) the inorganic filler preferably has a maximum particle size of 0.1 to 5 ⁇ m, more preferably 0.1 to 3 ⁇ m, and particularly preferably 0.1 to 1 ⁇ m. When the maximum particle size exceeds 5 ⁇ m, resolution and insulation reliability tend to be impaired.
  • the content of the (D) inorganic filler is 30 to 60% by mass based on the total solid content of the photosensitive resin composition from the viewpoints of resolution and low thermal expansion coefficient. 30 to 55% by mass, and more preferably 35 to 50% by mass.
  • the content of the inorganic filler is within the above range, the low thermal expansion coefficient, heat resistance, insulation reliability, thermal shock resistance, resolution, film strength and the like can be further improved.
  • the filling amount exceeds 60% by mass, it becomes difficult to disperse in the resin, and the flowability of the photosensitive resin composition tends to decrease. If the filling amount is less than 30% by mass, the thermal expansion coefficient is not sufficiently reduced during heating, and there is a tendency that warpage cannot be reduced, and crack resistance during reflow mounting tends to be difficult to obtain. is there.
  • (E) Curing agent used in the photosensitive resin composition of the present invention, a compound that cures itself by heat, ultraviolet rays, or (A) a carboxyl group, a hydroxyl group and heat of an acid-modified vinyl group-containing epoxy resin, A compound that is cured by reaction with ultraviolet rays or the like is preferable.
  • (E) By using a hardening
  • Examples of the curing agent include thermosetting compounds such as epoxy compounds, melamine compounds, urea compounds, oxazoline compounds, and block type isocyanates.
  • Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol S type epoxy resin, and biphenyl type epoxy resin.
  • epoxy resins such as naphthalene type epoxy resin, dicyclo type epoxy resin, hydantoin type epoxy resin, heterocyclic epoxy resin such as triglycidyl isocyanurate, and bixylenol type epoxy resin.
  • Examples of the melamine compound include triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine, triaminotriazine, hexa (N -Methyl) melamine, hexamethoxymelamine, hexabutoxylated melamine and the like.
  • Examples of the urea compound include dimethylol urea.
  • the curing agent cures by reacting with a carboxyl group, a hydroxyl group, and a glycidyl group with heat, ultraviolet rays, etc., from the viewpoint of further improving the heat resistance of the cured film and the adhesion to the underfill material or the substrate.
  • a compound as an essential component As such a compound, the said melamine compound etc. can be mentioned, for example.
  • the curing agent preferably contains an epoxy compound (epoxy resin) and / or a block type isocyanate from the viewpoint of further improving the heat resistance of the cured film, and the epoxy compound and the block type isocyanate. It is more preferable to use together.
  • the block type isocyanate an addition reaction product of a polyisocyanate compound and an isocyanate blocking agent is used.
  • the polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate.
  • isocyanate blocking agent examples include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ⁇ -caprolactam, ⁇ -palerolactam, ⁇ -butyrolactam and ⁇ -propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid Alcohol blocking agents such as chill and ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl methyl
  • curing agent is used individually by 1 type or in combination of 2 or more types.
  • the content of the curing agent is preferably 2 to 40% by mass, more preferably 3 to 30% by mass based on the total solid content of the photosensitive resin composition, and more preferably 5 to 20% by mass. % Is particularly preferred.
  • the content of the (E) curing agent per 100 parts by mass of the (A) acid-modified vinyl group-containing epoxy resin is 75 to 140 parts by mass, preferably 75. Is 135 parts by mass, more preferably 80-130 parts by mass.
  • the content of the (E) curing agent per 100 parts by mass of the component (A) is less than 75 parts by mass, the improvement in adhesion to the underfill material and the substrate and chemical resistance tends to be insufficient.
  • the curing agent preferably contains an epoxy resin and a melamine compound as essential components.
  • the content of the epoxy resin Is preferably 15 to 100 parts by weight, more preferably 20 to 90 parts by weight, still more preferably 25 to 80 parts by weight per 100 parts by weight of the (A) acid-modified vinyl group-containing epoxy resin.
  • the content of the melamine compound is preferably 15 to 100 parts by mass per 100 parts by mass of the (A) acid-modified vinyl group-containing epoxy resin from the viewpoint of improving adhesion to the underfill material and the substrate and chemical resistance. More preferably, it is 20 to 90 parts by mass, and further preferably 25 to 80 parts by mass.
  • the photosensitive resin composition of the present invention includes (F) a pigment, (G) an elastomer, (H) an epoxy resin curing agent, (I) It may further contain a plastic resin, other additives and the like.
  • F a pigment
  • G an elastomer
  • H an epoxy resin curing agent
  • I It may further contain a plastic resin, other additives and the like.
  • the photosensitive resin composition of the present invention preferably contains (F) a pigment in order to improve the identification and appearance of the production apparatus.
  • the pigment is preferably used according to a desired color when the wiring is concealed.
  • a colorant that develops a desired color may be appropriately selected and used. For example, phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black A known colorant such as is preferred.
  • the content of the (F) pigment is preferably 0.1 to 10% by mass, based on the total solid content in the photosensitive resin composition, from the viewpoint of concealing the wiring. More preferably, the content is 0.1 to 5% by mass, and still more preferably 0.5 to 3% by mass.
  • the photosensitive resin composition of this invention further contains (G) elastomer.
  • (G) elastomer By containing an elastomer, the flexibility of the cured film formed from the photosensitive resin composition, the underfill material, the adhesion to the substrate, and the like can be further improved. That is, by adding the (G) elastomer to the photosensitive resin composition of the present invention, the crosslinking reaction (curing reaction) proceeds by ultraviolet rays or heat, so that the (A) acid-modified vinyl group-containing epoxy resin is cured and contracted. Thus, the problem that distortion (internal stress) is applied to the inside of the resin and flexibility and adhesiveness are reduced can be solved.
  • (G) elastomers examples include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, and silicone elastomers.
  • These (G) elastomers are composed of a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness.
  • styrene elastomer examples include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, and styrene-ethylene-propylene-styrene block copolymer.
  • styrene derivatives such as ⁇ -methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene and the like can be used in addition to styrene.
  • Tufprene, Sorprene T, Asaprene T, Tuftec (trade name, manufactured by Asahi Kasei Co., Ltd.), Elastomer AR (trade name, manufactured by Aron Kasei Co., Ltd.), Kraton G, Califlex (above, Shell Japan) Co., Ltd., product name), JSR-TR, TSR-SIS, Dynalon (above, JSR JSR Co., Ltd., product name), Denka STR (Denka Co., Ltd., product name), Quintac (Nihon Zeon Co., Ltd., Product name), TPE-SB series (commercial name, manufactured by Sumitomo Chemical Co., Ltd.), Lavalon (commercial name, manufactured by Mitsubishi Chemical Co., Ltd.), Septon, Hibler (above, product name manufactured by Kuraray Co., Ltd.), Sumiflex (Sumitomo) Bakelite Co., Ltd., trade name), Rheostomer, Actimer (abotulo
  • the olefin elastomer is a copolymer of ⁇ -olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene.
  • ⁇ -olefin having 2 to 20 carbon atoms
  • specific examples thereof include ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene
  • EPR ethylene-propylene copolymer
  • EPDM ethylene-propylene-diene copolymer
  • dicyclopentadiene 1,4-hexadiene
  • cyclooctadiene methylene norbornene
  • ethylidene norbornene butadiene
  • Examples thereof include
  • ethylene / ⁇ -olefin copolymer rubber ethylene / ⁇ -olefin / non-conjugated diene copolymer rubber, propylene / ⁇ -olefin copolymer rubber, butene / ⁇ -olefin copolymer rubber Can be mentioned.
  • Miralastoma Mitsubishi Chemical Co., Ltd., trade name
  • EXACT Exxon Chemical Co., trade name
  • ENGAGE Low Chemical Co., Ltd.
  • hydrogenated styrene-butadiene rubber DYNABON HSBR JSR Corporation, trade name
  • butadiene-acrylonitrile copolymer NBR series JSR Corporation, trade name
  • both terminal carboxyl group-modified butadiene-acrylonitrile copolymer XER series JSR Corporation, trade name
  • BF-1000 trade name, manufactured by Nippon Soda Co., Ltd.
  • PB-3600 trade name, manufactured by Daicel Corporation
  • Urethane elastomers are composed of structural units consisting of a hard segment composed of low-molecular glycol and diisocyanate, and a soft segment composed of high-molecular (long-chain) diol and diisocyanate.
  • low-molecular glycol for example, short-chain diols such as ethylene glycol, propylene glycol, 1,4-butanediol, bisphenol A and the like can be used.
  • the number average molecular weight of the short chain diol is preferably 48 to 500.
  • polystyrene resin examples include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene / 1,4-butylene adipate), polycaprolactone, and poly (1,6 -Hexylene carbonate) and poly (1,6-hexylene neopentylene adipate).
  • the number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000.
  • urethane-based elastomers include PANDEX T-2185, T-2983N (trade name, manufactured by DIC Corporation), and sylactolan E790 (trade name).
  • polyester elastomer examples include those obtained by polycondensation of a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof.
  • dicarboxylic acid examples include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which hydrogen atoms of these aromatic nuclei are substituted with methyl groups, ethyl groups, phenyl groups, and the like, Examples thereof include 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. These compounds can be used individually by 1 type or in combination of 2 or more types.
  • diol compound examples include fats such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol.
  • fats such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol.
  • Group diol and alicyclic diol, or dihydric phenol represented by the following general formula (4).
  • Y 11 represents an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, —O—, —S—, or —SO 2 —, wherein R 21 and R 22 each independently represents a halogen atom or an alkyl group having 1 to 12 carbon atoms, p and q each independently represents an integer of 0 to 4, and r represents an integer of 0 or 1.
  • dihydric phenol represented by the general formula (4) examples include bisphenol A, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) propane, and resorcin. These compounds can be used individually by 1 type or in combination of 2 or more types.
  • a multi-block copolymer having an aromatic polyester (for example, polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) portion as a soft segment component can be used.
  • aromatic polyester for example, polybutylene terephthalate
  • aliphatic polyester for example, polytetramethylene glycol
  • Polyamide elastomers are broadly classified into two types: polyether block amide type and polyether ester block amide type using polyamide for the hard segment and polyether or polyester for the soft segment.
  • polyamide polyamide-6, 11, 12 or the like
  • polyether polyoxyethylene, polyoxypropylene, polytetramethylene glycol, or the like
  • UBE polyamide elastomer product name, manufactured by Ube Industries, Ltd.
  • Daiamide product name, manufactured by Daicel Evonik Co., Ltd.
  • PEBAX product name, manufactured by Toray Industries, Inc.
  • Grilon ELY MS Japan Co., Ltd.
  • an acrylic ester is a main component, and ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, or the like is used. Moreover, glycidyl methacrylate, allyl glycidyl ether, etc. can be used as a crosslinking point monomer. Furthermore, acrylonitrile and ethylene can be copolymerized.
  • an acrylonitrile-butyl acrylate copolymer an acrylonitrile-butyl acrylate-ethyl acrylate copolymer, an acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, or the like can be used.
  • Silicone elastomers are composed mainly of organopolysiloxane, for example, and are classified into polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. Some are modified with vinyl groups, alkoxy groups, and the like. Specific examples include KE series (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), SE series, CY series, SH series (above, trade name by Toray Dow Corning Co., Ltd.), and the like.
  • a rubber-modified epoxy resin can also be used.
  • the rubber-modified epoxy resin includes, for example, a part or all of the epoxy groups of the bisphenol F type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol novolac type epoxy resin or cresol novolac type epoxy resin. It can be obtained by modification with terminal carboxylic acid-modified butadiene-acrylonitrile rubber, terminal amino-modified silicone rubber or the like.
  • both end carboxyl group-modified butadiene-acrylonitrile copolymer Espel which is a polyester elastomer having a hydroxyl group (Espel 1612, 1620, trade name, manufactured by Hitachi Chemical Co., Ltd.) Epoxidized polybutadiene, etc. are preferred.
  • Espel 1612, 1620, trade name, manufactured by Hitachi Chemical Co., Ltd. Epoxidized polybutadiene, etc.
  • An elastomer that is liquid at room temperature is particularly preferred.
  • (G) Elastomer content When the elastomer (G) is used, its content is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferable that the content be ⁇ 10% by mass. (G) By setting the elastomer content in the range of 1 to 20% by mass, the thermal shock resistance and the adhesive strength between the underfill material and the cured film can be further improved while maintaining good developability. it can. Moreover, when using for a thin film substrate, the curvature property of a thin film substrate can be reduced.
  • (H) an epoxy resin curing agent can be added for the purpose of further improving various properties such as heat resistance, adhesion, and chemical resistance of the cured film to be formed. .
  • (H) epoxy resin curing agent examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4- Imidazole derivatives such as methyl-5-hydroxymethylimidazole; guanamines such as acetoguanamine and benzoguanamine; diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazide Polyamines such as these organic acid salts and / or epoxy adducts: amine complexes of boron trifluoride; trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, Tertiary amines such as lysine, N
  • (Content of (H) epoxy resin curing agent) When (H) an epoxy resin curing agent is used, its content is preferably 0.01 to 20% by mass, based on the total solid content of the photosensitive resin composition, preferably 0.1 to 10% by mass. More preferably.
  • thermoplastic resin a thermoplastic resin can be added to the photosensitive resin composition of the present invention.
  • thermoplastic resin examples include acrylic resin and urethane resin.
  • the content in the case of containing a thermoplastic resin is preferably 1 to 30% by mass, more preferably 5 to 20% by mass based on the total solid content of the photosensitive resin composition. .
  • organic fine particles such as melamine and organic bentonite
  • polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol and pyrogallol, benton, montmorillonite and the like.
  • additives such as thickeners, silicone-based, fluorine-based and vinyl resin-based antifoaming agents, silane coupling agents, and diluents can be added.
  • flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphate compounds of phosphorous compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters can also be added.
  • an organic solvent can be used as the diluent.
  • the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as 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 carbonization such as octane and decane
  • Examples thereof include petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.
  • the photosensitive resin composition of the present invention can be obtained by uniformly kneading and mixing the above-described components with a roll mill, a bead mill or the like.
  • the cured film of the present invention is a cured film formed by curing the photosensitive resin composition of the present invention, and is usually formed as a patterned pattern cured film.
  • This pattern cured film is formed by, for example, applying a photosensitive resin composition of the present invention on a substrate such as a copper clad laminate and drying to form a coating film, and irradiating the coating film with active light to form a pattern.
  • the pattern resin film can be produced by sequentially performing a step of exposing to a shape, a step of removing an unexposed portion by development to obtain a pattern resin film, and a step of curing the pattern resin film.
  • the photosensitive resin composition of the present invention can be used, for example, to form an image as follows and to produce a cured film such as a permanent mask resist.
  • a substrate such as a copper-clad laminate by a screen printing method, a spray method, a roll coating method, a curtain coating method, an electrostatic coating method or the like with a film thickness of 10 to 200 ⁇ m, and then a coating film is applied.
  • the negative film is brought into direct contact (or non-contact through a transparent film) and active light (eg, ultraviolet light) is preferably applied at an exposure dose of 10 to 1,000 mJ / cm 2.
  • active light eg, ultraviolet light
  • the unexposed portion is dissolved and removed (developed) with a dilute alkaline aqueous solution or an organic solvent to obtain a patterned resin film.
  • the patterned resin film as an exposed portion is sufficiently cured by post-exposure (ultraviolet light exposure) and / or post-heating to obtain a cured film.
  • the post-exposure is preferably performed at an exposure amount of 1 to 5 J / cm 2 , for example, and the post-heating is preferably performed at 100 to 200 ° C. for 30 minutes to 12 hours.
  • the photosensitive resin composition of this invention can also be laminated
  • the photosensitive element of this invention has a support body and the photosensitive layer which uses the photosensitive resin composition of this invention on this support body, for example.
  • the thickness of the layer made of the photosensitive resin composition is not particularly limited, but is preferably 10 to 100 ⁇ m.
  • the support include polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polyolefins such as polypropylene and polyethylene.
  • the thickness of the support is not particularly limited, but is preferably in the range of 5 to 100 ⁇ m.
  • the photosensitive layer made of the photosensitive resin composition is preferably formed by applying and drying a solution of the photosensitive resin composition on a support.
  • the coating film can be dried using hot air drying, a far infrared ray, or a dryer using near infrared rays.
  • the drying temperature is, for example, preferably 60 to 120 ° C., more preferably 70 to 110 ° C., More preferably, it is 80 to 100 ° C.
  • the drying time is, for example, preferably 1 to 60 minutes, more preferably 2 to 30 minutes, and further preferably 5 to 20 minutes.
  • a protective layer can be laminated on the surface of the photosensitive layer opposite to the surface in contact with the support.
  • a polymer film such as polyethylene or polypropylene may be used.
  • the polymer film similar to the carrier film mentioned above may be used, and a different polymer film may be used.
  • the printed wiring board of this invention comprises the permanent mask resist formed with the photosensitive resin composition of this invention.
  • the permanent mask resist formed from the photosensitive resin composition of the present invention has high rigidity and excellent adhesion to the substrate and the underfill material, so that removal of the permanent mask resist and wiring board warpage are eliminated. A printed wiring board can be obtained.
  • a photosensitive layer is provided on a substrate, for example, a metal-clad laminate such as a copper-clad laminate using the photosensitive resin composition of the present invention or the photosensitive element of the present invention.
  • the obtained solution was cooled to 60 ° C., 2 parts by mass of triphenylphosphine was added, and the mixture was heated to 100 ° C. until the acid value of the solution reached 1 mgKOH / g, and the resin (A ′) was A solution containing was obtained.
  • THPAC tetrahydrophthalic anhydride
  • carbitol acetate 85 parts by mass of carbitol acetate were added, heated to 80 ° C., reacted for about 6 hours, cooled, and the solid content was 73 parts by mass.
  • a solution % THPAC-modified bisphenol F type novolak epoxy acrylate (hereinafter referred to as “acid-modified vinyl group-containing epoxy resin (A-1)”; acid value: 75 mgKOH / g, weight average molecular weight: 10,000) A solution was obtained.
  • Examples 1 to 3, Comparative Examples 1 to 4 Each material shown in the following Table 1 was blended in the blending amount (unit: parts by mass) shown in the same table, then kneaded with a three-roll mill, and carbitol acetate was added so that the solid content concentration became 70% by mass. A photosensitive resin composition was obtained. In addition, the compounding quantity of each material in following Table 1 shows the compounding quantity of solid content.

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Abstract

L'invention fournit une composition de résine photosensible qui permet une amélioration en termes de gauchissement mise en œuvre dans la formation d'une réserve de masque permanent pour carte de circuit imprimé de type mince, et qui est dotée d'une excellente adhérence vis-à-vis d'un substrat, y compris dans des conditions de durcissement rigoureuses. Plus précisément, l'invention concerne une composition de résine photosensible qui comprend une résine époxy comprenant un groupe vinyle modifié par un acide (A), un monomère photopolymérisable (B) possédant une liaison éthyléniquement insaturée, un initiateur de photopolymérisation (C), une charge inorganique (D), et un agent de durcissement (E) comprenant un composé mélamine. La teneur en charge inorganique (D), est comprise entre 30 et 60% en masse de la quantité totale de matière solide contenue dans la composition de résine photosensible. La teneur en agent de durcissement (E) est comprise entre 75 et 140 parties en masse pour 100 parties en masse de résine époxy comprenant un groupe vinyle modifié par un acide (A).
PCT/JP2017/013343 2017-03-30 2017-03-30 Composition de résine photosensible, film durci à motif ainsi que procédé de fabrication de celui-ci, élément photosensible, et carte de circuit imprimé ainsi que procédé de fabrication de celle-ci Ceased WO2018179260A1 (fr)

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CN114270261A (zh) * 2019-08-14 2022-04-01 昭和电工材料株式会社 感光性树脂组合物、感光性树脂膜、多层印刷配线板和半导体封装体、以及多层印刷配线板的制造方法
WO2025066478A1 (fr) * 2023-09-28 2025-04-03 太阳油墨（苏州）有限公司 Composition de résine exempte de mélamine et développable en milieu alcalin, film sec, produit durci et composant électronique comprenant ledit produit durci

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WO2001079325A1 (fr) * 2000-04-18 2001-10-25 Zeon Corporation Composition de resine photosensible
JP2002014466A (ja) * 2000-06-28 2002-01-18 Taiyo Ink Mfg Ltd 感光性樹脂組成物
JP2009251585A (ja) * 2008-04-11 2009-10-29 Hitachi Chem Co Ltd 感光性樹脂組成物及びそれを用いた感光性エレメント
JP2013218146A (ja) * 2012-04-10 2013-10-24 Hitachi Chemical Co Ltd 保護膜用感光性樹脂組成物

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JP2001066794A (ja) * 1999-08-27 2001-03-16 Hitachi Chem Co Ltd レジストパターンの製造法及びレジストパターン
WO2001079325A1 (fr) * 2000-04-18 2001-10-25 Zeon Corporation Composition de resine photosensible
JP2002014466A (ja) * 2000-06-28 2002-01-18 Taiyo Ink Mfg Ltd 感光性樹脂組成物
JP2009251585A (ja) * 2008-04-11 2009-10-29 Hitachi Chem Co Ltd 感光性樹脂組成物及びそれを用いた感光性エレメント
JP2013218146A (ja) * 2012-04-10 2013-10-24 Hitachi Chemical Co Ltd 保護膜用感光性樹脂組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114270261A (zh) * 2019-08-14 2022-04-01 昭和电工材料株式会社 感光性树脂组合物、感光性树脂膜、多层印刷配线板和半导体封装体、以及多层印刷配线板的制造方法
WO2025066478A1 (fr) * 2023-09-28 2025-04-03 太阳油墨（苏州）有限公司 Composition de résine exempte de mélamine et développable en milieu alcalin, film sec, produit durci et composant électronique comprenant ledit produit durci

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