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WO2017170958A1 - Composition de résine durcissable, film sec, produit durci et carte imprimée - Google Patents

Composition de résine durcissable, film sec, produit durci et carte imprimée Download PDF

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Publication number
WO2017170958A1
WO2017170958A1 PCT/JP2017/013453 JP2017013453W WO2017170958A1 WO 2017170958 A1 WO2017170958 A1 WO 2017170958A1 JP 2017013453 W JP2017013453 W JP 2017013453W WO 2017170958 A1 WO2017170958 A1 WO 2017170958A1
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WIPO (PCT)
Prior art keywords
resin composition
curable resin
group
cured product
resin
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PCT/JP2017/013453
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English (en)
Japanese (ja)
Inventor
千穂 植田
岡田　和也
信人 伊藤
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太陽インキ製造株式会社
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Application filed by 太陽インキ製造株式会社 filed Critical 太陽インキ製造株式会社
Priority to KR1020187031079A priority Critical patent/KR102369508B1/ko
Priority to JP2018509482A priority patent/JP6967508B2/ja
Priority to CN201780018353.6A priority patent/CN109073969B/zh
Publication of WO2017170958A1 publication Critical patent/WO2017170958A1/fr
Priority to JP2021173393A priority patent/JP2022009428A/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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 a curable resin composition, a dry film, a cured product, and a printed wiring board.
  • IC package instead of IC packages called QFP (Quad Flat Pack Package), SOP (Small Outline Package), etc., BGA (Ball Grid Array), CSP (Chip Scale Package), etc. IC package called is used.
  • FC-BGA Flexible Chip Ball Grid Array
  • FC-BGA Flexible Resist Opening
  • a printed wiring board also referred to as a package substrate
  • SRO solder Resist Opening
  • Patent Document 1 discloses that the crack resistance is improved by an elastomer.
  • an object of the present invention is to provide a curable resin composition capable of obtaining a cured product having excellent crack resistance when a high temperature load is applied, a dry film having a resin layer obtained from the composition, the composition or the dry composition. It is providing the hardened
  • Stress mainly consists of (1) stress generated by thermal linear expansion (CTE) difference between solder resist and peripheral members (copper, base material, etc.), and (2) gas generated by thermal history during packaging (solder resist And (3) stress (strain) generated by the crosslinking reaction in the solder resist due to the thermal history after mounting.
  • CTE thermal linear expansion
  • strain stress generated by the crosslinking reaction in the solder resist due to the thermal history after mounting.
  • a method of blending an elastomer or the like into a solder resist to relieve stress or a method of reducing the solder resist to a high glass transition temperature (Tg) and a low CTE is based on the stress generated in (1) above.
  • the behavior of the viscous component by DMA is a very important physical property for predicting the characteristics of a solder resist whose Tg is lower than the melting temperature of the solder.
  • the change behavior of Tan ⁇ obtained by DMA has an important meaning, and a material having a large maximum value of the Tan ⁇ peak (for example, a material having physical properties as shown in FIG. 1) depends on mounting electronic components. A material that is flexible and flexible for the purpose of relieving mechanical stress is considered to be suitable.
  • a material having a small maximum value of Tan ⁇ peak for example, a material having physical properties as shown in FIG. 2). Found that it is rigid and less temperature dependent so as not to lose stress.
  • the Tan ⁇ value of DMA is 0.15 or less, the viscosity component in the cured product is small. It is possible to suppress the reaction from proceeding in part or causing a change in physical properties due to sparse cross-linking structure due to molecular motion in the vicinity of Tg. That is, since there is little temperature dependence and there are few physical property changes before and after Tg, the stress which generate
  • the average particle diameter of the inorganic filler is set to a specific range, a specific reactive group is introduced into the inorganic filler, and the epoxy equivalent of the epoxy resin is within a specific value range. From the viewpoint that the cross-linking becomes dense, it has been found that it is effective for the stress (2).
  • the curable resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a thermosetting component, (C) a compound having an ethylenically unsaturated group, (D) a photopolymerization initiator, and (E ) A resin composition containing a surface-treated inorganic filler, wherein the (E) surface-treated inorganic filler has an average particle size of 100 nm to 1 ⁇ m, and (A) the alkali-soluble resin, It has a reactive group capable of reacting with at least one of the (B) thermosetting component and the (C) compound having an ethylenically unsaturated group, and as the (B) thermosetting component, an epoxy equivalent of 300 g / eq.
  • the curable resin composition of the present invention has an epoxy equivalent of 300 g / eq.
  • the following epoxy resins preferably include (B-1) a bifunctional or higher functional epoxy resin having a softening point of 40 ° C. or lower and (B-2) a bifunctional or higher functional epoxy resin having a softening point of 40 ° C. or lower.
  • the compounding amount of the compound (C) having an ethylenically unsaturated group is preferably less than 20 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin.
  • the blending amount of the (E) surface-treated inorganic filler is preferably 35% by mass or more in the solid content of the curable resin composition.
  • the curable resin composition of the present invention has a storage elastic modulus of 150 ° C. when a dynamic viscoelasticity measurement is performed from 25 ° C. to 300 ° C. under the conditions of a frequency of 1 Hz and a heating rate of 5 ° C./min. It is preferably 1 GPa or more and the change rate of the storage elastic modulus from 25 ° C. to 150 ° C. is within 70%.
  • CTE ⁇ 2 of the cured product is preferably 110 ppm or less.
  • the Tg of the cured product is preferably 160 ° C. or higher.
  • the curable resin composition of the present invention is preferably used for forming a solder resist.
  • the dry film of the present invention is characterized by having a resin layer obtained by applying the curable resin composition to the film and drying it.
  • the cured product of the present invention is obtained by curing the curable resin composition or the resin layer of the dry film.
  • the printed wiring board of the present invention is characterized by having the cured product.
  • the curable resin composition which can obtain the hardened
  • the cured product of the resin layer and a printed wiring board having the cured product can be provided.
  • FIG. 1 is an image diagram showing storage elastic modulus, loss elastic modulus, and Tan ⁇ of a cured product having a large maximum value of Tan ⁇ peak.
  • FIG. 2 is an image diagram showing storage elastic modulus, loss elastic modulus, and Tan ⁇ of a cured product having a small maximum value of Tan ⁇ peak.
  • the curable resin composition of the present invention is such that the maximum value of Tan ⁇ of the cured product is 0.15 or less in the temperature range of 25 to 300 ° C. With such physical properties, the temperature of the cured film is low. Stable crack resistance can be obtained even when exposed to high temperatures.
  • the physical properties of the cured product such as Tan ⁇ are further provided with a high-pressure mercury lamp after irradiating the resin layer after drying the resin composition with ultraviolet rays at about 500 mJ / cm 2. It means physical properties of a cured product having a thickness of 40 ⁇ m obtained by irradiating with an exposure amount of 1 J / cm 2 in a UV conveyor furnace and then heating at 160 ° C.
  • the measured physical properties such as Tan ⁇ are based on a chart obtained by measuring from 25 ° C. to 300 ° C. under the conditions of a frequency of 1 Hz and a heating rate of 5 ° C./min.
  • the loss elastic modulus (viscous component) is decreased, the storage elastic modulus (elastic component) is increased, or both are performed. In other words, the elastic component may be increased as much as possible in the cured product rather than the viscous component.
  • Means for setting the maximum value of Tan ⁇ to 0.15 or less is not particularly limited, but the average particle diameter is 100 nm to 1 ⁇ m, and (A) an alkali-soluble resin, (B) a thermosetting component, and (C) ethylene.
  • E When the average particle diameter of an inorganic filler is 1 micrometer or less, the surface area per volume is large and it can have many said reactive groups. On the other hand, when the average particle size is 100 nm or more, the shrinkage of the cured product is suppressed and the crack resistance is improved.
  • Epoxy equivalent is 300 g / eq. As a thermosetting component.
  • the number of cross-linking points with (A) alkali-soluble resin increases, so that the cross-linking density increases and unreacted (A) alkali-soluble resin and the like can be reduced.
  • the maximum value of Tan ⁇ is reduced, the cured product is less likely to undergo a sudden change in elastic modulus at a high temperature around 150 ° C., and crack resistance is further improved. Therefore, the above (E) inorganic filler and epoxy equivalent are 300 g / eq.
  • the maximum value of Tan ⁇ of the cured product becomes 0.15 or less in the range of 25 to 300 ° C., and stable crack resistance can be obtained. It is preferable that the maximum value of Tan ⁇ is 0.13 or less because crack resistance is further improved.
  • Tan ⁇ of the cured product can be reduced by reducing the blending amount of the compound (C) having an ethylenically unsaturated group.
  • the storage elastic modulus at 150 ° C. of the cured product of the curable resin composition of the present invention may be any value as long as the maximum value of Tan ⁇ of the cured product is 0.15 or less, but is 1 GPa or more. Is preferred. More preferably, it is 2 GPa or more.
  • the storage elastic modulus is 1 GPa or more, resistance of the cured product to the water vapor pressure inside the package is improved, and crack resistance and insulation reliability are improved. Conventionally, in order to obtain crack resistance at high temperatures, it has been preferred that the change in storage elastic modulus is large for stress absorption.
  • the rate of change in the storage elastic modulus is reduced to maintain the toughness even at high temperatures, thereby suppressing the generation of stress and the generation of cracks. It is.
  • the change rate of the storage elastic modulus is small, and the change rate of the storage elastic modulus at 25 ° C. to 150 ° C. is preferably within 70%. More preferably, it is within 65%.
  • the CTE ⁇ 2 of the cured product of the curable resin composition of the present invention is preferably 110 ppm or less, more preferably 100 ppm or less. As CTE ⁇ 2 is smaller, changes in physical properties can be reduced even at high temperatures.
  • the curable resin composition of the present invention preferably has a Tg (glass transition temperature) of 160 ° C. or higher. More preferably, it is 165 ° C. or higher. The higher the Tg, the less the change in physical properties at high temperatures.
  • (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.
  • the alkali-soluble resin is, for example, a resin containing one or more alkali-soluble groups among phenolic hydroxyl groups, thiol groups, and carboxyl groups, preferably a compound having two or more phenolic hydroxyl groups, a carboxyl group-containing resin. , A compound having a phenolic hydroxyl group and a carboxyl group, and a compound having two or more thiol groups.
  • (A) As the alkali-soluble resin a carboxyl group-containing resin or a phenolic hydroxyl group-containing resin can be used, but from the viewpoint of reactivity with (B) a thermosetting component and (E) an inorganic filler, a carboxyl group-containing resin. Is preferred.
  • the alkali-soluble resin having a smaller weight average molecular weight is preferred because the proportion of alkali-soluble groups in the alkali-soluble resin increases and the crosslink density of the cured product increases.
  • the alkali-soluble resin preferably has a weight average molecular weight of 10,000 or less in terms of polystyrene when measured by weight average molecular weight (Mw) gel permeation chromatography (GPC).
  • alkali-soluble resin has an ethylenically unsaturated group in a molecule
  • numerator other than a carboxyl group from a viewpoint of developability, photocurability, and developability.
  • carboxyl group-containing resin those derived from acrylic acid, methacrylic acid or derivatives thereof are preferable.
  • Specific examples of the carboxyl group-containing resin include compounds listed below (which may be either oligomers or polymers).
  • a difunctional or higher polyfunctional epoxy resin is reacted with (meth) acrylic acid, and the hydroxyl group present in the side chain is dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.
  • the bifunctional or higher polyfunctional epoxy resin is preferably solid.
  • a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group.
  • a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group.
  • the bifunctional epoxy resin is preferably solid.
  • An epoxy compound having two or more epoxy groups in one molecule is combined with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and (meth) acrylic acid or the like.
  • the resulting reaction product has many alcoholic hydroxyl groups such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic anhydride.
  • a carboxyl group-containing photosensitive resin obtained by reacting a basic acid anhydride.
  • An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate.
  • a carboxyl group-containing photosensitive resin obtained by reacting the resulting reaction product with a polybasic acid anhydride.
  • Carboxy group-containing photosensitivity obtained by copolymerization of unsaturated carboxylic acid such as (meth) acrylic acid and unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, and isobutylene. resin.
  • unsaturated carboxylic acid such as (meth) acrylic acid
  • unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, and isobutylene. resin.
  • a carboxyl group obtained by reacting a difunctional acid such as adipic acid, phthalic acid or hexahydrophthalic acid with a polyfunctional oxetane resin as described later and adding a dibasic acid anhydride to the resulting primary hydroxyl group Contains polyester resin.
  • a carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth) acryloyl group in one molecule to the carboxyl group-containing resin such as (1) to (7) described above.
  • the main chain derived from a phenol resin or an epoxy resin is separated from the ethylenically unsaturated group of the side chain.
  • a chain extension structure so that a certain distance is generated between the main chain and the ethylenically unsaturated group.
  • Such a structure is preferable for improving the reactivity between side chain ethylenically unsaturated groups.
  • the carboxyl group-containing resin having a chain extension structure and an ethylenically unsaturated group for example, the carboxyl group-containing resins described in (3), (4), (5), and (8) are preferable.
  • the acid value of the alkali-soluble resin is preferably 40 to 150 mgKOH / g.
  • the acid value of the carboxyl group-containing resin is 40 mgKOH / g or more, alkali development is improved.
  • cured material pattern can be drawn easily by making an acid value into 150 mgKOH / g or less. More preferably, it is 50 to 130 mgKOH / g.
  • the blending amount of the alkali-soluble resin is, for example, 15 to 60% by mass, preferably 20 to 60% by mass, based on the total solid content of the composition excluding the solvent.
  • the content By setting the content to 15% by mass or more, preferably 20% by mass or more, the coating film strength can be improved. Further, when the content is 60% by mass or less, viscosity becomes appropriate and workability is improved. More preferably, it is 30 to 50% by mass.
  • the curable resin composition of the present invention has an epoxy equivalent of 300 g / eq.
  • the following epoxy resin is included, and 200 g / eq. Is more preferable from the viewpoint of improving the crosslink density and further improving the crack resistance. It is as follows.
  • Epoxy resin includes epoxidized vegetable oil; bisphenol A type epoxy resin; hydroquinone type epoxy resin; bisphenol type epoxy resin; thioether type epoxy resin; brominated epoxy resin; novolac type epoxy resin; biphenol novolac type epoxy resin; Resin; Hydrogenated bisphenol A type epoxy resin; Glycidylamine type epoxy resin; Hydantoin type epoxy resin; Alicyclic epoxy resin; Trihydroxyphenylmethane type epoxy resin; Alkylphenol type epoxy resin (for example, bixylenol type epoxy resin); Type epoxy resin; bisphenol S type epoxy resin; bisphenol A novolak type epoxy resin; tetraphenylolethane type epoxy resin; Diglycidyl phthalate resin; Tetraglycidyl xylenoyl ethane resin; Naphthalene group-containing epoxy resin; Epoxy resin having dicyclopentadiene skeleton; Triphenylmethane type epoxy resin; Epoxy resin having dicyclopentadiene skeleton; Tripheny
  • An epoxy resin can be used individually by 1 type or in combination of 2 or more types.
  • novolac type epoxy resins bisphenol type epoxy resins, bixylenol type epoxy resins, biphenol type epoxy resins, biphenol novolac type epoxy resins, naphthalene type epoxy resins, epoxy resins having a silsesquioxane skeleton, and triphenylmethane
  • At least one of the type epoxy resins is preferred.
  • Epoxy equivalent is 300 g / eq.
  • the following commercially available epoxy resins include EXP7241 (triphenylmethane type epoxy resin), HP6000 (epoxy resin having a naphthalene group), Epicron N-740 (phenol novolac type epoxy resin) manufactured by DIC, Nippon Steel & Sumikin Chemical Co., Ltd.
  • Examples include Epototo YDC-1312 (hydroquinone type epoxy resin) and YSLV-80XY (bisphenol F type epoxy resin).
  • thermosetting component contains two or more polyfunctional epoxy resins from the viewpoint of lowering Tan ⁇ .
  • polyfunctional means two or more functional groups.
  • the composition of the present invention preferably contains (B-1) a bifunctional or higher functional epoxy resin having a softening point of 40 ° C. or lower as the (B) thermosetting component.
  • B-2) It is preferable to include a mixture with a bifunctional or higher functional epoxy resin having a softening point exceeding 40 ° C. (B-1) By including a bifunctional or higher functional epoxy resin with a softening point of 40 ° C.
  • (E) it is possible to achieve high filling of inorganic fillers, resulting in low CTE and low Tan ⁇ , and crack resistance in thermal cycle tests. Will improve.
  • (B-2) by including a bifunctional or higher functional epoxy resin having a softening point exceeding 40 ° C., the glass transition temperature (Tg) of the entire curable resin composition can be increased. As a result, heat resistance such as PCT resistance and reliability such as crack resistance in a thermal cycle test can be further improved.
  • the softening point means a value measured according to the method described in JIS K 7234.
  • the bifunctional or higher functional epoxy resin having a softening point of 40 ° C. or lower may be a known resin, but is preferably liquid at room temperature, for example.
  • B-1 Commercially available bifunctional or higher functional epoxy resins having a softening point of 40 ° C.
  • the content of the (B-1) bifunctional or higher functional epoxy resin having a softening point of 40 ° C. or lower is such that (B-1) the softening point is 40 ° C. or lower with respect to 1 equivalent of the alkali-soluble group of the alkali-soluble resin.
  • the epoxy group of the bifunctional or higher functional epoxy resin is preferably in the range of 0.2 to 1.8 equivalents.
  • the softening point of the bifunctional or higher functional epoxy resin having a softening point of 40 ° C. or lower is preferably ⁇ 80 to 30 ° C., more preferably ⁇ 70 to 20 ° C.
  • B-2 Commercially available bifunctional or higher functional epoxy resins having a softening point exceeding 40 ° C. include, for example, ICTEP-S (softening point: 110 ° C.), TEPIC-H, N870, DIC manufactured by Nissan Chemical Co., Ltd.
  • HP-7200 softening point: 60 ° C
  • HP-4700 softening point: 90 ° C
  • HP-4710 softening point: 96 ° C
  • EXA-7241 softening point: 70 ° C
  • NC-3000L softening point: 52 ° C
  • NC-7000L softening point: 86 ° C
  • CER-3000L softening point: 93 ° C
  • EPPN-502H softening point: 67 ° C.
  • Epototo YSLV-80XY softening point: 80 ° C.
  • EPICLON-N660 softening point: 61 to 69 ° C.
  • YDC-1312 softening point: 140 ° C.
  • the softening point of a bifunctional or higher functional epoxy resin having a softening point exceeding 40 ° C. is preferably 50 ° C. or higher, and more preferably 60 ° C. or higher.
  • the upper limit of the softening point in the (B-2) bifunctional or higher functional epoxy resin having a softening point exceeding 40 ° C. is not particularly limited, but is about 400 ° C. or lower. It is preferable that it is 80 degrees C or less from a viewpoint of the workability at the time of forming into a dry film.
  • the blending ratio of (B-1) a bifunctional or higher functional epoxy resin having a softening point of 40 ° C. or less and (B-2) an epoxy resin having a softening point of more than 40 ° C. is (B-1) the softening point is 40 ° C. or less.
  • Equivalent ratio of epoxy group (b-1) of bifunctional or higher epoxy resin to (B-2) epoxy group (b-2) of bifunctional or higher epoxy resin having a softening point exceeding 60 ° C. (b-1) : (B-2) is preferably 3: 7 to 9: 1, more preferably 4: 6 to 8: 2. When the ratio of the epoxy group (b-1) is 3 to 9, it is possible to achieve both low Tan ⁇ and high Tg.
  • Epoxy equivalent is 300 g / eq.
  • the following epoxy resin it is particularly preferable to include a trifunctional or higher functional epoxy resin from the viewpoint of increasing the crosslinking density among the epoxy resins.
  • the structure of the tri- or higher functional epoxy resin is not particularly limited as long as it is an epoxy resin having three or more epoxy groups. Among them, the epoxy equivalent is 200 g / eq. From the viewpoint of further increasing the crosslinking density.
  • the following trifunctional or higher epoxy resins are more preferable.
  • an epoxy resin having a silsesquioxane skeleton can be more suitably used as the thermosetting component.
  • the epoxy resin having a silsesquioxane skeleton is a silsesquioxane, that is, a network polymer or polyhedral cluster having a structure of (RSiO 1.5 ) n obtained by hydrolyzing a trifunctional silane.
  • Any compound having an epoxy group-containing group is not particularly limited. Each silicon of silsesquioxane is bonded with an average of 1.5 oxygen atoms and one hydrocarbon group.
  • the epoxy resin having a silsesquioxane skeleton preferably has a silsesquioxane skeleton represented by the following general formula (1).
  • R 1 to R 4 are each independently a group having a SiO bond or an organic group, and at least one of R 1 to R 4 is a group having an epoxy group
  • a group refers to a group containing a carbon atom.
  • the structure of the silsesquioxane is not particularly limited, and a silsesquioxane having a known and conventional structure such as a random structure, a ladder structure, a complete cage structure, or an incomplete cage structure can be used.
  • the group having an SiO bond that R 1 to R 4 can take is not particularly limited, a group having an SiO bond and an aliphatic skeleton, a group having an SiO bond and an aromatic skeleton, a group having an SiO bond and a hetero atom, and the like And is preferably within the range of the equivalent of the above thermosetting functional group (epoxy group).
  • the organic group containing a carbon atom that can be taken by R 1 to R 4 is not particularly limited, and examples thereof include an aliphatic group such as a methyl group, an aromatic group such as a phenyl group, and a group having a hetero atom.
  • the organic group is preferably an organic group having 1 to 30 carbon atoms, and is preferably within an equivalent range of the thermosetting functional group (epoxy group).
  • At least one of R 1 to R 4 is a group having an epoxy group, and the group having an epoxy group is not particularly limited as long as the group having SiO bond or the organic group has an epoxy group. .
  • thermosetting component is, for example, 1 to 100 parts by weight, preferably 10 to 80 parts by weight, and more preferably 20 to 60 parts by weight with respect to 100 parts by weight of the (A) alkali-soluble resin.
  • the curable resin composition of the present invention has an epoxy equivalent of 300 g / eq. Within the range not impairing the effects of the present invention.
  • epoxy resins such as melamine resin, benzoguanamine resin, melamine derivative, benzoguanamine derivative, isocyanate compound, block isocyanate compound, cyclocarbonate compound, epoxy equivalent is 300 g / eq.
  • Known compounds such as epoxy resins, oxetane compounds, episulfide resins, bismaleimides, carbodiimide resins, and the like can be used.
  • the compound having a plurality of cyclic (thio) ether groups in the molecule is a compound having a plurality of 3, 4 or 5-membered cyclic (thio) ether groups in the molecule.
  • a compound having a group that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, that is, a polyfunctional episulfide resin.
  • the curable resin composition of the present invention contains (C) a compound having an ethylenically unsaturated group.
  • a compound having an ethylenically unsaturated group a compound having one or more ethylenically unsaturated groups in the molecule is preferably used.
  • a photopolymerizable oligomer, a photopolymerizable vinyl monomer, or the like, which is a conventionally known compound having an ethylenically unsaturated group can be used.
  • the compound (C) having an ethylenically unsaturated group mentioned here does not include (A) an alkali-soluble resin having an ethylenically unsaturated group and (E) a surface-treated inorganic filler. .
  • Examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers.
  • Examples of (meth) acrylate oligomers include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, epoxy (meth) acrylates such as bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meta ) Acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate, and the like.
  • photopolymerizable vinyl monomer known and commonly used monomers, for example, styrene derivatives such as styrene, chlorostyrene and ⁇ -methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl- vinyl ethers such as n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide (Meth) acrylamides such as rilamide and N-butoxymethylacrylamide; allyl compounds such as triallyl isocyan
  • the compounding amount of the compound (C) having an ethylenically unsaturated group is preferably less than 20 parts by mass, more preferably 5 to 18 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. More preferably, it is 10 to 15 parts by mass.
  • (C) By reducing the compounding quantity of the compound which has an ethylenically unsaturated group, the compound which has an unreacted ethylenically unsaturated group in hardened
  • photopolymerization initiator Any photopolymerization initiator may be used as long as it is a known photopolymerization initiator as a photopolymerization initiator or a photoradical generator.
  • photopolymerization initiator examples include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) -phenylphosphine oxide Bisacylphosphine oxides such as (IR
  • a photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type.
  • monoacylphosphine oxides and oxime esters are preferable, and oxime esters having high sensitivity are most preferable.
  • the oxime esters preferably have one or more oxime ester groups.
  • ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- , 1- (O-acetyloxime) is more preferred.
  • the blending amount of the photopolymerization initiator is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin.
  • the amount is 0.5 parts by mass or more, the surface curability is good, and when the amount is 20 parts by mass or less, halation hardly occurs and good resolution is obtained.
  • the curable resin composition of the present invention has an average particle size of 100 nm to 1 ⁇ m and (A) an alkali-soluble resin, (B) a thermosetting component, and (C) at least one compound having an ethylenically unsaturated group, Contains (E) a surface-treated inorganic filler having a reactive group capable of reacting.
  • the inorganic filler is not particularly limited, and known and commonly used fillers such as silica, crystalline silica, Neuburg silica, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic mica Inorganic fillers such as aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate and zinc white can be used.
  • silica is preferable, and since the surface area is small and stress is dispersed throughout, it is difficult to become a starting point of cracks, and from the viewpoint of excellent resolution, spherical silica is more preferable.
  • Examples of the reactive group of the (E) surface-treated inorganic filler include (meth) acryloyl group, vinyl group, cyclic (thio) ether group, acidic group, and basic group.
  • Examples of the cyclic (thio) ether group include an epoxy group, an oxetanyl group, and an episulfide group.
  • Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, an alcoholic hydroxyl group, a thiol group, a sulfone group, and a phosphate group.
  • Examples of the basic group include an amino group, an amide group, and an ammonium group.
  • the reactive group of the surface-treated inorganic filler is preferably any one of a (meth) acryloyl group, a vinyl group, and a cyclic (thio) ether group.
  • the reactive group of the surface-treated inorganic filler is a cyclic (thio) ether group, it is excellent in (A) reactivity with an alkali-soluble resin, and is a (meth) acryloyl group or vinyl group (A) ) Excellent reactivity with the ethylenically unsaturated group of the alkali-soluble resin.
  • the method for introducing the reactive group into the inorganic filler is not particularly limited, and may be introduced using a known and commonly used method.
  • the surface treatment agent having the reactive group for example, the coupling having the reactive group.
  • the surface of the inorganic filler may be treated with an agent or the like.
  • a surface treatment with a coupling agent is preferable.
  • a silane coupling agent a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, or the like can be used. Among these, a silane coupling agent is preferable.
  • silane coupling agent capable of introducing the reactive group into the inorganic filler examples include a silane coupling agent having a vinyl group, a silane coupling agent having a methacryl group, a silane coupling agent having an acrylic group, and an epoxy group.
  • examples of the silane coupling agent include a silane coupling agent and a carboxyl group-containing silane coupling agent, and among them, a silane coupling agent having at least one of a (meth) acryl group and a vinyl group is preferable.
  • the surface-treated inorganic filler should just be mix
  • a pre-dispersion liquid in which an inorganic filler is pre-dispersed in a solvent or a resin component is more preferable that the pre-dispersed liquid is blended in the composition after blending or sufficiently surface-treating when the surface-untreated inorganic filler is pre-dispersed in the solvent.
  • the average particle size of the surface-treated inorganic filler is preferably 100 to 800 nm, more preferably 100 to 700 nm, and even more preferably 200 to 700 nm.
  • the average particle diameter of the surface-treated inorganic filler is not only the particle diameter of the primary particles but also the average particle diameter including the particle diameter of the secondary particles (aggregates) (D50 ).
  • the average particle size can be determined by a laser diffraction particle size distribution measuring device. Examples of the measuring apparatus using the laser diffraction method include Nanotrac wave manufactured by Nikkiso Co., Ltd.
  • thermosetting catalyst The curable resin composition of the present invention preferably contains a thermosetting catalyst.
  • thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole.
  • Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine.
  • the blending amount of the thermosetting catalyst is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the (B) thermosetting component.
  • the curable resin composition of the present invention can contain a curing agent.
  • the curing agent include phenol resins, polycarboxylic acids and acid anhydrides thereof, cyanate ester resins, active ester resins, maleimide compounds, and alicyclic olefin polymers.
  • curing agent can be used individually by 1 type or in combination of 2 or more types.
  • the curable resin composition of the present invention may contain a colorant.
  • a colorant known colorants such as red, blue, green, yellow, black, and white can be used, and any of pigments, dyes, and pigments may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.
  • the addition amount of the colorant is not particularly limited, but is preferably 10 parts by mass or less, particularly preferably 0.1 to 7 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin.
  • the curable resin composition of the present invention can contain an organic solvent for the purpose of preparing the composition and adjusting the viscosity when applied to a substrate or a carrier film.
  • organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether , Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol
  • additives include thermal polymerization inhibitors, UV absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial / antifungal agents, antifoaming agents, leveling agents, thickening agents Agent, adhesion imparting agent, thixotropic agent, photoinitiator aid, sensitizer, thermoplastic resin, organic filler, mold release agent, surface treatment agent, dispersant, dispersion aid, surface modifier, stabilizer , Phosphor, AB type or ABA type block copolymer, and the like.
  • the curable resin composition of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-component or two-component or more.
  • the dry film of the present invention has a resin layer obtained by applying and drying the curable resin composition of the present invention on a carrier film.
  • the curable resin composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and then a comma coater, a blade coater, a lip coater, a rod coater, and a squeeze coater. Apply a uniform thickness on the carrier film using a reverse coater, transfer roll coater, gravure coater, spray coater or the like. Thereafter, the applied composition is usually dried at a temperature of 40 to 130 ° C. for 1 to 30 minutes to form a resin layer.
  • the coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 3 to 150 ⁇ m, preferably 5 to 60 ⁇ m.
  • a plastic film is used as the carrier film.
  • a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used.
  • the thickness of the carrier film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 ⁇ m. More preferably, it is in the range of 15 to 130 ⁇ m.
  • the peelable cover film for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used.
  • a cover film what is necessary is just a thing smaller than the adhesive force of a resin layer and a carrier film when peeling a cover film.
  • the resin layer may be formed by applying and drying the curable resin composition of the present invention on the cover film, and a carrier film may be laminated on the surface. That is, as the film to which the curable resin composition of the present invention is applied when producing a dry film in the present invention, either a carrier film or a cover film may be used.
  • the printed wiring board of the present invention has a curable resin composition of the present invention or a cured product obtained from a resin layer of a dry film.
  • the curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using the organic solvent, and a dip coating method is performed on a substrate.
  • the organic solvent contained in the composition is volatilized and dried (temporary drying) at a temperature of 60 to 100 ° C.
  • a tack-free resin layer is formed.
  • a resin layer is formed on a base material by peeling a carrier film.
  • Examples of the base material include printed wiring boards and flexible printed wiring boards that have been previously formed with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy.
  • PEN polyethylene naphthalate
  • Volatile drying performed after the application of the curable resin composition of the present invention is performed in a dryer using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (equipped with a heat source of an air heating method using steam).
  • the method can be carried out using a method in which hot air is brought into countercurrent contact and a method in which the hot air is blown onto the support.
  • a resin layer on the printed wiring board After forming a resin layer on the printed wiring board, it is selectively exposed with active energy rays through a photomask having a predetermined pattern, and the unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3 to 3 mass% sodium carbonate aqueous solution). ) To form a cured product pattern. Further, the cured product is irradiated with active energy rays and then heat-cured (for example, 100 to 220 ° C.), irradiated with active energy rays after heat-curing, or is subjected to final finish curing (main curing) only by heat-curing. A cured film having excellent properties such as properties and hardness is formed.
  • a dilute alkaline aqueous solution for example, 0.3 to 3 mass% sodium carbonate aqueous solution.
  • the exposure apparatus used for the active energy ray irradiation may be any apparatus that irradiates ultraviolet rays in the range of 350 to 450 nm, equipped with a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, etc.
  • a direct drawing apparatus for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer
  • the lamp light source or laser light source of the direct drawing machine may have a maximum wavelength in the range of 350 to 450 nm.
  • the exposure amount for image formation varies depending on the film thickness and the like, but can be generally in the range of 10 to 1000 mJ / cm 2 , preferably 20 to 800 mJ / cm 2 .
  • the developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.
  • the curable resin composition of the present invention is preferably used for forming a cured film on a printed wiring board, more preferably used for forming a permanent film, and more preferably a solder resist, Used to form interlayer insulation layers and coverlays. Further, it is suitable for forming a printed wiring board having a fine pitch wiring pattern which requires a high degree of reliability, such as a package substrate, particularly a permanent film (particularly a solder resist) for FC-BGA.
  • a cured product having excellent crack resistance when a high temperature load is applied can be obtained, which is suitable for applications exposed to high temperature conditions such as in-vehicle applications.
  • reaction solution was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide.
  • the nonvolatile content was 62.1%, and the hydroxyl value was 182.2 mgKOH / g (307. 9 g / eq.) Of a novolak-type cresol resin propylene oxide reaction solution. This was an average of 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
  • reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution.
  • 332.5 parts of the obtained novolak acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was supplied at a rate of 10 ml / min.
  • Examples 1 to 17, Comparative Examples 1 to 5 The above resin solution (varnish) was blended together with various components shown in Tables 1 to 3 in proportions (parts by mass) shown in Tables 1 to 3, premixed with a stirrer, and then kneaded with a three-roll mill, A curable resin composition was prepared.
  • the curable resin composition obtained as described above was diluted by adding 300 g of methyl ethyl ketone, and stirred for 15 minutes with a stirrer to obtain a coating solution.
  • the coating solution is applied onto a 38 ⁇ m thick polyethylene terephthalate film (Embret PTH-25 manufactured by Unitika Co., Ltd.) having an arithmetic surface roughness Ra of 150 nm, usually dried at a temperature of 80 ° C. for 15 minutes, and a photosensitive material having a thickness of 20 ⁇ m.
  • a functional resin layer was formed.
  • a 18 ⁇ m-thick polypropylene film (OPP-FOA manufactured by Futamura Co., Ltd.) was bonded onto the photosensitive resin layer to produce a photosensitive dry film.
  • the polyethylene film is peeled from the photosensitive dry film obtained as described above, and the photosensitive resin layer of the photosensitive dry film is bonded to the copper foil surface side.
  • a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.)
  • the substrate and the photosensitive resin layer were laminated by heating and laminating under conditions of pressure: 0.8 MPa, 70 ° C., 1 minute, and vacuum: 133.3 Pa. Adhered.
  • the photosensitive dry film is exposed (exposure amount: 400 to 600 mJ / cm 2 ), and then the polyethylene terephthalate film is peeled off from the photosensitive dry film.
  • the photosensitive resin layer was exposed. Thereafter, development was performed for 60 seconds under conditions of 30 ° C. and a spray pressure of 2 kg / cm 2 using a 1 wt% Na 2 CO 3 aqueous solution to form a resin layer having a predetermined resist pattern. Subsequently, the resin layer was irradiated with an exposure amount of 1 J / cm 2 in a UV conveyor furnace equipped with a high-pressure mercury lamp, and then heated at 160 ° C. for 60 minutes to completely cure the resin layer to prepare a cured coating film.
  • a high-pressure mercury lamp short arc lamp
  • ⁇ Crack resistance (TCT resistance)> The surface of a circuit board (50 mm ⁇ 50 mm ⁇ 0.4 mmt) with a 250 ⁇ m bump pitch to be connected to C4 is chemically polished, the polyethylene film is peeled off from the photosensitive dry film obtained as described above, and the surface is polished. Next, the photosensitive resin layer of the photosensitive dry film was bonded to the surface on the other side, and subsequently, using a vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho), the degree of pressure was 0.8 MPa, 70 ° C., 1 minute, Vacuum lamination was performed under the condition of 133.3 Pa, and the substrate and the photosensitive resin layer were brought into close contact with each other.
  • MVLP-500 vacuum laminator
  • a polyethylene terephthalate film is formed from the photosensitive dry film. It peeled and the photosensitive resin layer was exposed. Thereafter, development was performed for 60 seconds under conditions of 30 ° C. and a spray pressure of 2 kg / cm 2 using a 1 wt% Na 2 CO 3 aqueous solution to form a resin layer having a predetermined resist pattern.
  • the resin layer was irradiated with an exposure amount of 1 J / cm 2 in a UV conveyor furnace equipped with a high-pressure mercury lamp, and then heated at 160 ° C. for 60 minutes to completely cure the resin layer to form a cured film.
  • a TST evaluation substrate provided with a cured coating thereon was produced.
  • heat treatment was performed at 125 ° C. for 24 hours as preconditioning, and humidification treatment was performed at 60 ° C. and humidity 60% for 48 hours, and reflow 260 ° C. was performed three times.
  • the obtained substrate was put into a thermal cycle machine in which a temperature cycle between ⁇ 65 ° C. and 175 ° C.
  • NC-3000L (biphenylene type epoxy resin, epoxy equivalent: 273 g / eq., Bifunctional, softening point: 52 ° C.) * 23: EXA-7241 manufactured by DIC (triphenylmethane type epoxy resin, epoxy equivalent: 168 g / eq., Trifunctional, softening point: 70 ° C.) * 24: EPICLON-N660 manufactured by DIC (cresol novolac type epoxy resin, epoxy equivalent: 210 g / eq., Bifunctional, softening point: 61 to 69 ° C.)

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  • Polymers & Plastics (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
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  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
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Abstract

L'invention concerne : une composition de résine durcissable qui peut fournir un produit durci qui présente une excellente résistance à la fissuration lorsqu'une charge à température élevée est appliquée à celui-ci ; et analogue. L'invention concerne une composition de résine durcissable qui contient (A) une résine soluble dans les alcalis, (B) un composant thermodurcissable, (C) un composé ayant un groupe éthyléniquement insaturé, (D) un initiateur de photopolymérisation et (E) une charge minérale traitée en surface, et qui est caractérisée en ce que : la charge minérale (E) a un diamètre de particule moyen de 100 nm à 1 µm, et comprend un groupe réactif qui peut réagir avec la résine soluble dans les alcalis (A) et/ou le composant thermodurcissable (B) et/ou le composé (C) ayant un groupe éthyléniquement insaturé ; une résine époxy ayant un poids équivalent époxy inférieur ou égal à 300 g/éq. est contenue en tant que composant thermodurcissable (B) ; et par rapport à un produit durci obtenu à partir de la composition de résine et ayant une épaisseur de 40 µm, la valeur maximale de Tan δ déterminée par la mesure de viscoélasticité dynamique effectuée à une fréquence de 1 Hz à une vitesse de chauffage de 5 °C/min depuis 25 °C jusqu' à 300 °C est inférieure ou égale à 0,15.
PCT/JP2017/013453 2016-03-31 2017-03-30 Composition de résine durcissable, film sec, produit durci et carte imprimée WO2017170958A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018123695A1 (fr) * 2016-12-28 2018-07-05 太陽インキ製造株式会社 Composition durcissable, résine de base, agent de durcissement, film sec, produit durci, et carte à circuit imprimé
JP2018151628A (ja) * 2017-03-10 2018-09-27 日本化薬株式会社 感光性樹脂組成物、その硬化物及び物品
WO2019131353A1 (fr) * 2017-12-25 2019-07-04 ペルノックス株式会社 Composition et pâte thermodurcissables
JP2019178304A (ja) * 2018-03-30 2019-10-17 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板
JP2020052362A (ja) * 2018-09-28 2020-04-02 太陽インキ製造株式会社 硬化物の製造方法、これに用いる感光性樹脂組成物、ドライフィルム、硬化物および電子部品
KR20200055123A (ko) * 2018-08-27 2020-05-20 고오 가가쿠고교 가부시키가이샤 감광성 수지 조성물, 드라이 필름, 및 프린트 배선판
JP2022019406A (ja) * 2020-07-17 2022-01-27 味の素株式会社 感光性樹脂組成物
JP2022037501A (ja) * 2020-08-25 2022-03-09 味の素株式会社 感光性樹脂組成物

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* Cited by examiner, † Cited by third party
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JP7316071B2 (ja) * 2019-03-18 2023-07-27 太陽ホールディングス株式会社 硬化性樹脂組成物、ドライフィルム、硬化物および電子部品
JPWO2021182365A1 (fr) * 2020-03-09 2021-09-16
CN113801433B (zh) * 2020-06-12 2025-07-04 味之素株式会社 树脂组合物
JP7554585B2 (ja) * 2020-06-15 2024-09-20 日東電工株式会社 接着シート
WO2023190455A1 (fr) * 2022-03-29 2023-10-05 太陽ホールディングス株式会社 Composition de résine photosensible, produit durci, carte de circuit imprimé et procédé de production de carte de circuit imprimé

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011164270A (ja) * 2010-02-08 2011-08-25 Taiyo Holdings Co Ltd 光硬化性樹脂組成物、ドライフィルム、硬化物及びプリント配線板
WO2013022068A1 (fr) * 2011-08-10 2013-02-14 日立化成工業株式会社 Composition de résine photosensible, film photosensible, réserve permanente et procédé de production de réserve permanente
JP2013228722A (ja) * 2012-03-27 2013-11-07 Taiyo Ink Mfg Ltd 難燃性硬化性樹脂組成物、ドライフィルム、難燃性被膜およびプリント配線板
JP2014156601A (ja) * 2013-01-15 2014-08-28 Taiyo Ink Mfg Ltd 硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP2014160271A (ja) * 2014-04-16 2014-09-04 Hitachi Chemical Co Ltd 感光性樹脂組成物及び感光性フィルム、永久レジスト
JP2016038587A (ja) * 2014-08-08 2016-03-22 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板
JP2016177174A (ja) * 2015-03-20 2016-10-06 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3247091B2 (ja) 1997-11-28 2002-01-15 日立化成工業株式会社 光硬化性樹脂組成物及びこれを用いた感光性エレメント
CN1325532C (zh) * 2002-04-15 2007-07-11 东亚合成株式会社 活性能量线固化型树脂组合物和其固化物
JP4997038B2 (ja) * 2007-07-27 2012-08-08 株式会社ブリヂストン 更生タイヤ用トレッド及び更生タイヤ
JP2012073601A (ja) * 2010-08-31 2012-04-12 Fujifilm Corp 感光性組成物、並びに、感光性フィルム、永久パターン、永久パターン形成方法、及びプリント基板
JP5620017B2 (ja) * 2011-12-27 2014-11-05 太陽インキ製造株式会社 ドライフィルム、積層構造体、プリント配線板、及び積層構造体の製造方法
KR101473556B1 (ko) * 2012-03-27 2014-12-16 다이요 잉키 세이조 가부시키가이샤 난연성 경화성 수지 조성물, 드라이 필름, 난연성 피막 및 인쇄 배선판
WO2013146251A1 (fr) 2012-03-29 2013-10-03 株式会社村田製作所 Composant de bobine
WO2013161756A1 (fr) * 2012-04-23 2013-10-31 日立化成株式会社 Composition de résine photosensible, film photosensible, réserve de masque permanent et procédé de production de réserve de masque permanent
JP6240399B2 (ja) * 2012-05-29 2017-11-29 太陽インキ製造株式会社 感光性組成物及びその硬化層を有するプリント配線板
JP5576545B1 (ja) * 2013-03-11 2014-08-20 太陽インキ製造株式会社 光硬化性樹脂組成物、そのドライフィルムおよび硬化物、並びにそれらを用いて形成された硬化皮膜を有するプリント配線板
JP5572737B1 (ja) * 2013-06-04 2014-08-13 太陽インキ製造株式会社 光硬化熱硬化性樹脂組成物、硬化物、及びプリント配線板
JP5660692B2 (ja) * 2013-12-02 2015-01-28 太陽ホールディングス株式会社 感光性ドライフィルム及びそれを用いた積層構造体
CN106662813B (zh) * 2014-06-12 2021-02-26 太阳油墨制造株式会社 固化性树脂组合物、干膜、固化物及印刷电路板

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011164270A (ja) * 2010-02-08 2011-08-25 Taiyo Holdings Co Ltd 光硬化性樹脂組成物、ドライフィルム、硬化物及びプリント配線板
WO2013022068A1 (fr) * 2011-08-10 2013-02-14 日立化成工業株式会社 Composition de résine photosensible, film photosensible, réserve permanente et procédé de production de réserve permanente
JP2013228722A (ja) * 2012-03-27 2013-11-07 Taiyo Ink Mfg Ltd 難燃性硬化性樹脂組成物、ドライフィルム、難燃性被膜およびプリント配線板
JP2014156601A (ja) * 2013-01-15 2014-08-28 Taiyo Ink Mfg Ltd 硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP2014160271A (ja) * 2014-04-16 2014-09-04 Hitachi Chemical Co Ltd 感光性樹脂組成物及び感光性フィルム、永久レジスト
JP2016038587A (ja) * 2014-08-08 2016-03-22 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板
JP2016177174A (ja) * 2015-03-20 2016-10-06 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018123695A1 (fr) * 2016-12-28 2018-07-05 太陽インキ製造株式会社 Composition durcissable, résine de base, agent de durcissement, film sec, produit durci, et carte à circuit imprimé
JP2018151628A (ja) * 2017-03-10 2018-09-27 日本化薬株式会社 感光性樹脂組成物、その硬化物及び物品
WO2019131353A1 (fr) * 2017-12-25 2019-07-04 ペルノックス株式会社 Composition et pâte thermodurcissables
JP6596611B1 (ja) * 2017-12-25 2019-10-23 ペルノックス株式会社 熱硬化性組成物及びペースト
JP2019178304A (ja) * 2018-03-30 2019-10-17 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板
KR20200055123A (ko) * 2018-08-27 2020-05-20 고오 가가쿠고교 가부시키가이샤 감광성 수지 조성물, 드라이 필름, 및 프린트 배선판
CN111295621A (zh) * 2018-08-27 2020-06-16 互应化学工业株式会社 感光性树脂组合物、干膜和印刷配线板
JPWO2020045024A1 (ja) * 2018-08-27 2020-12-17 互応化学工業株式会社 感光性樹脂組成物、ドライフィルム、及びプリント配線板
JP7197924B2 (ja) 2018-08-27 2022-12-28 互応化学工業株式会社 感光性樹脂組成物、ドライフィルム、及びプリント配線板
KR102506139B1 (ko) * 2018-08-27 2023-03-03 고오 가가쿠고교 가부시키가이샤 감광성 수지 조성물, 드라이 필름, 및 프린트 배선판
JP2020052362A (ja) * 2018-09-28 2020-04-02 太陽インキ製造株式会社 硬化物の製造方法、これに用いる感光性樹脂組成物、ドライフィルム、硬化物および電子部品
JP2022019406A (ja) * 2020-07-17 2022-01-27 味の素株式会社 感光性樹脂組成物
JP7306343B2 (ja) 2020-07-17 2023-07-11 味の素株式会社 感光性樹脂組成物
JP2022037501A (ja) * 2020-08-25 2022-03-09 味の素株式会社 感光性樹脂組成物
JP7354963B2 (ja) 2020-08-25 2023-10-03 味の素株式会社 感光性樹脂組成物

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