TW202343142A - Curable resin composition, dry film, cured product, and electronic component - Google Patents

Curable resin composition, dry film, cured product, and electronic component Download PDF

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TW202343142A
TW202343142A TW112125183A TW112125183A TW202343142A TW 202343142 A TW202343142 A TW 202343142A TW 112125183 A TW112125183 A TW 112125183A TW 112125183 A TW112125183 A TW 112125183A TW 202343142 A TW202343142 A TW 202343142A
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resin
group
film
resin composition
alkali
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TW112125183A
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Chinese (zh)
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柴田大介
柴﨑陽子
舟越千弘
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日商太陽控股股份有限公司
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    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/14—Polyamide-imides
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement

Abstract

Provided are the following: a curable resin composition which exhibits excellent developing performance and gives a cured product having excellent flexibility, adhesive properties and heat resistance; a dry film having a resin layer obtained from the composition; a cured product of the composition or of the resin layer of the dry film; and an electronic component having the cured product. This curable resin composition contains (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a compound having an ethylenically unsaturated group and (D) a thermosetting resin, and is characterized by containing, as the thermosetting resin (D): (D-1) a thermosetting resin, which has one or more structures represented by formulae (d-1-1) to (d-1-4) and which has a number average molecular weight of 1000 or less; and (D-2) a difunctional thermosetting resin having a number average molecular weight of 1000-3000. (In formula (d-1-4), R moieties are each independently a hydrogen atom or a methyl group. However, it is not possible for all the R moieties to be hydrogen atoms.).

Description

硬化性樹脂組成物、乾膜、硬化物，及電子零件Curable resin compositions, dry films, hardened materials, and electronic parts

本發明係關於硬化性樹脂組成物、乾膜、硬化物，及電子零件。The present invention relates to curable resin compositions, dry films, cured products, and electronic parts.

作為印刷配線板等之配線基板，係有於在稱為芯材的玻璃等之纖維中含浸環氧樹脂等者貼附銅等之金屬箔，以蝕刻法形成電路者，或藉由進一步將絕緣性樹脂組成物塗覆或層合薄片狀之絕緣性樹脂組成物來形成絕緣層後，形成電路者等。作為多層印刷配線板之製造方法，自以往已知有將形成有電路之複數個電路板，隔著作為接著絕緣層之預浸體進行層合壓製，藉由貫通孔而連接各層電路間之方法。相對於此，作為多層印刷配線板之製造方法，於內層電路板之導體層上交互堆疊層間絕緣材與導體層的增層方式之製造技術受到注目(例如參照專利文獻1、2)。 [先前技術文獻] [專利文獻] As a wiring board such as a printed wiring board, a fiber such as glass called a core material is impregnated with an epoxy resin or the like, and a metal foil such as copper is attached thereto, and a circuit is formed by etching, or by further insulating A circuit is formed by coating or laminating a sheet-like insulating resin composition with an insulating resin composition to form an insulating layer. As a manufacturing method of a multilayer printed wiring board, a method of laminating and pressing a plurality of circuit boards having circuits formed therebetween with a prepreg as a bonding insulating layer, and connecting the circuits on each layer through through holes has been conventionally known. . In contrast, as a manufacturing method of a multilayer printed wiring board, a build-up manufacturing technology in which interlayer insulating materials and conductive layers are alternately stacked on the conductive layer of an inner circuit board has attracted attention (see, for example, Patent Documents 1 and 2). [Prior technical literature] [Patent Document]

[專利文獻1]：日本特開2006-182991號公報(申請專利範圍等) [專利文獻2]：日本特開2013-36042號公報(申請專利範圍等) [Patent Document 1]: Japanese Patent Application Laid-Open No. 2006-182991 (Patent Application Scope, etc.) [Patent Document 2]: Japanese Patent Application Publication No. 2013-36042 (Patent Application Scope, etc.)

[發明所欲解決之課題][Problem to be solved by the invention]

於晶圓上進行封裝後切出晶片的晶圓等級封裝所用之層間絕緣材中，就生產效率之觀點，為了一舉形成微細的圖型，能夠以光微影術形成圖型之鹼顯像型的感光性層間絕緣材之要求增高。Among the interlayer insulating materials used in wafer-level packaging where the wafer is packaged and then the wafers are cut out, from the viewpoint of production efficiency, in order to form fine patterns in one fell swoop, the alkali development type can form patterns using photolithography. The requirements for photosensitive interlayer insulation materials have increased.

又，伴隨電子零件之小型化，對於層間絕緣材係有配線之高密度化的要求，為了確保配線或零件連接部之信賴性，對於印刷配線板之材料係要求高的耐熱性。藉由使用具有剛性且對稱性優良的骨架之硬化性樹脂，可提高材料之耐熱性，但該方法中會產生材料變硬而脆，龜裂耐性降低之問題。因而，為了賦予優良的龜裂耐性，係要求將柔軟性進一步提高。但是，為了提高柔軟性，例如使用分子量大的硬化性樹脂時，顯像性變差，在維持顯像性的同時，為了賦予優良龜裂耐性而提高柔軟性係困難的。又，就信賴性之觀點，亦要求高的耐熱性及與配線之密合性。In addition, along with the miniaturization of electronic components, interlayer insulating materials are required to increase the density of wiring. In order to ensure the reliability of wiring or component connection parts, the materials of printed wiring boards are required to have high heat resistance. By using a curable resin with a rigid and symmetrical skeleton, the heat resistance of the material can be improved. However, this method causes problems in that the material becomes hard and brittle, and the crack resistance is reduced. Therefore, in order to provide excellent crack resistance, it is required to further improve the flexibility. However, in order to improve flexibility, for example, when a curable resin with a large molecular weight is used, the developability becomes poor, and it is difficult to improve the flexibility in order to provide excellent crack resistance while maintaining the developability. In addition, from the viewpoint of reliability, high heat resistance and tight adhesion to wiring are also required.

因而，本發明之目的為提供顯像性優良，且硬化物之柔軟性、密合性及耐熱性優良的硬化性樹脂組成物、具有由該組成物所得到之樹脂層的乾膜、該組成物或該乾膜之樹脂層的硬化物，及具有該硬化物之電子零件。Therefore, an object of the present invention is to provide a curable resin composition that is excellent in developability and has excellent flexibility, adhesion and heat resistance of the cured product, and a dry film having a resin layer obtained from the composition, and the composition. or the cured product of the resin layer of the dry film, and electronic parts having the cured product.

本發明者等人為了解決上述課題而深入探討的結果，發現藉由摻合特定2種熱硬化性樹脂作為熱硬化性樹脂，可解決上述課題，而完成本發明。As a result of intensive research in order to solve the above-mentioned problems, the present inventors found that the above-mentioned problems can be solved by blending two specific types of thermosetting resins as thermosetting resins, and completed the present invention.

亦即，本發明之硬化性樹脂組成物，為含有(A)鹼可溶性樹脂、(B)光聚合起始劑、(C)具有乙烯性不飽和基之化合物，與(D)熱硬化性樹脂之硬化性樹脂組成物，其特徵為含有(D-1)包含下述式(d-1-1)~(d-1-4)表示之構造中任1者以上，且數平均分子量為1000以下之熱硬化性樹脂，及(D-2)數平均分子量為1000~3000且2官能之熱硬化性樹脂，作為前述(D)熱硬化性樹脂。 (式(d-1-4)中，R分別獨立地表示氫原子或甲基。惟，R全部為氫原子之情況除外)。 That is, the curable resin composition of the present invention contains (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a compound having an ethylenically unsaturated group, and (D) a thermosetting resin. A curable resin composition characterized by containing (D-1) any one or more of the structures represented by the following formulas (d-1-1) to (d-1-4), and having a number average molecular weight of 1000 The following thermosetting resins and (D-2) a bifunctional thermosetting resin with a number average molecular weight of 1000 to 3000 are used as the aforementioned (D) thermosetting resin. (In the formula (d-1-4), R each independently represents a hydrogen atom or a methyl group. However, the case where all R are hydrogen atoms is excepted).

本發明之硬化性樹脂組成物，前述(A)鹼可溶性樹脂，較佳含有具有下述式(1)及(2)表示之至少一方之構造與鹼可溶性官能基的醯胺醯亞胺樹脂。 In the curable resin composition of the present invention, the alkali-soluble resin (A) preferably contains a amide imine resin having at least one structure represented by the following formulas (1) and (2) and an alkali-soluble functional group.

本發明之乾膜，其特徵為具有將前述硬化性樹脂組成物塗佈於薄膜上並乾燥而得到之樹脂層。The dry film of the present invention is characterized by having a resin layer obtained by applying the curable resin composition on a film and drying it.

本發明之硬化物，其特徵為將前述硬化性樹脂組成物或前述乾膜之樹脂層硬化而成。The cured product of the present invention is characterized by curing the resin layer of the aforementioned curable resin composition or the aforementioned dry film.

本發明之電子零件，其特徵為具備前述硬化物而成。 [發明之效果] The electronic component of the present invention is characterized by having the above-mentioned hardened material. [Effects of the invention]

依照本發明，可提供顯像性優良，且硬化物之柔軟性、密合性及耐熱性優良的硬化性樹脂組成物、具有由該組成物所得到之樹脂層的乾膜、該組成物或該乾膜之樹脂層的硬化物，及具有該硬化物之電子零件。又，藉由提高硬化物之柔軟性，可對硬化物賦予優良的龜裂耐性。According to the present invention, it is possible to provide a curable resin composition having excellent developability and excellent flexibility, adhesion and heat resistance of the cured product, a dry film having a resin layer obtained from the composition, the composition or The cured product of the resin layer of the dry film, and the electronic component having the cured product. In addition, by improving the flexibility of the hardened material, excellent crack resistance can be imparted to the hardened material.

本發明者等人發現藉由摻合分子量大之熱硬化性樹脂，會提高柔軟性，但可能起因於分子量的大小，係為顯像性不良者。又，係密合性及耐熱性亦不良者。因而，得知藉由摻合使分子量為特定範圍，且2官能之熱硬化性樹脂(亦即上述(D-2))，且進一步合併使用具有特定環狀骨架，且低分子量之熱硬化性樹脂(亦即上述(D-1))，可得到顯像性優良，且硬化物之柔軟性、密合性及耐熱性優良的硬化性樹脂組成物。又，藉由提高硬化物之柔軟性，可對硬化物賦予優良的龜裂耐性。The present inventors found that by blending a thermosetting resin with a large molecular weight, flexibility can be improved, but the result may be poor developability due to the size of the molecular weight. In addition, the adhesiveness and heat resistance are also poor. Therefore, it was found that by blending a bifunctional thermosetting resin with a molecular weight in a specific range (that is, the above (D-2)), and further using a thermosetting resin with a specific cyclic skeleton and a low molecular weight in combination The resin (that is, the above (D-1)) can provide a curable resin composition that is excellent in developability and has excellent flexibility, adhesion and heat resistance of the cured product. In addition, by improving the flexibility of the hardened material, excellent crack resistance can be imparted to the hardened material.

以下詳述本發明之硬化性樹脂組成物所含有之成分。The components contained in the curable resin composition of the present invention will be described in detail below.

[(A)鹼可溶性樹脂] 本發明之硬化性樹脂組成物，含有鹼可溶性樹脂。鹼可溶性樹脂例如可列舉具有2個以上酚性羥基之化合物、含有羧基之樹脂、具有酚性羥基及羧基之化合物、具有2個以上硫醇基之化合物。其中，尤以鹼可溶性樹脂為含有羧基之樹脂或酚樹脂時，由於與基底之密合性提高故較佳。特別是由於顯像性優良，故鹼可溶性樹脂更佳為含有羧基之樹脂。鹼可溶性樹脂可為具有乙烯性不飽和基之鹼可溶性樹脂、亦可為不具有乙烯性不飽和基之鹼可溶性樹脂。 [(A) Alkali-soluble resin] The curable resin composition of the present invention contains an alkali-soluble resin. Examples of the alkali-soluble resin include compounds having two or more phenolic hydroxyl groups, resins containing carboxyl groups, compounds having phenolic hydroxyl groups and carboxyl groups, and compounds having two or more thiol groups. Among them, the alkali-soluble resin is particularly preferable since it has improved adhesion to the substrate when it is a carboxyl group-containing resin or a phenol resin. In particular, since it has excellent developability, the alkali-soluble resin is more preferably a resin containing a carboxyl group. The alkali-soluble resin may be an alkali-soluble resin having an ethylenically unsaturated group or an alkali-soluble resin not having an ethylenically unsaturated group.

含有羧基之樹脂之具體例子，可列舉如以下所列舉之化合物(寡聚物及聚合物均可)。再者，本說明書中，(甲基)丙烯酸酯，係總稱丙烯酸酯、甲基丙烯酸酯及該等的混合物之用語，其他類似表述亦相同。Specific examples of the carboxyl group-containing resin include the compounds listed below (both oligomers and polymers are acceptable). In addition, in this specification, (meth)acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and other similar expressions are also the same.

(1)藉由(甲基)丙烯酸等之不飽和羧酸，與苯乙烯、α-甲基苯乙烯、低級烷基(甲基)丙烯酸酯、異丁烯等之含有不飽和基之化合物的共聚合所得之含有羧基之樹脂。(1) Copolymerization of unsaturated carboxylic acids such as (meth)acrylic acid and unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, etc. The obtained resin contains carboxyl groups.

(2)藉由脂肪族二異氰酸酯、分支脂肪族二異氰酸酯、脂環式二異氰酸酯、芳香族二異氰酸酯等之二異氰酸酯，與二羥甲基丙酸、二羥甲基丁酸等之含有羧基之二醇化合物及聚碳酸酯系多元醇、聚醚系多元醇、聚酯系多元醇、聚烯烴系多元醇、丙烯酸系多元醇、雙酚A系環氧烷加成體二醇、具有酚性羥基及醇性羥基之化合物等之二醇化合物的加成聚合反應而得之含有羧基之胺基甲酸酯樹脂。(2) By using diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, etc., and dimethylol propionic acid, dimethylol butyric acid, etc. containing carboxyl groups Diol compounds and polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, and have phenolic properties Carboxyl group-containing urethane resin obtained by addition polymerization of diol compounds such as hydroxyl and alcoholic hydroxyl compounds.

(3)對藉由脂肪族二異氰酸酯、分支脂肪族二異氰酸酯、脂環式二異氰酸酯、芳香族二異氰酸酯等之二異氰酸酯化合物，與聚碳酸酯系多元醇、聚醚系多元醇、聚酯系多元醇、聚烯烴系多元醇、丙烯酸系多元醇、雙酚A系環氧烷加成體二醇、具有酚性羥基及醇性羥基之化合物等之二醇化合物的加成聚合反應而得之胺基甲酸酯樹脂的末端使酸酐反應而成之末端含有羧基之胺基甲酸酯樹脂。(3) For diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, etc., and polycarbonate polyols, polyether polyols, polyester polyols, etc. Obtained from the addition polymerization reaction of glycol compounds such as polyols, polyolefin polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups. Urethane resin is a urethane resin containing a carboxyl group at its terminal end by reacting an acid anhydride.

(4)藉由二異氰酸酯，與雙酚A型環氧樹脂、氫化雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、聯二甲酚型環氧樹脂、聯酚型環氧樹脂等之2官能環氧樹脂之(甲基)丙烯酸酯或其部分酸酐改質物、含有羧基之二醇化合物及二醇化合物之加成聚合反應而得之含有羧基之胺基甲酸酯樹脂。(4) By using diisocyanate, it can be combined with bisphenol A-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, and dixylenol-type epoxy resin. , (meth)acrylate or partial acid anhydride modifications of bifunctional epoxy resins such as biphenolic epoxy resins, carboxyl group-containing diol compounds and carboxyl group-containing amines obtained by addition polymerization of diol compounds. methyl formate resin.

(5)於上述(2)或(4)之樹脂之合成中，添加(甲基)丙烯酸羥基烷酯等之分子中具有1個羥基與1個以上之(甲基)丙烯醯基的化合物，而末端(甲基)丙烯醯化之含有羧基之胺基甲酸酯樹脂。(5) In the synthesis of the resin in the above (2) or (4), add a compound having one hydroxyl group and one or more (meth)acrylyl groups in the molecule such as hydroxyalkyl (meth)acrylate, The terminal (meth)acrylate contains carboxyl urethane resin.

(6)於上述(2)或(4)之樹脂之合成中，添加異佛酮二異氰酸酯與季戊四醇三丙烯酸酯之等莫耳反應物等分子中具有1個異氰酸酯基與1個以上之(甲基)丙烯醯基的化合物，而末端(甲基)丙烯醯化之含有羧基之胺基甲酸酯樹脂。(6) In the synthesis of the resin in the above (2) or (4), add molar reactants such as isophorone diisocyanate and pentaerythritol triacrylate, etc., which have one isocyanate group and more than one (methane) in the molecule. (meth)acrylyl compound, and a carboxyl-containing urethane resin with terminal (meth)acrylate.

(7)使(甲基)丙烯酸與多官能環氧樹脂反應，對側鏈所存在之羥基加成鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐等之2元酸酐而得之含有羧基之樹脂。(7) React (meth)acrylic acid with multifunctional epoxy resin, and add 2 of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. to the hydroxyl groups present in the side chain A resin containing carboxyl groups derived from acid anhydrides.

(8)使(甲基)丙烯酸與將2官能環氧樹脂之羥基進一步以表氯醇環氧化而得之多官能環氧樹脂反應，對所生成之羥基加成2元酸酐而得之含有羧基之樹脂。(8) A polyfunctional epoxy resin obtained by reacting (meth)acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the generated hydroxyl group to obtain a carboxyl group-containing of resin.

(9)使二羧酸與多官能氧雜環丁烷樹脂反應，對所生成之1級羥基加成2元酸酐而得之含有羧基之聚酯樹脂。(9) A carboxyl group-containing polyester resin obtained by reacting a dicarboxylic acid with a polyfunctional oxetane resin and adding a dibasic acid anhydride to the generated primary hydroxyl group.

(10)對使1分子中具有複數個酚性羥基之化合物與環氧乙烷、環氧丙烷等之環氧烷反應而得之反應生成物使含有不飽和基之單羧酸進行反應，再對所得之反應生成物使多元酸酐進行反應而得之含有羧基之樹脂。(10) The reaction product obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide is reacted with a monocarboxylic acid containing an unsaturated group, and then A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride with the obtained reaction product.

(11)對使1分子中具有複數個酚性羥基之化合物與碳酸伸乙酯、碳酸伸丙酯等之環狀碳酸酯化合物反應而得之反應生成物使含有不飽和基之單羧酸進行反應，再對所得之反應生成物使多元酸酐進行反應而得之含有羧基之樹脂。(11) The reaction product obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethyl carbonate or propyl carbonate is treated with a monocarboxylic acid containing an unsaturated group. The reaction product is reacted with a polybasic acid anhydride to obtain a carboxyl-containing resin.

(12)使p-羥基苯乙醇等之1分子中具有至少1個醇性羥基與1個酚性羥基的化合物，與(甲基)丙烯酸等之含有不飽和基之單羧酸與1分子中具有複數個環氧基之環氧化合物反應，對所得之反應生成物之醇性羥基，使馬來酸酐、四氫鄰苯二甲酸酐、偏苯三甲酸酐、苯均四酸酐、己二酸酐等之多元酸酐進行反應而得之含有羧基之樹脂。(12) A compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenylethyl alcohol, and a monocarboxylic acid containing an unsaturated group, such as (meth)acrylic acid, in one molecule Reaction of epoxy compounds with multiple epoxy groups, and the alcoholic hydroxyl group of the reaction product obtained is maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, etc. A resin containing carboxyl groups obtained by reacting polybasic acid anhydrides.

(13)對上述(1)~(12)等記載的含有羧基之樹脂進一步加成(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸α-甲基縮水甘油酯等之分子中具有1個環氧基與1個以上之(甲基)丙烯醯基的化合物而成之含有羧基之樹脂。(13) The carboxyl group-containing resin described in the above (1) to (12) is further added with glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, etc. in the molecule having 1 A carboxyl-containing resin composed of a compound of an epoxy group and one or more (meth)acrylyl groups.

上述含有羧基之樹脂當中，較佳含有上述(7)、(8)、(10)、(11)、(13)記載的含有羧基之樹脂之至少任1種。就絕緣信賴性更加提高的觀點，較佳含有上述(10)、(11)記載的含有羧基之樹脂。Among the above-mentioned carboxyl group-containing resins, it is preferable to contain at least one of the carboxyl group-containing resins described in the above (7), (8), (10), (11), and (13). From the viewpoint of further improving insulation reliability, it is preferable to contain the carboxyl group-containing resin described in (10) and (11) above.

具有酚性羥基之化合物，例如可列舉具有聯苯基骨架或伸苯基骨架或其雙方骨架之化合物，或使用酚、鄰甲酚、對甲酚、間甲酚、2,3-二甲酚、2,4-二甲酚、2,5-二甲酚、2,6-二甲酚、3,4-二甲酚、3,5-二甲酚、兒茶酚、間苯二酚、氫醌、甲基氫醌、2,6-二甲基氫醌、三甲基氫醌、五倍子酚、間苯三酚等所合成的具有各種骨架之酚樹脂。Examples of compounds having a phenolic hydroxyl group include compounds having a biphenyl skeleton, a phenyl skeleton, or both skeletons, and phenol, o-cresol, p-cresol, m-cresol, and 2,3-xylenol can be used. , 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, Phenol resins with various skeletons synthesized from hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, gallic acid, phloroglucinol, etc.

又，具有酚性羥基之化合物，例如可列舉酚酚醛清漆樹脂、烷基酚酚醛清漆樹脂、雙酚A酚醛清漆樹脂、二環戊二烯型酚樹脂、Xylok型酚樹脂、萜烯改質酚樹脂、聚乙烯基酚類、雙酚F、雙酚S型酚樹脂、聚-p-羥基苯乙烯、萘酚與醛類之縮合物、二羥基萘與醛類之縮合物等之公知慣用之酚樹脂。Examples of the compound having a phenolic hydroxyl group include phenol novolak resin, alkylphenol novolak resin, bisphenol A novolac resin, dicyclopentadiene-type phenol resin, Xylok-type phenol resin, and terpene-modified phenol. Resins, polyvinyl phenols, bisphenol F, bisphenol S type phenol resins, poly-p-hydroxystyrene, condensates of naphthol and aldehydes, condensates of dihydroxynaphthalene and aldehydes, etc. are known and commonly used Phenolic resin.

酚樹脂之市售品，例如可列舉HF1H60(明和化成公司製)、Phenolite TD-2090、Phenolite TD-2131(大日本印刷公司製)、Besmol CZ-256-A(DIC公司製)、Shonol BRG-555、Shonol BRG-556(昭和電工公司製)、CGR-951(丸善石油公司製)、聚乙烯基酚之CST70、CST90、S-1P、S-2P(丸善石油公司製)。Examples of commercially available phenolic resins include HF1H60 (manufactured by Meiwa Kasei Co., Ltd.), Phenolite TD-2090, Phenolite TD-2131 (manufactured by Dai Nippon Printing Co., Ltd.), Besmol CZ-256-A (manufactured by DIC Corporation), Shonol BRG- 555. Shonol BRG-556 (manufactured by Showa Denko Co., Ltd.), CGR-951 (manufactured by Maruzen Oil Co., Ltd.), polyvinyl phenol CST70, CST90, S-1P, and S-2P (manufactured by Maruzen Oil Co., Ltd.).

又，鹼可溶性樹脂，亦可適合地使用具有下述式(1)或(2) 表示之至少一方之構造，與鹼可溶性官能基的醯胺醯亞胺樹脂。藉由含有具有直接鍵結於環己烷環或苯環之醯亞胺鍵的樹脂，可得到強韌性及耐熱性優良的硬化物。特別是具有(1)表示之構造的醯胺醯亞胺樹脂，由於光的透過性優良，因此可提高解像性。前述醯胺醯亞胺樹脂，較佳為具有透明性，例如於前述醯胺醯亞胺樹脂之乾燥塗膜25μm，波長365nm之光的透過率較佳為70%以上。 Moreover, an alkali-soluble resin having the following formula (1) or (2) can also be suitably used. At least one of the structures represented is a amide imine resin with an alkali-soluble functional group. By containing a resin having an imine bond directly bonded to a cyclohexane ring or a benzene ring, a cured product with excellent toughness and heat resistance can be obtained. In particular, the amide amide imine resin having the structure represented by (1) has excellent light transmittance and therefore can improve the resolution. The above-mentioned amide-imide resin is preferably transparent. For example, when the dry coating film of the above-mentioned amide-imine resin is 25 μm, the transmittance of light with a wavelength of 365 nm is preferably 70% or more.

前述醯胺醯亞胺樹脂中。式(1)及(2)之構造的含量，較佳為10~70質量%。藉由使用該樹脂，可得到溶劑溶解性優良，且耐熱性、拉伸強度或伸度等之物性及尺寸安定性優良的硬化物。較佳為10~60質量%、更佳為20~50質量%。In the aforementioned amide amide imine resin. The content of the structures of formulas (1) and (2) is preferably 10 to 70% by mass. By using this resin, it is possible to obtain a cured product that is excellent in solvent solubility and has excellent physical properties such as heat resistance, tensile strength, elongation, and dimensional stability. Preferably it is 10-60 mass %, More preferably, it is 20-50 mass %.

具有式(1)表示之構造的醯胺醯亞胺樹脂，特別是具有式(3A)或(3B) (式(3A)及(3B)中，各自地，R為1價有機基，較佳為H、CF 3或CH 3，X為直接鍵結或2價有機基，較佳為直接鍵結、CH 2或C(CH 3) 2等之伸烷基)表示之構造的樹脂，由於拉伸強度或伸度等之物性及尺寸安定性優良故較佳。就溶解性或機械物性之觀點，前述醯胺醯亞胺樹脂，可適合地使用具有式(3A)及(3B)之構造10~100質量%的樹脂。更佳為20~80質量%。 A amide-imine resin having a structure represented by formula (1), especially a amide-imine resin having a structure represented by formula (3A) or (3B) (In formulas (3A) and (3B), R is a monovalent organic group, preferably H, CF 3 or CH 3 , and X is a direct bond or a divalent organic group, preferably a direct bond, A resin having a structure represented by an alkylene group such as CH 2 or C(CH 3 ) 2 is preferred because it has excellent physical properties such as tensile strength and elongation and dimensional stability. From the viewpoint of solubility or mechanical properties, 10 to 100% by mass of the above-mentioned amide imine resin having a structure of formulas (3A) and (3B) can be suitably used. More preferably, it is 20~80 mass %.

前述醯胺醯亞胺樹脂，就溶解性或機械物性之觀點，較佳可使用含有式(3A)及(3B)之構造5~100莫耳%的醯胺醯亞胺樹脂。更佳為5~98莫耳%、又更佳為10~98莫耳%、特佳為20~80莫耳%。From the viewpoint of solubility or mechanical properties, it is preferable to use a amide imine resin containing 5 to 100 mol% of the structure of formulas (3A) and (3B). More preferably, it is 5~98 mol%, still more preferably, it is 10~98 mol%, and particularly preferably, it is 20~80 mol%.

又，具有式(2)表示之構造的醯胺醯亞胺樹脂，特別是具有式(4A)或(4B) (式(4A)及(4B)中，各自地，R為1價有機基，較佳為H、CF 3或CH 3，X為直接鍵結或2價有機基，較佳為直接鍵結、CH 2或C(CH 3) 2等之伸烷基)表示之構造的樹脂，由於可得到拉伸強度或伸度等之機械物性優良的硬化物故較佳。就溶解性或機械物性之觀點，前述醯胺醯亞胺樹脂，可適合地使用具有式(4A)及(4B)之構造10~100質量%的樹脂。更佳為20~80質量%。 Also, a amide amide imine resin having a structure represented by formula (2), particularly having formula (4A) or (4B) (In the formulas (4A) and (4B), respectively, R is a monovalent organic group, preferably H, CF 3 or CH 3 , and X is a direct bond or a divalent organic group, preferably a direct bond, A resin having a structure represented by an alkylene group such as CH 2 or C (CH 3 ) 2 is preferred because a cured product having excellent mechanical properties such as tensile strength and elongation can be obtained. From the viewpoint of solubility or mechanical properties, 10 to 100% by mass of the above-mentioned amide imine resin having a structure of formulas (4A) and (4B) can be suitably used. More preferably, it is 20~80 mass %.

前述醯胺醯亞胺樹脂，就展現良好機械物性之理由，亦佳可使用含有式(4A)及(4B)之構造2~95莫耳%的醯胺醯亞胺樹脂。更佳為10~80莫耳%。Since the aforementioned amide imine resin exhibits good mechanical properties, it is also preferable to use a amide imine resin containing 2 to 95 mol% of the structure of formulas (4A) and (4B). More preferably, it is 10~80 mol%.

前述醯胺醯亞胺樹脂，可藉由公知之方法得到。具有(1)之構造的醯胺醯亞胺樹脂，例如可使用具有聯苯基骨架之二異氰酸酯化合物，與環己烷多羧酸酐來得到。The aforementioned amide amide imine resin can be obtained by a known method. The amide imine resin having the structure (1) can be obtained by using, for example, a diisocyanate compound having a biphenyl skeleton and a cyclohexane polycarboxylic anhydride.

具有聯苯基骨架之二異氰酸酯化合物，可列舉4,4’-二異氰酸酯-3,3’-二甲基-1,1’-聯苯、4,4’-二異氰酸酯-3,3’-二乙基-1,1’-聯苯、4,4’-二異氰酸酯-2,2’-二甲基-1,1’-聯苯、4,4’-二異氰酸酯-2,2’-二乙基-1,1’-聯苯、4,4’-二異氰酸酯-3,3’-二-三氟甲基-1,1’-聯苯、4,4’-二異氰酸酯-2,2’-二-三氟甲基-1,1’-聯苯等。其他，亦可使用二苯基甲烷二異氰酸酯等之芳香族聚異氰酸酯化合物等。Examples of diisocyanate compounds having a biphenyl skeleton include 4,4'-diisocyanate-3,3'-dimethyl-1,1'-biphenyl and 4,4'-diisocyanate-3,3'- Diethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'- Diethyl-1,1'-biphenyl, 4,4'-diisocyanate-3,3'-di-trifluoromethyl-1,1'-biphenyl, 4,4'-diisocyanate-2, 2'-bis-trifluoromethyl-1,1'-biphenyl, etc. In addition, aromatic polyisocyanate compounds such as diphenylmethane diisocyanate can also be used.

環己烷多羧酸酐，可列舉環己烷三羧酸酐、環己烷四羧酸酐等。Examples of cyclohexane polycarboxylic acid anhydride include cyclohexane tricarboxylic acid anhydride, cyclohexane tetracarboxylic acid anhydride, and the like.

又，具有(2)之構造的醯胺醯亞胺樹脂，例如可使用上述具有聯苯基骨架之二異氰酸酯化合物，與具有2個酸酐基之多羧酸酐來得到。Moreover, the amide imine resin having the structure (2) can be obtained by using, for example, the above-mentioned diisocyanate compound having a biphenyl skeleton and a polycarboxylic anhydride having two acid anhydride groups.

具有2個酸酐基之多羧酸酐，可列舉苯均四酸二酐、二苯甲酮-3,3’,4,4’-四羧酸二酐、二苯基醚-3,3’,4,4’-四羧酸二酐、苯-1,2,3,4-四羧酸二酐、聯苯-3,3’,4,4’-四羧酸二酐、聯苯-2,2’,3,3’-四羧酸二酐、雙(2,3-二羧基苯基)甲烷二酐、雙(3,4-二羧基苯基)甲烷二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、2,2-雙(2,3-二羧基苯基)丙烷二酐、2,3-雙(3,4-二羧基苯基)丙烷二酐、雙(3,4-二羧基苯基)碸二酐、雙(3,4-二羧基苯基)醚二酐、乙二醇雙脫水偏苯三甲酸酯等之烷二醇雙脫水偏苯三甲酸酯等。Examples of polycarboxylic anhydrides with two anhydride groups include pyromellitic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and diphenyl ether-3,3', 4,4'-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-2 ,2',3,3'-tetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 2,2-bis(2,3-dicarboxyphenyl) Propane dianhydride, 2,3-bis(3,4-dicarboxyphenyl) propane dianhydride, bis(3,4-dicarboxyphenyl)tere dianhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, ethylene glycol dihydrated trimellitate, etc., alkanediol dihydrated trimellitate, etc.

前述醯胺醯亞胺樹脂，於上述式(1)、(2)之構造以外，進一步具有鹼可溶性之官能基。藉由具有鹼可溶性之官能基，會成為可鹼顯像之樹脂組成物。作為鹼可溶性之官能基，係含有羧基、酚系羥基、磺基等者，較佳為含有羧基者。The aforementioned amide imine resin further has an alkali-soluble functional group in addition to the structures of the above formulas (1) and (2). By having alkali-soluble functional groups, it becomes a resin composition that can be developed by alkali. Examples of alkali-soluble functional groups include those containing carboxyl groups, phenolic hydroxyl groups, sulfo groups, etc., and those containing carboxyl groups are preferred.

再者，前述醯胺醯亞胺樹脂之具體例子，可列舉DIC公司製Unidic V-8000系列、Nippon 高度紙工業公司製SOXR-U。In addition, specific examples of the aforementioned amide imine resin include Unidic V-8000 series manufactured by DIC Corporation and SOXR-U manufactured by Nippon High Paper Industry Co., Ltd.

鹼可溶性樹脂之酸價，較佳為20~120mgKOH/g之範圍、更佳為30~100mgKOH/g之範圍。藉由使鹼可溶性樹脂之酸價成為上述範圍，可良好地進行鹼顯像，可形成正常的硬化物之圖型。鹼可溶性樹脂之重量平均分子量，雖依樹脂骨架而異，但一般而言較佳為2,000~150,000。重量平均分子量為2,000以上時，乾燥塗膜之不黏著(tack-free)性、曝光後之塗膜的耐濕性、解像性為良好。另一方面，重量平均分子量為150,000以下時，顯像性與儲存安定性良好。更佳為5,000~100,000。The acid value of the alkali-soluble resin is preferably in the range of 20 to 120 mgKOH/g, more preferably in the range of 30 to 100 mgKOH/g. By setting the acid value of the alkali-soluble resin within the above range, alkali development can be performed favorably and a normal pattern of the cured product can be formed. The weight average molecular weight of the alkali-soluble resin varies depending on the resin skeleton, but generally it is preferably 2,000 to 150,000. When the weight average molecular weight is 2,000 or more, the tack-free properties of the dried coating film, the moisture resistance and resolution of the exposed coating film are good. On the other hand, when the weight average molecular weight is 150,000 or less, the developability and storage stability are good. Better is 5,000~100,000.

鹼可溶性樹脂可1種單獨使用、亦可組合2種以上使用。使用前述醯胺醯亞胺樹脂作為鹼可溶性樹脂時，藉由得到樹脂層與基材之密合性良好之乾膜，乾膜之作業性優良，因此較佳為合併使用其他鹼可溶性樹脂(亦即，不含式(1)及(2)之構造的鹼可溶性樹脂)，其他鹼可溶性樹脂，較佳為以環氧樹脂為起始原料之含有羧基之樹脂、具有胺基甲酸酯骨架之含有羧基之樹脂(亦稱為含有羧基之胺基甲酸酯樹脂)、具有不飽和羧酸之共聚合構造的含有羧基之樹脂、以酚化合物為起始原料之含有羧基之樹脂，及對該等含有羧基之樹脂加成分子中具有1個環氧基與1個以上之(甲基)丙烯醯基的化合物而成之含有羧基之樹脂之至少任一者。The alkali-soluble resin may be used individually by 1 type, or in combination of 2 or more types. When the aforementioned amide imine resin is used as an alkali-soluble resin, a dry film with good adhesion between the resin layer and the base material is obtained, and the workability of the dry film is excellent. Therefore, it is preferable to use other alkali-soluble resins (also known as alkali-soluble resins) in combination. That is, excluding alkali-soluble resins with structures of formulas (1) and (2)), other alkali-soluble resins are preferably carboxyl-containing resins using epoxy resins as starting materials, and resins with a urethane skeleton. Carboxyl group-containing resin (also known as carboxyl group-containing urethane resin), carboxyl group-containing resin having a copolymer structure of unsaturated carboxylic acid, carboxyl group-containing resin using phenolic compounds as starting materials, and the At least any one of the carboxyl group-containing resins obtained by adding a carboxyl group-containing resin to a compound having one epoxy group and one or more (meth)acrylyl groups in the molecule.

前述醯胺醯亞胺樹脂與前述其他鹼可溶性樹脂之摻合比例，相對於前述醯胺醯亞胺樹脂與前述其他鹼可溶性樹脂之合計量而言，前述醯胺醯亞胺樹脂之比例較佳為30~95質量%、更佳為40~85質量%。藉由成為上述之範圍，可得到具有良好之強韌性與耐熱性的硬化物。The blending ratio of the aforementioned amide imine resin and the aforementioned other alkali-soluble resins is better than the total amount of the aforementioned amide imine resin and the aforementioned other alkali soluble resins. It is 30-95 mass %, more preferably, it is 40-85 mass %. By falling within the above range, a cured product having good strength, toughness and heat resistance can be obtained.

[(B)光聚合起始劑] 本發明之硬化性樹脂組成物，含有光聚合起始劑。光聚合起始劑，可1種單獨使用、亦可組合2種以上使用。 [(B) Photopolymerization initiator] The curable resin composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more types.

光聚合起始劑，較佳含有選自由包含通式(I)表示之構造之肟酯系、包含通式(II)表示之構造之α-胺基苯乙酮系、包含通式(III)表示之構造之醯基膦氧化物系，及包含通式(IV)表示之構造之二茂鈦系所成之群的1種或2種以上。The photopolymerization initiator preferably contains an oxime ester system having a structure represented by the general formula (I), an α-aminoacetophenone system having a structure represented by the general formula (II), and an oxime ester system having a structure represented by the general formula (II). One or two or more types of the group consisting of the acylphosphine oxide system having the structure represented by the general formula (IV) and the titanocene system having the structure represented by the general formula (IV).

通式(I)中，R 1表示氫原子、苯基、烷基、環烷基、烷醯基或苯甲醯基。R 2表示苯基、烷基、環烷基、烷醯基或苯甲醯基。 In the general formula (I), R 1 represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkyl group or a benzyl group. R 2 represents a phenyl group, an alkyl group, a cycloalkyl group, an alkyl group or a benzyl group.

R 1及R 2表示之苯基，亦可具有取代基，取代基例如可列舉碳數1~6之烷基、苯基、鹵素原子等。 The phenyl group represented by R 1 and R 2 may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen atom.

R 1及R 2表示之烷基，較佳為碳數1~20之烷基，烷基鏈中亦可包含1個以上之氧原子。又，亦可經1個以上之羥基取代。R 1及R 2表示之環烷基，較佳為碳數5~8之環烷基。R 1及R 2表示之烷醯基，較佳為碳數2~20之烷醯基。R 1及R 2表示之苯甲醯基，亦可具有取代基，取代基例如可列舉碳數1~6之烷基、苯基等。 The alkyl group represented by R 1 and R 2 is preferably an alkyl group with 1 to 20 carbon atoms, and the alkyl chain may also contain one or more oxygen atoms. In addition, it may be substituted by one or more hydroxyl groups. The cycloalkyl group represented by R 1 and R 2 is preferably a cycloalkyl group having 5 to 8 carbon atoms. The alkyl group represented by R 1 and R 2 is preferably an alkyl group having 2 to 20 carbon atoms. The benzyl group represented by R 1 and R 2 may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and the like.

通式(II)中，R 3及R 4係各自獨立地表示碳數1~12之烷基或芳基烷基，R 5及R 6係各自獨立地表示氫原子，或碳數1~6之烷基，或者2者亦可鍵結而形成環狀烷基醚基。 In the general formula (II), R 3 and R 4 each independently represent an alkyl group or arylalkyl group having 1 to 12 carbon atoms, and R 5 and R 6 each independently represent a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms. The alkyl group, or the two can be bonded to form a cyclic alkyl ether group.

通式(III)中，R 7及R 8係各自獨立地表示碳數1~10之烷基、環己基、環戊基、芳基，或經鹵素原子、烷基或烷氧基取代之芳基，或碳數1~20之羰基(惟，雙方為碳數1~20之羰基的情況除外)。 In the general formula (III), R 7 and R 8 each independently represent an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl group substituted by a halogen atom, an alkyl group or an alkoxy group. group, or a carbonyl group with 1 to 20 carbon atoms (except when both parties are carbonyl groups with 1 to 20 carbon atoms).

通式(IV)中，R 9及R 10係各自獨立地表示鹵素原子、芳基、鹵化芳基、雜環含有鹵化芳基。 In the general formula (IV), R 9 and R 10 each independently represent a halogen atom, an aryl group, a halogenated aryl group, or a heterocyclic ring containing a halogenated aryl group.

肟酯系光聚合起始劑之具體例子，可列舉1,2-辛二酮-1-[4-(苯硫基)-2-(O-苯甲醯基肟)]、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)等。市售品可列舉BASF Japan公司製之CGI-325、Irgacure OXE01、Irgacure OXE02、ADEKA公司製N-1919、NCI-831等。亦可適合地使用分子內具有2個肟酯基之光聚合起始劑或具有咔唑構造之光聚合起始劑。具體而言，可列舉下述通式(V)表示之肟酯化合物。 (通式(V)中，X表示氫原子、碳數1~17之烷基、碳數1~8之烷氧基、苯基、苯基(經碳數1~17之烷基、碳數1~8之烷氧基、胺基、具備碳數1~8之烷基的烷基胺基或二烷基胺基取代)、萘基(經碳數1~17之烷基、碳數1~8之烷氧基、胺基、具備碳數1~8之烷基的烷基胺基或二烷基胺基取代)，Y、Z分別表示氫原子、碳數1~17之烷基、碳數1~8之烷氧基、鹵基、苯基、苯基(經碳數1~17之烷基、碳數1~8之烷氧基、胺基、具備碳數1~8之烷基的烷基胺基或二烷基胺基取代)、萘基(經碳數1~17之烷基、碳數1~8之烷氧基、胺基、具備碳數1~8之烷基的烷基胺基或二烷基胺基取代)、蒽基、吡啶基、苯并呋喃基、苯并噻吩基，Ar係表示鍵結，或碳數1~10之伸烷基、伸乙烯基、伸苯基、伸聯苯基、伸吡啶基、伸萘基、噻吩、伸蒽基、伸噻吩基、伸呋喃基、2,5-吡咯-二基、4,4’-二苯乙烯-二基、4,2’-苯乙烯-二基，n為0或1之整數)。 Specific examples of the oxime ester photopolymerization initiator include 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyl oxime)], ethyl ketone,1 -[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyl oxime), etc. Commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, NCI-831 manufactured by ADEKA, etc. A photopolymerization initiator having two oxime ester groups in the molecule or a photopolymerization initiator having a carbazole structure can also be suitably used. Specific examples include oxime ester compounds represented by the following general formula (V). (In the general formula (V), 1~8 alkoxy group, amine group, alkylamino group or dialkylamino group having an alkyl group having 1~8 carbon atoms substituted), naphthyl group (substituted with an alkyl group having 1~17 carbon atoms, 1 carbon atoms ~8 alkoxy group, amine group, alkylamino group or dialkylamino group with an alkyl group having 1 to 8 carbon atoms substituted), Y and Z respectively represent a hydrogen atom, an alkyl group with 1 to 17 carbon atoms, Alkoxy group with 1 to 8 carbon atoms, halo group, phenyl group, phenyl group (alkyl group with 1 to 17 carbon atoms, alkoxy group with 1 to 8 carbon atoms, amino group, alkyl group with 1 to 8 carbon atoms) Alkyl amino group or dialkylamino group substituted), naphthyl group (substituted by alkyl group with carbon number 1 to 17, alkoxy group with carbon number 1 to 8, amine group, alkyl group with carbon number 1 to 8 Alkylamino or dialkylamino substitution), anthryl, pyridyl, benzofuranyl, benzothienyl, Ar represents bonding, or alkylene or vinylidene groups with 1 to 10 carbon atoms , phenylene, biphenyl, pyridinyl, naphthylene, thiophene, anthracenyl, thienyl, furyl, 2,5-pyrrole-diyl, 4,4'-stilbene- Diyl, 4,2'-styrene-diyl, n is an integer of 0 or 1).

特別地，通式(V)中，係以X、Y分別為甲基或乙基，Z為甲基或苯基，n為0，Ar為鍵結，或伸苯基、伸萘基、噻吩或伸噻吩基為佳。In particular, in the general formula (V), X and Y are methyl or ethyl respectively, Z is methyl or phenyl, n is 0, Ar is bond, or phenyl, naphthyl, thiophene Or a thienyl group is preferred.

又，較佳的咔唑肟酯化合物，亦可列舉能夠以下述通式(VI)表示之化合物。 (通式(VI)中，R 1表示碳原子數1~4之烷基，或可經硝基、鹵素原子或碳原子數1~4之烷基取代之苯基。R 2表示碳原子數1~4之烷基、碳原子數1~4之烷氧基，或可經碳原子數1~4之烷基或烷氧基取代之苯基。R 3表示可經氧原子或硫原子連結，且可經苯基取代之碳原子數1~20之烷基、可經碳原子數1~4之烷氧基取代之苯甲基。R 4表示硝基，或X-C(=O)-表示之醯基。X表示可經碳原子數1~4之烷基取代之芳基、噻吩基、嗎啉基、硫苯基，或下述式(VII)表示之構造) Preferable carbazole oxime ester compounds include compounds represented by the following general formula (VI). (In the general formula (VI), R 1 represents an alkyl group with 1 to 4 carbon atoms, or a phenyl group that may be substituted by a nitro group, a halogen atom, or an alkyl group with 1 to 4 carbon atoms. R 2 represents the number of carbon atoms. Alkyl group with 1 to 4 carbon atoms, alkoxy group with 1 to 4 carbon atoms, or phenyl group which may be substituted with alkyl group or alkoxy group with 1 to 4 carbon atoms. R 3 means it can be connected through an oxygen atom or a sulfur atom , and an alkyl group with 1 to 20 carbon atoms that may be substituted by a phenyl group, and a benzyl group that may be substituted with an alkoxy group with 1 to 4 carbon atoms. R 4 represents nitro, or XC(=O)- acyl group.

α-胺基苯乙酮系光聚合起始劑之具體例子，可使用(4-嗎啉基苯甲醯基)-1-苯甲基-1-二甲基胺基丙烷(Omnirad 369、IGM Resins公司製)、4-(甲硫基苯甲醯基)-1-甲基-1-嗎啉基乙烷(Omnirad 907、IGM Resins公司製)、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮(Omnirad 379、IGM Resins公司製)等之市售化合物或其溶液。Specific examples of the α-aminoacetophenone photopolymerization initiator include (4-morpholinylbenzyl)-1-phenylmethyl-1-dimethylaminopropane (Omnirad 369, IGM Resins), 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane (Omnirad 907, IGM Resins), 2-(dimethylamino)-2 Commercially available compounds such as -[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (Omnirad 379, manufactured by IGM Resins) or other solution.

醯基膦氧化物系光聚合起始劑之具體例子，可列舉2,4,6-三甲基苯甲醯基二苯基膦氧化物、雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基膦氧化物等。市售品可列舉IGM Resins公司製之Omnirad TPO、Omnirad 819等。Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzyl acyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, etc. Commercially available products include Omnirad TPO and Omnirad 819 manufactured by IGM Resins.

二茂鈦系光聚合起始劑，可列舉雙(η5-2、4-環戊二烯-1-基)-雙(2、6-二氟-3-(1H-吡咯-1-基)-苯基)鈦。市售品可列舉IGMResins公司製之Omnirad 784等。Titanium-based photopolymerization initiators include bis(eta5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl) -phenyl) titanium. Commercially available products include Omnirad 784 manufactured by IGM Resins.

其他光聚合起始劑，例如可列舉苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚等之苯偶姻與苯偶姻烷基醚類；苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、1,1-二氯苯乙酮等之苯乙酮類；2-甲基蒽醌、2-乙基蒽醌、2-t-丁基蒽醌、1-氯蒽醌、2-戊基蒽醌等之蒽醌類；2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2-氯噻噸酮、2,4-二異丙基噻噸酮等之噻噸酮類；苯乙酮二甲基縮酮、苯甲基二甲基縮酮等之縮酮類；二苯甲酮等之二苯甲酮類；氧雜蒽酮(xanthone)類；3,3’4,4’-四-(tert-丁基過氧基羰基)二苯甲酮等各種過氧化物類；1,7-雙(9-吖啶基)庚烷等。Other photopolymerization initiators include, for example, benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc.; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc. Ketones; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, 2-pentylanthraquinone, etc.; 2,4-dimethyl Thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; acetophenone dimethyl ketal, Ketals such as benzyldimethyl ketal; benzophenones such as benzophenone; xanthone; 3,3'4,4'-tetra-(tert-butanol) Peroxycarbonyl)benzophenone and other peroxides; 1,7-bis(9-acridinyl)heptane, etc.

上述光聚合起始劑以外，亦能夠與N,N-二甲基胺基苯甲酸乙酯、N,N-二甲基胺基苯甲酸異戊酯、苯甲酸戊基-4-二甲基胺酯、三乙胺、三乙醇胺等之三級胺類般的公知慣用之光增感劑的1種或2種以上組合來使用。進一步地，要求更深的光硬化深度時，可依需要組合使用3-取代香豆素色素、無色染料(leuco dye)等作為硬化助劑。In addition to the above-mentioned photopolymerization initiator, it can also be combined with N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, and benzoic acid pentyl-4-dimethyl benzoate. One type or a combination of two or more types of commonly known photosensitizers such as tertiary amines such as amine esters, triethylamine, and triethanolamine are used. Furthermore, when a deeper photohardening depth is required, 3-substituted coumarin pigments, leuco dyes, etc. can be used in combination as hardening aids as needed.

光聚合起始劑之摻合量，相對於鹼可溶性樹脂100質量份而言，較佳為0.05~30質量份、更佳為0.1~20質量份、又更佳為0.1~15質量份。藉由使光聚合起始劑之摻合量成為上述範圍，可充分產生反應所必要的自由基，又，可使光透過至深部，因此可避免硬化物變脆等之問題。The blending amount of the photopolymerization initiator is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and still more preferably 0.1 to 15 parts by mass relative to 100 parts by mass of the alkali-soluble resin. By setting the blending amount of the photopolymerization initiator within the above range, free radicals necessary for the reaction can be sufficiently generated, and light can be transmitted deep into the photopolymerization initiator. Therefore, problems such as brittleness of the cured product can be avoided.

[(C)具有乙烯性不飽和基之化合物] 本發明之硬化性樹脂組成物，亦可含有具有乙烯性不飽和基之化合物。具有乙烯性不飽和基之化合物，可藉由活性能量線之照射而光硬化，使樹脂層之照射部對鹼水溶液不溶化，或幫助不溶化。具有乙烯性不飽和基之化合物，可使用公知慣用之感光性單體的光聚合性寡聚物、光聚合性乙烯基單體等。具有乙烯性不飽和基之化合物，可使用感光性(甲基)丙烯酸酯化合物。具有乙烯性不飽基之化合物，可1種單獨使用、亦可組合2種以上使用。再者，本案說明書中，「具有乙烯性不飽和基之化合物」，係不包含具有乙烯性不飽和基之鹼可溶性樹脂。 [(C) Compounds having ethylenically unsaturated groups] The curable resin composition of the present invention may also contain a compound having an ethylenically unsaturated group. Compounds with ethylenically unsaturated groups can be photohardened by irradiation with active energy rays, making the irradiated portion of the resin layer insolubilizable to alkali aqueous solutions, or assisting in solubilization. As the compound having an ethylenically unsaturated group, photopolymerizable oligomers, photopolymerizable vinyl monomers, and the like of commonly used photosensitive monomers can be used. As the compound having an ethylenically unsaturated group, a photosensitive (meth)acrylate compound can be used. The compound having an ethylenically unsaturated group may be used alone or in combination of two or more types. Furthermore, in the description of this case, "compounds having an ethylenically unsaturated group" does not include alkali-soluble resins having an ethylenically unsaturated group.

具有乙烯性不飽和基之化合物，可使用慣用公知之聚酯(甲基)丙烯酸酯、聚醚(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯、碳酸酯(甲基)丙烯酸酯、環氧基(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯，具體而言，可列舉丙烯酸2-羥基乙酯、丙烯酸2-羥基丙酯等之丙烯酸羥基烷酯類；乙二醇、甲氧基四乙二醇、聚乙二醇、丙二醇等之二醇之二丙烯酸酯類；N,N-二甲基丙烯醯胺、N-羥甲基丙烯醯胺、N,N-二甲基胺基丙基丙烯醯胺等之丙烯醯胺類；丙烯酸N,N-二甲基胺基乙酯、丙烯酸N,N-二甲基胺基丙酯等之丙烯酸胺基烷酯類；己二醇、三羥甲基丙烷、季戊四醇、二季戊四醇、參-羥基乙基異三聚氰酸酯等之多元醇或此等之環氧乙烷加成體、環氧丙烷加成體，或ε-己內酯加成體等之多元丙烯酸酯類；苯氧基丙烯酸酯、雙酚A二丙烯酸酯，及此等之酚類之環氧乙烷加成體或環氧丙烷加成體等之多元丙烯酸酯類；甘油二縮水甘油基醚、甘油三縮水甘油基醚、三羥甲基丙烷三縮水甘油基醚、異三聚氰酸三縮水甘油酯等之縮水甘油基醚之多元丙烯酸酯類；不限於上述，亦可列舉將聚醚多元醇、聚碳酸酯二醇、羥基末端聚丁二烯、聚酯多元醇等之多元醇予以直接丙烯酸酯化，或透過二異氰酸酯予以胺基甲酸酯丙烯酸酯化而得的丙烯酸酯類及三聚氰胺丙烯酸酯，及對應於上述丙烯酸酯之各甲基丙烯酸酯類之至少任1種等。As the compound having an ethylenically unsaturated group, commonly known polyester (meth)acrylate, polyether (meth)acrylate, urethane (meth)acrylate, and carbonate (meth)acrylate can be used. Acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, specific examples include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate. Categories; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, etc.; N,N-dimethylacrylamide, N-hydroxymethylacrylamide, Acrylamides such as N,N-dimethylaminopropylacrylamide; acrylic amines such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate Alkyl esters; polyols such as hexylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, hydroxyethylisocyanurate or their ethylene oxide adducts, propylene oxide Adducts, or polyacrylates such as ε-caprolactone adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or epoxy of these phenols Polyacrylates such as propane adducts; glycidyl groups such as glyceryl diglycidyl ether, glyceryl triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanate, etc. Ether polyacrylates; not limited to the above, examples include direct acrylation of polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadiene, polyester polyols, etc., or through diene Acrylates and melamine acrylates obtained by esterifying isocyanates with urethane acrylates, and at least one of each methacrylates corresponding to the above-mentioned acrylates.

進一步地，可列舉使丙烯酸與甲酚酚醛清漆型環氧樹脂等之多官能環氧樹脂反應而得之環氧基丙烯酸酯樹脂，或進一步對該環氧基丙烯酸酯樹脂之羥基，使季戊四醇三丙烯酸酯等之羥基丙烯酸酯與異佛酮二異氰酸酯等之二異氰酸酯之半胺基甲酸酯化合物進行反應而得之環氧基胺基甲酸酯丙烯酸酯化合物等。如此的環氧基丙烯酸酯系樹脂，可在不使指觸乾燥性降低之下，提高光硬化性。Further examples include an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolak type epoxy resin, or further converting the hydroxyl group of the epoxy acrylate resin to pentaerythritol trisulfide. Epoxy urethane acrylate compounds, etc. obtained by reacting hydroxyacrylates such as acrylates with semi-urethane compounds of diisocyanates such as isophorone diisocyanate. Such an epoxy acrylate resin can improve photocurability without reducing touch dryness.

具有乙烯性不飽和基之化合物之摻合量，相對於鹼可溶性樹脂100質量份而言，較佳為1~60質量份、更佳為5~55質量份、又更佳為10~50質量份。藉由使(D)成分之摻合量成為上述範圍，可得到良好的光反應性，且一併具備耐熱性。The blending amount of the compound having an ethylenically unsaturated group is preferably 1 to 60 parts by mass, more preferably 5 to 55 parts by mass, and still more preferably 10 to 50 parts by mass relative to 100 parts by mass of the alkali-soluble resin. share. By setting the blending amount of component (D) within the above range, good photoreactivity can be obtained while also having heat resistance.

[(D)熱硬化性樹脂] 本發明之硬化性樹脂組成物，含有(D-1)包含下述式(d-1-1)~(d-1-4)表示之構造中任1者以上，且數平均分子量1000以下之熱硬化性樹脂，及(D-2)數平均分子量1000~3000且2官能之熱硬化性樹脂，作為(D)熱硬化性樹脂。 [(D) Thermosetting resin] The curable resin composition of the present invention contains (D-1) any one or more of the structures represented by the following formulas (d-1-1) to (d-1-4), and has a number average molecular weight of 1000 or less. Thermosetting resin, and (D-2) a bifunctional thermosetting resin with a number average molecular weight of 1000 to 3000, as (D) thermosetting resin.

(式(d-1-4)中，R分別獨立地表示氫原子或甲基。惟，R全部為氫原子之情況除外)。 (In the formula (d-1-4), R each independently represents a hydrogen atom or a methyl group. However, the case where all R are hydrogen atoms is excepted).

前述(D-1)及(D-2)中之熱硬化性樹脂，可列舉多官能環氧化合物、多官能氧雜環丁烷化合物、環硫樹脂等之分子中具有2個以上之環狀醚基及/或環狀硫醚基的化合物、聚異氰酸酯化合物、封端異氰酸酯化合物等1分子內具有2個以上之異氰酸酯基，或封端化異氰酸酯基的化合物、三聚氰胺樹脂、苯并胍胺樹脂等之胺樹脂及其衍生物、雙馬來醯亞胺、噁嗪、環碳酸酯化合物、碳二醯亞胺樹脂等之公知的熱硬化性樹脂。其中尤以多官能環氧化合物為佳。多官能環氧化合物，可使用1分子中具有至少2個環氧基的公知慣用之多官能環氧樹脂。惟，前述(D-2)之熱硬化性樹脂中為2官能。Examples of the thermosetting resins in the aforementioned (D-1) and (D-2) include polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, etc., which have two or more cyclic rings in the molecule. Compounds with ether group and/or cyclic thioether group, polyisocyanate compounds, blocked isocyanate compounds, etc. having two or more isocyanate groups in one molecule, or compounds with blocked isocyanate groups, melamine resin, benzoguanamine resin Well-known thermosetting resins such as amine resins and their derivatives, bismaleimide, oxazines, cyclic carbonate compounds, carbodiimide resins, etc. Among them, polyfunctional epoxy compounds are particularly preferred. As the polyfunctional epoxy compound, a well-known and commonly used polyfunctional epoxy resin having at least two epoxy groups in one molecule can be used. However, the thermosetting resin (D-2) mentioned above is bifunctional.

前述(D-1)之熱硬化性樹脂，只要包含上述特定之環狀構造，亦即，式(d-1-1)之萘構造、式(d-1-2)之二環戊二烯構造、式(d-1-3)之聯苯構造，及式(d-1-4)之具有甲基之聯苯構造的任1者以上，且數平均分子量為1000以下，則無特殊限定。例如，可列舉DIC公司製HP-4032(萘型環氧樹脂)、DIC公司製HP-7200L(二環戊二烯型環氧樹脂)、日本化藥公司製NC-3000L(聯苯型環氧樹脂)、三菱化學公司製YX-4000(具有甲基之聯苯型環氧樹脂)、DIC公司製HP4710(萘型環氧樹脂)等。前述(D-1)之熱硬化性樹脂，可1種單獨使用、亦可組合2種以上使用。The thermosetting resin of the aforementioned (D-1) must contain the above-mentioned specific cyclic structure, that is, the naphthalene structure of the formula (d-1-1) and the dicyclopentadiene of the formula (d-1-2). There are no special restrictions if there is more than one of the structure, the biphenyl structure of formula (d-1-3), and the biphenyl structure of formula (d-1-4) having a methyl group, and the number average molecular weight is 1000 or less. . For example, HP-4032 (naphthalene type epoxy resin) manufactured by DIC Corporation, HP-7200L (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation, NC-3000L (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Resin), Mitsubishi Chemical Corporation's YX-4000 (biphenyl-type epoxy resin with methyl group), DIC Corporation's HP4710 (naphthalene-type epoxy resin), etc. The thermosetting resin of (D-1) mentioned above may be used individually by 1 type, or may be used in combination of 2 or more types.

前述(D-1)之熱硬化性樹脂之中，就解像性之觀點，尤以具有脂環式骨架之二環戊二烯型環氧樹脂為佳。Among the aforementioned thermosetting resins (D-1), dicyclopentadiene-type epoxy resin having an alicyclic skeleton is particularly preferred from the viewpoint of resolution.

前述(D-2)之熱硬化性樹脂，只要係數平均分子量1000~3000且為2官能之熱硬化性樹脂則無特殊限定。例如可列舉三菱化學公司製jER1002、jER1003、jER1055、jER1004、jER1007等。前述(D-2)之熱硬化性樹脂，可1種單獨使用、亦可組合2種以上使用。The thermosetting resin (D-2) mentioned above is not particularly limited as long as it has a coefficient average molecular weight of 1,000 to 3,000 and is a bifunctional thermosetting resin. Examples include jER1002, jER1003, jER1055, jER1004, jER1007 manufactured by Mitsubishi Chemical Corporation. The thermosetting resin of (D-2) mentioned above may be used individually by 1 type, or may be used in combination of 2 or more types.

前述(D-1)及(D-2)之熱硬化性樹脂之數平均分子量，為經凝膠滲透層析(GPC)測定的標準聚苯乙烯換算之值。The number average molecular weight of the thermosetting resins of the aforementioned (D-1) and (D-2) is a standard polystyrene-converted value measured by gel permeation chromatography (GPC).

前述(D-1)及(D-2)之熱硬化性樹脂之摻合量，相對於鹼可溶性樹脂100質量份而言，合計較佳為30~200質量份、更佳為40~160質量份、又更佳為50~140質量份。The blending amount of the aforementioned thermosetting resins (D-1) and (D-2) is preferably 30 to 200 parts by mass, and more preferably 40 to 160 parts by mass relative to 100 parts by mass of the alkali-soluble resin. parts, preferably 50 to 140 parts by mass.

前述(D-1)及(D-2)之熱硬化性樹脂之摻合比例，相對於前述(D-1)及(D-2)之熱硬化性樹脂之合計量而言，(D-1)之比例較佳為40~95質量%、更佳為50~90質量%。藉由成為上述之範圍，可得到顯像性更優良，且硬化物之柔軟性、密合性及耐熱性更優良的硬化物。The blending ratio of the thermosetting resins of the aforementioned (D-1) and (D-2), relative to the total amount of the thermosetting resins of the aforementioned (D-1) and (D-2), is (D- The proportion of 1) is preferably 40 to 95 mass%, more preferably 50 to 90 mass%. By being within the above range, it is possible to obtain a cured product that has better developability and further has better flexibility, adhesion and heat resistance of the cured product.

((E)熱硬化促進劑) 本發明之硬化性樹脂組成物，亦可含有熱硬化促進劑。熱硬化促進劑，可1種單獨使用、亦可組合2種以上使用。 ((E) Thermal hardening accelerator) The curable resin composition of the present invention may also contain a thermal curing accelerator. The thermal hardening accelerator can be used alone or in combination of two or more types.

熱硬化促進劑，可列舉咪唑、2-甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、4-苯基咪唑、1-氰基乙基-2-苯基咪唑、1-(2-氰基乙基)-2-乙基-4-甲基咪唑等之咪唑衍生物；二氰二胺、苯甲基二甲胺、4-(二甲基胺基)-N,N-二甲基苯甲胺、4-甲氧基-N,N-二甲基苯甲胺、4-甲基-N,N-二甲基苯甲胺等之胺化合物；己二酸二醯肼、癸二酸二醯肼等之肼化合物；三苯基膦等之磷化合物等。又，此等以外，亦可使用胍胺、乙醯胍胺、苯并胍胺、三聚氰胺、2,4-二胺基-6-甲基丙烯醯氧基乙基-S-三嗪、2-乙烯基-2,4-二胺基-S-三嗪、2-乙烯基-4,6-二胺基-S-三嗪/異三聚氰酸加成物、2,4-二胺基-6-甲基丙烯醯氧基乙基-S-三嗪/異三聚氰酸加成物等之S-三嗪衍生物。Examples of thermal hardening accelerators include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 1-cyanoethyl -Imidazole derivatives such as 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamine, benzyldimethylamine, 4-(dimethylamine) Methylamine)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc. Amine compounds; hydrazine compounds such as adipic acid dihydrazine and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine, etc. Moreover, in addition to these, guanamine, aceguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, 2- Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino -S-triazine derivatives such as 6-methacryloxyethyl-S-triazine/isocyanuric acid adduct.

市售之熱硬化促進劑，例如可列舉四國化成工業公司製之2MZ-A、2MZ-OK、2PHZ、2P4BHZ、2P4MHZ(均為咪唑系化合物之商品名)、San-Apro公司製之U-CAT3503N、U-CAT3502T(均為二甲胺之封端異氰酸酯化合物之商品名)、DBU、DBN、U-CATSA102、U-CAT5002(均為二環式脒化合物及其鹽)等。Commercially available thermal hardening accelerators include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ manufactured by Shikoku Chemical Industry Co., Ltd. (all are trade names of imidazole compounds), and U-A manufactured by San-Apro Corporation. CAT3503N, U-CAT3502T (all are trade names of dimethylamine blocked isocyanate compounds), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and their salts), etc.

熱硬化促進劑之摻合量，相對於鹼可溶性樹脂100質量份而言，較佳為0.1~10質量份、更佳為0.1~5.0質量份。0.1質量份以上時硬化物之耐熱性成為良好，10質量份以下時保存安定性成為良好。The blending amount of the thermal hardening accelerator is preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 5.0 parts by mass relative to 100 parts by mass of the alkali-soluble resin. When it is 0.1 parts by mass or more, the heat resistance of the hardened material becomes good, and when it is 10 parts by mass or less, the storage stability becomes good.

((F)有機溶劑) 為了樹脂組成物之調製，或為了調整用以對基板或載體薄膜塗佈之黏度，本發明之硬化性樹脂組成物中，可使用有機溶劑。如此的有機溶劑，可列舉酮類、芳香族烴類、二醇醚類、二醇醚乙酸酯類、酯類、醇類、脂肪族烴、石油系溶劑等。更具體而言，係甲基乙基酮、環己酮等之酮類；甲苯、二甲苯、四甲苯等之芳香族烴類；賽珞蘇、甲基賽珞蘇、丁基賽珞蘇、卡必醇、甲基卡必醇、丁基卡必醇、丙二醇單甲基醚、二丙二醇單甲基醚、二丙二醇二乙基醚、三乙二醇單乙基醚等之二醇醚類；乙酸乙酯、乙酸丁酯、二丙二醇甲基醚乙酸酯、丙二醇甲基醚乙酸酯、丙二醇乙基醚乙酸酯、丙二醇丁基醚乙酸酯等之酯類；乙醇、丙醇、乙二醇、丙二醇等之醇類；辛烷、癸烷等之脂肪族烴；石油醚、石油腦、氫化石油腦、溶劑石油腦等之石油系溶劑等。有機溶劑，可1種單獨使用、亦可組合2種以上使用。 ((F)organic solvent) In order to prepare the resin composition, or to adjust the viscosity for coating the substrate or carrier film, an organic solvent can be used in the curable resin composition of the present invention. Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, they are ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellulose, methylcellulose, butylcellulose, Glycol ethers such as carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc. ;Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, etc.; ethanol, propanol Alcohols such as ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha, etc. The organic solvent can be used alone or in combination of two or more types.

(無機填充劑) 本發明之硬化性樹脂組成物，亦可含有無機填充劑。無機填充劑例如可使用二氧化矽、硫酸鋇、滑石、黏土、碳酸鎂、碳酸鈣、氧化鋁、氫氧化鋁、水鋁石、雲母粉、水滑石、Sillitin、Sillikolloid等之公知慣用之無機填充劑。此等之中，尤可適合使用線膨脹係數小的二氧化矽。無機填充劑，可1種單獨使用、亦可組合2種以上使用。 (Inorganic filler) The curable resin composition of the present invention may also contain an inorganic filler. Examples of inorganic fillers that can be used include silica, barium sulfate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, diaspore, mica powder, hydrotalcite, Sillitin, Sillikolloid, etc. agent. Among these, silicon dioxide with a small linear expansion coefficient is particularly suitably used. Inorganic fillers can be used alone or in combination of two or more types.

無機填充劑之摻合量，相對於鹼可溶性樹脂100質量份而言，較佳為150質量份以下、更佳為120質量份以下。藉由摻合無機填充劑，可充分得到線膨脹係數之減低效果。為150質量份以下時，本發明之硬化性樹脂組成物的硬化物之柔軟性成為良好。The blending amount of the inorganic filler is preferably 150 parts by mass or less, more preferably 120 parts by mass or less based on 100 parts by mass of the alkali-soluble resin. By blending inorganic fillers, the linear expansion coefficient reduction effect can be fully obtained. When the content is 150 parts by mass or less, the cured product of the curable resin composition of the present invention has good flexibility.

(硬化劑) 本發明之硬化性樹脂組成物可含有硬化劑。硬化劑可列舉酚樹脂、多羧酸及其酸酐、氰酸酯樹脂、活性酯樹脂、馬來醯亞胺化合物、脂環式烯烴聚合物等。硬化劑可1種單獨或組合2種以上使用。 (hardener) The curable resin composition of the present invention may contain a curing agent. Examples of the hardening agent include phenol resins, polycarboxylic acids and their anhydrides, cyanate ester resins, active ester resins, maleimide compounds, alicyclic olefin polymers, and the like. A hardener can be used individually by 1 type or in combination of 2 or more types.

(其他任意成分) 本發明之硬化性樹脂組成物中，亦可摻合電子材料之領域中所公知慣用的其他添加劑。其他添加劑可列舉熱聚合抑制劑、紫外線吸收劑、偶合劑、可塑劑、難燃劑、抗靜電劑、抗老化劑、抗菌/防黴劑、消泡劑、調平劑、增黏劑、密合性賦予劑、搖變性賦予劑、著色劑、光起始助劑、增感劑、熱可塑性樹脂、有機填充劑、脫模劑、表面處理劑、分散劑、分散助劑、表面改質劑、安定劑、螢光體等。 (other optional ingredients) The curable resin composition of the present invention may also be blended with other additives known and commonly used in the field of electronic materials. Other additives include thermal polymerization inhibitors, ultraviolet absorbers, coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial/antifungal agents, defoaming agents, leveling agents, tackifiers, density Compatibility imparting agent, thixotropy imparting agent, colorant, photoinitiating agent, sensitizer, thermoplastic resin, organic filler, release agent, surface treatment agent, dispersant, dispersing aid, surface modifier , stabilizers, fluorophores, etc.

又，本發明之硬化性樹脂組成物，在不損及本發明之效果的範圍，亦可含有前述(D-1)及(D-2)以外之熱硬化性樹脂。Furthermore, the curable resin composition of the present invention may contain thermosetting resins other than the aforementioned (D-1) and (D-2) within a range that does not impair the effects of the present invention.

本發明之硬化性樹脂組成物，適合作為印刷配線板之絕緣性硬化被膜的形成用，更適合作為絕緣性永久被膜的形成用，又更適合作為包覆層(cover lay)、防焊劑、層間絕緣材的形成用，特別適合作為層間絕緣材之形成用。又，適於形成要求高度信賴性的印刷配線板，例如封裝基板，特別是FC-BGA用之永久被膜(特別是層間絕緣材)。再者，本發明之硬化性樹脂組成物，亦可使用於形成焊料壩等。作為電子零件，亦可為印刷配線板以外的用途，例如電感器等被動零件。本發明之硬化性樹脂組成物可為液狀型、亦可為使液狀型樹脂組成物乾燥而得之乾膜型。就保存安定性之觀點，液狀型樹脂組成物亦可為2液型等，但亦可為1液型。又，較佳為負型。The curable resin composition of the present invention is suitable for forming an insulating cured film on a printed wiring board, is more suitable for forming an insulating permanent film, and is more suitable for use as a cover lay, a solder resist, and an interlayer. It is used for the formation of insulating materials, especially suitable for the formation of interlayer insulating materials. In addition, it is suitable for forming permanent coatings (especially interlayer insulating materials) for printed wiring boards that require high reliability, such as packaging substrates, especially FC-BGAs. Furthermore, the curable resin composition of the present invention can also be used to form solder dams and the like. As electronic components, it can also be used for purposes other than printed wiring boards, such as passive components such as inductors. The curable resin composition of the present invention may be a liquid type or a dry film type obtained by drying the liquid resin composition. From the viewpoint of storage stability, the liquid resin composition may be a 2-liquid type, etc., but may also be a 1-liquid type. Moreover, a negative type is preferable.

[乾膜] 本發明之乾膜，為具有將本發明之硬化性樹脂組成物塗佈於薄膜(以下亦稱為「載體薄膜」)上，之後乾燥而得的樹脂層者。本發明之乾膜，可將本發明之硬化性樹脂組成物以有機溶劑稀釋而調整為適切的黏度，並以缺角輪塗佈器、刮刀塗佈器、唇口塗佈器、棒式塗佈器、擠壓式塗佈器、逆輥塗佈器、轉送輥塗佈器、凹版塗佈器、噴霧塗佈器等於載體薄膜上塗佈為均勻厚度，通常以50~120℃之溫度乾燥1~30分鐘而得到。塗佈膜厚並無特殊限制，一般而言，以乾燥後之膜厚計，係以5~150μm、較佳為10~60μm之範圍適當設定即可。薄膜不限於載體薄膜，亦可為覆蓋膜。 [dry film] The dry film of the present invention has a resin layer obtained by applying the curable resin composition of the present invention on a film (hereinafter also referred to as a "carrier film") and then drying it. The dry film of the present invention can be prepared by diluting the curable resin composition of the present invention with an organic solvent and adjusting it to an appropriate viscosity, and applying it with a notched wheel applicator, a blade applicator, a lip applicator, or a rod-type applicator. Spreader, squeeze coater, reverse roll coater, transfer roll coater, gravure coater, spray coater etc. can coat the carrier film to a uniform thickness, usually dried at a temperature of 50~120℃ It takes 1~30 minutes. There is no special limit to the coating film thickness. Generally speaking, based on the film thickness after drying, it can be appropriately set in the range of 5 to 150 μm, preferably 10 to 60 μm. The film is not limited to the carrier film and may also be a cover film.

載體薄膜可適合地使用塑膠薄膜，較佳使用聚對苯二甲酸乙二酯等之聚酯薄膜、聚醯亞胺薄膜、聚醯胺醯亞胺薄膜、聚丙烯薄膜、聚苯乙烯薄膜等之塑膠薄膜。載體薄膜之厚度並無特殊限制，一般而言係於10~150μm之範圍適當選擇。The carrier film can suitably be a plastic film, preferably a polyester film such as polyethylene terephthalate, a polyimide film, a polyamide imide film, a polypropylene film, a polystyrene film, etc. Plastic film. The thickness of the carrier film is not particularly limited, and is generally appropriately selected within the range of 10 to 150 μm.

於載體薄膜上塗佈本發明之硬化性樹脂組成物後，進一步地亦能夠以防止於塗膜表面附著灰塵等為目的，於膜的表面層合可剝離之覆蓋膜。可剝離之覆蓋膜，例如可使用聚乙烯薄膜、聚四氟乙烯薄膜、聚丙烯薄膜、經表面處理的紙等，只要剝離覆蓋膜時，膜與覆蓋膜之接著力較膜與載體薄膜之接著力更小者即可。After the curable resin composition of the present invention is coated on the carrier film, a peelable cover film can be laminated on the surface of the film for the purpose of preventing dust from adhering to the surface of the coating film. Peelable cover films can be used, for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc., as long as the adhesion between the film and the cover film is greater than the adhesion between the film and the carrier film when the cover film is peeled off. The one with smaller strength will do.

將本發明之硬化性樹脂組成物塗佈於載體薄膜上後所進行的揮發乾燥，可使用熱風循環式乾燥爐、IR爐、加熱板、對流烘箱等(使用具備以蒸氣之空氣加熱方式的熱源者，使乾燥機內之熱風逆流接觸之方法及由噴嘴對支持體吹送的方式)來進行。The curable resin composition of the present invention is volatilized and dried after being coated on a carrier film. A hot air circulation drying oven, an IR oven, a heating plate, a convection oven, etc. can be used (a heat source equipped with an air heating method using steam is used). Or, the method of making the hot air in the dryer come into contact with countercurrent and the method of blowing the support from the nozzle) is carried out.

[硬化物] 本發明之硬化物，為使本發明之硬化性樹脂組成物硬化而成者，及使本發明之乾膜之樹脂層硬化而成者。 [hardened material] The cured product of the present invention is obtained by curing the curable resin composition of the present invention, and is obtained by curing the resin layer of the dry film of the present invention.

依照本發明之硬化性樹脂組成物，可得到柔軟性優良的硬化物，因此亦可適合地使用於形成膜厚薄的硬化物，例如膜厚10μm以下之硬化物。According to the curable resin composition of the present invention, a cured product with excellent flexibility can be obtained, and therefore it can be suitably used to form a cured product with a thin film thickness, for example, a cured product with a film thickness of 10 μm or less.

[電子零件] 本發明之電子零件，為具備本發明之硬化物者。本發明之電子零件，可藉由將本發明之硬化性樹脂組成物直接塗佈之方法，與使用本發明之乾膜的方法而得到。以下，作為電子零件，以製造印刷配線板的情況為例來說明，但本發明不限定於此。 [Electronic parts] The electronic component of the present invention is provided with the hardened material of the present invention. The electronic component of the present invention can be obtained by directly coating the curable resin composition of the present invention or using the dry film of the present invention. Hereinafter, the case of manufacturing a printed wiring board as an electronic component will be described as an example, but the present invention is not limited thereto.

以直接塗佈之方法來製造印刷配線板時，係於形成有電路的印刷配線板上直接塗佈本發明之硬化性樹脂組成物，形成樹脂組成物之塗膜後，將雷射光等之活性能量線直接依圖型照射，或通過形成有圖型之光罩選擇性地照射活性能量線藉以曝光，將未曝光部以稀鹼水溶液顯像而形成阻劑圖型。進一步地，藉由對阻劑圖型例如以100~2000mJ/cm 2照射活性能量線，例如加熱至約140~200℃之溫度使其硬化，來製造具有硬化物之圖型的印刷配線板。再者，活性能量線對阻劑圖型的照射，係以使形成阻劑圖型之影像時的曝光中未反應之(C)成分等幾乎完全地硬化反應為目的來進行。 When manufacturing a printed wiring board by a direct coating method, the curable resin composition of the present invention is directly coated on a printed wiring board on which a circuit is formed. After forming a coating film of the resin composition, the activity of laser light or the like is Energy rays are directly irradiated according to the pattern, or active energy rays are selectively irradiated through a patterned mask to expose, and the unexposed parts are developed with a dilute alkali aqueous solution to form a resist pattern. Furthermore, by irradiating the resist pattern with active energy rays at, for example, 100 to 2000 mJ/cm 2 , and heating to a temperature of about 140 to 200° C. to cure the resist pattern, a printed wiring board having a pattern of cured material is manufactured. In addition, the irradiation of active energy rays on the resist pattern is performed with the purpose of almost completely curing the component (C) that has not reacted during the exposure when forming the image of the resist pattern.

使用乾膜時，係於形成有電路的印刷配線板上貼合本發明之乾膜，來層合樹脂層後，與上述同樣地進行曝光後，剝離載體薄膜，進行顯像。之後，藉由對樹脂層照射活性能量線，例如加熱至約140~200℃之溫度使其硬化，來製造具有硬化物之圖型的印刷配線板。再者，硬化被膜之圖型形成，可藉由光微影術法形成、亦可藉由網版印刷法等來形成。When a dry film is used, the dry film of the present invention is bonded to a printed wiring board on which a circuit is formed, and a resin layer is laminated. After exposure in the same manner as above, the carrier film is peeled off and developed. Thereafter, the resin layer is irradiated with active energy rays and heated to, for example, a temperature of about 140 to 200° C. to cure the resin layer, thereby producing a printed wiring board having a pattern of the cured product. Furthermore, the pattern formation of the hardened film can be formed by photolithography or screen printing.

活性能量線之照射所用的曝光機，只要係搭載高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、水銀短弧燈等，且可於350~450nm之範圍照射紫外線的裝置即可，進而亦可使用例如藉由來自電腦之CAD數據而直接以活性能量線描繪影像之直接成像裝置般的直接描繪裝置。直接描繪裝置的光源，只要使用水銀短弧燈、LED、最大波長350~450nm之範圍的雷射光，則氣體雷射、固體雷射均可。用於阻劑圖型之影像形成的曝光量雖依膜厚等而異，但一般而言可為20~1500mJ/cm 2、較佳為20~1200mJ/cm 2之範圍內。 The exposure machine used for irradiating active energy rays can be used as long as it is equipped with a high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, mercury short arc lamp, etc., and can irradiate ultraviolet rays in the range of 350~450nm. For example, a direct drawing device such as a direct imaging device that draws images directly with active energy rays based on CAD data from a computer. The light source of the direct drawing device can be a gas laser or a solid laser as long as a mercury short arc lamp, LED, or laser light with a maximum wavelength of 350~450 nm is used. Although the exposure amount used for image formation of the resist pattern varies depending on the film thickness, etc., it can generally be in the range of 20~1500mJ/ cm2 , preferably 20~1200mJ/ cm2 .

顯像方法可採用浸漬法、淋洗法、噴霧法、毛刷法等，顯像液可使用氫氧化鉀、氫氧化鈉、碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨、胺類等之鹼水溶液。 [實施例] The imaging method can be dipping method, leaching method, spray method, brush method, etc. The developing liquid can be potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines. alkaline aqueous solution. [Example]

以下，顯示出本發明之實施例及比較例，以具體說明本發明，但本發明當然不限定於下述實施例。再者，以下記載有「份」及「%」者，只要無特別指明，均為質量基準。Hereinafter, Examples and Comparative Examples of the present invention are shown to illustrate the present invention in detail. However, the present invention is of course not limited to the following Examples. In addition, the following descriptions of "parts" and "%" are based on mass unless otherwise specified.

＜鹼可溶性樹脂1之合成例(合成例1)＞ 對二乙二醇單乙基醚乙酸酯600g給入鄰甲酚酚醛清漆型環氧樹脂〔DIC公司製EPICLON N-695、軟化點95℃、環氧當量214、平均官能基數7.6〕1070g(縮水甘油基數(芳香環總數)：5.0莫耳)、丙烯酸360g(5.0莫耳)，及氫醌1.5g，於100℃加熱攪拌，均勻溶解。接著，給入三苯基膦4.3g，加熱至110℃反應2小時後，昇溫至120℃進一步進行12小時反應。對所得之反應液給入芳香族系烴(SOLVESSO 150)415g、甲基-5-降莰烯-2,3-二羧酸酐534g(3.0莫耳)，於110℃進行4小時反應，冷卻後，得到固體成分酸價89mgKOH/g、固體成分65%之甲酚酚醛清漆型含有羧基之樹脂溶液。凝膠滲透層析(GPC)之測定結果，重量平均分子量係8000。 <Synthesis example of alkali-soluble resin 1 (Synthesis example 1)> 1070g ( Number of glycidyl groups (total number of aromatic rings): 5.0 moles), 360g of acrylic acid (5.0 moles), and 1.5g of hydroquinone, heat and stir at 100°C to dissolve evenly. Next, 4.3 g of triphenylphosphine was added, and the mixture was heated to 110° C. and reacted for 2 hours. The temperature was then raised to 120° C. and the reaction was further carried out for 12 hours. 415g of aromatic hydrocarbon (SOLVESSO 150) and 534g (3.0 mol) of methyl-5-norbornene-2,3-dicarboxylic anhydride were added to the obtained reaction liquid, and the reaction was carried out at 110°C for 4 hours, and then cooled , a cresol novolac-type resin solution containing carboxyl groups with a solid content of 89 mgKOH/g and a solid content of 65% was obtained. According to the measurement results of gel permeation chromatography (GPC), the weight average molecular weight is 8,000.

＜鹼可溶性樹脂2之合成例(合成例2)＞ 對附有攪拌裝置、溫度計及冷凝器之燒瓶，給入GBL(γ-丁內酯)848.8g、MDI(二苯基甲烷二異氰酸酯)57.5g(0.23莫耳)、DMBPDI(4,4’-二異氰酸酯-3,3’-二甲基-1,1’-聯苯)59.4g(0.225莫耳)、TMA(偏苯三甲酸酐)67.2g(0.35莫耳)與TMA-H(環己烷-1,3,4-三羧酸-3,4-酐)29.7g(0.15莫耳)，一邊進行攪拌一邊注意發熱之下昇溫到80℃，於該溫度下花費1小時溶解、反應，進一步花費2小時昇溫至160℃後，於該溫度下反應5小時。反應係在碳酸氣的發泡下進行，系統內變為棕色的透明液體。如此方式地，得到於25℃之黏度為7Pa･s之固體成分17%且溶液酸價5.3(KOHmg/g)的含有羧基之醯胺醯亞胺樹脂之溶液(樹脂溶解於γ-丁內酯之樹脂組成物、固體成分17%)。該樹脂為具有上述式(1)與式(2)之構造的含有羧基之醯胺醯亞胺樹脂。再者，樹脂之固體成分酸價為31.2(KOHmg/g)、重量平均分子量為34,000。 <Synthesis example of alkali-soluble resin 2 (Synthesis example 2)> To a flask equipped with a stirring device, a thermometer and a condenser, add 848.8g of GBL (γ-butyrolactone), 57.5g (0.23 mol) of MDI (diphenylmethane diisocyanate), DMBPDI (4,4'- Diisocyanate-3,3'-dimethyl-1,1'-biphenyl) 59.4g (0.225 mol), TMA (trimellitic anhydride) 67.2g (0.35 mol) and TMA-H (cyclohexane -1,3,4-tricarboxylic acid-3,4-anhydride) 29.7g (0.15 mol), while stirring and paying attention to the heat, raise the temperature to 80°C, spend 1 hour at this temperature to dissolve and react, and further It took 2 hours to raise the temperature to 160°C, and then reacted at this temperature for 5 hours. The reaction is carried out under the foaming of carbonic acid gas, and the system turns into a brown transparent liquid. In this way, a solution of carboxyl group-containing amide imine resin (resin dissolved in γ-butyrolactone) with a solid content of 17% and a solution acid value of 5.3 (KOHmg/g) with a viscosity of 7 Pa･s at 25°C was obtained. Resin composition, solid content 17%). This resin is a carboxyl group-containing amide imine resin having the structure of the above-mentioned formula (1) and formula (2). Furthermore, the acid value of the solid content of the resin is 31.2 (KOHmg/g), and the weight average molecular weight is 34,000.

＜硬化性樹脂組成物之調製＞ 遵照下述表1、2中所示之配方，將各成分摻合、攪拌，以3輥分散，分別調製樹脂組成物。再者，表中之摻合量表示質量份。 ＜Preparation of curable resin composition＞ According to the recipes shown in Tables 1 and 2 below, each component is blended, stirred, and dispersed with three rolls to prepare a resin composition. In addition, the blending amount in the table represents parts by mass.

＜柔軟性(斷裂延伸)之評估＞ 於厚度38μm之PET薄膜，以間隙30μm之塗抹器塗佈各樹脂組成物，以熱風循環式乾燥爐80℃乾燥20分鐘，得到具有各組成物之樹脂層的乾膜。之後，對厚度18μm之銅箔，以真空層合機在90℃、壓力0.4MPa之條件壓接60秒，層合各組成物之樹脂層。接著，對所得之評估基板，使用搭載高壓水銀燈之曝光裝置以400mJ/cm 2進行曝光，剝離PET薄膜，將30℃之1質量%碳酸鈉水溶液以噴霧壓0.2MPa之條件顯像120秒。顯像後於UV輸送帶爐以累積曝光量1000mJ/cm 2之條件進行紫外線照射後，於180℃加熱60分鐘使其硬化，剝離銅箔而得到硬化膜之樣品。將所製作之硬化塗膜的樣品切割為3mm寬×30mm長。將該試驗片使用TA Instruments公司製RSA-G2，以夾頭間10mm，1mm/min之速度進行拉伸試驗。 評估基準如以下所示。 ○：延伸10%以上 △：延伸5%以上、未達10% ×：延伸未達5% <Evaluation of flexibility (elongation at break)> Coat each resin composition on a PET film with a thickness of 38 μm using an applicator with a gap of 30 μm, and dry it in a hot air circulation drying oven at 80°C for 20 minutes to obtain a resin layer with each composition. of dry film. Thereafter, a copper foil with a thickness of 18 μm was pressed and bonded for 60 seconds using a vacuum laminator at 90° C. and a pressure of 0.4 MPa, and the resin layers of each composition were laminated. Next, the obtained evaluation substrate was exposed at 400 mJ/cm 2 using an exposure device equipped with a high-pressure mercury lamp, the PET film was peeled off, and a 1 mass % sodium carbonate aqueous solution at 30° C. was developed for 120 seconds at a spray pressure of 0.2 MPa. After development, the film was irradiated with ultraviolet rays in a UV conveyor belt oven at a cumulative exposure of 1000 mJ/cm 2 , then heated at 180°C for 60 minutes to harden, and the copper foil was peeled off to obtain a sample of the cured film. The prepared hardened coating film sample was cut into 3 mm width × 30 mm length. This test piece was subjected to a tensile test using RSA-G2 manufactured by TA Instruments at a distance of 10 mm between the chucks and a speed of 1 mm/min. The evaluation criteria are as follows. ○: Stretch more than 10% △: Stretch more than 5% but less than 10% ×: Stretch less than 5%

＜密合性之評估＞ (步驟1) 對厚度38μm之PET薄膜，以間隙30μm之塗抹器塗佈各樹脂組成物，以熱風循環式乾燥爐80℃乾燥20分鐘，製作形成有各組成物之樹脂層的薄膜。 (步驟2) 於對厚度1.6mm之FR-4覆銅層合板以使用氯化鐵(III)之蝕刻法將銅完全去除後之板(以下僅稱為「蝕刻去除(etch out)板」)，將4邊較該第1蝕刻去除板稍小的18μm厚之電解銅箔的4邊以耐藥品性黏著膠帶進行固定。該狀態下，貼有膠帶的部位以外係為電解銅箔露出之狀態。接著，以MEC公司製etchBOND CZ-8101將所貼附之電解銅箔化學研磨，製作附銅箔之基板。 (步驟3) 將前述步驟1所製作之薄膜的樹脂層面，以真空層合機，以90℃、壓力0.4MPa之條件60秒壓接於前述步驟2所製作之附銅箔之基板的銅箔面，將各組成物之樹脂層予以層合。接著，對所得之評估基板，使用搭載高壓水銀燈之曝光裝置，以400mJ/cm 2曝光，剝離PET薄膜，將30℃之1質量%碳酸鈉水溶液以噴霧壓0.2MPa之條件顯像120秒。顯像後於UV輸送帶爐以累積曝光量1000mJ/cm 2之條件進行紫外線照射後，於180℃加熱60分鐘使其硬化，製作於附銅箔之基板的銅箔上形成有各組成物之硬化膜的試驗片。 (步驟4) 於步驟3所製作之試驗片的硬化膜面，將4邊較試驗片之銅箔稍小的第2蝕刻去除板以2液性環氧系接著劑(Araldite Standard)進行接著，於60℃硬化4小時。硬化後以切割器切出所接著之第2蝕刻去除板的大小，自第1蝕刻去除板脫離，將正反面翻轉，製作第2蝕刻去除板所接著之各組成物的硬化膜上形成有經化學研磨之銅箔的剝離強度測定用樣品。 (測定) 將所製作之剝離強度測定用樣品切出1cm寬、長7cm以上，使用島津製作所製小型桌上試驗機EZ-SX，使用90°印刷剝離治具，求出於90度之角度的密合強度。 評估基準如以下所示。 ○：密合性5N/cm以上 △：密合性4N/cm以上、未達5N/cm ×：密合性未達3N/cm <Evaluation of Adhesion> (Step 1) Apply each resin composition to a PET film with a thickness of 38 μm using an applicator with a gap of 30 μm, and dry it in a hot air circulation drying oven at 80°C for 20 minutes to produce a film with each composition. Resin layer film. (Step 2) Completely remove the copper from the FR-4 copper-clad laminate with a thickness of 1.6mm using ferric (III) chloride etching (hereinafter referred to as the "etch out board") , the four sides of an 18 μm-thick electrolytic copper foil that is slightly smaller than the first etched removal plate are fixed with chemical-resistant adhesive tape. In this state, the electrolytic copper foil is exposed except for the area where the tape is attached. Next, the attached electrolytic copper foil was chemically polished using etchBOND CZ-8101 manufactured by MEC Corporation to produce a substrate with copper foil. (Step 3) Press the resin layer of the film produced in Step 1 above to the copper foil of the substrate with copper foil produced in Step 2 using a vacuum laminator at 90°C and a pressure of 0.4MPa for 60 seconds. Next, the resin layers of each composition are laminated. Next, the obtained evaluation substrate was exposed to 400 mJ/cm 2 using an exposure device equipped with a high-pressure mercury lamp, the PET film was peeled off, and a 1 mass % sodium carbonate aqueous solution at 30°C was developed for 120 seconds at a spray pressure of 0.2 MPa. After development, it is irradiated with ultraviolet rays in a UV conveyor belt furnace at a cumulative exposure of 1000mJ/ cm2 , and then heated at 180°C for 60 minutes to harden. The copper foil of the copper foil-attached substrate is formed on the copper foil of each composition. Test piece of hardened film. (Step 4) On the cured film surface of the test piece produced in Step 3, attach a second etching removal plate that is slightly smaller on four sides than the copper foil of the test piece with a 2-liquid epoxy adhesive (Araldite Standard). Harden at 60°C for 4 hours. After hardening, use a cutter to cut out the size of the second etching removal plate to be attached, separate it from the first etching removal plate, turn over the front and back, and prepare the second etching removal plate. The chemical cured film of each component to be attached is formed on Sample for measuring the peel strength of ground copper foil. (Measurement) The prepared sample for peel strength measurement was cut out to a width of 1 cm and a length of 7 cm or more, and using a small desktop testing machine EZ-SX manufactured by Shimadzu Corporation and a 90° printed peeling jig, the angle at an angle of 90 degrees was determined. Adhesion strength. The evaluation criteria are as follows. ○: Adhesion 5N/cm or more △: Adhesion 4N/cm or more, less than 5N/cm ×: Adhesion less than 3N/cm

＜顯像性之評估＞ 於厚度38μm之PET薄膜，以間隙30μm之塗抹器塗佈各樹脂組成物，以熱風循環式乾燥爐80℃乾燥20分鐘，製作形成有各組成物之樹脂層的薄膜。將所製作之薄膜的樹脂層面，以真空層合機以90℃、壓力0.4MPa之條件60秒壓接於厚度1.6mm之FR-4覆銅層合板前述步驟，層合各組成物之樹脂層，剝離PET薄膜。接著，對所得之評估基板，將30℃之1質量%碳酸鈉水溶液以噴霧壓0.2MPa之條件進行顯像。將於10分鐘以下即可顯像的樣品作為能夠顯像。將即使以10分鐘以上之顯像亦無法顯像之樣品作為無法顯像。 評估基準如以下所示。 ○：能夠顯像 ×：無法顯像 ＜Evaluation of imaging properties＞ Each resin composition was applied to a PET film with a thickness of 38 μm using an applicator with a gap of 30 μm, and dried in a hot air circulation drying oven at 80°C for 20 minutes to prepare a film with a resin layer of each composition. The resin layer of the produced film was pressed onto an FR-4 copper-clad laminate with a thickness of 1.6mm for 60 seconds using a vacuum laminator at 90°C and a pressure of 0.4MPa. The resin layers of each composition were laminated in the previous steps. , peel off the PET film. Next, the obtained evaluation substrate was developed using a 1 mass % sodium carbonate aqueous solution at 30° C. and a spray pressure of 0.2 MPa. Samples that can be developed in less than 10 minutes are considered to be developable. Samples that cannot be developed even if developed for more than 10 minutes are regarded as undevelopable. The evaluation criteria are as follows. ○: Able to develop ×: Unable to develop

＜耐熱性(玻璃轉移點)之評估＞ 於厚度38μm之PET薄膜，以間隙30μm之塗抹器塗佈各樹脂組成物，以熱風循環式乾燥爐80℃乾燥20分鐘，得到具有各組成物之樹脂層的乾膜。之後，對厚度18μm之銅箔，以真空層合機在90℃、壓力0.4MPa之條件壓接60秒，層合各組成物之樹脂層。接著，對所得之評估基板，使用搭載高壓水銀燈之曝光裝置以400mJ/cm 2進行曝光，將30℃之1質量%碳酸鈉水溶液以噴霧壓0.2MPa之條件顯像120秒，剝離PET薄膜。顯像後於UV輸送帶爐以累積曝光量1000mJ/cm 2之條件進行紫外線照射後，於180℃加熱60分鐘使其硬化，剝離銅箔而得到硬化膜之樣品。將所製作之硬化塗膜的樣品切割為3mm寬×30mm長。將該試驗片使用TA Instruments公司製TMA(Thermomechanical Analysis)Q400，以拉伸模式，以夾頭間16mm、荷重50mN、氮環境下，以5℃/分鐘由20℃昇溫至300℃，接著，以10℃/分鐘由300℃降溫至-40℃，進一步以5℃/分鐘由-40℃昇溫至300℃來測定。由以5℃/分鐘由-40℃昇溫至300℃時的反曲點得到玻璃轉移點(Tg)。 評估基準如以下所示。 ◎：Tg 170℃以上 〇：Tg 160℃以上、未達170℃ △：Tg 150℃以上、未達160℃ ×：Tg 150℃以下 <Evaluation of heat resistance (glass transfer point)> Coat each resin composition on a PET film with a thickness of 38 μm using an applicator with a gap of 30 μm, and dry it in a hot air circulation drying oven at 80°C for 20 minutes to obtain a resin with each composition. layer of dry film. Thereafter, a copper foil with a thickness of 18 μm was pressed and bonded for 60 seconds using a vacuum laminator at 90° C. and a pressure of 0.4 MPa, and the resin layers of each composition were laminated. Next, the obtained evaluation substrate was exposed at 400 mJ/cm 2 using an exposure device equipped with a high-pressure mercury lamp, and a 1 mass % sodium carbonate aqueous solution at 30° C. was developed for 120 seconds at a spray pressure of 0.2 MPa, and the PET film was peeled off. After development, the film was irradiated with ultraviolet rays in a UV conveyor belt oven at a cumulative exposure of 1000 mJ/cm 2 , then heated at 180°C for 60 minutes to harden, and the copper foil was peeled off to obtain a sample of the cured film. The prepared hardened coating film sample was cut into 3 mm width × 30 mm length. The test piece was heated from 20°C to 300°C at a rate of 5°C/min in the tensile mode with a gap of 16mm between the chucks, a load of 50mN, and a nitrogen environment. The temperature was measured by cooling from 300°C to -40°C at 10°C/min, and then increasing the temperature from -40°C to 300°C at 5°C/min. The glass transition point (Tg) was obtained from the inflection point when the temperature was raised from -40°C to 300°C at 5°C/min. The evaluation criteria are as follows. ◎: Tg 170℃ or more 〇: Tg 160℃ or more but less than 170℃ △: Tg 150℃ or more but less than 160℃ ×: Tg 150℃ or less

鹼可溶性樹脂1：上述所合成之甲酚酚醛清漆型含有羧基之樹脂，表中之量為塗漆(varnish)量(固體成分65%) 鹼可溶性樹脂2：上述所合成之具有式(1)與式(2)之構造的含有羧基之醯胺醯亞胺樹脂，表中之量為塗漆量(固體成分17%) 光聚合起始劑：Omnirad TPO，IGM Resins公司製 具有乙烯性不飽和基之化合物1：二季戊四醇六丙烯酸酯 具有乙烯性不飽和基之化合物2：二環戊二烯二丙烯酸酯 熱硬化性樹脂1：萘型環氧樹脂HP-4032(數平均分子量：237)DIC公司製 熱硬化性樹脂2：二環戊二烯型環氧樹脂HP-7200L(數平均分子量：347)DIC公司製 熱硬化性樹脂3：聯苯型環氧樹脂NC-3000L(數平均分子量：700)日本化藥公司製 熱硬化性樹脂4：聯苯型環氧樹脂YX-4000(數平均分子量：265)三菱化學公司製 熱硬化性樹脂5：雙酚A型環氧樹脂jER1002(2官能、數平均分子量：1200)三菱化學公司製 熱硬化性樹脂6：雙酚A型環氧樹脂jER1004(2官能、數平均分子量：1650)三菱化學公司製 熱硬化性樹脂7：雙酚A型環氧樹脂jER1007(2官能、數平均分子量：2900)三菱化學公司製 熱硬化性樹脂8：雙酚A型環氧樹脂jER1001(數平均分子量：900)三菱化學公司製 熱硬化性樹脂9：雙酚A型環氧樹脂jER1009(數平均分子量：3800、軟化點：144℃)三菱化學公司製 熱硬化性樹脂10：酚酚醛清漆型環氧樹脂N-775(數平均分子量：670)DIC公司製 熱硬化促進劑：1B2PZ 四國化成工業公司製 溶劑：丙二醇單甲基醚乙酸酯 Alkali-soluble resin 1: Cresol novolak type resin containing carboxyl groups synthesized above, the amount in the table is the varnish amount (solid content 65%) Alkali-soluble resin 2: the carboxyl group-containing amide imine resin synthesized above and having the structure of formula (1) and formula (2). The amount in the table is the coating amount (solid content 17%) Photopolymerization initiator: Omnirad TPO, manufactured by IGM Resins Compound 1 with ethylenically unsaturated group: dipentaerythritol hexaacrylate Compound 2 with ethylenically unsaturated group: dicyclopentadiene diacrylate Thermosetting resin 1: Naphthalene type epoxy resin HP-4032 (number average molecular weight: 237) manufactured by DIC Corporation Thermosetting resin 2: dicyclopentadiene-type epoxy resin HP-7200L (number average molecular weight: 347) manufactured by DIC Corporation Thermosetting resin 3: biphenyl-type epoxy resin NC-3000L (number average molecular weight: 700) manufactured by Nippon Chemical Co., Ltd. Thermosetting resin 4: biphenyl-type epoxy resin YX-4000 (number average molecular weight: 265) manufactured by Mitsubishi Chemical Corporation Thermosetting resin 5: Bisphenol A type epoxy resin jER1002 (bifunctional, number average molecular weight: 1200) manufactured by Mitsubishi Chemical Corporation Thermosetting resin 6: Bisphenol A type epoxy resin jER1004 (bifunctional, number average molecular weight: 1650) manufactured by Mitsubishi Chemical Corporation Thermosetting resin 7: Bisphenol A type epoxy resin jER1007 (bifunctional, number average molecular weight: 2900) manufactured by Mitsubishi Chemical Corporation Thermosetting resin 8: bisphenol A type epoxy resin jER1001 (number average molecular weight: 900) manufactured by Mitsubishi Chemical Corporation Thermosetting resin 9: Bisphenol A type epoxy resin jER1009 (number average molecular weight: 3800, softening point: 144°C) manufactured by Mitsubishi Chemical Corporation Thermosetting resin 10: Phenol novolak type epoxy resin N-775 (number average molecular weight: 670) manufactured by DIC Corporation Thermal hardening accelerator: 1B2PZ manufactured by Shikoku Chemical Industry Co., Ltd. Solvent: propylene glycol monomethyl ether acetate

由上表所示之結果，可知實施例之硬化性樹脂組成物，顯像性優良，且硬化物之柔軟性、密合性及耐熱性優良。From the results shown in the table above, it can be seen that the curable resin compositions of the Examples have excellent developability, and the cured product has excellent flexibility, adhesion and heat resistance.

Claims (5)

一種硬化性樹脂組成物，其係含有(A)鹼可溶性樹脂、(B)光聚合起始劑、(C)具有乙烯性不飽和基之化合物，與(D)熱硬化性樹脂之硬化性樹脂組成物，其特徵為 含有(D-1)包含下述式(d-1-1)~(d-1-3)表示之構造中任1者以上，且數平均分子量為1000以下之熱硬化性樹脂，及(D-2)數平均分子量為1000~3000且2官能之熱硬化性樹脂，作為前述(D)熱硬化性樹脂； 。 A curable resin composition containing (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a compound having an ethylenically unsaturated group, and (D) a thermosetting resin. A composition characterized by containing (D-1) a thermally hardened thermosetting structure that contains at least one of the structures represented by the following formulas (d-1-1) to (d-1-3) and has a number average molecular weight of 1000 or less. thermosetting resin, and (D-2) a bifunctional thermosetting resin with a number average molecular weight of 1000 to 3000, as the aforementioned (D) thermosetting resin; . 如請求項1之硬化性樹脂組成物，其中前述(A)鹼可溶性樹脂，含有具有下述式(1)及(2)表示之至少一方之構造與鹼可溶性官能基的醯胺醯亞胺樹脂； 。 The curable resin composition of claim 1, wherein the alkali-soluble resin (A) contains an amide imine resin having at least one structure represented by the following formulas (1) and (2) and an alkali-soluble functional group. ; . 一種乾膜，其特徵為具有將如請求項1之硬化性樹脂組成物塗佈於薄膜上並乾燥而得到之樹脂層。A dry film characterized by having a resin layer obtained by applying the curable resin composition according to claim 1 on a film and drying it. 一種硬化物，其特徵為將如請求項1或2之硬化性樹脂組成物或如請求項3之乾膜之樹脂層硬化而成。A cured product characterized by curing the resin layer of the curable resin composition according to claim 1 or 2 or the dry film according to claim 3. 一種電子零件，其特徵為具備如請求項4之硬化物而成。An electronic component characterized by having the hardened material according to claim 4.
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