TW201530252A - Alkali developable photosensitive resin composition, dry film, cured object, and printed circuit board - Google Patents

Alkali developable photosensitive resin composition, dry film, cured object, and printed circuit board Download PDF

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TW201530252A
TW201530252A TW103109910A TW103109910A TW201530252A TW 201530252 A TW201530252 A TW 201530252A TW 103109910 A TW103109910 A TW 103109910A TW 103109910 A TW103109910 A TW 103109910A TW 201530252 A TW201530252 A TW 201530252A
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alkali
resin composition
photosensitive resin
resin
manufactured
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TW103109910A
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TWI574105B (en
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Mamoru Yonemoto
guo-bin Pu
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Taiyo Ink Suzhou Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Abstract

An alkali developable photosensitive resin composition, a dry film, cured object, and a printed circuit board. The alkali developable photosensitive resin composition comprises alkali-soluble resin (A), a photopolymerization initiator (B), a thermosetting component (C), a thermosetting accelerator (D), and barite (E).

Description

鹼顯影型感光性樹脂組合物、乾膜和固化物以及印刷電路板 Alkali-developing photosensitive resin composition, dry film and cured product, and printed circuit board

本發明提供具有指觸乾燥性、密合性、耐焊接熱性能、耐溶劑性等各種特性，且化學鍍錫耐性、化學鍍金耐性優異的鹼顯影型感光性樹脂組合物。進而，提供使用該鹼顯影型感光性樹脂組合物而形成的乾膜、使用該鹼顯影型感光性樹脂組合物或其乾膜而形成的固化物、及具有該固化物的印刷電路板。 The present invention provides an alkali-developable photosensitive resin composition which has various properties such as dry touchability, adhesion, solder heat resistance, and solvent resistance, and is excellent in electroless tin plating resistance and chemical gold plating resistance. Furthermore, a dry film formed using the alkali-developable photosensitive resin composition, a cured product formed using the alkali-developable photosensitive resin composition or a dry film thereof, and a printed circuit board having the cured product are provided.

通常，作為民用印刷電路板以及產業用印刷電路板的阻焊劑，從高精度化、高密度化的觀點出發，使用藉由紫外線照射後顯影而形成圖像、並加熱固化(完全固化)的阻焊劑，出於對環境問題的顧慮，代替焊接整平，化學鍍錫、化學鍍金等方式存在增加的傾向，阻焊劑也要求化學鍍錫、化學鍍金等的耐性。 In general, as a solder resist for a consumer printed circuit board and an industrial printed circuit board, from the viewpoint of high precision and high density, an image formed by development after ultraviolet irradiation and heat-cured (completely cured) are used. In the case of soldering agents, in place of soldering and leveling, there is a tendency to increase the number of methods such as electroless tin plating and electroless gold plating, and the solder resist also requires resistance such as electroless tin plating or electroless gold plating.

作為這種阻焊劑，專利文獻1中公開了能夠形成耐熱性、密合性、化學鍍金耐性、化學鍍錫耐性優異的塗膜的可鹼顯影的感光性樹脂組合物。另外，專利文獻2中公開 了能夠形成化學鍍錫耐性優異的固化膜的圖案而不會產生指觸乾燥性惡化等問題的光固化性/熱固化性樹脂組合物。 As such a solder resist, Patent Document 1 discloses an alkali-developable photosensitive resin composition capable of forming a coating film having excellent heat resistance, adhesion, chemical gold plating resistance, and chemical tin plating resistance. In addition, Patent Document 2 discloses A photocurable/thermosetting resin composition capable of forming a pattern of a cured film having excellent chemical tin plating resistance without causing problems such as deterioration in dryness of the touch.

然而，上述樹脂組合物的化學鍍錫耐性、化學鍍金耐性尚不充分。 However, the chemical tin plating resistance and the chemical gold plating resistance of the above resin composition are not sufficient.

現有技術文獻 Prior art literature 專利文獻 Patent literature

專利文獻1：日本國特許第4840865號 Patent Document 1: Japanese Patent No. 4840865

專利文獻2：日本國公開2009-733991 Patent Document 2: Japanese National Publication 2009-733991

本發明的目的在於提供具有指觸乾燥性、密合性、耐焊接熱性能、耐溶劑性等各種特性，且化學鍍錫耐性、化學鍍金耐性優異的鹼顯影型感光性樹脂組合物。 An object of the present invention is to provide an alkali-developable photosensitive resin composition which is excellent in electroless tin plating resistance and chemical gold plating resistance, and has various properties such as dry touchability, adhesion, solder heat resistance, and solvent resistance.

為了達成前述目的，本發明提供下述(1)~(8)的技術方案。 In order to achieve the above object, the present invention provides the following technical solutions (1) to (8).

(1)提供一種鹼顯影型感光性樹脂組合物，其特徵在於，含有：(A)鹼溶性樹脂、(B)光聚合引發劑、(C)熱固化性成分、(D)熱固化性促進劑、和(E)重晶石。 (1) An alkali-developable photosensitive resin composition comprising: (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a thermosetting component, and (D) a thermosetting property promotion Agent, and (E) barite.

(2)根據(1)之鹼顯影型感光性樹脂組合物，其特徵在於，(D)熱固化性促進劑含有三聚氰胺、三聚氰胺的有機 酸鹽、咪唑化合物中的至少任一者。 (2) The alkali-developable photosensitive resin composition according to (1), wherein (D) the thermosetting accelerator contains organic melamine or melamine At least one of an acid salt and an imidazole compound.

(3)根據(1)之鹼顯影型感光性樹脂組合物，其特徵在於，還含有雙氰胺。 (3) The alkali-developable photosensitive resin composition according to (1), which further comprises dicyandiamide.

(4)根據(1)之鹼顯影型感光性樹脂組合物，其特徵在於，還含有結晶性二氧化矽和滑石中的至少任一者。 (4) The alkali-developable photosensitive resin composition according to (1), which further comprises at least one of crystalline cerium oxide and talc.

(5)根據(1)之鹼顯影型感光性樹脂組合物，其特徵在於，(A)鹼溶性樹脂為含羧基樹脂。 (5) The alkali-developable photosensitive resin composition according to (1), wherein the (A) alkali-soluble resin is a carboxyl group-containing resin.

(6)一種乾膜，其特徵在於，其是將(1)~(5)中任一項之鹼顯影型感光性樹脂組合物塗布在薄膜上並乾燥而成的。 (6) A dry film obtained by applying the alkali-developable photosensitive resin composition according to any one of (1) to (5) onto a film and drying the film.

(7)一種固化物，其特徵在於，其是利用(1)~(5)中任一項之鹼顯影型感光性樹脂組合物、或者是利用將(1)~(5)中任一項之鹼顯影型感光性樹脂組合物塗布在薄膜上並乾燥而成的乾膜來得到的。 (7) A cured product of the alkali-developable photosensitive resin composition according to any one of (1) to (5), or using any one of (1) to (5) The alkali-developable photosensitive resin composition is obtained by applying a dry film formed by drying on a film.

(8)一種印刷電路板，其具有固化物，所述固化物是利用(1)~(5)中任一項之鹼顯影型感光性樹脂組合物、或者是利用將(1)~(5)中任一項之鹼顯影型感光性樹脂組合物塗布在薄膜上並乾燥而成的乾膜來得到的。 (8) A printed circuit board having a cured product obtained by using the alkali-developable photosensitive resin composition according to any one of (1) to (5) or using (1) to (5) The alkali-developable photosensitive resin composition according to any one of them is obtained by applying a dry film formed by drying on a film.

根據本發明，可以提供具有指觸乾燥性、密合性、耐焊接熱性能、耐溶劑性等各種特性，且化學鍍錫耐性、化學鍍金耐性優異的鹼顯影型感光性樹脂組合物。 According to the present invention, it is possible to provide an alkali-developable photosensitive resin composition which has various properties such as dry touch resistance, adhesion, solder heat resistance, solvent resistance, and chemical tin plating resistance and chemical gold plating resistance.

本發明為一種鹼顯影型感光性樹脂組合物，其特徵在於，含有：(A)鹼溶性樹脂、(B)光聚合引發劑、(C)熱固化性成分、(D)熱固化性促進劑、和(E)重晶石。 The present invention provides an alkali-developable photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a thermosetting component, and (D) a thermosetting accelerator. And (E) barite.

以下，針對本發明的鹼顯影型感光性樹脂組合物的各成分進行具體說明。 Hereinafter, each component of the alkali-developable photosensitive resin composition of the present invention will be specifically described.

(A)鹼溶性樹脂 (A) alkali soluble resin

本發明的鹼溶性樹脂能夠賦予化學鍍金耐性和化學鍍錫耐性。作為鹼溶性樹脂，較佳地使用含羧基樹脂或含酚性羥基樹脂。由此，能夠使由可固化性樹脂組合物形成的塗膜借助顯影而形成圖案。 The alkali-soluble resin of the present invention can impart electroless gold plating resistance and chemical tin plating resistance. As the alkali-soluble resin, a carboxyl group-containing resin or a phenol-containing hydroxy resin is preferably used. Thereby, the coating film formed from the curable resin composition can be patterned by development.

作為含羧基樹脂，以賦予鹼顯影性為目的，可以使用公知之分子中具有羧基的各種含羧基樹脂。特別是可固化性樹脂組合物為具有感光性的可固化性樹脂組合物時，分子中具有烯屬不飽和雙鍵的含羧基感光性樹脂在固化性、耐顯影性的方面是較佳的。其中，該不飽和雙鍵較佳地源自丙烯酸或甲基丙烯酸或者其衍生物。 As the carboxyl group-containing resin, for the purpose of imparting alkali developability, various carboxyl group-containing resins having a carboxyl group in a known molecule can be used. In particular, when the curable resin composition is a photosensitive curable resin composition, the carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is preferable in terms of curability and development resistance. Among them, the unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof.

另外，僅使用不具有烯屬不飽和雙鍵的含羧基樹脂時，為了使組合物具有光固化性，較佳地使用本發明的感光性化合物或其低聚物、後述分子中具有2個以上烯屬不飽和基團的化合物，即光聚合性單體的組合物。 Further, when only a carboxyl group-containing resin having no ethylenically unsaturated double bond is used, in order to impart photocurability to the composition, it is preferred to use the photosensitive compound of the present invention or an oligomer thereof, and two or more molecules to be described later. A compound of an ethylenically unsaturated group, that is, a composition of a photopolymerizable monomer.

作為含羧基樹脂的具體例子，較佳地列舉下面化合物(低聚物和聚合物均可)。 As specific examples of the carboxyl group-containing resin, the following compounds (both oligomers and polymers) are preferably exemplified.

(1)藉由(甲基)丙烯酸等不飽和羧酸與含不飽和基團之化合物(例如，苯乙烯、α-甲基苯乙烯、(甲基)丙烯酸C1-C6烷基酯、異丁烯等)的共聚合反應而得到含羧基樹脂。 (1) An unsaturated carboxylic acid such as (meth)acrylic acid and a compound containing an unsaturated group (for example, styrene, α-methylstyrene, C1-C6 alkyl (meth)acrylate, isobutylene, etc.) The copolymerization reaction gives a carboxyl group-containing resin.

(2)藉由二異氰酸酯(例如，脂肪族二異氰酸酯、支鏈脂肪族二異氰酸酯、脂環式二異氰酸酯、芳香族二異氰酸酯等)與含羧基二醇之化合物(例如，二羥甲基丙酸、二羥甲基丁酸等)及二元醇化合物(例如，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、丙烯酸類多元醇、雙酚A系環氧烷加成物二元醇、具有酚性羥基及醇性羥基的化合物等)的加成聚合反應而得到含羧基聚胺酯樹脂。 (2) a compound (for example, dimethylolpropionic acid) containing a diisocyanate (for example, an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate, or the like) and a carboxyl group-containing diol (for example, dimethylolpropionic acid) , dimethylol butyric acid, etc.) and diol compounds (for example, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A) An addition polymerization reaction of an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group, or the like to obtain a carboxyl group-containing polyurethane resin.

(3)藉由二異氰酸酯化合物(例如，脂肪族二異氰酸酯、支鏈脂肪族二異氰酸酯、脂環式二異氰酸酯、芳香族二異氰酸酯等)與二元醇化合物(例如，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、丙烯酸類多元醇、雙酚A系環氧烷加成物二元醇、具有酚性羥基和醇性羥基的化合物等)的加成聚合反應而得到聚胺酯樹脂，接著使其末端與二元酸酐(例如，丙酸酐、琥珀酸酐、馬來酸酐、鄰苯二甲酸酐等)反應而得到含末端羧基聚胺酯樹脂。 (3) by a diisocyanate compound (for example, an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate, etc.) and a glycol compound (for example, a polycarbonate polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group, etc.) The addition polymerization reaction produces a polyurethane resin, and then the terminal is reacted with a dibasic acid anhydride (for example, propionic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, etc.) to obtain a terminal carboxyl group-containing polyurethane resin.

(4)藉由二異氰酸酯與二官能性環氧樹脂的(甲基)丙烯酸酯(例如，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、聯苯酚型環氧樹脂等)或使其一部分被二元酸酐(例如，丙酸酐、琥珀酸酐、馬來酸酐、鄰苯二甲酸酐等)改質而成的酸酐改質物、含羧基二醇化合物以及二元醇化合物的加成聚合反應而得到的感光性含羧基聚胺酯樹脂。 (4) (meth) acrylates of diisocyanate and difunctional epoxy resin (for example, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, double Phenol S type epoxy resin, bisphenol type An epoxy resin, a biphenol type epoxy resin, or the like, or an acid anhydride modified product obtained by modifying a part of a dibasic acid anhydride (for example, propionic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, etc.), A photosensitive carboxyl group-containing polyurethane resin obtained by addition polymerization of a carboxy diol compound and a diol compound.

(5)藉由在上述的(2)或(4)的樹脂的合成中加入分子中具有1個羥基和1個以上之(甲基)丙烯醯基的化合物(例如，(甲基)丙烯酸羥基烷酯等)而得到末端(甲基)丙烯醯化的含羧基聚胺酯樹脂。 (5) A compound having one hydroxyl group and one or more (meth)acryl fluorenyl groups in the molecule (for example, (meth)acrylic acid hydroxyl group) is added to the synthesis of the resin of (2) or (4) above. The alkyl (meth) acrylated carboxyl group-containing polyurethane resin is obtained by an alkyl ester or the like.

(6)藉由在上述的(2)或(4)的樹脂的合成中加入等莫耳量之分子中具有1個異氰酸酯基和多於1個之(甲基)丙烯醯基的化合物(例如，異佛爾酮二異氰酸酯與季戊四醇三丙烯酸酯)莫耳而得到末端(甲基)丙烯醯化的含羧基聚胺酯樹脂。 (6) by adding a compound having one isocyanate group and more than one (meth)acryl fluorenyl group in a molar amount of molecules in the synthesis of the resin of (2) or (4) above (for example) , isophorone diisocyanate and pentaerythritol triacrylate) to obtain a terminal (meth) propylene-deposited carboxyl group-containing polyurethane resin.

(7)使如後所述的之二官能性或多於二官能性的多官能性(固態)環氧樹脂與(甲基)丙烯酸反應，使存在於側鏈的羥基與二元酸酐(例如，鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐等)進行加成反應而得到含羧基感光性樹脂。 (7) reacting a difunctional or more than difunctional polyfunctional (solid) epoxy resin as described later with (meth)acrylic acid to form a hydroxyl group present in a side chain with a dibasic acid anhydride (for example) An addition reaction is carried out by phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or the like to obtain a carboxyl group-containing photosensitive resin.

(8)使如後所述的之二官能性(固態)環氧樹脂的羥基進一步用表氯醇環氧化而得到多官能性環氧樹脂，接著與(甲基)丙烯酸反應，然而使生成的羥基與二元酸酐(例如，鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐等)進行加成反應而得到含羧基感光性樹脂。 (8) The hydroxyl group of the difunctional (solid) epoxy resin as described later is further epoxidized with epichlorohydrin to obtain a polyfunctional epoxy resin, followed by reaction with (meth)acrylic acid, but the resulting The hydroxyl group is subjected to an addition reaction with a dibasic acid anhydride (for example, phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride) to obtain a carboxyl group-containing photosensitive resin.

(9)使多官能性酚化合物(例如，酚醛清漆)與環狀醚(例如，環氧乙烷)、環狀碳酸酯(例如，碳酸亞丙酯)進行加成反應，將得到的羥基用(甲基)丙烯酸部分酯化，接著使剩餘的羥基與多元酸酐反應而得到含羧基感光性樹脂。 (9) subjecting a polyfunctional phenol compound (for example, a novolac) to a cyclic ether (for example, ethylene oxide) or a cyclic carbonate (for example, propylene carbonate) to carry out an addition reaction, and the obtained hydroxyl group is used. The (meth)acrylic acid is partially esterified, and then the remaining hydroxyl group is reacted with a polybasic acid anhydride to obtain a carboxyl group-containing photosensitive resin.

(10)將上述(1)~(9)的樹脂進一步與分子中具有1個環氧基和1個以上之(甲基)丙烯醯基的化合物(例如，(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸α-甲基縮水甘油酯等)進行加成反應而得到含羧基感光性樹脂。 (10) The resin of the above (1) to (9) is further added to a compound having one epoxy group and one or more (meth)acryl fluorenyl groups in the molecule (for example, glycidyl (meth)acrylate, The (meth)acrylic acid α-methylglycidyl ester or the like is subjected to an addition reaction to obtain a carboxyl group-containing photosensitive resin.

需要說明的是，(甲基)丙烯酸酯是統稱丙烯酸酯、甲基丙烯酸酯及其混合物的術語，以下其他的類似表達也一樣。 It should be noted that (meth) acrylate is a term collectively referred to as acrylate, methacrylate, and mixtures thereof, and the other similar expressions below are also the same.

作為上述含羧基樹脂的市售品，可以使用R-2000(對應上述(6)，DIC株式會社製造)、PCR-1160H(日本化藥株式會社製造)、VB5301、VB5305(以上MITSUBISHI RAYON CO.,LTD製造)等。 As a commercial product of the above-mentioned carboxyl group-containing resin, R-2000 (corresponding to (6), manufactured by DIC Corporation), PCR-1160H (manufactured by Nippon Kayaku Co., Ltd.), VB5301, VB5305 (above MITSUBISHI RAYON CO., LTD manufacturing) and so on.

如上所述的含羧基樹脂在主鏈聚合物的側鏈上具有多個游離的羧基，因此能夠利用稀鹼水溶液進行顯影。 The carboxyl group-containing resin as described above has a plurality of free carboxyl groups in the side chain of the main chain polymer, and thus can be developed with a dilute aqueous alkali solution.

這種含羧基樹脂的酸值較佳地為40~200mgKOH/g。含羧基樹脂的酸值為40mgKOH/g以上時，鹼顯影變得容易，另一方面，不足200mgKOH/g時，利用由顯影液以溶解曝光部分，而使正常的抗蝕圖案的描繪變得容易。更佳地為45~120mgKOH/g。 The acid value of such a carboxyl group-containing resin is preferably from 40 to 200 mgKOH/g. When the acid value of the carboxyl group-containing resin is 40 mgKOH/g or more, alkali development becomes easy. On the other hand, when it is less than 200 mgKOH/g, it is easy to draw a normal resist pattern by dissolving the exposed portion by the developer. . More preferably, it is 45 to 120 mgKOH/g.

另外，含羧基樹脂的重量平均分子量根據樹脂骨架而 不同，但通常較佳地為2000~150000。重量平均分子量為2000以上時，有時不黏性能變得良好，而且曝光後的塗膜的耐濕性也良好，顯影時也不會使膜變薄，解析度優異。另一方面，重量平均分子量不足150000時，有時顯影性明顯變得良好，貯藏穩定性也變得良好。更佳地為5000~100000。 In addition, the weight average molecular weight of the carboxyl group-containing resin is based on the resin skeleton. Different, but usually preferably from 2,000 to 150,000. When the weight average molecular weight is 2,000 or more, the non-tack property is good, and the moisture resistance of the coating film after exposure is also good, and the film is not thinned during development, and the resolution is excellent. On the other hand, when the weight average molecular weight is less than 150,000, the developability is remarkably good, and the storage stability is also good. More preferably, it is 5000 to 100,000.

這種含羧基樹脂的含量較佳地為全部組合物的20~60重量%。含量為20重量%以上時，有時膜強度提高。另一方面，為60重量%以下時，組合物的黏性降低，塗布性等提高。更佳地為30~50重量%。 The content of such a carboxyl group-containing resin is preferably from 20 to 60% by weight based on the total composition. When the content is 20% by weight or more, the film strength may increase. On the other hand, when it is 60% by weight or less, the viscosity of the composition is lowered, and the coatability and the like are improved. More preferably, it is 30 to 50% by weight.

可使用非前述所列舉之含羧基樹脂的物質使用，亦可以使用該物質中的任一者或多者之混合物。 A substance other than the above-mentioned carboxyl group-containing resin may be used, and a mixture of any one or more of the substances may also be used.

其中，從化學鍍耐性的觀點出發，特佳地使用，於前述例示(8)中，使下述通式(1)所示的多官能性環氧化合物(a)和含不飽和基團之單羧酸(b)的反應產物與多元酸酐(c)反應而得到含羧基固化型樹脂(以下，稱為鹼溶性樹脂A)、以及於前述例示(1)中，藉由(d)含羧基之(甲基)丙烯酸系共聚樹脂與(e)1分子中具有環氧乙烷環和烯屬不飽和基團的化合物反應而得到含羧基共聚樹脂(以下，稱為鹼溶性樹脂B)中的至少任一者。 In the above-mentioned example (8), the polyfunctional epoxy compound (a) represented by the following general formula (1) and an unsaturated group-containing group are particularly preferably used. The reaction product of the monocarboxylic acid (b) is reacted with the polybasic acid anhydride (c) to obtain a carboxyl group-containing curable resin (hereinafter referred to as an alkali-soluble resin A), and in the above-exemplified (1), by (d) a carboxyl group The (meth)acrylic copolymer resin is reacted with (e) a compound having an oxirane ring and an ethylenically unsaturated group in one molecule to obtain a carboxyl group-containing copolymer resin (hereinafter referred to as an alkali-soluble resin B). At least either.

(式中，X表示1分子中具有2個縮水甘油基之芳香 族環氧樹脂的芳香環殘基，M表示縮水甘油基和/或氫原子，Z表示脂肪族或芳香族二元酸的殘基，p表示1~20的整數。) (wherein X represents an aromatic having 2 glycidyl groups in one molecule An aromatic ring residue of a family epoxy resin, M represents a glycidyl group and/or a hydrogen atom, Z represents a residue of an aliphatic or aromatic dibasic acid, and p represents an integer of 1-20. )

本發明的鹼溶性樹脂A的密合性、撓性、耐水性、耐化學藥品性優異，但指觸乾燥性、利用曝光的表面固化性(高靈敏度)差。另外，鹼溶性樹脂B的耐熱性、耐化學藥品性、指觸乾燥性、表面固化性(高靈敏度)優異，但顯影性存在弊端。本發明中，為了兼具鹼溶性樹脂A和鹼溶性樹脂B的特性而以適宜的比例將其組合，而能夠均衡地兼顧所有特性。關於適宜的比例，前述鹼溶性樹脂A：B為20：1~1：20，特佳地為15：1~1：15。 The alkali-soluble resin A of the present invention is excellent in adhesion, flexibility, water resistance, and chemical resistance, but is inferior in touch dryness and surface hardenability (high sensitivity) by exposure. Further, the alkali-soluble resin B is excellent in heat resistance, chemical resistance, dry touch property, and surface curability (high sensitivity), but the developability has drawbacks. In the present invention, in order to combine the characteristics of the alkali-soluble resin A and the alkali-soluble resin B, they are combined at an appropriate ratio, and all characteristics can be balanced. With respect to a suitable ratio, the alkali-soluble resin A:B is 20:1 to 1:20, particularly preferably 15:1 to 1:15.

鹼溶性樹脂A是使前述通式(1)所示的多官能性環氧化合物(a)和含不飽和基團之單羧酸(b)的反應產物與多元酸酐(c)反應而得到的含羧基固化型樹脂。 The alkali-soluble resin A is obtained by reacting a reaction product of the polyfunctional epoxy compound (a) represented by the above formula (1) and a monocarboxylic acid (b) containing an unsaturated group with a polybasic acid anhydride (c). A carboxyl group-containing curable resin.

此處，多官能性環氧化合物(a)是如下得到的：使1分子中具有2個縮水甘油基的芳香族環氧樹脂(以下，稱為二官能芳香族環氧樹脂)與1分子中具有2個羧基的脂肪族或芳香族二元酸在公知的酯化催化劑(例如，膦類、鹼金屬化合物、胺類等)的存在下交替聚合，使生成的醇性的仲羥基與表鹵代醇在公知的溶劑中(例如，非質子性極性溶劑如二甲基亞碸、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等，或芳香族烴類溶劑如、甲苯、二甲苯等)和在鹼金屬氫氧化物(例如，氫氧化鈉等)的存在下進行反應，從而得到(表鹵代醇的反應量相對於1莫耳之羥基為0~1 莫耳)。 Here, the polyfunctional epoxy compound (a) is obtained by using an aromatic epoxy resin having two glycidyl groups in one molecule (hereinafter referred to as a difunctional aromatic epoxy resin) and one molecule. An aliphatic or aromatic dibasic acid having two carboxyl groups is alternately polymerized in the presence of a known esterification catalyst (for example, a phosphine, an alkali metal compound, an amine, etc.) to form an alcoholic secondary hydroxyl group and a surface halogen. The alcohol is in a known solvent (for example, an aprotic polar solvent such as dimethyl hydrazine, N,N-dimethylformamide, N,N-dimethylacetamide, or the like, or an aromatic hydrocarbon The solvent (for example, toluene, xylene, etc.) is reacted with an alkali metal hydroxide (for example, sodium hydroxide or the like) to obtain (the reaction amount of the epihalohydrin is 0 to 1 mol of the hydroxyl group). 1 Moore).

將1莫耳之多官能性環氧化合物(a)和0.9~1.2莫耳之含不飽和基團之單羧酸(b)進行混合，和在有機溶劑的存在下或不存在下、在阻聚劑(例如，氫醌、氧氣等)和反應催化劑(例如，叔胺如三乙胺等、季銨鹽如三乙基苄基氯化銨等、咪唑化合物如2-乙基-4-甲基咪唑等、磷化合物如三苯基膦等)的共存下通常在約80~140℃下進行反應，從而得到環氧丙烯酸酯化合物。 Mixing 1 mole of the polyfunctional epoxy compound (a) with 0.9 to 1.2 moles of the unsaturated group-containing monocarboxylic acid (b), and in the presence or absence of an organic solvent, in the presence of a polymerization agent (for example, hydroquinone, oxygen, etc.) and a reaction catalyst (for example, a tertiary amine such as triethylamine or the like, a quaternary ammonium salt such as triethylbenzylammonium chloride or the like, an imidazole compound such as 2-ethyl-4-methyl In the coexistence of a group of imidazoles or the like, a phosphorus compound such as triphenylphosphine, etc., the reaction is usually carried out at about 80 to 140 ° C to obtain an epoxy acrylate compound.

藉由使由上述反應生成的環氧丙烯酸酯化合物的醇性羥基與多元酸酐(c)反應而得到鹼溶性樹脂A，在該反應中，調整多元酸酐(c)的用量，使得生成的鹼溶性樹脂A的酸值如前所述為40~200mgKOH/g。反應在有機溶劑的存在下或不存在下通常在約50~130℃下進行。此時，根據需要，也可添加叔胺如三乙胺等、季銨鹽如三乙基苄基氯化銨等、咪唑化合物如2-乙基-4-甲基咪唑等、磷化合物如三苯基膦等作為催化劑。 The alkali-soluble resin A is obtained by reacting an alcoholic hydroxyl group of the epoxy acrylate compound produced by the above reaction with the polybasic acid anhydride (c), and in the reaction, the amount of the polybasic acid anhydride (c) is adjusted so that the alkali solubility is formed. The acid value of the resin A is 40 to 200 mgKOH/g as described above. The reaction is usually carried out at about 50 to 130 ° C in the presence or absence of an organic solvent. At this time, a tertiary amine such as triethylamine or the like, a quaternary ammonium salt such as triethylbenzylammonium chloride or the like, an imidazole compound such as 2-ethyl-4-methylimidazole or the like, a phosphorus compound such as three may be added as needed. Phenylphosphine or the like is used as a catalyst.

作為前述二官能性芳香族環氧樹脂，可以使用二縮水甘油醚(例如，聯苯酚型、聯二甲酚型、雙酚型或萘型)。例如，作為聯苯酚型二縮水甘油醚，可列舉出三菱化學株式會社製造的商品名“EPICOAT YL-6056”，作為聯二甲酚型二縮水甘油醚，可列舉出三菱化學株式會社製造的商品名“EPICOAT YX-4000”等，作為雙酚型二縮水甘油醚，可列舉出住友化學工業株式會社製造的商品名“SUMI-EPOXY ESA-011”、“SUMI-EPOXY ELA-115”等雙 酚A型環氧樹脂、或者DIC株式會社製造的商品名“EPICLON 830S”等雙酚F型環氧樹脂、或者DIC株式會社製造的商品名“EPICLON EXA1514”等雙酚S型環氧樹脂，作為萘型二縮水甘油醚，可列舉出DIC株式會社製造的商品名“EPICLON HP-4032(D)”等，其可以單獨使用或組合兩種以上使用。 As the difunctional aromatic epoxy resin, diglycidyl ether (for example, a biphenol type, a bisphenol type, a bisphenol type or a naphthalene type) can be used. For example, the product name "EPICOAT YL-6056" manufactured by Mitsubishi Chemical Corporation can be used as the biphenol-type diglycidyl ether, and the product of Mitsubishi Chemical Co., Ltd. can be mentioned as the bisphenol type diglycidyl ether. "EPICOAT YX-4000", etc., as the bisphenol type diglycidyl ether, the product names "SUMI-EPOXY ESA-011" and "SUMI-EPOXY ELA-115" manufactured by Sumitomo Chemical Industries, Ltd. A bisphenol-type epoxy resin such as a phenol A-type epoxy resin or a bisphenol F-type epoxy resin such as "EPICLON 830S" manufactured by DIC Corporation, or a product name "EPICLON EXA1514" manufactured by DIC Corporation. The naphthalene type diglycidyl ether is exemplified by the trade name "EPICLON HP-4032 (D)" manufactured by DIC Corporation, and may be used alone or in combination of two or more.

作為1分子中具有2個羧基的二元酸，可以使用1,4-環己烷二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、六氫間苯二甲酸、六氫對苯二甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、衣康酸、琥珀酸、己二酸、己二烯二酸、癸二酸等。從紫外線的透過性、撓性賦予的方面觀點，較佳地使用脂肪族或脂環式的二羧酸化合物。其可以單獨使用或組合兩種以上使用。 As the dibasic acid having two carboxyl groups in one molecule, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, or hexahydro-p-benzene can be used. Dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, itaconic acid, succinic acid, adipic acid, hexadienedioic acid, sebacic acid, and the like. An aliphatic or alicyclic dicarboxylic acid compound is preferably used from the viewpoint of ultraviolet light permeability and flexibility. They may be used singly or in combination of two or more.

作為前述含不飽和基團之單羧酸(b)的代表性例子，可列舉出含羥基丙烯酸酯的不飽和二元酸酐加成物，例如，丙烯酸、甲基丙烯酸、或者(甲基)丙烯酸羥乙酯、(甲基)丙烯酸羥丙酯、(甲基)丙烯酸羥丁酯、三羥甲基丙烷二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、(甲基)丙烯酸苯基縮水甘油酯、(甲基)丙烯酸己內酯加成物等。此處特佳地的是，丙烯酸和甲基丙烯酸中的至少任一者。這些含不飽和基團之單羧酸可以單獨使用或組合兩種以上使用。 Representative examples of the unsaturated group-containing monocarboxylic acid (b) include a hydroxy acrylate-containing unsaturated dibasic acid anhydride adduct such as acrylic acid, methacrylic acid, or (meth)acrylic acid. Hydroxyethyl ester, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di(meth) acrylate, pentaerythritol tri(meth) acrylate, dipentaerythritol penta (methyl) An acrylate, a phenyl glycidyl (meth)acrylate, a caprolactone (meth)acrylate, or the like. Particularly preferred herein is at least any one of acrylic acid and methacrylic acid. These unsaturated group-containing monocarboxylic acids may be used singly or in combination of two or more.

作為上述多元酸酐(c)，可列舉出脂肪族或芳香族多元酸酐，例如，甲基四氫鄰苯二甲酸酐、四氫鄰苯二甲酸 酐、六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、納迪克酸酐、3,6-內亞甲基四氫鄰苯二甲酸酐、甲基內亞甲基四氫鄰苯二甲酸酐、四溴鄰苯二甲酸酐等脂環式二元酸酐、琥珀酸酐、馬來酸酐、衣康酸酐、辛烯基琥珀酸酐、十二碳烯基琥珀酸酐、十五碳烯基琥珀酸酐、鄰苯二甲酸酐、偏苯三酸酐等。亦可以使用其一種或兩種以上之混合物。 The polybasic acid anhydride (c) may, for example, be an aliphatic or aromatic polybasic acid anhydride, for example, methyltetrahydrophthalic anhydride or tetrahydrophthalic acid. Anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methyl endomethylenetetrahydroortene An alicyclic dibasic acid anhydride such as dicarboxylic anhydride or tetrabromophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, dodecenyl succinic anhydride, pentadecenyl amber Anhydride, phthalic anhydride, trimellitic anhydride, and the like. It is also possible to use one or a mixture of two or more kinds thereof.

接著，鹼溶性樹脂B為藉由(d)含羧基(甲基)丙烯酸系共聚樹脂與(e)1分子中具有環氧乙烷環和烯屬不飽和基團的化合物反應而得到的具有羧基的共聚系樹脂。 Next, the alkali-soluble resin B is a carboxyl group obtained by reacting (d) a carboxyl group-containing (meth)acrylic copolymer resin with (e) a compound having an oxirane ring and an ethylenically unsaturated group in one molecule. Copolymer resin.

(d)含羧基(甲基)丙烯酸系共聚樹脂是藉由使(甲基)丙烯酸酯與1分子中具有1個不飽和基團和至少1個羧基的化合物共聚而得到的。作為構成(d)含羧基(甲基)丙烯酸系類共聚樹脂的(甲基)丙烯酸酯，可列舉出含羥基(甲基)丙烯酸酯類，例如，(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯等(甲基)丙烯酸烷基酯類、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸羥丙酯、(甲基)丙烯酸羥丁酯、己內酯改質(甲基)丙烯酸2-羥乙酯等，和二醇改質(甲基)丙烯酸酯類，例如，甲氧基二乙二醇(甲基)丙烯酸酯、乙氧基二乙二醇(甲基)丙烯酸酯、異辛基氧基二乙二醇(甲基)丙烯酸酯、苯氧基三乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯等。其可以單獨使用，也可以混合2種以上使用。 (d) The carboxyl group-containing (meth)acrylic copolymer resin is obtained by copolymerizing a (meth) acrylate with a compound having one unsaturated group and at least one carboxyl group in one molecule. Examples of the (meth) acrylate constituting the (d) carboxyl group-containing (meth)acrylic copolymer resin include hydroxy group-containing (meth) acrylates such as methyl (meth) acrylate and (methyl). Ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, alkyl (meth) acrylate, etc., (methyl) ) 2-hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate, etc., and diol modification (A) Acrylates, for example, methoxydiethylene glycol (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, isooctyloxy diethylene glycol (meth) acrylate Ester, phenoxy triethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, and the like. These may be used alone or in combination of two or more.

另外，作為1分子中具有1個不飽和基團和至少1個羧基的化合物，可列舉出丙烯酸、甲基丙烯酸、不飽和基團與羧酸之間進行了鏈延長的改質不飽和單羧酸(例如(甲基)丙烯酸β-羧乙酯、2-丙烯醯氧基乙基琥珀酸、2-丙烯醯氧基乙基六氫鄰苯二甲酸)、藉由內酯改質而具有酯鍵的不飽和單羧酸、具有醚鍵的改質不飽和單羧酸、和分子中包含2個以上羧基的物質如馬來酸等。其可以單獨使用，也可以混合2種以上使用。 Further, examples of the compound having one unsaturated group and at least one carboxyl group in one molecule include modified unsaturated monocarboxylic acid in which chain extension is carried out between acrylic acid, methacrylic acid, and an unsaturated group and a carboxylic acid. An acid (for example, β-carboxyethyl (meth)acrylate, 2-propenyloxyethyl succinic acid, 2-propenyloxyethylhexahydrophthalic acid), having an ester by upgrading the lactone A bond of an unsaturated monocarboxylic acid, a modified unsaturated monocarboxylic acid having an ether bond, and a substance having two or more carboxyl groups in the molecule such as maleic acid. These may be used alone or in combination of two or more.

作為(e)1分子中具有環氧乙烷環與烯屬不飽和基團的化合物，只要是1分子中具有烯屬不飽和基團和環氧乙烷環的化合物即可，例如可列舉出(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸α-甲基縮水甘油酯、(甲基)丙烯酸3,4-環氧環己基甲酯、(甲基)丙烯酸3,4-環氧環己基乙酯、(甲基)丙烯酸3,4-環氧環己基丁酯、3,4-環氧環己基甲基氨基丙烯酸酯等，其中，較佳地(甲基)丙烯酸3,4-環氧環己基甲酯。這些(e)1分子中具有環氧乙烷環和烯屬不飽和基團的化合物可以單獨使用，也可以混合2種以上使用。 The compound having an oxirane ring and an ethylenically unsaturated group in the molecule (e) may be a compound having an ethylenically unsaturated group and an oxirane ring in one molecule, and examples thereof include, for example, Glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxy ring (meth)acrylate Hexylethyl ester, 3,4-epoxycyclohexylbutyl (meth)acrylate, 3,4-epoxycyclohexylmethylamino acrylate, etc., among which 3,4-cyclo(meth)acrylate is preferred. Oxycyclohexyl methyl ester. The compound having an oxirane ring and an ethylenically unsaturated group in the (e) molecule may be used singly or in combination of two or more.

作為含酚性羥基樹脂，可以使用具有酚性羥基的化合物，例如具有聯苯骨架、或亞苯基骨架、或這兩種骨架的化合物，或者使用含酚性羥基化合物，例如苯酚、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、鄰苯二酚、間苯二酚、氫醌、甲基氫醌、2,6-二甲基氫醌、三甲基氫醌、連苯三酚、間苯三酚等以合成具有各種骨架的含酚性 羥基樹脂。 As the phenolic hydroxyl group-containing resin, a compound having a phenolic hydroxyl group, for example, a compound having a biphenyl skeleton or a phenylene skeleton, or both skeletons, or a phenol-containing hydroxy compound such as phenol or o-cresol may be used. , p-cresol, m-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3 , 5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, phloroglucinol To synthesize phenolic compounds with various skeletons Hydroxyl resin.

例如可以使用公知慣用的酚醛樹脂，例如，苯酚酚醛清漆樹脂、烷基苯酚酚醛清漆樹脂、雙酚A酚醛清漆樹脂、雙環戊二烯型酚醛樹脂、Xylok型酚醛樹脂、萜烯改質酚醛樹脂、聚乙烯基苯酚類、雙酚F、雙酚S型酚醛樹脂、聚對羥基苯乙烯、萘酚和醛類的縮合物、二羥基萘和醛類的縮合物等。 For example, a conventionally used phenol resin such as a phenol novolak resin, an alkylphenol novolak resin, a bisphenol A novolak resin, a dicyclopentadiene type phenol resin, a Xylok type phenol resin, a terpene modified phenol resin, or the like may be used. A condensate of a polyvinyl phenol, a bisphenol F, a bisphenol S type phenol resin, a polyparaxyl styrene, a naphthol and an aldehyde, a condensate of a dihydroxy naphthalene and an aldehyde, and the like.

其可以單獨使用或組合兩種以上使用。 They may be used singly or in combination of two or more.

作為所述之含酚性羥基樹脂的市售品，可列舉出HF1H60(明和化成株式會社製造)PHENOLITE TD-2090、PHENOLITE TD-2131(大日本印刷株式會社製造)、Besmol CZ-256-A(DIC株式會社製造)、Shonol BRG-555、Shonol BRG-556(昭和電工株式會社製造)、CGR-951(丸善石油化學株式會社製造)、或者聚乙烯基苯酚CST70、CST90、S-1P、S-2P(丸善石油化學株式會社製造)等。這些含酚性羥基樹脂可以單獨使用或適當組合兩種以上使用。 As a commercially available product containing the phenolic hydroxy resin, HF1H60 (manufactured by Akwa Chemical Co., Ltd.) PHENOLITE TD-2090, PHENOLITE TD-2131 (manufactured by Dainippon Printing Co., Ltd.), and Besmol CZ-256-A ( Manufactured by DIC Corporation, Shonol BRG-555, Shonol BRG-556 (made by Showa Denko KK), CGR-951 (made by Maruzen Petrochemical Co., Ltd.), or polyvinyl phenol CST70, CST90, S-1P, S- 2P (manufactured by Maruzen Petrochemical Co., Ltd.) and the like. These phenolic hydroxy resins may be used singly or in combination of two or more.

本發明中，作為鹼溶性樹脂，可以使用含羧基樹脂和含酚性羥基樹脂中的任一者、或者其混合物。 In the present invention, as the alkali-soluble resin, any one of a carboxyl group-containing resin and a phenol-containing hydroxy resin or a mixture thereof can be used.

(B)光聚合引發劑 (B) Photopolymerization initiator

本發明的感光性樹脂組合物含有光聚合引發劑。作為光聚合引發劑，可以使用公知的任意光聚合引發劑，其中較佳地具有肟酯基的肟酯系光聚合引發劑、α-氨基苯乙酮系光聚合引發劑、醯基氧化膦系光聚合引發劑，更佳地α- 氨基苯乙酮系光聚合引發劑。光聚合引發劑可以單獨使用一種，也可以組合兩種以上使用。 The photosensitive resin composition of this invention contains a photoinitiator. As the photopolymerization initiator, any known photopolymerization initiator can be used. Among them, an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and a fluorenyl phosphine oxide system are preferable. Photopolymerization initiator, more preferably α- Aminoacetophenone photopolymerization initiator. The photopolymerization initiator may be used singly or in combination of two or more.

作為α-氨基苯乙酮系光聚合引發劑，具體而言，可列舉出2-甲基-1-[4-(甲基硫代)苯基]-2-嗎啉代丙酮-1、2-苄基-2-二甲基氨基-1-(4-嗎啉代苯基)-丁烷-1-酮、2-(二甲基氨基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮、N,N-二甲基氨基苯乙酮等。作為市售品，可列舉出BASF Japan Ltd.製造的IRGACURE907、IRGACURE369、IRGACURE379等。 Specific examples of the α-aminoacetophenone-based photopolymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1, 2 -benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl) Methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone, and the like. As a commercial item, IRGACURE907, IRGACURE369, IRGACURE379, etc. by BASF Japan Ltd. are mentioned.

這種光聚合引發劑的含量相對於100重量份之前述鹼溶性樹脂，較佳地為0.01~15重量份。為0.01重量份以上時，與其它的引發劑一樣，在銅上的光固化性充分時，密合性、耐溶劑性等塗膜特性有時會提高。另一方面，為15重量份以下時，塗膜表面的光吸收適度，存在深部固化性提高的傾向。相對於100重量份之前述鹼溶性樹脂，更佳地為0.5~10重量份。 The content of the photopolymerization initiator is preferably 0.01 to 15 parts by weight based on 100 parts by weight of the alkali-soluble resin. When it is 0.01 parts by weight or more, similar to other initiators, when the photocurability on copper is sufficient, coating film properties such as adhesion and solvent resistance may be improved. On the other hand, when it is 15 parts by weight or less, the light absorption on the surface of the coating film is moderate, and the deep curability tends to be improved. More preferably, it is 0.5 to 10 parts by weight with respect to 100 parts by weight of the aforementioned alkali-soluble resin.

光引發助劑或敏化劑 Photoinitiator or sensitizer

在本發明的感光性樹脂組合物中，除了上述光聚合引發劑之外，還可以適宜地使用光引發助劑或敏化劑。作為光引發助劑或敏化劑，可列舉出苯偶姻化合物、苯乙酮化合物、蒽醌化合物、噻噸酮化合物、縮酮化合物、二苯甲酮化合物、叔胺化合物以及呫噸酮化合物等。這些化合物有時也可以作為光聚合引發劑使用，但較佳地與光聚合引 發劑組合使用。此外，光引發助劑或敏化劑可以單獨使用一種，也可以組合兩種以上使用。 In the photosensitive resin composition of the present invention, in addition to the above photopolymerization initiator, a photoinitiator or a sensitizer can be suitably used. Examples of the photoinitiator or sensitizer include a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a tertiary amine compound, and a xanthone compound. Wait. These compounds may also be used as photopolymerization initiators, but preferably with photopolymerization The hair spray is used in combination. Further, the photoinitiator or the sensitizer may be used singly or in combination of two or more.

這些當中，較佳者為噻噸酮化合物及叔胺化合物。尤其是藉由含有噻噸酮化合物，可以提高深部固化性。 Among these, preferred are thioxanthone compounds and tertiary amine compounds. In particular, deep curability can be improved by containing a thioxanthone compound.

作為噻噸酮化合物，例如可列舉出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。 Examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone. Wait.

關於光引發助劑或敏化劑的含量，相對於100重量份之前述鹼溶性樹脂，較佳地為0.01~20重量份。光引發助劑或敏化劑的含量為0.1重量份以上時，存在能夠得到充分的敏化效果的傾向。另一方面，為20重量份以下時，塗膜表面的光吸收適度，存在深部固化性提高的傾向。相對於100重量份之鹼溶性樹脂，更佳地為0.1~10重量份。 The content of the photoinitiator or the sensitizer is preferably 0.01 to 20 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content of the photoinitiator or the sensitizer is 0.1 part by weight or more, a sufficient sensitizing effect tends to be obtained. On the other hand, when it is 20 parts by weight or less, the light absorption on the surface of the coating film is moderate, and the deep curability tends to be improved. More preferably, it is 0.1 to 10 parts by weight with respect to 100 parts by weight of the alkali-soluble resin.

光聚合引發劑、光引發助劑和敏化劑的總量相對於100重量份之前述鹼溶性樹脂較佳地為35重量份以下。為35重量份以下時，根據其光吸收，存在深部固化性提高的傾向。 The total amount of the photopolymerization initiator, the photoinitiator aid, and the sensitizer is preferably 35 parts by weight or less based on 100 parts by weight of the aforementioned alkali-soluble resin. When it is 35 parts by weight or less, the deep curability tends to be improved depending on the light absorption.

(C)熱固化性成分 (C) Thermosetting component

本發明的光固化性樹脂組合物包含熱固化成分。藉由添加熱固化成分，可以期待耐熱性提高。作為本發明中所使用的熱固化成分，可以使用胺基樹脂(例如，三聚氰胺樹脂、苯並胍胺樹脂、三聚氰胺衍生物、苯並胍胺衍生物 等)、和公知的熱固化性樹脂(例如，封端異氰酸酯化合物、環碳酸酯化合物、多官能性環氧化合物、多官能性氧雜環丁烷化合物、環硫樹脂、雙馬來亞醯胺、碳二亞胺樹脂等)。特佳的是，分子中具有多個環狀醚基和環狀硫醚基中的至少任一者(以下簡寫為環狀(硫)醚基)的熱固化成分。 The photocurable resin composition of the present invention contains a thermosetting component. Heat resistance can be expected to be improved by adding a thermosetting component. As the thermosetting component used in the present invention, an amine-based resin (for example, a melamine resin, a benzoguanamine resin, a melamine derivative, a benzoguanamine derivative) can be used. And other known thermosetting resins (for example, blocked isocyanate compounds, cyclic carbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, bismaleimide) , carbodiimide resin, etc.). Particularly preferred is a thermosetting component having at least one of a plurality of cyclic ether groups and cyclic thioether groups (hereinafter abbreviated as cyclic (thio)ether groups) in the molecule.

上述分子中具有多個環狀(硫)醚基的熱固化成分是分子中具有多個3、4或5員環的環狀(硫)醚基中的任一基團或兩種基團的化合物，例如可列舉出：分子內具有多個環氧基的化合物，即多官能性環氧化合物；分子內具有多個氧雜環丁烷基的化合物，即多官能性氧雜環丁烷化合物；分子內具有多個硫醚基的化合物，即環硫樹脂等，其中，較佳者為多官能性環氧樹脂。 The thermosetting component having a plurality of cyclic (thio)ether groups in the above molecule is any one or two groups of a cyclic (thio)ether group having a plurality of 3, 4 or 5 membered rings in the molecule. Examples of the compound include a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound; and a compound having a plurality of oxetane groups in the molecule, that is, a polyfunctional oxetane compound. A compound having a plurality of thioether groups in the molecule, that is, an episulfide resin or the like, and among them, a polyfunctional epoxy resin is preferred.

作為前述多官能性環氧化合物，可列舉出雙酚A型環氧樹脂(例如，ADEKA株式會社製造的Adekasizer O-130P、Adekasizer O-180A、Adekasizer D-32、Adekasizer D-55等環氧化植物油；三菱化學株式會社製造的jER828、jER834、jER1001、jER1004；大賽璐化學工業株式會社製造的EHPE3150；DIC株式會社製造的EPICLON 840、EPICLON 850、EPICLON 1050、EPICLON 2055；東都化成株式會社製造的EPOTOHTO YD-011、YD-013、YD-127、YD-128；陶氏化學公司製造的D.E.R.317、D.E.R.331、D.E.R.661、D.E.R.664；住友化學工業株式會社製造的SUMI-EPOXY ESA-011、ESA-014、ELA-115、 ELA-128；旭化成工業株式會社製造的A.E.R.330、A.E.R.331、A.E.R.661、A.E.R.664等(均為商品名))、YDC-1312、氫醌型環氧樹脂、YSLV-80XY雙酚型環氧樹脂、YSLV-120TE硫醚型環氧樹脂(均為東都化成株式會社製造)、溴化環氧樹脂(例如，三菱化學株式會社製造的jERYL903；DIC株式會社製造的EPICLON 152、EPICLON 165；東都化成株式會社製造的EPOTOHTO YDB-400、YDB-500；陶氏化學公司製造的D.E.R.542；住友化學工業株式會社製造的SUMI-EPOXY ESB-400、ESB-700；旭化成工業株式會社製造的A.E.R.711、A.E.R.714等(均為商品名))、酚醛清漆型環氧樹脂(例如，三菱化學株式會社製造的jER152、jER154；陶氏化學公司製造的D.E.N.431、D.E.N.438；DIC株式會社製造的EPICLON N-730、EPICLON N-770、EPICLON N-865；東都化成株式會社製造的EPOTOHTO YDCN-701、YDCN-704；日本化藥株式會社製造的EPPN-201、EOCN-1025、EOCN-1020、EOCN-104S、RE-306；住友化學工業株式會社製造的SUMI-EPOXY ESCN-195X、ESCN-220；旭化成工業株式會社製造的A.E.R.ECN-235、ECN-299等(均為商品名))、聯苯酚酚醛清漆型環氧樹脂(例如，日本化藥株式會社製造的NC-3000、NC-3100等)、雙酚F型環氧樹脂(例如，DIC株式會社製造的EPICLON 830；三菱化學株式會社製造的jER807；東都化成株式會社製造的EPOTOHTO YDF-170、YDF-175、YDF-2004等(均為商品 名))、氫化雙酚A型環氧樹脂(例如，東都化成株式會社製造的EPOTOHTO ST-2004、ST-2007、ST-3000(商品名)等)、縮水甘油胺型環氧樹脂(例如，三菱化學株式會社製造的jER604；東都化成株式會社製造的EPOTOHTO YH-434；住友化學工業株式會社製造的SUMI-EPOXY ELM-120等(均為商品名))、乙內醯脲型環氧樹脂、脂環式環氧樹脂(例如，大賽璐化學工業株式會社製造的CELLOXIDE 2021等(均為商品名))、三羥基苯基甲烷型環氧樹脂(例如，三菱化學株式會社製造的YL-933、陶氏化學公司製造的T.E.N.、EPPN-501、EPPN-502等(均為商品名))、聯二甲酚型或聯苯酚型環氧樹脂或者其混合物(例如，三菱化學株式會社製造的YL-6056、YX-4000、YL-6121(均為商品名)等)、雙酚S型環氧樹脂(例如，日本化藥株式會社製造的EBPS-200；ADEKA株式會社製造的EPX-30、DIC株式會社製造的EXA-1514(商品名)等)、雙酚A酚醛清漆型環氧樹脂(例如，三菱化學株式會社製造的jER157S(商品名)等)、四羥苯基乙烷型環氧樹脂(例如，三菱化學株式會社製造的jERYL-931等(均為商品名))、雜環式環氧樹脂(例如，日產化學工業株式會社製造的TEPIC等(均為商品名))、鄰苯二甲酸二縮水甘油酯樹脂(例如，日本油脂株式會社製造的BLEMMER DGT等)、四縮水甘油基二甲苯醯基乙烷樹脂(tetraglycidyl xylenoyl ethane)(例如，東都化成株式會社製造的ZX-1063等)、含萘基環氧樹脂(例如， 新日鐵化學株式會社製造的ESN-190、ESN-360、DIC株式會社製造的HP-4032、EXA-4750、EXA-4700等)、具有雙環戊二烯骨架的環氧樹脂(例如，DIC株式會社製造的HP-7200、HP-7200H等)、甲基丙烯酸縮水甘油酯共聚系環氧樹脂(例如，日本油脂株式會社製造的CP-50S、CP-50M等)、和環己基馬來醯亞胺和甲基丙烯酸縮水甘油酯的共聚環氧樹脂、環氧改質的聚丁二烯橡膠衍生物(例如大賽璐化學工業株式會社製造的PB-3600等)、CTBN改質環氧樹脂(例如東都化成株式會社製造的YR-102、YR-450等)、異氰脲酸1,3,5-三縮水甘油酯(例如，日產化學工業株式會社製造的TEPIC-G等)，但並不限定於此。這些環氧樹脂可單獨使用或組合2種以上使用，其中，特佳地酚醛清漆型環氧樹脂、聯二甲酚型環氧樹脂、聯苯酚型環氧樹脂、聯苯酚酚醛清漆型環氧樹脂、萘型環氧樹脂、異氰脲酸1,3,5-三縮水甘油酯、或者其混合物。 Examples of the polyfunctional epoxy compound include bisphenol A type epoxy resins (for example, epoxidized vegetable oils such as Adekasizer O-130P, Adekasizer O-180A, Adekasizer D-32, and Adekasizer D-55 manufactured by ADEKA CORPORATION). JER828, jER834, jER1001, and jER1004 manufactured by Mitsubishi Chemical Corporation; EHPE3150 manufactured by Daicel Chemical Industries, Ltd.; EPICLON 840, EPICLON 850, EPICLON 1050, and EPICLON 2055 manufactured by DIC Corporation; and EPOTOHTO YD manufactured by Toho Chemical Co., Ltd. -011, YD-013, YD-127, YD-128; DER317, DER331, DER661, DER664 manufactured by Dow Chemical Co., Ltd.; SUMI-EPOXY ESA-011, ESA-014 manufactured by Sumitomo Chemical Industries, Ltd. , ELA-115, ELA-128; AER330, AER331, AER661, AER664, etc. (all trade names) manufactured by Asahi Kasei Kogyo Co., Ltd., YDC-1312, hydroquinone epoxy resin, YSLV-80XY bisphenol epoxy resin YSLV-120TE thioether epoxy resin (both manufactured by Tohto Kasei Co., Ltd.) and brominated epoxy resin (for example, jERYL903 manufactured by Mitsubishi Chemical Corporation; EPICLON 152 and EPICLON 165 manufactured by DIC Corporation; EPOTOHTO YDB-400 and YDB-500 manufactured by the company; DER542 manufactured by Dow Chemical Co., Ltd.; SUMI-EPOXY ESB-400 and ESB-700 manufactured by Sumitomo Chemical Industries, Ltd.; AER711 and AER714 manufactured by Asahi Kasei Kogyo Co., Ltd. (available as a product name), a novolak-type epoxy resin (for example, jER152 and jER154 manufactured by Mitsubishi Chemical Corporation; DEN431 and DEN438 manufactured by Dow Chemical Co., Ltd.; and EPICLON N-730 manufactured by DIC Corporation, EPICLON N-770, EPICLON N-865; EPOTOHTO YDCN-701 and YDCN-704 manufactured by Toshiro Kasei Co., Ltd.; EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE- manufactured by Nippon Kayaku Co., Ltd. 306; live SUMI-EPOXY ESCN-195X and ESCN-220 manufactured by Chemical Industry Co., Ltd.; AERECN-235, ECN-299, etc. (all are trade names) manufactured by Asahi Kasei Kogyo Co., Ltd.), and a biphenol novolac type epoxy resin (for example) , Nippon Chemical Co., Ltd., NC-3000, NC-3100, etc., bisphenol F-type epoxy resin (for example, EPICLON 830 manufactured by DIC Corporation; jER807 manufactured by Mitsubishi Chemical Corporation; manufactured by Toho Chemical Co., Ltd.) EPOTOHTO YDF-170, YDF-175, YDF-2004, etc. Name)), a hydrogenated bisphenol A type epoxy resin (for example, EPOTOHTO ST-2004, ST-2007, ST-3000 (trade name) manufactured by Tohto Kasei Co., Ltd.), or a glycidylamine type epoxy resin (for example, JER604 manufactured by Mitsubishi Chemical Corporation; EPOOTOH YH-434 manufactured by Tohto Kasei Co., Ltd.; SUMI-EPOXY ELM-120 (both brand names) manufactured by Sumitomo Chemical Industries, Ltd.) An alicyclic epoxy resin (for example, CELLOXIDE 2021 (all trade name) manufactured by Daicel Chemical Industries, Ltd.) and a trihydroxyphenylmethane type epoxy resin (for example, YL-933 manufactured by Mitsubishi Chemical Corporation, TEN, EPPN-501, EPPN-502, etc. (both trade names) manufactured by The Dow Chemical Company, bis-xylenol type or biphenol type epoxy resin or a mixture thereof (for example, YL-made by Mitsubishi Chemical Corporation) 6056, YX-4000, YL-6121 (all are trade names), etc., bisphenol S-type epoxy resin (for example, EBPS-200 manufactured by Nippon Kayaku Co., Ltd.; EPX-30, DIC strain manufactured by ADEKA Co., Ltd.) EXA-1514 (trade name) manufactured by the company, bisphenol A novolac type epoxy Fat (for example, jER157S (trade name) manufactured by Mitsubishi Chemical Corporation, etc.), tetrahydroxyphenylethane type epoxy resin (for example, jERYL-931 (all are trade names) manufactured by Mitsubishi Chemical Corporation), miscellaneous A ring-shaped epoxy resin (for example, TEPIC (trade name) manufactured by Nissan Chemical Industries, Ltd.), diglycidyl phthalate resin (for example, BLEMMER DGT manufactured by Nippon Oil & Fats Co., Ltd.), and four shrinkage Tetraglycidyl xylenoyl ethane (for example, ZX-1063 manufactured by Toshiro Kasei Co., Ltd.) or naphthyl-containing epoxy resin (for example, ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, and EXA-4700 manufactured by DIC Corporation, and epoxy resin having a dicyclopentadiene skeleton (for example, DIC strain) HP-7200, HP-7200H, etc. manufactured by Kosaku Co., Ltd., glycidyl methacrylate copolymer epoxy resin (for example, CP-50S, CP-50M, manufactured by Nippon Oil & Fats Co., Ltd.), and cyclohexylmala A copolymerized epoxy resin of an amine and glycidyl methacrylate, an epoxy-modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Industries, Ltd.), and a CTBN modified epoxy resin (for example) YR-102, YR-450, etc. manufactured by Tosho Kasei Co., Ltd., and 1,3,5-triglycidyl isocyanurate (for example, TEPIC-G manufactured by Nissan Chemical Industries, Ltd.), but is not limited herein. These epoxy resins may be used alone or in combination of two or more. Among them, a particularly preferred novolak type epoxy resin, a bisphenol type epoxy resin, a biphenol type epoxy resin, and a biphenol novolac type epoxy resin may be used. , naphthalene type epoxy resin, isocyanuric acid 1,3,5-triglycidyl ester, or a mixture thereof.

作為多官能性氧雜環丁烷化合物，例如可列舉出雙〔(3-甲基-3-氧雜環丁烷基甲氧基)甲基〕醚、雙〔(3-乙基-3-氧雜環丁烷基甲氧基)甲基〕醚、1,4-雙〔(3-甲基-3-氧雜環丁烷基甲氧基)甲基〕苯、1,4-雙〔(3-乙基-3-氧雜環丁烷基甲氧基)甲基〕苯、丙烯酸(3-甲基-3-氧雜環丁烷基)甲酯、丙烯酸(3-乙基-3-氧雜環丁烷基)甲酯、甲基丙烯酸(3-甲基-3-氧雜環丁烷基)甲酯、甲基丙烯酸(3-乙基-3-氧雜環丁烷基)甲酯、其低聚物或共聚物等多官能氧雜 環丁烷類，以及氧雜環丁烷醇與具有羥基之樹脂的醚化物(例如，酚醛清漆樹脂、聚(對羥基苯乙烯)、cardo型雙酚類、杯芳烴類、間苯二酚杯芳烴(calixresorcinarene)類、或者倍半矽氧烷(silsesquioxane)等)。另外，亦可以列舉出具有氧雜環丁烷環的不飽和單體與(甲基)丙烯酸烷基酯的共聚物等。 Examples of the polyfunctional oxetane compound include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether and bis[(3-ethyl-3-). Oxetane methoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-double [ (3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, acrylic acid (3-ethyl-3) -oxetanyl)methyl ester, (3-methyl-3-oxetanyl)methyl methacrylate, methacrylic acid (3-ethyl-3-oxetanyl) Polyfunctional oxygen such as methyl ester, oligomer or copolymer thereof Cyclobutanes, and etherates of oxetane and hydroxyl group-containing resins (for example, novolak resins, poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, resorcinol cups) An aromatic hydrocarbon (calixresorcinarene), or a silsesquioxane, etc.). Further, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate may, for example, be mentioned.

作為分子中具有多個環狀硫醚基的化合物，例如可列舉出三菱化學株式會社製造的雙酚A型環硫樹脂YL7000等。另外，也可以使用以相同的合成方法將酚醛清漆型環氧樹脂中之環氧基的氧原子替換成硫原子而得到的環硫樹脂等。 Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Further, an episulfide resin obtained by replacing the oxygen atom of the epoxy group in the novolak epoxy resin with a sulfur atom by the same synthesis method may be used.

這種分子中具有多個環狀(硫)醚基的熱固化成分的含量相對於1當量之前述鹼溶性樹脂的羧基或羥基，較佳地為0.6~2.5當量。含量為0.6當量以上時，固化物中不會殘留羧基或羥基，而提供耐熱性等。另一方面，為2.5當量以下時，由於低分子量的環狀(硫)醚基不會殘留在乾燥塗膜中，因此塗膜的強度等提高。更較佳地為0.8~2.0当量。 The content of the thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is preferably from 0.6 to 2.5 equivalents per equivalent of the carboxyl group or the hydroxyl group of the alkali-soluble resin. When the content is 0.6 equivalent or more, a carboxyl group or a hydroxyl group does not remain in the cured product, and heat resistance and the like are provided. On the other hand, when it is 2.5 equivalent or less, since the low molecular weight cyclic (thio)ether group does not remain in the dry coating film, the strength and the like of the coating film are improved. More preferably, it is 0.8 to 2.0 equivalents.

(D)熱固化性促進劑 (D) Thermosetting accelerator

本發明中使用熱固化性促進劑。由此，能夠使化學鍍金耐性和化學鍍錫耐性一起提高。其中，適宜使用三聚氰胺、三聚氰胺的有機酸鹽、及咪唑化合物。 A thermosetting accelerator is used in the present invention. Thereby, the electroless gold plating resistance and the electroless tin plating resistance can be improved together. Among them, an organic acid salt of melamine, melamine, and an imidazole compound are suitably used.

作為三聚氰胺或三聚氰胺的有機酸鹽，可以使用三聚 氰胺、或者三聚氰胺與等莫耳的有機酸反應而成的物質。三聚氰胺的有機酸鹽可以如下得到：將三聚氰胺溶解在沸水中，添加溶解於親水性溶劑如水或醇等的有機酸，將析出的鹽過濾，從而得到。三聚氰胺分子中的1個胺基的反應性快，而其他2個胺基的反應性低，因此、反應按照化學計量進行，所生成之三聚氰胺分子中的1個胺基與1個有機酸的加成反應而得到的三聚氰胺鹽。作為有機酸，可以考慮使用含羧基化合物、酸性磷酸酯化合物、含磺酸化合物，但更佳地含羧基化合物。 As an organic acid salt of melamine or melamine, trimerization can be used. A substance formed by the reaction of cyanamide or melamine with an organic acid such as a molar. The organic acid salt of melamine can be obtained by dissolving melamine in boiling water, adding an organic acid dissolved in a hydrophilic solvent such as water or alcohol, and filtering the precipitated salt. One amine group in the melamine molecule has a high reactivity, while the other two amine groups have low reactivity. Therefore, the reaction is performed stoichiometrically, and one amine group and one organic acid in the produced melamine molecule are added. The melamine salt obtained in the reaction. As the organic acid, a carboxyl group-containing compound, an acid phosphate compound, or a sulfonic acid-containing compound can be considered, but a carboxyl group-containing compound is more preferable.

三聚氰胺和三聚氰胺的有機酸鹽的較佳含量相對於100重量份之前述鹼溶性樹脂，為0.5~25重量份，更佳地為0.5~20重量份。 The content of the organic acid salt of melamine and melamine is preferably 0.5 to 25 parts by weight, more preferably 0.5 to 20 parts by weight, per 100 parts by weight of the above alkali-soluble resin.

從化學鍍金耐性變得更良好的觀點，藉由將三聚氰胺和三聚氰胺的有機酸鹽的含量設為相對於100重量份之前述含羧基樹脂為0.5~25重量份是較佳的。 The content of the organic acid salt of melamine and melamine is preferably 0.5 to 25 parts by weight based on 100 parts by weight of the carboxyl group-containing resin, from the viewpoint that the chemical gold plating resistance is further improved.

作為咪唑系化合物(I)，例如，可列舉出2-甲基咪唑(2MZ)、2-十一烷基咪唑(C112)、2-十七烷基咪唑(C17Z)、1,2二甲基咪唑(1,2DMZ)、2-乙基-4-甲基咪唑(2E4MZ)、2-苯基咪唑(2PZ)、2-苯基-4-甲基咪唑(2P4MZ)、1-苄基-2-甲基咪唑(1B2MZ)、1-氰基乙基-2-甲基咪唑(2MZ-CN)、1-氰基乙基-2-乙基-4-甲基咪唑(2E4MZ-CN)、1-氰基乙基-2-十一烷基咪唑(C11Z-CN)、1-氰基乙基-2-苯基咪唑(2PZ-CN)、1-氰基乙基-2-乙基-4-甲基偏苯三酸咪唑鹽(2E4MZ-CNS)、1-氰基乙基-2-十一烷基偏苯三酸咪唑鹽(C11Z- CNS)、1-氰基乙基-2-苯基偏苯三酸咪唑鹽(2PZ-CNS)、2,4-二胺基-6-(2’-甲基咪唑基-(1’))-乙基-均三(2MZ-A)、2,4-二胺基-6-(2’-十一烷基咪唑基)-乙基-均三(C11Z-A)、2,4-二胺基-6-(2’-乙基-4-甲基咪唑基-(1’))-乙基-均三(2E4MZ-A)、2,4-二胺基-6-(2’甲基咪唑基-(1’))-乙基-均三異氰脲酸加成物(2MA-OK)、2-苯基咪唑異氰脲酸加成物(2PZ-OK)、2-甲基咪唑異氰脲酸加成物(2MZ-OK)、2-苯基-4,5-二羥基甲基咪唑(2PHZ)、2-苯基-4-甲基-5-羥基甲基咪唑(2P4MHZ)、1-氰基乙基-2-苯基-4,5-二(2-氰基乙氧基)甲基咪唑(2PHZ-CN)、2-甲基咪唑啉(2MZL-F)、2-苯基咪唑啉(2PZL)、1-十二烷基-2-甲基-3-苄基咪唑氯鹽(SFZ)、1-苄基-2-苯基咪唑鹽酸鹽(1B2PZ-HCL)、1-苄基-2-苯基偏苯三酸咪唑鹽(1B2PZ-S)、2,4-二胺基-6-乙烯基-均三(VT)、2,4-二胺基-6-甲基丙烯醯氧基-均三(MAVT)、2,4-二胺基-6-乙烯基-1,3,5-三異氰脲酸加成物(VT-OK)、2,4-二胺基-6-甲基丙烯醯氧基-1,3,5-三異氰脲酸加成物或其有機酸鹽類等，括弧內之縮寫均為四國化成工業株式會社製造的商品名，且其中，根據反應溫度區域，較佳者為2PHZ。 Examples of the imidazole-based compound (I) include 2-methylimidazole (2MZ), 2-undecylimidazole (C112), 2-heptadecylimidazole (C17Z), and 1,2 dimethyl group. Imidazole (1,2DMZ), 2-ethyl-4-methylimidazole (2E4MZ), 2-phenylimidazole (2PZ), 2-phenyl-4-methylimidazole (2P4MZ), 1-benzyl-2 -methylimidazole (1B2MZ), 1-cyanoethyl-2-methylimidazole (2MZ-CN), 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN), 1 -Cyanoethyl-2-undecylimidazole (C11Z-CN), 1-cyanoethyl-2-phenylimidazole (2PZ-CN), 1-cyanoethyl-2-ethyl-4 -methyl trimellitic acid imidazolium salt (2E4MZ-CNS), 1-cyanoethyl-2-undecyl trimellitic acid imidazolium salt (C11Z-CNS), 1-cyanoethyl-2-benzene Imidazolyl imidazolium salt (2PZ-CNS), 2,4-diamino-6-(2'-methylimidazolyl-(1'))-ethyl-all three (2MZ-A), 2,4-diamino-6-(2'-undecylimidazolyl)-ethyl-all three (C11Z-A), 2,4-diamino-6-(2'-ethyl-4-methylimidazolyl-(1'))-ethyl-all three (2E4MZ-A), 2,4-diamino-6-(2'methylimidazolyl-(1'))-ethyl-all three Isocyanuric acid adduct (2MA-OK), 2-phenylimidazole isocyanuric acid adduct (2PZ-OK), 2-methylimidazole isocyanuric acid adduct (2MZ-OK), 2 -Phenyl-4,5-dihydroxymethylimidazole (2PHZ), 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ), 1-cyanoethyl-2-phenyl-4 ,5-bis(2-cyanoethoxy)methylimidazole (2PHZ-CN), 2-methylimidazoline (2MZL-F), 2-phenylimidazoline (2PZL), 1-dodecyl -2-methyl-3-benzylimidazolium chloride (SFZ), 1-benzyl-2-phenylimidazolium hydrochloride (1B2PZ-HCL), 1-benzyl-2-phenyltrimellitic acid imidazole Salt (1B2PZ-S), 2,4-diamino-6-vinyl-all three (VT), 2,4-diamino-6-methylpropenyloxy-all three (MAVT), 2,4-diamino-6-vinyl-1,3,5-three Isocyanuric acid adduct (VT-OK), 2,4-diamino-6-methylpropenyloxy-1,3,5-three The isocyanuric acid addition product or an organic acid salt thereof, and the abbreviation in the parentheses are all trade names manufactured by Shikoku Chemicals Co., Ltd., and among them, 2PHZ is preferable depending on the reaction temperature region.

咪唑化合物的較佳含量相對於100重量份之前述鹼溶性樹脂，為0.1~20重量份，更佳地為0.1~10重量份。 The content of the imidazole compound is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the alkali-soluble resin.

另外，在本發明的鹼顯影型感光性樹脂組合物中，作為熱固化性促進劑，較佳地進一步使用其他的胺化合物、特別是雙氰胺。藉由使用雙氰胺，進一步促進熱固化性， 因此化學鍍錫耐性變得更加良好。 Further, in the alkali-developable photosensitive resin composition of the present invention, as the thermosetting accelerator, other amine compounds, particularly dicyandiamide, are preferably further used. Further promoting thermal curability by using dicyandiamide, Therefore, the chemical tin plating resistance becomes more favorable.

(E)重晶石 (E) barite

本發明中，使用重晶石。重晶石是指由硫酸鋇形成的礦物，與利用化學反應製造的沉澱性鋇鹽不同。原本硫酸鋇用表面處理劑(例如，矽烷系、鈦酸酯系等)進行表面處理，從而與樹脂的親和性優異，但是，從另一個方面來看，由於耐化學藥品性的降低，化學鍍錫耐性變差。因此，使用未進行表面處理的重晶石，使樹脂不會受到表面劑的影響，其結果，能夠維持化學鍍錫耐性並賦予化學鍍金耐性。 In the present invention, barite is used. Barite refers to a mineral formed from barium sulfate, which is different from a precipitated barium salt produced by a chemical reaction. The original barium sulfate is surface-treated with a surface treatment agent (for example, a decane type or a titanate type), and is excellent in affinity with a resin. However, from another point of view, electroless plating is caused by a decrease in chemical resistance. Tin resistance is getting worse. Therefore, the barite which is not surface-treated is used so that the resin is not affected by the surface agent, and as a result, the electroless tin plating resistance can be maintained and the electroless gold plating resistance can be imparted.

重晶石(E)的較佳含量相對於100重量份之前述鹼溶性樹脂，為10~200重量份，更佳地為10~100重量份。 The content of the barite (E) is preferably 10 to 200 parts by weight, more preferably 10 to 100 parts by weight per 100 parts by weight of the alkali-soluble resin.

從化學鍍金耐性和化學鍍錫耐性變得更良好的方面，將重晶石(E)的含量設為相對於100重量份之前述鹼溶性樹脂為10~200重量份是較佳的。 The content of the barite (E) is preferably 10 to 200 parts by weight based on 100 parts by weight of the alkali-soluble resin, from the viewpoints of more favorable chemical plating resistance and chemical tin plating resistance.

結晶性二氧化矽和滑石中的至少任一者 At least one of crystalline ceria and talc

本發明中，較佳地進一步使用結晶性二氧化矽和滑石中的至少任一者。由此，能夠進一步提高化學鍍錫耐性。 In the present invention, at least one of crystalline ceria and talc is preferably further used. Thereby, the electroless tin plating resistance can be further improved.

結晶性二氧化矽和滑石中的至少任一者的較佳平均粒徑為0.1~10μm，更佳地為0.5~5μm。 The preferred average particle diameter of at least any of the crystalline ceria and talc is from 0.1 to 10 μm, more preferably from 0.5 to 5 μm.

結晶性二氧化矽和滑石中的至少任一者的較佳含量相對於100重量份之前述鹼溶性樹脂為30~400重量份，更較地為50~300重量份。 A preferred content of at least one of the crystalline ceria and talc is 30 to 400 parts by weight, more preferably 50 to 300 parts by weight, per 100 parts by weight of the alkali-soluble resin.

從化學鍍錫耐性變得更良好的方面，將結晶性二氧化矽和滑石中的至少任一者的含量設為相對於100重量份之前述鹼溶性樹脂為30~400重量份是較佳的。 It is preferable that the content of at least one of the crystalline cerium oxide and the talc is 30 to 400 parts by weight based on 100 parts by weight of the alkali-soluble resin, from the viewpoint that the chemical tin plating resistance is further improved. .

本發明中，還可以根據需要進一步混合公知慣用的著色劑(例如，酞菁藍、酞菁綠、碘綠、雙偶氮黃、結晶紫、氧化鈦、炭黑、萘黑等、)和公知慣用的添加劑類(例如，有機矽系、氟系、高分子系等的消泡劑等)。 In the present invention, a conventionally known coloring agent (for example, phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc.) may be further blended as needed, and is known. A conventional additive (for example, an antifoaming agent such as an organic oxime system, a fluorine system or a polymer system).

此外，本發明中，較佳地使用稀釋劑。作為稀釋劑，使用在室溫(約20~30℃)下為液態的光聚合性單體、有機溶劑。使用這些稀釋劑的目的是，使前述鹼溶性樹脂溶解，將組合物調整為適於各種塗布方法的黏度。另外，在室溫下為液態的光聚合性單體具有提高組合物的光反應性的目的、和有利於在鹼水溶液中的溶解性的作用。但是，大量使用在室溫下為液態的光聚合性單體時，得不到塗膜的指觸乾燥性，而且還存在塗膜的特性也惡化的傾向，因此相對於100重量份之前述鹼溶性樹脂，該光聚合性單體的適當含量為100重量份以下，較佳地為50重量份以下，且為10重量份以上。關於有機溶劑，只要在規定的乾燥條件下能夠乾燥，不會對乾燥塗膜造成不良影響，其用量僅受限於塗布方法，通常，相對於100重量份之前述鹼溶性樹脂，較佳地為200重量份以下且10重量份以上。 Further, in the present invention, a diluent is preferably used. As the diluent, a photopolymerizable monomer or an organic solvent which is liquid at room temperature (about 20 to 30 ° C) is used. The purpose of using these diluents is to dissolve the aforementioned alkali-soluble resin and adjust the composition to a viscosity suitable for various coating methods. Further, the photopolymerizable monomer which is liquid at room temperature has an object of improving the photoreactivity of the composition and a function of facilitating solubility in an aqueous alkali solution. However, when a photopolymerizable monomer which is liquid at room temperature is used in a large amount, the dryness of the coating film is not obtained, and the properties of the coating film tend to be deteriorated. Therefore, the base is used in an amount of 100 parts by weight. The soluble resin, the content of the photopolymerizable monomer is preferably 100 parts by weight or less, preferably 50 parts by weight or less, and 10 parts by weight or more. The organic solvent can be dried under a predetermined drying condition without adversely affecting the dried coating film, and the amount thereof is limited only by the coating method. Usually, it is preferably 100 parts by weight of the alkali-soluble resin. 200 parts by weight or less and 10 parts by weight or more.

作為在室溫下為液態的光聚合性單體，例如可列舉出含羥基丙烯酸酯類(例如，丙烯酸2-羥乙酯、丙烯酸2- 羥丙酯、季戊四醇三丙烯酸酯、二季戊四醇五丙烯酸酯等)；丙烯醯胺衍生物(例如，丙烯醯胺、N-羥甲基丙烯醯胺等)；水溶性的丙烯酸酯類(例如，聚乙二醇二丙烯酸酯、聚丙二醇二丙烯酸酯等)；多官能醇的多官能性聚酯丙烯酸酯類(例如，三羥甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇六丙烯酸酯等)；多官能醇或雙酚A(例如，三羥甲基丙烷、氫化雙酚A等)；多官能酚的環氧乙烷加成物或環氧丙烷加成物的丙烯酸酯類(例如，聯苯酚等)；上述含羥基丙烯酸酯的異氰酸酯改質物的多官能性或單官能性胺聚胺酯丙烯酸酯；雙酚A二縮水甘油醚、氫化雙酚A二縮水甘油醚或苯酚酚醛清漆環氧樹脂的(甲基)丙烯酸加成物的環氧丙烯酸酯類、以及與上述丙烯酸酯類相應的甲基丙烯酸酯類等，這些可以單獨使用或組合兩種以上使用。 Examples of the photopolymerizable monomer which is liquid at room temperature include hydroxyl group-containing acrylates (for example, 2-hydroxyethyl acrylate and acrylic acid 2- Hydroxypropyl ester, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc.; acrylamide derivatives (for example, acrylamide, N-methylol acrylamide, etc.); water-soluble acrylates (for example, poly Polyethylene glycol diacrylate, polypropylene glycol diacrylate, etc.; polyfunctional polyester acrylates of polyfunctional alcohols (for example, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc.) a polyfunctional alcohol or bisphenol A (for example, trimethylolpropane, hydrogenated bisphenol A, etc.); an ethylene oxide adduct of a polyfunctional phenol or an acrylate of a propylene oxide adduct (for example, Biphenyl or the like; a polyfunctional or monofunctional amine polyurethane acrylate of the above-mentioned hydroxyl group-containing isocyanate modified product; bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or phenol novolac epoxy resin The epoxy acrylate of the (meth)acrylic acid addition product, the methacrylates corresponding to the above acrylates, and the like may be used alone or in combination of two or more.

另外，作為有機溶劑，可列舉出酮類(例如，甲乙酮、環己酮等)；芳香族烴類(例如，甲苯、二甲苯、四甲苯等)；二醇醚類(例如，溶纖劑、甲基溶纖劑、丁基溶纖劑、卡必醇、甲基卡必醇、丁基卡必醇、丙二醇單甲醚、丙二醇單***、二丙二醇二***、三乙二醇單***等)；乙酸酯類(例如，乙酸乙酯、乙酸丁酯、溶纖劑乙酸酯、丁基溶纖劑乙酸酯、卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇單甲醚乙酸酯、二丙二醇單甲醚乙酸酯等)；醇類(例如，乙醇、丙醇、乙二醇、丙二醇等)；脂肪族烴(例如，辛烷、癸烷等)；石油系溶劑(例如， 石油醚、石腦油、氫化石腦油、溶劑石腦油等)，其可以單獨使用或者以兩種以上的混合物的形式來使用。這種有機溶劑不僅可以在製備組合物時使用，還可以在合成前述鹼溶性樹脂時使用，或者也可以為了稀釋合成後的反應溶液而添加。另外，為了用於在基板、載體膜上塗布而進行的黏度調整，也可以使用有機溶劑。本發明的鹼顯影型感光性樹脂組合物可以藉由較佳地地以前述比率混合前述之成分，和用輥磨機等均勻地混合分散而得到。 Further, examples of the organic solvent include ketones (for example, methyl ethyl ketone or cyclohexanone); aromatic hydrocarbons (for example, toluene, xylene, tetramethylbenzene, etc.); glycol ethers (for example, cellosolve, Methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc.; Esters (eg, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate) , dipropylene glycol monomethyl ether acetate, etc.); alcohols (eg, ethanol, propanol, ethylene glycol, propylene glycol, etc.); aliphatic hydrocarbons (eg, octane, decane, etc.); petroleum-based solvents (eg, Petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha, etc., which may be used singly or in the form of a mixture of two or more. Such an organic solvent can be used not only in the preparation of the composition, but also in the synthesis of the alkali-soluble resin, or in the case of diluting the reaction solution after the synthesis. Moreover, an organic solvent can also be used for the viscosity adjustment for coating on a board|substrate and a carrier film. The alkali-developable photosensitive resin composition of the present invention can be obtained by mixing the above components in a preferred ratio and uniformly mixing and dispersing them by a roll mill or the like.

如上述說明的本發明的鹼顯影型感光性樹脂組合物經過如以下說明的方法而製成將導通孔塞住的感光性樹脂皮膜，即，經過如下的方法形成固化物圖案：塗膜形成方法，將本發明的感光性樹脂組合物填充到導通孔中，並且在表面上塗布，進行乾燥；光固化處理方法，對經過該塗膜形成方法而得到的塗膜選擇性地照射活性能量射線；鹼顯影方法，在光固化處理方法後使用鹼顯影液去除未照射部分，得到圖案；以及，固化方法，將鹼顯影方法中得到的圖案加熱並固化。 The alkali-developing photosensitive resin composition of the present invention as described above is formed into a photosensitive resin film that plugs a via hole by a method as described below, that is, a cured product pattern is formed by the following method: coating film forming method The photosensitive resin composition of the present invention is filled in a via hole and coated on the surface to be dried; and the photocuring treatment method selectively irradiates the coating film obtained by the coating film forming method with an active energy ray; In the alkali developing method, after the photo-curing treatment method, the un-irradiated portion is removed using an alkali developing solution to obtain a pattern; and, in the curing method, the pattern obtained in the alkali developing method is heated and solidified.

(1)塗膜形成方法 (1) Coating film forming method

在該方法中，藉由印刷將本發明的感光性樹脂組合物填充到預先形成有電路的印刷電路板的導通孔的部分。填充使用能對導通孔的部分選擇性填充的絲網、通常從單側進行填充。填充後在雙面利用絲網印刷法、簾塗法、噴塗法、輥塗法塗布本發明的感光性樹脂組合物。利用絲網印 刷法進行塗布時，也可以省去前述對導通孔進行填充的方法，同時進行塗布和對導通孔的填充。 In this method, the photosensitive resin composition of the present invention is filled by printing into a portion of a via hole of a printed circuit board on which a circuit is formed in advance. The filling uses a screen that selectively fills a portion of the via, typically filling from one side. After the filling, the photosensitive resin composition of the present invention is applied on both sides by a screen printing method, a curtain coating method, a spray coating method, or a roll coating method. Screen printing When the coating method is applied, the above-described method of filling the via holes may be omitted, and coating and filling of the via holes may be performed at the same time.

塗布後，在60℃~90℃的溫度下去除組合物中所含的揮發性成分，進行乾燥，形成在導通孔中所填充的乾燥塗膜。此時，選擇能夠使導通孔中的溶劑也揮發的溫度、時間是重要的。 After the application, the volatile component contained in the composition is removed at a temperature of 60 ° C to 90 ° C and dried to form a dried coating film filled in the via hole. At this time, it is important to select a temperature and time at which the solvent in the via hole is also volatilized.

(2)光固化處理(曝光)方法 (2) Photocuring treatment (exposure) method

在該方法中，對在前述方法(1)中得到的乾燥塗膜選擇性地照射活性能量射線。此處，關於曝光，隔著形成有圖案的光掩模照射活性能量射線即可。作為曝光光源，通常低壓汞燈、中壓汞燈、高壓汞燈、超高壓汞燈、氙燈、金屬鹵化物燈等是適合的。 In this method, the dried coating film obtained in the above method (1) is selectively irradiated with an active energy ray. Here, regarding the exposure, the active energy ray may be irradiated through the photomask on which the pattern is formed. As the exposure light source, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp or the like is usually suitable.

曝光中的光線的照射量根據黏結劑聚合物的重量平均分子量、單體比、含量、光聚合性化合物的種類/含量、光聚合引發劑的種類/含量、光聚合引發助劑的種類/含量等來適宜選擇。 The amount of light to be exposed during exposure depends on the weight average molecular weight of the binder polymer, the monomer ratio, the content, the type/content of the photopolymerizable compound, the type/content of the photopolymerization initiator, and the type/content of the photopolymerization initiator. Wait for a suitable choice.

(3)鹼顯影方法 (3) Alkali development method

使完成前述(2)的方法的曝光後的塗膜顯影。顯影用淋洗將顯影液噴灑於曝光後的塗膜，去除未曝光部分的塗膜。作為顯影液，可列舉出稀鹼性水溶液(例如，碳酸鈉、碳酸鉀、氫氧化鈉、氫氧化鉀、四甲基氫氧化銨、有機胺等)。利用顯影去除未曝光部分，形成塗膜圖案。顯 影後，通常進行水洗乾燥。 The exposed coating film of the method of the above (2) is developed. The developing solution is sprayed onto the exposed coating film to remove the coating film of the unexposed portion. The developing solution may, for example, be a dilute alkaline aqueous solution (for example, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide or an organic amine). The unexposed portion is removed by development to form a coating film pattern. Display After the filming, it is usually washed with water.

(4)固化方法 (4) curing method

將完成前述(3)的方法的基板上的塗膜圖案加熱使其熱固化。 The coating film pattern on the substrate on which the method of the above (3) is completed is heated to be thermally cured.

熱固化係為了抑制導通孔中的塗膜的固化收縮、抑制塗膜的滲出、空泡而進行多級固化。 The heat curing is performed in order to suppress the curing shrinkage of the coating film in the via hole, suppress the bleeding of the coating film, and form a bubble.

多級固化是在將溫度和時間分為兩階段或三階段來進行加熱固化的方法。通常可以適當地選擇在60~80℃下30~60分鐘、在100~120℃下0~40分鐘、然後在150~160℃下40~90分鐘的溫度和時間。為了充分地得到化學鍍錫耐性、化學鍍金耐性，較佳地在不產生空泡的範圍內使多級固化的條件盡可能地短。 Multi-stage curing is a method in which the temperature and time are divided into two or three stages for heat curing. Generally, the temperature and time at 30 to 60 minutes at 60 to 80 ° C, 0 to 40 minutes at 100 to 120 ° C, and then 40 to 90 minutes at 150 to 160 ° C can be appropriately selected. In order to sufficiently obtain the electroless tin plating resistance and the electroless gold plating resistance, it is preferable to make the conditions of the multistage curing as short as possible within a range where no voids are generated.

藉由以上說明的方法，能夠得到具有各種優異特性(例如，指觸乾燥性、密合性、耐焊接熱性能、耐溶劑性等)且化學鍍金耐性、化學鍍錫耐性優異的固化塗膜。 According to the method described above, a cured coating film having various excellent properties (for example, dry touch properties, adhesion, solder heat resistance, solvent resistance, etc.) and excellent in electroless gold plating resistance and chemical tin plating resistance can be obtained.

實施例 Example 基板製作條件： Substrate production conditions:

按照表1中示出的組成，將各成分用溶解器混合，使其均勻分散，得到固化性樹脂組合物。利用絲網印刷法使用100目的聚酯絲網將所述組合物以20~30μm的厚度整面地塗布到有形成圖案之銅通孔印刷電路基板上。接著，使用80℃的熱風迴圈式乾燥爐將塗膜乾燥30分鐘，利用 後述試驗方法和評價方法進行指觸乾燥性和顯影性的試驗。 According to the composition shown in Table 1, each component was mixed with a dissolver and uniformly dispersed to obtain a curable resin composition. The composition was applied over the entire surface of the patterned copper via printed circuit board with a thickness of 20 to 30 μm by a screen printing method using a 100-mesh polyester screen. Next, the coating film was dried using a hot air loop drying oven at 80 ° C for 30 minutes. The test methods and evaluation methods described later were tested for dry touch and developability.

接著，使具有抗蝕圖案的負片密合至塗膜，使用紫外線曝光裝置(ORC MANUFACTURING CO.,LTD.製造，型號HMW-680GW)照射紫外線(曝光量300mJ/cm2)，接著用1重量%碳酸鈉水溶液、在0.2MPa的噴壓下顯影60秒，製作試驗基板。 Next, the negative film having the resist pattern was adhered to the coating film, and ultraviolet rays (exposure amount: 300 mJ/cm 2 ) were irradiated using an ultraviolet exposure apparatus (manufactured by ORC MANUFACTURING CO., LTD., model number HMW-680 GW), followed by 1% by weight. The sodium carbonate aqueous solution was developed under a spray pressure of 0.2 MPa for 60 seconds to prepare a test substrate.

備註：KAYARAD ZAR-1035：主體樹脂，雙酚A型環氧丙烯酸酯樹脂，日本化藥株式會社製造 Remarks: KAYARAD ZAR-1035: main resin, bisphenol A epoxy acrylate resin, manufactured by Nippon Kayaku Co., Ltd.

共聚樹脂P(ACA)Z250：主體樹脂，和酸基丙烯酸酯，CYCLOMER P(ACA)Z250，大賽璐化學工業株式會社製造 Copolymer resin P(ACA)Z250: main resin, and acid acrylate, CYCLOMER P (ACA) Z250, manufactured by Daicel Chemical Industry Co., Ltd.

酞菁綠：顏料，LIONOL GREEM 2YS，TOYO INK CO.,LTD. Phthalocyanine green: pigment, LIONOL GREEM 2YS, TOYO INK CO., LTD.

KS-66：消泡劑，有機矽，信越有機矽株式會社製造 KS-66: Defoamer, organic 矽, manufactured by Shin-Etsu Organic Co., Ltd.

2PHZ-PW：固化催化劑，2-苯基-4,5-二羥基甲基咪唑，四國化成工業株式會社製造 2PHZ-PW: Curing catalyst, 2-phenyl-4,5-dihydroxymethylimidazole, manufactured by Shikoku Chemicals Co., Ltd.

三聚氰胺：固化催化劑，2,4,6-三胺基-1,3,5-三，揚州三得利化工公司製造 Melamine: curing catalyst, 2,4,6-triamino-1,3,5-three , manufactured by Yangzhou Suntory Chemical Company

三聚氰胺衍生物(THPA三聚氰胺)：固化催化劑、三聚氰胺鄰苯二甲酸鹽，四國化成工業株式會社製造 Melamine derivative (THPA melamine): curing catalyst, melamine phthalate, manufactured by Shikoku Chemicals Co., Ltd.

三聚氰胺、三聚氰胺衍生物、咪唑化合物以外的熱固化性促進劑(DICY)：固化催化劑，雙氰胺，DCDA，揚州三得利化工公司製造 Melamine, melamine derivative, thermosetting accelerator other than imidazole compound (DICY): curing catalyst, dicyandiamide, DCDA, manufactured by Yangzhou Suntory Chemical Co., Ltd.

ITX：引發劑，2-異丙基噻噸酮，揚州三得利化工公司製造 ITX: Initiator, 2-isopropyl thioxanthone, manufactured by Yangzhou Suntory Chemical Co., Ltd.

IRGCURE907：引發劑，2-甲基-1-(4-甲基硫代苯基)-2-嗎啉代丙烷-1-酮、BASF Janpan Ltd.製造 IRGCURE907: Initiator, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, manufactured by BASF Janpan Ltd.

結晶性二氧化矽：填料，A8，UNIMI株式會社製造 Crystalline cerium oxide: filler, A8, manufactured by UNIMI Corporation

重晶石：填料，BSN-OF，廣州集美納米科技公司製造 Barite: filler, BSN-OF, manufactured by Guangzhou Jimei Nano Technology Co., Ltd.

硫酸鋇：填料，沉澱性硫酸鋇，B-30，堺化學工業株式會社製造 Barium sulfate: filler, precipitated barium sulfate, B-30, manufactured by Nippon Chemical Industry Co., Ltd.

TP-A25：填料，滑石，富士滑石工業株式會社製造 TP-A25: filler, talc, manufactured by Fuji Talc Industry Co., Ltd.

DPM：溶劑，二丙二醇單甲醚，陶氏化學公司製造 DPM: solvent, dipropylene glycol monomethyl ether, manufactured by The Dow Chemical Company

DPHA：光聚合性單體，二季戊四醇六丙烯酸酯，日本化藥株式會社製造 DPHA: photopolymerizable monomer, dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.

RE306：環氧樹脂，甲酚酚醛清漆型環氧樹脂，日本 化藥株式會社製造 RE306: Epoxy resin, cresol novolak type epoxy resin, Japan Chemical Co., Ltd.

TEPIC-G：環氧樹脂，異氰脲酸1,3,5-三縮水甘油酯，日產化學工業株式會社製造 TEPIC-G: Epoxy resin, 1,3,5-triglycidyl isocyanurate, manufactured by Nissan Chemical Industry Co., Ltd.

評價方法： Evaluation method:

(1)化學鍍金耐性：對於前述試驗基板的固化膜，使用市售的化學鍍鎳液、化學鍍金液，在85℃~90℃的溫度下以鍍覆厚度為鎳3μm、金0.03μm的方式進行化學鍍，按照以下的基準評價固化膜的變色、剝離狀態。 (1) Electroless gold plating resistance: For the cured film of the test substrate, a commercially available electroless nickel plating solution or an electroless gold plating solution is used, and a plating thickness of nickel 3 μm and gold 0.03 μm is applied at a temperature of 85 ° C to 90 ° C. Electroless plating was performed, and the discoloration and peeling state of the cured film were evaluated according to the following criteria.

○：固化膜無變色、剝離等異常情況。 ○: The cured film was free from abnormalities such as discoloration and peeling.

△：固化膜僅稍有剝離，存在滲出。 △: The cured film was only slightly peeled off, and there was bleeding.

×：觀察到固化膜的浮起、剝離，發現滲鍍。 ×: The floating and peeling of the cured film were observed, and bleeding was observed.

(2)化學鍍錫耐性：對前述試驗基板的固化膜進行前處理(酸性脫脂+軟蝕刻+硫酸處理)，使用市售的化學鍍錫液，在使鍍覆厚度為1μm的條件(70℃、12分鐘)下進行化學鍍錫。對該鍍覆後的評價基板，進行利用玻璃紙黏合帶的剝離試驗，對固化膜層的剝離進行評價。 (2) Electroless tin plating resistance: pretreatment of the cured film of the test substrate (acid degreasing + soft etching + sulfuric acid treatment), using a commercially available electroless tin plating solution, and a plating thickness of 1 μm (70 ° C) Electroless tin plating was carried out under 12 minutes). The peeling test by the cellophane adhesive tape was performed on the board|substrate after evaluation of the board|substrate, and the peeling of the cured film layer was evaluated.

○：固化膜無變色、剝離等異常情況。 ○: The cured film was free from abnormalities such as discoloration and peeling.

△：固化膜僅稍有剝離，存在滲出。 △: The cured film was only slightly peeled off, and there was bleeding.

×：觀察到固化膜的浮起、剝離，發現滲鍍。 ×: The floating and peeling of the cured film were observed, and bleeding was observed.

(3)指觸乾燥性：藉由目視按照以下的基準評價前述試驗基板製作方法中曝光後的負片的剝離情況。 (3) Finger Dryness: The peeling of the negative film after exposure in the test substrate production method was evaluated by visual observation according to the following criteria.

○：膜無黏痕。 ○: The film has no stick marks.

△：觀察到膜稍有黏痕。 △: A slight stickiness of the film was observed.

×：發現膜的整面有黏痕。 ×: The entire surface of the film was found to have a sticky mark.

(4)密合性：根據JIS D 0202的試驗方法，將前述試驗基板的固化膜劃格成棋盤格狀，接著，按照以下的基準評價利用玻璃紙黏合帶的剝離試驗後的剝離狀態。 (4) Adhesiveness: The cured film of the test substrate was cut into a checkerboard shape according to the test method of JIS D 0202, and then the peeling state after the peeling test by the cellophane adhesive tape was evaluated according to the following criteria.

○：100/100都沒有剝離 ○: 100/100 is not stripped

△：100/100劃格部稍許剝離 △: 100/100 cross section slightly peeled off

×：0/100~90/100產生剝離 ×: 0/100/90/100 peeling

(5)耐焊接熱性能：根據JIS C 6481的試驗方法，將前述試驗基板用松香系焊劑和無清洗焊劑、在260℃的焊料浴中進行3次10秒鐘浸漬，按照以下的基準評價膜的變化。 (5) Welding heat resistance: The test substrate was immersed in a solder bath at 260 ° C for three times for 10 seconds in a solder bath of 260 ° C according to the test method of JIS C 6481, and the film was evaluated according to the following criteria. The change.

○：固化膜無剝離等異常情況 ○: There is no abnormality such as peeling of the cured film.

△：觀察到固化膜有變色 △: The cured film was observed to be discolored.

×：固化膜存在浮起、剝離 ×: The cured film is floated and peeled off.

(6)耐溶劑性：將前述試驗基板的固化皮膜在丙二醇單甲醚乙酸酯中、在20℃下浸漬30分鐘，確認固化膜的狀態。評價基準如下。 (6) Solvent resistance: The cured film of the test substrate was immersed in propylene glycol monomethyl ether acetate at 20 ° C for 30 minutes to confirm the state of the cured film. The evaluation criteria are as follows.

○：固化膜無剝離、白化等變色。 ○: The cured film was free from discoloration such as peeling or whitening.

△：固化膜稍有白化等變色。 △: The cured film was slightly whitened and discolored.

×：固化膜存在剝離、白化等變色。 X: The cured film was discolored by peeling or whitening.

評價結果：將上述評價結果一併示於表1。由表1明顯可知，本發明的鹼顯影型感光性樹脂組合物具有各種優異特性(例如，指觸乾燥性、密合性、耐焊接熱性能、耐溶劑性等)且化學鍍錫耐性、化學鍍金耐性優異。 Evaluation results: The above evaluation results are shown together in Table 1. As is apparent from Table 1, the alkali-developable photosensitive resin composition of the present invention has various excellent properties (for example, dry touch, adhesion, solder heat resistance, solvent resistance, etc.) and electroless tin resistance, chemical Excellent gold plating resistance.

Claims (8)

一種鹼顯影型感光性樹脂組合物，其特徵在於，含有：(A)鹼溶性樹脂、(B)光聚合引發劑、(C)熱固化性成分、(D)熱固化性促進劑、和(E)重晶石。 An alkali-developable photosensitive resin composition comprising: (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a thermosetting component, (D) a thermosetting accelerator, and ( E) Barite. 根據申請專利範圍第1項之鹼顯影型感光性樹脂組合物，其特徵在於，(D)熱固化性促進劑含有三聚氰胺、三聚氰胺的有機酸鹽、咪唑化合物中的至少任一者。 The alkali-developable photosensitive resin composition according to the first aspect of the invention, wherein the (D) thermosetting accelerator contains at least one of melamine, an organic acid salt of melamine, and an imidazole compound. 根據申請專利範圍第1項之鹼顯影型感光性樹脂組合物，其特徵在於，還含有雙氰胺。 The alkali-developable photosensitive resin composition according to the first aspect of the invention is characterized in that it further contains dicyandiamide. 根據申請專利範圍第1項之鹼顯影型感光性樹脂組合物，其特徵在於，還含有結晶性二氧化矽和滑石中的至少任一者。 The alkali-developable photosensitive resin composition according to the first aspect of the invention is characterized in that it further contains at least one of crystalline cerium oxide and talc. 根據申請專利範圍第1項之鹼顯影型感光性樹脂組合物，其特徵在於，(A)鹼溶性樹脂為含羧基樹脂。 The alkali-developable photosensitive resin composition according to the first aspect of the invention, wherein the (A) alkali-soluble resin is a carboxyl group-containing resin. 一種乾膜，其特徵在於，其是將申請專利範圍第1~5項中任一項之鹼顯影型感光性樹脂組合物塗布在薄膜上並乾燥而成的。 A dry film obtained by applying the alkali-developable photosensitive resin composition according to any one of claims 1 to 5 to a film and drying the film. 一種固化物，其特徵在於，其是利用申請專利範圍第1~5項中任一項之鹼顯影型感光性樹脂組合物、或者是利用將申請專利範圍第1~5項中任一項之鹼顯影型感光性樹脂組合物塗布在薄膜上並乾燥而成的乾膜來得到的。 A cured product of the alkali-developable photosensitive resin composition according to any one of claims 1 to 5, or the use of any one of claims 1 to 5 The alkali-developable photosensitive resin composition is obtained by applying a dry film formed by drying on a film. 一種印刷電路板，其具有固化物，所述固化物是利用申請專利範圍第1~5項中任一項之鹼顯影型感光性樹脂組合物、或者是利用將申請專利範圍第1~5項中任一項 之鹼顯影型感光性樹脂組合物塗布在薄膜上並乾燥而成的乾膜來得到的。 A printed circuit board having a cured product, which is an alkali-developable photosensitive resin composition according to any one of claims 1 to 5, or a use of the first to fifth patents. Any of them The alkali-developable photosensitive resin composition is obtained by applying a dry film formed by drying on a film.
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JP6360900B2 (en) 2018-07-18
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CN104808436B (en) 2017-11-24
JP2017506361A (en) 2017-03-02
TWI574105B (en) 2017-03-11

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