TWI480687B - A photohardenable thermosetting resin composition, a dry film and a cured product thereof, and a printed circuit board using the same - Google Patents

A photohardenable thermosetting resin composition, a dry film and a cured product thereof, and a printed circuit board using the same Download PDF

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TWI480687B
TWI480687B TW099111994A TW99111994A TWI480687B TW I480687 B TWI480687 B TW I480687B TW 099111994 A TW099111994 A TW 099111994A TW 99111994 A TW99111994 A TW 99111994A TW I480687 B TWI480687 B TW I480687B
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group
resin
compound
carboxyl group
film
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TW201042387A (en
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Nobuhito Ito
Masao Arima
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Taiyo Holdings Co Ltd
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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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • General Chemical & Material Sciences (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Description

光硬化性熱硬化性樹脂組成物、其乾式薄膜及硬化物以及使用此等之印刷電路板Photocurable thermosetting resin composition, dry film and cured product thereof, and printed circuit board using the same

本發明係關於藉由稀鹼水溶液可顯像之光硬化性熱硬化性樹脂組成物，特別為藉由紫外線曝光或雷射曝光進行光硬化之防焊劑用組成物、其乾式薄膜及硬化物、以及具有使用其所形成之硬化被膜的印刷電路板。The present invention relates to a photocurable thermosetting resin composition which can be developed by a dilute aqueous alkali solution, particularly a composition for a solder resist which is photocured by ultraviolet exposure or laser exposure, a dry film and a cured product thereof, And a printed circuit board having a hardened film formed using the same.

現在一部分的民生用印刷電路板以及幾乎所有的產業用印刷電路板的防焊劑，由高精度、高密度的觀點來看，使用經紫外線照射後，進行顯像而形成影像，在熱及/或光照射加工硬化(本硬化)的液狀顯像型防焊劑。而由對環境問題之顧慮來看，作為顯像液使用稀鹼水溶液的鹼性顯像型的光阻焊劑已成為主流，於實際印刷電路板之製造上，已經大量地被使用。又，隨著近年電子機器之輕薄短小化，對應印刷電路板的高密度化，防焊劑亦被要求作業性或高性能化。At present, some of the printed circuit boards for the people's livelihood and the solder resists of almost all industrial printed circuit boards are imaged by ultraviolet light irradiation from the viewpoint of high precision and high density, and are formed in the heat and/or heat. A liquid developing type solder resist that is hardened by work (light hardening). In view of environmental concerns, an alkaline development type photoresist which uses a dilute aqueous alkali solution as a developing solution has become a mainstream, and has been widely used in the manufacture of practical printed circuit boards. In addition, in recent years, the weight and thickness of electronic devices have been shortened, and in order to increase the density of printed circuit boards, solder resists have been required to have workability and high performance.

然而，現行的鹼顯像型之光阻焊劑於耐久性的點來看仍有問題。即，過去的熱硬化型、溶劑顯像型者相比其耐鹼性、耐水性、耐熱性等較劣。此為鹼顯像型光阻焊劑可於鹼性顯像，故具有親水性基，即具有羧基或羥基者作為主成，藥液、水、水蒸氣等容易浸透，使得耐藥品性降低或降低阻被膜與銅之密著性。其結果，作為耐藥品性之耐酸性、耐鹼性弱，特別於BGA(ball grid array)或CSP( Chip Scale Package)等半導體封包中，特別以耐濕熱性之PCT耐性(蒸汽鍋測試耐性)為必要，但如此嚴謹條件下，僅能耐的住數小時~數十小時程度為現狀。又，鹼顯像型阻焊劑於在加濕條件下外加電壓之狀態下的HAST試驗(高度加速壽命試驗)中幾乎皆確認出因數小時的遷移產生而顯示不良結果。However, current alkali-developing type photo solder resists are still problematic in terms of durability. That is, in the past, the thermosetting type and the solvent developing type are inferior in alkali resistance, water resistance, heat resistance, and the like. Since the alkali-developing type photoresist can be alkaline-developed, it has a hydrophilic group, that is, a carboxyl group or a hydroxyl group is used as a main component, and a chemical solution, water, water vapor, or the like is easily impregnated, so that chemical resistance is lowered or lowered. The adhesion of the film to the copper is tight. As a result, it is chemically resistant to acid and alkali, and is particularly useful for BGA (ball grid array) or CSP ( In semiconductor packages such as Chip Scale Package, it is necessary to particularly resist PCT resistance (steam pot test resistance), but under such strict conditions, it is only a few hours to several tens of hours. Further, in the HAST test (highly accelerated life test) in which the alkali-developing type solder resist was applied under a humidification condition, almost all of the migration of the factor was confirmed to cause a poor result.

另一方面，使用於過去的防焊劑之含有羧基之樹脂，一般使用藉由環氧樹脂之改性所衍生之環氧丙烯酸酯改性樹脂。On the other hand, as the carboxyl group-containing resin used in the conventional solder resist, an epoxy acrylate-modified resin derived by modification of an epoxy resin is generally used.

特開昭61-243869號公報(專利文獻1)中揭示，由於漆用酚醛型環氧化合物與不飽和一鹼酸之反應生成物中加成酸酐的感光性樹脂、光聚合啟始劑、稀釋劑及環氧化合物所成之防焊劑組成物。又，特開平3-250012號公報(專利文獻2)中揭示，於水楊醛與一價酚之反應生成物中反應環氧氯丙烷所得之環氧樹脂中加成(甲基)丙烯酸，再反應多元性羧酸或該無水物所得之感光性樹脂、光聚合啟始劑、有機溶劑等所成之防焊劑組成物。JP-A-61-243869 (Patent Document 1) discloses a photosensitive resin, a photopolymerization initiator, and a dilution of an acid anhydride formed by reacting a phenolic epoxy compound with an unsaturated monobasic acid. A flux composition made of a solvent and an epoxy compound. Japanese Patent Publication No. 3-250012 (Patent Document 2) discloses the addition of (meth)acrylic acid to an epoxy resin obtained by reacting epichlorohydrin with a reaction product of salicylaldehyde and monovalent phenol. A flux composition formed by reacting a polyvalent carboxylic acid or a photosensitive resin obtained by the anhydrate, a photopolymerization initiator, an organic solvent, or the like.

一般的環氧丙烯酸酯改性樹脂為，作為原料使用之環氧樹脂幾乎都已含有大量氯離子雜質，經環氧丙烯酸酯改性後，非常難以除去此。又，含有氯離子雜質之絕緣材料為絕緣信賴性較差者為公知的事實。In the general epoxy acrylate-modified resin, almost all of the epoxy resins used as raw materials contain a large amount of chloride ion impurities, and it is very difficult to remove them after being modified by epoxy acrylate. Further, an insulating material containing a chloride ion impurity is a well-known fact that the insulation reliability is poor.

[先行技術文獻][Advanced technical literature] [專利文獻][Patent Literature]

[專利文獻1]特開昭61-243869號公報(申請專利範圍)[Patent Document 1] JP-A-61-243869 (Patent Application)

[專利文獻2]特開平3-250012號公報(申請專利範圍)[Patent Document 2] Japanese Patent Laid-Open No. Hei-3-250012 (Application No.)

本發明係有鑑於如前述過去技術的問題所成者，其主要目的為提供可形成具有優良絕緣信賴性、耐藥品性，又具有作為半導體封包用防焊劑為重要之PCT耐性、HAST耐性、無電解鍍金耐性的硬化被膜之光硬化性熱硬化性樹脂組成物。The present invention has been made in view of the problems of the prior art as described above, and its main object is to provide PCT resistance, HAST resistance, and the like which are excellent in insulation reliability and chemical resistance, and which are important as solder resists for semiconductor packages. A photocurable thermosetting resin composition of an electrolytic gold plating resistant hardened film.

本發明的進一步目的為提供藉由使用如此光硬化性熱硬化性樹脂組成物所得之如上述各特性優良的乾式薄膜及硬化物、以及藉由該乾式薄膜或硬化物形成防焊劑等硬化被膜而成之印刷電路板。A further object of the present invention is to provide a dry film and a cured product which are excellent in the above-described properties obtained by using such a photocurable thermosetting resin composition, and a hardened film such as a solder resist or the like by the dry film or cured product. Into the printed circuit board.

欲達當前述目的，本發明提供一種含有(A)含有羧基之樹脂(但，將環氧樹脂作為啟始原料之含有羧基之樹脂除外)、(B)光聚合啟始劑、及(C)胺基樹脂為特徴之藉由稀鹼水溶液可顯像之光硬化性熱硬化性樹脂組成物。In order to achieve the above object, the present invention provides a resin containing (A) a carboxyl group-containing resin (except for a carboxyl group-containing resin having an epoxy resin as a starting material), (B) a photopolymerization initiator, and (C) The amine-based resin is a photocurable thermosetting resin composition which is developed by a dilute aqueous alkali solution.

上述含有羧基之樹脂(A)以未含有羥基為佳，進一步具有感光性基為佳。本發明的光硬化性熱硬化性樹脂組成物之較佳型態中，前述胺基樹脂(C)為具有烷氧基甲基之胺基樹脂，且含有熱硬化性成分(D)、更佳為具有環狀醚結構及/或環狀硫醚結構的熱硬化性成分，較佳為進一步含有著色劑(G)之而使用於防焊劑。The carboxyl group-containing resin (A) preferably contains no hydroxyl group, and further preferably has a photosensitive group. In a preferred embodiment of the photocurable thermosetting resin composition of the present invention, the amine-based resin (C) is an amino-based resin having an alkoxymethyl group and contains a thermosetting component (D), preferably The thermosetting component having a cyclic ether structure and/or a cyclic thioether structure preferably further contains a coloring agent (G) and is used for a solder resist.

又，本發明為提供一種將前述光硬化性熱硬化性樹脂組成物塗佈於載體膜並乾燥所得之光硬化性熱硬化性的乾式薄膜、及將前述光硬化性熱硬化性樹脂組成物或乾式薄膜進行光硬化，較佳為在波長350nm~410nm的光源下光硬化成圖型狀所得之硬化物。Moreover, the present invention provides a photocurable thermosetting dry film obtained by applying the photocurable thermosetting resin composition to a carrier film and drying the composition, and the photocurable thermosetting resin composition or The dry film is photocured, and is preferably a cured product obtained by photohardening into a pattern at a light source having a wavelength of 350 nm to 410 nm.

又，本發明亦提供一種具有將前述光硬化性熱硬化性樹脂組成物或乾式薄膜藉由紫外線的直接描繪而光硬化成圖型狀後，經熱硬化所得之硬化被膜的印刷電路板。又，使用本發明的組成物所得之硬化被膜與使用過去的阻焊劑組成物所得之硬化被膜相比較，可顯著發揮硬化被膜之低鹵化的効果。即，對於今後被預想的「硬化被膜的進一步無鹵素化」的要求，使用本發明的組成物所得之硬化被膜具有優良的有利條件。Moreover, the present invention also provides a printed circuit board having a cured film obtained by thermally curing the photocurable thermosetting resin composition or the dry film by direct drawing of ultraviolet rays into a pattern. Further, the cured film obtained by using the composition of the present invention can remarkably exhibit the effect of lowering the halogenation of the cured film as compared with the cured film obtained by using the conventional solder resist composition. In other words, the hardened film obtained by using the composition of the present invention has excellent favorable conditions for the future desired "dehalogenation of the cured film".

本發明的光硬化性熱硬化性樹脂組成物中，作為藉由稀鹼水溶液可顯像之成分，因使用未將環氧樹脂作為啟始原料的含有羧基之樹脂(A)，故所含之鹵素量顯著變低，所得之硬化被膜(塗膜)的電氣特性提高。又，與此組合而含有之胺基樹脂，特別為具有烷氧基甲基之胺基樹脂(C)可提高所得之硬化被膜的疏水性，特別對鍍金耐性具效果，與未將環氧樹脂作為啟始原料的含有羧基之樹脂併用時，進一步對於PCT耐性與HAST耐性之向上有著相當效果。因此，藉由使用本發明的光硬化性熱硬化性樹脂組成物，可形成具有顯著優良絕緣信賴性、耐藥品性，且作為半導體封包用防焊劑具有重要PCT耐性、HAST耐性、無電解鍍金耐性之硬化被膜。In the photocurable thermosetting resin composition of the present invention, as a component which can be developed by a dilute aqueous alkali solution, a carboxyl group-containing resin (A) which does not use an epoxy resin as a starting material is used, and thus The amount of halogen is remarkably low, and the electrical properties of the obtained hardened film (coating film) are improved. Further, the amine-based resin contained in combination therewith, particularly the amino-based resin (C) having an alkoxymethyl group, can improve the hydrophobicity of the obtained cured film, particularly for the gold plating resistance, and the epoxy resin is not provided. When the carboxyl group-containing resin is used as a starting material, it has a considerable effect on the upward direction of PCT resistance and HAST resistance. Therefore, by using the photocurable thermosetting resin composition of the present invention, it is possible to form remarkably excellent insulation reliability and chemical resistance, and to have important PCT resistance, HAST resistance, and electroless gold plating resistance as a solder resist for semiconductor encapsulation. Hardened film.

實施發明的型態Type of implementation of the invention

如前述，本發明的光硬化性熱硬化性樹脂組成物之特徵為，含有未將環氧樹脂作為啟始原料的含有羧基之樹脂(A)、光聚合啟始劑(B)及胺基樹脂，特別為具有烷氧基甲基之胺基樹脂(C)為特徵。As described above, the photocurable thermosetting resin composition of the present invention is characterized by containing a carboxyl group-containing resin (A), a photopolymerization initiator (B), and an amine resin without using an epoxy resin as a starting material. Specifically, it is characterized by an amino group-containing resin (C) having an alkoxymethyl group.

作為上述含有羧基之樹脂(A)，僅為未將環氧樹脂作為啟始原料的含有羧基之樹脂即可，可使用過去公知之各種含有羧基之樹脂，但其中亦以分子中具有乙烯性不飽和雙鍵的含有羧基之感光性樹脂由光硬化性或耐顯像性之面來看為佳。而該不飽和雙鍵以來自丙烯酸或甲基丙烯酸或彼等衍生物者為佳。且，僅使用不具有乙烯性不飽和雙鍵的含有羧基之樹脂時，欲使組成物具有光硬化性，如後述必須併用分子中具有1個以上乙烯性不飽和基的化合物(感光性單體)。The carboxyl group-containing resin (A) may be a carboxyl group-containing resin which does not use an epoxy resin as a starting material, and various conventionally known carboxyl group-containing resins may be used, but in the case of having a vinyl group in the molecule, The carboxyl group-containing photosensitive resin having a saturated double bond is preferred from the viewpoint of photocurability or development resistance. Preferably, the unsaturated double bond is derived from acrylic acid or methacrylic acid or a derivative thereof. In addition, when only a carboxyl group-containing resin having no ethylenic unsaturated double bond is used, the composition is required to have photocurability, and a compound having one or more ethylenically unsaturated groups in the molecule (photosensitive monomer) must be used in combination as described below. ).

作為可使用於本發明的含有羧基之樹脂(A)之具體例，以以下所列舉的化合物(寡聚物及聚合物皆可)為佳。Specific examples of the carboxyl group-containing resin (A) which can be used in the present invention are preferably the following compounds (oligomers and polymers).

(1)雙酚A、雙酚F、雙酚S、漆用酚醛型酚樹脂、 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1分子中具有2個以上酚性羥基之化合物、與環氧乙烷、環氧丙烷等伸烷基氧化物進行反應所得之反應生成物中，使(甲基)丙烯酸等含有不飽和基之單羧酸進行反應所得之反應生成物中使馬來酸酐、四氫苯二甲酸酐、偏苯三酸酐、均苯四甲酸酐、己二酸等多元酸酐進行反應所得的含有羧基之感光性樹脂。(1) bisphenol A, bisphenol F, bisphenol S, phenolic phenolic resin for lacquer, Poly-p-hydroxystyrene, a condensate of naphthol and an aldehyde, a condensate of dihydroxynaphthalene and an aldehyde, a compound having two or more phenolic hydroxyl groups in one molecule, and ethylene oxide, propylene oxide, etc. In the reaction product obtained by the reaction of the alkylene oxide, maleic anhydride, tetrahydrophthalic anhydride, and trimellitic anhydride are obtained by reacting a monocarboxylic acid containing an unsaturated group such as (meth)acrylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as trimesic anhydride or adipic acid.

(2)1分子中具有2個以上酚性羥基之化合物與伸乙基碳酸酯、伸丙基碳酸酯等環狀碳酸酯化合物進行反應所得之反應生成物中，使含有不飽和基之單羧酸進行反應，所得之反應生成物中使多元酸酐進行反應所得的含有羧基之感光性樹脂。(2) A reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as an ethyl carbonate or a propyl carbonate, and a monocarboxylic acid having an unsaturated group The acid is subjected to a reaction, and the obtained reaction product is a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride.

(3)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二異氰酸酯化合物、與具有聚碳酸酯系多元醇、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系伸烷基氧化物加成體二醇、酚性羥基及醇性羥基之化合物等二醇化合物藉由聚加成反應之脲烷樹脂的末端上使酸酐進行反應所成的末端含有羧基之脲烷樹脂。(3) a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a polycarbonate-based polyol, a polyether-based polyol, or a polyester-based polyol; a diol compound such as a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide addition diol, a phenolic hydroxyl group or an alcoholic hydroxyl group, by a polyaddition reaction urethane resin A urethane resin having a carboxyl group at the terminal end which is formed by reacting an acid anhydride at the end.

(4)二異氰酸酯、與二羥甲基丙酸、二羥甲基酪酸等含有羧基之二醇化合物、與二醇化合物藉由聚加成反應的含有羧基之脲烷樹脂的合成中，加入羥基烷基(甲基)丙烯酸酯等分子中具有1個羥基與1個以上之(甲基)丙烯醯基的化合物，得到末端經(甲基)丙烯酸化的含有羧 基之脲烷樹脂。(4) a diisocyanate, a diol compound containing a carboxyl group such as dimethylolpropionic acid or dimethylol butyric acid, and a carboxy group-containing urethane resin which is reacted with a diol compound by a polyaddition reaction, and a hydroxyl group is added. a compound having one hydroxyl group and one or more (meth)acryl fluorenyl groups in a molecule such as an alkyl (meth) acrylate, and a terminally (meth) acrylated carboxy group is obtained. Base urethane resin.

(5)二異氰酸酯、與含有羧基之二醇化合物、與二醇化合物藉由聚加成反應的含有羧基之脲烷樹脂的合成中，加入異佛爾酮二異氰酸酯與季戊四醇三丙烯酸酯的等莫耳反應物等，分子中具有1個異氰酸酯基與1個以上的(甲基)丙烯醯基之化合物，得到末端經(甲基)丙烯酸化的含有羧基之脲烷樹脂。(5) In the synthesis of a diisocyanate, a diol compound containing a carboxyl group, and a urethane resin containing a carboxyl group by a polyaddition reaction with a diol compound, isophorone diisocyanate and pentaerythritol triacrylate are added. An auric reactant or the like, a compound having one isocyanate group and one or more (meth) acrylonitrile groups in the molecule, and a (meth) acrylated carboxyl group-containing urethane resin is obtained.

(6)(甲基)丙烯酸等不飽和羧酸、與苯乙烯、α -甲基苯乙烯、低級烷基(甲基)丙烯酸酯、異丁烯等不飽和基含有化合物藉由共聚合所得的含有羧基之樹脂。(6) an unsaturated carboxylic acid such as (meth)acrylic acid or a carboxyl group obtained by copolymerization with an unsaturated group-containing compound such as styrene, α -methylstyrene, lower alkyl (meth) acrylate or isobutylene Resin.

(7)如後述於官能氧雜環丁烷樹脂、使己二酸、苯二甲酸、六氫苯二甲酸等二羧酸進行反應，於所生成的1級羥基中，加成苯二甲酸酐、四氫苯二甲酸酐、六氫苯二甲酸酐等2元酸酐之含有羧基的聚酯樹脂中，再加成環氧丙基(甲基)丙烯酸酯、α-甲基環氧丙基(甲基)丙烯酸酯等1分子中具有1個環氧基與1個以上的(甲基)丙烯醯基之化合物所成之含有羧基之感光性樹脂。(7) As described later in the functional oxetane resin, a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid is reacted, and phthalic anhydride is added to the produced first-order hydroxyl group. a carboxyl group-containing polyester resin such as tetrahydrophthalic anhydride or hexahydrophthalic anhydride, which is further added with a glycidyl (meth)acrylate or an α-methylepoxypropyl group. A photosensitive resin containing a carboxyl group formed of a compound having one epoxy group and one or more (meth)acryl fluorenyl groups in one molecule such as a methyl acrylate.

(8)於前述(1)~(7)的含有羧基之樹脂中，加成1分子中具有環狀醚基與(甲基)丙烯醯基之化合物的含有羧基之感光性樹脂。(8) A carboxyl group-containing photosensitive resin having a compound having a cyclic ether group and a (meth) acrylonitrile group in one molecule, in the carboxyl group-containing resin of the above (1) to (7).

且，本說明書中，所謂(甲基)丙烯酸酯為總稱丙烯酸酯、甲基丙烯酸酯及彼等混合物之用語，對於其他類似表現亦相同。Further, in the present specification, the term "(meth)acrylate" is a generic term for acrylate, methacrylate, and the like, and the same applies to other similar expressions.

本發明所使用的含有羧基之樹脂(A)因未將環氧樹 脂作為啟始原料使用，故具有鹵化物含有量非常少之特徵。本發明所使用的含有羧基之樹脂的氯離子雜質含有量為0~100ppm，較佳為0~50ppm，更佳為0~30ppm。The carboxyl group-containing resin (A) used in the present invention does not have an epoxy tree Since fat is used as a starting material, it has a characteristic that the halide content is very small. The carboxyl group-containing resin used in the present invention has a chloride ion impurity content of 0 to 100 ppm, preferably 0 to 50 ppm, more preferably 0 to 30 ppm.

又，本發明所使用的含有羧基之樹脂(A)可容易得到未含有羥基之樹脂。一般已知羥基之存在為，具有藉由氫鍵可提高密著性之優良特徵，但顯著降低耐濕性。以下說明與一般使用於防焊劑的環氧丙烯酸酯改性樹脂進行比較的本發明含有羧基之樹脂的優點。Further, the carboxyl group-containing resin (A) used in the present invention can easily obtain a resin which does not contain a hydroxyl group. It is generally known that the presence of a hydroxyl group has an excellent feature of improving adhesion by hydrogen bonding, but significantly lowers moisture resistance. The advantages of the carboxyl group-containing resin of the present invention which is generally compared with an epoxy acrylate-modified resin which is generally used for a solder resist will be described below.

不具有氯份之酚漆用酚醛樹脂可容易入手。將此藉由經烷基氧化物改性的酚樹脂一部分的丙烯酸化、及酸酐之導入，可得到在雙鍵等量300~550、酸價40~120mgKOH/g的範圍下理論上不具有羥基之樹脂。A phenolic resin for phenol paint without chlorine can be easily used. By acrylation of a part of the phenol resin modified with an alkyl oxide and introduction of an acid anhydride, it is possible to obtain a theoretically no hydroxyl group in the range of 300 to 550 double bonds and 40 to 120 mg KOH/g in acid value. Resin.

另一方面，若將藉由類似之酚漆用酚醛樹脂經合成的環氧樹脂之環氧基全進行丙烯酸化，於全羥基導入酸酐時，在雙鍵等量400~500下酸價會大幅度超過100mgKOH/g，及曝光後亦無法得到具有耐顯像性之被膜。且，因酸濃度高，故使耐水性劣化，顯著降低絕緣信賴性、PCT耐性。即，自類似之酚漆用酚醛型環氧樹脂所衍生的環氧丙烯酸酯系樹脂使羥基完全消失係為非常困難。On the other hand, if the epoxy group of the epoxy resin synthesized by the phenolic resin similar to the phenol paint is all acrylated, when the acid anhydride is introduced into the total hydroxyl group, the acid value will be large at the double bond equivalent of 400 to 500. When the amplitude exceeds 100 mgKOH/g, and the film having the development resistance is not obtained after the exposure. Further, since the acid concentration is high, the water resistance is deteriorated, and the insulation reliability and PCT resistance are remarkably lowered. That is, it is extremely difficult to completely disappear a hydroxyl group from an epoxy acrylate-based resin derived from a phenolic epoxy resin similar to a phenol paint.

又，脲烷樹脂亦藉由合併羥基與異氰酸酯基之當量，可容易合成未含羥基之樹脂。較佳樹脂係為未使用將光氣作為啟始原料的異氰酸酯化合物、未使用環氧鹵丙烷之原料所合成的氯離子雜質量0~30ppm的含有羧基之樹脂，更佳為合成理論上未含有羥基的樹脂。Further, the urethane resin can also easily synthesize a resin having no hydroxyl group by combining the equivalents of a hydroxyl group and an isocyanate group. Preferably, the resin is a carboxyl group-containing resin having a chloride ion mass of 0 to 30 ppm synthesized without using an isocyanate compound containing phosgene as a starting material and a raw material not using epihalohydrin, and more preferably theoretically not contained. Hydroxyl resin.

由如此觀點得知，使用先前作為具體例所示的含有羧基之樹脂(1)~(5)為特佳。From such a viewpoint, it is particularly preferable to use the carboxyl group-containing resins (1) to (5) which have been conventionally shown as specific examples.

又，對於與先前所示含有不飽和基的化合物藉由共聚合所得的含有羧基之樹脂(6)，作為一分子中具有環狀醚基與(甲基)丙烯醯基之化合物，因將3,4-環氧基環己基甲基甲基丙烯酸酯進行反應的含有羧基之感光性樹脂亦使用脂環式環氧基，故鹵素量較少而較佳。Further, the carboxyl group-containing resin (6) obtained by copolymerization with the compound containing an unsaturated group as described above is used as a compound having a cyclic ether group and a (meth)acryl fluorenyl group in one molecule, since Further, since the carboxyl group-containing photosensitive resin in which 4-cyclooxycyclohexylmethyl methacrylate is reacted also uses an alicyclic epoxy group, the amount of halogen is small, which is preferable.

另一方面，於含有羧基之樹脂(6)將作為1分子中具有環狀醚基與(甲基)丙烯醯基的化合物之環氧丙基甲基丙烯酸酯進行反應者、或共聚合作為含有不飽和基的化合物之環氧丙基甲基丙烯酸酯者，有著氯量過多之顧慮。又，於脲烷樹脂的合成時，作為二醇化合物亦可使用環氧丙烯酸酯。雖會摻入鹵素成分，但可控制鹵素量等點來看可使用。On the other hand, a resin having a carboxyl group (6) is reacted or copolymerized as a glycidyl methacrylate having a cyclic ether group and a (meth)acryl fluorenyl group in one molecule. The epoxy group methacrylate of the unsaturated group compound has a concern of excessive chlorine. Further, in the synthesis of a urethane resin, an epoxy acrylate may be used as the diol compound. Although a halogen component is incorporated, it can be used by controlling the amount of halogen.

如上述的含有羧基之樹脂(A)，於骨架‧聚合物之側鏈上具有多數游離羧基，可藉由稀鹼水溶液進行顯像。The carboxyl group-containing resin (A) as described above has a plurality of free carboxyl groups in the side chain of the skeleton ‧ polymer, and can be developed by a dilute aqueous alkali solution.

又，上述含有羧基之樹脂(A)的酸價為40~200mgKOH/g之範圍，較佳為40~120mgKOH/g之範圍。含有羧基之樹脂的酸價未達40mgKOH/g時，難以進行鹼性顯像，另一方面，該調配量超過200mgKOH/g時，藉由顯像液的曝光部會溶解，故線條會縮小至必須量以上，或依情況，在無曝光部與未曝光部之區別下於顯像液中溶解剝離，難以進行正常光阻圖型之描繪而不佳。Further, the acid value of the carboxyl group-containing resin (A) is in the range of 40 to 200 mgKOH/g, preferably 40 to 120 mgKOH/g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, it is difficult to perform alkaline development. On the other hand, when the compounding amount exceeds 200 mgKOH/g, the exposed portion of the developing solution is dissolved, so that the line is reduced to It is necessary to be more than or equal to the amount or, depending on the case, to dissolve and peel off in the developing liquid in the absence of the exposed portion and the unexposed portion, and it is difficult to perform the drawing of the normal photoresist pattern.

又，上述含有羧基之樹脂(A)的重量平均分子量依樹脂骨架不同而不同，但一般為2,000~150,000，更佳為5,000~100,000之範圍。重量平均分子量未達2,000時，不剝落性能有時會劣化，曝光後的被膜耐濕性會惡化而於顯像時產生膜減少，且有時解像度會大大地劣化。另一方面，重量平均分子量超過150,000時，有時顯像性會顯著惡化，有時貯藏安定性會劣化。Further, the weight average molecular weight of the carboxyl group-containing resin (A) varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is less than 2,000, the non-peeling performance may be deteriorated, and the moisture resistance of the film after exposure may be deteriorated, and the film may be reduced during development, and the resolution may be greatly deteriorated. On the other hand, when the weight average molecular weight exceeds 150,000, the developability may be remarkably deteriorated, and the storage stability may be deteriorated.

如此含有羧基之樹脂(A)之調配量於全組成物中為，20~60質量%，較佳為30~50質量%。該調配量比上述範圍少時，被膜強度會降低故不佳。另一方面，該調配量比上述範圍多時，黏性會變高、或塗佈性等會降低故不佳。The compounding amount of the carboxyl group-containing resin (A) is, in the total composition, 20 to 60% by mass, preferably 30 to 50% by mass. When the blending amount is less than the above range, the film strength is lowered, which is not preferable. On the other hand, when the amount is more than the above range, the viscosity is increased, or the coatability and the like are lowered, which is not preferable.

作為光聚合啟始劑(B)，使用選自具有下述一般式(I)所示基的肟酯系光聚合啟始劑(B1)、具有下述一般式(II)所示基的α-胺基乙醯苯系光聚合啟始劑(B2)、及具有下述式(III)所示基的醯基膦氧化物系光聚合啟始劑(B3)所成群之1種以上的光聚合啟始劑為佳。As the photopolymerization initiator (B), an oxime ester-based photopolymerization initiator (B1) selected from the group represented by the following general formula (I) and α having the group represented by the following general formula (II) are used. One or more groups of the group consisting of an aminoethyl benzene-based photopolymerization initiator (B2) and a fluorenylphosphine oxide-based photopolymerization initiator (B3) having a group represented by the following formula (III) Photopolymerization initiators are preferred.

(式中，R1 表示氫原子、苯基(可由碳數1~6的烷基、苯基、或鹵素原子取代)、碳數1~20的烷基(可由1個以上的羥基取代、烷基鏈的中間可具有1個以上之氧原子)、碳數5~8的環烷基、碳數2~20的烷醯基或苯甲醯基(可由碳數為1~6的烷基或苯基取代)，R2 表示苯基(可由碳數1~6的烷基、苯基或鹵素原子取代)、碳數1~20的烷基(可由1個以上的羥基取代、烷基鏈的中間可具有1個以上之氧原子)、碳數5~8的環烷基、碳數2~20的烷醯基或苯甲醯基(可由碳數為1~6的烷基或苯基取代)，R3 及R4 各獨立表示碳數1~12的烷基或芳基烷基，R5 及R6 各獨立表示氫原子、碳數1~6的烷基、或2個經結合的環狀烷基醚基，R7 及R8 各獨立表示可由碳數1~10的直鏈狀或分支狀的烷基、環己基、環戊基、芳基、或鹵素原子、烷基或烷氧基取代之芳基，但R7 及R8 的一方可表示R-C(=O)-基(其中R為碳數1~20的烴基))。(wherein R 1 represents a hydrogen atom, a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (may be substituted by one or more hydroxyl groups, and an alkane The base chain may have one or more oxygen atoms in the middle, a cycloalkyl group having 5 to 8 carbon atoms, an alkyl fluorenyl group having 2 to 20 carbon atoms or a benzhydryl group (which may be an alkyl group having 1 to 6 carbon atoms or Phenyl substituted), R 2 represents a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (which may be substituted by one or more hydroxyl groups, and an alkyl chain) Intermediate may have one or more oxygen atoms), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzhydryl group (substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group) And R 3 and R 4 each independently represent an alkyl group or an arylalkyl group having 1 to 12 carbon atoms, and R 5 and R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 2 bonded groups. a cyclic alkyl ether group, each of R 7 and R 8 independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or a halogen atom, an alkyl group or an alkyl group. An aryl group substituted with an oxy group, but one of R 7 and R 8 may represent an RC(=O)- group (wherein R is a hydrocarbon group having 1 to 20 carbon atoms)).

作為具有前述一般式(I)所示基的肟酯系光聚合啟始劑，較佳為下述式(IV)所示2-(乙醯氧基亞胺基甲基)噻噸-9-酮、下述一般式(V)所示化合物、下述一般式(VI)所示化合物可舉出。其中亦以下述式(IV)所示2-(乙醯氧基亞胺基甲基)噻噸-9-酮、及式(V)所示化合物為較佳。The oxime ester-based photopolymerization initiator having the group represented by the above general formula (I) is preferably 2-(ethyloxyiminomethyl)thioxanthene-9- represented by the following formula (IV). The ketone, the compound represented by the following general formula (V), and the compound represented by the following general formula (VI) are exemplified. Among them, 2-(ethyloxyiminomethyl)thioxanthene-9-one represented by the following formula (IV) and a compound represented by the formula (V) are preferred.

(式中，R9 表示氫原子、鹵素原子、碳數1~12的烷基、環戊基、環己基、苯基、苯甲基、苯甲醯基、碳數2~12的烷醯基、碳數2~12的烷氧基羰基(構成烷氧基之烷基得碳數為2以上時，烷基可由1個以上之羥基取代，烷基鏈之中間可具有1個以上之氧原子)、或苯氧基羰基，R10 、R12 各獨立表示苯基(可由碳數1~6的烷基、苯基或鹵素原子取代)、碳數1~20的烷基(可由1個以上的羥基取代、烷基鏈的中間可具有1個以上之氧原子)、碳數5~8的環烷基、碳數2~20的烷醯基或苯甲醯基(可由碳數為1~6的烷基或苯基取代)，R11 表示氫原子、苯基(可由碳數1~6的烷基、苯基或鹵素原子取代)、碳數1~20的烷基(可由1個以上的羥基取代，烷基鏈之中間可具有1個以上之氧原子)、碳數5~8的環烷基、碳數2~20的烷醯基或苯甲醯基(可由碳數為1~6的烷基或苯基取代)。)(wherein R 9 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzamyl group, or an alkylene group having 2 to 12 carbon atoms; And an alkoxycarbonyl group having 2 to 12 carbon atoms (when the alkyl group constituting the alkoxy group has a carbon number of 2 or more, the alkyl group may be substituted by one or more hydroxyl groups, and the alkyl chain may have one or more oxygen atoms in the middle of the alkyl chain. And phenoxycarbonyl, R 10 and R 12 each independently represent a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom) or an alkyl group having 1 to 20 carbon atoms (may be one or more) The hydroxy group may have one or more oxygen atoms in the middle of the alkyl chain), the cycloalkyl group having 5 to 8 carbon atoms, the alkyl fluorenyl group having 2 to 20 carbon atoms or the benzamidine group (the number of carbon atoms may be 1~) 6 alkyl or phenyl substituted), R 11 represents a hydrogen atom, a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (may be one or more) The hydroxy group may have one or more oxygen atoms in the middle of the alkyl chain), the cycloalkyl group having 5 to 8 carbon atoms, the alkyl fluorenyl group having 2 to 20 carbon atoms or the benzhydryl group (the number of carbon atoms may be 1~) 6 alkyl or phenyl substituted).)

(式中，R13 及R14 各獨立表示碳數1~12的烷基，R15 、R16 、R17 及R18 各獨立表示氫原子或碳數1~6的烷基，n表示0~5的整數。)(wherein R 13 and R 14 each independently represent an alkyl group having 1 to 12 carbon atoms, and R 15 , R 16 , R 17 and R 18 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents 0. An integer of ~5.)

作為具有前述一般式(I)所示基的肟酯系光聚合啟始劑之販賣品，可舉出Ciba Japan(股)製的CGI-325、IRGACURE OXE01、IRGACURE OXE02等。這些肟酯系光聚合啟始劑可單獨或組合2種以上使用。The commercial product of the oxime ester-based photopolymerization initiator having the group represented by the above formula (I) includes CGI-325, IRGACURE OXE01, IRGACURE OXE02, and the like manufactured by Ciba Japan Co., Ltd. These oxime ester-based photopolymerization initiators may be used alone or in combination of two or more.

作為具有前述一般式(II)所示基的α-胺基乙醯苯系光聚合啟始劑，有2-甲基-1-[4-(甲基硫)苯基]-2-嗎啉代丙酮-1、2-苯甲基-2-二甲基胺基-1-(4-嗎啉代苯基)-丁烷-1-酮、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、N,N-二甲基胺基乙醯苯等可舉出。作為販賣品，有Ciba Japan(股)製的IRGACURE907、IRGACURE369、IRGACURE379等可舉出。As the α-aminoethyl phthalide photopolymerization initiator having the above formula (II), there is 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine Acetone-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-dimethylaminoethyl benzene benzene, etc. may be mentioned . As the merchandise, IRGACURE 907, IRGACURE 369, IRGACURE 379, etc., manufactured by Ciba Japan Co., Ltd., may be mentioned.

作為具有前述一般式(III)所示基的醯基膦氧化物系光聚合啟始劑，有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-戊基膦氧化物等可舉出。作為販賣品，有BASF公司製的Lucirin TPO、Ciba Japan(股)製的IRGACURE819等可舉出。As a mercaptophosphine oxide photopolymerization initiator having the above-mentioned general formula (III), there are 2,4,6-trimethylbenzimidyl diphenylphosphine oxide, double (2, 4) ,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, etc. Can be mentioned. As a commercial item, Lucirin TPO by BASF Corporation, IRGACURE 819 by Ciba Japan Co., Ltd., etc. are mentioned.

如此光聚合啟始劑(B)之調配量，對於前述含有羧基之樹脂(A)100質量份而言為0.01~30質量份，較佳為0.5~15質量份之範圍。該調配量未達0.01質量份時，在銅上的光硬化性會不足，被膜會剝離、或耐藥品性等被膜特性會降低而不佳。另一方面，該調配量超過30質量份時，光聚合啟始劑(B)於防焊劑被膜表面的光吸收會變的激烈，有著深部硬化性降低之傾向而不佳。The amount of the photopolymerization initiator (B) is from 0.01 to 30 parts by mass, preferably from 0.5 to 15 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). When the amount is less than 0.01 part by mass, the photocurability on copper may be insufficient, the film may be peeled off, or the film properties such as chemical resistance may be lowered. On the other hand, when the amount is more than 30 parts by mass, the light absorption of the photopolymerization initiator (B) on the surface of the solder resist film becomes intense, and the tendency of deep curing property is lowered.

且，具有前述式(I)所示基的肟酯系光聚合啟始劑之情況，該調配量對於前述含有羧基之樹脂(A)100質量份而言，較佳為由0.01~20質量份，更佳為由0.01~5質量份之範圍所選出。Further, in the case of the oxime ester-based photopolymerization initiator having the group represented by the above formula (I), the compounding amount is preferably from 0.01 to 20 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A). More preferably, it is selected from the range of 0.01 to 5 parts by mass.

作為可使用於本發明光硬化性熱硬化性樹脂組成物的其他較佳光聚合啟始劑、光啟始助劑及增感劑，可舉出苯偶因化合物、乙醯苯化合物、蒽醌化合物、噻噸酮化合物、酮縮醇化合物、二苯甲酮化合物、呫噸酮化合物、及3級胺化合物等。Other preferred photopolymerization initiators, photoinitiating aids, and sensitizers which can be used in the photocurable thermosetting resin composition of the present invention include benzoin compounds, acetophenone compounds, and hydrazines. A compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a xanthone compound, a tertiary amine compound, and the like.

若要舉出苯偶因化合物的具體例，例如有苯偶因、苯偶因甲基醚、苯偶因乙基醚、苯偶因異丙基醚。Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

若要舉出乙醯苯化合物的具體例，例如有乙醯苯、2,2-二甲氧基-2-苯基乙醯苯、2,2-二乙氧基-2-苯基乙醯苯、1,1-二氯乙醯苯。Specific examples of the acetophenone compound include, for example, acetophenone, 2,2-dimethoxy-2-phenylethyl benzene, and 2,2-diethoxy-2-phenyl acetamidine. Benzene, 1,1-dichloroacetamidine.

若要舉出蒽醌化合物的具體例，例如有2-甲基蒽醌、2-乙基蒽醌、2-t-丁基蒽醌、1-氯蒽醌。Specific examples of the hydrazine compound include 2-methyl hydrazine, 2-ethyl hydrazine, 2-t-butyl hydrazine, and 1-chloro hydrazine.

若要舉出噻噸酮化合物的具體例，例如有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。Specific examples of the thioxanthone compound include, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropyl Thiophenone.

若要舉出酮縮醇化合物的具體例，例如有乙醯苯二甲基酮縮醇、苯甲基二甲基酮縮醇。Specific examples of the ketal compound include, for example, acetophenone ketal and benzyl dimethyl ketal.

若要舉出二苯甲酮化合物的具體例，例如有二苯甲酮、4-苯甲醯基二苯基硫化物、4-苯甲醯基-4’-甲基二苯基硫化物、4-苯甲醯基-4’-乙基二苯基硫化物、4-苯甲醯基-4’-丙基二苯基硫化物。Specific examples of the benzophenone compound include benzophenone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, 4-Benzylmercapto-4'-ethyldiphenyl sulfide, 4-benzylidene-4'-propyldiphenyl sulfide.

若要舉出3級胺化合物的具體例，例如有乙醇胺化合物、具有二烷基胺基苯結構之化合物，例如有4,4’-二甲基胺基二苯甲酮(日本曹達公司製NISSOCURE MABP)、4,4’-二乙基胺基二苯甲酮(保土谷化學公司製EAB)等二烷基胺基二苯甲酮、7-(二乙基胺基)-4-甲基-2H-1-苯並吡喃-2-酮(7-(二乙基胺基)-4-甲基香豆素)等含有二烷基胺基之香豆素化合物、4-二甲基胺基安息香酸乙酯(日本化藥公司製KAYACURE EPA)、2-二甲基胺基安息香酸乙酯(International Biosynthetic公司製Quantacure DMB)、4-二甲基胺基安息香酸(n-丁氧基)乙基(International Biosynthetic公司製Quantacure BEA)、p-二甲基胺基安息香酸異戊基乙基酯(日本化藥公司製KAYACURE DMBI)、4-二甲基胺基安息香酸2-乙基己基(Van Dyk公司製Escalol 507)、4,4’-二乙基胺基二苯甲酮(保土谷化學公司製EAB)。Specific examples of the tertiary amine compound include, for example, an ethanolamine compound and a compound having a dialkylaminobenzene structure, for example, 4,4'-dimethylaminobenzophenone (NISSOCURE, manufactured by Nippon Soda Co., Ltd.) MABP), 4,4'-diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.), dialkylaminobenzophenone, 7-(diethylamino)-4-methyl -2H-1-benzopyran-2-one (7-(diethylamino)-4-methylcoumarin) and the like, a dialkylamino group-containing coumarin compound, 4-dimethyl group Ethyl benzoic acid ethyl ester (KAYACURE EPA, manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylamino benzoic acid ethyl ester (Quantacure DMB manufactured by International Biosynthetic Co., Ltd.), 4-dimethylamino benzoic acid (n-butoxy) Ethyl group (Quantacure BEA, manufactured by International Biosynthetic Co., Ltd.), p-dimethylamino benzoic acid isoamylethyl ester (KAYACURE DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4-dimethylamino benzoic acid 2-B Hexyl group (Escalol 507, manufactured by Van Dyk Co., Ltd.), 4,4'-diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.).

上述中亦以噻噸酮化合物及3級胺化合物為佳。本發明的組成物中因含有噻噸酮化合物，故由深部硬化性的面來看為佳，其中亦以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噻噸酮化合物為佳。The above is also preferably a thioxanthone compound and a tertiary amine compound. Since the composition of the present invention contains a thioxanthone compound, it is preferably a deep-hardening surface, and 2,4-dimethylthioxanthone and 2,4-diethylthioxanthone are also used. A thioxanthone compound such as 2-chlorothioxanthone or 2,4-diisopropylthioxanthone is preferred.

作為如此噻噸酮化合物的調配量，對於上述含有羧基之樹脂(A)100質量份而言，較佳為20質量份以下，更佳為10質量份以下之比率。噻噸酮化合物的調配量過多時，厚膜硬化性會降低，導致製品的成本提高故不佳。The amount of the thioxanthone compound to be added is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the carboxyl group-containing resin (A). When the amount of the thioxanthone compound is too large, the thick film hardenability is lowered, resulting in an increase in the cost of the product, which is not preferable.

作為3級胺化合物，具有二烷基胺基苯結構的化合物為佳，其中亦以二烷基胺基二苯甲酮化合物，最大吸收波長為350~410nm之含有二烷基胺基的香豆素化合物為特佳。作為二烷基胺基二苯甲酮化合物，以4,4’-二乙基胺基二苯甲酮的毒性低為佳。最大吸收波長為350~410nm之含有二烷基胺基之香豆素化合物，其最大吸收波長於紫外線區域，故著色較少，無色透明之感光性組成物為準，使用著色顏料，可提供反映著色顏料本身顏色的著色防焊劑膜。特別以7-(二乙基胺基)-4-甲基-2H-1-苯並吡喃-2-酮對於波長400~410nm之雷射光具有優良增感效果故較佳。As a tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and a dialkylaminobenzophenone compound is also used, and a dialkylamine group-containing couma bean having a maximum absorption wavelength of 350 to 410 nm is used. The compound is particularly good. As the dialkylaminobenzophenone compound, the toxicity of 4,4'-diethylaminobenzophenone is preferably low. A coumarin compound containing a dialkylamine group having a maximum absorption wavelength of 350 to 410 nm, the maximum absorption wavelength of which is in the ultraviolet region, so that the coloring is less, and the colorless and transparent photosensitive composition is correct, and the coloring pigment can be used to provide reflection. A colored solder resist film of the color of the coloring pigment itself. Particularly, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one has an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

作為如此3級胺化合物的調配量，對於上述含有羧基之樹脂(A)100質量份而言，較佳為0.1~20質量份，更佳為0.1~10質量份之比率。3級胺化合物的調配量若為0.1質量份以下時，有著無法得到充分增感效果之傾向。該調配量超過20質量份時，藉由3級胺化合物之在乾燥防焊劑被膜的表面之光吸收會變的激烈，有著深部硬化性降低之傾向。The amount of the above-mentioned tertiary amine compound is preferably from 0.1 to 20 parts by mass, more preferably from 0.1 to 10 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). When the amount of the tertiary amine compound is 0.1 part by mass or less, the effect of sufficiently sensitizing is not obtained. When the amount is more than 20 parts by mass, the light absorption on the surface of the dry solder resist film by the tertiary amine compound becomes intense, and the deep hardenability tends to be lowered.

彼等的光聚合啟始劑、光啟始助劑及增感劑可單獨或作為2種類以上之混合物使用。These photopolymerization initiators, photoinitiating aids, and sensitizers may be used singly or as a mixture of two or more types.

如此光聚合啟始劑、光啟始助劑、及增感劑的總量對於前述含有羧基之樹脂(A)100質量份而言，以成為35質量份以下之範圍者為佳。該調配量超過35質量份時，藉由這些光吸收有深部硬化性降低之傾向。The total amount of the photopolymerization initiator, the photoinitiator, and the sensitizer is preferably in the range of 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin (A). When the amount is more than 35 parts by mass, the deep sclerosing property tends to be lowered by the absorption of these light.

使用於本發明光硬化性熱硬化性樹脂組成物的具有烷氧基甲基之胺基樹脂(C)不僅作為本發明組成物中之交聯劑成分作用，可提高所得防焊劑之疏水性而具有優良功能。特別對鍍金耐性具效果，與未將環氧樹脂作為啟始原料的含有羧基之樹脂併用時，對於PCT耐性與HAST耐性有進一步效果。The amino group-containing resin (C) having an alkoxymethyl group used in the photocurable thermosetting resin composition of the present invention acts not only as a crosslinking agent component in the composition of the present invention, but also improves the hydrophobicity of the obtained solder resist. Has excellent features. In particular, it has an effect on gold plating resistance, and has a further effect on PCT resistance and HAST resistance when used in combination with a carboxyl group-containing resin which does not use an epoxy resin as a starting material.

作為胺基樹脂(C)可舉出三聚氰胺衍生物、苯並鳥糞胺衍生物等，特別可舉出具有烷氧基甲基之三聚氰胺衍生物、苯並鳥糞胺衍生物等。例如有羥甲基三聚氰胺化合物、羥甲基苯並鳥糞胺化合物、羥甲基甘脲化合物及羥甲基尿素化合物等。且烷氧基甲基化三聚氰胺化合物、烷氧基甲基化苯並鳥糞胺化合物、烷氧基甲基化甘脲化合物及烷氧基甲基化尿素化合物係將各羥甲基三聚氰胺化合物、羥甲基苯並鳥糞胺化合物、羥甲基甘脲化合物及羥甲基尿素化合物的羥甲基轉換為烷氧基甲基而得到。對於該烷氧基甲基的種類並無特別限定，例如有甲氧基甲基、乙氧基甲基、丙氧基甲基、丁氧基甲基等。特別以對人體或環境良好的甲醛水濃度為0.2%以下之三聚氰胺衍生物為佳。Examples of the amine-based resin (C) include a melamine derivative and a benzoguanamine derivative, and specific examples thereof include a melamine derivative having an alkoxymethyl group and a benzoguanamine derivative. For example, there are a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, a methylol urea compound, and the like. And the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the alkoxymethylated urea compound are each methylol melamine compound, The methylol benzoguanamine compound, the methylol glycoluril compound, and the methylol group of the methylol urea compound are converted into an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. In particular, a melamine derivative having a formaldehyde water concentration of 0.2% or less which is good for the human body or the environment is preferred.

作為這些販賣品，例如有CYMEL300、同301、同303、同370、同325、同327、同701、同266、同267、同238、同1141、同272、同202、同1156、同1158、同1123、同1170、同1174、同UFR65、同300(以上，三井Cyanamid層合(股)製)、NIKALACMx-750、同Mx-032、同Mx-270、同Mx-280、同Mx-290、同Mx-706、同Mx-708、同Mx-40、同Mx-31、同Ms-11、同Mw-30、同Mw-30HM、同Mw-390、同Mw-100LM、同Mw-750LM、(以上，(股)三和化學製)等可舉出。As these sales items, for example, there are CYMEL300, the same 301, the same 303, the same 370, the same 325, the same 327, the same 701, the same 266, the same 267, the same 238, the same 1141, the same 272, the same 202, the same 1156, the same 1158 , the same 1123, the same 1170, the same 1174, the same UFR65, the same 300 (above, Mitsui Cyanamid laminated (share) system), NIKALACMx-750, the same Mx-032, the same Mx-270, the same Mx-280, the same Mx- 290, the same Mx-706, the same Mx-708, the same Mx-40, the same Mx-31, the same Ms-11, the same Mw-30, the same Mw-30HM, the same Mw-390, the same Mw-100LM, the same Mw- 750LM, (above, (three) and chemical) can be mentioned.

作為如上述之熱硬化成分的胺基樹脂(C)可單獨或併用2種以上。The amine-based resin (C) which is a thermosetting component as described above may be used alone or in combination of two or more.

如此胺基樹脂(C)的調配量對於前述含有羧基之樹脂(A)100質量份而言為5質量份以上，50質量份以下為佳，更佳為5質量份以上，30份質量份以下。前述胺基樹脂(C)的調配量未達5質量份時，作為本發明目的之效果無法被確認，另一方面，該調配量超過50質量份時，乾燥被膜之黏著性會惡化，恐怕會引起顯像不良等現象而不佳。The amount of the amine-based resin (C) is preferably 5 parts by mass or more, more preferably 50 parts by mass or less, more preferably 5 parts by mass or more, and 30 parts by mass or less, based on 100 parts by mass of the carboxyl group-containing resin (A). . When the amount of the above-mentioned amine-based resin (C) is less than 5 parts by mass, the effect of the object of the present invention cannot be confirmed. On the other hand, when the amount is more than 50 parts by mass, the adhesion of the dried film may be deteriorated. It is not good to cause poor imaging.

本發明的光硬化性熱硬化性樹脂組成物因要賦予耐熱性，故可加入前述胺基樹脂(C)以外的其他熱硬化性成分(D)。作為使用於本發明的熱硬化成分(D)，可使用嵌段異氰酸酯化合物、馬來酸酐縮亞胺、苯並噁嗪層合、碳化二亞胺層合樹脂、環碳酸酯化合物、多官能環氧化合物、多官能氧雜環丁烷化合物、表硫化物樹脂等公知慣用之熱硬化性樹脂。彼等中較佳熱硬化成分(D)為，1分子中具有2個以上的環狀醚基及/或環狀硫醚基(以下簡稱為環狀(硫)醚基)的熱硬化性成分。Since the photocurable thermosetting resin composition of the present invention is required to impart heat resistance, it is possible to add a thermosetting component (D) other than the above-described amine-based resin (C). As the thermosetting component (D) used in the present invention, a blocked isocyanate compound, maleic anhydride imide, benzoxazine laminate, carbodiimide laminated resin, cyclic carbonate compound, polyfunctional ring can be used. A known thermosetting resin such as an oxygen compound, a polyfunctional oxetane compound, or a surface sulfide resin. Among them, the thermosetting component (D) is a thermosetting component having two or more cyclic ether groups and/or cyclic thioether groups (hereinafter simply referred to as cyclic (thio)ether groups) in one molecule. .

這些具有環狀(硫)醚基之熱硬化性成分(D)的販賣品種類很多，藉由該結構可賦予多様化特性。又，藉由組成物中之羧基與環狀(硫)醚基，特別為與環氧基進行熱硬化反應時可形成強固3次元交聯網路，形成具有耐藥品性、焊接耐熱性或無電解鍍金耐性之防焊劑。此時，已知羧基與環狀(硫)醚基(例如環氧基)藉由熱硬化反應生成羥基，此為提高與一般基材或支持體之密著性的效果。These thermosetting components (D) having a cyclic (thio)ether group have many types of sold products, and the structure can impart multi-tanning characteristics. Moreover, by the thermo-hardening reaction of the carboxyl group in the composition with the cyclic (thio)ether group, particularly with the epoxy group, a strong 3-dimensional cross-linking network can be formed to form chemical resistance, solder heat resistance or electrolessness. Gold-plated resistant solder resist. At this time, it is known that a carboxyl group and a cyclic (thio)ether group (for example, an epoxy group) form a hydroxyl group by a thermosetting reaction, which is an effect of improving the adhesion to a general substrate or a support.

然而，羥基的形成會提高親水性，有著使其後的絕緣信賴性、PCT耐性惡化的顧慮。於是本發明中，於羧基與環狀(硫)醚基(例如環氧基)藉由熱硬化反應所生成之羥基上，進一步與具有烷氧基甲基的胺基樹脂(C)進行反應，可形成進一步強固3次元交聯網路，創造出提高疏水性之反應系統。即，藉由羧基與環狀(硫)醚基(例如環氧基)的熱硬化反應所生成之羥基與具有烷氧基甲基之胺基樹脂(C)進行反應，可控制羥基量，可同時提高耐水性與密著性。此時，藉由併用後述熱硬化觸媒，先將含有羧基之樹脂(A)的羧基與熱硬化性成分(D)的環狀(硫)醚基(例如環氧基)進行反應，於所生成之羥基與具有烷氧基甲基的胺基樹脂(C)進行反應而硬化的2段階硬化方法對於特性提高有進一步效果。However, the formation of a hydroxyl group enhances hydrophilicity, and there is a concern that the subsequent insulation reliability and PCT resistance are deteriorated. Therefore, in the present invention, the carboxyl group and the cyclic (thio)ether group (for example, an epoxy group) are further reacted with an amino group-containing resin (C) on a hydroxyl group formed by a thermosetting reaction. A stronger three-dimensional cross-linking network can be formed to create a reaction system that enhances hydrophobicity. That is, the hydroxyl group formed by the thermosetting reaction of a carboxyl group and a cyclic (thio)ether group (for example, an epoxy group) is reacted with an amino group-containing resin (C) having an alkoxymethyl group to control the amount of the hydroxyl group. At the same time improve water resistance and adhesion. In this case, by using a thermosetting catalyst to be described later, the carboxyl group of the carboxyl group-containing resin (A) and the cyclic (thio)ether group (for example, an epoxy group) of the thermosetting component (D) are first reacted. The two-stage hardening method in which the generated hydroxyl group is reacted with the amino group-containing resin (C) having an alkoxymethyl group to be hardened has a further effect on the improvement of characteristics.

如此分子中具有2個以上的環狀(硫)醚基之熱硬化性成分(D)為，分子中具有2個以上的3、4或5員環的環狀醚基、或環狀硫醚基的任一方、或具有2個以上的該2種類基之化合物，例如分子中具有至少2個以上的環氧基之化合物，即多官能環氧化合物(D-1)、分子中具有至少2個以上之氧雜環丁基的化合物，即多官能氧雜環丁烷化合物(D-2)、分子中具有至少2個以上之硫醚基的化合物，即表硫化物樹脂(D-3)等可舉出。The thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is a cyclic ether group having two or more 3, 4 or 5 membered rings in the molecule, or a cyclic thioether. Any one of the groups or a compound having two or more of the two kinds of groups, for example, a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound (D-1) having at least 2 in the molecule More than one oxetanyl compound, that is, a polyfunctional oxetane compound (D-2), a compound having at least two or more thioether groups in the molecule, that is, a surface sulfide resin (D-3) Etc.

作為前述多官能環氧化合物(D-1)，例如可舉出日本環氧樹脂公司製的jER828、jER834、jER1001、jER1004、DIC(股)製的EPICLON840、EPICLON850、EPICLON1050、EPICLON2055、東都化成公司製的EPOTOTOYD-011、YD-013、YD-127、YD-128、The Dow Chemical Company製的D.E.R. 317、D.E.R. 331、D.E.R. 661、D.E.R. 664、Huntsman Advanced Materials(股)製的Araldite6071、Araldite6084、AralditeGY250、AralditeGY260、住友化學工業公司製的SumiepoxyESA-011、ESA-014、ELA-115、ELA-128、旭化成工業公司製的A.E.R. 330、A.E.R. 331、A.E.R. 661、A.E.R. 664等(皆為商品名)的雙酚A型環氧樹脂；日本環氧樹脂公司製的jERYL903、DIC(股)製的EPICLON152、EPICLON165、東都化成公司製的EPOTOTOYDB-400、YDB-500、The Dow Chemical Company製的D.E.R. 542、Huntsman Advanced Materials(股)製的Araldite8011、住友化學工業公司製的SumiepoxyESB-400、ESB-700、旭化成工業公司製的A.E.R. 711、A.E.R. 714等(皆為商品名)的溴化環氧樹脂；日本環氧樹脂公司製的jER152、jER154、The Dow Chemical Company製的D.E.N. 431、D.E.N. 438、DIC(股)製的EPICLONN-730、EPICLONN-770、EPICLONN-865、東都化成公司製的EPOTOTOYDCN-701、YDCN-704、Huntsman Advanced Materials(股)製的AralditeECN1235、AralditeECN1273、AralditeECN1299、AralditeXPY307、日本化藥公司製的EPPN-201、EOCN-1025、EOCN-1020、EOCN-104S、RE-306、住友化學工業公司製的SumiepoxyESCN-195X、ESCN-220、旭化成工業公司製的A.E.R.ECN-235、ECN-299等(皆為商品名)的漆用酚醛型環氧樹脂；DIC(股)製的EPICLON830、日本環氧樹脂公司製jER807、東都化成公司製的EPOTOTOYDF-170、YDF-175、YDF-2004、Huntsman Advanced Materials(股)製的AralditeXPY306等(皆為商品名)的雙酚F型環氧樹脂；東都化成公司製的EPOTOTOST-2004、ST-2007、ST-3000(商品名)等氫化雙酚A型環氧樹脂；日本環氧樹脂公司製的jER604、東都化成公司製的EPOTOTOYH-434、Huntsman Advanced Materials(股)製的AralditeMY720、住友化學工業公司製的SumiepoxyELM-120等(皆為商品名)的環氧丙胺型環氧樹脂；Huntsman Advanced Materials(股)製的AralditeCY-350(商品名)等海因(hydantoin)型環氧樹脂；Daicel化學工業公司製的CELLOXIDE2021、Huntsman Advanced Materials(股)製的AralditeCY175、CY179等(皆為商品名)之脂環式環氧樹脂；日本環氧樹脂公司製的YL-933、The Dow Chemical Company製的T.E.N.、EPPN-501、EPPN-502等(皆為商品名)之三羥基苯基甲烷型環氧樹脂；日本環氧樹脂公司製的YL-6056、YX-4000、YL-6121(皆為商品名)等bixylenol型或雙酚型環氧樹脂或彼等之混合物；日本化藥公司製EBPS-200、(股)ADEKA製EPX-30、DIC(股)製的EXA-1514(商品名)等雙酚S型環氧樹脂；日本環氧樹脂公司製的jER157S(商品名)等雙酚A漆用酚醛型環氧樹脂；日本環氧樹脂公司製的jERYL-931、Huntsman Advanced Materials(股)製的Araldite163等(皆為商品名)之tetraphenylolethane型環氧樹脂；Huntsman Advanced Materials(股)製的AralditePT810、日產化學工業公司製的TEPIC等(皆為商品名)之雜環式環氧樹脂；日油公司製BLEMMERDGT等二環氧丙基鄰苯二甲酸酯樹脂；東都化成公司製ZX-1063等四環氧丙基二甲酚乙烷樹脂；新日鐵化學公司製ESN-190、ESN-360、DIC(股)製HP-4032、EXA-4750、EXA-4700等萘基含有環氧樹脂；DIC(股)製HP-7200、HP-7200H等具有二環戊二烯基骨架之環氧樹脂；日本油脂公司製CP-50S、CP-50M等環氧丙基甲基丙烯酸酯共聚合系環氧樹脂；進一步可舉出環己基馬來酸酐縮亞胺與環氧丙基甲基丙烯酸酯之共聚合環氧樹脂；CTBN改性環氧樹脂(例如東都化成公司製的YR-102、YR-450等)；環氧基改性之聚丁二烯橡膠衍生物(例如Daicel化學工業製PB-3600等)等，但不限定於此。Examples of the polyfunctional epoxy compound (D-1) include jER828, jER834, jER1001, jER1004 manufactured by Nippon Epoxy Co., Ltd., EPICLON 840, EPICLON 850, EPICLON 1050, EPICLON 2055, manufactured by Toho Chemical Co., Ltd., manufactured by DIC Co., Ltd. EPOTOTOYD-011, YD-013, YD-127, YD-128, DER 317, DER 331, DER 661, DER 664 manufactured by The Dow Chemical Company, Araldite 6071, Araldite 6084, Araldite GY250, Araldite GY260 manufactured by Huntsman Advanced Materials Co., Ltd. SumiepoxyESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Industries Co., Ltd., AER 330, AER 331, AER 661, AER 664, etc. (both trade names) manufactured by Asahi Kasei Kogyo Co., Ltd. Epoxy resin; JERYL903 manufactured by Japan Epoxy Resin Co., Ltd., EPICLON 152, EPICLON 165 manufactured by DIC Co., Ltd., EPOTOTOYDB-400 manufactured by Dongdu Chemical Co., Ltd., YDB-500, DER 542 manufactured by The Dow Chemical Company, and Huntsman Advanced Materials ( Araldite 8011, manufactured by Sumitomo Chemical Industries Co., Ltd., Sumiepoxy ESB-400, ESB-700, AER 711 manufactured by Asahi Kasei Kogyo Co., Ltd., AER 714, etc. Brominated epoxy resin; jER152, jER154 manufactured by Nippon Epoxy Co., Ltd., DEN 431, DEN 438 manufactured by The Dow Chemical Company, EPICLONN-730, EPICLONN-770, EPICLONN-865 manufactured by DIC Co., Ltd. EPOTOTOYDCN-701, YDCN-704, manufactured by Dongdu Chemical Co., Ltd., Araldite ECN1235 manufactured by Huntsman Advanced Materials, Araldite ECN1273, Araldite ECN1299, Araldite XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S manufactured by Nippon Kayaku Co., Ltd. Refractory phenolic epoxy resin for lacquering, such as RE-306, Sumiepoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Co., Ltd., AERECN-235, ECN-299, etc. (all are trade names) manufactured by Asahi Kasei Kogyo Co., Ltd.; EPICLON 830, JER807 manufactured by Nippon Epoxy Co., Ltd., EPOTOTOY DF-170, YDF-175, YDF-2004 manufactured by Dongdu Chemical Co., Ltd., Araldite XPY306 manufactured by Huntsman Advanced Materials Co., Ltd. (both trade names), bisphenol F-type epoxy resin; hydrogenated bisphenol A type epoxy resin such as EPOTOTOST-2004, ST-2007, ST-3000 (trade name) manufactured by Dongdu Chemical Co., Ltd.; jER604 manufactured by Japan Epoxy Resin Co., Ltd., manufactured by Toho Chemical Co., Ltd. EPOTOTOYH-4 34. Araldite MY720 manufactured by Huntsman Advanced Materials Co., Ltd., Sumiepoxy ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (both trade names), epoxy propylamine epoxy resin; Araldite CY-350 manufactured by Huntsman Advanced Materials Co., Ltd. Name) Hydantoin type epoxy resin; CELLOXIDE 2021 manufactured by Daicel Chemical Industry Co., Ltd., Araldite CY175 manufactured by Huntsman Advanced Materials Co., Ltd., CY179 (all are trade names), alicyclic epoxy resin; YL-933 manufactured by Resin Co., Ltd., TEN, EPPN-501, EPPN-502, etc. (all trade names) manufactured by The Dow Chemical Company, trihydroxyphenylmethane type epoxy resin; YL-made by Japan Epoxy Co., Ltd. 60x, YX-4000, YL-6121 (all are trade names) such as bixylenol type or bisphenol type epoxy resin or a mixture thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30, DIC made by ADEKA Bisphenol S-type epoxy resin such as EXA-1514 (trade name) manufactured by Japan Co., Ltd.; phenolic epoxy resin for bisphenol A paint such as jER157S (trade name) manufactured by Japan Epoxy Resin Co., Ltd.; Japan Epoxy Resin Co., Ltd. JERYL-931, Araldite16 made by Huntsman Advanced Materials Tetraphenylolethane type epoxy resin of 3 (all are trade names); Araldite PT810 by Huntsman Advanced Materials, TEPIC of Nissan Chemical Industries Co., Ltd. (all are trade names), heterocyclic epoxy resin; Preparation of digoxypropyl phthalate resin such as BLEMMERDGT; tetraethoxypropyl xylenol ethane resin such as ZX-1063 manufactured by Dongdu Chemical Co., Ltd.; ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. DIC (share) system such as HP-4032, EXA-4750, EXA-4700 and other naphthalene groups containing epoxy resin; DIC (stock) HP-7200, HP-7200H and other epoxy resin having a dicyclopentadienyl skeleton; Epoxy propyl methacrylate copolymerized epoxy resin such as CP-50S and CP-50M manufactured by Nippon Oil & Fat Co., Ltd.; further, a total of cyclohexylmaleic anhydride imide and pepoxypropyl methacrylate Polymeric epoxy resin; CTBN modified epoxy resin (such as YR-102, YR-450, manufactured by Dongdu Chemical Co., Ltd.); epoxy-modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Industry Co., Ltd.) Etc. etc., but is not limited to this.

作為前述多官能氧雜環丁烷化合物(D-2)，有雙[(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、(3-甲基-3-氧雜環丁烷基)甲基丙烯酸酯、(3-乙基-3-氧雜環丁烷基)甲基丙烯酸酯、(3-甲基-3-氧雜環丁烷基)甲基甲基丙烯酸酯、(3-乙基-3-氧雜環丁烷基)甲基甲基丙烯酸酯或這些寡聚物或共聚物等多官能氧雜環丁烷類以外，亦可舉出與氧雜環丁醇漆用酚醛樹脂、聚(p-羥基苯乙烯)、cardo型雙酚類、芳杯類、calyx resorcinarenes類、或乙基矽倍半環丙烷等具有羥基之樹脂的醚化物等可舉出。其他亦可舉出具有氧雜環丁烷環的不飽和單體與烷基(甲基)丙烯酸酯之共聚物等。As the above polyfunctional oxetane compound (D-2), there are bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-) 3-oxetanylmethoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4- Bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl 3-oxetanyl)methacrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetane Methyl methacrylate or a polyfunctional oxetane such as these oligomers or copolymers, and oxetane An ether compound of a resin having a hydroxyl group such as a phenol resin, a polyphenol (p-hydroxystyrene), a cardo type bisphenol, an aromatic cup, a calyx resorcinarenes, or an ethyl sulfonium sesquicyclopropane may be mentioned. Other examples thereof include a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

作為前述分子中具有2個以上的環狀硫醚基之表硫化物樹脂(D-3)，例如有日本環氧樹脂公司製的YL7000(雙酚A型表硫化物樹脂)、或東都化成(股)製YSLV-120TE等可舉出。又，使用同様之合成方法，亦可使用將漆用酚醛型環氧樹脂的環氧基之氧原子由硫原子取代的表硫化物樹脂等。As the episulfide resin (D-3) having two or more cyclic thioether groups in the above-mentioned molecule, for example, YL7000 (bisphenol A-type sulfide resin) manufactured by Nippon Epoxy Co., Ltd., or Dongdu Chemical Co., Ltd. The stock system YSLV-120TE and the like can be cited. Further, a synesulfide resin obtained by substituting a sulfur atom of an epoxy group of a phenolic epoxy resin for a paint with a sulfur atom may be used.

前述分子中具有2個以上的環狀(硫)醚基之熱硬化性成分(D)的調配量對於前述含有羧基之樹脂(A)的羧基1當量而言，較佳為0.6~2.5當量，更佳為0.8~2.0當量之範圍。分子中具有2個以上的環狀(硫)醚基之熱硬化性成分(D)的調配量未達0.6時，於防焊劑膜會殘留羧基，使得耐熱性、耐鹼性、電絕緣性等降低，故不佳。另一方面，該調配量超過2.5當量時，因低分子量的環狀(硫)醚基會殘留於乾燥被膜，而使得被膜之強度等降低而不佳。The amount of the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is preferably from 0.6 to 2.5 equivalents per equivalent of the carboxyl group of the carboxyl group-containing resin (A). More preferably, it is in the range of 0.8 to 2.0 equivalents. When the amount of the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is less than 0.6, the carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation, and the like are caused. Lower, so it is not good. On the other hand, when the amount is more than 2.5 equivalents, the low molecular weight cyclic (thio)ether group remains in the dried film, and the strength of the film or the like is lowered.

使用上述分子中具有2個以上的環狀(硫)醚基之熱硬化性成分(D)時，含有化觸媒者為佳。作為如此熱硬化觸媒，例如有咪唑、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-氰乙基-2-苯基咪唑、1-(2-氰乙基)-2-乙基-4-甲基咪唑等咪唑衍生物；胍縮脲、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-二甲基苯甲胺等胺化合物、己二酸二醯肼、癸二酸二醯肼等肼化合物；三苯基膦等磷化合物等可舉出。又，作為市販，例如有四國化成工業公司製的2MZ-A、2MZ-OK、2PHZ、2P4BHZ、2P4MHZ(皆為咪唑系化合物之商品名)、san-apro公司製的U-CAT(註冊商標)3503N、U-CAT3502T(皆為二甲胺之嵌段異氰酸酯化合物的商品名)、DBU、DBN、U-CATSA102、U-CAT5002(皆為二環式脒化合物及其鹽)等可舉出。並無特別限定於彼等，僅為環氧樹脂或氧雜環丁烷化合物之熱硬化觸媒、或促進環氧基及/或氧雜環丁基與羧基之反應者即可，可單獨或混合2種以上使用。又，亦可使用鳥糞胺、乙醯鳥糞胺、苯並鳥糞胺、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.三聚異氰酸加成物、2,4-二胺基-6-甲基丙烯醯氧基乙基-S-三嗪‧三聚異氰酸加成物等S-三嗪衍生物，較佳為作為這些密著性賦予劑可發揮功能之化合物與前述熱硬化觸媒併用。When the thermosetting component (D) having two or more cyclic (thio)ether groups in the above molecule is used, it is preferred to contain a catalytic agent. As such a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethylidene Imidazole derivatives such as 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; urethrazine, benzyldimethylamine, 4-(dimethyl Amine compounds such as amino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine An antimony compound such as diammonium adipate or diterpene sebacate; a phosphorus compound such as triphenylphosphine or the like can be mentioned. In addition, as a market vendor, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all are imidazole-based compounds) manufactured by Shikoku Chemicals Co., Ltd., and U-CAT (registered trademark) manufactured by San-apro Co., Ltd. 3503N, U-CAT3502T (all trade names of dimethylamine block isocyanate compounds), DBU, DBN, U-CATSA102, U-CAT5002 (all of which are bicyclic hydrazine compounds and salts thereof) and the like can be mentioned. It is not particularly limited to these, but only a thermosetting catalyst of an epoxy resin or an oxetane compound, or a reaction promoting an epoxy group and/or an oxetanyl group and a carboxyl group, either alone or Mix two or more types. Also, guanamine, guanamine, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-ethylene can also be used. -2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine. Trimeric isocyanate adduct, 2,4-diamino- An S-triazine derivative such as a 6-methacryloxyethyl-S-triazine/trimeric isocyanate addition product, preferably a compound which functions as the adhesion imparting agent and the aforementioned heat Harden the catalyst and use it together.

這些熱硬化觸媒之調配量以一般量的比率為充分，例如對於含有羧基之樹脂(A)或分子中具有2個以上的環狀(硫)醚基之熱硬化性成分(D)100質量份而言，較佳為0.1~20質量份，更佳為0.5~15.0質量份。The amount of the thermosetting catalyst is sufficient in a ratio of a general amount, for example, a resin having a carboxyl group (A) or a thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule. The portion is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.

本發明的光硬化性熱硬化性樹脂組成物中欲提高組成物之硬化性及所得之硬化膜的強韌性，可加入1分子中具有2個以上的異氰酸酯基或嵌段化異氰酸酯基之化合物(E)。如此1分子中具有2個以上的異氰酸酯基或嵌段化異氰酸酯基之化合物(E)為，1分子中具有2個以上之異氰酸酯基的化合物，即可舉出聚異氰酸酯化合物(E-1)、或1分子中具有2個以上的嵌段化異氰酸酯基之化合物，即可舉出嵌段異氰酸酯化合物(E-2)等可舉出。In the photocurable thermosetting resin composition of the present invention, in order to increase the curability of the composition and the toughness of the obtained cured film, a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule may be added ( E). The compound (E) having two or more isocyanate groups or blocked isocyanate groups in one molecule is a compound having two or more isocyanate groups in one molecule, and examples thereof include a polyisocyanate compound (E-1). The compound having two or more blocked isocyanate groups in one molecule may, for example, be a blocked isocyanate compound (E-2).

作為前述聚異氰酸酯化合物(E-1)，例如可使用芳香族聚異氰酸酯、脂肪族聚異氰酸酯或脂環式聚異氰酸酯。作為芳香族聚異氰酸酯之具體例，可舉出4,4’-二苯基甲烷二異氰酸酯、2,4-甲次苯基二異氰酸酯、2,6-甲次苯基二異氰酸酯、萘-1,5-二異氰酸酯、o-伸苯二甲基二異氰酸酯、m-伸苯二甲基二異氰酸酯及2,4-甲次苯基二聚物。作為脂肪族聚異氰酸酯之具體例，可舉出四伸甲基二異氰酸酯、六伸甲基二異氰酸酯、伸甲基二異氰酸酯、三甲基六伸甲基二異氰酸酯、4,4-伸甲基雙(環己基異氰酸酯)及異佛爾酮二異氰酸酯。作為脂環式聚異氰酸酯之具體例，可舉出雙環庚烷三異氰酸酯。以及先前所舉出的異氰酸酯化合物之加成物、縮二脲體及三聚異氰酸酯體可舉出。As the polyisocyanate compound (E-1), for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-methylphenyl diisocyanate, 2,6-methylphenyl diisocyanate, and naphthalene-1. 5-diisocyanate, o-phenylene diisocyanate, m-phenylene diisocyanate and 2,4-methylphenyl dimer. Specific examples of the aliphatic polyisocyanate include tetramethylammonium diisocyanate, hexamethylene diisocyanate, methyl diisocyanate, trimethylhexamethylene diisocyanate, and 4,4-methyl methyl double. (cyclohexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Further, an adduct of an isocyanate compound, a biuret, and a trimeric isocyanate which are mentioned above are mentioned.

含於嵌段異氰酸酯化合物(E-2)之嵌段化異氰酸酯基為，異氰酸酯基藉由與嵌段劑之反應而被保護的一時性不活性化的基。於所定溫度進行加熱時，該嵌段劑會解離而形成異氰酸酯基。The blocked isocyanate group contained in the blocked isocyanate compound (E-2) is a one-time inactive group in which the isocyanate group is protected by reaction with a block agent. Upon heating at a predetermined temperature, the blocker dissociates to form an isocyanate group.

作為嵌段異氰酸酯化合物(E-2)，使用異氰酸酯化合物(c)與異氰酸酯嵌段劑(d)之加成反應生成物。作為與嵌段劑進行反應所得之異氰酸酯化合物(c)，可舉出三聚異氰酸酯型、縮二脲型、加成型等。作為該異氰酸酯化合物(c)，例如可使用芳香族聚異氰酸酯、脂肪族聚異氰酸酯或脂環式聚異氰酸酯。作為芳香族聚異氰酸酯、脂肪族聚異氰酸酯、脂環式聚異氰酸酯之具體例，可舉出先前所例示之化合物。As the blocked isocyanate compound (E-2), an addition reaction product of the isocyanate compound (c) and the isocyanate block agent (d) is used. The isocyanate compound (c) obtained by the reaction with the block agent may, for example, be a trimeric isocyanate type, a biuret type, or an addition molding. As the isocyanate compound (c), for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate, the aliphatic polyisocyanate, and the alicyclic polyisocyanate include the compounds exemplified above.

作為異氰酸酯嵌段劑(d)，例如可舉出酚、甲酚、二甲苯酚、氯酚及乙基酚等酚系嵌段劑；ε-己內醯胺、δ-戊內醯胺、γ-丁內醯胺及β-丙內醯胺等內醯胺系嵌段劑；乙醯乙酸乙酯及乙醯基丙酮等活性伸甲基系嵌段劑；甲醇、乙醇、丙醇、丁醇、戊醇、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丁基醚、二乙二醇單甲基醚、丙二醇單甲基醚、苯甲基醚、乙醇酸甲酯、乙醇酸丁酯、二丙酮醇、乳酸甲酯及乳酸乙酯等醇系嵌段劑；甲醛肟、乙醛肟、丙酮肟、甲基乙基酮肟、二乙醯基單肟、環己烷肟等肟系嵌段劑；丁基硫醇、己基硫醇、t-丁基硫醇、硫酚、甲基硫酚、乙基硫酚等硫醇系嵌段劑；乙酸醯胺、苯甲醯胺等酸醯胺系嵌段劑；琥珀酸亞胺及馬來酸亞胺等亞胺系嵌段劑；二甲代苯胺、苯胺、丁胺、二丁胺等胺系嵌段劑；咪唑、2-乙基咪唑等咪唑系嵌段劑；伸甲基亞胺及伸丙基亞胺等亞胺系嵌段劑等。Examples of the isocyanate blocker (d) include phenolic blockers such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; ε-caprolactam, δ-valeroinamide, and γ - an internal guanamine blocker such as butyrolactam or β-propionalamine; an active methyl group blocker such as ethyl acetate and acetonitrile; methanol, ethanol, propanol, butanol , pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, glycolic acid Alcohol blockers such as methyl ester, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate; formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, diethyl hydrazino monohydrazine, a thiol blocker such as cyclohexane hydrazine; a thiol blocker such as butyl thiol, hexyl thiol, t-butyl thiol, thiophenol, methyl thiophenol or ethyl thiophenol; An amide group such as benzylamine; an imine block such as succinimide or maleimide; an amine block such as dimethylaniline, aniline, butylamine or dibutylamine Imidazole block such as imidazole or 2-ethylimidazole Agent; an imine blocker such as methylimine or propylimine.

嵌段異氰酸酯化合物(E-1)可為販賣品，例如可舉出SUMIJULE BL-3175、BL-4165、BL-1100、BL-1265、Desmodur TPLS-2957、TPLS-2062、TPLS-2078、TPLS-2117、Desmotherm2170、Desmotherm2265(以上，住化拜耳脲烷公司製，商品名)、Colonate 2512、Colonate 2513、Colonate 2520(以上，日本聚脲烷工業公司製，商品名)、B-830、B-815、B-846、B-870、B-874、B-882(三井化學(股)製，商品名)、TPA-B80E、17B-60PX、E402-B80T(旭化成化學公司製，商品名)等。且，SUMIJULE BL-3175、BL-4265係由作為嵌段劑使用甲基乙基肟所得者。The blocked isocyanate compound (E-1) may be a commercially available product, and examples thereof include SUMIJULE BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS- 2117, Desmotherm 2170, Desmotherm 2265 (above, manufactured by Baying Urea Co., Ltd., trade name), Colonate 2512, Colonate 2513, Colonate 2520 (above, manufactured by Japan Polyurethane Industry Co., Ltd., trade name), B-830, B-815 , B-846, B-870, B-874, B-882 (manufactured by Mitsui Chemicals Co., Ltd., trade name), TPA-B80E, 17B-60PX, E402-B80T (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name). Further, SUMIJULE BL-3175 and BL-4265 are obtained by using methyl ethyl hydrazine as a block agent.

上述的1分子中具有2個以上的異氰酸酯基或嵌段化異氰酸酯基之化合物(E)可單獨使用1種或組合2種以上使用。The compound (E) having two or more isocyanate groups or blocked isocyanate groups in the above-mentioned one molecule may be used alone or in combination of two or more.

如此1分子中具有2個以上的異氰酸酯基或嵌段化異氰酸酯基之化合物(E)的調配量，對於前述含有羧基之樹脂(A)100質量份而言為1~100質量份，較佳為2~70質量份的比率為適當。前述調配量未達1質量份時，無法得到充分之被膜強韌性而不佳。另一方面，該調配量超過100質量份時，因保存安定性會降低而不佳。The compounding amount of the compound (E) having two or more isocyanate groups or blocked isocyanate groups in one molecule is preferably from 1 to 100 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin (A). The ratio of 2 to 70 parts by mass is appropriate. When the amount of the above formulation is less than 1 part by mass, it is not preferable to obtain sufficient film toughness. On the other hand, when the blending amount exceeds 100 parts by mass, the storage stability may be lowered.

本發明的光硬化性熱硬化性樹脂組成物中，欲促進羥基或羧基與異氰酸酯基之硬化，可加入脲烷化觸媒(F)。作為脲烷化觸媒(F)，可使用選自錫系觸媒(F-1)、金屬氯化物(F-2)、金屬乙醯丙酮鹽(F-3)、金屬硫酸鹽(F-4)、胺化合物(F-5)、或/及胺鹽(F-6)所成群之1種以上的脲烷化觸媒為佳。In the photocurable thermosetting resin composition of the present invention, a urethane-catalyzed catalyst (F) may be added to promote the curing of a hydroxyl group, a carboxyl group and an isocyanate group. As the urethane catalyst (F), a tin-based catalyst (F-1), a metal chloride (F-2), a metal acetonide salt (F-3), a metal sulfate (F-) can be used. 4) One or more kinds of urethane catalysts in which the amine compound (F-5) or the amine salt (F-6) is a group are preferred.

作為前述錫系觸媒(F-1)，例如有辛酸亞錫、二丁基錫二月桂酸鹽等有機錫化合物、無機錫化合物等可舉出。Examples of the tin-based catalyst (F-1) include an organic tin compound such as stannous octoate or dibutyltin dilaurate, and an inorganic tin compound.

作為前述金屬氯化物(F-2)為由Cr、Mn、Co、Ni、Fe、Cu或Al所成之金屬氯化物，例如有氯化第二鈷、氯化第一鎳、氯化鐵等可舉出。The metal chloride (F-2) is a metal chloride formed of Cr, Mn, Co, Ni, Fe, Cu or Al, and examples thereof include second cobalt chloride, first nickel chloride, iron chloride, and the like. Can be mentioned.

作為前述金屬乙醯丙酮鹽(F-3)為由Cr、Mn、Co、Ni、Fe、Cu或Al所成之金屬的乙醯丙酮鹽，例如有鈷乙醯丙酮、鎳乙醯丙酮、鐵乙醯丙酮等舉出。The metal acetoacetone (F-3) is an ethyl acetonide salt of a metal formed of Cr, Mn, Co, Ni, Fe, Cu or Al, and examples thereof include cobalt acetonitrile, nickel acetonitrile, and iron. Ethyl acetonide and the like are cited.

作為前述金屬硫酸鹽(F-4)為由Cr、Mn、Co、Ni、Fe、Cu或Al所成之金屬的硫酸鹽，例如有硫酸銅等可舉出。The sulfate of the metal in which the metal sulfate (F-4) is made of Cr, Mn, Co, Ni, Fe, Cu or Al, for example, copper sulfate or the like can be mentioned.

作為前述胺化合物(F-5)，例如有過去公知的三伸乙基二胺、N,N,N’,N’-四甲基-1,6-己烷二胺、雙(2-二甲基胺基乙基)醚、N,N,N’,N”,N”-五甲基二伸乙基三胺、N-甲基嗎啉、N-乙基嗎啉、N,N-二甲基乙醇胺、二嗎啉代二乙基醚、N-甲基咪唑、二甲基胺基吡啶、三嗪、N’-(2-羥基乙基)-N,N,N’-三甲基-雙(2-胺基乙基)醚、N,N-二甲基己醇胺、N,N-二甲基胺基乙氧基乙醇、N,N,N’-三甲基-N’-(2-羥基乙基)伸乙基二胺、N-(2-羥基乙基)-N,N’,N”,N”-四甲基二伸乙基三胺、N-(2-羥基丙基)-N,N’,N”,N”-四甲基二伸乙基三胺、N,N,N’-三甲基-N’-(2-羥基乙基)丙烷二胺、N-甲基-N’-(2-羥基乙基)哌嗪、雙(N,N-二甲基胺基丙基)胺、雙(N,N-二甲基胺基丙基)異丙醇胺、2-胺基奎寧、3-胺基奎寧、4-胺基奎寧、2-奎寧環醇、3-奎寧環醇、4-奎寧環醇、1-(2’-羥基丙基)咪唑、1-(2’-羥基丙基)-2-甲基咪唑、1-(2’-羥基乙基)咪唑、1-(2’-羥基乙基)-2-甲基咪唑、1-(2’-羥基丙基)-2-甲基咪唑、1-(3’-胺基丙基)咪唑、1-(3’-胺基丙基)-2-甲基咪唑、1-(3’-羥基丙基)咪唑、1-(3’-羥基丙基)-2-甲基咪唑、N,N-二甲基胺基丙基-N’-(2-羥基乙基)胺、N,N-二甲基胺基丙基-N’,N’-雙(2-羥基乙基)胺、N,N-二甲基胺基丙基-N’,N’-雙(2-羥基丙基)胺、N,N-二甲基胺基乙基-N’,N’-雙(2-羥基乙基)胺、N,N-二甲基胺基乙基-N’,N’-雙(2-羥基丙基)胺、三聚氰胺或/及苯並鳥糞胺等可舉出。As the above-mentioned amine compound (F-5), for example, triethylethylene diamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, bis (2-di) which are known in the past are known. Methylaminoethyl)ether, N,N,N',N",N"-pentamethyldiethylideneamine, N-methylmorpholine, N-ethylmorpholine, N,N- Dimethylethanolamine, dimorpholino diethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N'-(2-hydroxyethyl)-N,N,N'-trimethyl Base-bis(2-aminoethyl)ether, N,N-dimethylhexanolamine, N,N-dimethylaminoethoxyethanol, N,N,N'-trimethyl-N '-(2-Hydroxyethyl)-extended ethyldiamine, N-(2-hydroxyethyl)-N,N',N",N"-tetramethyldiethylideneamine, N-(2 -hydroxypropyl)-N,N',N",N"-tetramethyldiethylideneamine, N,N,N'-trimethyl-N'-(2-hydroxyethyl)propane II Amine, N-methyl-N'-(2-hydroxyethyl)piperazine, bis(N,N-dimethylaminopropyl)amine, bis(N,N-dimethylaminopropyl) Isopropanolamine, 2-aminoquinine, 3-aminoquinine, 4-aminoquinine, 2-quinuclidinol, 3-quinuclidinol, 4-quinuclidinol, 1-( 2'-hydroxypropyl)imidazole, 1-(2'-hydroxypropyl)-2-methylimidazole , 1-(2'-hydroxyethyl)imidazole, 1-(2'-hydroxyethyl)-2-methylimidazole, 1-(2'-hydroxypropyl)-2-methylimidazole, 1-( 3'-Aminopropyl)imidazole, 1-(3'-aminopropyl)-2-methylimidazole, 1-(3'-hydroxypropyl)imidazole, 1-(3'-hydroxypropyl) -2-methylimidazole, N,N-dimethylaminopropyl-N'-(2-hydroxyethyl)amine, N,N-dimethylaminopropyl-N', N'-double (2-hydroxyethyl)amine, N,N-dimethylaminopropyl-N',N'-bis(2-hydroxypropyl)amine, N,N-dimethylaminoethyl-N ',N'-bis(2-hydroxyethyl)amine, N,N-dimethylaminoethyl-N',N'-bis(2-hydroxypropyl)amine, melamine or/and benzoin Fecal amines and the like can be mentioned.

作為前述胺鹽(F-6)，例如有DBU(1,8-二吖-雙環[5,4,0]十一碳烯-7)之有機酸鹽系的胺鹽等可舉出。As the amine salt (F-6), for example, an amine salt of an organic acid salt of DBU (1,8-difluorene-bicyclo[5,4,0]undecene-7) may be mentioned.

前述脲烷化觸媒(F)的調配量一般量的比率即充分，例如對於含有羧基之樹脂(A)100質量份而言，較佳為0.1~20質量份，更佳為0.5~10.0質量份。The ratio of the amount of the urethane-catalyzed catalyst (F) to a normal amount is sufficient. For example, for 100 parts by mass of the carboxyl group-containing resin (A), it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10.0 by mass. Share.

本發明的光硬化性樹脂組成物可添加(G)著色劑。作為著色劑，可使用紅(G-1)、藍(G-2)、綠(G-3)、黃(G-4)等慣用公知之著色劑，亦可使用顏料、染料、色素。但，由環境負荷減低以及對人體之影響的觀點來看，不含鹵素者為佳。The (G) coloring agent can be added to the photocurable resin composition of the present invention. As the coloring agent, a conventionally known coloring agent such as red (G-1), blue (G-2), green (G-3), or yellow (G-4) can be used, and a pigment, a dye, or a coloring matter can also be used. However, from the viewpoint of environmental load reduction and influence on the human body, it is preferable that the halogen-free one is preferable.

紅色著色劑(G-1)：Red colorant (G-1):

作為紅色著色劑有單偶氮系、雙偶氮系、AzoLake系、苯並咪唑酮系、苝系、吡咯並吡咯二酮系、縮合偶氮系、蒽醌系、喹吖酮系等，具體可舉出如以下之顏色指數(C.I.；The Society of Dyers and Colourists發行)號碼者。Examples of the red coloring agent include a monoazo type, a bisazo type, an AzoLake type, a benzimidazolone type, an anthraquinone type, a pyrrolopyrroledione type, a condensed azo type, an anthraquinone type, and a quinophthalone type. The color index (CI; The Society of Dyers and Colourists) number can be cited as follows.

單偶氮系：Pigment Red 1、2、3、4、5、6、8、9、12、14、15、16、17、21、22、23、31、32、112、114、146、147、151、170、184、187、188、193、210、245、253、258、266、267、268、269。Monoazo system: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147 , 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.

雙偶氮系：Pigment Red 37、38、41。Bisazo: Pigment Red 37, 38, 41.

monoazolake層合系：Pigment Red 48：1、48：2、48：3、48：4、49：1、49：2、50：1、52：1、52：2、53：1、53：2、57：1、58：4、63：1、63：2、64：1、68。Monoazolake laminate: Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2 57:1, 58:4, 63:1, 63:2, 64:1, 68.

苯並咪唑酮系：Pigment Red 171、Pigment Red 175、Pigment Red 176、Pigment Red 185、Pigment Red 208。Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.

苝系：Solvent Red 135、Solvent Red 179、Pigment Red 123、Pigment Red 149、Pigment Red 166、Pigment Red 178、Pigment Red 179、Pigment Red 190、Pigment Red 194、Pigment Red 224。The system is: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.

吡咯並吡咯二酮系：Pigment Red 254、Pigment Red 255、Pigment Red 264、Pigment Red 270、Pigment Red 272。Pyrrolopyrroledione: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

縮合偶氮系：Pigment Red 220、Pigment Red 144、Pigment Red 166、Pigment Red 214、Pigment Red 220、Pigment Red 221、Pigment Red 242。Condensed azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.

蒽醌系：Pigment Red 168、Pigment Red 177、Pigment Red 216、Solvent Red 149、Solvent Red 150、Solvent Red 52、Solvent Red 207。蒽醌: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.

喹吖酮系：Pigment Red 122、Pigment Red 202、Pigment Red 206、Pigment Red 207、Pigment Red 209。Quinone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

藍色著色劑(G-2)：Blue colorant (G-2):

作為藍色著色劑有酞菁素系、蒽醌系，顏料系可分類為色素(Pigment)之化合物，具體可舉出如下述者：Pigment Blue 15、Pigment Blue 15：1、Pigment Blue 15：2、Pigment Blue 15：3、Pigment Blue 15：4、Pigment Blue 15：6、Pigment Blue 16、Pigment Blue 60。Examples of the blue coloring agent include a phthalocyanine-based or an anthraquinone-based, and the pigment-based compound can be classified into a pigment, and specific examples thereof include Pigment Blue 15, Pigment Blue 15:1, and Pigment Blue 15:2. , Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 60.

作為染料系可使用Solvent Blue 35、Solvent Blue 63、Solvent Blue 68、Solvent Blue 70、Solvent Blue 83、Solvent Blue 87、Solvent Blue 94、Solvent Blue 97、Solvent Blue 122、Solvent Blue 136、Solvent Blue 67、Solvent Blue 70等。上述以外亦可使用金屬取代或無取代之酞菁素化合物。As the dye system, Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent can be used. Blue 70 and so on. A metal-substituted or unsubstituted phthalocyanine compound may also be used in addition to the above.

綠色著色劑(G-3)：Green colorant (G-3):

作為綠色著色劑，同様有酞菁素系、蒽醌系、苝系，具體可使用Pigment Green 7、Pigment Green 36、Solvent Green 3、Solvent Green 5、Solvent Green 20、Solvent Green 28等。上述以外亦可使用金屬取代或無取代之酞菁素化合物。As the green coloring agent, there are phthalocyanine, lanthanide, and lanthanide, and specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like can be used. A metal-substituted or unsubstituted phthalocyanine compound may also be used in addition to the above.

黃色著色劑(G-4)：Yellow colorant (G-4):

作為黃色著色劑有單偶氮系、雙偶氮系、縮合偶氮系、苯並咪唑酮系、異吲哚啉酮系、蒽醌系等，具體可舉出以下者。Examples of the yellow coloring agent include a monoazo type, a bisazo type, a condensed azo type, a benzimidazolone type, an isoindolinone type, an anthraquinone type, and the like, and specific examples thereof include the following.

蒽醌系：Solvent Yellow 163、Pigment Yellow 24、Pigment Yellow 108、Pigment Yellow 193、Pigment Yellow 147、Pigment Yellow 199、Pigment Yellow 202。Lanthanum: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

異吲哚啉酮系：Pigment Yellow 110、Pigment Yellow 109、Pigment Yellow 139、Pigment Yellow 179、Pigment Yellow 185。Isoindolinone series: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

縮合偶氮系：Pigment Yellow 93、Pigment Yellow 94、Pigment Yellow 95、Pigment Yellow 128、Pigment Yellow 155、Pigment Yellow 166、Pigment Yellow 180。Condensed azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

苯並咪唑酮系：Pigment Yellow 120、Pigment Yellow 151、Pigment Yellow 154、Pigment Yellow 156、Pigment Yellow 175、Pigment Yellow 181。Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.

單偶氮系：Pigment Yellow 1、2、3、4、5、6、9、10、12、61、62、62：1、65、73、74、75、97、100、104、105、111、116、167、168、169、182、183。Monoazo system: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111 , 116, 167, 168, 169, 182, 183.

雙偶氮系：Pigment Yellow 12、13、14、16、17、55、63、81、83、87、126、127、152、170、172、174、176、188、198。Diazo system: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

其他，以調整色調為目的亦可加入紫、橘、咖啡、黑等著色劑。In addition, coloring agents such as purple, orange, coffee, and black may be added for the purpose of adjusting the color tone.

若要具體例示，有Pigment Violet 19、23、29、32、36、38、42、Solvent Violet 13、36、C.I.色素橘1、C.I.色素橘5、C.I.色素橘13、C.I.色素橘14、C.I.色素橘16、C.I.色素橘17、C.I.色素橘24、C.I.色素橘34、C.I.色素橘36、C.I.色素橘38、C.I.色素橘40、C.I.色素橘43、C.I.色素橘46、C.I.色素橘49、C.I.色素橘51、C.I.色素橘61、C.I.色素橘63、C.I.色素橘64、C.I.色素橘71、C.I.色素橘73、C.I.色素棕23、C.I.色素棕25、C.I.色素黑1、C.I.色素黑7等。To be specifically illustrated, there are Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black 7, and the like.

如前述之著色劑(G)的調配比率雖無特別限定，對於前述含有羧基之樹脂(A)100質量份而言，較佳為0~10質量份，特佳為0.1~5質量份之比率下進行充分。The blending ratio of the above-mentioned coloring agent (G) is not particularly limited, and is preferably from 0 to 10 parts by mass, particularly preferably from 0.1 to 5 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). Undertake is full.

使用於本發明的光硬化性熱硬化性樹脂組成物之分子中具有2個以上的乙烯性不飽和基之化合物(H)為，藉由活性能量線照射進行光硬化，使前述含有羧基之樹脂(A)於鹼水溶液中不溶化、或幫助不溶化者。作為如此化合物，有乙二醇、甲氧基四乙二醇、聚乙二醇、丙二醇等甘醇之二丙烯酸酯類；己烷二醇、三羥甲基丙烷、季戊四醇、二季戊四醇層合、參-羥基乙基三聚異氰酸酯等多元醇或彼等的環氧乙烷加成物或環氧丙烷加成物等多價丙烯酸酯類；苯氧基丙烯酸酯、雙酚A二丙烯酸酯、及彼等的酚類的環氧乙烷加成物或環氧丙烷加成物等多價丙烯酸酯類；甘油二環氧丙基醚、甘油三環氧丙基醚、三羥甲基丙烷三環氧丙基醚、三環氧丙基三聚異氰酸酯等環氧丙基醚之多價丙烯酸酯類；及三聚氰胺丙烯酸酯、及/或對應上述丙烯酸酯之各甲基丙烯酸酯類等可舉出。The compound (H) having two or more ethylenically unsaturated groups in the molecule of the photocurable thermosetting resin composition of the present invention is photocured by irradiation with an active energy ray to form the carboxyl group-containing resin. (A) Those who do not dissolve in an aqueous alkali solution or help to dissolve. Examples of such a compound include diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, and dipentaerythritol; a polyvalent acrylate such as a polyhydric alcohol such as a hydroxyethyl tripolyisocyanate or an ethylene oxide adduct thereof or a propylene oxide adduct; a phenoxy acrylate, a bisphenol A diacrylate, and Polyvalent acrylates such as oxirane ethylene oxide adducts or propylene oxide adducts; glycerol diepoxypropyl ether, glycerol triepoxypropyl ether, trimethylolpropane tricyclic Polyvalent acrylates of glycidyl ethers such as oxypropyl ether and triepoxypropyl trimer isocyanate; and melamine acrylates and/or methacrylates corresponding to the above acrylates, and the like.

且，於甲酚漆用酚醛型環氧樹脂等多官能環氧樹脂，使丙烯酸進行反應之環氧丙烯酸酯樹脂、或進一步於該環氧丙烯酸酯樹脂的羥基上使季戊四醇三丙烯酸酯等羥基丙烯酸酯與異佛爾酮二異氰酸酯等二異氰酸酯的半脲烷化合物進行反應的環氧基脲烷丙烯酸酯化合物等可舉出。如此環氧丙烯酸酯系樹脂不會使指觸乾燥性降低，而可提高光硬化性。Further, a polyfunctional epoxy resin such as a phenolic epoxy resin for cresol paint, an epoxy acrylate resin for reacting acrylic acid, or a hydroxyacrylic acid such as pentaerythritol triacrylate further on a hydroxyl group of the epoxy acrylate resin An epoxy urethane acrylate compound in which an ester is reacted with a semi-urea compound of a diisocyanate such as isophorone diisocyanate may, for example, be mentioned. Such an epoxy acrylate-based resin can improve the photocurability without lowering the touch drying property.

如此分子中具有2個以上的乙烯性不飽和基之化合物(H)的調配量對於前述含有羧基之樹脂(A)100質量份而言為5~100質量份，較佳為1~70質量份之比率。前述調配量未達5質量份時，光硬化性會降低，藉由活性能量線照射後的鹼性顯像，難以形成圖型故不佳。另一方面，該調配量超過100質量份時，對於鹼水溶液之溶解性會降低，使被膜容易變脆而不佳。The compounding amount of the compound (H) having two or more ethylenically unsaturated groups in the molecule is 5 to 100 parts by mass, preferably 1 to 70 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). The ratio. When the amount of the compound is less than 5 parts by mass, the photocurability is lowered, and it is difficult to form a pattern by alkaline development after irradiation with an active energy ray, which is not preferable. On the other hand, when the amount is more than 100 parts by mass, the solubility in the aqueous alkali solution is lowered, and the film is liable to be brittle.

本發明的光硬化性熱硬化性樹脂組成物因可提高該被膜之物理強度等，故若必要可添加填充物(I)。作為如此填充物(I)，可使用公知慣用的無機或有機填充物，但特別以使用硫酸鋇、球狀二氧化矽及滑石為佳。且，欲得到白色外觀或難燃性，可使用氧化鈦或金屬氧化物、氫氧化鋁等金屬氫氧化物作為體質顏料填充物。彼等填充物(I)的調配量對於前述含有羧基之樹脂(A)100質量份而言，較佳為200質量份以下，更佳為0.1~150質量份，最佳為1~100質量份。填充物的調配量超過200質量份時，組成物的黏度會變高、或印刷性會降低、或硬化物會變脆而不佳。In the photocurable thermosetting resin composition of the present invention, since the physical strength and the like of the film can be improved, the filler (I) can be added if necessary. As such a filler (I), a conventionally known inorganic or organic filler can be used, but in particular, barium sulfate, spherical cerium oxide, and talc are preferably used. Further, in order to obtain a white appearance or flame retardancy, a metal hydroxide such as titanium oxide, metal oxide or aluminum hydroxide can be used as the bulk pigment filler. The amount of the filler (I) is preferably 200 parts by mass or less, more preferably 0.1 to 150 parts by mass, most preferably 1 to 100 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). . When the amount of the filler is more than 200 parts by mass, the viscosity of the composition may become high, or the printability may be lowered, or the cured product may become brittle.

本發明的光硬化性熱硬化性樹脂組成物中以指觸乾燥性的改善、處理性的改善等為目的而可膠黏劑聚合物。例如可使用聚酯系聚合物、聚脲烷系聚合物、聚酯脲烷系聚合物、聚醯胺系聚合物、聚酯醯胺系聚合物、丙烯酸系聚合物、纖維素系聚合物、聚乳酸系聚合物、苯氧基系聚合物等。彼等的膠黏劑聚合物可單獨或作為2種類以上之混合物使用。The photocurable thermosetting resin composition of the present invention is an adhesive polymer for the purpose of improving the dryness of the touch, improving the handleability, and the like. For example, a polyester-based polymer, a polyurea-based polymer, a polyester urethane-based polymer, a polyamid-based polymer, a polyester amide-based polymer, an acrylic polymer, a cellulose-based polymer, or the like can be used. A polylactic acid-based polymer, a phenoxy polymer, or the like. These adhesive polymers may be used singly or as a mixture of two or more types.

本發明的光硬化性熱硬化性樹脂組成物中以柔軟性之賦予、改善硬化物的脆度為目的下可使用彈性體。例如可使用聚酯系彈性體、聚脲烷系彈性體、聚酯脲烷系彈性體、聚醯胺系彈性體、聚酯醯胺系彈性體、丙烯酸系彈性體、烯烴系彈性體。又，亦可使用將具有種種骨架的環氧樹脂的一部份或全部的環氧基以兩末端羧酸改性型丁二烯-丙烯腈橡膠經改性的樹脂等。進一步可使用含有丙烯酸的聚丁二烯系彈性體、含有羥基之聚丁二烯系彈性體、含有羥基之異戊二烯系彈性體。彼等的彈性體可單獨或作為2種類以上之混合物使用。In the photocurable thermosetting resin composition of the present invention, an elastomer can be used for the purpose of imparting flexibility and improving the brittleness of the cured product. For example, a polyester-based elastomer, a polyurea-based elastomer, a polyester urethane-based elastomer, a polyamide-based elastomer, a polyester amide-based elastomer, an acrylic elastomer, or an olefin-based elastomer can be used. Further, a resin obtained by modifying a part or all of the epoxy groups of the epoxy resin having various skeletons with a carboxylic acid-modified butadiene-acrylonitrile rubber at both ends may be used. Further, a polybutadiene-based elastomer containing acrylic acid, a polybutadiene-based elastomer containing a hydroxyl group, or an isoprene-based elastomer containing a hydroxyl group can be used. These elastomers may be used singly or as a mixture of two or more types.

且，本發明的光硬化性熱硬化性樹脂組成物於上述含有羧基之樹脂(A)的合成或組成物之調整、或欲塗佈於基板或載體膜的黏度調整，可使用有機溶劑。Further, in the photocurable thermosetting resin composition of the present invention, an organic solvent can be used for the adjustment of the synthesis or composition of the carboxyl group-containing resin (A) or the viscosity of the substrate or the carrier film to be applied.

作為如此有機溶劑，可舉出酮類、芳香族烴類、甘醇醚類、甘醇醚乙酸酯類、酯類、醇類、脂肪族烴、石油系溶劑等。更具體可舉出甲基乙酮、環己酮等酮類；甲苯、二甲苯、四甲基苯等芳香族烴類；賽路蘇、甲基賽路蘇、丁基賽路蘇、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甘醇醚類；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酯類；乙醇、丙醇、乙二醇、丙二醇等醇類；辛烷、癸烷等脂肪族烴；石油醚、石油石腦油、氫化石油石腦油、溶劑石腦油等石油系溶劑等。如此有機溶劑可單獨或作為2種以上之混合物使用。Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; 赛路苏, methyl 赛路苏, butyl 赛路苏, 卡必Alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers; Esters such as ester, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate; ethanol, propanol, ethylene glycol Alcohols such as propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. The organic solvent may be used singly or as a mixture of two or more.

一般高分子材料大多一經氧化後，會引起接連的氧化劣化，導致高分子素材的功能降低，故本發明的光硬化性熱硬化性樹脂組成物欲防止氧化，可添加(1)使所產生之自由基無效化的自由基捕捉劑(J-1)或/及(2)分解所產生之過氧化物成為無害物質，不再產生新自由基的過氧化物分解劑(J-2)等抗氧化劑(J)。In general, when the polymer material is oxidized, the oxidative degradation is caused in succession, and the function of the polymer material is lowered. Therefore, the photocurable thermosetting resin composition of the present invention is intended to prevent oxidation, and (1) the freedom to be produced can be added. The radical scavenger (J-1) or/and (2) the peroxide generated by the decomposition becomes a harmless substance, and an antioxidant such as a peroxide decomposing agent (J-2) which no longer generates a new radical (J).

作為自由基捕捉劑作用的抗氧化劑(J-1)，其具體化合物可舉出氫醌、4-t-丁基兒茶酚、2-t-丁基氫醌、氫醌單甲基醚、2,6-二-t-丁基-p-甲酚、2,2-伸甲基-雙(4-甲基-6-t-丁基酚)、1,1,3-參(2-甲基-4-羥基-5-t-丁基苯基)丁烷、1,3,5-三甲基-2,4,6-參(3,5-二-t-丁基-4-羥基苯甲基)苯、1,3,5-參(3’,5’-二-t-丁基-4-羥基苯甲基)-S-三嗪-2,4,6-(1H,3H,5H)三酮等酚系、間苯酮、苯並醌等醌系化合物、雙(2,2,6,6-四甲基-4-哌啶基)-癸二酸酯、吩噻嗪等胺系化合物等。Examples of the specific antioxidant of the antioxidant (J-1) which acts as a radical scavenger include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methyl-bis(4-methyl-6-t-butylphenol), 1,1,3-ginic (2- Methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-paran (3,5-di-t-butyl-4- Hydroxybenzyl)benzene, 1,3,5-gin (3',5'-di-t-butyl-4-hydroxybenzyl)-S-triazine-2,4,6-(1H, 3H, 5H) ketones such as ketones, isophthalones, benzindenes, etc., bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate, phenothiazine An amine compound such as a azine.

自由基捕捉劑可為販賣品，例如有AdekastubAO-30、AdekastubAO-330、AdekastubAO-20、AdekastubLA-77、AdekastubLA-57、AdekastubLA-67、AdekastubLA-68、AdekastubLA-87(以上，(股)ADEKA製，商品名)、IRGANOX1010、IRGANOX1035、IRGANOX1076、IRGANOX1135、TINUVIN 111FDL、TINUVIN123、TINUVIN 144、TINUVIN 152、TINUVIN 292、TINUVIN 5100(以上，Ciba Japan(股)製，商品名)等可舉出。The radical scavenger may be sold, for example, Adekastub AO-30, Adekastub AO-330, Adekastub AO-20, Adekastub LA-77, Adekastub LA-57, Adekastub LA-67, Adekastub LA-68, Adekastub LA-87 (above, ADEKA) , trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111 FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, Ciba Japan, product name) and the like can be mentioned.

作為過氧化物分解劑作用的抗氧化劑(J-2)，其具體化合物有三苯基亞磷酸酯等磷系化合物、季戊四醇四月桂基硫丙酸酯、二月桂基硫二丙酸酯、二硬脂醯基3,3’-硫二丙酸酯等硫系化合物等可舉出。As an antioxidant (J-2) which acts as a peroxide decomposer, a specific compound thereof is a phosphorus compound such as triphenylphosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, or a hard A sulfur-based compound such as a lipid sulfhydryl 3,3'-thiodipropionate or the like can be given.

過氧化物分解劑可為販賣品，例如有AdekastubTPP(旭電化公司製，商品名)、MARKAO-412S((股)ADEKA製，商品名)、SUMILIZERTPS(住友化學公司製，商品名)等可舉出。The peroxide decomposing agent may be, for example, a product such as Adekastub TPP (product name manufactured by Asahi Kasei Co., Ltd.), MARKAO-412S (product name: ADEKA, product name), SUMILIZERTPS (manufactured by Sumitomo Chemical Co., Ltd., trade name), and the like. Out.

上述抗氧化劑(J)可單獨使用1種或組合2種以上使用。These antioxidants (J) may be used alone or in combination of two or more.

又，一般高分子材料會吸收光，藉此引起分解‧劣化，故本發明的光硬化性熱硬化性樹脂組成物中，欲對紫外線進行安定化對策，除可使用上述抗氧化劑以外，亦可使用紫外線吸收劑(K)。In addition, in the photocurable thermosetting resin composition of the present invention, it is desired to stabilize the ultraviolet rays, and the antioxidant may be used in addition to the above-mentioned antioxidant. Use UV absorber (K).

作為紫外線吸收劑(K)，有二苯甲酮衍生物、苯甲酸酯衍生物、苯並***衍生物、三嗪衍生物、苯並噻唑衍生物、肉桂酸酯衍生物、鄰胺苯甲酸酯衍生物、二苯甲醯基甲烷衍生物等可舉出。作為二苯甲酮衍生物之具體例，有2-羥基-4-甲氧基二苯甲酮、2-羥基-4-n-辛氧基二苯甲酮、2,2’-二羥基-4-甲氧基二苯甲酮及2,4-二羥基二苯甲酮等可舉出。作為苯甲酸酯衍生物之具體例，有2-乙基己基水楊酸酯、苯基水楊酸酯、p-t-丁基苯基水楊酸酯、2,4-二-t-丁基苯基-3,5-二-t-丁基-4-羥基苯甲酸酯及十六烷基-3,5-二-t-丁基-4-羥基苯甲酸酯等可舉出。作為苯並***衍生物之具體例，有2-(2’-羥基-5’-t-丁基苯基)苯並***、2-(2’-羥基-5’-甲基苯基)苯並***、2-(2’-羥基-3’-t-丁基-5’-甲基苯基)-5-氯苯並***、2-(2’-羥基-3’,5’-二-t-丁基苯基)-5-氯苯並***、2-(2’-羥基-5’-甲基苯基)苯並***及2-(2’-羥基-3’,5’-二-t-戊基苯基)苯並***等可舉出。作為三嗪衍生物之具體例，有羥基苯基三嗪、雙乙基己氧基酚甲氧基苯基三嗪等可舉出。As the ultraviolet absorber (K), there are a benzophenone derivative, a benzoate derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative, a cinnamate derivative, an ortho-aminobenzene. A formate derivative, a benzhydrylmethane derivative, etc. are mentioned. Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2,2'-dihydroxy- 4-methoxybenzophenone and 2,4-dihydroxybenzophenone may, for example, be mentioned. Specific examples of the benzoate derivative include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, and 2,4-di-t-butyl. Phenyl-3,5-di-t-butyl-4-hydroxybenzoate and cetyl-3,5-di-t-butyl-4-hydroxybenzoate may, for example, be mentioned. Specific examples of the benzotriazole derivative include 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole and 2-(2'-hydroxy-5'-methylphenyl group. Benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3', 5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy- 3',5'-di-t-pentylphenyl)benzotriazole and the like can be mentioned. Specific examples of the triazine derivative include hydroxyphenyltriazine and bisethylhexyloxyphenol methoxyphenyltriazine.

作為紫外線吸收劑(K)可為販賣品，例如有TINUVIN PS、TINUVIN 99-2、TINUVIN 109、TINUVIN 384-2、TINUVIN 900、TINUVIN 928、TINUVIN 1130、TINUVIN 400、TINUVIN 405、TINUVIN 460、TINUVIN 479(以上，Ciba Japan(股)製，商品名)等可舉出。As the ultraviolet absorber (K), it can be sold, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (The above, Ciba Japan, stock name) and the like can be mentioned.

上述紫外線吸收劑(K)可單獨使用1種或組合2種以上使用，與前述抗氧化劑(J)併用，可達到的本發明之光硬化性熱硬化性樹脂組成物所得之成形物的安定化。The ultraviolet ray absorbing agent (K) may be used singly or in combination of two or more kinds thereof, and the molded article obtained by the photocurable thermosetting resin composition of the present invention which can be obtained by using the antioxidant (J) together can be stabilized. .

本發明的光硬化性熱硬化性樹脂組成物中，欲提高感度，作為連鎖移動劑可使用公知慣用的N苯基甘胺酸類、苯氧基乙酸類、硫苯氧基乙酸類、氫硫基噻唑等。若要舉出連鎖移動劑之具體例，例如有氫硫基琥珀酸、氫硫基乙酸、氫硫基丙酸、蛋胺酸、半胱胺酸、硫水楊酸及其衍生物等具有羧基之連鎖移動劑；氫硫基乙醇、氫硫基丙醇、氫硫基丁醇、氫硫基丙烷二醇、氫硫基丁烷二醇、羥基苯硫醇及其衍生物等具有羥基之連鎖移動劑；1-丁烷硫醇、丁基-3-氫硫基丙酸酯、甲基-3-氫硫基丙酸酯、2,2-(伸乙基二氧基)二乙烷硫醇、乙烷硫醇、4-甲基苯硫醇、月桂基硫醇、丙烷硫醇、丁烷硫醇、戊烷硫醇、1-辛烷硫醇、環戊烷硫醇、環己烷硫醇、硫甘油、4,4-硫聯苯硫醇等。In the photocurable thermosetting resin composition of the present invention, in order to improve the sensitivity, a well-known conventional N-phenylglycine, phenoxyacetic acid, thiophenoxyacetic acid, or thiol group can be used as the chain shifting agent. Thiazole and the like. Specific examples of the linkage mobile agent, such as thiosuccinic acid, thioacetic acid, thiopropyl propionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof, have carboxyl groups. Chain-shifting agent; chain of hydroxyl groups such as thioethyl alcohol, thiopropyl propanol, thiobutanol, thiopropyl propane diol, thiophanyl butane diol, hydroxy benzene thiol and its derivatives Moving agent; 1-butane thiol, butyl-3-hydrothiopropionate, methyl-3-hydrothiopropionate, 2,2-(extended ethyldioxy)diethane sulphide Alcohol, ethanethiol, 4-methylbenzenethiol, lauryl mercaptan, propane thiol, butane thiol, pentane thiol, 1-octane thiol, cyclopentane thiol, cyclohexane Mercaptan, thioglycerol, 4,4-thiobiphenylthiol, and the like.

且，作為多官能性硫醇系化合物，雖無特別限定，例如有己烷-1,6-二硫醇、癸烷-1,10-二硫醇、二氫硫基二乙基醚、二氫硫基二乙基硫化物等脂肪族硫醇類、伸苯二甲基二硫醇、1,4-苯二硫醇等芳香族硫醇類；乙二醇雙(氫硫基乙酸酯)、聚乙二醇雙(氫硫基乙酸酯)、丙二醇雙(氫硫基乙酸酯)、甘油參(氫硫基乙酸酯)、三羥甲基乙烷參(氫硫基乙酸酯)、三羥甲基丙烷參(氫硫基乙酸酯)、季戊四醇肆(氫硫基乙酸酯)、二季戊四醇陸(氫硫基乙酸酯)等多元醇之聚(氫硫基乙酸酯)類；乙二醇雙(3-氫硫基丙酸酯)、聚乙二醇雙(3-氫硫基丙酸酯)、丙二醇雙(3-氫硫基丙酸酯)、甘油參(3-氫硫基丙酸酯)、三羥甲基乙烷參(氫硫基丙酸酯)、三羥甲基丙烷參(3-氫硫基丙酸酯)、季戊四醇肆(3-氫硫基丙酸酯)、二季戊四醇陸(3-氫硫基丙酸酯)等多元醇的聚(3-氫硫基丙酸酯)類；1,4-雙(3-氫硫基丁醯氧基)丁烷、1,3,5-參(3-氫硫基丁氧基乙基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、季戊四醇肆(3-氫硫基丁酸酯)等聚(氫硫基丁酸酯)類等可舉出。Further, the polyfunctional thiol compound is not particularly limited, and examples thereof include hexane-1,6-dithiol, decane-1,10-dithiol, dihydrothiodiethyl ether, and dihydrogen. An aromatic thiol such as an aliphatic thiol such as thiodiethyl sulfide, benzene dimethyl dithiol or 1,4-benzenedithiol; ethylene glycol bis(hydrothioacetate) , polyethylene glycol bis(hydrothioacetate), propylene glycol bis(hydrothioacetate), glycerol ginseng (thiol acetate), trimethylolethane thiol (hydrothioacetic acid) Polyesters such as esters, trimethylolpropane ginseng (thiol acetate), pentaerythritol bismuth (thiol acetate), dipentaerythritol tert (thylthioacetate) Acid esters; glycol bis(3-hydrothiopropionate), polyethylene glycol bis(3-hydrothiopropionate), propylene glycol bis(3-hydrothiopropionate), glycerol Ginseng (3-hydrothiopropionate), trimethylolethane sulphate (hydrothiopropionate), trimethylolpropane ginseng (3-hydrothiopropionate), pentaerythritol bismuth (3- Poly(3-hydrothiopropionate) of polyhydric alcohols such as thiopropyl propionate and dipentaerythritol (3-hydrothiopropionate); 1,4-bis(3-hydrogen sulfide) Butyloxy)butane, 1,3,5-gin(3-hydrothiobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)- Poly(hydrogenthiobutyrate) such as triketone or pentaerythritol oxime (3-hydrogenthiobutyrate) may, for example, be mentioned.

且作為連鎖移動劑作用之具有氫硫基的雜環化合物，例如有氫硫基-4-丁內酯(別名：2-氫硫基-4-γ-丁內酯)、2-氫硫基-4-甲基-4-丁內酯、2-氫硫基-4-乙基-4-丁內酯、2-氫硫基-4-丁氫硫內酯、2-氫硫基-4-丁內醯胺、N-甲氧基-2-氫硫基-4-丁內醯胺、N-乙氧基-2-氫硫基-4-丁內醯胺、N-甲基-2-氫硫基-4-丁內醯胺、N-乙基-2-氫硫基-4-丁內醯胺、N-(2-甲氧基)乙基-2-氫硫基-4-丁內醯胺、N-(2-乙氧基)乙基-2-氫硫基-4-丁內醯胺、2-氫硫基-5-戊內酯、2-氫硫基-5-戊內醯胺、N-甲基-2-氫硫基-5-戊內醯胺、N-乙基-2-氫硫基-5-戊內醯胺、N-(2-甲氧基)乙基-2-氫硫基-5-戊內醯胺、N-(2-乙氧基)乙基-2-氫硫基-5-戊內醯胺及2-氫硫基-6-己內醯胺等。And a heterocyclic compound having a thiol group acting as a chain shifting agent, for example, thiothio-4-butyrolactone (alias: 2-hydrothio-4-γ-butyrolactone), 2-hydrogenthio group -4-methyl-4-butyrolactone, 2-hydrothio-4-ethyl-4-butyrolactone, 2-hydrothio-4-butanethiolactone, 2-hydrothio-4 - Butyrolactam, N-methoxy-2-hydrothio-4-butylidene, N-ethoxy-2-hydrothio-4-butylidene, N-methyl-2 -Hexylthio-4-butylidene, N-ethyl-2-hydrothio-4-butylidene, N-(2-methoxy)ethyl-2-hydrothio-4- Butane amide, N-(2-ethoxy)ethyl-2-hydrothio-4-butylidene, 2-hydrothio-5-valerolactone, 2-hydrothio-5- Valdecamine, N-methyl-2-hydrothio-5-pentalamine, N-ethyl-2-hydrothio-5-pentalamine, N-(2-methoxy) Ethyl-2-hydrothio-5-pentalamine, N-(2-ethoxy)ethyl-2-hydrothio-5-pentalamine and 2-hydrothio-6-hexyl Endoamine and the like.

特別作為以不損害光硬化性熱硬化性樹脂組成物的顯像性之連鎖移動劑的具有氫硫基之雜環化合物，以氫硫基苯並噻唑、3-氫硫基-4-甲基-4H-1,2,4-***、5-甲基-1,3,4-噻二唑-2-硫醇、1-苯基-5-氫硫基-1H-四唑為佳。彼等的連鎖移動劑可單獨或併用2種以上。In particular, as a heterocyclic compound having a hydrogenthio group as a linkage shifting agent which does not impair the developability of a photocurable thermosetting resin composition, thiothibenzothiazole, 3-hydrothio-4-methyl group -4H-1,2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-hydrothio-1H-tetrazole is preferred. These chain-shifting agents may be used alone or in combination of two or more.

本發明的光硬化性熱硬化性樹脂組成物中，欲提高層間密著性、或感光性樹脂層與基材之密著性，可使用密著促進劑。具體例可舉出苯並咪唑、苯並噁唑、苯並噻唑、2-氫硫基苯並咪唑、2-氫硫基苯並噁唑、2-氫硫基苯並噻唑(商品名：川口化學工業(股)製AccelM)、3-嗎啉代甲基-1-苯基-***-2-硫酮、5-胺基-3-嗎啉代甲基-噻唑-2-硫酮、2-氫硫基-5-甲基硫-噻二唑、***、四唑、苯並***、羧基苯並***、胺基含有苯並***、矽烷偶合劑等。In the photocurable thermosetting resin composition of the present invention, an adhesion promoter may be used in order to improve interlayer adhesion or adhesion between the photosensitive resin layer and the substrate. Specific examples thereof include benzimidazole, benzoxazole, benzothiazole, 2-hydrothiobenzimidazole, 2-hydrothiobenzoxazole, 2-hydrothiobenzothiazole (trade name: Kawaguchi) Acrylic acid (Accel M), 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-Hydroxythio-5-methylsulfide-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amine group containing benzotriazole, decane coupling agent and the like.

本發明的光硬化性熱硬化性樹脂組成物若必要中若必要進一步可添加微粉二氧化矽、有機膨潤體、蒙脫石、水滑石等觸變化劑。作為觸變化劑的經時安定性以有機膨潤體、水滑石為佳，特別以水滑石的電氣特性優良。又，可添加熱聚合禁止劑、或矽氧烷系、氟系、高分子系等消泡劑及/或塗平劑、咪唑系、噻唑系、***系等矽烷偶合劑、防鏽劑等公知慣用之添加劑類。The photocurable thermosetting resin composition of the present invention may further contain a modifier such as fine powder of ceria, organic swelling, montmorillonite or hydrotalcite if necessary. The stability over time of the thixotropic agent is preferably an organic swelling or hydrotalcite, and particularly the hydrotalcite is excellent in electrical characteristics. Further, a thermal polymerization inhibiting agent, an antifoaming agent such as a fluorinating system, a fluorine-based or a polymer-based polymer, and/or a coating agent, a decane coupling agent such as an imidazole-based, a thiazole-based or a triazole-based, a rust preventive agent, or the like may be added. Commonly used additives.

前述熱聚合禁止劑可使用於防止前述聚合性化合物的熱聚合或經時性聚合。作為熱聚合禁止劑，例如有4-甲氧基酚、氫醌、烷基或芳基取代氫醌、t-丁基兒茶酚、焦棓酚、2-羥基二苯甲酮、4-甲氧基-2-羥基二苯甲酮、氯化第一銅、吩噻嗪、氯醌、萘基胺、β-萘酚、2,6-二-t-丁基-4-甲酚、2,2’-伸甲基雙(4-甲基-6-t-丁基酚)、吡啶、硝基苯、二硝基苯、苦味酸、4-甲苯胺、甲基藍、銅有機螯合劑反應物、水楊酸甲酯、及吩噻嗪、亞硝基化合物、亞硝基化合物與Al之螯合等可舉出。The aforementioned thermal polymerization inhibiting agent can be used for preventing thermal polymerization or time-lapse polymerization of the aforementioned polymerizable compound. As a thermal polymerization inhibitor, for example, 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methyl Oxy-2-hydroxybenzophenone, first copper chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2 , 2'-extended methyl bis(4-methyl-6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methyl blue, copper The organic chelating agent reactant, methyl salicylate, phenothiazine, nitroso compound, nitroso compound and Al chelate can be mentioned.

本發明的光硬化性熱硬化性樹脂組成物為，例如以前述有機溶劑調整為適合塗佈方法之黏度，於基材上藉由浸漬塗佈法、流動塗佈法、輥塗佈法、棒塗佈法、網版印刷法、簾幕印刷法等方法進行塗佈，以約60~100℃的溫度將含於組成物中的有機溶劑進行揮發乾燥(假乾燥)而可形成不剝落的被膜。其後，藉由接觸式(或非接觸方式)，通過形成圖型的光罩，選擇性地藉由活性能量線進行曝光、或藉由雷射直接曝光機進行直接圖型曝光，將未曝光部藉由稀鹼水溶液(例如0.3~3%碳酸蘇打水溶液)進行顯像而形成光阻圖型。且，例如於約140~180℃的溫度下進行加熱並進行熱硬化，使前述含有羧基之樹脂(A)的羧基、與分子中具有2個以上的環狀醚基及/或環狀硫醚基之熱硬化性成分(D)進行反應，進一步經該反應所生成之羥基上進一步反應具有烷氧基甲基之胺基樹脂(C)，形成強固3次元交聯網路，因提高疏水性，可形成耐熱性、耐藥品性、耐吸濕性、密著性、電氣特性等各特性優良的硬化被膜。The photocurable thermosetting resin composition of the present invention is, for example, adjusted to have a viscosity suitable for the coating method by the organic solvent, and is applied to a substrate by a dip coating method, a flow coating method, a roll coating method, or a rod. Coating by a coating method, a screen printing method, a curtain printing method, or the like, and the organic solvent contained in the composition is volatilized and dried (false drying) at a temperature of about 60 to 100 ° C to form a film that does not peel off. . Thereafter, by contact (or non-contact), by forming a patterned mask, selectively exposing by active energy lines, or direct pattern exposure by a laser direct exposure machine, unexposed The photoresist pattern is formed by developing a dilute aqueous alkali solution (for example, 0.3 to 3% aqueous soda carbonate solution). Further, for example, heating is carried out at a temperature of about 140 to 180 ° C and thermosetting, and the carboxyl group of the carboxyl group-containing resin (A) and two or more cyclic ether groups and/or cyclic thioethers in the molecule are obtained. The thermosetting component (D) is reacted, and the amino group-containing resin (C) having an alkoxymethyl group is further reacted on the hydroxyl group formed by the reaction to form a strong 3-dimensional cross-linking route, thereby improving hydrophobicity. A cured film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties can be formed.

作為上述基材，可使用預先形成電路的印刷電路板或可撓性印刷電路板以外，亦可使用紙-酚樹脂、紙-環氧樹脂、玻璃布-環氧樹脂、玻璃-聚醯亞胺、玻璃布/不織布-環氧樹脂、玻璃布/紙-環氧樹脂、合成纖維-環氧樹脂、氟樹脂‧聚乙烯‧PPO‧氰酸酯等複合材的所有等級(FR-4等)的貼銅層合板、聚醯亞胺薄膜、PET薄膜、玻璃基板、陶瓷基板、晶圓板等。As the substrate, a printed circuit board or a flexible printed circuit board in which a circuit is formed in advance may be used, and paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimine may also be used. , glass cloth / non-woven fabric - epoxy resin, glass cloth / paper - epoxy resin, synthetic fiber - epoxy resin, fluororesin, polyethylene, PPO, cyanate ester and other composite grades (FR-4, etc.) Copper-clad laminate, polyimide film, PET film, glass substrate, ceramic substrate, wafer board, etc.

塗佈本發明的光硬化性熱硬化性樹脂組成物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、熱對流烤箱等(使用具備經蒸氣的空氣加熱方式之熱源者，將乾燥機內的熱風進行向流接觸的方法及藉由噴嘴吹賦於支持體的方式)進行。The volatilization drying performed after applying the photocurable thermosetting resin composition of the present invention may be a hot air circulation type drying furnace, an IR furnace, a hot plate, a heat convection oven or the like (using a heat source having a vapor-heated air heating method) The hot air in the dryer is brought into contact with the flow and the method of blowing the nozzle into the support by the nozzle.

如上述，塗佈本發明之光硬化性熱硬化性樹脂組成物，使其揮發乾燥後，對於所得之被膜，進行曝光(活性能量線之照射)。被膜的曝光部(藉由活性能量線照射之部分)會硬化。As described above, the photocurable thermosetting resin composition of the present invention is applied and volatilized and dried, and then the obtained film is exposed (irradiation of active energy rays). The exposed portion of the film (the portion irradiated by the active energy ray) is hardened.

作為上述活性能量線照射所使用的曝光機，可使用直接描繪裝置(例如藉者由電腦的CAD數據以直接雷射描繪影像的雷射直接影像裝置)、具備金屬鹵素燈的曝光機、具備(超)高壓水銀燈之曝光機、具備水銀超高壓力的弧光燈的曝光機、或使用(超)高壓水銀燈等紫外線燈的直接描繪裝置。作為活性能量線，若使用最大波長為350~410nm之範圍的雷射光，氣體雷射、固體雷射皆可。又，該曝光量依據膜厚等而相異，但一般為5~200mJ/cm2 ，較佳為5~100mJ/cm2 ，更佳為5~50mJ/cm2 之範圍內。作為上述直接描繪裝置，例如可使用日本orbotech公司製，PENTAX公司製等者，若為可發振最大波長為350~410nm的雷射光之裝置即可的任一裝置。As the exposure machine used for the active energy ray irradiation, a direct drawing device (for example, a laser direct imaging device that directly images laser images by computer CAD data), an exposure machine with a metal halide lamp, and the like can be used ( Ultra) high-pressure mercury lamp exposure machine, exposure machine with mercury ultra-high pressure arc lamp, or direct drawing device using ultraviolet light such as (ultra) high-pressure mercury lamp. As the active energy ray, if a laser beam having a maximum wavelength of 350 to 410 nm is used, a gas laser or a solid laser may be used. Further, the exposure amount varies depending on the film thickness or the like, but is generally 5 to 200 mJ/cm 2 , preferably 5 to 100 mJ/cm 2 , and more preferably 5 to 50 mJ/cm 2 . As the above-described direct drawing device, for example, a device manufactured by Japan Orbotech Co., Ltd., manufactured by PENTAX Co., Ltd., or the like, which is a device capable of oscillating laser light having a maximum wavelength of 350 to 410 nm, can be used.

作為前述顯像方法，可使用浸漬法、沖洗法、噴霧法、刷子法等，作為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、胺類等鹼水溶液。As the developing method, a dipping method, a rinsing method, a spraying method, a brush method, or the like can be used, and as the developing liquid, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia, or the like can be used. An aqueous alkali solution such as an amine.

本發明的光硬化性熱硬化性樹脂組成物以液狀下直接塗佈於基材的方法以外，亦可為具有預先於聚乙烯對苯二甲酸酯等薄膜將防焊劑進行塗佈並乾燥所形成的防焊劑層之乾式薄膜的形態下使用。將本發明的光硬化性熱硬化性樹脂組成物作為乾式薄膜使用時的情況如以下所示。In addition to the method of directly applying the photocurable thermosetting resin composition of the present invention to the substrate in a liquid form, the solder resist may be applied and dried in a film such as polyethylene terephthalate. The dry film of the formed solder resist layer is used in the form of a dry film. The case where the photocurable thermosetting resin composition of the present invention is used as a dry film is as follows.

乾式薄膜為具有以載體膜、防焊劑層、視必要所使用的可剝離之覆蓋薄膜的順序所層合之結構者。防焊劑層為，將鹼性顯像性光硬化性熱硬化性樹脂組成物塗佈於載體膜或覆蓋薄膜並乾燥所得之層。於載體膜形成防焊劑層後，將覆蓋薄膜層合其上、或於覆蓋薄膜形成防焊劑層，若將該層合體層合於載體膜即可得到乾式薄膜。The dry film is a structure having a structure in which a carrier film, a solder resist layer, and a peelable cover film used as necessary are laminated. The solder resist layer is a layer obtained by applying an alkali developable photocurable thermosetting resin composition to a carrier film or a cover film and drying the composition. After the solder resist layer is formed on the carrier film, the cover film is laminated thereon or a solder resist layer is formed on the cover film, and a dry film can be obtained by laminating the laminate on the carrier film.

作為載體膜，可使用2~150μm厚度之聚酯薄膜等熱可塑性薄膜。As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm can be used.

防焊劑層為，將鹼性顯像性光硬化性熱硬化性樹脂組成物以葉片塗佈、凸緣塗佈、雙輥筒塗佈、薄膜塗佈等於載體膜或覆蓋薄膜均勻塗佈至10~150μm的厚度並乾燥後形成。The solder resist layer is obtained by uniformly coating the alkaline developing photocurable thermosetting resin composition with blade coating, flange coating, double roll coating, and film coating equal to the carrier film or the cover film. It is formed by a thickness of ~150 μm and dried.

作為覆蓋薄膜，可使用聚乙烯薄膜、聚丙烯薄膜等，但與防焊劑層的接著力比載體膜還小者為佳。As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but the adhesion to the solder resist layer is preferably smaller than that of the carrier film.

使用乾式薄膜於印刷電路板上製作保護膜(永久保護膜)時，將覆蓋薄膜剝落，重疊防焊劑層與形成電路之基材，使用層合物等進行貼合，於形成電路之基材上形成防焊劑層。對於所形成之防焊劑層，與前述相同下進行曝光、顯像、加熱硬化，即可形成硬化被膜。載體膜於曝光前或曝光後之任一進行剝離即可。When a protective film (permanent protective film) is formed on a printed circuit board by using a dry film, the cover film is peeled off, and the solder resist layer and the substrate on which the circuit is formed are laminated, and laminated using a laminate or the like on the substrate on which the circuit is formed. A solder resist layer is formed. The formed solder resist layer is exposed, developed, and heat-cured in the same manner as described above to form a cured film. The carrier film may be peeled off before or after exposure.

[實施例][Examples]

以下表示實施例及比較例對本發明作具體說明，但本發明並未限定於下述實施例。且，以下中「份」及「%」中若無特別說明則全以質量作基準。The present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited to the following examples. In addition, unless otherwise stated in the following "parts" and "%", all are based on quality.

合成例1Synthesis Example 1

於具備溫度計、氮氣導入裝置兼伸烷基氧化物導入裝置及攪拌裝置的高壓蒸汽釜，裝入漆用酚醛型甲酚樹脂(昭和高分子(股)製，商品名「Shonol CRG951」、OH當量：119.4)119.4g、氫氧化鉀1.19g及甲苯119.4g，一邊攪拌一邊將系統內以氮氣取代，並加熱昇溫。其次，徐徐滴入環氧丙烷63.8g，於125~132℃、0~4.8kg/cm2 下進行16小時反應。其後，冷卻至室溫，於該反應溶液中添加89%磷酸1.56g並混合中和氫氧化鉀，得到不揮發部分62.1%，羥價為182.2g/eq.之漆用酚醛型甲酚樹脂的環氧丙烷反應溶液。此為每酚性羥基1當量下伸烷基氧化物為平均1.08莫耳所加成者。A high-pressure steam kettle equipped with a thermometer, a nitrogen gas introduction device, an alkyl oxide introduction device, and a stirring device, and a phenolic cresol resin (product of the Showa Polymer Co., Ltd., trade name "Shonol CRG951", OH equivalent) : 119.4) 119.4 g, 1.19 g of potassium hydroxide, and 119.4 g of toluene, and the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was slowly added dropwise, and the reaction was carried out for 16 hours at 125 to 132 ° C and 0 to 4.8 kg/cm 2 . Thereafter, the mixture was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to the reaction solution, and potassium hydroxide was mixed and neutralized to obtain a nonvolatile portion of 62.1%, and a phenolic phenolic cresol resin having a hydroxyl value of 182.2 g/eq. The propylene oxide reaction solution. This is an average of 1.08 moles per 1 equivalent of the alkylene oxide per phenolic hydroxyl group.

其次，將所得之漆用酚醛型甲酚樹脂的伸烷基氧化物反應溶液293.0g、丙烯酸43.2g、甲磺酸11.53g、甲基氫醌0.18g及甲苯252.9g裝入於具備攪拌機、溫度計及空氣吹入管的反應器，空氣以10ml/分鐘的速度吹入，並一邊攪拌一邊進行110℃之12小時反應。藉由反應所生成之水，作為與甲苯之共沸混合物，餾出12.6g之水。其後，冷卻至室溫，將所得之反應溶液以15%氫氧化鈉水溶液35.35g進行中和，其次進行水洗。其後，於蒸餾器將甲苯由二乙二醇單乙基醚乙酸酯118.1g取代並餾去，得到漆用酚醛型丙烯酸酯樹脂溶液。其次，將所得之漆用酚醛型丙烯酸酯樹脂溶液332.5g及三苯基膦1.22g，裝入於具備攪拌器、溫度計及空氣吹入管的反應器，將空氣以10ml/分鐘之速度吹入並一邊攪拌，一邊徐徐加入四氫苯二甲酸酐60.8g，在95~101℃進行6小時反應。得到固體物的酸價88mgKOH/g、不揮發部分71%的含有羧基之感光性樹脂的樹脂溶液。以下將此稱為清漆A-1。Next, the obtained lacquer was charged with 293.0 g of an alkylene oxide reaction solution of a phenolic cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone, and 252.9 g of toluene, which were equipped with a stirrer and a thermometer. The air was blown into the reactor of the tube, and air was blown at a rate of 10 ml/min, and the reaction was carried out at 110 ° C for 12 hours while stirring. Water formed by the reaction was distilled off as 12.00 g of water as an azeotropic mixture with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution, followed by water washing. Thereafter, toluene was replaced with 118.1 g of diethylene glycol monoethyl ether acetate in a distiller and distilled off to obtain a phenolic acrylate resin solution for lacquer. Next, 332.5 g of a phenolic acrylate resin solution and 1.22 g of triphenylphosphine were added to a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml/min. While stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added, and the reaction was carried out at 95 to 101 ° C for 6 hours. A resin solution of a carboxyl group-containing photosensitive resin having an acid value of 88 mg KOH/g of a solid matter and 71% of a nonvolatile portion was obtained. This is referred to as varnish A-1 hereinafter.

合成例2Synthesis Example 2

於具備溫度計、攪拌機及迴流冷卻器之5公升的可分離式燒瓶中，投入作無聚合物多元醇的聚己內酯二醇(Daicel化學工業(股)製PLACCEL208、分子量830)1,245g、作為具有羧基的二羥基化合物之二羥甲基丙酸201g、作為聚異氰酸酯之異佛爾酮二異氰酸酯777g及作為具有羥基的(甲基)丙烯酸酯之2-羥基乙基丙烯酸酯119g、進一步投入In a 5 liter separable flask equipped with a thermometer, a stirrer, and a reflux condenser, polycaprolactone diol (PLACCEL 208 manufactured by Daicel Chemical Industry Co., Ltd., molecular weight 830) of 1,5 g was used as a polymer-free polyol. 201 g of dimethylolpropionic acid having a carboxyl group, 777 g of isophorone diisocyanate as a polyisocyanate, and 119 g of 2-hydroxyethyl acrylate as a (meth) acrylate having a hydroxyl group, further input

p-甲氧基酚及二-t-丁基-羥基甲苯各0.5g。一邊攪拌一般加熱至60℃並停止，添加二丁基錫二桂酸鹽0.8g。反應容器內的溫度開始降低時再度加熱，以80℃繼續攪拌，以紅外線吸收光譜確認異氰酸酯基之吸收光譜(2280cm-1 )消失時為反應終了，得到黏稠液體之脲烷丙烯酸酯化合物。使用卡必醇乙酸酯調整至不揮發部分=50質量%。得到固體物之酸價47mgKOH/g、不揮發部分50%之具有羧基的脲烷(甲基)丙烯酸酯化合物之樹脂溶液。以下將此稱為清漆A-2。Each of p-methoxyphenol and di-t-butyl-hydroxytoluene was 0.5 g. While stirring, the mixture was heated to 60 ° C and stopped, and 0.8 g of dibutyltin dilaurate was added. When the temperature in the reaction vessel began to decrease, the temperature was again heated, and stirring was continued at 80 ° C. When the absorption spectrum of the isocyanate group (2280 cm -1 ) disappeared by the infrared absorption spectrum, the reaction was terminated to obtain a urethane acrylate compound of a viscous liquid. The carbitol acetate was adjusted to a nonvolatile portion = 50% by mass. A resin solution of a urethane (meth) acrylate compound having a carboxyl group of 47 mg KOH/g of a solid matter and 50% of a nonvolatile portion was obtained. This is referred to as varnish A-2 hereinafter.

合成例3Synthesis Example 3

於具備攪拌機、溫度計、還流冷卻器、滴定漏斗及氮氣導入管的2公升的可分離式燒瓶中，加入作為溶劑的二乙二醇二甲基醚900g、及作為聚合啟始劑的t-丁基過氧化2-乙基己酸酯(日油(股)製，商品名；PERBUTYL O)21.4g，並加熱至90℃。加熱後於此將甲基丙烯酸309.9g、甲基丙烯酸甲酯116.4g、及內酯改性2-羥基乙基甲基丙烯酸酯(PEROYL FM1：Daicel化學工業(股)製)109.8g與聚合啟始劑之雙(4-t-丁基環己基)過氧化二碳酸酯(日油(股)製，商品名；PEROYLTCP)21.4g同時花3小時滴入，且再進行6小時熟成，得到含有羧基之共聚合樹脂。且，反應於氮氣環境下進行。In a 2 liter separable flask equipped with a stirrer, a thermometer, a reflow cooler, a titration funnel, and a nitrogen introduction tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butyl as a polymerization initiator were added. Base 2-oxidized 2-ethylhexanoate (manufactured by Nippon Oil Co., Ltd., trade name; PERBUTYL O) 21.4 g, and heated to 90 °C. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (PEROYL FM1: manufactured by Daicel Chemical Industry Co., Ltd.) were polymerized. The bis(4-t-butylcyclohexyl)peroxydicarbonate (manufactured by Nippon Oil Co., Ltd., trade name; PEROYLTCP) 21.4 g was added dropwise for 3 hours, and further matured for 6 hours to obtain a copolymerized resin of a carboxyl group. Moreover, the reaction was carried out under a nitrogen atmosphere.

其次，於所得的含有羧基之共聚合樹脂加入3,4-環氧基環己基甲基丙烯酸酯(Daicel化學工業(股)製，商品名；cyclomerA200)363.9g、作為開環觸媒之二甲基苯甲胺3.6g、作為聚合抑制劑之氫醌單甲基醚1.80g，加熱至100℃，藉由攪拌進行環氧基之開環加成反應。16小時後，得到固體成分酸價為108.9mgKOH/g、重量平均分子量為25,000、固體成分54%之樹脂溶液。以下將此稱為清漆A-3。Next, 3,4-epoxycyclohexyl methacrylate (manufactured by Daicel Chemical Industry Co., Ltd., trade name; cyclomer A200), 363.9 g, was added as a ring-opening catalyst to the obtained carboxyl group-containing copolymer resin. 3.6 g of benzyl benzylamine and 1.80 g of hydroquinone monomethyl ether as a polymerization inhibitor were heated to 100 ° C, and a ring-opening addition reaction of an epoxy group was carried out by stirring. After 16 hours, a resin solution having a solid content of 108.9 mgKOH/g, a weight average molecular weight of 25,000, and a solid content of 54% was obtained. This is referred to as varnish A-3 hereinafter.

比較合成例1Comparative Synthesis Example 1

於二乙二醇單乙基醚乙酸酯600g裝入正甲酚漆用酚醛型環氧樹脂(DIC(股)製，EPICLON N-695，軟化點95℃，環氧基當量214，平均官能基數7.6)1070g(環氧丙基數(芳香環總數)：5.0莫耳)、丙烯酸360g(5.0莫耳)、及氫醌1.5g，於100℃加熱攪拌而均勻溶解。其次，裝入三苯基膦4.3g，於110℃加熱並進行2小時反應後，升溫至120℃再進行12小時反應。於所得之反應液中加入芳香族系烴(Solvesso 150)415g、四氫苯二甲酸酐456.0g(3.0莫耳)，在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%之樹脂溶液。以下將此稱為清漆R-1。600 g of diethylene glycol monoethyl ether acetate was charged with phenolic epoxy resin (made by DIC), EPICLON N-695, softening point 95 ° C, epoxy equivalent 214, average functionality Base 7.6) 1070 g (epoxypropyl number (total number of aromatic rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were uniformly stirred by heating and stirring at 100 °C. Next, 4.3 g of triphenylphosphine was charged, and the mixture was heated at 110 ° C for 2 hours, and then heated to 120 ° C for further 12 hours. 415 g of an aromatic hydrocarbon (Solvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added to the obtained reaction liquid, and the reaction was carried out at 110 ° C for 4 hours, and after cooling, a solid content acid value of 89 mgKOH/g was obtained. A resin solution containing 65% solids. This is referred to as varnish R-1 hereinafter.

比較合成例2Comparative Synthesis Example 2

裝入甲酚漆用酚醛型環氧樹脂(日本化藥(股)製，EOCN-104S、軟化點92℃，環氧基當量220)2200份、二羥甲基丙酸134份、丙烯酸648.5份、甲基氫醌4.6份、卡必醇乙酸酯1131份及溶劑石腦油484.9份，於90℃進行加熱攪拌，溶解反應混合物。其次，將反應液冷卻至60℃，裝入三苯基膦13.8份，於100℃加熱，並進行約32小時之反應，得到酸價為0.5mgKOH/g之反應物。其次，於此裝入四氫苯二甲酸酐364.7份、卡必醇乙酸酯137.5份及溶劑石腦油58.8份，於95℃進行加熱，並進行約6小時之反應後冷卻，得到固體成分酸價40mgKOH/g、不揮發部分65%的含有羧基之感光性樹脂的樹脂溶液。以下將此稱為清漆R-2。A phenolic epoxy resin (made by Nippon Chemical Co., Ltd., EOCN-104S, softening point 92 ° C, epoxy equivalent 220) 2200 parts, 134 parts of dimethylolpropionic acid, and 648.5 parts of acrylic acid were charged. 4.6 parts of methylhydroquinone, 1131 parts of carbitol acetate, and 484.9 parts of solvent naphtha were heated and stirred at 90 ° C to dissolve the reaction mixture. Next, the reaction liquid was cooled to 60 ° C, charged with 13.8 parts of triphenylphosphine, heated at 100 ° C, and reacted for about 32 hours to obtain a reactant having an acid value of 0.5 mg KOH / g. Next, 364.7 parts of tetrahydrophthalic anhydride, 137.5 parts of carbitol acetate, and 58.8 parts of solvent naphtha were charged, and the mixture was heated at 95 ° C, and reacted for about 6 hours, followed by cooling to obtain a solid component. A resin solution of a carboxyl group-containing photosensitive resin having an acid value of 40 mgKOH/g and a nonvolatile portion of 65%. This is referred to as varnish R-2 hereinafter.

比較合成例3Comparative Synthesis Example 3

將環氧基當量800、軟化點79℃的雙酚F型固型環氧樹脂400份溶解於環氧氯丙烷925份與二甲基亞碸462.5份後，攪拌下在70℃花100分鐘添加98.5%NaOH 81.2份。添加後再在70℃進行3小時反應。其次，將過剩的未反應環氧氯丙烷及二甲基亞碸之大半於減壓下餾去，將含有副生鹽與二甲基亞碸之反應生成物溶解於甲基異丁酮750份，且加入30%NaOH 10份，於70℃進行1小時反應。反應終了後，以水200份進行2次水洗。油水分離後，藉由油層蒸餾回收甲基異丁酮，得到環氧基當量290、軟化點62℃的環氧樹脂(a-1)370份。裝入所得之環氧樹脂(a-1)2900份(10當量)、丙烯酸720份(10當量)、甲基氫醌2.8份、卡必醇乙酸酯1950份，於90℃加熱並攪拌，溶解反應混合物。其次，將反應液冷卻至60℃，裝入三苯基膦16.7份，加熱至100℃，進行約32小時之反應，得到酸價為1.0mgKOH/g之反應物。其次於此裝入琥珀酸酐786份(7.86莫耳)、卡必醇乙酸酯423份，加熱至95℃，進行約6小時之反應，得到固體成分酸價100mgKOH/g、固體成分65%之樹脂溶液。以下將此稱為清漆R-3。400 parts of bisphenol F-type solid epoxy resin having an epoxy equivalent weight of 800 and a softening point of 79 ° C was dissolved in 925 parts of epichlorohydrin and 462.5 parts of dimethyl hydrazine, and then stirred at 70 ° C for 100 minutes with stirring. 98.5% NaOH 81.2 parts. After the addition, the reaction was carried out at 70 ° C for 3 hours. Next, most of the excess unreacted epichlorohydrin and dimethyl hydrazine are distilled off under reduced pressure, and the reaction product containing the by-product salt and dimethyl hydrazine is dissolved in 750 parts of methyl isobutyl ketone. And 10 parts of 30% NaOH was added, and the reaction was carried out at 70 ° C for 1 hour. After the completion of the reaction, the mixture was washed twice with 200 parts of water. After the oil-water separation, methyl isobutyl ketone was recovered by oil layer distillation to obtain 370 parts of an epoxy resin (a-1) having an epoxy group equivalent of 290 and a softening point of 62 °C. 2900 parts (10 equivalents) of the obtained epoxy resin (a-1), 720 parts (10 equivalents) of acrylic acid, 2.8 parts of methylhydroquinone, 1950 parts of carbitol acetate, and heated and stirred at 90 ° C, The reaction mixture was dissolved. Next, the reaction liquid was cooled to 60 ° C, and 16.7 parts of triphenylphosphine was charged, and the mixture was heated to 100 ° C to carry out a reaction for about 32 hours to obtain a reactant having an acid value of 1.0 mgKOH/g. Next, 786 parts (7.86 mol) of succinic anhydride and 423 parts of carbitol acetate were charged, and the mixture was heated to 95 ° C for about 6 hours to obtain a solid content acid value of 100 mgKOH/g and a solid content of 65%. Resin solution. This is hereinafter referred to as varnish R-3.

實施例1、2及比較例1~3Examples 1, 2 and Comparative Examples 1 to 3

使用上述各合成例所得之樹脂溶液，與下述表1所示種種成分同時以表1所示比率(質量份)進行調配，以攪拌機進行預混合後，以3根輥硏磨機進行混煉，調製出光硬化性熱硬化性樹脂組成物。將所得之光硬化性熱硬化性樹脂組成物以JPCA規格為準，藉由使用燒瓶燃燒處理離子層析法，定量鹵化物含有量(氯物與溴物之合計)。其結果合併於表1所示。The resin solution obtained by each of the above Synthesis Examples was blended with the various components shown in Table 1 below in the ratio (parts by mass) shown in Table 1, and premixed by a stirrer, followed by kneading by a three-roll honing machine. A photocurable thermosetting resin composition is prepared. The obtained photocurable thermosetting resin composition was subjected to flask combustion treatment ion chromatography to quantify the halide content (total of chlorine and bromine) in accordance with the JPCA specification. The results are combined in Table 1.

由上述表1所示結果可得知，使用未將環氧樹脂作為啟始原料的含有羧基之樹脂(A-1、A-2)的實施例1、2之光硬化性熱硬化性樹脂組成物，與使用將環氧樹脂作為啟始原料的含有羧基之感光性樹脂(R-1,R-2,R-3)的比較例1~3之光硬化性熱硬化性樹脂組成物相比較下，具有顯著較少鹵素量。As is apparent from the results shown in the above Table 1, the photocurable thermosetting resin of Examples 1 and 2 in which the carboxyl group-containing resin (A-1, A-2) was not used as the starting material of the epoxy resin was used. The photocurable thermosetting resin composition of Comparative Examples 1 to 3 using a carboxyl group-containing photosensitive resin (R-1, R-2, R-3) using an epoxy resin as a starting material was compared. Below, there is a significantly lower amount of halogen.

實施例3~10及比較例4~6Examples 3 to 10 and Comparative Examples 4 to 6

使用上述合成例之樹脂溶液，與下述表2所示種種成分同時以表2所示比率(質量份)進行調配，並以攪拌機進行預混合後，以3根輥硏磨機進行混煉，調製出防焊劑用感光性樹脂組成物。其此將所得之感光性樹脂組成物的分散度藉由Eriksen公司製粒度測定器進行粒度測定並評估後得知15μm以下。The resin solution of the above-mentioned synthesis example was mixed with the various components shown in the following Table 2 in the ratio (parts by mass) shown in Table 2, and premixed by a stirrer, followed by kneading by a three-roll honing machine. A photosensitive resin composition for a solder resist is prepared. The degree of dispersion of the obtained photosensitive resin composition was measured by particle size measurement by a particle size analyzer manufactured by Eriksen Co., Ltd., and it was found to be 15 μm or less.

性能評估：Performance evaluation:

<最適曝光量><Optimum exposure amount>

將銅厚18μm的電路圖型基板經銅表面粗化處理(Mec(股)製MECetchBONDCZ-8100)後再經水洗並乾燥後，將前述實施例及比較例的光硬化性熱硬化性樹脂組成物藉由網版印刷法進行全面塗佈，在80℃的熱風循環式乾燥爐進行60分鐘乾燥。乾燥後，使用具備高壓水銀燈的曝光裝置介著Step Tablet(Kodak No.2)進行曝光，將顯像(30℃，0.2MPa，1wt%碳酸鈉水溶液)進行60秒時，所殘存的Step Tablet之圖型為7段時作為最適曝光量。The circuit pattern substrate having a copper thickness of 18 μm was subjected to roughening treatment on a copper surface (MECetchBONDCZ-8100 manufactured by Mec Co., Ltd.), washed with water, and dried, and then the photocurable thermosetting resin composition of the above examples and comparative examples was borrowed. It was completely coated by a screen printing method, and dried in a hot air circulating drying oven at 80 ° C for 60 minutes. After drying, the exposure was carried out by a stepping apparatus (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp, and the remaining Step Tablet was carried out by performing development (30 ° C, 0.2 MPa, 1 wt% aqueous sodium carbonate solution) for 60 seconds. The optimum exposure is when the pattern is 7 segments.

<顯像性><developmentality>

將前述實施例及比較例的光硬化性熱硬化性樹脂組成物，於貼銅基板上藉由網版印刷法進行塗佈至乾燥後膜厚為約25μm，在80℃之熱風循環式乾燥爐進行30分鐘乾燥。乾燥後藉由1wt%碳酸鈉水溶液進行顯像，以計時器計算至除去乾燥被膜之時間。The photocurable thermosetting resin composition of the above examples and comparative examples was applied to a copper-clad substrate by a screen printing method to a hot air circulating drying oven having a film thickness of about 25 μm after drying at 80 ° C. Dry for 30 minutes. After drying, development was carried out by using a 1 wt% aqueous solution of sodium carbonate, and the time until the dried film was removed was counted by a timer.

<最大顯像生命><Maximum imaging life>

將前述實施例及比較例之組成物於經圖型形成的銅箔基板上以網版印刷進行全面塗佈，在80℃下乾燥並自20分鐘至80分鐘間，每隔10分鐘取出基板，冷卻至室溫。於該基板將30℃之1wt%碳酸鈉水溶液以噴霧壓0.2MPa的條件下進行60秒顯像，將不會留下殘渣之最大容許乾燥時間作為最大顯像生命。The compositions of the foregoing examples and comparative examples were completely coated by screen printing on a copper foil substrate formed by the pattern, dried at 80 ° C, and the substrate was taken out every 10 minutes from 20 minutes to 80 minutes. Cool to room temperature. On the substrate, a 1 wt% sodium carbonate aqueous solution at 30 ° C was developed under a spray pressure of 0.2 MPa for 60 seconds, and the maximum allowable drying time without leaving a residue was taken as the maximum development life.

<黏著性><adhesiveness>

將前述實施例及比較例的組成物於經圖型形成的銅箔基板上以網版印刷進行全面塗佈，在80℃之熱風循環式乾燥爐進行30分鐘乾燥，冷卻至室溫。於該基板上將PET製負型薄膜，以ORC公司製HMW-GW20於1分鐘減壓條件下進行壓著，其後，將剝開負型薄膜時的薄膜貼附狀態以以下基準進行評估。The compositions of the above examples and comparative examples were completely coated by screen printing on a copper foil substrate formed by the pattern, dried in a hot air circulating drying oven at 80 ° C for 30 minutes, and cooled to room temperature. On the substrate, a negative film made of PET was pressed under reduced pressure of HMW-GW20 manufactured by ORC Co., Ltd. under reduced pressure for 1 minute, and then the state of film sticking when the negative film was peeled off was evaluated on the following basis.

○：剝開薄膜時，完全無抵抗，且於被膜上無留下痕跡。○: When the film was peeled off, it was completely resistant, and no trace was left on the film.

△：剝開薄膜時，僅稍有抵抗，於被膜上稍留下痕跡。△: When the film was peeled off, it was only slightly resistant, leaving a slight trace on the film.

×：剝開薄膜時，有抵抗，且於被膜有明顯的痕跡。×: When the film is peeled off, it is resistant and has obvious marks on the film.

特性試驗：Characteristic test:

將前述實施例及比較例的組成物於經圖型形成的銅箔基板上以網版印刷進行全面塗佈，在80℃進行30分鐘乾燥，冷卻至室溫。於該基板使用具備高壓水銀燈之曝光裝置以最適曝光量將防焊劑圖型進行曝光，將30℃的1wt%碳酸鈉水溶液在噴霧壓0.2MPa之條件下進行90秒顯像，得到光阻圖型。將該基板於UV輸送爐以積算曝光量1000mJ/cm2 的條件下進行紫外線照射後，在130℃進行60分鐘，其次在150℃進行30分鐘加熱並使其硬化。對於所得之印刷基板(評估基板)評估如以下之特性。The compositions of the above examples and comparative examples were completely coated by screen printing on a copper foil substrate formed by the pattern, dried at 80 ° C for 30 minutes, and cooled to room temperature. The substrate was exposed to an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp, and a 1 wt% sodium carbonate aqueous solution at 30 ° C was developed under a spray pressure of 0.2 MPa for 90 seconds to obtain a photoresist pattern. . The substrate was subjected to ultraviolet irradiation under the conditions of an integrated exposure amount of 1000 mJ/cm 2 in a UV transfer furnace, and then heated at 130 ° C for 60 minutes, and then heated at 150 ° C for 30 minutes to be cured. The following characteristics were evaluated for the obtained printed substrate (evaluation substrate).

<耐酸性><acid resistance>

將評估基板於10vol%H2 SO4 水溶液並在室溫下浸漬30分鐘，浸透性或被膜的溶離由目視確認，且藉由剝離膠帶確定剝落。The substrate was evaluated in a 10 vol% H 2 SO 4 aqueous solution and immersed at room temperature for 30 minutes, and the permeability or dissolution of the film was visually confirmed, and peeling was confirmed by a release tape.

○：並未確認到變化者○: No change was confirmed

△：稍有變化者△: slightly changed

×：於被膜上有膨脹或膨潤脫落者×: There is swelling or swelling on the film.

<耐鹼性><Alkaline resistance>

將評估基板於10vol%NaOH水溶液並在室溫下浸漬30分鐘，浸透性或被膜的溶離由目視確認，且藉由剝離膠帶確定剝落。The evaluation substrate was immersed in a 10 vol% aqueous NaOH solution and immersed at room temperature for 30 minutes, and the permeability or dissolution of the film was visually confirmed, and peeling was confirmed by a release tape.

○：並未確認到變化者○: No change was confirmed

△：稍有變化者△: slightly changed

×：於被膜上有膨脹或膨潤脫落者×: There is swelling or swelling on the film.

<焊接耐熱性><Welding heat resistance>

將塗佈松香系助熔劑的評估基板，浸漬於預先設定為260℃的焊接槽，再以改性醇洗淨助熔劑後，藉由目視對於光阻層的膨脹‧剝落進行評估。判定基準如以下所示。The evaluation substrate coated with the rosin-based flux was immersed in a solder bath set at 260 ° C in advance, and the flux was washed with a modified alcohol, and then the expansion and flaking of the photoresist layer were visually evaluated. The judgment criteria are as follows.

○：即使重複進行3次以上的10秒浸漬，亦無確認出剝落。○: No peeling was observed even if the immersion was repeated three or more times for 10 seconds.

△：重複進行3次以上的10秒浸漬時稍有剝落。△: When peeling was repeated three times or more for 10 seconds, it was slightly peeled off.

×：進行3次以內的10秒浸漬時，於光阻層確認出膨脹、剝落。X: When immersed for 10 seconds within 3 times, expansion and peeling were confirmed in the photoresist layer.

<耐無電解鍍金性><electroless gold plating resistance>

使用販賣品之無電解鎳鍍敷浴及無電解鍍金浴，以鎳5μm、金0.05μm之條件下進行鍍敷，藉由剝離膠帶評估光阻層之剝落有無或鍍敷的浸透之有無後，藉由剝離膠帶評估光阻層的剝落有無。判定基準如以下所示。Using an electroless nickel plating bath and an electroless gold plating bath of a commercial product, plating was carried out under the conditions of nickel 5 μm and gold 0.05 μm, and the presence or absence of peeling of the photoresist layer or the presence or absence of plating penetration was evaluated by a release tape. The peeling of the photoresist layer was evaluated by a peeling tape. The judgment criteria are as follows.

◎：浸透且無剝落。◎: soaked and not peeled off.

○：鍍敷後雖確認稍有浸透，但剝離膠帶後並無剝落。○: Although it was confirmed that it was slightly saturated after plating, it did not peel off after peeling off the tape.

△：鍍敷後僅稍有見到浸透，剝離膠帶後亦見到剝落。△: Only a slight penetration was observed after plating, and peeling was also observed after peeling off the tape.

×：鍍敷後有剝落。×: Peeling after plating.

<PCT耐性><PCT tolerance>

將形成防焊劑硬化被膜之評估基板，使用PCT裝置(Espec(股)製HAST SYSTEM TPC-412MD)，在121℃、飽和、0.2MPa之條件下進行168小時處理，評估被膜之狀態。判定基準如以下。The evaluation substrate on which the solder resist hardening film was formed was subjected to treatment for 168 hours under conditions of 121 ° C, saturation, and 0.2 MPa using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by Espec Co., Ltd.) to evaluate the state of the film. The criterion is as follows.

○：無膨脹、剝落、變色、溶離者○: no swelling, peeling, discoloration, dissolving

△：稍有膨脹、剝落、變色、溶離者△: slightly expanded, peeled off, discolored, dissolved

×：見到多數膨脹、剝落、變色、溶離者×: Most people who see swelling, flaking, discoloration, and dissolving

<HAST特性><HAST characteristics>

於形成梳型電極(線/空間=20μ/20μ)之BT基板，形成防焊劑硬化被膜，作重評估基板。將該評估基板放入130℃、濕度85%的環境下之高溫高濕槽，加入電壓12V之電荷，進行168小時，槽內HAST試驗。經168小時後的槽內絕緣電阻值依據下述判斷基準進行評估。A BT substrate on which a comb-shaped electrode (line/space = 20 μ/20 μ) was formed, and a solder resist hardening film was formed to evaluate the substrate. The evaluation substrate was placed in a high-temperature and high-humidity bath at 130 ° C and a humidity of 85%, and a charge of 12 V was applied thereto for 168 hours in a tank HAST test. The insulation resistance value in the tank after 168 hours was evaluated in accordance with the following criteria.

○：108 Ω以上○: 10 8 Ω or more

△：106 ~108 Ω△: 10 6 ~ 10 8 Ω

×：106 Ω以下×: 10 6 Ω or less

實施例11~15及比較例7~9Examples 11 to 15 and Comparative Examples 7 to 9

將以表2所示調配比率所調製之實施例4、7、8、9、10及比較例4、5、6的各組成物以甲基乙酮進行稀釋，塗佈於PET薄膜上，並以80℃進行30分鐘乾燥，形成厚度20μm之感光性樹脂組成物層。再於其上貼上覆蓋薄膜製作出乾式薄膜，將各作為實施例11~15及比較例7~9。Each of the compositions of Examples 4, 7, 8, 9, 10 and Comparative Examples 4, 5, and 6 prepared at the mixing ratio shown in Table 2 was diluted with methyl ethyl ketone and applied to a PET film, and The film was dried at 80 ° C for 30 minutes to form a photosensitive resin composition layer having a thickness of 20 μm. Further, a cover film was attached thereto to prepare a dry film, and each of them was used as Examples 11 to 15 and Comparative Examples 7 to 9.

<乾式薄膜評估><Dry film evaluation>

由如上述所得之乾式薄膜剝落覆蓋薄膜，於經圖型形成之銅箔基板上，熱層合薄膜，再於與前述實施例的被膜特性評估所使用的基板同様條件下進行曝光。曝光後剝落載體膜，將30℃的1wt%碳酸鈉水溶液以噴霧壓0.2MPa的條件進行90秒顯像，得到光阻圖型。將該基板以UV輸送爐於積算曝光量1000mJ/cm2 的條件下進行紫外線照射後，進行在130℃之60分鐘，其次在150℃之30分鐘加熱並硬化。對於具有所得之硬化被膜的試驗基板，以前述試驗方法及評估方法進行各特性之評估試驗。結果如表4所示。The film was peeled off from the dry film obtained as described above, and the film was thermally laminated on the copper foil substrate formed by the pattern, and exposed to the same conditions as those used in the evaluation of the film properties of the foregoing examples. After the exposure, the carrier film was peeled off, and a 1 wt% sodium carbonate aqueous solution at 30 ° C was developed under the conditions of a spray pressure of 0.2 MPa for 90 seconds to obtain a photoresist pattern. The substrate was subjected to ultraviolet irradiation under the conditions of an integrated exposure amount of 1000 mJ/cm 2 in a UV transfer furnace, and then heated at 130 ° C for 60 minutes, and then heated and cured at 150 ° C for 30 minutes. For the test substrate having the obtained hardened film, an evaluation test of each characteristic was carried out by the aforementioned test method and evaluation method. The results are shown in Table 4.

由前述表3及表4所示結果可得知，本發明的光硬化性熱硬化性樹脂組成物適用於作為兼具半導體封包用防焊劑所必要的無電解鍍金耐性、PCT耐性、HAST特性(電氣特性)之光硬化性熱硬化性樹脂組成物。As can be seen from the results shown in the above Tables 3 and 4, the photocurable thermosetting resin composition of the present invention is suitable for use as an electroless gold plating resistance, PCT resistance, and HAST characteristic which are required for a solder paste for semiconductor encapsulation ( A photocurable thermosetting resin composition having electrical properties).

Claims (10)

一種光硬化性熱硬化性樹脂組成物，其可藉由稀鹼水溶液進行顯像，其特徵為含有(A)含有羧基之樹脂(但，將環氧樹脂作為啟始原料之含有羧基之樹脂除外)、(B)光聚合啟始劑、(C)具有烷氧基甲基之胺基樹脂、(D)具有環狀醚結構及/或環狀硫醚結構之熱硬化性成分；前述(A)含有羧基之樹脂為(1)使1分子中具有2個以上酚性羥基之化合物、與伸烷基氧化物進行反應所得之反應生成物，再與含有不飽和基之單羧酸進行反應，使所得之反應生成物與多元酸酐進行反應所得之含有羧基之感光性樹脂；(2)使1分子中具有2個以上酚性羥基之化合物與環狀碳酸酯化合物進行反應所得之反應生成物，再與含有不飽和基之單羧酸進行反應，使所得之反應生成物與多元酸酐進行反應所得之含有羧基之感光性樹脂；(3)二異氰酸酯化合物，與在二醇化合物藉由聚加成反應而成之脲烷樹脂之末端上使酸酐進行反應所成之末端含有羧基之脲烷樹脂；(4)在二異氰酸酯、含有羧基之二醇化合物、與二醇化合物藉由聚加成反應而成之含有羧基之脲烷樹脂的合成中，加入分子中具有1個羥基與1個以上之(甲基)丙 烯醯基的化合物，而末端經(甲基)丙烯酸化之含有羧基之脲烷樹脂；(5)在二異氰酸酯、含有羧基之二醇化合物、與二醇化合物藉由聚加成反應而成之含有羧基之脲烷樹脂的合成中，加入分子中具有1個異氰酸酯基與1個以上的(甲基)丙烯醯基之化合物，而末端經(甲基)丙烯酸化之含有羧基之脲烷樹脂。 (6)藉由不飽和羧酸與不飽和基含有化合物之共聚合所得之含有羧基之樹脂；(7)使氧雜環丁烷樹脂與二羧酸進行反應，於所生成之1級羥基中加成2元酸酐而成之含有羧基之聚酯樹脂中，再加成1分子中具有1個環氧基與1個以上之(甲基)丙烯醯基之化合物而成之含有羧基之感光性樹脂；或(8)於前述(1)~(7)之含有羧基之樹脂中，加成1分子中具有環狀醚基與(甲基)丙烯醯基之化合物而成之含有羧基之感光性樹脂。 A photocurable thermosetting resin composition which can be imaged by a dilute aqueous alkali solution and which is characterized by containing (A) a carboxyl group-containing resin (except for a carboxyl group-containing resin which uses an epoxy resin as a starting material) And (B) a photopolymerization initiator, (C) an amino group-containing resin having an alkoxymethyl group, (D) a thermosetting component having a cyclic ether structure and/or a cyclic thioether structure; The resin containing a carboxyl group is (1) a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with an alkylene oxide, and then reacting with a monocarboxylic acid containing an unsaturated group. a photosensitive resin containing a carboxyl group obtained by reacting the obtained reaction product with a polybasic acid anhydride, and (2) a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound, a photosensitive resin containing a carboxyl group obtained by reacting a monocarboxylic acid containing an unsaturated group to obtain a reaction product obtained by reacting the obtained reaction product with a polybasic acid anhydride; (3) a diisocyanate compound, and a polyaddition compound in the diol compound Urea a urethane resin having a carboxyl group at the end of the resin at the end of the resin; (4) a urea containing a carboxyl group in a diisocyanate, a diol compound containing a carboxyl group, and a diol compound by a polyaddition reaction In the synthesis of an alkane resin, a hydroxyl group and one or more (meth) propyl groups are added to the molecule. a compound containing an olefin group and a (meth)acrylated carboxyl group-containing urethane resin; (5) a diisocyanate, a carboxyl group-containing diol compound, and a diol compound by polyaddition reaction In the synthesis of a urethane resin containing a carboxyl group, a compound having one isocyanate group and one or more (meth)acryl fluorenyl groups in the molecule and a carboxyl group-containing urethane resin having a terminal (meth) acrylated end are added. (6) a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid and an unsaturated group-containing compound; (7) reacting an oxetane resin with a dicarboxylic acid to form a first-order hydroxyl group Photosensitive property of a carboxyl group-containing polyester resin obtained by adding a two-membered acid anhydride to a compound having one epoxy group and one or more (meth)acryl fluorenyl groups in one molecule (8) Photosensitive property of a carboxyl group-containing resin having a cyclic ether group and a (meth)acryl fluorenyl group in one molecule of the resin containing a carboxyl group in the above (1) to (7) Resin. 如申請專利範圍第1項之光硬化性熱硬化性樹脂組成物，其中前述含有羧基之樹脂(A)為未含有羥基者。 The photocurable thermosetting resin composition according to claim 1, wherein the carboxyl group-containing resin (A) is a hydroxyl group-free resin. 如申請專利範圍第1項之光硬化性熱硬化性樹脂組成物，其中前述含有羧基之樹脂(A)為具有乙烯性不飽和雙鍵者。 The photocurable thermosetting resin composition according to claim 1, wherein the carboxyl group-containing resin (A) is an ethylenically unsaturated double bond. 如申請專利範圍第1項之光硬化性熱硬化性樹脂組成物，其為進一步含有著色劑(G)且使用於防焊劑用途上者。 The photocurable thermosetting resin composition of claim 1 which further contains a coloring agent (G) and is used for a solder resist application. 一種乾式薄膜，其特徵為具有將前述如申請專利範圍第1項至第4項中任一項之光硬化性熱硬化性樹脂組成物塗佈於載體膜並乾燥所得之前述光硬化性熱硬化性的乾燥被膜者。 A dry film comprising the photocurable thermosetting resin composition according to any one of claims 1 to 4, which is applied to a carrier film and dried to obtain the photocurable thermosetting. Sexual dry film. 一種光硬化性熱硬化性樹脂組成物之硬化物，其特徵為將前述如申請專利範圍第1項至第4項中任一項之光硬化性熱硬化性樹脂組成物經光硬化所得者。 A cured product of a photocurable thermosetting resin composition, which is obtained by photocuring the photocurable thermosetting resin composition according to any one of claims 1 to 4 above. 一種光硬化性熱硬化性樹脂組成物之硬化物，其特徵為將前述如申請專利範圍第5項之乾式薄膜之乾燥被膜經光硬化所得者。 A cured product of a photocurable thermosetting resin composition, which is obtained by photohardening a dried film of the dry film of the fifth aspect of the patent application. 如申請專利範圍第6項或第7項之硬化物，其為以波長350nm~410nm的光源進行光硬化成圖型狀而得者。 A cured product of the sixth or seventh aspect of the patent application is obtained by photohardening a light source having a wavelength of 350 nm to 410 nm. 一種印刷電路板，其特徵為具有將前述如申請專利範圍第1項至第4項中任一項之光硬化性熱硬化性樹脂組成物以紫外線的直接描繪進行光硬化成圖型狀後，進行熱硬化所得之硬化被膜者。 A printed circuit board characterized in that the photocurable thermosetting resin composition according to any one of the first to fourth aspects of the invention is photohardened into a pattern by direct drawing of ultraviolet rays. A hardened film obtained by thermal hardening. 一種印刷電路板，其特徵為具有將前述如申請專利範圍第5項之乾式薄膜之乾燥被膜以紫外線的直接描繪進行光硬化成圖型狀後，進行熱硬化所得之硬化被膜者。A printed circuit board comprising a cured film obtained by thermally curing a dried film of the dry film of the fifth aspect of the invention, which is photohardened by direct drawing of ultraviolet rays.
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