TWI357434B - - Google Patents

Description

1357434 Ο) 九、發明說明 【發明所屬之技術領域】 本發明係有關一種製造印刷配線板時有用的光硬化 性·熱硬化性樹脂組成物，更詳言之，係有關具有經時安 定性優異的塗覆性，且耐熱性·密接性.電氣特性優異的 刷配線板用光硬化性•熱硬化性組成物，及使用其之印刷 配線板。 【先前技術】 由於最近半導體零件急速進步，故有電子機器小型輕 量化、高性能化、多功能化的傾向，伴隨此等要求進行印 刷配線板之高密度化。該印刷配線板所使用的阻焊劑，係 使用以紫外線圖案曝光、顯像以形成畫像，且以熱及光照 射加工硬化（本硬化）的液狀顯像型阻焊劑。此外，就考慮 環境問題而言，以使用稀鹼水溶液之鹼顯像型液狀阻焊劑 作爲顯像液（例如專利文獻])爲主流。 該液狀阻焊劑，係在印刷配線板上藉由篩網印刷法、 簾幕塗覆法、噴霧塗覆法、輥塗覆法等全面塗覆光阻劑， 且爲使可接觸曝光時進行使有機溶劑揮發之假乾燥，然 後，曝光•顯像形成圖案，予以熱硬化，製得耐熱性•電 絕緣性優異的硬化塗膜。 然而，液狀阻焊劑對印刷配線板之塗覆性，會有經時 變化的問題。藉由該塗覆性之變化’銅箔端部變薄，電鍍 或焊接時產生剝落’引起外觀不佳情形。 -4 - v-> (2) (2)1357434 —般而言，塗覆性可藉由配合二氧化矽、硫酸鋇、滑 石等之無機塡充劑或超微粉二氧化矽、有機皂土、蠟類等 之觸變性賦予劑（例如專利文獻2)予以調整。然而，無機 塡充劑或超微粉二氧化矽，與有機溶劑或樹脂之親和性會 經時提高，且觸變性（以下稱爲觸變性）降低的問題。另 外’有機皂土雖經時變化情形少，惟多量使用時會有電絕 緣性降低的問題。此外，蠟類亦有含二甲苯等之有害有機 溶劑的問題。 [專利文獻1]日本特開平1-141904號公報（申請專利 範圍） [專利文獻2 ]日本特開2 0 0 3 - 9 6 3 6 8號公報（申請專利 範圍） 【發明內容】 因此’本發明係爲解決習知技術具有的上述問題者， 其主要目的係提供一種對篩網印刷法、簾幕塗覆法、噴霧 塗覆法 '輥塗覆法等而言，具有經時安定性的塗覆性，且 耐熱性•密接性.電絕緣性優異的印刷配線板用光硬化 性·熱硬化性組成物，及使用其之印刷配線板。 另外’提供一種可減少造成環境污染原因之有害物質 的光硬化性*熱硬化性組成物。 本發明人等爲達成上述目的’再三深入硏究檢討的結 果’發現在含有（A) —分子中具有1個以上羧基之含羧基 樹脂' (B)光聚合起始劑、（D)稀釋劑' (E)塡充劑 '及（F) (3) (3)1357434 環氧樹脂之組成物中，配合（C)聚羥基羧酸酯系添加劑之 光硬化性·熱硬化性樹脂組成物，對篩網印刷法、簾幕塗 覆法 '噴霧塗覆法、輥塗覆法等而言，具有經時安定性之 塗覆性’且不會使耐熱性.密接性·電絕緣性等降低，遂 而完成本發明。 另外’發現上述（C)聚羥基羧酸酯系添加劑，沒有使 用二甲苯等有害的有機溶劑之必要性。 [發明效果] 本發明之光硬化性•熱硬化性組成物，對篩網印刷 法、簾幕塗覆法、噴霧塗覆法、輥塗覆法等而言，具有經 時安定性之塗覆性，且於製造印刷配線板時之電鍍處理時 或焊接時可防止塗膜剝落的不良品或塗膜下垂之外觀不良 品等情形，以及可在沒有含環境污染原因之有害有機溶劑 的揮發性有機化合物（VOC)下予以油墨化。 而且，由於具有經時安定的塗覆性，故可大量生產本 發明之光硬化性·熱硬化性樹脂組成物，降低成本。此 外’對降低製造印刷配線板時之不良率極有貢獻，且可使 製品低價格化。 [爲實施發明之最佳形態] 本發明之光硬化性·熱硬化性樹脂組成物的基本形 態’係提供一種光硬化性·熱硬化性樹脂組成物，其特徵 爲含有（A) —分子中具有1個以上羧基之含羧基樹脂、（B) -6 - (4) (4)1357434 光聚合起始劑、（C)聚羥基羧酸酯系添加劑、（D)稀釋劑、 (E)塡充劑、及（F)環氧樹脂。較佳的形態係提供一種組成 物’其特徵爲上述（C)聚羥基羧酸酯系添加劑不含二甲苯 (以下簡稱爲無二甲苯）之添加劑。而且，提供一種組成 物，其特徵爲上述光硬化性·熱硬化性樹脂組成物另含有 (G)非鹵素系有機顏料。 此外’另一形態係提供一種印刷配線板，其特徵爲使 上述光硬化性·熱硬化性樹脂組成物具有藉由活性能量線 照射及/或加熱 '硬化所得的阻焊層及/或樹脂絕緣層。 於下述中，詳細說明有關本發明之光硬化性.熱硬化 性樹脂組成物之各構成成份。 首先，在上述（A)—分子中含有1個以上羧基之含羧 基樹脂’可使用具有殘基之樹脂，具體而言可使用（A，）本 身具有乙烯性不飽和雙鍵之含羧基的感光性樹脂及（A)不 含乙烯性不飽和雙鍵之含羧基的樹脂，沒有特別限制，惟 以使用下述列舉的樹脂（可爲寡聚物及聚合物）較佳。 (1) 藉由不飽和孩酸與具有不飽和雙鍵之化合物共聚 合，製得的含羧基之樹脂， (2) 藉由在不飽和殘酸與具有不飽和雙鍵之化合物的 共聚物中加成作爲側基之乙綠性不飽和基（例如加成甲基 丙烯酸環氧丙酯），製得的含羧基之感光性樹脂， (3) 藉由在一分子中具有環氧基與不飽和雙鍵之化合 物及具有不飽和雙鍵之化合物的共聚物中，使不飽和單较 酸反應，在生成的二級羧基中使飽和或不飽和多元酸野反 (5) (5)1357434 應’製得的含羧基之感光性樹脂， (4) 在具有不飽和雙鍵之酸酐，與具有其他不飽和雙 鍵的化合物之共聚物中，使在一分子中具有羧基與不飽和 雙鍵之化合物反應，製得的含羧基之感光性樹脂， (5) 使多官能環氧化合物與不飽和單羧酸反應，在生 成的羧基中使飽和或不飽和多元酸野反應，製得的含羧基 之感光性樹脂， (6) 在含羧基之聚合物中使飽和或不飽和多元酸酐反 應後，在生成的羧酸中使一分子中具有環氧基與不飽和雙 鍵之化合物反應’製得的含羥基及羧基之感光性樹脂， (7) 在多官能環氧化合物、與不飽和單羧酸、與在一 分子中至少具有1個醇性羥基、及具有1個除與環氧基反 應的醇性羥基以外之反應性基的反應生成物中，使飽和或 不飽和多元酸酐反應製得的含羧基之感光性樹脂， (8) 對在一分子中至少具有2個氧雜環丁烷環之多官 能氧雜環丁烷化合物中使不飽和單羧酸反應所得的改性氧 雜環丁烷樹脂中之一級羥基而言，使飽和或不飽和多元酸 酐反應製得的含羧基之感光性樹脂等。 於此等之中，以在一分子中具有2個以上感光性不飽 和雙鍵的含羧基之感光性樹脂，尤以上述（5)含羧基之感 光性樹脂較佳。 上述（A)含羧基之樹脂，由於主鍵（backbone) ·聚合物 之側鏈上具有多數游離的羧基’故可藉由稀鹼水溶液顯 像。 -8- (6) (6)1357434 此外，上述（A)含羧基之樹脂的酸價爲4〇〜 200mgKOH/g，較佳者爲45〜120mgKOH/g。含羧基之樹 脂的酸價小於40mgKOH/g時不容易鹸顯像，另外’大於 200mgKOH/g時由於藉由顯像進行曝光部之溶解’致使線 條較必要以上者爲細，視其所需在沒有區別曝光部與未曝 光部下以顯像液溶解剝離，不易描繪正常的光阻圖案，故 不爲企求。 該（A)含羧基之樹脂的配合量，在全部組成物中爲20 〜60質量％，較佳者爲30〜50質量％。小於上述範圔 時，塗膜強度降低，不爲企求。另外，大於上述範圍時， 黏性增尚且印刷性等降低，不爲企求。 本發明所使用的（B)光聚合起始劑，例如有苯偶因、 苯偶因甲醚、苯偶因***、苯偶因異丙醚等之苯偶因與苯 偶因烷醚類；苯乙酮、2，2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2 -苯基苯乙酮、2,2 -二乙氧基-2-苯基苯乙酮、 ]sl -二氯化苯乙酮等之苯乙酮類；2·甲基(甲基硫化） 苯基]-2 -嗎啉基丙_〗·酮' 2-苯甲基-2-二甲基胺基-1-(4 -嗎 啉基苯基）· 丁酮-1等之胺基苯乙酮類；2_甲基蒽醌、2_乙 基蒽醌、2-第3· 丁基蒽醌、]_氯化蒽醌等之蒽醌類：κ —甲基噻噸酮、2-二乙基噻噸酮、2 -氯化噻噸酮、2,4-—異丙基噻噸酮等之噻噸酮類；苯乙酮二甲縮醒' 苯甲基 —甲基縮醛等之縮醛類；二苯甲酮等之二苯甲酮類；或咕 D頓酮類；（2,6_二甲氧基苯甲醯基）_2,4:4_戊基氧化膦、雙 (2,4:6 -二甲基苯甲醯基）_苯基氧化膦、2:4,6三甲基苯甲 (7) 13574341357434 Ο 发明 发明 发明 发明 【 【 【 【 【 【 【 【 【 【 【 【 【 【 本 本 】 本 本 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 The coating property, the heat resistance, the adhesion, the photocurability of the brush wiring board which is excellent in electrical characteristics, the thermosetting composition, and the printed wiring board using the same. [Prior Art] Due to the rapid advancement of semiconductor components, there is a tendency for electronic devices to be smaller, lighter, higher-performance, and more versatile, and the demand for higher density of printed wiring boards is required. The solder resist used in the printed wiring board is a liquid developing type solder resist which is exposed to an ultraviolet pattern and developed to form an image, and is hardened by heat and light (this hardening). Further, in consideration of environmental problems, an alkali-developing liquid solder resist using a dilute aqueous alkali solution is mainly used as a developing liquid (for example, Patent Document). The liquid solder resist is coated on the printed wiring board by a screen printing method, a curtain coating method, a spray coating method, a roll coating method, etc., and is used for contact exposure. The organic solvent is volatilized and dried, and then exposed and developed to form a pattern, which is thermally cured to obtain a cured film excellent in heat resistance and electrical insulation. However, the coating property of the liquid solder resist on the printed wiring board may have a problem of changing with time. By the change in the coating property, the end portion of the copper foil is thinned, and peeling occurs during plating or welding, resulting in a poor appearance. -2 - v-> (2) (2) 1357434 In general, the coating property can be combined with an inorganic chelating agent such as cerium oxide, barium sulfate, talc or ultrafine powder of cerium oxide or organic bentonite. A thixotropy-imparting agent such as wax or the like (for example, Patent Document 2) is adjusted. However, the affinity of the inorganic chelating agent or the ultrafine powder cerium oxide with an organic solvent or a resin may be improved over time, and the thixotropy (hereinafter referred to as thixotropic) is lowered. In addition, although the organic bentonite has little change with time, there is a problem that the electrical insulation is lowered when used in a large amount. In addition, waxes also have problems with harmful organic solvents such as xylene. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The invention aims to solve the above problems of the prior art, and its main object is to provide a time-dependent stability for a screen printing method, a curtain coating method, a spray coating method, a roll coating method, and the like. Coating property, heat resistance, adhesion, photocurability and thermosetting composition for a printed wiring board having excellent electrical insulating properties, and a printed wiring board using the same. Further, a photocurable* thermosetting composition capable of reducing harmful substances causing environmental pollution is provided. In order to achieve the above object, the present inventors have found that a carboxyl group-containing resin having one or more carboxyl groups in the molecule (A) is found to be the result of the review. (B) Photopolymerization initiator, (D) diluent ' (E) 塡 剂 ' ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( For the screen printing method, the curtain coating method, the spray coating method, the roll coating method, etc., it has the coating property with stability over time, and does not reduce heat resistance, adhesion, electrical insulation, and the like. The present invention has been completed. Further, it has been found that the above (C) polyhydroxycarboxylic acid ester-based additive does not have the necessity of using a harmful organic solvent such as xylene. [Effect of the Invention] The photocurable thermosetting composition of the present invention has a coating for stability over time for screen printing, curtain coating, spray coating, roll coating, and the like. And in the case of electroplating during the manufacture of a printed wiring board, or in the case of soldering, it is possible to prevent the peeling of the coating film or the defective appearance of the coating film, and the volatility of the harmful organic solvent in the absence of environmental pollution. The organic compound (VOC) is inked. Further, since the coating property with stability over time is obtained, the photocurable and thermosetting resin composition of the present invention can be produced in a large amount, and the cost can be reduced. In addition, it contributes to a reduction in the defect rate when manufacturing a printed wiring board, and the product can be reduced in price. [Best Mode for Carrying Out the Invention] The basic form of the photocurable and thermosetting resin composition of the present invention provides a photocurable and thermosetting resin composition characterized by containing (A) - in a molecule Carboxyl group-containing resin having one or more carboxyl groups, (B) -6 - (4) (4) 1357434 photopolymerization initiator, (C) polyhydroxycarboxylate additive, (D) diluent, (E) 塡Charge, and (F) epoxy resin. A preferred embodiment provides a composition which is characterized in that the (C) polyhydroxycarboxylic acid ester-based additive contains no xylene (hereinafter referred to as xylene-free) additive. Further, a composition is provided in which the photocurable thermosetting resin composition further contains (G) a non-halogen organic pigment. Further, another embodiment provides a printed wiring board characterized in that the photocurable thermosetting resin composition has a solder resist layer and/or a resin insulating layer which is cured by active energy ray irradiation and/or heat curing. Floor. In the following, each constituent component of the photocurable thermosetting resin composition of the present invention will be described in detail. First, in the above (A)—the carboxyl group-containing resin containing one or more carboxyl groups in the molecule, a resin having a residue can be used, and specifically, (A,) a carboxyl group-containing photosensitive film having an ethylenically unsaturated double bond can be used. The resin and (A) the carboxyl group-containing resin which does not contain an ethylenically unsaturated double bond are not particularly limited, and it is preferred to use the following resins (which may be oligomers and polymers). (1) a carboxyl group-containing resin obtained by copolymerizing an unsaturated acid with a compound having an unsaturated double bond, (2) by a copolymer of an unsaturated residual acid and a compound having an unsaturated double bond Addition of a green-green unsaturated group as a pendant group (for example, addition of glycidyl methacrylate), a carboxyl group-containing photosensitive resin, (3) having an epoxy group in one molecule and not In a copolymer of a compound having a saturated double bond and a compound having an unsaturated double bond, the unsaturated monomer is reacted with an acid, and a saturated or unsaturated polybasic acid is reacted in the generated secondary carboxyl group (5) (5) 1357434. 'Production of a carboxyl group-containing photosensitive resin, (4) In a copolymer having an unsaturated double bond anhydride and a compound having another unsaturated double bond, having a carboxyl group and an unsaturated double bond in one molecule The compound reacts to obtain a carboxyl group-containing photosensitive resin, (5) reacts a polyfunctional epoxy compound with an unsaturated monocarboxylic acid, and reacts a saturated or unsaturated polybasic acid in the resulting carboxyl group to obtain a carboxyl group. Photosensitive resin, (6) polymerization in carboxyl group a photosensitive resin containing a hydroxyl group and a carboxyl group obtained by reacting a saturated or unsaturated polybasic acid anhydride with a compound having an epoxy group and an unsaturated double bond in the produced carboxylic acid, (7) a polyfunctional epoxy compound, a reaction product with an unsaturated monocarboxylic acid, a reactive group having at least one alcoholic hydroxyl group in one molecule, and one alcoholic hydroxyl group reactive with an epoxy group a carboxyl group-containing photosensitive resin obtained by reacting a saturated or unsaturated polybasic acid anhydride, (8) unsaturated in a polyfunctional oxetane compound having at least two oxetane rings in one molecule A carboxyl group-containing photosensitive resin obtained by reacting a saturated or unsaturated polybasic acid anhydride with a monohydroxy group in the modified oxetane resin obtained by the reaction of a monocarboxylic acid. Among these, the carboxyl group-containing photosensitive resin having two or more photosensitive unsaturated double bonds in one molecule is particularly preferably the above (5) carboxyl group-containing photosensitive resin. The above (A) carboxyl group-containing resin can be imaged by a dilute aqueous alkali solution due to a backbone having a plurality of free carboxyl groups in the side chain of the polymer. -8- (6) (6) 1357434 Further, the acid value of the above (A) carboxyl group-containing resin is from 4 to 200 mgKOH/g, preferably from 45 to 120 mgKOH/g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, it is not easy to be imaged, and when 'more than 200 mgKOH/g, the dissolution of the exposed portion is caused by development', the line is finer than necessary, and it is required to be There is no difference between the exposed portion and the unexposed portion, which is dissolved and peeled off by the developing solution, and it is difficult to draw a normal resist pattern, which is not desirable. The compounding amount of the (A) carboxyl group-containing resin is from 20 to 60% by mass, preferably from 30 to 50% by mass, based on the total composition. When it is less than the above, the film strength is lowered and it is not desirable. On the other hand, when it is larger than the above range, the viscosity increases and the printability and the like are lowered, which is not desirable. (B) Photopolymerization initiator used in the present invention, for example, benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-benzene Acetophenones such as acetophenone, ssl-acetophenone dichloride, etc.; 2. methyl (methyl sulfide) phenyl]-2-morpholinylpropanoid ketone' 2-benzyl group Amino acetophenones such as -2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1; 2-methyl oxime, 2-ethyl hydrazine, 2- 3rd butyl hydrazine, ] _ hydrazine hydrazine, etc.: κ-methyl thioxanthone, 2-diethyl thioxanthone, 2-chlorothioxanthone, 2,4- a thioxanthone such as isopropyl thioxanthone; an acetal such as acetophenone dimethyl acetal benzyl benzyl acetal; a benzophenone such as benzophenone; or hydrazine D Butanone; (2,6-dimethoxybenzylidene)_2,4:4-pentylphosphine oxide, bis(2,4:6-dimethylbenzylidene)-phenylphosphine oxide , 2:4,6 trimethylbenzene (7) 1357434

醯基二苯基氧化膦 '乙基- 2,4,6·三甲基苯甲醯基苯基磷酸 酯等之氧化膦類；各種過氧化物類等，此等習知慣用的光 聚合起始劑可單獨使用或2種以上組合使用。此等（Β)光 聚合起始劑之配合量，在全部組成物中爲0.2〜10質量 %，較佳者爲0· 5〜5質量％。上述配合量小於組成物全體 量之〇·2質量％時，光硬化性降低且於曝光.顯像後不易 形成圖案’故不爲企求。另外，大於10質量％時，藉由 光游離聚合起始劑本身之光吸收，造成厚膜硬化性降低且 爲成本提筒的原因，故不爲企求β 上述（Β)光聚合起始劑，可與Ν，Ν-二甲基胺基苯甲酸 乙酯、Ν,Ν-二甲基胺基苯甲酸異戊酯、戊基-‘二甲基胺 基苯甲酸酯、三乙胺、三乙醇胺等之三級胺類的光增感劑 單獨或2種以上組合使用。 '此外’可組合在可視光範圍內以游離基聚合爲開始的 千葉·特殊·化學公司製衣魯卡奇亞（音譯）784等之吉塔 羅仙（音譯）系光聚合起始劑、羅衣克（音譯）染料等作爲硬 化助劑使用。 本發明特徵之（C)聚羥基羧酸酯系添加劑，例如由二 孩酸二甲酯等之二羧酸二烷酯與鏈烷醇胺類之酯交換反應 所合成者’具體例如比克（音譯）化學.日本公司製之 BYK-R606 等。 該聚經基羧酸酯與習知的聚羧酸醯胺系添加劑不同， 係藉由含有羥基（例如第]圖中約3 4 3 0cin.1的吸收）及酯鍵 (例如第]圖中約]7 4 0 c m ·1的吸收），可溶於異丁醇等之醇 -10 - (8) (8)1357434 類’不需使用如二甲苯等之有害揮發性有機化合物 (VOC)。另外’可使用較習知的聚殘酸醯胺爲少量（約]/5 〜〗/3之量），賦予經時安定性優異的觸變性。此係習知的 聚羧酸醯胺爲蠟狀，對沒有均勻分散而言，本發明之聚羥 基羧酸酯由於在組成物中可均勻分散，故可以少量賦予優 異的觸變性。 而且，該聚羥基羧酸酯不僅可作爲觸變性賦予劑，且 可藉由控制配合量（例如在組成物中約配合〇 . 2質量％以 上）’亦可使用作爲無光澤化劑（消艷劑）》 該（C)聚羥基羧酸酯系添加劑之配合量，在全部組成 物中爲〇·〇】〜]·〇〇質量。/。、較佳者爲0.05〜0.8質量％» (C)聚羥基羧酸酯系添加劑之配合量小於上述範圍時，無 法得到充分的觸變性。另外大於上述範圍時，由於會產生 針孔或間斷情形，不爲企求。 此外，該聚羥基羧酸酯系添加劑，藉由併用親水性二 氧化矽’可形成網目構造且提高觸變性，更爲提高效果之 安定性。 本發明所使用的（D)稀釋劑，係爲調整該組成物之黏 度、提高作業性，且提高交聯密度、提高密接性等時所使 用者，可使用光聚合性單體等之反應性稀釋劑或習知慣用 的有機溶劑。 上述光聚合性單體例如有2 -乙基己基（甲基）丙烯酸 酯、環己基（甲基）丙烯酸酯等之烷基（甲基）丙烯酸酯類； 2-羥基乙基（甲基）丙烯酸酯、2-羥基丙基（甲基）丙烯酸酯 -11 - (9) (9)1357434 等之羥基烷基（甲基）丙烯酸酯類；乙二醇、丙二n、二叾 二醇、二丙二醇等之環氧烷基衍生物的單或二（甲基）丙稀 酸酯類；己二醇 '三羥甲基丙烷、季戊四醇、二三經甲基 丙烷、二季戊四醇、參羥基乙基異氰酸酯等之多元醇或此 等之環氧乙院或環氧丙院加成物的多元（甲基）丙燒酸n 類；苯氧基乙基（甲基）丙烯酸酯、雙酚 A之聚乙氧基二 (甲基）丙烯酸酯等之苯酚類的環氧乙烷或環氧丙院加成物 之（甲基）丙稀酸醋類；丙三醇二環氧丙酸、三經甲基丙院 三環氧丙醚、三環氧丙基異氰酸醋等之環氧两酸的（甲基） 丙烯酸酯類；以及蜜胺（甲基）丙烯酸酯等》 此等可以單獨使用或2種以上組合使用，就組成物之 液體安定性而言以含親水性基之（甲基）丙烯酸酯類較佳， 另就光硬化性而言以多官能性之（甲基）丙烯酸酯類較佳。 此等光聚合單體之使用範圍在全部組成物中爲20質量％ 以下，較佳者爲】〇質量％以下。大於該範圍時，指觸乾 燥性不佳，故不爲企求。 而且，於本說明書中（甲基）丙烯酸酯係爲丙烯酸酯、 甲基丙烯酸酯及此等之混合物的總稱，有關其他類似的表 示亦相同。 上述有機溶劑可使用甲基乙酮、環己酮等之酮類；甲 苯' 二甲苯 '四甲苯等之芳香族烴類；溶纖劑、甲基溶纖 劑、丁基溶纖劑、卡必醇、甲基卡必醇、丁基卡必醇、丙 二醇單甲醚、二丙二醇單甲醚 '二丙二醇二***' 三丙二 醇單甲醚等之醇醚類；醋酸乙酯、醋酸丁酯、乳酸丁酯、 -12 - (10) 溶纖劑乙酸酯、丙二醇單甲醚乙酸酯、二丙二醇單甲醚乙 酸酯、碳酸丙二酯等之酯類；辛烷、癸烷等之脂肪族烴 類；石油醚、石腦油'溶劑石腦油等之石油系溶劑等習知 的有機溶劑。此等有機溶劑可以單獨使用或二種以上組合 使用。 該有機溶劑之使用量係視塗覆方法或使用的有機溶劑 之沸點而不同，沒有特別的限制，一般而言在全部組成物 中爲50質量％以下，較佳者爲30質量％以下，更佳者爲 2 0質量％以下。含有多量的高沸點有機溶劑時，指觸乾燥 性降低且於塗覆後直至假乾燥前會產生皺摺情形，故不爲 企求。 本發明所使用的（E)塡充劑，可使用習知的無機塡充 劑或有機塡充劑，以倂用上述（C)聚羥基羧酸酯系添加劑 時，具有形成網目構造且提高觸變性、提高效果安定性作 用之親水性二氧化矽較佳。 而且，此處之親水性二氧化矽係爲使一般的二氧化矽 所粉碎者，除使粒子表面以有機化合物疏水化處理者（疏 水性二氧化矽）以外者。 除親水性二氧化矽以外之無機塡充物，可使用硫酸 鋇、滑石、黏土、疏水性二氧化矽、氧化鋁、氫氧化鋁、 碳酸鈣、有機皂土、雲母粉等之習知慣用者。此等具有提 高塗膜之強度或硬度的效果，可視其所需使用。 另外，上述有機塡充物例如聚乙烯、聚丙烯、聚苯乙 烯 '丙烯腈-苯乙烯共聚物、丙烯腈-丁二烯-苯乙烯共聚 -13- (11) (11)1357434 物、聚碳酸酯 '聚甲基丙稀酸甲醋等之各種丙焴酸醋、聚 醯亞胺、聚醯胺、聚酯 '聚氯化乙烯基' 聚氯化次乙烯 基、聚二乙烯苯、氟系樹脂、聚氧化亞苯基'聚硫化亞苯 基、聚甲基戊烯、尿素樹脂、蜜胺樹脂、苯并鳥糞胺樹 脂、聚縮醛樹脂、呋喃樹脂、聚矽氧烷樹脂、環氧樹脂硬 化物等。 此等（E)塡充劑之配合量，在全部組成物中爲40質量 %以下、較佳者爲5〜3 0質量％。塡充劑之配合比例大於 上述範圍時，塗膜特性降低且不易得到充分的印刷性，故 不爲企求。該（E)塡充劑亦具有防止銅箔端部等之塗膜變 爲極薄的作用，以適量配合具有1〇μηι以下粒徑者較佳。 本發明之（F)環氧樹脂可使用習知的各種環氧樹脂， 例如雙酚Α型環氧樹脂、雙酚F型環氧樹脂、雙酚S型 環氧樹脂、溴化雙酚A型環氧樹脂、加氫雙酚a型環氧 樹脂、雙酚型環氧樹脂 '雙二甲苯酚型環氧樹脂、苯酚酚 醛淸漆型環氧樹脂、甲酚酚醛淸漆型環氧樹脂、溴化苯酚 酚醛淸漆型環氧樹脂、雙酚A之酚醛淸漆型環氧樹脂、 三羥基苯基甲烷型環氧樹脂、四羥苯基乙烷型環氧樹脂、 含萘架構之苯酚酚醛淸漆型環氧樹脂、含二環戊二烯架構 之苯酚酚醛淸漆型環氧樹脂等之環氧丙醚化合物；對酞酸 二環氧丙酯、六氫酞酸二環氧丙酯、二聚酸二環氧丙酯等 之環氧丙酯化合物；賴西魯（音譯）化學公司製之EH PE-3150 等脂環 式環氧 樹脂； 三 環氧丙 基異氰 酸酯等 之雜環 式環氧樹脂；H N ’ ： N :-四環氧丙基間二甲苯二瞭、 -14 - (12) 1357434 N，N，N’，N5-四環氧丙基雙胺基甲基環己烷、N，N•二環氧丙 基苯胺等之環氧丙胺類、或環氧丙基（甲基）丙烯酸酯與具 有乙烯性不飽和雙鍵之化合物的共聚物等習知之環氧化合 物，就指觸乾燥性、耐熱性而言由以苯酚酚醛淸漆型環氧 樹脂、甲酌酚醒淸漆型環氧樹脂、雙酣型或雙二甲苯酚型 環氧樹脂或此等之混合物或三環氧丙基異氰酸酯更佳。此 等之（F)環氧樹脂可以單獨使用或2種以上組合使用。 % 此等之（F)環氧樹脂與上述（A)含羧基之樹脂熱硬化， 可提高耐熱性、密接性等。此等（F)環氧樹脂之配合量， 對上述（A)含羧基之樹脂的1當量羧基而言，環氧基爲〇.8 〜2.0當量 '較佳者爲1.〇〜1.8當量。（F)環氧樹脂之配合 量於環氧基小於0.8當量時’殘留有未反應的羧基，且硬 化被膜之吸濕性增高’ P C T耐性容易降低，且焊接耐熱性 或耐無電鍍性亦容易降低。此外，（F)環氧樹脂之配合量 於環氧基大於2.0當量時’塗膜之顯像性或硬化被膜之耐 φ 無電鍍性不佳，且P CT耐性亦不佳。 本發明之光硬化性·熱硬化性樹脂組成物，可視其所 需以無機顏料 '有機顏料、有機染料等著色，由於有機染 料爲引起感度降低的原因，故以使用無機顏料或有機顔料 較佳。具體而言，例如酞菁.藍 '酞菁.綠 '碘.綠、二 重氣黃、結晶紫、氧化駄 '碳黑、蔡黑等。另外.，就環境 問題而言以使用（G)非鹵素系有機顏料較佳。 此等顏料類之配合量除氧化鈦外，一般而言在組成物 中爲5質量％以下。若大於上述範圍時，光硬化性降低， -15- (13) (13)1357434 不爲企求。而且，使用氧化鈦時，一般在組成物中使用 】5質量％以下。 另外’本發明之光硬化性.熱硬化性樹脂組成物，可 添加咪唑鹽類或三氟化硼複合物、有機金屬鹽等作爲潛在 性硬化觸媒。此外，就防止印刷配線板之電路、即銅之氧 化爲目的時’可添加腺嘌呤、乙烯基三嗪、二氰基二醯 月女、正甲苯基縮二胍、蜜胺等之化合物、或此等之鹽。一 般而言，此等化合物之配合比例在組成物中爲5質量％以 下’藉由添加此等，可提高硬化塗膜之耐藥品性或與銅箔 之黏合性。 此外，本發明之光硬化性♦熱硬化性樹脂組成物，在 不會降低塗膜特性之範圍內，視其所需可添加氫醌、氫醌 單甲醚 '第3 -丁基兒茶酚、焦培酚、吩噻嗪等習知之熱 聚合禁止劑、聚矽氧烷系、氟系、高分子系等之消泡劑及 /或水平劑、咪唑系、噻唑系、***系等之矽烷偶合劑等 習知的添加劑類。 具有上述組成之本發明光硬化性·熱硬化性樹脂組成 物，視其所需予以稀釋調整成適合塗覆方法的黏度，使其 藉由篩網印刷法、簾幕塗覆法、分布塗覆法、輥塗覆法等 之方法塗覆於例如形成有電路的印刷配線板上，藉由在例 如60〜]〇〇°C之溫度下使組成物中所含的有機溶劑揮發乾 燥，形成沒有皺摺的塗膜。 然後，使形成有所定圖案的光罩通過，藉由選擇性活 性能量線曝光 > 使未曝光部藉由稀鹼水溶液顯像，形成光 -16 - (14) (14)1357434 阻圖案’然後，照射活性能量線後加熱硬化；或加熱硬化 後照射活性能量線，或僅以加熱硬化予以最後的加工硬化 (本硬化），可形成密接性、硬度、焊接耐熱性、耐藥品 牲、耐溶劑性、電絕緣性、耐電蝕性、解像性、耐電鍍 胜、PCT耐性、及耐吸濕性優異的硬化被膜（阻焊被膜）。 特別是藉由照射活性能量線後加熱硬化，或加熱硬化後照 射活性能量線之步驟，使未反應的感光基反應，可製得耐 電蝕性、耐電鍍性' 耐吸濕性優異的硬化被膜。 上述顯像所使用的鹼水溶液可使用氫氧化鉀、氫氧化 鈉、碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、銨、胺類等之鹼 水溶液。而且，爲使光硬化時之照射光源以低壓水銀燈、 中壓水銀燈、高壓水銀燈、超高壓水銀燈、氙氣燈、金屬 滷化燈等爲宜。其他可利用雷射光線等作爲活性能量線。 【實施方式】 [實施例] 於下述中以實施例及比較例具體說明有關本發明，惟 本發明不受下述實施例所限制。而且’於下述中沒有特別 限制時，「份」係全部表示「質量份」。 合成例 使215份甲酚酚醛淸漆型環氧樹脂之Ν·6 80(大日本 油墨化學工業公司製、環氧當量=215)加入附有攪拌機及 回流冷卻器之四口燒瓶中’再加入196份丙二醇單甲醚乙 -17 - (15) (15)1357434 酸醋予以加熱熔融。然後，加入〇. 4 6份作爲聚合禁止劑 之甲基氫醌、1.38份作爲反應觸媒之三苯基膦。使該混合 物在95〜105 °C下加熱，慢慢地滴入72.0份（1.0當量）丙 烯酸’製得酸價爲0.9mgKOH/g之反應生成物。使該反應 生成物（羥基：1當量）冷卻至80〜90°C，加入76.0份（0.5 當量）四氫酞酸酐’約反應8小時，冷卻後取出。如此所 得的（A)含羧基之樹脂係不揮發份爲65%、固成分之酸價 爲77mgKOH/g。於下述中，該淸漆稱爲A-1淸漆。 使上述合成例所得的含羥基之樹脂淸漆（A-1淸漆）使 用的表1所示配合比例，以3條輥磨混練，製得光硬化 性•熱硬化性樹脂組成物之各主劑。另外，使表2所示之 配合比例以3條輥磨混練，製得上述光硬化性•熱硬化性 樹脂組成物之硬化劑。 而且，所得的光硬化性·熱硬化性樹脂組成物，以丙 二醇單甲醚乙酸酯調整成黏度約爲200dPa . s。Phosphine oxides such as decyl diphenylphosphine oxide 'ethyl-2,4,6·trimethylbenzimidyl phosphate; various peroxides, etc., such conventional photopolymerization The initiators may be used singly or in combination of two or more. The blending amount of the (yttrium) photopolymerization initiator is 0.2 to 10% by mass, preferably 0.5 to 5% by mass based on the total composition. When the blending amount is less than 2% by mass based on the total amount of the composition, the photocurability is lowered, and it is difficult to form a pattern after exposure and development. On the other hand, when it is more than 10% by mass, the light absorption by the photo-free polymerization initiator itself causes a decrease in the thick film hardenability and is a cause of cost reduction, so that it is not required to obtain the above-mentioned (Β) photopolymerization initiator. And ethyl hydrazine, dimethyl-dimethylamino benzoate, hydrazine, decyl-dimethylaminobenzoic acid isoamyl ester, amyl-'dimethylamino benzoate, triethylamine, three A light sensitizer of a tertiary amine such as ethanolamine is used singly or in combination of two or more kinds. 'In addition' can be combined with the free radical polymerization in the visible light range. Chiba Special Chemical Co., Ltd., the clothing of Lukachiya 784, etc., is a photopolymerization initiator, Luo A dye, such as a dye, is used as a hardening aid. The (C) polyhydroxycarboxylic acid ester-based additive of the present invention is synthesized, for example, by a transesterification reaction of a dialkyl dicarboxylate such as dimethyl dicarboxylate with an alkanolamine. Transliteration) Chemical. BYK-R606 made by Japanese company. The polycarboxylic acid carboxylate differs from the conventional polycarboxylate amide-based additive by a hydroxyl group (for example, an absorption of about 3 4 3 0 cin.1 in the figure) and an ester bond (for example, in the figure). Approximately 7 4 0 cm ·1 absorption), soluble in isobutanol and other alcohols -10 - (8) (8) 1357434 'Do not use harmful volatile organic compounds (VOC) such as xylene. Further, it is possible to use a relatively small amount of polyunsaturated guanamine as an amount (about /5 〜 3/3), and to impart thixotropy excellent in stability over time. The conventional polycarboxylates are waxy, and the polyhydroxycarboxylates of the present invention can be uniformly dispersed in the composition without uniform dispersion, so that excellent thixotropy can be imparted in a small amount. Further, the polyhydroxycarboxylic acid ester can be used not only as a thixotropic imparting agent, but also by controlling the compounding amount (for example, about 0.2% by mass or more in the composition). The amount of the (C) polyhydroxycarboxylic acid ester-based additive is 〇·〇]~]·〇〇 in all the compositions. /. Preferably, it is 0.05 to 0.8% by mass. (C) When the amount of the polyhydroxycarboxylic acid ester-based additive is less than the above range, sufficient thixotropy cannot be obtained. Further, when it is larger than the above range, pinholes or discontinuities may occur, which is not desirable. Further, the polyhydroxycarboxylic acid ester-based additive can form a network structure by using hydrophilic ruthenium dioxide, and can improve thixotropy and further improve the stability of the effect. The (D) diluent used in the present invention is a user who can adjust the viscosity of the composition, improve the workability, increase the crosslinking density, and improve the adhesion, etc., and can use a photopolymerizable monomer or the like. A diluent or a conventional organic solvent. The photopolymerizable monomer is, for example, an alkyl (meth) acrylate such as 2-ethylhexyl (meth) acrylate or cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate Ester, 2-hydroxypropyl (meth) acrylate-11 - (9) (9) 1357434, etc. hydroxyalkyl (meth) acrylates; ethylene glycol, propylene di, dinonylene glycol, two Mono or di(meth) acrylates of alkylene oxide derivatives such as propylene glycol; hexanediol 'trimethylolpropane, pentaerythritol, ditrimethylpropane, dipentaerythritol, hydroxyethyl isocyanate Polyols of this type, or such poly(methyl)propionic acid n-types of epoxy epoxide or epoxy propylene adduct; phenoxyethyl (meth) acrylate, bisphenol A poly a phenolic oxirane such as oxydi(meth)acrylate or a (meth)acrylic acid acetonate of a propylene oxide addition; glycerol diepoxypropionic acid, trimethylmethyl a (meth) acrylate of epoxy bis-epoxypropyl ether, tri-epoxypropyl isocyanate, etc.; and melamine (meth) acrylate These may be used singly or in combination of two or more. It is preferable to use a hydrophilic group-containing (meth) acrylate in terms of liquid stability of the composition, and to be polyfunctional in terms of photocurability. (Meth) acrylates are preferred. The use range of such a photopolymerizable monomer is 20% by mass or less in all the compositions, and preferably 〇% by mass or less. When it is larger than this range, the dryness of the touch is not good, so it is not desirable. Further, in the present specification, the (meth) acrylate is a general term for acrylate, methacrylate, and the like, and the other similar expressions are also the same. As the organic solvent, a ketone such as methyl ethyl ketone or cyclohexanone; an aromatic hydrocarbon such as toluene 'xylene' tetramethylbenzene; a cellosolve, a methyl cellosolve, a butyl cellosolve, carbitol, or the like; Alcohol ethers such as methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether 'dipropylene glycol diethyl ether' tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate , -12 - (10) esters of cellosolve acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate, etc.; aliphatic hydrocarbons such as octane and decane A conventional organic solvent such as a petroleum solvent such as petroleum ether or naphtha 'solvent naphtha. These organic solvents may be used singly or in combination of two or more. The amount of the organic solvent to be used is not particularly limited, and is generally 50% by mass or less, preferably 30% by mass or less, based on the boiling point of the coating method or the organic solvent to be used. The best is 20% by mass or less. When a large amount of a high-boiling organic solvent is contained, the dryness of the touch is lowered and wrinkles are generated after the coating until the pseudo-drying, so that it is not desirable. The (E) chelating agent used in the present invention may be a conventional inorganic chelating agent or an organic cerium filling agent, and when the above (C) polyhydroxycarboxylic acid ester-based additive is used, it has a mesh structure and improves touch. Hydrophilic cerium oxide which denatures and enhances the effect of stability is preferred. Further, the hydrophilic cerium oxide here is one in which the general cerium oxide is pulverized, except that the surface of the particles is hydrophobized with an organic compound (hydrophobic cerium oxide). In addition to hydrophilic cerium oxide, conventional chelators such as barium sulfate, talc, clay, hydrophobic cerium oxide, aluminum oxide, aluminum hydroxide, calcium carbonate, organic bentonite, mica powder, etc. can be used. . These have the effect of increasing the strength or hardness of the film, and can be used as desired. Further, the above organic ruthenium such as polyethylene, polypropylene, polystyrene 'acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer-13-(11)(11)1357434, polycarbonate Various kinds of acryl vinegar, polyethylenimine, polydecylamine, polyester 'polychlorinated vinyl' poly(polyvinylidene), polydivinylbenzene, fluorine Resin, polyoxyphenylene 'polysulfoxyphenylene, polymethylpentene, urea resin, melamine resin, benzoguanamine resin, polyacetal resin, furan resin, polyoxyalkylene resin, epoxy Hardened resin, etc. The blending amount of the (E) chelating agent is 40% by mass or less, preferably 5 to 30% by mass based on the total composition. When the blending ratio of the chelating agent is more than the above range, the coating film characteristics are lowered and it is difficult to obtain sufficient printability, so that it is not desired. The (E) chelating agent also has a function of preventing the coating film of the end portion of the copper foil or the like from becoming extremely thin, and it is preferable to mix the particles having a particle size of 1 μm or less in an appropriate amount. The (F) epoxy resin of the present invention may be a conventional epoxy resin such as a bisphenol fluorene type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, or a brominated bisphenol A type. Epoxy resin, hydrogenated bisphenol a type epoxy resin, bisphenol type epoxy resin 'bis xylenol type epoxy resin, phenol novolac lacquer type epoxy resin, cresol novolac lacquer type epoxy resin, bromine Phenol novolac lacquer type epoxy resin, bisphenol A phenolic lacquer type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetrahydroxyphenylethane type epoxy resin, phenol novolac with naphthalene structure a styrofoam compound such as a lacquer epoxy resin or a phenol novolac lacquer epoxy resin containing a dicyclopentadiene structure; diglycidyl citrate, diglycidyl hexahydrophthalate, and a glycidyl ester compound such as polyglycidyl polyacrylate; an alicyclic epoxy resin such as EH PE-3150 manufactured by Lai Xilu Chemical Co., Ltd.; a heterocyclic epoxy resin such as triepoxypropyl isocyanate Resin; HN ' : N :-tetraepoxypropyl m-xylene, -14 - (12) 1357434 N, N, N', N5-tetraepoxy a glycidylamine such as propyldiaminomethylcyclohexane or N,N-diepoxypropylaniline, or a glycidyl (meth)acrylate and a compound having an ethylenically unsaturated double bond; A conventional epoxy compound such as a copolymer, in terms of dryness and heat resistance, is a phenol novolac type epoxy resin, a phenolic enamel type epoxy resin, a biguanide type or a bisxylenol type. Epoxy resins or mixtures of these or trisethoxypropyl isocyanate are preferred. These (F) epoxy resins may be used singly or in combination of two or more. % (F) Epoxy Resin and the above (A) carboxyl group-containing resin are thermally cured to improve heat resistance, adhesion, and the like. The amount of the epoxy resin to be added to the (A) carboxyl group-containing resin is from 〇. 8 to 2.0 equivalents, preferably from 1. to 1.8 equivalents. (F) When the epoxy group is less than 0.8 equivalents, the epoxy group remains unreacted, and the hygroscopicity of the cured film is increased. PCT resistance is easily lowered, and solder heat resistance or electroless resistance is also easy. reduce. Further, when the amount of the epoxy resin (F) is more than 2.0 equivalents, the development of the coating film or the resistance of the cured film is not good, and the PCT resistance is also poor. The photocurable and thermosetting resin composition of the present invention may be colored with an inorganic pigment 'organic pigment, an organic dye or the like as required, and the organic dye is preferred because of the use of an inorganic pigment or an organic pigment. . Specifically, for example, phthalocyanine, blue 'phthalocyanine, green', iodine, green, double gas yellow, crystal violet, cerium oxide, carbon black, and black. Further, it is preferable to use (G) a non-halogen type organic pigment in terms of environmental problems. In addition to the titanium oxide, the amount of the pigments is generally 5% by mass or less in the composition. If it is larger than the above range, the photocurability is lowered, and -15-(13) (13) 1357434 is not desirable. Further, when titanium oxide is used, it is generally used in the composition of 5% by mass or less. Further, the photocurable thermosetting resin composition of the present invention may contain an imidazole salt or a boron trifluoride complex or an organic metal salt as a latent curing catalyst. Further, in order to prevent oxidation of the circuit of the printed wiring board, that is, copper, 'a compound such as adenine, vinyltriazine, dicyanoquinone, n-tolyldiamine, melamine, or the like may be added, or These salts. In general, the compounding ratio of these compounds is 5% by mass or less in the composition. By adding these, the chemical resistance of the cured coating film or the adhesion to the copper foil can be improved. Further, in the photocurable ♦ thermosetting resin composition of the present invention, hydroquinone or hydroquinone monomethyl ether '3 -butylcatechol can be added as needed within a range that does not lower the characteristics of the coating film. A thermal polymerization inhibitor such as pyrophenol or phenothiazine, a defoaming agent and/or a leveling agent such as a polyoxyalkylene-based, a fluorine-based or a polymer-based, an imidazole-based, a thiazole-based or a triazole-based compound. A conventional additive such as a decane coupling agent. The photocurable thermosetting resin composition of the present invention having the above composition is diluted and adjusted to a viscosity suitable for the coating method by screen printing, curtain coating, and distribution coating. A method such as a roll coating method or the like is applied to, for example, a printed wiring board on which a circuit is formed, and the organic solvent contained in the composition is volatilized and dried at a temperature of, for example, 60 to 〇〇 ° C to form no Wrinkled coating. Then, the mask forming a predetermined pattern is passed, and the exposed portion is exposed by a selective active energy ray; the unexposed portion is developed by a dilute aqueous alkali solution to form a light -16 (14) (14) 1357434 resist pattern 'then After the active energy ray is irradiated, it is heated and hardened; or the active energy ray is irradiated after heating and hardening, or the final work hardening (the present hardening) is performed only by heat hardening, thereby forming adhesion, hardness, solder heat resistance, drug resistance, solvent resistance A cured film (solder resist film) excellent in properties, electrical insulation, electrical corrosion resistance, resolution, electroplating resistance, PCT resistance, and moisture absorption resistance. In particular, by irradiating the active energy ray, heating or hardening, or heating and hardening, and irradiating the active energy ray, the unreacted photosensitive group is reacted to obtain a cured film excellent in corrosion resistance and electroplating resistance. As the aqueous alkali solution used for the above development, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonium or an amine can be used. Further, in order to light harden, the light source is preferably a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp or the like. Others may use laser light or the like as an active energy ray. [Embodiment] [Examples] The present invention is specifically described by way of Examples and Comparative Examples, but the present invention is not limited by the following examples. Further, when there is no particular limitation in the following, "parts" means "parts by mass". In the synthesis example, 215 parts of cresol novolac type epoxy resin 6·6 80 (manufactured by Dainippon Ink and Chemicals Co., Ltd., epoxy equivalent = 215) was added to a four-necked flask equipped with a stirrer and a reflux condenser. 196 parts of propylene glycol monomethyl ether B-17-(15) (15) 1357434 vinegar was heated and melted. Then, 46 parts of methylhydroquinone as a polymerization inhibiting agent and 1.38 parts of triphenylphosphine as a reaction catalyst were added. The mixture was heated at 95 to 105 ° C, and 72.0 parts (1.0 equivalents) of acrylic acid was slowly added dropwise to obtain a reaction product having an acid value of 0.9 mgKOH/g. The reaction product (hydroxyl group: 1 equivalent) was cooled to 80 to 90 ° C, and 76.0 parts (0.5 equivalent) of tetrahydrophthalic anhydride was added for about 8 hours, and after cooling, it was taken out. The (A) carboxyl group-containing resin thus obtained had a nonvolatile content of 65% and the solid content had an acid value of 77 mgKOH/g. In the following, the enamel paint is referred to as A-1 lacquer. The mixing ratio of the hydroxyl group-containing resin enamel paint (A-1 lacquer) obtained in the above-mentioned synthesis example was mixed by three roll mills to obtain each of the photocurable and thermosetting resin compositions. Agent. Further, the blending ratio shown in Table 2 was kneaded by three roll mills to obtain a curing agent for the photocurable thermosetting resin composition. Further, the obtained photocurable thermosetting resin composition was adjusted to have a viscosity of about 200 dPa·s with propylene glycol monomethyl ether acetate.

(D -18 - (16)1357434(D -18 - (16) 1357434

表I 實施例主劑 比較例主劑 1 2 3 1 2 A-l淸漆 60.0 60.0 60.0 60.0 60.0 Irg-369*1 4.0 4.0 4.0 4.0 4.0 BYK-R606*2 0.04 0.14 0.3 _ _ BYK-405·3 _ 一 • 0.5 BYK-354*4 4.0 4.0 4.0 4.0 4.0 DPHA·5 4.0 4.0 4.0 4.0 4.0 PMA·6 1.0 1.0 1.0 1.0 1.0 尼普希魯 (音譯)L-300” 1.0 1.0 1.0 1.0 1.0 衣姆希魯 (音譯)A-f8 10.0 10.0 10.0 10.0 10.0 硫酸銀 20.0 20.0 20.0 20.0 20.0 銅酞菁 0.5 0.5 0.5 0.5 0.5 二重氮黃 0.1 0.1 0.1 0.1 0.1 二氰基二醯胺 0.1 0.1 0.1 0.1 0.1 蜜胺 0.8 0.8 0.8 0.8 0.8 備註 *1 :千葉特殊化公司製光聚合起始劑、2-苯甲基-2-二甲基胺基-]-(4-嗎啉基苯基)-丁-1-酮 *2 :日本比克(音譯)化學公司製、聚羥基羧酸酯系添加劑 *3 :日本比克(音譯)化學公司製、聚羧酸醯胺系添加劑 *4 :日本比克(音譯)化學公司製、丙烯酸系水平劑·消泡劑 *5 :日本化藥製、二季戊四醇六丙烯酸酯 *6 :丙二醇單甲醚乙酸酯. *7 :東曹(音譯）·二氧化矽公司製、親水性超微粉二氧化矽 *8 :龍森工業公司製、結晶性二氧化矽Table I Example Main Agent Comparative Example Main Agent 1 2 3 1 2 Al淸 Paint 60.0 60.0 60.0 60.0 60.0 Irg-369*1 4.0 4.0 4.0 4.0 4.0 BYK-R606*2 0.04 0.14 0.3 _ _ BYK-405·3 _ • 0.5 BYK-354*4 4.0 4.0 4.0 4.0 4.0 DPHA·5 4.0 4.0 4.0 4.0 4.0 PMA·6 1.0 1.0 1.0 1.0 1.0 Niphill (transliteration) L-300” 1.0 1.0 1.0 1.0 1.0 衣姆希鲁 (transliteration) ) A-f8 10.0 10.0 10.0 10.0 10.0 Silver sulfate 20.0 20.0 20.0 20.0 20.0 Copper phthalocyanine 0.5 0.5 0.5 0.5 0.5 Diazo yellow 0.1 0.1 0.1 0.1 0.1 Dicyanodiamine 0.1 0.1 0.1 0.1 0.1 Melamine 0.8 0.8 0.8 0.8 0.8 Remarks*1: Photopolymerization initiator of Chiba Special Chemical Co., Ltd., 2-benzyl-2-dimethylamino-]-(4-morpholinylphenyl)-butan-1-one*2: Made by Japan BAK Chemical Co., Ltd., a polyhydroxy carboxylic acid ester additive*3: a polycarboxylate amide-based additive manufactured by Japan BAK Chemical Co., Ltd. *4: manufactured by Japan BAK Chemical Co., Ltd. Acrylic level agent and defoamer*5: Made from Nippon Chemical Co., Ltd., dipentaerythritol hexaacrylate*6: Propylene glycol monomethyl ether acetate. *7: Tosoh Co., Ltd. Hydrophilic silicon dioxide superfine powder * 8: Long Sen Industry Co., Ltd., crystalline silicon dioxide

-19 - (17) 1357434 表2 硬化劑 E-157CA75*9 5.0 耶皮克頓（音譯） 828*10 35.0 TEPIC-H*11 10.0 DPHA*5 15.0 PMA*6 15.0 備註 *9 :日本環氧樹脂公司製、耶皮克頓(音譯)157S70以固成份70% 溶解於卡必醇乙酸酯之淸漆 *10 :日本環氧樹脂公司製、雙酚A型環氧樹脂 *11 :日產化學公司製、高熔點型三環氧丙基異氰酸酯 *5 :日本化藥製、二季戊四醇六丙烯酸酯 *6 :丙二醇單甲醚乙酸醋-19 - (17) 1357434 Table 2 Hardener E-157CA75*9 5.0 Yepiketon 828*10 35.0 TEPIC-H*11 10.0 DPHA*5 15.0 PMA*6 15.0 Remarks *9: Japanese epoxy resin Company system, yipikton (transliteration) 157S70 with 70% solid content dissolved in carbitol acetate lacquer *10: Japan Epoxy resin company, bisphenol A epoxy resin *11: Nissan Chemical Co., Ltd. , high melting point trisepoxypropyl isocyanate *5: manufactured by Nippon Chemical Co., Ltd., dipentaerythritol hexaacrylate *6: propylene glycol monomethyl ether acetate vinegar

性能評估： (1 )保存安定性（黏度、觸變性） 使上述實施例1〜3及比較例1，2之光硬化性•熱硬 化性樹脂組成物的主劑之初期黏度、與在5 0 °C之恆溫槽 中放置1，2,3,4,7日之經時黏度，以下述條件測定。 黏度計：克布雷頓（音譯）型黏度計（頓齊梅克（音譯）公 司製）Evaluation of performance: (1) Preservation stability (viscosity, thixotropy) The initial viscosity of the main component of the photocurable thermosetting resin composition of the above Examples 1 to 3 and Comparative Examples 1 and 2, and The viscosity over time of 1, 2, 3, 4, and 7 days in a constant temperature bath of °C was measured under the following conditions. Viscometer: Créton (visual) type viscometer (Don Simek (transliteration) system)

測定溫度：2 5 °CMeasuring temperature: 2 5 °C

錐回轉數：5 r p m / m i η、及 5 0 r p m / m i η -20 - (18) 1357434 τ · I (觸變性之參考値） =(上述 5rpm/min 値）/(上述 50rpm/min 値） (2)保存安定性（塗覆性） 使上述實施例1〜3及比較例1，2之光硬化性•熱硬 化性樹脂組成物的主劑、與硬化劑各以重量比4 : 1混 合’調整各光硬化性•熱硬化性樹脂組成物。而且，同樣 地使用在50 °C之恆溫槽中放置1,2,3,4,7日之主劑，觀察 φ 塗覆性之經時變化。 使上述各組成物以隙縫式簾幕塗覆器，以乾燥膜厚約 爲20μηι塗覆於形成有電路之銅箔基板，在室溫下平置、 乾燥1 〇分鐘後，懸掛於專用紫膠，在熱風循環式乾燥爐 內、8 0 °C下乾燥I 5分鐘後，如下述評估塗覆性。 〇：沒有皺摺、均勻塗覆 △:有雛摺產生、上部與下部之膜厚有差別 X :有顯著皺摺產生、且會看見銅箔 (3)感度 與上述相同地調整的各光硬化性•熱硬化性樹脂組成 物以隙縫式簾幕塗覆器、以乾燥膜厚約爲2 0 μηι塗覆於基 板上’在室溫下平置 '乾燥1 0分鐘後，懸掛於專用紫 膠，在熱風循環式乾燥爐內、80 °C下乾燥1；5分鐘後，使 克拉古（音譯）No.2之階段式小平板密接，以累計光量爲 3 0 0m J/cm2曝光，藉由 I w t % N a 2 C Ο 3水溶液、以噴霧壓 0.2MPa顯像1分鐘後，由階段式小平板所得的段數評估 (19) 1357434 感度。 (4) 顯像線 與上述相同地調整的各光硬化性.熱硬化性樹脂組成 物以隙縫式簾幕塗覆器 '以乾燥膜厚約爲20μπι塗覆於形 成有電路之銅箔基板上，在室溫下平置、乾燥10分鐘 後’懸掛於專用紫膠，在熱風循環式乾燥爐內' 80t下使 φ 乾燥時間各以5分鐘間隔變化的基板。在該基板上塗覆負 薄膜，使阻焊圖案曝光，且藉由1 Wt%Na2C03水溶液、以 噴霧壓0.2MPa顯像1分鐘後，觀察假乾燥後之顯像線（可 顯像之最長乾燥時間）。 (5) 表面狀態 與上述相同地調整的各光硬化性•熱硬化性樹脂組成 物以隙縫式簾幕塗覆器、以乾燥膜厚約爲2 0 μπι塗覆於形 φ 成有電路之銅箔基板上，在室溫下平置、乾燥1〇分鐘 後’懸掛於專用紫膠，在熱風循環式乾燥爐內、80 °C下使 乾燥時間各以5分鐘間隔變化的基板。在該基板上塗覆負 薄膜，使阻焊圖案曝光，且藉由1 wt%Na2C03水溶液、以 噴霧壓0.2MPa顯像1分鐘後，在熱風循環式乾燥爐中' 15 0°C下熱硬化6〇分鐘。 所得硬化塗膜之表面狀態以目視評估。 (6)焊接耐熱性 -22- (20) (20)1357434 與上述同樣地調整的各光硬化性•熱硬化性樹脂組成 物，以隙縫式簾幕塗覆器塗覆乾燥膜厚約爲20μηΊ塗覆於 形成有電路之銅箔基板上，在室溫下平置 '乾燥10分鐘 後，在熱風循環式乾燥爐內、80°C下乾燥15分鐘。在該 基板上塗覆負薄膜，使阻焊圖案曝光，且藉由 1 wt%Na2C03水溶液、以噴霧壓〇.2MPa顯像1分鐘後， 在熱風循環式乾燥爐內、15(TC下乾燥60分鐘。使該基板 塗覆松香系助焊劑，在預先加熱至260°C之焊接槽中浸漬 3 0秒，以丙二醇單甲醚洗淨助焊劑後，藉由目視評估光 阻層之膨脹•剝落.變色情形。 〇：完全沒有變化者 △:稍有變化者 X :塗膜膨脹且剝落者 如此所得的實施例1〜3及比較例1，2之光硬化性· 熱硬化性樹脂組成物的評估結果如表3所示。Number of cone revolutions: 5 rpm / mi η, and 5 0 rpm / mi η -20 - (18) 1357434 τ · I (reference thixotropy 値) = (5 rpm/min 上述 above) / (50 rpm/min above) (2) Storage stability (coating property) The main component of the photocurable thermosetting resin composition of the above Examples 1 to 3 and Comparative Examples 1 and 2 and the curing agent were each mixed at a weight ratio of 4:1. 'Adjust each photocurability•thermosetting resin composition. Further, the main component of 1, 2, 3, 4, and 7 days was placed in a thermostat bath at 50 ° C in the same manner, and the change in the coating property of φ was observed. The above-mentioned respective compositions are applied to a copper foil substrate on which a circuit is formed by using a slit film coater with a dry film thickness of about 20 μm, and are placed at room temperature for one minute and then suspended in a special shellac. After drying for 5 minutes at 80 ° C in a hot air circulating drying oven, the coatability was evaluated as follows. 〇: no wrinkles, uniform coating △: there is a fold of the original, the film thickness of the upper part and the lower part is different. X: There is a significant wrinkle, and the copper foil (3) is seen to have the same degree of light hardening as the above. The thermosetting resin composition is applied to the substrate by a slit curtain coater at a dry film thickness of about 20 μm, and is dried at room temperature for 10 minutes, and then suspended in a special shellac. After drying in a hot air circulating drying oven at 80 ° C for 1 minute and 5 minutes, the staged small plate of Kragu (No. 2) was closely contacted to expose the accumulated light amount to 300 m J/cm 2 by I. After wt% N a 2 C Ο 3 aqueous solution, after 1 minute of development at a spray pressure of 0.2 MPa, the number of segments obtained from the staged small plate was evaluated (19) 1357434 sensitivity. (4) The respective photohardenability of the developing line adjusted in the same manner as described above. The thermosetting resin composition is applied to the copper foil substrate on which the circuit is formed by a slit curtain coater at a dry film thickness of about 20 μm. After standing at room temperature for 10 minutes, the substrate was suspended from a special shellac and changed in the hot air circulating drying oven at 80 ° intervals at intervals of 5 minutes. A negative film was coated on the substrate, and the solder resist pattern was exposed, and after 1 minute of development with a spray pressure of 0.2 MPa by an aqueous solution of 1 Wt% Na 2 CO 3 , the development line after the pseudo-drying was observed (the longest drying time of the image can be developed) ). (5) Each of the photocurable and thermosetting resin compositions whose surface conditions are adjusted in the same manner as described above is applied to a copper having a circuit shape by a slit curtain coater at a dry film thickness of about 20 μm. On the foil substrate, after drying at room temperature for 1 minute, the substrate was suspended from a special shellac, and the drying time was changed at intervals of 5 minutes in a hot air circulating drying oven at 80 °C. A negative film was coated on the substrate, the solder resist pattern was exposed, and the image was developed by a 1 wt% Na 2 CO 3 aqueous solution at a spray pressure of 0.2 MPa for 1 minute, and then thermally cured at a temperature of 15 ° C in a hot air circulating drying oven. Minutes. The surface state of the obtained hardened coating film was visually evaluated. (6) Solder heat resistance -22- (20) (20) 1357434 Each of the photocurable and thermosetting resin compositions adjusted in the same manner as described above was coated with a slit curtain coater to have a dry film thickness of about 20 μη. It was applied to a copper foil substrate on which a circuit was formed, and was allowed to stand flat at room temperature for 10 minutes, and then dried in a hot air circulating drying oven at 80 ° C for 15 minutes. A negative film was coated on the substrate, the solder resist pattern was exposed, and after 1 minute of development by spraying with a 1 wt% Na 2 CO 3 solution at a spray pressure of 2 MPa, it was dried in a hot air circulating drying oven at 15 (TC for 60 minutes). The substrate was coated with a rosin flux, and immersed in a solder bath previously heated to 260 ° C for 30 seconds. After the flux was washed with propylene glycol monomethyl ether, the expansion and peeling of the photoresist layer was visually evaluated. In the case of discoloration: 〇: No change at all Δ: slight change X: Evaluation of photocuring and thermosetting resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 obtained by swelling the film and peeling off The results are shown in Table 3.

(D -23- (21) 1357434(D -23- (21) 1357434

表3 I 實施例 比較例 1 2 3 1 2 ⑴黏度σ· I値） 初期値 204(1.37) 210(1.44) 204(1.55) 204(1.12) 201(1.42) 50〇C ' 1 日 210(1.36) 207(1.42) 210(1.53) 192(1.06) 207(1.40) 50t、2 日 204(1.37) 201(1.42) 207(1.53) 186(1.02) 201(1.40) 50。。、3 日 204(1.35) 207(1.39) 207(1.51) 189(1.02) 195(1.39) 50〇C ' 4 日 198(1.32) 207(1.37) 201(1.50) 189(1.01) 195(1.36) 5(TC、7 日 198(1.28) 201(1.33) 204(1.45) 195(1.01) 198(1.29) (2)塗覆性 初期値 〇 〇 〇 Δ 〇 50。。、1 日 〇 〇 〇 X 〇 50〇C、2 日 〇 〇 〇 X 〇 50°C、3 日 〇 〇 〇 X 〇 50。(：、4 日 Δ 〇 . 〇 X 〇. 50°C、7 日 △ Δ 〇 X Δ (3)感度(300mJ/cm2) 6段 6段 6段 6段 6段 (4)顯像線(80°C) 80分鐘 80分鐘 80分鐘 80分鐘 80分鐘 (5)表面狀態 有光澤 有光澤 無光澤 有光澤 有光澤 (6)焊接耐熱性 〇 〇 〇 〇 〇 組成物中有無二甲苯 Μ Μ Μ 川、 Μ y » 有 如上所述可知，使用聚羥基羧酸酯系添加劑之BYK-R606的實施例，不含二甲苯，黏度、觸變性之經時安定 性優異，塗覆性變化情形亦少。另外，以配合量約W3量⑤ -24 - (22) (22)1357434 之實施例2可得與添加約〇.5%一般所使用的聚羧酸醯胺 系添加劑之BYK-40 5的比較例2同等的觸變性* 此外，可知即使配合該聚羥基羧酸酯系添加劑之 BYK-R6 06時，感度 '顯像線 '焊接耐熱性等之塗膜特性 不會降低。 【圖面之簡單說明J [第1圖] 係表示實施例1〜3所使用的聚經基殘酸醋系添加劑 B YK-R606 之 IR 光譜。 -25Table 3 I Example Comparative Example 1 2 3 1 2 (1) Viscosity σ · I値) Initial 値 204 (1.37) 210 (1.44) 204 (1.55) 204 (1.12) 201 (1.42) 50 〇 C ' 1 210 (1.36) 207(1.42) 210(1.53) 192(1.06) 207(1.40) 50t, 2nd 204(1.37) 201(1.42) 207(1.53) 186(1.02) 201(1.40) 50. . 3, 204 (1.35) 207 (1.39) 207 (1.51) 189 (1.02) 195 (1.39) 50 〇 C ' 4 198 (1.32) 207 (1.37) 201 (1.50) 189 (1.01) 195 (1.36) 5 (TC, 7 198 (1.28) 201 (1.33) 204 (1.45) 195 (1.01) 198 (1.29) (2) Initial coating 値〇〇〇 Δ 〇 50., 1 day 〇〇〇 X 〇 50 〇C, 2 days 〇〇〇X 〇50°C, 3 days 〇〇〇X 〇50. (:, 4 days Δ 〇. 〇X 〇. 50°C, 7 days △ Δ 〇X Δ (3) Sensitivity (300mJ/cm2) 6 segments, 6 segments, 6 segments, 6 segments, 6 segments, (4) imaging line (80 ° C) 80 minutes, 80 minutes, 80 minutes, 80 minutes, 80 minutes, 80 minutes (5) The surface is shiny, shiny, dull and shiny. Gloss (6) Soldering heat resistance 〇〇〇〇〇 Composition with or without xylene Μ Μ 、 、 Μ y y » As described above, the example of BYK-R606 using a polyhydroxycarboxylic acid ester additive does not contain Xylene, viscosity and thixotropy are excellent in stability over time, and coating properties are also less. In addition, in Example 2, the amount of W3 is about 5 -24 - (22) (22) 1357434. 〇.5% of the general use of polycarboxylate amide additives In the case of the BYK-R6 06 of the comparative example 2 of the BYK-40 5, it is understood that the coating properties of the soldering heat resistance of the sensitivity 'developing line' are not lowered even when the BYK-R6 06 of the polyhydroxycarboxylic acid ester additive is blended. [Simple description of the drawing J [Fig. 1] shows the IR spectrum of the polyacetate-based residual vinegar-based additive B YK-R606 used in Examples 1 to 3. -25

Claims (1)

13574341357434 第094104100號專利申請案中文申請專利範圍修正本 民國100年9月28日修正 十、申請專利範圍 1· 一種光硬化性•熱硬化性樹脂組成物，其特徵爲 含有（A)在一分子中具有丨個以上羧基之含羧基的樹脂、 (B)光聚合起始劑、（C)聚羥基羧酸酯系添加劑、（D)稀釋 劑、（E)塡充劑、及（F)環氧樹脂。Patent Application No. 094104100 Revision of Patent Application for Chinese Patent Application September 28, 100 Revision of the Republic of China, Patent Application Scope 1. A photocurable and thermosetting resin composition characterized by containing (A) in one molecule a carboxyl group-containing resin having more than one carboxyl group, (B) a photopolymerization initiator, (C) a polyhydroxycarboxylate additive, (D) a diluent, (E) a ruthenium, and (F) an epoxy Resin. 2.如申請專利範圍第1項之光硬化性•熱硬化性樹 脂組成物’其中該（C)聚羥基羧酸酯系添加劑係由二羧酸 二烷酯與烷醇胺之酯交換反應所合成。 3 .如申請專利範圍第1項之光硬化性.熱硬化性樹 脂組成物，其中該（C)聚羥基羧酸酯系添加劑之含量，在 組成物中爲〇 . 〇 1〜1 · 0 0質量％。 4 ·如申請專利範圍第1項之光硬化性.熱硬化性樹 脂組成物，其中該（E)塡充劑爲親水性二氧化矽。2. The photocurable thermosetting resin composition of claim 1 wherein the (C) polyhydroxycarboxylate additive is a transesterification reaction of a dialkyl dicarboxylate with an alkanolamine. synthesis. 3. The photocurable thermosetting resin composition of claim 1, wherein the content of the (C) polyhydroxycarboxylate additive is 〇. 〇1~1 · 0 0 quality%. 4. The photocurable thermosetting resin composition of claim 1, wherein the (E) chelating agent is hydrophilic cerium oxide. 5.如申請專利範圍第1〜4項中任一項之光硬化性· 熱硬化性樹脂組成物，其中另含有（G)非鹵素系有機顏 料。 6. 一種印刷配線板，其特徵爲具有使如申請專利範 圍第1〜5項中任一項之光硬化性·熱硬化性樹脂組成物 藉由活性能量線照射及/或加熱硬化所得的阻焊層及/或樹 脂絕緣層。5. The photocurable and thermosetting resin composition according to any one of claims 1 to 4, further comprising (G) a non-halogen organic pigment. 6. A printed wiring board, which is characterized in that the photocurable thermosetting resin composition according to any one of claims 1 to 5 is cured by active energy ray irradiation and/or heat curing. Solder layer and/or resin insulation layer.