TW201009500A

TW201009500A - Photopolymer composition, solder resist composition for print circuit boards and print circuit boards

Info

Publication number: TW201009500A
Application number: TW98123425A
Authority: TW
Inventors: Takao Ohno; Tatsuya Kiyota; Hiroyasu Nishiyama; Yasuyuki Hasegawa
Original assignee: Tamura Kaken Corp
Priority date: 2008-08-26
Filing date: 2009-07-10
Publication date: 2010-03-01
Also published as: JP5485599B2; JP2010079261A

Abstract

The present invention provides a liquid resin composition, which has fewer problems such as white coating discoloration and a declined reflectance caused by ultraviolet (UV) irradiation and thermal history, and can form patterns at a low exposure. The photosensitive resin composition of the present invention contains: (A) an active energy ray-curable resin, which is formed from a reaction of an alicyclic epoxide containing an ethylenically unsaturated bond, and a carboxyl of a copolymer resin, wherein the copolymer resin is prepared by a monomer selected from a group consisting of acrylic acid and acrylic acid ester, and a monomer selected from a group consisting of methacrylic acid and methacrylic acid ester; (B) a thiol compound; (C) a photopolymerization initiator; (D) a diluent; (E) a rutile type titanium dioxide; and (F) an epoxy thermosetting compound.

Description

201009500 六、發明說明： C發明所屬·^技術領域3 發明領域本發明係關於一種感光性樹脂組成物、印刷配線板用之阻焊劑組成物及印刷配線板。 ' 發明背景 0 印刷配線板是在基板上形成導體電路的圖案，以便在該圖案的焊接襯墊上以焊接的方式搭載電子零件，除其焊接襯墊外之電路部分要被覆以阻焊劑膜作為永久保護皮膜。藉此，防止焊料在將電子零件焊接於印刷配線板時附 * 一著於不必要的部分，同時防止電路導體直接曝露於空氣中而因氧化或濕度而受到腐蝕。伴隨著提昇印刷配線基板之配線密度（微細化）的要求，阻焊劑組成物也被要求要有高解析度、要高精度化， % 無淪是民生用基板、產業用基板，從網板印刷法，到位置精度、導體邊緣部的被覆性良好之液態感光阻焊劑法(照片顯影法)都已受到建議。這樣的阻焊劑組成物在例如以下的文獻中已有記載。其他還有，可用烯鹼水溶液顯影的鹼性顯影型感光阻焊劑組成物被提出（專利文獻7)。這些液態阻焊劑組成物，是透過在環氧丙烯酸酯中導入羧基的方式，賦予感光性或在烯鹼水溶液的顯影性。但是，在該組成物中，因為進一步對其塗膜施行曝光、顯影 201009500 乂形成所需的阻焊圖案(resist pattern)後通常會使其發生熱硬化，故通常會含有環氧化物做為熱硬化成分，並施仃使上述環氧丙烯酸g旨與所導人之㈣發生反應之加熱處里以使其形成密著性、石更度、耐熱性、電氣絕緣性等優良之阻焊膜。這種情形，通常是併用環氧樹脂和環氧樹脂用硬化劑。先前技術文獻專利文獻專利文獻1特開昭5 0-144431號公報專利文獻2特開昭49-5923號公報專利文獻3特開昭61 -243 8 69號公報專利文獻4特開2001 -23 3 842號公報專利文獻5特開2001-302871號公報專利文獻6特開2003 -280193號公報專利文獻7特開2006-259150號公報專利文獻8特願2007-047295 C 明内；3 發明概要發明欲解決之課題但是’尤其是使用白色阻焊劑時，加熱塗膜以使其硬化時會發生變色，有著色的現象，光反射率下降。在白色阻焊劑的情形中，因為變色和反射率的降低特別明顯，故會有招致商品價值下降之虞，解決方案受到需求。另一方面’阻焊劑組成物必須以比較低的曝光量進行硬化，存在 201009500 著自相矛盾的課題。為解決該問題，本案申請人在專利文獻8中揭示—種感光性樹脂組成物，其主成分是以脂環族環氧化物為原料的感光性樹脂。但是，對於該組成物而言，在加熱後的變色改善等的點上，也留下進一步改善的餘地。本發明的課題是提供一種因uv照射、熱歷程而導致之白色塗膜的變色及反射率降低的情形少，而且，能以低曝光量形成圖案之液態樹脂組成物。用以欲解決課題之手段本發明係關於一種感光性樹脂組成物，特徵在於其含有·· 、3 (A) 使含有乙烯性不飽和鍵之脂環族環氧化物，對選自丙烯酸及丙烯酸酯組成之族群的單體與選自甲基丙烯酸及甲基丙烯酸酯組成之組群的單體形成之共聚性樹脂的羧基進行反應而形成之活性能量線硬化性樹脂， (B) 硫醇系化合物， (C) 光聚合起始劑， (D) 稀釋劑， (E) 金紅石型二氧化鈦，及 (F) 環氧系熱硬化性化合物。另外，本發明係關於一種印刷配線板用之阻焊劑組成物，特徵在於其係由前述感光性樹脂組成物所組成。此外，本發明係關於一種搭載電子零件前或搭載後的印刷配線板，其具有該阻焊劑組成物的硬化膜。 201009500 發明效果由本發明的感光性樹脂組成物所形成之白色塗膜，因 uv照射、熱歷程而導致之變色及反射率降低的情形少而且，能以低曝光量形成圖案。 C實施方式：j 用以實施發明之最佳形態以下，關於本發明組成物的各成分進行描述。 [(A)使含有乙烯性不飽和鍵之脂環族環氧化物，對選自丙烯酸和丙烯酸酯組成之族群的單體與選自甲基丙烯酸和曱基丙烯酸酯組成之族群的單體形成之共聚性樹脂的羧基進行反應而形成之活性能量線硬化性樹脂] (A)疋由岫述共聚物與脂環族環氧化物的反應所獲得之’活性能量線硬化性樹脂。脂環族環氧化物是含有脂環式骨架和環氧基之化合物乃至於樹脂，骨架是由脂肪族環式化合物或其鏈形成。環氧§量並無特殊限制，通常在1，〇〇〇以下，以使用1〇〇〜5〇〇者為佳。關於脂肪族環式化合物，可例示如環己烷、環戊燒。另外，脂環族環氧化物含有乙烯性不飽和鍵。該乙烯性不飽和鍵，以例如丙烯酸基、甲基丙烯酸基的不飽和鍵為宜。脂環族環氧化物可例示如，Daicei chemical Industries， LTD.製「CELL〇XIDE 2021P」,r CELLOXTDF 2000 ,、 201009500The present invention relates to a photosensitive resin composition, a solder resist composition for a printed wiring board, and a printed wiring board. BACKGROUND OF THE INVENTION A printed wiring board is a pattern in which a conductor circuit is formed on a substrate so that electronic parts are soldered on the solder pads of the pattern, and a circuit portion other than the solder pads is coated with a solder resist film. Permanently protect the film. Thereby, the solder is prevented from being attached to an unnecessary portion when soldering the electronic component to the printed wiring board, while preventing the circuit conductor from being directly exposed to the air and being corroded by oxidation or humidity. With the increase in the wiring density (fineness) of the printed wiring board, the solder resist composition is required to have high resolution and high precision, and it is a substrate for industrial use and an industrial substrate. The liquid photo-resistance soldering method (photo development method) to the positional accuracy and the coating property at the edge of the conductor has been recommended. Such a solder resist composition is described, for example, in the following documents. Further, an alkaline development type photosensitive resist composition developed with an aqueous solution of an alkene solution has been proposed (Patent Document 7). These liquid solder resist compositions impart photosensitivity or developability in an aqueous alkali solution by introducing a carboxyl group into the epoxy acrylate. However, in this composition, since the coating film is further exposed and developed, 201009500 乂 is formed into a desired resist pattern, which usually causes thermal hardening, and therefore usually contains epoxide as heat. The soldering agent is used to form a solder resist film which is excellent in adhesion, stoneness, heat resistance, electrical insulation, and the like in the heating place where the epoxy acrylate is reacted with the person (4). In this case, a hardener for epoxy resin and epoxy resin is usually used in combination. CITATION LIST Patent Literature PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT LIST OF THE INVENTION Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The problem to be solved is that, in particular, when a white solder resist is used, the coating film is heated to cause discoloration when it is hardened, and there is a coloring phenomenon, and the light reflectance is lowered. In the case of a white solder resist, since the reduction in discoloration and reflectance is particularly noticeable, there is a risk that the value of the product will fall, and the solution is demanded. On the other hand, the solder resist composition must be hardened with a relatively low exposure, and there is a contradiction between 201009500. In order to solve this problem, the applicant of the present invention disclosed a photosensitive resin composition whose main component is a photosensitive resin using an alicyclic epoxide as a raw material. However, this composition leaves room for further improvement in terms of improvement in discoloration after heating and the like. An object of the present invention is to provide a liquid resin composition which is less likely to cause discoloration and a decrease in reflectance of a white coating film due to uv irradiation or thermal history, and which can form a pattern with a low exposure amount. Means for Solving the Problems The present invention relates to a photosensitive resin composition characterized in that it contains (3) an alicyclic epoxide containing an ethylenically unsaturated bond, and is selected from the group consisting of acrylic acid and acrylic acid. An active energy ray-curable resin formed by reacting a monomer of a group having an ester composition with a carboxyl group of a copolymer resin formed from a monomer of a group consisting of methacrylic acid and methacrylic acid ester, and (B) a thiol-based resin a compound, (C) a photopolymerization initiator, (D) a diluent, (E) a rutile-type titanium oxide, and (F) an epoxy-based thermosetting compound. Further, the present invention relates to a solder resist composition for a printed wiring board, characterized in that it is composed of the above-mentioned photosensitive resin composition. Further, the present invention relates to a printed wiring board before or after mounting an electronic component, which has a cured film of the solder resist composition. According to the photosensitive resin composition of the present invention, the white coating film formed by the photosensitive resin composition of the present invention has a small amount of discoloration and a decrease in reflectance due to uv irradiation and heat history, and can be patterned with a low exposure amount. C Embodiment: j Best Mode for Carrying Out the Invention Hereinafter, each component of the composition of the present invention will be described. [(A) forming an alicyclic epoxide containing an ethylenically unsaturated bond, forming a monomer selected from the group consisting of acrylic acid and acrylate, and a monomer selected from the group consisting of methacrylic acid and methacrylic acid ester An active energy ray-curable resin formed by reacting a carboxyl group of a copolymer resin] (A) An active energy ray-curable resin obtained by reacting a copolymer with an alicyclic epoxide. The alicyclic epoxide is a compound containing an alicyclic skeleton and an epoxy group or a resin, and the skeleton is formed of an aliphatic cyclic compound or a chain thereof. The amount of the oxygen § is not particularly limited, and is usually 1 or less, preferably 1 to 5 Torr. As the aliphatic cyclic compound, for example, cyclohexane or cyclopentene can be exemplified. Further, the alicyclic epoxide contains an ethylenically unsaturated bond. The ethylenically unsaturated bond is preferably an unsaturated bond such as an acrylic group or a methacryl group. The alicyclic epoxide can be exemplified by "CELL 〇 XIDE 2021P" manufactured by Daicei Chemical Industries, LTD., r CELLOXTDF 2000, and 201009500.

此外，化合物名乃至於樹脂名町例示如，3,4_環氧環己烯基甲基_3'，4，-環氧環己烯甲酸酯O+epoxycydohexyi-methyl-SW-epoxycyclohexenecarboxylate) 、一氧化乙稀基環己烯1,2-環氧-4_乙烯基環己烷（vinylcyclohexene monoxide l，2-epoxy-4-vinylcyclohexane)、1，2 : 8,9二氧化萜二稀（1，2 :8,9-diepoxylimonene)、2,2-雙（經甲基)-i-丁醇的 1,2-環氧基-4-(2-環氧乙烧基）環己烧 (2,2-bis(hydoroxymethyl) 1 -butanol of l-2-ep〇xy-4(2-oxiranyl)-CyCl〇hexane)加成產物2,2-雙（羥甲基）〜丨—丁醇的 1，2-環氧基+(2-環氧乙烷基)環己烷加成產物和3,4-環氧環乙烯基甲基环氧环己烯基甲酸酯等。另外’脂環族環氧化物的結構式可例示如下。【化1】In addition, the compound name is, for example, a resin name, such as 3,4-epoxycyclohexenylmethyl_3',4,-epoxycydohexyi-methyl-SW-epoxycyclohexenecarboxylate, 1,2-epoxy-4-vinylcyclohexane, 1,2:8, 8,9 cerium oxide dilute (1,2-epoxy-4-vinylcyclohexane) , 2:8,9-diepoxylimonene), 2,2-bis(methyl)-i-butanol 1,2-epoxy-4-(2-epoxyethyl)cyclohexane (2 ,2-bis(hydoroxymethyl) 1 -butanol of l-2-ep〇xy-4(2-oxiranyl)-CyCl〇hexane) Addition product 2,2-bis(hydroxymethyl)~indole-butanol 1 A 2-epoxy+(2-oxiranyl)cyclohexane addition product and a 3,4-epoxycyclovinylmethylepoxycyclohexenylcarboxylate. Further, the structural formula of the 'alicyclic epoxide can be exemplified as follows. 【化1】

【化3】 0： 0 7 201009500 【化4】[化3] 0: 0 7 201009500 【化4】

前述共聚物樹脂是由選自丙烯酸及丙烯酸酯組成之族群的一種或兩種以上之單體和，選自曱基丙烯酸及甲基丙烯酸酯組成之族群的一種或兩種以上的單體經共聚合反應而獲得之共聚物。將例如，由丙烯酸和曱基丙烯酸經共聚合反應而獲得之共聚物示於以下。【化5】丙烯酸酯甲基丙稀酸睹The copolymer resin is one or two or more monomers selected from the group consisting of acrylic acid and acrylate, and one or two or more monomers selected from the group consisting of methacrylic acid and methacrylic acid ester. a copolymer obtained by polymerization. For example, a copolymer obtained by copolymerization of acrylic acid and mercaptoacrylic acid is shown below.化 5 acrylate methacrylate

COOH COOR COOH COOR 另外，由丙烯酸酯和甲基丙烯酸酯之經共聚合反應而獲得的共聚物示於以下。R為烷基，以甲基或乙基為佳。 201009500 【化6】力烯酸酯COOH COOR COOH COOR Further, a copolymer obtained by copolymerization of an acrylate and a methacrylate is shown below. R is an alkyl group, preferably a methyl group or an ethyl group. 201009500 【化6】 olefinic acid ester

COOHCOORCOOH 〇〇〇„ Ο 前述共聚物的製法並無特殊限制，可以㈣習知㈣法。另外共聚㈣質量平均分子量以1G_〜3_為佳，雙鍵當量以300〜500為佳。前述共聚物在1分子中至少含有2個羧基。i分子中存在的羧基個數並無特殊限制，惟以10〜500個為宜。接著，使前述共聚物的羧基與脂環族環氧化物的環氧基發生反應。於是，通過環氧基與羧基的反應，環氧基如下所述地，發生開裂而與羥基生成酯鍵。獲得之活性能量線硬化性樹脂含有源自環氧基的乙烯性不飽和鍵。再者， Ri為氫、烷基，或者羥烷基，以氫或曱基為佳。【化7】COOHCOORCOOH 〇〇〇 Ο 制 The preparation method of the above copolymer is not particularly limited, and may be (4) a conventional (four) method. Further, the copolymer (4) preferably has a mass average molecular weight of 1 G 〜 3 _ and a double bond equivalent of 300 〜 500. There are at least two carboxyl groups in one molecule. The number of carboxyl groups present in the i molecule is not particularly limited, but is preferably from 10 to 500. Next, the carboxyl group of the aforementioned copolymer and the epoxy of the alicyclic epoxide are used. Then, the epoxy group reacts with the carboxyl group, and the epoxy group is cleaved to form an ester bond with the hydroxyl group as described below. The obtained active energy ray-curable resin contains an epoxy group derived from an epoxy group. Further, Ri is hydrogen, an alkyl group, or a hydroxyalkyl group, preferably hydrogen or a mercapto group.

9 201009500 在前述共聚物與脂環族環氧化物的反應中，相對於脂環族環氧化物含有之環氧基每〖當量，使前述共聚物以羧基的當量數為0.7〜1.2當量進行反應為佳。若前述共聚物量之 · 羧基的當量數不足0.7當量，於後續製程的合成反應時就會有發生凝膠化的情形’或者樹脂的安定性降低。另外，若共聚物過剩’則因剩餘許多未反應的羧基，故有使硬化物的各種特性(例如耐水性等）降低之虞。脂環族環氧化物與共聚物的反應’宜在加熱狀態下進行，其反應溫度以8〇〜140 °C為佳。反應溫度若超過140。(： ’合成就會變得困難，若不 ® 足80°C則反應速度會變慢，不適合於實際製造。脂環族環氧化物與共聚物在稀釋劑中的反應，稀釋劑的混合量相對於反應系的總質量，以20〜50%為佳。 - (A)的具體例，可例示如 Daicel Chemical Industries, LTD. 製「Cyclomer P (ACA) Z-251」、「CyclomerP(ACA)Z-250」、「CyclomerP(ACA)Z-300」。再者，Daicel Chemical Industries，LTD.製「Cyclomer P (ACA) Z-251」係以上述化 ❹ 7的結構式表示。 [(B)硫醇系化合物] 意指含有硫醇基之有機化合物，可例示如，3-酼基丙酸、Μ基丙酸甲氧基丁酯、酼基丙酸辛酯、巯基丙酸十三院S旨、三經甲基丙烧三硫代丙酸酯（trimethylolpropane tris(thiopropionate))、三經甲基丙烧三（3 -疏基丙酸S旨）、季戊四醇四硫代丙酸醋（pentaerythritol tetrakis(thio-propionate))等，尤其以三經甲基丙烧三硫代丙酸醋及/或季 10 201009500 戊四醇四硫代丙酸醋為佳。 [Ο光聚合起始劑] 為使祕多g能環氧樹脂之光硬化的光聚即無特殊限制，可银如i 别 ^ 了舉例如，肟系起始劑、安息香、安息香女心香乙醚、女息香異丙醚、安息香正丁醚、安息香：丁醚、苯乙酮、二甲胺基笨乙酮、二甲氧基—2—苯基苯+乙_、2,2-二乙氧基_2_苯基苯乙^j、2-經基_2甲基土丙烧 1 嗣(^-Hydroxyj-methyl-l-phenylpropan-l- one)、 1-羥基環己基苯基酮、 2 甲基 _ι_ 〔4_( 曱硫基 ) 苯基〕馬琳基-丙烧—1—蜗（2_methyi_i_[4_(methylthio) phenyl]-2-(4-morpholinyl)-l-one)、4-(2-羥基乙氧基）苯基 2 ( I 基-2-丙基）酿J (4_(2_hydroxyethoxy)phenyl-2- (hydroxyl-2-propyl)ketone)、二苯甲 _(benzophenone)、對苯基二苯甲酮、4,4'-二乙基胺二苯甲酮、二氯二苯甲酮、2-甲基蒽醌、2-乙基蒽醌、2-叔丁基蒽醌、2-胺基蒽醌、2-甲基硫雜蒽酮（2-methylthioxanthone)、2-乙基硫雜蒽銅、2_ 氣硫雜蒽酮、2,4-二甲基硫雜蒽酮、2,4-二乙基硫雜蒽酮、苯偶酿二甲基縮酮(benzil dimethyl ketal)、苯乙酮二甲基縮胴（acetophenone dimethyl ketal)、對二曱胺基安息香酸乙酯、2,4,6-三曱基苯曱醯基-二苯基膦氧化物 (2,4,6-trimethylbenzoyl-diphenylphosphine oxide)、雙（2,4,6- 三甲基苯甲醯基）-苯基膦氧化物（bis(2,4,6-trimethyl-benzoyl-phenylphosphineoxide)等。可將其等單獨或組合做使用。 201009500 [(D)稀釋劑] (D)稀釋劑由光聚合性單體及有機溶_至少—触 . 成。因為g合性稀釋劑又被稱為反應性稀釋劑，所叫 · 會使上述⑷齡的感級樹脂更充分地進行光硬化是= 了獲得具㈣酸性、耐熱性、_性等之塗膜而使用者。反應性稀釋劑’以使用1分子中至少有2個雙鍵之化合物為佳。為調節含有域(A)成分的感紐樹脂之喊㈣崎和乾燥性，亦可使用非反應性稀釋劑之有機溶劑，但是2 果沒有這個必要也可以不使用有機溶劑。另外，當僅靠上參述(A)感光性樹脂的光硬化性就足夠時，亦可不使用光聚合性單體。該光聚合性單體(反應性稀釋劑）代表性者，可舉例如， 1，4_丁一醇一（甲基）丙稀酸醋、1,6-己二醇二（甲基）丙稀酸 ' 6旨、新戊二醇二（甲基）丙稀酸醋（ne〇pentyl glyc〇l di(meth)acrylate)、聚乙二醇二（曱基）丙稀酸酯、新戊二醇己·一酸一（曱基）丙稀酸醋（neopentyl glycol adipate ◎ di(meth)acrylate)、羥基三曱基乙酸新戊二醇二（甲基）丙烯酸酯、二甲基丙烯酸三環[5.2.1.02,6]癸-8-基酯（dicyclo-pentanyl di(meth)acrylate)、己内酯變性二甲基丙烯酸三環 [5.2.1.02,6]癸-8-基酯、環氧乙烷變性二（曱基）丙烯酸酯磷酸酯、烯丙基化環己基二（甲基）丙烯酸酯、異氰脲酸二（曱基）丙稀酸醋（isocyanurate di(meth)acrylate)、三經甲基丙烧三（甲基）丙烯酸酯、二季戊四酵三（甲基）丙烯酸酯、丙酸變性二季戊四醇三（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸 12 201009500 醋、環氧丙烷變性三羥甲基丙烷三（甲基）丙烯酸酯、三（丙稀醢氧乙基）異氰腺酸醋（tris (acryloxyethyl)isocyanurate)、丙酸變性_季戊四醇五（甲基）丙稀酸g旨、二季戊四醇六（甲基）丙烯酸酯、己内酯變性二季戊四醇六（曱基）丙烯酸酯等之反應性稀釋劑。上述2〜6官能以外的其他多官能反應性稀釋劑，無論是單品或複數個混合系的任一種都可以使用。該反應性稀釋劑的添加量’相對於感光性樹脂100質量分，以2 〇〜 40質量分為佳。其添加量如果太少，就不能得到充分的光硬化’在硬化塗膜的耐酸性等方面不能獲得充分的特性，另外’若過多，則黏性強，曝光時照相底版薄膜(artw〇rk film) 變得容易發生黏著到基板的情形，難以得到作為目的之硬化塗膜。從光硬化性、硬化塗膜的耐酸性、耐熱性等之物性’防止照相底版薄膜黏著到基板的點來看，反應性稀釋劑的添加量’相對於(A)感光性樹脂1〇〇質量分，以4 〇〜3〇質量分較佳。上述的有機溶劑可舉例如，甲乙酮、環己酮等之酮類，甲笨、二甲苯等之芳香族烴類，甲醇、異丙醇、環己醇等之醇類’環己烧、甲基環己烷等之脂環式烴類、石油醚、石油腦(naphtha)等之石油系溶劑類，溶纖劑、丁基溶纖劑等之溶纖劑類、卡必醇(carbit〇l)、丁卡必醇等之卡必醇類，乙酸乙Sa、乙酸丁醋、溶纖劑醋酸g旨（ceii〇s〇ive aeetate)、丁基溶纖劑醋酸醋、卡必醇乙酸醋（carbit〇i acetate)、丁卡必醇乙酸酯等之乙酸酯類等。使用有機溶劑時，其使用量， 13 201009500 相對於(A)感光性樹脂loo質量分，以4〇〜5〇〇質量分為佳。 [(E)金紅石型二氧化鈦] 是具有金紅石結晶構造之二氧化欽粒子使_白& 化。該粒子的平均粒徑並無特殊限制，惟以〇〇1〜為佳。此外，金紅石型二氧化鈥粒子的表面處理劑亦無特殊限制。 [(F)環氧系熱硬化性化合物] 是在感光性樹脂組成物中，為了在使塗膜曝光，顯影後的後硬化(post cure)處理後獲得足夠強物的塗膜（塗膜強度、耐熱性、耐久性、耐藥品性、耐環境性等）而加入者。環氧系熱硬化性化合物的代表性化合物，雖以丨分子中至少有1個環氧基，較佳為有2個以上的環氧基之環氧樹脂 (包含環氧低聚物）為合適，但並不限於此。可舉例如，使雙酚A與環氧氣丙烷(epichlorohydrin)在鹼的存在下進行反應所獲得之雙酚A型環氧樹脂，使雙酚A與福馬林(f〇rmalin) 發生縮合反應所獲得之樹脂的環氧化物’在這些樹脂中，用漠化雙酚A取代雙酚A而形成者，使酚醛樹脂（n〇v〇lac resin)與環氧氣丙烧反應而產生縮水甘油趟化之盼酸型環乳樹月曰（盼醒型環氧樹脂(phen〇i n〇volac epoxy resin)、鄰甲盼酸型環氧樹脂、對-叔丁酚酚醛型等），使雙酚F或雙酚S 與環氧氯丙烷反應而得到之雙酚F型或雙酚S型環氧樹脂，進一步為含有環氧環己基、環氧三環癸基、環氧環戊基等之脂環式環氧樹脂，鄰苯二甲酸二縮水甘油酯（phthalic acid diglycidylester)、四氫鄰苯二甲酸二縮水甘油酯、六氫鄰苯 201009500 二甲酸二縮水甘油酯、對-羥基安息香酸二縮水甘油酯 (p-hydroxybenzoic acid diglycidyl ester)、二聚酸縮水甘油酯等之縮水甘油酯樹脂，四縮水甘油基二氨基二苯基甲烷 (tetraglycidyl diamino-diphenyl methane)、對氨基笨盼三縮水甘油等之縮水甘油胺(glycidyl amine)系樹脂，（丙婦、聚丙烯)二醇二縮水甘油醚、聚四亞甲基二醇二縮水甘油醚、丙三醇縮水甘油醚(glycerol polyglycidyl ether)、三羥甲基丙烧聚縮水甘油醚(trimethylolpropane polyglydicyl ether)、間苯二齡二縮水甘油醚' 1，6-己二醇二縮水甘油醚、（乙稀、丙烯)二醇二縮水甘油醚、山梨醇聚縮水甘油醚、山梨醇酐聚縮水甘油醚、季戊四醇聚縮水甘油謎等之縮水甘油醚樹脂，異氰腺酸三(2,3_環氧丙基)酯、異氰腺酸三縮水甘油三 (2-羥乙基）酯等之含有三嗪環的三縮水甘油異氰脲酸酯，雙環戊二稀型環氧樹脂等。熱硬化性化合物(F)既可單獨使用，亦可倂用複數種使用。本發明之感光性樹脂組成物中，（A)活性能量線硬化性樹脂的含量以10〜50質量％為佳。另外，（B)硫醇系化合物的含量以〇〇1質量0/〇以上為佳，藉此，白色塗膜的變色等之防止效果更為提高。從這個觀點來看，（B)硫醇系化合物的含量以〇.5質量％以上更佳，1.0質量％以上更為合適。另外，（B)硫醇系化合物的含量以5.0質量％以下為佳，藉此，即無虞對阻焊劑的保存安定性造成不良影響。從這個觀點出發，以2 〇質量％以下更佳。 15 201009500 本發明的組成物中，（C)光聚合起始劑的質量比以o.i 〜10.0質量％為佳，0.2〜5.〇質量％更佳。 ~ 本發明的組成物中’（D)稀釋劑的質量比以1.0〜1〇,〇質 - 量％為佳’ 3.0〜6.0質量％更佳。本發明的組成物中，透過將(E)金紅石型二氧化鈦的質量比定為5質量％以上可提高塗膜的白色度。從這個觀點出發，（E)的質量比定為20質量％以上更佳，30質量％以上又更好。此外’（E)的質量比即使超過50質量％白色度亦不會提高，而且在強度等的點上有不良影響，故(E)的質量比以〇 50質量％以下為佳，40質量％以下更佳。本發明的組成物中，（F)環氧系熱硬化性化合物的質量比’以1.0〜30質量％為佳，5.0〜20質量％更佳。本發明的感光性樹脂組成物中，上述成分(A)〜(F)以、外’可依需要而使其含有各種添加劑，例如消泡劑、流平劑（leveling agent)等之塗料用添加劑。上述(A)〜（F)及依需要被混合之其他成分，利用三輥磨、球磨機、砂磨機等捏合裝置，或高迷混合機、行星攪 © 拌機(planetary mixer)等攪拌裝置加以捏合或混合，可獲得本發明的感光性樹脂組成物。將如上所述地處理而得到之本發明的感光性樹脂組成物，對，例如具有蚀刻覆銅積層板的鋼箱而形成之電路圖案的印刷配線板，以所需的厚度，例如5〜1〇〇μιη的厚度施行塗布。塗布的方法，雖然目前-般多是使用網板印刷法做全面印刷’不過包含這個在内’只要是可以均勻塗布的 16 201009500 塗布方法，不論哪種方法都可以使用。例如，喷塗機、熱熔塗布機、塗布棒、塗布器（applicator)、刮刀式塗布機(bia(je coater)、刀式塗布機（knife coater)、氣刀塗布機（air knife coater)、幕式淋塗機（curtain flow coater)、親筒塗布機、凹版印刷塗布機(gravure coater)、平版印刷（offset printing)、浸塗機、刷毛塗布，其他一般的方法全部可以使用。塗布後，可依需要用熱風爐或遠紅外線爐等進行預烘’亦即進行臨時性乾燥，使塗膜表面形成不黏的狀態。預烘的溫度大體上以50〜100°C左右為佳。接著’使用LDI(laser Direct imaging)的錯射直接成像進行曝光。或者，使用會讓活性能量線形成不通過狀態之負型光罩(negative mask)施行利用活性能量線的曝光。負型光罩雖然分別在活性能量線為紫外線之情形中使用負片 (negative film)，電子射線的情形中使用金屬性光罩，X射線的情形中使用鉛光罩，但是為了可以使用簡單的負片，在印刷配線板的製造中多是使用紫外線作為活性能量線。紫外線的照射量大體上為1 〇〜1 OOOmJ/ cm2。曝光，在製造印刷配線板時是以，例如密著使電路圖案的焊接襯墊以外形成透光性之圖案的負片，再自其上方照射紫外線的方式來進行，但是對應於該焊接襯塾之非曝光區域則用稀鹼水溶液除去’藉以使塗膜顯影。這個除去操作可以是未曝光部分的溶解、膨潤、剝離等之任一形式。此時所使用的稀驗水溶液通常是0.5〜5%的碳酸鈉水溶液，惟亦可使用其他的鹼。 17 201009500 其次，在含有熱硬化性化合物的情形中是例如，用 70 c的熱風爐或遠紅外線爐等之乾燥機等加熱例如 2〇〜8〇分鐘，或者‘賴紫外_方式進行後硬化，I! 此可以使阻焊皮膜形成。如此處理而獲得以阻焊膜被覆之印刷配線板電子零件可藉熔錫波焊接法或，回料接法崎焊接以連接、固定並搭載於其上，形成一個電子電路單元。該電子零件搭載前之被覆阻焊皮膜的印刷配線板，該印刷配線板上搭載了電子零件之電子零件搭載後的印職 © 線板之任一者都包含於本發明中。【實施例】 (實施例1) 將各成分以下述的質量比混合製作阻焊劑組成物。詳、細的成分量示於以下。9 201009500 In the reaction of the above copolymer with the alicyclic epoxide, the above copolymer is reacted in an equivalent amount of the carboxyl group of 0.7 to 1.2 equivalents per equivalent of the epoxy group contained in the alicyclic epoxide. It is better. When the number of equivalents of the carboxyl group in the amount of the copolymer is less than 0.7 equivalent, gelation may occur in the synthesis reaction in the subsequent process, or the stability of the resin may be lowered. Further, if the copolymer is excessive, there are many unreacted carboxyl groups remaining, so that various properties (e.g., water resistance, etc.) of the cured product are lowered. The reaction of the alicyclic epoxide with the copolymer is preferably carried out under heating, and the reaction temperature is preferably from 8 Torr to 140 °C. The reaction temperature exceeds 140. (: 'Synthesis becomes difficult. If it is not 80 ° C, the reaction rate will be slower and it is not suitable for actual production. The reaction of alicyclic epoxide and copolymer in diluent, the amount of diluent With respect to the total mass of the reaction system, it is preferably 20 to 50%. - Specific examples of (A) include "Cyclomer P (ACA) Z-251" and "Cyclomer P (ACA)" manufactured by Daicel Chemical Industries, LTD. "Cyclomer P (ACA) Z-300" manufactured by Daicel Chemical Industries, Ltd. is represented by the structural formula of the above-mentioned chemical formula 7. [(B) The thiol-based compound is an organic compound containing a thiol group, and examples thereof include 3-mercaptopropionic acid, methoxypropyl mercaptopropionate, octyl decyl propionate, and mercaptopropionic acid. , trimethylolpropane tris (thiopropionate), trimethyl methacrylate tris(3-propionyl propionate S), pentaerythritol tetrathioacetate (pentaerythritol tetrakis ( Thio-propionate)), etc., especially with trimethyl methacrylate trithiopropionate and/or season 10 201009500 pentaerythritol tetrathiopropionic acid Vinegar is preferred. [Twilight Polymerization Initiator] There is no particular limitation on the light-hardening of the light-curing epoxy resin, and silver can be used as an initiator, benzoin, etc. Benzoin female heart scented ether, feminine isopropyl ether, benzoin n-butyl ether, benzoin: dibutyl ether, acetophenone, dimethylamino acetophenone, dimethoxy-2-phenylbenzene + B, 2, 2-Diethoxy-2-phenylphenylethylidene, 2-hydroxyl-methyl-l-phenylpropan-l-one, 1-hydroxycyclohexyl Phenyl ketone, 2 methyl _ι_ [4_(decylthio)phenyl] marinyl-i-[4_(methylthio) phenyl]-2-(4-morpholinyl)-l-one) , 4-(2-hydroxyethoxy)phenyl 2 (I-yl-2-propyl), J (4_(2-hydroxyethoxy)phenyl-2-(hydroxyl-2-propyl)ketone), benzophenone ), p-phenyl benzophenone, 4,4'-diethylamine benzophenone, dichlorobenzophenone, 2-methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl Bismuth, 2-aminopurine, 2-methylthioxanthone, 2-ethylthiazepine, 2_gas thioxanthone, 2,4- Methyl thia fluorenone, 2,4-diethyl thioxanthone, benzil dimethyl ketal, acetophenone dimethyl ketal, p-quinone Ethyl benzoic acid ethyl ester, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethyl Bis(2,4,6-trimethyl-benzoyl-phenylphosphineoxide) or the like. They can be used individually or in combination. 201009500 [(D) Diluent] (D) Diluent is formed by photopolymerizable monomer and organic solvent. Since the g-compatible diluent is also called a reactive diluent, it is called to make the above-mentioned (4)-age sensitive resin more fully photocurable = to obtain a coating film having (4) acidity, heat resistance, _ness, etc. And the user. The reactive diluent ' is preferably a compound having at least two double bonds in one molecule. In order to adjust the squeakyness and dryness of the sensitizing resin containing the domain (A) component, an organic solvent of a non-reactive diluent may also be used, but if it is not necessary, the organic solvent may not be used. Further, when only the photocurability of the photosensitive resin (A) is sufficient, the photopolymerizable monomer may not be used. Representative examples of the photopolymerizable monomer (reactive diluent) include 1,4-butanol mono(methyl)acrylic acid vinegar and 1,6-hexanediol di(methyl)propyl chloride. Dilute acid, neopentyl glycol bis(meth)acrylate, polyethylene glycol bis(indenyl) acrylate, neopentyl Neopentyl glycol adipate ◎ di(meth)acrylate, hydroxytrimercaptoacetic acid neopentyl glycol di(meth)acrylate, trimethacrylic acid tricyclo[ 5.2.1.02,6]dicyclo-pentanyl di(meth)acrylate, caprolactone denatured tricyclohexyl dimethacrylate [5.2.1.02,6]癸-8-yl ester, epoxy B Alkenyl-denatured bis(indenyl) acrylate phosphate, allylated cyclohexyl di(meth) acrylate, isocyanurate di(meth)acrylate, three-jinge Methylpropane tris(meth)acrylate, dipentaerythritol tris(meth)acrylate, propionic acid denatured dipentaerythritol tri(meth)acrylate, pentaerythritol tris(meth)acrylic acid 12 201009500 Vinegar, propylene oxide denatured trimethylolpropane tri(meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid denaturation _ pentaerythritol five (methyl A reactive diluent such as acrylic acid, dipentaerythritol hexa(meth) acrylate or caprolactone denatured dipentaerythritol hexakisyl acrylate. Any of the polyfunctional reactive diluents other than the above 2 to 6 functional groups may be used in either a single product or a plurality of mixed systems. The amount of addition of the reactive diluent is preferably 2 parts by mass to 40 parts by mass based on 100 parts by mass of the photosensitive resin. If the amount of addition is too small, sufficient photohardening cannot be obtained. 'Sufficient characteristics cannot be obtained in terms of acid resistance of the cured coating film, etc. In addition, if too much, the viscosity is strong, and the photographic film (artw〇rk film) is exposed. When it is easy to adhere to a substrate, it is difficult to obtain a hardened coating film as a target. From the point of view of the photocurability, the acid resistance of the cured coating film, and the physical properties of the heat-resistant coating, the amount of the reactive diluent added is relative to the (A) photosensitive resin. The score is preferably 4 〇 to 3 〇. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as methyl bromide and xylene, and alcohols such as methanol, isopropanol and cyclohexanol. An alicyclic hydrocarbon such as cyclohexane, a petroleum solvent such as petroleum ether or naphtha, a cellosolve such as a cellosolve or a butyl cellosolve, or a carbitol or a butyl group. Carbitol such as carbitol, ethyl acetate Sa, acetic acid butyl vinegar, cellosolve acetic acid g (ceii〇sive aeetate), butyl cellosolve acetate vinegar, carbitol acetate (carbit〇i acetate) An acetate such as tetracaine acetate or the like. When using an organic solvent, the amount of use, 13 201009500 is better than (A) photosensitive resin loo mass fraction, and is preferably 4 〇 to 5 〇〇. [(E) Rutile Titanium Dioxide] is a oxidized crystal having a rutile crystal structure to make _white & The average particle diameter of the particles is not particularly limited, but 〇〜 1 is preferred. Further, the surface treatment agent for the rutile-type cerium oxide particles is not particularly limited. [(F) epoxy-based thermosetting compound] is a coating film in which a sufficiently strong substance is obtained in a photosensitive resin composition in order to expose a coating film and post-curing treatment after development (coating strength) , heat resistance, durability, chemical resistance, environmental resistance, etc.). A representative compound of the epoxy-based thermosetting compound is preferably an epoxy resin (including an epoxy oligomer) having at least one epoxy group in the fluorene molecule, preferably two or more epoxy groups. , but not limited to this. For example, a bisphenol A type epoxy resin obtained by reacting bisphenol A and epichlorohydrin in the presence of a base can be obtained by subjecting bisphenol A to a condensation reaction with fumarine (f〇rmalin). The epoxide of the resin is formed by replacing bisphenol A with desertified bisphenol A in these resins, and reacting the phenolic resin (n〇v〇lac resin) with epoxidized propylene to produce glycidyl hydride.酸型环曰 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( a bisphenol F-type or bisphenol S-type epoxy resin obtained by reacting phenol S with epichlorohydrin, and further an alicyclic ring containing an epoxycyclohexyl group, an epoxytricyclononyl group, an epoxycyclopentyl group or the like Oxygen resin, phthalic acid diglycidylester, diglycidyl tetrahydrophthalate, hexahydroortylene 201009500 diglycidyl dicarboxylate, diglycidyl p-hydroxybenzoate ( P-hydroxybenzoic acid diglycidyl ester), dimer acid glycidyl ester, etc. A water-glycidyl ester resin, tetraglycidyl diamino-diphenyl methane, a glycidyl amine resin such as p-amino-p-triglycidyl, or the like. Alcohol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglydicyl ether, isophthalic acid Diglycidyl ether ' 1,6-hexanediol diglycidyl ether, (ethylene, propylene) glycol diglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, pentaerythritol polyglycidol Triglycidyl ether resin, tris(2,3-epoxypropyl) isocyanate, tris(2-hydroxyethyl) isocyanate, triazine ring-containing triglycidyl Isocyanurate, dicyclopentadiene epoxy resin, and the like. The thermosetting compound (F) may be used singly or in combination of plural kinds. In the photosensitive resin composition of the present invention, the content of the (A) active energy ray-curable resin is preferably 10 to 50% by mass. Further, the content of the (B) thiol compound is preferably 质量〇 1 or more, and the effect of preventing discoloration of the white coating film or the like is further improved. From this point of view, the content of the (B) thiol compound is preferably 5% by mass or more, and more preferably 1.0% by mass or more. Further, the content of the (B) thiol compound is preferably 5.0% by mass or less, whereby the flawlessness adversely affects the storage stability of the solder resist. From this point of view, it is preferably 2 〇 mass% or less. 15 201009500 In the composition of the present invention, the mass ratio of the (C) photopolymerization initiator is preferably from 0.1 to 10.0% by mass, more preferably from 0.2 to 5.5% by mass. ~ The mass ratio of the '(D) diluent in the composition of the present invention is preferably 1.0 to 1 Torr, and the amount of enamel-% is preferably '3.0 to 6.0% by mass. In the composition of the present invention, the whiteness of the coating film can be improved by setting the mass ratio of the (E) rutile-type titanium oxide to 5% by mass or more. From this point of view, the mass ratio of (E) is preferably 20% by mass or more, and more preferably 30% by mass or more. In addition, the mass ratio of '(E) does not increase even if it exceeds 50% by mass, and it has an adverse effect on the strength, etc. Therefore, the mass ratio of (E) is preferably 50% by mass or less, and 40% by mass. The following is better. In the composition of the present invention, the mass ratio of the (F) epoxy-based thermosetting compound is preferably 1.0 to 30% by mass, more preferably 5.0 to 20% by mass. In the photosensitive resin composition of the present invention, the components (A) to (F) may contain various additives such as an antifoaming agent and a leveling agent, as needed. . The above (A) to (F) and other components to be mixed as needed are kneaded by a three-roll mill, a ball mill, a sand mill, or the like, or a stirring device such as a mixer or a planetary mixer. The photosensitive resin composition of the present invention can be obtained by kneading or mixing. The photosensitive resin composition of the present invention obtained by the above treatment is, for example, a printed wiring board having a circuit pattern formed by etching a steel box of a copper clad laminate, to have a desired thickness, for example, 5 to 1 Apply the thickness of 〇〇μιη. The coating method, although currently, is generally printed by screen printing, but contains the following. As long as it is a coating method that can be uniformly applied, the method of coating can be used. For example, a spray coater, a hot melt coater, a coating bar, an applicator, a bla coater, a knife coater, an air knife coater, A curtain flow coater, a master coater, a gravure coater, an offset printing, a dip coater, a brush coat, and other general methods can be used. It can be pre-baked in a hot air oven or a far-infrared furnace as needed, that is, temporary drying is performed to make the surface of the coating film non-sticky. The pre-baking temperature is preferably about 50 to 100 ° C. Exposure using direct-image directing of LDI (laser Direct imaging), or exposure using active energy lines using a negative mask that causes the active energy rays to form a non-passing state. Negative masks are separately A negative film is used in the case where the active energy ray is ultraviolet ray, a metallic reticle is used in the case of an electron ray, and a lead ray is used in the case of X ray, but in order to be usable In the manufacture of a printed wiring board, ultraviolet rays are often used as the active energy ray. The amount of ultraviolet ray irradiation is generally 1 〇 to 1 OOOmJ/cm2. Exposure is made by, for example, sealing the printed wiring board. A negative film of a light transmissive pattern is formed outside the solder pad of the circuit pattern, and is irradiated with ultraviolet rays from above, but the non-exposed area corresponding to the soldering pad is removed with a dilute aqueous alkali solution. This removal operation may be any one of dissolution, swelling, peeling, etc. of the unexposed portion. The rare aqueous solution used at this time is usually 0.5 to 5% aqueous sodium carbonate solution, but other alkalis may be used. Next, in the case of containing a thermosetting compound, for example, it is heated by a dryer such as a 70 c hot air furnace or a far-infrared furnace or the like, for example, for 2 〇 to 8 〇 minutes, or after hardening by the ultraviolet ray method, I! This can form a solder resist film. The electronic component of the printed wiring board which is covered by the solder resist film can be processed by a solder wave soldering method or a reflow soldering method. An electronic circuit unit is formed by being connected, fixed, and mounted thereon. The electronic component is mounted on a printed wiring board coated with a solder resist film, and the electronic component is mounted on the printed wiring board. [Embodiment] (Example 1) Each component was mixed at a mass ratio described below to prepare a solder resist composition. The details of the components are shown below.

(A) Daicel Chemical Industries, LTD.製「Cyclomer P (ACA) Z-251 j 40% 質量 (B) 三羥甲基丙烷三硫代丙酸酯 0.05質量％ © (C) 醯基膦系光聚合起始劑（Ciba Specialty Chemical Corp.製「IRGACURE 819」）0·3 質量％ (D) 稀釋劑(DPHA) 5質量％ (E) 紅金石系二氧化鈦（石原產業公司製rCR—80」） 35質量％ (F) 環氧系熱硬化性化合物（大日本油墨化學工業公司製「EPICLON 860」）10 質量％ 18 201009500 以下為剩餘部分消泡劑，KS-66(信越シリ口一^社製）搖變劑（Thixotropic Agent)，AEROSIL R-97(NIPPON AEROSIL CO.，LTD製） DICY-7(Japan Epoxy Resins Co.，Ltd.製）(A) "Cyclomer P (ACA) Z-251 j 40% by mass (B) Trimethylolpropane trithiopropionate 0.05% by mass produced by Daicel Chemical Industries, LTD. © (C) Mercaptophosphine photopolymerization Starting agent ("IRGACURE 819" manufactured by Ciba Specialty Chemical Corp.) 0. 3 mass% (D) Thinner (DPHA) 5 mass% (E) Red gold-based titanium dioxide (rCR-80 manufactured by Ishihara Sangyo Co., Ltd.) 35 mass % (F) Epoxy-based thermosetting compound ("EPICLON 860", manufactured by Dainippon Ink and Chemicals Co., Ltd.) 10% by mass 18 201009500 The following is the remaining defoamer, KS-66 (Shin-Etsutsu Sakaguchi Co., Ltd.) Shake Thixotropic Agent, AEROSIL R-97 (manufactured by NIPPON AEROSIL CO., LTD) DICY-7 (manufactured by Japan Epoxy Resins Co., Ltd.)

Dowanol DPM(協和發酵工業公司製） EDGAC(Daicel Chemical Industries, LTD.製）Dowanol DPM (made by Kyowa Fermentation Co., Ltd.) EDGAC (manufactured by Daicel Chemical Industries, LTD.)

Solvesso 150(ExxonMobil Corp.製）Solvesso 150 (manufactured by ExxonMobil Corp.)

滑石硫酸鋇三聚氰胺 (實施例2) 與實施例1同樣地處理製作以下組成的組成物。但是， (A)〜(F)以外與實施例1相同。Talc Barium sulfate melamine (Example 2) A composition having the following composition was produced in the same manner as in Example 1. However, the same as in the first embodiment except for (A) to (F).

(A) Daicel Chemical Industries，LTD.製「Cyclomer P (ACA)Z-251」 40% 質量 (B) 三羥甲基丙烷三硫代丙酸酯 i質量％ (C) 醯基膦系光聚合起始劑(Ciba Specialty Chemical. Corp.製「IRGACURE 819」）0.3 質量％ (D) 稀釋劑(DPHA) 5質量％ (E) 紅金石系二氧化鈦（石原產業公司製「CR-80」） 35質量％ (F) 環氧系熱硬化性化合物（大日本油墨化學工業公司製「EPICLON 860」） 10 質量％ 19 201009500 (實施例3) 與實施例1同樣地處理製作以下組成的組成物。但是’ (A)〜(F)以外與實施例1相同。 (A) Daicel Chemical Industries, LTD.製「Cyclomer P(ACA)Z-251」 40% 質量 (B) 三羥甲基丙烷三硫代丙酸酯 5質量％ (C) 醯基膦系光聚合起始劑（Ciba Specialty Chemical Corp.製「IRGACURE 819」）0.3質量％ (D) 稀釋劑(DPHA) 5質量％ (E) 紅金石系二氧化鈦（石原產業公司製「CR-80」） 35質量°/〇 (F) 環氧系熱硬化性化合物（大日本油墨化學工業公司製「EPICLON 860」）10 質量％ (實施例4) 與實施例1同樣地處理製作以下組成的組成物。但是， (A)〜(F)以外與實施例1相同。(A) "Cyclomer P (ACA) Z-251" manufactured by Daicel Chemical Industries, LTD. 40% by mass (B) Trimethylolpropane trithiopropionate i% by mass (C) Phosphonylphosphonium photopolymerization Starting agent ("IRGACURE 819" manufactured by Ciba Specialty Chemical Co., Ltd.) 0.3% by mass (D) Thinner (DPHA) 5% by mass (E) Red sapphire titanium dioxide ("CR-80" manufactured by Ishihara Sangyo Co., Ltd.) 35 mass% (F) Epoxy-based thermosetting compound ("EPICLON 860" manufactured by Dainippon Ink and Chemicals Co., Ltd.) 10% by mass 19 201009500 (Example 3) A composition having the following composition was produced in the same manner as in Example 1. However, the same as in the first embodiment except for '(A) to (F). (A) "Cyclomer P (ACA) Z-251" manufactured by Daicel Chemical Industries, LTD. 40% by mass (B) Trimethylolpropane trithiopropionate 5% by mass (C) Phosphylphosphine photopolymerization Starting agent ("IRGACURE 819" manufactured by Ciba Specialty Chemical Corp.) 0.3% by mass (D) Thinner (DPHA) 5% by mass (E) Red sapphire titanium dioxide ("CR-80" manufactured by Ishihara Sangyo Co., Ltd.) 35 mass ° / (F) Epoxy-based thermosetting compound ("EPICLON 860" manufactured by Dainippon Ink and Chemicals Co., Ltd.) 10% by mass (Example 4) A composition having the following composition was produced in the same manner as in Example 1. However, the same as in the first embodiment except for (A) to (F).

(A) Daicel Chemical Industries, LTD.製「Cyclomer P (ACA) Z-251」 40% 質量 (B) 季戊四醇四硫代丙酸酯 1質量％ (C) 醯基膦系光聚合起始劑（Ciba Specialty Chemical Corp.製「IRGACURE 819」）0.3 質量％ (D) 稀釋劑(DPHA) 5質量％ (E) 紅金石系二氧化鈦（石原產業公司製「CR-80」） 35質量％ 201009500 (F)環氧系熱硬化性化合物（大日本油墨化學工業公司製「EPICLON 860」）10質量％ (實施例5) 與實施例1同樣地處理製作以下組成的組成物。但是， (A)〜(F)以外與實施例1相同。 (A) Daicel Chemical Industries，LTD.製「Cyclomer P (ACA) Z-251 j 40% 質量 (B) 三經甲基丙烧三硫代丙酸醋 1質量％(A) "Cyclomer P (ACA) Z-251" manufactured by Daicel Chemical Industries, LTD. 40% by mass (B) Pentaerythritol tetrathiopropionate 1% by mass (C) Mercaptophosphine-based photopolymerization initiator (Ciba) "IRGACURE 819" manufactured by Specialty Chemical Corp.) 0.3% by mass (D) Thinner (DPHA) 5% by mass (E) Red sapphire titanium dioxide ("CR-80" manufactured by Ishihara Sangyo Co., Ltd.) 35 mass% 201009500 (F) Oxygen-based thermosetting compound ("EPICLON 860" manufactured by Dainippon Ink and Chemicals Co., Ltd.) 10% by mass (Example 5) A composition having the following composition was produced in the same manner as in Example 1. However, the same as in the first embodiment except for (A) to (F). (A) "Cyclomer P (ACA) Z-251 j 40% by Daicel Chemical Industries, LTD. (B) Trimethoprim trithiopropionate 1% by mass

(C) 醯基膦系光聚合起始劑（Ciba Specialty Chemical Corp.製「IRGACURE 819」）0.3 質量％ (D) 稀釋劑(DPHA) 5質量％ (E) 紅金石系二氧化鈦（石原產業公司製「CR_8〇」） 35質量％ (F) 環氧系熱硬化性化合物（Japan Epoxy Resins Co.， Ltd.製「jER 807」）10質量。/〇 (比較例1) 與實施例1同樣地處理製作以下組成的組成物。但是，將實施例1的（A)〜(F)換成以下成分。 (G) 從脂環族環乳樹脂（Daicel Chemical Industries, LTD.製「EHPE-3150」），使反應發生而形成之活性能量線硬化性樹脂 40質量％ (B) 不含三羥甲基丙烷三硫代丙酸酯 (C) 酿基膦系光聚合起始劑(Ciba Specialty Chemical Corp.製「IRGACURE 819」）0.3質量％ 21 201009500 (D) 稀釋劑(DPHA) 5質量％ (E) 紅金石系·一氧化欽（石原產業公司製「CR-80」） 35質量％ (F) 環氧系熱硬化性化合物（大日本油墨化學工業公司製「EPICLON 860」）10 質量％ (比較例2) 與實施例1同樣地處理製作以下組成的組成物。但是，將實施例1的（A)〜(F)換成以下成分。(C) A mercaptophosphine-based photopolymerization initiator ("IRGACURE 819", manufactured by Ciba Specialty Chemical Corp.) 0.3% by mass (D) Thinner (DPHA) 5 mass% (E) Red gold-based titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd.) "CR_8〇") 35 mass% (F) epoxy thermosetting compound ("jER 807" manufactured by Japan Epoxy Resins Co., Ltd.) 10 mass. /〇 (Comparative Example 1) A composition having the following composition was produced in the same manner as in Example 1. However, (A) to (F) of Example 1 were replaced with the following components. (G) 40% by weight of active energy ray-curable resin formed by the formation of a reaction from an alicyclic cyclic latex resin ("EHPE-3150" manufactured by Daicel Chemical Industries, LTD.) (B) Trimethylolpropane-free Trithiopropionate (C) tyrosylphosphine-based photopolymerization initiator ("IRGACURE 819" manufactured by Ciba Specialty Chemical Corp.) 0.3% by mass 21 201009500 (D) Thinner (DPHA) 5 mass% (E) Red Goldstone-Ignition ("CR-80" manufactured by Ishihara Sangyo Co., Ltd.) 35% by mass (F) Epoxy-based thermosetting compound ("EPICLON 860" manufactured by Dainippon Ink and Chemicals Co., Ltd.) 10% by mass (Comparative Example 2) A composition having the following composition was produced in the same manner as in Example 1. However, (A) to (F) of Example 1 were replaced with the following components.

(G) 從脂環族環氧化物（Daicel Chemical Industries， LTD.製「EHPE-3150」）’使反應發生而形成之活性能量線硬化性樹脂 40質量％ (B) 三羥甲基丙烷三硫代丙酸酯 1質量％ (C) 醯基鱗系光聚合起始劑（Ciba Specialty Chemical Corp.製「IRGACURE 819」）0.3質量％ (D) 稀釋劑(DPHA) 5質量％(G) 40% by weight of active energy ray-curable resin formed by alicyclic epoxide ("EHPE-3150" manufactured by Daicel Chemical Industries, LTD.)" (B) Trimethylolpropane trisulfide Propionate 1% by mass (C) fluorenyl scaly photopolymerization initiator ("IRGACURE 819" manufactured by Ciba Specialty Chemical Corp.) 0.3% by mass (D) Thinner (DPHA) 5 mass%

(E) 紅金石系二氧化鈦（石原產業公司製「CR-80」） 35質量％ (F) 環氧系熱硬化性化合物（大日本油墨化學工業公司製「EPICLON 860」）10 質量％用3輥磨使實施例、比較例的各混合物混合分散，調製成感光性樹脂組成物。將該組成物塗膜的感光度、線性殘留、變色、反射率的結果示於表1。進行這些評價時，基板製作步驟及評價方法如下。表面處理：拋光研磨 22 201009500 塗布：塗膜膜厚：dry 20〜23μηι 預乾燥：75°C-20分鐘(厢式(BOX)爐内25分鐘）曝光：阻焊劑上：300mJ/cm2(才一夕社製 HMW-680GW) 顯影：l%Na2CO3-30t：-0.1MPa . sx90秒後硬化：150°C-60分鐘(BOX爐内7〇分鐘）變色評價：以目視評價在260°C加熱90分鐘後硬化塗膜的變色反射率評價：揭示450nm的反射率照射後：測定用滤光片棚截400nm以下的波長之UV照射（150J)後硬化塗膜的反射率加熱後：測定在260°C加熱90分鐘後硬化塗膜的反射率感光度：將21段格的階段式曝光表做成檢測板，以網板印刷法’將上述各例的感光性樹脂組成物塗成約35μιη的厚度(乾燥前）’使其乾燥再製作各別的塗布基板，以4〇〇ηα/ cm2 的照射量進行紫外線曝光，用1%的碳酸鈉水溶液以〇1 MPa. S的噴霧壓力施行9〇秒的顯影，以塗膜完全殘留之最大段格數進行評價。段格數越大表示感光特性越好。線性殘留：將鋼箔厚度為50μηι的QFP圖案做成檢測板上，以網版印刷法，將上述各例的感光性樹脂組成物塗布成35μηι的厚度(乾燥前）’使塗膜乾燥，製作各別的塗布基板，以400mJ/cm2的照射量施行紫外線曝光。此時，使用線寬為4〇〜150μηι且以ΙΟμιη為單位劃分之曝光薄膜。用1%的 23 201009500 碳酸鈉水溶液，以0.1Mpa. s的喷霧壓力施行90秒的顯影，評價塗膜殘留之最小線寬。線寬越小，感光特性越好。實施例比較例 1 2 3 4 5 1 2 感度 4 6 9 6 6 4 7 線性殘留（um) 80 50 40 50 50 150 100 變色 △ 〇〇〇〇 X Δ 反射率初期 92% 92% 92% 92% 92% 90% 90% 照射後 92% 92% 92% 92% 92% 90% 90% 加熱後 68% 82% 86% 82% 82% 50% 65% 【表1】(E) Red smectite titanium dioxide ("CR-80" manufactured by Ishihara Sangyo Co., Ltd.) 35% by mass (F) Epoxy-based thermosetting compound ("EPICLON 860" manufactured by Dainippon Ink and Chemicals Co., Ltd.) 10% by mass Each mixture of the examples and the comparative examples was mixed and dispersed to prepare a photosensitive resin composition. The results of the photosensitivity, linear residual, discoloration, and reflectance of the composition coating film are shown in Table 1. When these evaluations were performed, the substrate production step and evaluation method were as follows. Surface treatment: Polishing and polishing 22 201009500 Coating: Film thickness: dry 20~23μηι Pre-drying: 75°C-20 minutes (25 minutes in the box (BOX) furnace) Exposure: Solder resist: 300mJ/cm2 HIST-HMW-680GW) Development: l% Na2CO3-30t: -0.1MPa. Hardening after sx90 seconds: 150°C-60 minutes (7〇 minutes in BOX furnace) Color change evaluation: heat evaluation at 260°C by visual evaluation 90 Evaluation of the color change reflectance of the cured coating film after one minute: revealing the reflectance at 450 nm After the irradiation: the UV filter (150 J) at a wavelength of 400 nm or less after the measurement filter is cut, and the reflectance of the cured coating film is heated: measured at 260° The reflectance sensitivity of the cured coating film after heating for 90 minutes: A 21-stage stage exposure meter was used as a test plate, and the photosensitive resin composition of each of the above examples was applied to a thickness of about 35 μm by screen printing method ( Before drying) 'drying and then making each coated substrate, UV exposure at 4〇〇ηα/cm2, using a 1% sodium carbonate solution at a spray pressure of 〇1 MPa. S for 9 sec. Development was evaluated by the maximum number of segments in which the coating film was completely left. The larger the number of segments, the better the photographic characteristics. Linear residue: A QFP pattern having a steel foil thickness of 50 μm was formed on a test plate, and the photosensitive resin composition of each of the above examples was applied to a thickness of 35 μm (before drying) by a screen printing method to dry the coating film. Each of the coated substrates was subjected to ultraviolet exposure at an irradiation dose of 400 mJ/cm 2 . At this time, an exposure film having a line width of 4 Å to 150 μm and divided by ΙΟμιη is used. The development was carried out for 90 seconds at a spray pressure of 0.1 Mpa.s with a 1% 23 201009500 sodium carbonate aqueous solution, and the minimum line width of the coating film remaining was evaluated. The smaller the line width, the better the photographic characteristics. EXAMPLES Comparative Example 1 2 3 4 5 1 2 Sensitivity 4 6 9 6 6 4 7 Linear Residue (um) 80 50 40 50 50 150 100 Discoloration △ 〇〇〇〇X Δ Initial Reflectance 92% 92% 92% 92% 92% 90% 90% 92% after irradiation 92% 92% 92% 92% 90% 90% 68% after heating 82% 86% 82% 82% 50% 65% [Table 1]

得知在實施例1、2、3、4、5中，不僅線性殘留小，白色塗膜的變色也受到抑制，照射後、加熱後的反射率變化也少。相對於此，在比較例1、2中，線性殘留相對低劣，白色塗膜的變色大，加熱後反射率的變化也大。亦即，在本實把例中内部感光性良好，且白色塗膜的變色、加熱後In Examples 1, 2, 3, 4, and 5, not only the linear residue was small, but also the discoloration of the white coating film was suppressed, and the change in reflectance after the irradiation and after heating was small. On the other hand, in Comparative Examples 1 and 2, the linear residue was relatively inferior, the discoloration of the white coating film was large, and the change in reflectance after heating was also large. That is, in the actual example, the internal photosensitivity is good, and the white coating film is discolored and heated.

的反射率降低受到抑制，可知阻焊_成物的商品價值會顯著地提高。【圖式簡單說明】 (無）【主要元件符號說明】 (無） 24The decrease in reflectance is suppressed, and it is known that the value of the product of the solder resist is remarkably improved. [Simple description of the diagram] (none) [Description of main component symbols] (none) 24

Claims

201009500 VII. Patent application scope: 1. A photosensitive resin composition characterized by containing (A) a surface oxide containing an ethylenically unsaturated bond, which is composed of an acrylic acid and acrylic acid vinegar. An active energy ray-curable resin formed by reacting a monomer of a group with a group of a copolymer resin formed from a monomer composed of a group consisting of methacrylic acid and methacrylate; (B) a thiol compound ;

(C) a photopolymerization initiator; (D) a diluent; (E) a rutile-type titanium oxide; and (F) an epoxy-based thermosetting compound. 2. The photosensitive resin composition according to claim 2, wherein the content of the (B) thiol compound is 〇〇1 to 5 〇 mass 0/〇. 3. The photosensitive resin composition according to claim 1 or 2, wherein the (B) thiol compound contains trimethylolpropane trithiopropionate and pentaerythritol tetrathiopropionate. At least one of them. A solder resist composition for a printed wiring board, which is characterized in that it is composed of a photosensitive resin composition according to any one of claims 1 to 3. 5. A printed wiring board before or after mounting an electronic component is a cured film having a solder resist composition as described in claim 4 of the patent application. 25 201009500 IV. Designated representative map: (1) The representative representative of the case is: ( ). (None) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 201009500 Patent application No. 123425 Replacement page of the specification Revision date: November 1998

Further, the compound name and even the resin name can be exemplified by, for example, 3,4-cyclodecylcyclohexylmethyl-3',4'-epoxycyclohexenecarboxylate Pj-epoxycyclohexyl-methyl-S'y-epoxycyclohexanecarboxylate , 1, 4-epoxy-4-vinylcyclohexane, 1,2:8,8,9 cerium oxide, ethylenecyclohexene monoxide, 2-epoxy-4-vinylcyclohexane Di-(1,2:8,9-diepoxylimonene), 2,2-bis(methyl)-1-butanol 1,2-epoxy-4-(2-oxiranyl) ring Hexane (2,2-bis(hydoroxymethyl) 1-butanol of l-2-epoxy-4(2- oxiranyl)-cyclohexane) addition product. Further, the structural formula of the alicyclic epoxide can be exemplified as follows. 【化1】

[Chemical 2]

[化4] 201009500

R The copolymer resin is one or two or more monomers selected from the group consisting of acrylic acid and acrylate, and one or two or more monomers selected from the group consisting of methacrylic acid and methacrylic acid ester. A copolymer obtained by copolymerization. For example, a copolymer obtained by copolymerization of acrylic acid and methacrylic acid is shown below. 【化5】 Propanoate A OR

Me Me Me Methyl Acrylate Ο I OR Me

COOH COOR COOH COOR Further, a copolymer obtained by copolymerization of an acrylate and a mercapto acrylate is shown below. R is an alkyl group, preferably a methyl group or an ethyl group.