TW200815917A

TW200815917A - Photosensitive resin composition suitable for alkali development

Info

Publication number: TW200815917A
Application number: TW95136041A
Authority: TW
Inventors: Kazunori Nishio
Original assignee: Taiyo Ink Mfg Co Ltd
Priority date: 2006-09-28
Filing date: 2006-09-28
Publication date: 2008-04-01
Also published as: TWI331700B

Abstract

A photosensitive resin composition that has various characteristics of hole-filling, endured vacuole, heat-resistant, close seal, electric, electroless tin plating endurance and electroless gold plating endurance, and can be alkali developed is provided. The features of this invention are: combination of (A) let diverse acid anhydride react to get carboxyl contained photosensitive resin in the reaction product of multifunctional epoxy chemical compound (a) and unsaturated radical containing monocarboxylate shown in formula (I); and (B) carboxyl contained copolymer is formed by reaction of carboxyl contained (methyl) acrylic acid group copolymer (d) and a molecular (e) that contains epoxy ethane oxide and ethylene unsaturated radical chemical compound.

Description

200815917 (1) 九、發明說明【發明所屬之技術領域】本發明係有關一種適合使用作爲印刷電路板之永久光罩，且於曝光後藉由鹼水溶液顯像形成影像且進行加熱硬化，可形成耐熱性、密接性、無電解鍍金耐性、無電解鍍錫耐性優異的塗膜之可以鹼顯像的感光性樹脂組成物。【先前技術】一般而言，作爲民生用印刷電路板及產業用印刷電路板之焊接光阻劑，就高精度化、高密度化而言，使用於紫外線照射後，藉由顯像形成畫像，且加熱硬化（本硬化）之液狀顯像型焊接光阻劑，就考慮環境問題時，特別是使用使用稀鹼水溶液可以鹼顯像的光焊接光阻劑。使用該稀鹼水溶液之鹼顯像型焊接光阻劑，例如提案由在酚醛清漆型環氧化合物與不飽和一元酸之反應生成物中加成酸酐之感光性樹脂、光聚合引發劑、光聚合性單體及環氧化合物所成的焊接光阻組成物（專利文獻1 )。該鹼顯像型之焊接光阻劑，於印刷電路板之製造中被大量使用。近年來，在台灣或中國等之亞洲地區，爲抑制因在微孔週邊之焊接附著或助焊劑回流於裏面所導致的外觀不佳情形時，增加埋入微孔之加工處理，惟使用習知的鹼顯像型光焊接光阻劑作爲微孔之埋孔用時，容易引起所形成的焊接光阻膜於焊接校正時膨脹、被剝離的現象（以下簡稱 -4 - (2) (2)200815917 爲「空泡」）。另外，就環境問題而言增加無電解鍍錫、無電解鍍金等之加工處理取代焊接校正的傾向，鹼顯像型之焊接光阻劑亦被要求具有無電解鍍錫、無電解鍍金等之耐性。該焊接光阻劑，提案有在酚醛清漆型環氧化合物與不飽和一元酸之反應性生成物中使飽和或不飽和多元酸酐反應所得的預聚物、及在雙酚型環氧化合物與不飽和一元酸之反應性生成物中使飽和或不飽和多元酸酐反應所得的預聚物、及藉由使不飽和一元酸共聚合樹脂與含脂環式環氧基之不飽和化合物反應所得的預聚物所成的組成物（專利文獻2)。然而，上述之鹼顯像型焊接光阻劑，雖具有使用作爲埋孔用時優異的空泡塞孔性或空泡耐性，惟無電解鍍錫耐性、鍍金耐性不充分。因此，企求開發具有塞孔性、空泡耐性，且具有耐熱性或密接性、耐藥品性、電氣特性等各種特性，且無電解鍍錫耐性、無電解鍍金耐性優異的感光性樹脂組成物。〔專利文獻1〕日本特開昭6 1 -243 8 69號公報〔專利文獻2〕特W02003/059975號公報【發明內容】本發明之目的係爲提供一種具有塞孔性、空泡耐性，且具有耐熱性或密接性、電氣特性等各種特性，且無電解鍍錫耐性、無電解鍍金耐性優異的可以鹼顯像之感光性樹 -5- (3) 200815917 脂組成物。此外，本發明之另一目的係提供一種使用上述可以鹼顯像之感光性樹脂組成物、信賴性優異的印刷電路板。本發明人等爲達成上述目的時再三深入硏究的結果，發現含有（A)在以下述一般式（〗）所示之多官能環氧化合物（a)與含有不飽和基之單羧酸（b)的反應生成物中使多元酸酐（c )反應所得的含有羧基之感光性樹脂、 (B)藉由（d)含有羧基之（甲基）丙烯酸系共聚物樹脂與（e )在1分子中具有環氧乙烷環與乙烯性不飽和基之化合物反應所得的具羧基之共聚合樹脂、（C )光聚合引發劑、（D )反應性稀釋劑、（E )具有環氧基之化合物所成的可以鹼顯像之感光性樹脂組成物，具有塞孔性、空泡耐性，且具有耐熱性、密接性、電氣絕緣性等之各種特性，以及無電解鍍錫耐性、無電解鍍金耐性優異的可以鹼顯像之感光性樹脂組成物。〔化3〕 CH2^CH- -2—-C—-0—CHg 0200815917 (1) Nine, the invention belongs to the technical field of the invention. The present invention relates to a permanent reticle suitable for use as a printed circuit board, and which is formed by image formation by alkali aqueous solution after exposure and heat-hardening, can be formed. A photosensitive resin composition which can be alkali-developed by a coating film excellent in heat resistance, adhesion, electroless gold plating resistance, and electroless tin plating resistance. [Prior Art] In general, as a solder resist for a printed circuit board for industrial use and a printed circuit board for industrial use, high-precision and high-density use is used to form an image by development after ultraviolet irradiation. In the case of a liquid-type soldering resist which is heat-hardened (this hardening), in consideration of environmental problems, a light-welding photoresist which can be alkali-developed using a dilute aqueous alkali solution is particularly used. An alkali-developing type soldering resist using the dilute alkali aqueous solution, for example, a photosensitive resin, a photopolymerization initiator, and a photopolymerization which are added to an acid anhydride in a reaction product of a novolac type epoxy compound and an unsaturated monobasic acid A solder resist composition composed of a monomer and an epoxy compound (Patent Document 1). This alkali-developing type soldering resist is widely used in the manufacture of printed circuit boards. In recent years, in the Asian region such as Taiwan or China, in order to suppress the poor appearance due to solder adhesion around the micropores or flux reflow inside, the processing of embedding micropores is increased, but conventional use is known. When the alkali-developing type photo-welding photoresist is used as a buried hole for micropores, it is easy to cause the formed solder resist film to swell and be peeled off during welding correction (hereinafter referred to as -4 - (2) (2) 200815917 is "empty bubble"). In addition, in order to solve the environmental problem, the processing such as electroless tin plating and electroless gold plating is added instead of the welding correction, and the alkali developing type solder resist is also required to have resistance such as electroless tin plating or electroless gold plating. . The solder resist is proposed to be a prepolymer obtained by reacting a saturated or unsaturated polybasic acid anhydride in a reactive product of a novolac type epoxy compound and an unsaturated monobasic acid, and a bisphenol type epoxy compound and no a prepolymer obtained by reacting a saturated or unsaturated polybasic acid anhydride in a reactive product of a saturated monobasic acid, and a prepolymer obtained by reacting an unsaturated monobasic acid copolymerized resin with an alicyclic epoxy group-containing unsaturated compound A composition formed of a polymer (Patent Document 2). However, the above-described alkali-developing type solder resist has excellent void plugging properties or void resistance when used as a buried via, but has insufficient electroless tin plating resistance and insufficient gold plating resistance. For this reason, it has been desired to develop a photosensitive resin composition which has various properties such as heat resistance, adhesion, chemical resistance, and electrical properties, and which is excellent in electroless tin plating resistance and electroless gold plating resistance. [Patent Document 1] Japanese Laid-Open Patent Publication No. WO-A-2003-059975 (Patent Document 2) SUMMARY OF THE INVENTION The object of the present invention is to provide a plugging property and a bubble resistance, and An alkali-developable photosensitive tree having various properties such as heat resistance, adhesion, and electrical properties, and excellent in electroless tin plating resistance and electroless gold plating resistance. 5-(3) 200815917 Grease composition. Further, another object of the present invention is to provide a printed circuit board which is excellent in reliability by using the above-mentioned photosensitive resin composition which can be alkali-developed. As a result of further intensive research to achieve the above object, the present inventors have found that (A) a polyfunctional epoxy compound (a) represented by the following general formula (?) and a monocarboxylic acid containing an unsaturated group ( (b) a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride (c) in the reaction product, (b) (d) a carboxyl group-containing (meth)acrylic copolymer resin, and (e) in one molecule a carboxyl group-containing copolymer resin obtained by reacting a compound having an oxirane ring and an ethylenically unsaturated group, (C) a photopolymerization initiator, (D) a reactive diluent, and (E) a compound having an epoxy group The photosensitive resin composition which can be used for alkali development has plugging property and cavity resistance, and has various properties such as heat resistance, adhesion, electrical insulation, and electroless tin plating resistance and electroless gold plating resistance. An excellent photosensitive resin composition that can be alkali-developed. [Chemical 3] CH2^CH- -2--C--0-CHg 0

(式中，X係表示在1分子中具有2個環氧丙基之芳香族環氧樹脂的芳香環殘基，Μ係表示環氧丙基及/或氫原子，ζ係表示脂肪族或芳香族二元酸之殘基，Ρ係表示1 〜20之整數）。 -6 - (4) (4)200815917 換言之，本發明之可以鹼顯像的感光性樹脂組成物，其特徵爲組合其中所含的2種含羧基之感光性樹脂組成物 (A )及（B )使用。本發明所使用一方之可以鹼顯像的感光性樹脂組成物 (A )，係使在以上述一般式（I )所示之多官能環氧化合物（a )與含有不飽和基之單羧酸（b )的反應生成物中使多元酸酐（c )反應所得。換言之，含有羧基之感光性樹脂（A )係爲使以以上述X所示之芳香環及以z所示之脂肪族基或方香ί哀規則性重複含有的線狀環氧化合物（a ) 中使含不飽和基之單羧酸（b )反應，在所得的丙烯酸環氧基丙烯酸酯化合物中使多元酸酐（c )反應者，爲在線狀低聚物兩末端及側鏈上適當配置不飽和基之樹脂。此外，另一方具有羧基之共聚合樹脂（B)，係爲藉由（d)含羧基之（甲基）丙烯酸系共聚合樹脂、與（e) 在1分子中具有環氧乙烷環與乙烯性不飽和基之化合物反應所得的具羧基之共聚合樹脂。爲提高電解鍍錫耐性時，爲防止自塗膜與銅電路之界面浸透電鍍液及自塗膜表面浸透電鍍液時，必須使密接性、藉由曝光之表面硬化性（高感度）、耐藥品性全部皆優異。本發明之含羧基的感光性樹脂（A )，雖具有優異的密接性、可撓性、耐水性、耐藥品性，惟皺摺性、藉由曝光之表面硬化性（高感度）不佳。而且，具有羧基之共聚合樹脂（B)，雖具有優異的耐熱性、耐藥品性、皺摺 (5) 200815917 性、表面硬化性（高感度），惟顯像兼具該兩方的特性時，藉由以適當的光性樹脂（A)及具有羧基之共聚合卷特性之平衡性佳、且兩立。因此，含有此等二種類之含羧基及具有羧基之共聚合樹脂（B)，同 (C )、反應性稀釋劑（D )、具有_ 等所成的本發明之可以鹼顯像的感光塞孔性、藉由其選擇性曝光、顯像、優異的空泡耐性、耐熱性或密接性、等各種特性，具有優異的無電解鍍錫性之硬化皮膜。於下述中，詳細說明有關本發明樹脂組成物。首先，本發明構成可以組成物的含羧基之感光性樹脂（A ) 脂（B )的配合比例，以9 0 : 1 0〜3 佳。更佳的配合比例爲90: 10〜50: 9 0 : 1 0更高時，皺摺性惡化，反之，顯像性惡化，故不爲企求。其次，該爲30〜1 50mgKOH/g，較佳者爲40^ 圍。含有羧基之感光性樹脂（A)與脂（B )的二種類樹脂之合計酸値輕時，對鹼水溶液而言溶解性惡化，戶像。此外，較mgKOH/g更局時性有問題。本發明爲比例組合含羧基之感鼓脂（B )，可使全部 ;的感光性樹脂（A ) 時含有光聚合引發劑 I氧基之化合物（E ) 性樹脂組成物，具有本硬化，可提供具有耐藥品性、電絕緣性耐性、無電解鍍金耐可以驗顯像之感光性鹼顯像之感光性樹脂與具羧基之共聚合樹〇 : 7 0之比例配合較 5 0。（ A )之比例較較3 0 : 70更低時，二種樹脂之合計酸値 - 120 mgKOH/g 之範具有羧基之共聚合樹 ί 30 mgKOH/g 更低斤形成的塗膜不易顯，沒有視曝光條件而 (6) (6)200815917 定顯像至曝光部表面，故不爲企求。然後，含羧基之感光性樹脂（A )，係在以上述一般式（I)所示之多官能環氧化合物（a)與含不飽和基之單羧酸（b )之反應生成物中使多元酸酐（c )反應所得。此處，多官能環氧化合物（a )，係使在1分子中具有2個環氧丙基之芳香族環氧樹脂（以下稱爲二官能芳香族環氧樹脂）、與在1分子中具有2個羧基之脂肪族或芳香族二元酸，在膦類、鹼金屬化合物、胺類等之習知的酯化觸媒存在下交互聚合、生成的醇性二級羥基上使環氧氯丙院在二甲基亞楓、N，N -二甲基甲酿胺、n，N -二甲基乙醯胺等之非質子性極性溶劑、甲苯、二甲苯等之芳香族烴類等的習知溶劑中、苛性鈉等之鹼金屬氫氧化物存在下反應製得（環氧氯丙烷之反應量對1莫耳羥基而言在0〜1莫耳內任意選擇）。使多官能環氧化合物（a )與含不飽和基之單羧酸 (b )，對1莫耳多官能環氧化合物（a )中所含的環氧基而言以〇·9〜1.2莫耳之比例配合含不飽和基之單羧酸 (b)，且在有機溶劑存在下或不存在下，與氫醌或氧等之禁止聚合劑、及三乙胺等之三級胺、三乙基苯甲銨氯化物等之四級銨鹽、2-乙基-4-甲基咪唑等之咪唑化合物、三苯基膦等之磷化合物等反應觸媒共存下，通常在約80〜 1 °C下反應，製得環氧基丙烯酸酯化合物。在藉由上述反應所生成的環氧基丙烯酸酯化合物之醇性羥基中使多元酸酐（c )反應，製得含羧基之感光性樹 -9 - (7) 200815917 脂（A )，惟於該反應中多元酸酐（c )之使用量係以成的含羧基之感光性樹脂（A )的酸値爲 3 0〜 mgKOH/g予以調整。反應係在有機溶劑存在下或非下，通常在約5 0〜1 3 0 °C下進行。此時，視其所需亦加三乙胺等之三級胺、三乙基苯甲銨氯化物等之四鹽、2-乙基-4-甲基咪唑等之咪唑化合物、三苯基膦等化合物作爲觸媒。上述二官能芳香族環氧樹脂，可使用雙酚型、雙酚型、雙酚型或萘型等之二環氧丙醚。例如可使用雙二環氧丙醚之日本環氧樹脂（股）製之商品名「耶皮 (譯音）YL-6056」、雙二甲酚型二環氧丙醚之日本樹脂（股）製之商品名「耶皮克頓（譯音）YX-4000 雙酚型二環氧丙醚之住友化學工業（股）製之商品名米（譯音）環氧ESA-011」、「史米環氧ELA-115」雙酚A型環氧樹脂、或大日本油墨化學工業（股）製品名「耶皮谷龍（譯音）8 3 0S」等之雙酚F型環氧樹或大日本油墨化學工業（股）製之商品名「耶皮 EXA1514」等之雙酸S型環氧樹脂、萘型二環氧丙醚日本油墨化學工業（股）製之商品名「耶皮谷龍HP -(D )」等，此等可單獨使用或2種以上組合使用。在1分子中具有2個羧基之二元酸，可使用1，4-烷二羧酸、四氫酞酸、六氫酞酸、六氫異酞酸、六氫酸、酞酸、異酞酸、對酞酸、衣康酸、琥珀酸、己二黏康酸、癸二酸等’就紫外線之透過性、賦予撓性而使生 150 存在可添級銨之磷二甲酚型克頓環氧 J ' 「史等之之商脂、谷龍之大 403 2 環己對酞酸、言以 -10- (8) (8)200815917 脂肪族或脂環式二羧酸化合物較佳。此等可單獨或2種以上組合使用。上述含不飽和基之單羧酸（b)之典型例，如丙烯酸、甲基丙烯酸、或羥基乙基（甲基）丙烯酸酯、羥基丙基（甲基）丙烯酸酯、羥基丁基（甲基）丙烯酸酯、三羥甲基丙烷二（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、苯基環氧丙基 (甲基）丙烯酸酯、（甲基）丙烯酸己內酯加成物等含羥基之丙烯酸酯的不飽和二元酸酐加成物等。此處，更佳者爲丙烯酸及/或甲基丙烯酸。此等含不飽和基之單羧酸可單獨或2種以上組合使用。而且，於本說明書中（甲基）丙烯酸酯係爲丙烯酸酯與甲基丙烯酸酯之總稱用語，有關其他類似的表示亦相同。藉由上述反應所生成的環氧基丙烯酸酯化合物之醇性羥基中使多元酸酐（c )反應，製得含羧基之感光性樹脂 (A )，惟於該反應中多元酸酐（c )之使用量，係在生成的含羧基之感光性樹脂（A)的酸値爲30〜150mgKOH/g (較佳者爲40〜120mgKOH/g )之範圍內予以調整。含羧基之感光性樹脂（A )之酸値小於30mgKOH/g時，對鹼水溶液而言溶解性惡化，所形成的塗膜不易顯像。另外，大於150mgKOH/g時，沒有視曝光條件而定顯像直至曝光部之表面，故不爲企求。反應係在有機溶劑存在下或非存在下，在氫醌或氧等 -11 - (9) (9)200815917 之禁止聚合劑存在下，通常在約50〜130°C下進行。此時，視其所需亦可添加三級胺、四級銨鹽、咪唑化合物、磷化合物等作爲觸媒。上述多元酸酐（c )例如甲基四氫酞酸酐、四氫酞酸酐、六氫酞酸酐、甲基六氫酞酸酐、納吉克酸酐、3,6-內亞甲基四氫酞酸酐、甲基內亞甲基四氫酞酸酐、四溴酞酸酐等之脂環式二元酸酐；琥珀酸酐、馬來酸酐、衣康酸酐、辛烯基琥珀酸酐、十五烯基琥珀酸酐、酞酸酐、偏苯三酸酐等之脂肪族或芳香族多元酸酐。於此等之中可使用 1種或2種以上。其次’具有羧基之共聚合系樹脂（B)，係爲藉由使 (d)含有羧基之（甲基）丙烯酸系共聚合樹脂、與在1分子中具有環氧乙院環與乙j：希性不飽和基之化合物反應所得的具羧基之共聚合系樹脂。 (d)含有殘基之（甲基）丙烯酸系共聚合樹脂，係使（甲基）丙烯酸酯、與在丨分子中具有丨個不飽和基與至少1個羧基之化合物共聚合所得。構成含有羧基之（甲基）丙烯酸系共聚合樹脂（d)之（甲基）丙烯酸酯，例如（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙靖酸丙酯、（甲基）丙燃酸丁酯、（甲基）丙嫌酸戊酯（甲基）丙烯酸己酯等之（甲基）丙烯酸烷酯類、2-羥基乙基（甲基）丙烯酸酯、羥基丙基（甲基）丙烯酸酯、羥基丁基（甲基）丙烯酸酯、己內酯改性2_羥基乙基 (甲基）丙烯酸酯等之含羥基的（甲基）丙烯酸酯類、甲 -12· 200815917 (10) 氧基二乙二醇（甲基）丙烯酸酯、乙氧基二乙二醇（甲基）丙烯酸酯、異辛氧基二乙二醇（甲基）丙烯酸酯、丁氧基三乙二醇（甲基）丙烯酸酯、甲氧基三乙二醇（甲基）丙烯酸酯、甲氧基聚乙二醇（甲基）丙烯酸酯等之乙二醇改性（甲基）丙烯酸酯類等。此等可單獨使用，亦可以2種以上混合使用。而且，在1分子中具有1個不飽和基與至少1個竣基之化合物，丙烯酸、甲基丙烯酸、不飽和基與羧酸之間經鏈延長的改性不飽和單羧酸（例如β -羧基乙基（甲基）丙烯酸酯、2 -丙烯醯氧基乙基琥珀酸、2 -丙烯醯羥基乙基六氫酞酸、藉由內酯改性等之具有酯鍵的不飽和單羧酸、具有醚鍵之改性不飽和單羧酸、以及馬來酸等之在分子中含有2個以上羧基者等。此等可以單獨使用，亦可以2種以上混合使用。 (e)在1分子中具有環氧乙烷環與乙烯性不飽和基的化合物，爲在1分子中具有乙烯性不飽和基與環氧乙烷環之化合物即可，例如環氧丙基（甲基）丙烯酸酯、α-甲基環氧丙基（甲基）丙烯酸酯、3,4 -環氧基環己基甲基 (甲基）丙烯酸酯、3,4-環氧基環己基乙基（甲基）丙烯酸酯、3，4-環氧基環己基丁基（甲基）丙烯酸酯、3，4_環氧基環己基甲基胺基丙烯酸酯等。其中，以3,4-環氧基環己基甲基（甲基）丙烯酸酯較佳。在此等之1分子中具有環氧乙烷環與乙烯性不飽和基之化合物（e )，可以單獨使用或2種以上混合使用。 -13- (11) (11)200815917 其次，構成本發明之光硬化性·熱硬化性樹脂組成物的光聚合引發劑（C )，例如苯偶因、苯偶因甲醚、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、1，1-二氯苯乙酮、1-羥基環己基苯乙酮等之苯乙酮類；2 -甲基-1-(4 -甲基硫代苯基）-2 -嗎啉基丙烷-1 -酮、2 -苯甲基-2 -二甲基胺基-1-( 4-嗎啉基苯基）-丁酮-1，2-(二甲基胺基）-2-[ ( 4 -甲基苯基）甲基]-l-[4- ( 4-嗎啉基）苯基]-1-丁酮、N，N -二甲基胺基苯乙酮等之胺基苯乙酮類；2 -甲基蒽醌、2-乙基蒽醌、2-第3-丁基蒽醌、1-氯化蒽醌、2-戊基蒽醌、2 -胺基蒽醌等之蒽醌類；2,4 -二甲基噻噸酮、2,4-二乙基噻噸酮、2 -氯化噻噸酮、2,4 -二異丙基噻噸酮等之噻噸酮類；苯乙酮二甲基縮醛、苯甲基二甲基縮醛等之縮醛類；二苯甲酮、甲基二苯甲酮、4,4’-二氯二苯甲酮、 4，4’-雙二乙基胺基二苯甲酮、4-苯甲醯基-4，-甲基二苯基硫醚等之二苯甲酮類；2，4,6-三甲基苯甲醯基二苯基氧化鱗等。此等之光聚合引發劑，可以單獨使用或2種以上組合使用。另外，該光聚合引發劑（C )，可以使用1種或2種以上組合使用如N，N-二甲基胺基苯甲酸乙酯、N，N-二甲基胺基苯甲酸異戊酯、戊基-4-二甲基胺基苯甲酸酯、三乙胺、三乙醇胺等之三級胺類的光增感劑或光引發助劑。上述光聚合引發劑（C)之配合量（使用光增感劑或光引發助劑時爲此等之合計量），對含有羧基之感光性樹 -14 - (12) (12)200815917 脂（A)及（B)之合計量爲100質量份而言（作爲固成分’以下相同）爲1〜30質量份，較佳者爲5〜25質量份之比例。光聚合引發劑（C )之配合量較上述範圍更少時’即使進行活性能量線之照射時仍不會硬化、或必須增加照射時間，不易得到適當的皮膜特性。此外，較上述範圍更多量時，即使增加光聚合引發劑時，光硬化性沒有變化，就經濟性而言不爲企求。其次’構成本發明之光硬化性·熱硬化性樹脂組成物之反應性稀釋劑（D )，可使用在1分子中具有1個以上 (甲基）丙烯醯基、在室溫下爲液體、固體或半固體之感光性（甲基）丙烯酸酯化合物。例如2-羥基乙基（甲基）丙烯酸酯、（甲基）丙烯酸甲酯、2-羥基丙基（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、二季戊四醇五 (甲基）丙烯酸酯等之含羥基的（甲基）丙烯酸酯類；聚乙二醇二（甲基）丙烯酸酯、聚丙二醇二（甲基）丙烯酸酯等之水溶性（甲基）丙烯酸酯類；三羥甲基丙烷三（甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯等之多元醇的多官能聚酯（甲基）丙烯酸酯類；三羥甲基丙烷、加氫雙酚A等之多官能醇或雙酚A、雙酚等多價苯酚之氧化乙烯加成物及/或氧化丙烯加成物的（甲基）丙烯酸酯類；上述含羥基之（甲基）丙烯酸酯的異氰酸酯變成物之多官能或單官能聚胺基甲酸酯 (甲基）丙烯酸酯；雙酚A二環氧丙醚、加氫雙酚A二環氧丙醚或苯酚酚醛清漆環氧樹脂之（甲基）丙烯酸加成 -15- (13) (13)200815917 物的環氧基（甲基）丙烯酸酯類等，此等可單獨或2種以上組合使用。此等感光性（甲基）丙烯酸酯化合物之使用目的，係爲提高組成物之光反應性。然而，使用多量在室溫下爲液體之感光性（甲基）丙烯酸酯化合物時，由於無法得到塗膜之指觸乾燥性，且過份進行光交聯處理，有空泡耐性惡化的傾向，故不爲企求。感光性（甲基）丙烯酸酯化合物（D )之配合量，對上述含有羧基之感光性樹脂（A)與（B)之合計量爲1〇〇質量份而言爲5〜40質量份、較佳者爲5〜30質量份之比例。本發明之光硬化性•熱硬化性樹脂組成物中作爲熱硬化性成分所使用的環氧化合物（E )，例如日本環氧樹脂 (股）製之耶皮克頓 8 2 8、耶皮克頓 8 3 4、耶皮克頓 1〇〇1、耶皮克頓1 004、大日本油墨化學工業（股）製之耶皮谷龍840、耶皮谷龍8 5 0、耶皮谷龍1 050、耶皮谷龍 205 5、東都化成（股）製之耶柏頓頓（譯音）YD-011、 YD-013、YD-127、YD-128、住友化學工業（股）製之史米環氧 ESA-11、ESA-014、ELA-115、ELA-128 (皆爲商品名）等之雙酚A型環氧樹脂；日本環氧樹脂（股）製之耶皮克頓YL903、大日本油墨化學工業（股）製之耶皮谷龍152、耶皮谷龍165、東都化成（股）製之耶柏頓頓 YDB-4 00、YDB-500、住友化學工業（股）製之史米環氧 ESB-4 00、ESB-700 (皆爲商品名）等之溴化環氧樹脂；日本環氧樹脂（股）製之耶皮克頓152、耶皮克頓154、大 -16- (14) (14)200815917 曰本油墨化學工業（股）製之耶皮谷龍N-730、耶皮谷龍 N-770、耶皮谷龍N- 8 6 5、東都化成（股）製之耶伯頓頓 YDCN-701、YDCN-704、日本化藥（股）製之 EPPN-201、EOCN- 1 025、EOCN- 1 020、EOCN-104S、RE-3 06、住友化學工業（股）製之史米環氧 ESCN-195X、ESCN-220 (皆爲商品名）等之酚醛清漆型環氧樹脂；大日本油墨化學工業（股）製之耶皮谷龍830、日本環氧樹脂公司製之耶皮克頓807、東都化成（股）製之耶皮頓頓YDF-170、 YDF-175、YDF-2 0 04 (皆爲商品名）等之雙酚F型環氧樹脂；東都化成（股）製之耶皮頓頓 ST-2004、ST-2007、 ST-3 000 (皆爲商品名）等之加氫雙酚A型環氧樹脂；曰本環氧樹脂（股）製之耶皮克頓604、東都化成（股）製之耶皮頓頓YH-434、住友化學工業（股）製之史米環氧 ELM-1 20 (皆爲商品名）等之環氧丙胺型環氧樹脂；賴西魯（譯音）化學工業（股）製之西羅奇塞頓（譯音）202 1 (商品名）等之脂環式環氧樹脂；日本環氧樹脂（股）製之 YL-93 3、日本化藥（股）製之 EPPN-501、EPPN-502 (皆爲商品名）等之三羥基苯基甲烷型環氧樹脂；日本環氧樹脂（股）製之YL-6056、YX-4000 ' YL-6121 (皆爲商品名）等之雙二甲酚型或雙酚型環氧樹脂或此等之混合物；日本化藥（股）製之EBP S-200、旭電化工業（股）製之EPX-30、大日本油墨化學工業（股）製之EXA-1514 (皆爲商品名）等之雙酚S型環氧樹脂；日本環氧樹脂 (股）製之耶皮克頓157S (商品名）等之雙酚a酚醛清 -17- (15) (15)200815917 漆型環氧樹脂；日本環氧樹脂（股）製之耶皮克頓YL_ 931 (商品名）等之四苯酚基乙烷型環氧樹脂；日產化學 (股）製之TEP 1C (商品名）等之雜環式環氧樹脂；日本油脂（股）製之布雷馬（譯音）DGT (商品名）等之二環氧丙基酞酸酯樹脂；東都化成（股）製之ZX- 1 063 (商品名）等之四環氧丙基二甲苯醯基乙烷樹脂；新日鐵化學 (股）製之 ESN-190、ESN-3 60、大日本油墨化學工業 (股）製之 HP-4032、EXA-4750、EXA-4700 (皆爲商品名）等之含萘基的環氧樹脂；大日本油墨化學工業（股）製之HP7200、HP-7200H (皆爲商品名）等之具有二環戊二烯架構的環氧樹脂；日本油脂（股）製之CP-50S、CP-5 0M (皆爲商品名）等之環氧丙基甲基丙烯酸酯共聚合系環氧樹脂；環己基馬來醯亞胺與環氧丙基甲基丙烯酸酯之共聚合環氧樹脂等，此等環氧化合物可單獨使用或2種以上組合使用。環氧化合物（E)之配合量，對合計量爲100質量份之含有羧基的感光性樹脂（A)及（B)而言爲10〜70質量份、較佳者爲1 〇〜60質量份之比例。上述無機塡充劑（F )，以提高密接性、硬度等之特性爲目的時，可使用單獨或2種以上之硫酸鋇、鈦酸鋇、氧化矽粉、微粉狀氧化矽、無定形二氧化矽、滑石，黏土、碳酸鎂、碳酸鈣、氧化鋁、氫氧化鋁、雲母粉等之習知的無機塡充劑。本發明以抑制硬化塗膜之銲錫球附著爲目的時’必須 -18- (16) (16)200815917 使硬化塗膜之光澤度在AS TM 60°之値抑制於1〜50。爲該目的時，以選擇含有氧化矽粉、微粉狀氧化矽、無定形二氧化砂等之二氧化砂較佳。無機塡充劑（F )之配合量，對合計量爲1 〇〇質量份之含有羧基的感光性樹脂（A )及（B )而言，以含有60 〜200質量份、較佳者爲80〜200質量份之比例。本發明中爲調整適合於塗覆方法之黏度時，可使用有機溶劑。有機溶劑例如乙基甲酮、環己酮等之酮類；甲苯、二甲苯、四甲苯等之芳香族烴類；甲基溶纖劑、丁基溶纖劑、甲基卡必醇、丁基卡必醇、丙二醇單甲醚、二丙二醇單乙醚、二丙二醇二乙醚、三乙二醇單乙醚等之乙二醇醚類；醋酸乙酯、醋酸丁酯、丁基溶纖劑乙酸酯、卡必醇乙酸酯等之酯類；乙醇、丙醇、乙二醇、丙二醇等之醇類；辛烷、癸烷等之脂肪族烴；石油醚、石腦油、加氫石腦油、溶劑石腦油等之石油系溶劑等。另外，本發明中爲提高塗膜之強韌性、密接性、耐熱性、無電解鍍金耐性等之特性時，可使用硬化觸媒。硬化觸媒可使 2E4MZ-AZINE、C11Z-AZINE、2PHZ 等之咪唑衍生物、乙醯基鳥糞胺、苯并鳥糞胺等之鳥糞胺類、二氰二醯胺、尿素、尿素衍生物、蜜胺、多元醯肼等之聚胺類等習知的硬化劑類或硬化促進劑類單獨或2種以上組合使用。此外，於本發明中視其所需可以習知的無機顏料、有 -19- (17) (17)200815917 機顏料等著色。例如酞菁•藍、酞菁•綠、二偶氮黃、蒽醌系黃色顏料、苯并咪唑酮、氧化鈦、碳黑等。另外，視其所需可配合二氧化矽、有機膨潤土、蒙脫石等習知的流動調整劑、聚矽氧烷系、氟系、高分子系等習知的消泡劑或水平劑、咪唑系、噻唑系、三唑系、矽烷偶合劑等之密接賦予劑、習知的緩衝化劑等。本發明之可以鹼顯像的感光性樹脂組成物，係藉由使上述之配合成分、較佳者以上述之比例配合，且以輥磨等均勻混合分散製得。上述說明的本發明可以鹼顯像的感光性樹脂組成物，係爲經由下述說明的步驟，微孔中經塞孔的感光性樹脂皮膜。換言之，經由使本發明之感光性樹脂組成物塡充於微孔中，及塗覆於表面上，予以乾燥的塗膜形成步驟；在經由該塗膜形成步驟所得的於塗膜上選擇性照射活性能量線之光硬化處理步驟；於該塗膜硬化處理步驟後使用鹼顯像液，除去未照射部分，製得圖案之鹼顯像步驟；以及使以鹼顯像步驟所得的圖案加熱•硬化之硬化步驟；形成硬化物圖案。 (1 )塗膜形成步驟在該步驟中，先使本發明之感光性樹脂組成物藉由印刷進行塡充於形成有電路之印刷電路板的微孔部分。塡充係使用可在微孔部分選擇性塡充的篩網，通常自單側塡充。塡充後在兩面上藉由篩網印刷法、簾幕塗覆法、噴霧 -20- (18) (18)200815917 塗覆法、輥塗覆法，塗覆本發明之感光性樹脂組成物。藉由篩網印刷法塗覆時，亦可省略在上述之微孔中塡充的步驟’同時對微孔進行塗覆與塡充處理。於塗覆後，在6 0〜9 0 °C之溫度下除去組成物中所含的揮發成分，予以乾燥，形成微孔經塡充的乾燥塗膜。此時’微孔中之溶劑對選定可揮發的溫度、時間而言極爲重要。 (2 )光硬化處理步驟該步驟係在上述步驟（1 )所得的乾燥塗膜上選擇性照射活性能量線。此處，曝光亦可經由形成有圖案之光罩，選擇性照射活性能量線。曝光光源通常使用低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、氙氣燈、金屬鹵素燈等。曝光之光源的照射量，可藉由黏合聚合物之重量平均分子量、單體比、含量、光聚合性化合物之種類或含量、光聚合引發劑之種類或含量、光聚合引發助劑之種類或含量等適當選擇。 (3 )鹼顯像步驟使完成上述（2 )步驟之曝光後的塗膜進行顯像。顯像係於曝光後之塗膜上以噴淋器吹附顯像液，除去未曝光部分之塗膜。顯像液例如碳酸鈉、碳酸鉀、氫氧化鈉、氫氧化四甲銨、有機胺等之稀鹼性水溶液等。藉由顯像以除 -21 - (19) (19)200815917 去未曝光部分，形成塗膜圖案。顯像後，通常進行水洗且乾燥。 (4 )硬化步驟使完成上述（3 )之步驟的基板上之塗膜圖案加熱予以熱硬化。熱硬化係抑制微孔中塗膜之硬化收縮，抑制塗膜之滲透或空泡情形爲目的，進行分段式硬化。分段式硬化可使溫度與時間分爲二段式或三段式進行加熱硬化的方法。通常，適當選擇在60〜80 °C下30〜60 分鐘、在100〜120 °C下〇〜40分鐘、然後在150〜160 °C下 40〜90分鐘之溫度與時間使用。爲得充分的無電解鍍錫耐性、無電解鍍金耐性時，使分段式硬化之條件在不會產生空泡之範圍內盡量縮短較佳。藉由上述說明的步驟，可形成具有塞孔性、空泡耐性，且具有耐熱性、密接性、電絕緣性等之各種特性，以及無電解鍍錫耐性、無電解鍍金耐性優異的硬化塗膜。【實施方式】實施例於下述中，以實施例及比較例更具體地說明有關本發明，惟本發明不受下述實施例所限制。而且，於下述中「份」及「％」沒有特別限定時，全部爲質量份及質量 %。 -22- (20) (20)200815917 合成例1 在具備有氣體導入管、攪拌裝置、冷卻管、溫度計、及連續滴入用滴入漏斗之反應容器中，加入竣酸當量 86g/當量之1，4-環己烷二羧酸86份及雙酚A型環氧樹脂 (日本環氧樹脂（股）製、耶皮克頓8 2 8、環氧當量 189g/當量）378份，在氮氣氣體環境中、攪拌、H〇°C下溶解。然後，添加三苯基膦〇.3份，且使反應容器內之溫度昇溫至1 5 0 °C，且使溫度保持於1 5 0 °C ’約反應9 0分鐘，製得環氧當量464g/當量之環氧化合物。然後，使燒瓶內之溫度冷卻至40 °C，且加入卡必醇乙酸酯3 90份，進行加熱溶解，加入甲基氫醌0.46份、與三苯基膦1.38 份，在95〜105 °C下加熱，慢慢地滴入丙烯酸72份’反應 1 6小時。使該反應生成物冷卻至8 0〜9 0 °C，且加入四氫酞酸酐1 90份，反應8小時。該所得的含有羧基之感光性樹脂，不揮發份65%、固成分之酸値爲100mgKOH/g。於下述中，該樹脂溶液稱爲A-1清漆。合成例2 在具備有氣體導入管、攪拌裝置、冷卻管、溫度計、及鹼金屬氫氧化物水溶液的連續滴入用滴入漏斗之反應容器中，加入羧酸當量6 5 g/當量之衣康酸130份及雙酚A型環氧樹脂（日本環氧樹脂（股）製、耶皮克頓82 8、環氧當量189 g/當量）776份，在氮氣氣體環境中、攪拌、 -23- (21) (21)200815917 11 〇°C下溶解。然後，添加三苯基膦0.65份，且使反應容器內之溫度昇溫至15(TC，且使溫度保持於150°C，約反應 90分鐘，製得環氧當量443 g/當量之環氧化合物。然後，使燒瓶內之溫度冷卻至40°C，且加入環氧氯丙烷 1800 份、二甲基亞颯1 690份，在攪拌下昇溫保持於45 °C。然後，在60分鐘內連續滴入48 %氫氧化鈉水溶液 364份，再反應6小時。於反應完成後，減壓蒸餾大半部分之過剩的環氧氯丙烷及二甲基亞礪予以回收，使含有副生鹽與二甲基亞礪之反應生成物溶解於甲基異丁酮中予以水洗。使有機溶劑層與水層分離後，自有機溶劑層使甲基異丁酮減壓蒸餾予以餾去，製得環氧當量245 g/當量之多官能環氧樹脂。其次，使該多官能環氧樹脂 245份加入具備有攪拌裝置、冷卻管及溫度計之燒瓶中，加入卡必醇乙酸酯 240份，加熱溶解，加入甲基氫醌〇·46份、與三苯基膦 1.38份，在95〜105 °C下加熱，慢慢地滴入丙烯酸72份，反應1 6小時。使該反應生成物冷卻至8 0〜9 0 °C，且加入四氫酞酸酐1 29份，反應8小時。該所得的含有羧基之感光性樹脂，不揮發份65%、固成分之酸値爲100 mgKOH/g。於下述中，該樹脂溶液稱爲A-2清漆。合成例3 在具備有溫度計、攪拌機、滴入漏斗、及回流冷卻器之反應容器中，使作爲溶劑之二丙二醇單甲醚700.0g加熱至110°C，在3小時內滴入甲基丙烯酸270.0g、甲基丙 -24- (22) (22)200815917 烯酸甲酯153.0g、二丙二醇單甲醚2 94.〇g、及作爲聚合觸媒之第3-丁基過氧化-2-乙基己酸酯（日本油脂公司製伯布吉魯（譯音）〇) 1〇· 〇g之混合物’再於H〇°C下攪拌3 小時，使聚合觸媒失活，製得共聚合樹脂溶液。使該樹脂溶液冷卻後，加入3,4-環氧基環己基甲基丙烯酸酯（賴西魯化學工業（股）製塞谷羅魯馬（譯音）A400 ) 390.0g、三苯基膦5.0g、氫醌單甲醚I5g，於100°C中昇溫，且藉由攪拌進行環氧基之開環加成反應。該所得的含有羧基之感光性樹脂，重量平均分子量爲22,000，且不揮發份45wt%、固成分之酸値爲70mgKOH/g。於下述中，該樹脂溶液稱爲B-1清漆。合成例4 在具備有溫度計、攪拌機、滴入漏斗、及回流冷卻器之反應容器中，稱取甲酚酚醛清漆型環氧樹脂（耶皮谷龍 N-680、大日本油墨化學工業公司製、環氧當量=2 10) 210 份與卡必醇乙二酯96.4份，進行加熱溶解。然後，加入作爲聚合禁止劑之氫醌0.1份、與作爲反應觸媒之三苯基膦2 · 0份。使該混合物在9 5〜1 0 5 t下加熱，慢慢地滴入丙烯酸72份，直至酸値爲3.0mgKOH/g以下爲止，約反應1 6小時。使該反應生成物冷卻至8 0〜9 0 °C，加入四氫酞酸酐6 0 · 1份，藉由紅外線吸光分析，直至沒有酸酐之吸收波峰（1 78 0(:1^1 )爲止，約反應6小時。在該反應液中加入出光石油化學公司製之芳香族系溶劑衣夫羅魯（譯 -25- (23) (23)200815917 音）# 1 5 0 9 6.4份，予以稀釋後取出。該所得的含有羧基之感光性樹脂，不揮發份65%、固成分之酸値爲66 mgKOH/g。於下述中，該樹脂溶液稱爲R-1清漆。實施例1〜7及比較例1〜3 以表1所示之配合組成（數値爲質量份）爲準配合各成分，以3條輥磨個別進行混煉，調製鹼可溶性感光性樹脂組成物。使該物藉由立針、篩網印刷法，使用形成有可塡充微孔部分之圖案的90篩目之聚酯篩網，使形成圖案之銅通孔印刷電路基板之微孔充分塡充下進行印刷。另外，使用90篩目之聚酯篩網，在兩面上全面塗覆，使塗膜使用70 °C之熱風乾燥器乾燥40分鐘。然後，使具有光阻圖案之負型薄膜密接於塗膜上，使用紫外線曝光裝置 ((股）歐谷（譯音）製作所製，型式HMW-6 8 0GW)，照射紫外線（曝光量500m】/cm2 )，以1 %碳酸鉀水溶液 90秒鐘，以2.0kg/cm2之噴霧壓顯像，使未曝光部分溶解除去。然後，以熱風乾燥器進行8(TCx30分鐘、ll(Tcx3〇分鐘、1 6 0 °C X 4 0分鐘加熱硬化，製作試驗基板。有關所得的具有硬化皮膜之試驗基板，以下述試驗方法及評估方法進行皺摺性、密接性、焊接耐熱性、耐溶劑性、無電解鍍金耐性、無電解鍍錫耐性、空泡耐性之試驗。上述各試驗之評估結果如表2所示。 -26- 200815917 24(In the formula, X represents an aromatic ring residue having two epoxy propylene aromatic epoxy resins in one molecule, lanthanide represents a glycidyl group and/or a hydrogen atom, and lanthanoid represents an aliphatic or aromatic group. The residue of a dibasic acid, the lanthanide represents an integer from 1 to 20). -6 - (4) (4) 200815917 In other words, the photosensitive resin composition which can be alkali-developed in the present invention is characterized by combining two kinds of carboxyl group-containing photosensitive resin compositions (A) and (B) contained therein. )use. The photosensitive resin composition (A) which can be used for alkali development in the present invention is a polyfunctional epoxy compound (a) represented by the above general formula (I) and a monocarboxylic acid containing an unsaturated group. The reaction product of (b) is obtained by reacting a polybasic acid anhydride (c). In other words, the photosensitive resin (A) having a carboxyl group is a linear epoxy compound (a) which is repeatedly contained in an aromatic ring represented by the above X and an aliphatic group or a square fragrance shown by z. The unsaturation-containing monocarboxylic acid (b) is reacted, and the polybasic acid anhydride (c) is reacted in the obtained acrylic epoxy acrylate compound, and the two ends of the linear oligomer and the side chain are appropriately disposed. Saturated base resin. Further, the other side has a carboxyl group-containing copolymer resin (B) which is obtained by (d) a carboxyl group-containing (meth)acrylic copolymer resin and (e) having an oxirane ring and ethylene in one molecule. A carboxyl group-containing copolymer resin obtained by reacting a compound of a unsaturated group. In order to improve the resistance to electrolytic tin plating, in order to prevent the interface between the self-coating film and the copper circuit from impregnating the plating solution and the surface of the coating film from permeating the plating solution, it is necessary to make the adhesion, the surface hardenability by exposure (high sensitivity), and the drug resistance. All are excellent. The carboxyl group-containing photosensitive resin (A) of the present invention has excellent adhesion, flexibility, water resistance, and chemical resistance, but has excellent wrinkle property and surface hardenability (high sensitivity) by exposure. Further, the copolymerized resin (B) having a carboxyl group has excellent heat resistance, chemical resistance, wrinkles (5) 200815917, and surface hardenability (high sensitivity), but when the image exhibits both properties The balance between the properties of the appropriate photo-curable resin (A) and the copolymerized roll having a carboxyl group is good and is two-fold. Therefore, the photosensitive resin containing the carboxyl group and the carboxyl group-containing copolymer resin (B), the same (C), the reactive diluent (D), and the like, can be alkali-developed. The pore shape, the selective hardening, the development, the excellent vacancy resistance, the heat resistance, the adhesion, and the like, and the excellent hardening film having an electroless tin plating property. The resin composition of the present invention will be described in detail below. First, the mixing ratio of the carboxyl group-containing photosensitive resin (A) (B) constituting the composition of the present invention is preferably 90:10 to 3:3. A better blending ratio is 90: 10 to 50: 9 0 : 1 0 is higher, the wrinkle property is deteriorated, and conversely, the developing property is deteriorated, so it is not desirable. Next, it is 30 to 1 50 mgKOH/g, preferably 40%. When the total acidity of the two types of resins of the carboxyl group-containing photosensitive resin (A) and the fat (B) is light, the solubility in the aqueous alkali solution is deteriorated, and the image is formed. In addition, it is more problematic than mgKOH/g. The present invention is a compound (E) resin composition containing a photopolymerization initiator I oxy group in a photosensitive resin (A) in a ratio of a carboxyl group-containing damper (B), and has a local hardening property. Providing a photosensitive resin having chemical resistance, electrical insulating resistance, electroless gold plating resistance, and photosensitive organic image which can be visualized and developed, and a copolymerized resin having a carboxyl group: the ratio of 70 is more than 50. When the ratio of (A) is lower than 30:70, the total of the two resins is 値-120 mgKOH/g, and the copolymer of the carboxyl group is 30 mgKOH/g. (6) (6) 200815917 The image is displayed on the surface of the exposure portion without considering the exposure conditions, so it is not desirable. Then, the carboxyl group-containing photosensitive resin (A) is obtained by reacting the polyfunctional epoxy compound (a) represented by the above general formula (I) with the monocarboxylic acid (b) containing an unsaturated group. The polybasic acid anhydride (c) is obtained by a reaction. Here, the polyfunctional epoxy compound (a) is an aromatic epoxy resin having two epoxy propyl groups (hereinafter referred to as a difunctional aromatic epoxy resin) in one molecule, and has one molecule in one molecule. An aliphatic or aromatic dibasic acid having two carboxyl groups, which is polymerized in the presence of a conventional esterification catalyst such as a phosphine, an alkali metal compound or an amine to form an alcoholic secondary hydroxyl group. In the aprotic polar solvent such as dimethyl sulfoxide, N,N-dimethylamine, n,N-dimethylacetamide, or aromatic hydrocarbons such as toluene or xylene. It is known that the reaction is carried out in the presence of an alkali metal hydroxide such as caustic soda (the reaction amount of epichlorohydrin is arbitrarily selected in the range of 0 to 1 mol per 1 mol of the hydroxyl group). The polyfunctional epoxy compound (a) and the unsaturated group-containing monocarboxylic acid (b) are 〇·9~1 for the epoxy group contained in the 1 mol-functional epoxy compound (a). 2 molar ratio of the monocarboxylic acid (b) containing an unsaturated group, and in the presence or absence of an organic solvent, a polymerization inhibitor such as hydroquinone or oxygen, and a tertiary amine such as triethylamine, A reaction catalyst such as a quaternary ammonium salt such as triethylbenzylammonium chloride or an imidazole compound such as 2-ethyl-4-methylimidazole or a phosphorus compound such as triphenylphosphine is usually present at about 80%. The reaction was carried out at 1 ° C to obtain an epoxy acrylate compound. The polybasic acid anhydride (c) is reacted in an alcoholic hydroxyl group of the epoxy acrylate compound produced by the above reaction to obtain a carboxyl group-containing photosensitive tree-9-(7) 200815917 lipid (A). The amount of the polybasic acid anhydride (c) used in the reaction is adjusted so that the acid group of the carboxyl group-containing photosensitive resin (A) is 30 to mgKOH/g. The reaction is carried out in the presence or absence of an organic solvent, usually at about 50 to 130 °C. In this case, a tertiary salt such as triethylamine, a tetrasodium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, or triphenylphosphine may be added as needed. Compounds are used as catalysts. As the difunctional aromatic epoxy resin, a diglycidyl ether such as a bisphenol type, a bisphenol type, a bisphenol type or a naphthalene type can be used. For example, the product name "Yipi (transliteration) YL-6056" made of Japanese epoxy resin (bis) of bisglycidyl ether, and the Japanese resin (share) of bisxylenol type diglycidyl ether can be used. The product name "Yipikton (transliteration) YX-4000 Bisphenol type diepoxypropyl ether Sumitomo Chemical Industry Co., Ltd. product name m (transliteration) Epoxy ESA-011", "Semi Epoxy ELA- 115" Bisphenol A type epoxy resin, or Dainippon Ink Chemical Industry Co., Ltd. product name "Yippigulong (transliteration) 8 3 0S" and other bisphenol F type epoxy tree or Dainippon ink chemical industry The product name "Yeppei HP-(D)", etc., manufactured by Japan Ink Chemical Industry Co., Ltd., etc., such as "Jiepi EXA1514", etc. These may be used singly or in combination of two or more. A dibasic acid having two carboxyl groups in one molecule, and 1,4-alkanedicarboxylic acid, tetrahydrofurfuric acid, hexahydrophthalic acid, hexahydroisodecanoic acid, hexahydro acid, citric acid, isodecanoic acid can be used. For citric acid, itaconic acid, succinic acid, hexamethylene bismuthic acid, sebacic acid, etc., the ultraviolet ray permeability and flexibility are imparted to the surface. Oxygen J '"", such as the commercial fat, Gulongzhida 403 2 cyclohexanic acid, -10- (8) (8) 200815917 aliphatic or alicyclic dicarboxylic acid compounds are preferred. It may be used alone or in combination of two or more. Typical examples of the above unsaturated group-containing monocarboxylic acid (b), such as acrylic acid, methacrylic acid, or hydroxyethyl (meth) acrylate, hydroxypropyl (methyl) Acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenyl epoxide Unsaturation of hydroxyl group-containing acrylates such as (meth) acrylate and (meth) acrylate caprolactone adduct Further, it is preferably an acrylic acid anhydride and/or a methacrylic acid. These unsaturated group-containing monocarboxylic acids may be used singly or in combination of two or more. Further, in the present specification (methyl The acrylate is a general term for acrylate and methacrylate, and the other similar expressions are the same. The polybasic acid anhydride (c) is reacted in the alcoholic hydroxyl group of the epoxy acrylate compound formed by the above reaction. The carboxyl group-containing photosensitive resin (A) is obtained, but the amount of the polybasic acid anhydride (c) used in the reaction is 30 to 150 mgKOH/g of the acid group of the resulting carboxyl group-containing photosensitive resin (A). In the range of 40 to 120 mg KOH/g, the carboxyl group-containing photosensitive resin (A) has a solubility of less than 30 mgKOH/g, and the solubility in the aqueous alkali solution is deteriorated, and the formed coating film is hard to be imaged. In addition, when it is more than 150 mgKOH/g, it is not affected by the exposure conditions until the surface of the exposed portion, so it is not desirable. The reaction is in the presence or absence of an organic solvent, in the presence of hydrogen or oxygen, etc. -11 - ( 9) (9) 200815917 Prohibition of polymerization agent In the following, it is usually carried out at about 50 to 130 ° C. At this time, a tertiary amine, a quaternary ammonium salt, an imidazole compound, a phosphorus compound or the like may be added as a catalyst as needed. The above polybasic acid anhydride (c ) such as A Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, nagic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride An alicyclic dibasic acid anhydride such as tetrabromophthalic anhydride; an aliphatic or aromatic dimerization of succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadecyl succinic anhydride, phthalic anhydride, trimellitic anhydride, and the like An acid anhydride may be used alone or in combination of two or more kinds. Next, the 'copolymerized resin (B) having a carboxyl group is obtained by (d) a (meth)acrylic copolymer resin containing a carboxyl group, and having an epoxy ring and a j: in one molecule. A carboxyl group-containing copolymer resin obtained by reacting a compound of a unsaturated group. (d) A (meth)acrylic copolymer resin containing a residue obtained by copolymerizing a (meth) acrylate with a compound having a monounsaturated group and at least one carboxyl group in a ruthenium molecule. a (meth) acrylate constituting a carboxyl group-containing (meth)acrylic copolymer resin (d), such as methyl (meth) acrylate, ethyl (meth) acrylate, or propyl (methyl) propyl propyl acrylate And (meth)acrylic acid alkyl esters, 2-hydroxyethyl (meth) acrylate, etc., (meth)propionic acid butyl ester, (methyl) acrylic acid pentyl (meth) hexyl acrylate, a hydroxyl group-containing (meth) acrylate such as hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate or caprolactone modified 2-hydroxyethyl (meth) acrylate, -12· 200815917 (10) Oxydiethylene glycol (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, isooctyloxy diethylene glycol (meth) acrylate, D Ethylene glycol modification of oxytriethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, etc. ) acrylates and the like. These may be used singly or in combination of two or more. Further, a compound having one unsaturated group and at least one fluorenyl group in one molecule, a chain-extended modified unsaturated monocarboxylic acid (for example, β-) between acrylic acid, methacrylic acid, an unsaturated group and a carboxylic acid Carboxyethyl (meth) acrylate, 2-propenyl methoxyethyl succinic acid, 2-propenyl hydroxyethyl hexahydrophthalic acid, unsaturated monocarboxylic acid having ester bond modified by lactone And a modified unsaturated monocarboxylic acid having an ether bond, or a maleic acid or the like having two or more carboxyl groups in the molecule, etc. These may be used singly or in combination of two or more kinds. (e) In one molecule The compound having an oxirane ring and an ethylenically unsaturated group may be a compound having an ethylenically unsaturated group and an oxirane ring in one molecule, for example, a glycidyl (meth) acrylate, --methylepoxypropyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate , 3,4-epoxycyclohexylbutyl (meth) acrylate, 3,4-epoxycyclohexylmethylaminopropyl An acid ester or the like. Among them, 3,4-epoxycyclohexylmethyl (meth) acrylate is preferred, and a compound having an oxirane ring and an ethylenically unsaturated group in one molecule thereof (e) (2) (11) (11) 200815917 Next, a photopolymerization initiator (C) constituting the photocurable thermosetting resin composition of the present invention, for example, styrene Benzene and benzoin alkyl ethers such as benzoin methyl ether and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, Acetophenones such as 2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylacetophenone, etc.; 2-methyl-1-(4- Methylthiophenyl)-2- morpholinylpropan-1-one, 2-benzyl-2,dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-l-[4-(4-morpholinyl)phenyl]-1-butanone, N,N - Aminoacetophenones such as dimethylaminoacetophenone; 2-methylhydrazine, 2-ethylhydrazine, 2-tert-butylhydrazine, 1-pyridinium chloride, 2- Pentylpurine, 2-aminopurine Oxime; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc. Ketones; acetals such as acetophenone dimethyl acetal, benzyl dimethyl acetal; benzophenone, methyl benzophenone, 4,4'-dichlorobenzophenone, a benzophenone such as 4,4'-bisdiethylaminobenzophenone or 4-benzylidene-4,-methyldiphenyl sulfide; 2,4,6-trimethyl Benzyl fluorenyl diphenyl oxidized squam, etc. These photoinitiators can be used singly or in combination of two or more. The photopolymerization initiator (C) can be used singly or in combination of two or more kinds. Such as ethyl N,N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, pentyl-4-dimethylaminobenzoate, triethylamine, three A photo-sensitizer or photoinitiator aid for a tertiary amine such as ethanolamine. The amount of the above photopolymerization initiator (C) (for the total amount of the photo-sensitizer or photoinitiator), for the photosensitive tree containing a carboxyl group - 14 - (12) (12) 200815917 ( The total amount of A) and (B) is 100 parts by mass (the same as the solid content 'same or less) is 1 to 30 parts by mass, preferably 5 to 25 parts by mass. When the amount of the photopolymerization initiator (C) is less than the above range, the coating does not harden even when the active energy ray is irradiated, or the irradiation time must be increased, and it is difficult to obtain appropriate film properties. Further, when the amount is more than the above range, even if the photopolymerization initiator is added, the photocurability does not change, and it is not economical. In the following, the reactive diluent (D) constituting the photocurable thermosetting resin composition of the present invention may have one or more (meth) acrylonitrile groups in one molecule and a liquid at room temperature. A solid or semi-solid photosensitive (meth) acrylate compound. For example, 2-hydroxyethyl (meth) acrylate, methyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate a hydroxyl group-containing (meth) acrylate such as an ester; a water-soluble (meth) acrylate such as polyethylene glycol di(meth)acrylate or polypropylene glycol di(meth)acrylate; Polyfunctional polyester (meth) acrylates of polyols such as propane tri(meth) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.; trimethylolpropane a polyfunctional alcohol such as hydrogenated bisphenol A or an ethylene oxide adduct of a polyvalent phenol such as bisphenol A or bisphenol; and/or a (meth) acrylate of a propylene oxide adduct; Polyfunctional or monofunctional polyurethane (meth) acrylate of isocyanate of methyl acrylate; bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or phenol phenolic Varnish epoxy resin (meth)acrylic acid -15- (13) (13) 200 815 917 was an epoxy group containing (meth) acrylates, these may be used alone or in a combination use of two kinds. The purpose of using these photosensitive (meth) acrylate compounds is to increase the photoreactivity of the composition. However, when a large amount of a photosensitive (meth) acrylate compound which is liquid at room temperature is used, since the dryness of the coating film is not obtained, and the photocrosslinking treatment is excessively performed, the vacancy resistance tends to be deteriorated. Therefore, it is not for the sake of seeking. The amount of the photosensitive (meth) acrylate compound (D) is 5 to 40 parts by mass based on the total amount of the carboxyl group-containing photosensitive resin (A) and (B). The ratio is preferably 5 to 30 parts by mass. The epoxy compound (E) used as a thermosetting component in the photocurable thermosetting resin composition of the present invention, for example, Jupikton 8 2 8 manufactured by Nippon Epoxy Co., Ltd., Yeppick 8 3 4, yipikton 1 耶 1, yipikton 1 004, Jerzy Valley Dragon 840 made by Dainippon Ink Chemical Industry Co., Ltd., Yeppi Valley Dragon 8 5 0, Yeppi Valley Dragon 1 050, Yapi Gulong 205 5, East Duhua Huacheng (share) system, Yptonton (transliteration) YD-011, YD-013, YD-127, YD-128, Sumitomo Chemical Industry Co., Ltd. Bisphenol A type epoxy resin such as oxygen ESA-11, ESA-014, ELA-115, ELA-128 (all are trade names); Yepiketon YL903 made by Japan Epoxy Resin Co., Ltd., Dainippon Ink Chemical industry (share) system Yeppi Valley Dragon 152, Yeppi Valley Dragon 165, Dongdu Huacheng (share) system, Yptonton YDB-4 00, YDB-500, Sumitomo Chemical Industry Co., Ltd. Brominated epoxy resin such as oxygen ESB-4 00, ESB-700 (both are trade names); yuppieton 152, yipikton 154, large-16- (14) made of Japanese epoxy resin ) (14)200815917 曰本油Yeppun Long N-730, Yeppi Valley Dragon N-770, Yeppi Valley Dragon N- 8 6 5, and East Duhua Chemicals Co., Ltd., Ybtonton YDCN-701, YDCN- 704, EPPN-201, EOCN- 1 025, EOCN-1 020, EOCN-104S, RE-3 06, manufactured by Nippon Kayaku Co., Ltd., Sumi Epoxy ESCN-195X, ESCN manufactured by Sumitomo Chemical Industries Co., Ltd. -210 (all are trade names) and other novolak-type epoxy resins; Yippon Dragon 830 made by Dainippon Ink Chemical Industry Co., Ltd., Yepiketon 807 made by Japan Epoxy Co., Ltd., Dongdu Chemicals Co., Ltd. ) bisphenol F-type epoxy resin such as Yeptonton YDF-170, YDF-175, YDF-2 0 04 (both are trade names); and Eptonton ST-2004 manufactured by Dongdu Chemical Co., Ltd. , hydrogenated bisphenol A type epoxy resin such as ST-2007, ST-3 000 (all are trade names); yuppieton 604 made by 曰本 epoxy resin (share), manufactured by Dongdu Chemical Co., Ltd. Yipponton YH-434, Sumitomo Chemical Industries Co., Ltd. Sumi Epoxy ELM-1 20 (both trade names) and other epoxy propylamine epoxy resin; Lai Xilu (transliteration) chemical industry West Roach Seton (Transliteration) 202 1 (trade name) and other alicyclic epoxy resin; Japan epoxy resin (share) YL-93 3, Nippon Chemical Co., Ltd. EPPN-501, EPPN-502 (all Trihydroxyphenylmethane type epoxy resin such as the product name; bis-xylenol type or double such as YL-6056, YX-4000 'YL-6121 (all are trade names) made by Japan Epoxy Resin Co., Ltd. Phenolic epoxy resin or a mixture of these; EBP S-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Kasei Co., Ltd., EXA-1514 manufactured by Dainippon Ink Chemical Industry Co., Ltd. ( Bisphenol S type epoxy resin such as the product name; bisphenol a phenolic clear -17- (15) (15) 200815917 of the Japanese Epoxy resin (stock) Lacquer-type epoxy resin; tetraphenol-based ethane type epoxy resin such as Yippicton YL_931 (trade name) manufactured by Japan Epoxy Resin Co., Ltd.; TEP 1C (trade name) manufactured by Nissan Chemical Co., Ltd. Heterocyclic epoxy resin, etc.; diepoxypropyl phthalate resin such as Brahma DGT (trade name) made by Nippon Oil & Fat Co., Ltd.; ZX-made by Dongdu Chemical Co., Ltd. Tetra-glycidyl dimethyl decyl ethane hydride resin such as 1 063 (trade name); ESN-190, ESN-3 60 manufactured by Nippon Steel Chemical Co., Ltd., HP manufactured by Dainippon Ink Chemical Industry Co., Ltd. Naphthalene-based epoxy resin such as -4032, EXA-4750, and EXA-4700 (both are trade names); HP7200 and HP-7200H (both trade names) manufactured by Dainippon Ink Chemical Industry Co., Ltd. Epoxy resin of dicyclopentadiene structure; epoxy methacrylate copolymerized epoxy resin such as CP-50S and CP-5 0M (all trade name) manufactured by Nippon Oil & Fat Co., Ltd.; A copolymerized epoxy resin such as hexamethylene imine and a propylene glycol methacrylate, and these epoxy compounds may be used singly or in combination of two or more. The amount of the epoxy compound (E) is 10 to 70 parts by mass, preferably 1 to 60 parts by mass, based on 100 parts by mass of the carboxyl group-containing photosensitive resins (A) and (B). The ratio. In order to improve the properties of adhesion, hardness, and the like, the inorganic chelating agent (F) may be used alone or in combination of two or more kinds of barium sulfate, barium titanate, cerium oxide powder, fine powdered cerium oxide, and amorphous two. A conventional inorganic chelating agent such as cerium oxide, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica powder or the like. In the present invention, in order to suppress the adhesion of the solder ball of the hardened coating film, it is necessary to -18-(16) (16) 200815917 to suppress the gloss of the cured coating film to 1 to 50 after ASTM 60°. For this purpose, it is preferred to select a silica sand containing cerium oxide powder, fine powder cerium oxide, amorphous silica sand or the like. The amount of the inorganic chelating agent (F) is from 60 to 200 parts by mass, preferably 80%, based on 1 part by mass of the carboxyl group-containing photosensitive resins (A) and (B). ~200 parts by mass. In the present invention, in order to adjust the viscosity suitable for the coating method, an organic solvent can be used. Organic solvents such as ketones such as ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, butyl cellosolve, methyl carbitol, and butyl carbene Alcohol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol Esters such as acid esters; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha Such as petroleum solvents and the like. Further, in the present invention, in order to improve the properties such as toughness, adhesion, heat resistance, and electroless gold plating resistance of the coating film, a curing catalyst can be used. The hardening catalyst can be used as an imidazole derivative such as 2E4MZ-AZINE, C11Z-AZINE, 2PHZ, guanine guanamine, benzoguanamine, guanamine, dicyanamide, urea, urea derivatives. A known curing agent such as a melamine or a polyamine or a hardening accelerator or a curing accelerator is used singly or in combination of two or more kinds. Further, in the present invention, an inorganic pigment which is conventionally required, and a pigment such as -19-(17) (17) 200815917 machine pigment are used. For example, phthalocyanine blue, phthalocyanine green, diazo yellow, anthraquinone yellow pigment, benzimidazolone, titanium oxide, carbon black, and the like. Further, as required, a known flow regulator such as cerium oxide, organic bentonite or montmorillonite, a polysiloxane, a fluorine-based or a polymer-based antifoaming agent or a leveling agent, imidazole may be blended. A binding agent such as a thiazole system, a triazole system or a decane coupling agent, or a conventional buffering agent. The photosensitive resin composition which can be alkali-developed in the present invention is obtained by uniformly mixing and dispersing the above-mentioned compounding component, preferably in the above-described ratio, by roll milling or the like. The photosensitive resin composition which can be alkali-developed in the present invention described above is a photosensitive resin film which is plugged in the micropores through the procedure described below. In other words, a coating film forming step of drying the photosensitive resin composition of the present invention in the micropores and applying it to the surface, and selectively irradiating the coating film obtained through the coating film forming step a photohardening treatment step of an active energy ray; an alkali developing solution after removing the unirradiated portion using the alkali developing solution after the coating film hardening treatment step; and heating and hardening the pattern obtained by the alkali developing step a hardening step; forming a hardened pattern. (1) Coating film forming step In this step, the photosensitive resin composition of the present invention is first applied to the microporous portion of the printed circuit board on which the circuit is formed by printing. The sputum is a screen that can be selectively filled in the microporous portion, usually from one side. After the filling, the photosensitive resin composition of the present invention was applied on both sides by a screen printing method, a curtain coating method, a spray -20-(18) (18) 200815917 coating method, and a roll coating method. When the coating is applied by the screen printing method, the step of filling in the above-mentioned micropores may be omitted, and the micropores may be coated and filled. After the coating, the volatile component contained in the composition was removed at a temperature of 60 to 90 ° C and dried to form a microporous dried coating film. At this time, the solvent in the micropores is extremely important for the selected temperature and time of volatilization. (2) Photohardening treatment step This step selectively irradiates the active energy ray on the dried coating film obtained in the above step (1). Here, the exposure may also selectively illuminate the active energy ray via a mask formed with a pattern. The exposure light source usually uses a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like. The irradiation amount of the light source to be exposed may be the weight average molecular weight of the binder polymer, the monomer ratio, the content, the kind or content of the photopolymerizable compound, the kind or content of the photopolymerization initiator, the kind of the photopolymerization initiation aid or The content is appropriately selected. (3) Alkali development step The coating film after the exposure in the above step (2) is developed. The image was attached to the coating film after exposure by a shower with a developer to remove the coating film of the unexposed portion. The developing solution is, for example, a dilute alkaline aqueous solution such as sodium carbonate, potassium carbonate, sodium hydroxide, tetramethylammonium hydroxide or an organic amine. A coating film pattern is formed by developing to remove the unexposed portion by -21 - (19) (19) 200815917. After development, it is usually washed with water and dried. (4) Hardening step The coating film pattern on the substrate on which the above step (3) is completed is heated to be thermally hardened. The thermosetting system performs segmental hardening for the purpose of suppressing the hardening shrinkage of the coating film in the micropores and suppressing the bleeding or cavitation of the coating film. Segmented hardening allows temperature and time to be divided into two or three stages for heat hardening. Usually, it is suitably selected at 60 to 80 ° C for 30 to 60 minutes, at 100 to 120 ° C for 40 40 minutes, and then at 150 to 160 ° C for 40 to 90 minutes for temperature and time. In order to obtain sufficient electroless tin plating resistance and electroless gold plating resistance, the conditions of the segmentation hardening are preferably as short as possible within a range in which voids are not generated. By the above-described steps, it is possible to form a hardened coating film having plugging property and void resistance, and having various properties such as heat resistance, adhesion, electrical insulation, and the like, and electroless tin plating resistance and electroless gold plating resistance. . [Embodiment] In the following, the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited by the following examples. In addition, in the following, "parts" and "%" are not particularly limited, and all are parts by mass and mass %. -22- (20) (20) 200815917 Synthesis Example 1 In a reaction vessel equipped with a gas introduction pipe, a stirring device, a cooling pipe, a thermometer, and a drip funnel for continuous dripping, a tantalum equivalent of 86 g/equivalent was added. 86 parts of 4-cyclohexanedicarboxylic acid and 378 parts of bisphenol A type epoxy resin (made by Nippon Epoxy Resin Co., Ltd., yipikton 8 2 8 , epoxy equivalent 189 g/eq), in nitrogen gas In the environment, stir, dissolve at H〇 °C. Then, add triphenylphosphine ruthenium. After 3 parts, the temperature in the reaction vessel was raised to 150 ° C, and the temperature was maintained at 150 ° C for about 90 minutes to obtain an epoxy compound having an epoxy equivalent of 464 g / equivalent. Then, the temperature in the flask was cooled to 40 ° C, and 3 parts of carbitol acetate was added, and dissolved by heating, and methylhydroquinone was added. 46 parts, with triphenylphosphine 1. For 38 parts, heat at 95 to 105 ° C, and slowly add 72 parts of acrylic acid to react for 16 hours. The reaction product was cooled to 80 to 90 ° C, and 1 part of tetrahydrophthalic anhydride was added, and the mixture was reacted for 8 hours. The obtained carboxyl group-containing photosensitive resin had a nonvolatile content of 65% and a solid content of acid strontium of 100 mgKOH/g. In the following, the resin solution is referred to as A-1 varnish. Synthesis Example 2 In a reaction vessel equipped with a gas introduction tube, a stirring device, a cooling tube, a thermometer, and an aqueous alkali metal hydroxide aqueous solution for dropping into a dropping funnel, a carboxylic acid equivalent of 6 5 g/eq. 130 parts of acid and bisphenol A type epoxy resin (made by Nippon Epoxy Resin Co., Ltd., yipikton 82 8 , epoxy equivalent 189 g / equivalent), 776 parts, stirred under nitrogen atmosphere, -23- (21) (21) 200815917 11 Dissolved at 〇 °C. Then, adding triphenylphosphine 0. 65 parts, and the temperature in the reaction vessel was raised to 15 (TC, and the temperature was maintained at 150 ° C, and the reaction was carried out for about 90 minutes to obtain an epoxy compound having an epoxy equivalent of 443 g / equivalent. Then, the inside of the flask was made. The temperature was cooled to 40 ° C, and 1800 parts of epichlorohydrin and 1 690 parts of dimethyl hydrazine were added, and the temperature was maintained at 45 ° C under stirring. Then, 48 % aqueous sodium hydroxide solution was continuously added dropwise over 60 minutes. 364 parts, further reacted for 6 hours. After the reaction is completed, most of the excess epichlorohydrin and dimethyl hydrazine are distilled under reduced pressure to recover the reaction product containing the by-product salt and dimethyl hydrazine. After washing with methyl isobutyl ketone, the organic solvent layer is separated from the aqueous layer, and methyl isobutyl ketone is distilled off from the organic solvent layer under reduced pressure to obtain a polyfunctional ring having an epoxy equivalent of 245 g/eq. Oxygen resin. Next, 245 parts of the polyfunctional epoxy resin was placed in a flask equipped with a stirring device, a cooling tube, and a thermometer, 240 parts of carbitol acetate was added, and dissolved by heating, and methyl hydrazine was added. With triphenylphosphine 38 parts were heated at 95 to 105 ° C, and 72 parts of acrylic acid was slowly dropped, and reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C, and 1 29 parts of tetrahydrophthalic anhydride was added, and the mixture was reacted for 8 hours. The obtained carboxyl group-containing photosensitive resin had a nonvolatile content of 65% and a solid content of acid strontium of 100 mgKOH/g. In the following, the resin solution is referred to as A-2 varnish. Synthesis Example 3 In a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, a dipropylene glycol monomethyl ether 700 as a solvent was used. 0g was heated to 110 ° C, and methacrylic acid was added dropwise within 3 hours. 0g, methyl propyl -24- (22) (22) 200815917 methyl enoate 153. 0g, dipropylene glycol monomethyl ether 2 94. 〇g, and 3-butylperoxy-2-ethylhexanoate as a polymerization catalyst (Bobjiru (transliteration) 日本 by Nippon Oil Co., Ltd.) 1〇· 〇g mixture 're-H〇° The mixture was stirred for 3 hours at C to deactivate the polymerization catalyst to prepare a copolymerized resin solution. After cooling the resin solution, 3,4-epoxycyclohexyl methacrylate (Reserved by Reisir Chemical Industry Co., Ltd., Seymour Rouma) was introduced. 0g, triphenylphosphine 5. 0 g of hydroquinone monomethyl ether I5g was heated at 100 ° C, and a ring-opening addition reaction of an epoxy group was carried out by stirring. The obtained carboxyl group-containing photosensitive resin had a weight average molecular weight of 22,000, a non-volatile content of 45 wt%, and a solid content of acid strontium of 70 mgKOH/g. In the following, the resin solution is referred to as B-1 varnish. Synthesis Example 4 A cresol novolac type epoxy resin (Yupigulong N-680, manufactured by Dainippon Ink Chemical Industry Co., Ltd., was weighed in a reaction container equipped with a thermometer, a stirrer, a dropping funnel, and a reflux cooler. Epoxy equivalent = 2 10) 210 parts with carbitol ethylene glycol ester 96. 4 parts, dissolved by heating. Then, hydrogen hydrazine as a polymerization inhibitor is added. One part and 2 parts of triphenylphosphine as a reaction catalyst. The mixture was heated at 95 to 10 5 t, and 72 parts of acrylic acid was slowly added dropwise until the acidity was 3. It is about 0 mgKOH/g or less, and it is about 16 hours. The reaction product was cooled to 80 to 90 ° C, and 60 parts of tetrahydrophthalic anhydride was added, and analyzed by infrared absorption until there was no absorption peak of the acid anhydride (1 78 0 (:1 ^ 1 ), The reaction was carried out for about 6 hours, and the aromatic solvent Solvroru manufactured by Idemitsu Petrochemical Co., Ltd. was added to the reaction solution (Translation - 25 - (23) (23) 200815917 sound) # 1 5 0 9 6. 4 parts, diluted and taken out. The obtained carboxyl group-containing photosensitive resin had a nonvolatile content of 65% and a solid content of acid strontium of 66 mgKOH/g. In the following, the resin solution is referred to as R-1 varnish. Examples 1 to 7 and Comparative Examples 1 to 3 Each component was blended in accordance with the compounding composition shown in Table 1 (number of parts by mass), and kneaded by three roll mills to prepare an alkali-soluble photosensitive resin composition. . By using a 90-mesh polyester mesh formed with a pattern capable of filling the microporous portion, the micropores of the patterned copper via printed circuit board are fully filled by the vertical needle and screen printing method. Print down. Further, a 90 mesh mesh of polyester mesh was used, which was completely coated on both sides, and the film was dried by a hot air dryer at 70 ° C for 40 minutes. Then, the negative film having the photoresist pattern is adhered to the coating film, and ultraviolet irradiation (exposure amount 500 m)/cm 2 is irradiated using an ultraviolet exposure device (type: HMW-6 80 GW, manufactured by Ou Gu). ), with 1% potassium carbonate aqueous solution for 90 seconds, to 2. A spray pressure of 0 kg/cm2 was developed to dissolve and remove the unexposed portion. Then, the test substrate was prepared by a hot air dryer at 8 (TCx for 30 minutes, ll (Tcx3 〇 minute, 1600 ° C for 40 minutes), and the test substrate having the cured film obtained was obtained by the following test method and evaluation method. Tests for wrinkle, adhesion, solder heat resistance, solvent resistance, electroless gold plating resistance, electroless tin plating resistance, and bubble resistance. The evaluation results of the above tests are shown in Table 2. -26- 200815917 24

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-27- (25)200815917 〇〇〇〇 < X 卜寸 < 鎰 CN 〇〇〇〇〇 X 寸〇 X 〇 X 〇〇〇寸〇〇〇〇〇〇〇寸寸〇 in 〇〇〇〇〇 < 寸寸〇㈣寸 < 〇 < 〇〇〇 m 寸〇 cn 〇〇〇〇〇 <] 〇〇〇 |1( (N 〇〇〇〇〇 <1 (N 〇 r-H 〇〇〇〇〇〇寸寸〇 _ iH 菌甚 0 ^Γ) 鹪鸛 ν〇 a 蘅毖姻 a W Hi 職鑛 iS #: 壊 -28- (26) (26)200815917 於上述表2中各特性試驗試驗之評估方法，如下所述。 (1 )皺摺性：在上述試驗基板製作步驟中使曝光後之負型薄膜的剝離情形以目視、以下述基準予以評估。〇：皮膜上沒有皺摺情形者。 △:皮膜上僅有稍許皺摺情形者。 X:皮膜全面上有皺摺情形者。 (2 )密接性：以Π S D 0 2 0 2之試驗方法爲基準，在上述試驗基板之硬化皮膜上施予棋盤格狀之十字切割，然後，以下基準評估藉由玻璃膠帶剝離後的剝離情形。〇：1 00/1 00完全沒有剝離者。 △ : 1 00/1 00中有稍許十字切割部分被剝離者。 X: 0/100〜90/1 00產生剝離者。 (3 )焊接耐熱性：以Jis C 648 1之試驗方法爲基準，使上述試驗基板使用松香系助焊劑及無洗淨助焊劑，在260°C之焊接浴中浸漬10秒鐘3次，以下述基準評估皮膜之變化。〇：硬化皮膜上沒有剝離等之異常情形者。 △:硬化皮膜上僅稍有變色情形者。 X :硬化皮膜上有浮出、剝離情形者。 (4 )耐溶劑性：使上述試驗基板之硬化皮膜在丙二醇單甲醚乙酸酯中、20 °C下浸漬30分鐘，確認硬化皮膜之狀態。評估基準如下所述。〇：硬化皮膜上沒有剝離、白化等變色情形者。 -29 - (27) (27)200815917 △:硬化皮膜上有稍許白化等之變色情形者。 X :硬化皮膜上有剝離、白化等變色情形者。 (5 )無電解鍍金耐性：使上述試驗基板之硬化皮膜使用市售的無電解鎳液、無電解鍍金液，在85〜90°C之溫度下電鍍厚度係鎳爲3μηι、金爲〇.〇3μηι下進行無電解電鍍，硬化皮膜之變色、剝離狀態以下述基準評估。〇：硬化皮膜上沒有變色、剝離等異常情形者。 △ ··硬化皮膜上沒有剝離情形，有白化等之變色情形者。 X :硬化皮膜上有浮出、剝離情形，且有電鍍潛入情形者。 (6 )無電解鍍錫耐性：使上述試驗基板之硬化皮膜進行前處理（酸性脫脂+軟性飩刻+硫酸處理），使用市售的無電解鍍錫液，以電鍍厚度1 μηι之條件（7 0 °C、1 2分鐘）進行無電解鍍錫處理。有關於該電鍍後之評估基板，藉由玻璃膠帶進行剝離試驗，評估有關光阻層之剝離情形。〇：硬化皮膜上沒有變色、剝離等異常情形者。 △:硬化皮膜上僅有稍許剝離、滲透情形者。 X :硬化皮膜上有浮出、剝離等情形’有電鍍潛入情形者。 (7 )空泡耐性：使上述試驗基板藉由水平校正機進行焊接校正處理，進行膠帶剝離後，確認微孔部分之皮膜的剝離狀態。 -30- (28) 200815917 〇：在微孔5 00個孔中，沒有剝離情形者。 △:在微孔5 00個孔中產生1 0個以下剝離情形者。 X :在微孔500孔中產生1 0個以上剝離情形者。 (8 )光澤度：使上述試驗基板之表面使用微採光機 (比谷肯米（譯音）日本公司製），測定 60°之光澤度 (光澤値）。而且，60 °之光澤度係爲測定5處，以其平均値之小數點以下第一格四捨五入的整數値表示。由上述說明可知，藉由本發明，可形成具有塞孔性、空泡耐性，且具有耐熱性、密接性、電氣特性等之各種特性’以及無電解鍍錫耐性、無電解鍍金耐性優異的可以鹼現象之感光性樹脂組成物。 -31 --27- (25)200815917 〇〇〇〇< X 卜寸< 镒CN 〇〇〇〇〇X inch〇X 〇X 〇〇〇 inch inch inch inch 〇〇〇〇〇in 〇〇〇〇〇 < inch inch 四 (four) inch < 〇 < 〇〇〇m inch 〇cn 〇〇〇〇〇<] 〇〇〇|1( (N 〇〇〇〇〇<1 (N 〇rH 〇〇〇〇〇〇 inch inch 〇 i i 〇 i i i i i 〇〇 a a a a W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W The method is as follows: (1) Wrinkle property: In the test substrate production step, the peeling of the negative film after exposure was evaluated by visual observation and on the basis of the following criteria: 〇: There was no wrinkle on the film. : There is only a slight wrinkle on the film. X: The wrinkle is completely on the film. (2) Adhesiveness: Applying on the hardened film of the above test substrate based on the test method of Π SD 0 2 0 2 Chessboard After the cross cut, the following reference evaluates the peeling condition after peeling off by the glass tape. 〇: 1 00/1 00 is not peeled at all. △ : 1 00/1 00 has a slight cross-cut portion peeled off. X: 0/100~90/1 00 is peeled off. (3) Solder heat resistance: The test substrate is made of rosin-based flux and no-clean flux based on the test method of Jis C 648 1, at 260 ° C. In the solder bath, the film was immersed for 3 times for 10 times, and the change of the film was evaluated by the following criteria: 〇: There was no abnormality such as peeling on the hardened film. △: Only slightly discolored on the hardened film. X: On the hardened film (4) Solvent resistance: The cured film of the test substrate was immersed in propylene glycol monomethyl ether acetate at 20 ° C for 30 minutes, and the state of the cured film was confirmed. 〇: There is no discoloration or whitening on the hardened film. -29 - (27) (27)200815917 △: There is a slight discoloration of the hardened film, etc. X: Discoloration such as peeling and whitening on the hardened film Situation (5) no electricity Gold plating resistance: The hardened film of the above test substrate is subjected to electroless plating using a commercially available electroless nickel liquid or an electroless gold plating solution at a temperature of 85 to 90 ° C for a thickness of nickel of 3 μm and gold for 〇.〇3μηι. The discoloration and peeling state of the electroplated and hardened film were evaluated on the basis of the following criteria. 〇: There is no abnormality such as discoloration or peeling on the hardened film. △ ··There is no peeling on the hardened film, and there is a discoloration situation such as whitening. X: There is a floating and peeling on the hardened film, and there is a plating intrusion. (6) Electroless tin plating resistance: pretreatment of the hardened film of the above test substrate (acid degreasing + soft engraving + sulfuric acid treatment), using a commercially available electroless tin plating solution for plating a thickness of 1 μηι (7 Electroless tin plating treatment was carried out at 0 ° C for 12 minutes. Regarding the evaluation substrate after the plating, a peeling test was performed by a glass tape to evaluate the peeling condition of the photoresist layer. 〇: There is no abnormality such as discoloration or peeling on the hardened film. △: There is only a slight peeling and penetration on the hardened film. X: There are cases of floating, peeling, etc. on the hardened film. (7) Cavitation resistance: The test substrate was subjected to a welding correction process by a leveling machine, and after the tape was peeled off, the peeling state of the film of the microporous portion was confirmed. -30- (28) 200815917 〇: In the 500 holes of the micropores, there is no peeling condition. △: 10 or less peeling cases were generated in 500 holes of the micropores. X : A case where more than 10 peeling conditions were generated in the pores of the micropore 500. (8) Gloss: The surface of the above test substrate was measured for a gloss of 60° (gloss 値) using a micro-lighting machine (manufactured by 谷谷米米 (trans)). Further, the gloss of 60 ° is measured at 5 places, and is represented by an integer 値 rounded off by the first square below the decimal point of the average 値. As described above, according to the present invention, it is possible to form a base having excellent plugging property and void resistance, and having various properties such as heat resistance, adhesion, and electrical properties, and excellent electroless tin plating resistance and electroless gold plating resistance. A photosensitive resin composition of a phenomenon. -31 -

Claims

200815917 (1) X. Patent application scope 1. A photosensitive resin composition capable of alkali development, which comprises (A) a polyfunctional epoxy compound (a) represented by the following general formula (I) and containing a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride (c) in a reaction product of an unsaturated group of a monocarboxylic acid (b), (B) (d) a (meth)acrylic copolymer containing a carboxyl group The resin and (e) a carboxyl group-containing copolymer resin obtained by reacting a compound having an oxirane ring and an ethylenically unsaturated group in one molecule, (C) a photopolymerization initiator, (D) a reactive diluent, ( E) a compound having an epoxy group,

CH2-CH-CHi- -CH 广έΗ—CH2—〇- -0—ch2- -CH 疒 0_ 'z-CH—CH2

(In the formula, X represents an aromatic ring residue having two epoxy propylene aromatic epoxy resins in one molecule, lanthanide represents a glycidyl group and/or a hydrogen atom, and lanthanoid represents an aliphatic or aromatic group. The residue of the dibasic acid, ρ represents an integer from 1 to 20). 2. A photosensitive resin composition which can be alkali-developed as in the first aspect of the patent application, wherein the copolymerized resin having a carboxyl group is (d) a (meth)acrylic copolymer having a carboxyl group A resin having a carboxyl group obtained by reacting a resin with (e) a compound having an alicyclic epoxy group and an ethylenically unsaturated group in one molecule. 3. The photosensitive resin which can be alkali-developed as in the first application of the patent scope-32- (2) 200815917 composition, wherein the photosensitive resin (A) having a carboxyl group and the carboxy-polymerized resin (B) are combined The ratio is 90: 10~50: 50. 4. The photosensitive composition which can be alkali-developed as in the first aspect of the patent application, wherein the total amount is 100 parts by weight of the carboxyl group-containing resin (A) and the carboxyl group-containing copolymer resin (B). The compounding amount of the photoinitiator (C) is in the range of 1 to 30 parts by mass, and the amount of the counter-diluent (D) is in the range of 5 to 40 parts by mass, the compound having an oxy group (E) The photosensitive resin composition of the base which can be used in the range of 10 to 70 parts by mass, and the photosensitive resin composition of the base of any one of Claims 1 to 4, wherein the photosensitive group is 100 parts by mass of the photosensitive group The resin (A) and (B) may further contain 50 parts by mass of the inorganic chelating agent (F). 6. The photosensitive composition which can be alkali-developed according to item 5 of the patent application, wherein the inorganic chelating agent (F) contains cerium oxide. 7. The base photosensitive resin composition according to any one of claims 1 to 6, wherein after the coating is dried and subjected to active energy irradiation and development, the coating film obtained by heat curing is ASTM 60°. ~60 range. 8. A printed circuit board characterized by coating a photosensitive resin composition which can be alkali-developed as disclosed in any one of claims 1 to 6 and drying, after performing active energy ray irradiation and after development It is formed by heat-hardening a welded photoresist film. The base of the resin is photopolymerizable. It has a ring-like image containing -200 resin. The image of the line is 1 and it is a good one. -33- 200815917 Seven designated representatives: (1) The representative figure of this case is: No (2) ), the representative symbol of the representative figure is a simple description: no eight, if there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none