TWI331700B

TWI331700B -

Info

Publication number: TWI331700B
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: 2010-10-11
Also published as: TW200815917A

Description

ΓΙ331700 ⑴ 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)1331700 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野反應所得的預聚物、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、銨金耐性不充分。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61-243869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、無電解鏟金耐性優異的可以鹼顯像之感光性樹 -5- (3) 1331700 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（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 )反應所得的含有羧基之感光性樹脂、 φ (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〕ΓΙ331700 (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-hardened to form heat resistance. A photosensitive resin composition which can be alkali-developed by a coating film having excellent 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) 1331700 is "empty bubble"). In addition, in order to increase the tendency of electroless tin plating and electroless gold plating to replace the welding correction in terms of environmental problems, the alkali developing type solder resist is also required to have resistance such as electroless tin plating and electroless gold plating. . The solder resist is proposed to be a prepolymer obtained by reacting a saturated or unsaturated polybasic acid in a reactive product of a novolak type epoxy compound and an unsaturated monobasic acid, and a bisphenol type epoxy compound and a prepolymer obtained by reacting a saturated or unsaturated polybasic acid anhydride in a reactive product of an unsaturated monobasic acid, and a reaction obtained by reacting an unsaturated monobasic acid copolymerized resin with an alicyclic epoxy group-containing unsaturated compound A composition formed of a prepolymer (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 ammonium gold 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] JP-A-61-243869 (Patent Document 2) JP-A-2003-059975 SUMMARY OF THE INVENTION The object of the present invention is to provide a plugging property, a bubble resistance, and heat resistance. A photosensitive tree-5-(3) 1331700 fat composition which can be alkali-developed with various characteristics such as adhesion and electrical properties, and which is excellent in electroless tin plating resistance and electroless shovel resistance. 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 used for alkali development. The inventors of the present invention have further intensively studied the results of the above, and found that (A) a polyfunctional epoxy compound (a) represented by the following general formula (I) and a monocarboxylic acid having an unsaturated group are contained. a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride (c) in the reaction product of the acid (b), φ (B) by (d) a carboxyl group-containing (meth)acrylic copolymer 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, and (E) having an epoxy group The photosensitive resin composition which can be alkali-developed by the base compound has plugging property, voids, and has various properties such as heat resistance, adhesion, electrical insulation, and electroless tin plating resistance. A photosensitive resin composition which is excellent in electroless gold plating resistance and which can be alkali-developed. 〔化3〕

(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)1331700 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所示之脂肪族基或芳香環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銨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、皺措 (5) 1331700 性、表面硬化性（高感度），惟顯像性有問題。本發兼具該兩方的特性時，藉由以適當的比例組合含羧基光性樹脂（A)及具有羧基之共聚合樹脂（B)，可使特性之平衡性佳、且兩立。因此，含有此等二種類之含羧基的感光性樹脂（及具有羧基之共聚合樹脂（B)，同時含有光聚合引 (C )、反應性稀釋劑（D)、具有環氧基之化合物！等所成的本發明之可以鹼顯像的感光性樹脂組成物，塞孔性、藉由其選擇性曝光、顯像、本硬化，可提供優異的空泡耐性、耐熱性或密接性、耐藥品性、電絕等各種特性，具有優異的無電解鍍錫耐性、無電解鍍性之硬化皮膜。於下述中，詳細說明有關本發明可以鹼顯像之感樹脂組成物。首先，本發明構成可以鹼顯像之感光性組成物的含羧基之感光性樹脂（A)與具羧基之共聚脂（B )的配合比例，以90 : 10〜3 0 : 70之比例配佳。更佳的配合比例爲90: 10〜50: 50。（A)之比 90 : 1〇更高時，皺摺性惡化，反之，較30 : 70更低顯像性惡化，故不爲企求。其次，該二種樹脂之合計爲 30〜150mgKOH/g，較佳者爲 40〜120 mgKOH/g 圍。含有羧基之感光性樹脂（A)與具有羧基之共聚脂（B)的二種類樹脂之合計酸値較30 mgKOH/g 時，對鹼水溶液而言溶解性惡化，所形成的塗膜不像。此外，較150 mgKOH/g更高時，沒有視曝光條明爲之感全部：A ) 發劑 (E ) 具有具有緣性金耐光性樹脂合樹合較例較時，酸値之範合樹更低易顯件而 (6) (6)1331700 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)與含不飽和基之單殘酸（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烷在二甲基亞颯、N，N-二甲基甲醯胺、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莫耳羥基而言在〇〜i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中所含的環氧基而言以〜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〜 140°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) (7)1331700 脂（A)，惟於該反應中多元酸酐（c)之使用量係以使生成的含羧基之感光性樹脂（A)的酸値爲 3〇50 mgKOH/g予以調整。反應係在有機溶劑存在下或非存在下’通常在約5 0〜1 3 0 °C下進行。此時，視其所需亦可添加三乙胺等之三級胺、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作爲觸媒。上述二官能芳香族環氧樹脂，可使用雙酚型、雙二甲酚型、雙酚型或萘型等之二環氧丙醚。例如可使用雙酚型二環氧丙醚之日本環氧樹脂（股）製之商品名「耶皮克頓 (譯音）YL-6056」、雙二甲酚型二環氧丙醚之日本環氧樹脂（股）製之商品名「耶皮克頓（譯音）ΥΧ-4〇00」、雙酚型二環氧丙醚之住友化學工業（股）製之商品名「史米（譯音）環氧ESA-011」、「史米環氧ELA-115」等之雙酚Α型環氧樹脂、或大日本油墨化學工業（股）製之商品名「耶皮谷龍（譯音）8 3 0S」等之雙酚F型環氧樹脂、或大日本油墨化學工業（股）製之商品名「耶皮谷龍 EXA15 14」等之雙酣S型環氧樹脂、萘型二環氧丙醚之大曰本油墨化學工業（股）製之商品名「耶皮谷龍HP-403 2 (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-環己烷二羧酸、四氫酞酸、六氫酞酸、六氫異酞酸、六氫對酞酸、酞酸、異酞酸、對酞酸、衣康酸、琥珀酸、己二酸、黏康酸、癸二酸等，就紫外線之透過性、賦予撓性而言以 -10- (8) (8)1331700 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4〇〜l2〇mgKOH/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)1331700 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、四級錢鹽、咪哩化合物、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（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系樹脂。 (d)含有羧基之（甲基）丙烯酸系共聚合樹脂，係使（甲基）丙烯酸酯、與在1分子中具有1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）丙嫌酸系共聚合樹脂（d)之（甲基）丙嫌酸醋，例如（甲基）丙烯酸甲酯、（甲基）丙烯酸乙醋、（甲基）丙烯酸丙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸戊酯、（甲基）丙烯酸己酯等之（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、經基丁基（甲基）丙稀酸醋、己內醋改性2 -涇基乙基 (甲基）丙烯酸酯等之含羥基的（甲基）丙烯酸酯類、甲 -12- 1331700 (ίο) 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個羧基之化合物，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)1331700 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膦等。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)1331700 脂（A)及（B)之合計量爲1〇〇質量份而言（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二環氧丙酸、加氫雙酚A二環氧丙醚或苯酚酚醛清漆環氧樹脂之（甲基）丙嫌酸加成 -15- (13) (13)1331700 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 828、耶皮克頓 834、耶皮克頓 1〇〇1、耶皮克頓10 04、大日本油墨化學工業（股）製之耶皮谷龍840、耶皮谷龍8 50、耶皮谷龍1 050、耶皮谷龍 2055、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-400、YDB-500、住友化學工業（股）製之史米環氧 ESB-400、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)1331700 日本油墨化學工業（股）製之耶皮谷龍N-73〇、耶皮谷龍 N-770、耶皮谷龍N-865、東都化成（股）製之耶伯頓頓 YDCN-701、YDCN-704、曰本化藥（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83〇、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-2004 (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 0 00 (皆爲商品名）等之加氫雙酚A型環氧樹脂；日本環氧樹脂（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-4 00 0、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-2 00、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)1331700 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HP 72 00、HP-72 00H (皆爲商品名）等之具有二環戊二烯架構的環氧樹脂；曰本油脂（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)1331700 使硬化塗膜之光澤度在ASTM 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、無定形二氧化矽等之二氧化矽較佳。無機塡充劑（F)之配合量，對合計量爲丨00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)1331700 機顔料等著色。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，通常自單側墳充。塡充後在兩面上藉由篩網印刷法、簾幕塗覆法、噴霧 -20- (18) 1331700 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60〜90°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 φ 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)1331700 去未曝光部分，形成塗膜圖案。顯像後，通常進乾燥。水洗且 (4 )硬化步驟使完成上述（3)之步驟的基板上之塗膜圖以熱硬化》(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). -6 - (4) (4) 1331700 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 such that the aromatic epoxy ring represented by the above X and the aliphatic or aromatic ring represented by z are regularly and repeatedly contained in the linear epoxy compound (a). The monocarboxylic acid (b) containing an unsaturated group is reacted, and in the obtained acrylate acrylate acrylate compound, the polybasic acid anhydride (c) is reacted, and the unsaturated group is appropriately disposed at both ends and side chains of the linear oligomer. Further, the resin (B) having a carboxyl group on the other side is (d) a carboxyl group-containing (meth)acrylic copolymer resin, and (e) having ethylene oxide in one molecule. A carboxyl group-containing copolymer resin obtained by reacting a ring with a compound of an ethylenically 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 electro-ammonium solution and the surface of the self-coating film from impregnating the plating solution, it is necessary to make the adhesion "surface hardenability (high sensitivity) by exposure and resistance). All drug properties 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 copolymer resin (B) having a carboxyl group has excellent heat resistance, "resistance to chemicals, wrinkles (5) 1331700, and surface hardenability (high sensitivity), but there is a problem in development. In the case of the combination of the carboxyl group-containing photopolymer (A) and the carboxyl group-containing copolymer resin (B), the balance of the properties is good and the two are excellent. Therefore, the two types of carboxyl group-containing photosensitive resins (and the copolymerized resin (B) having a carboxyl group) contain a photopolymerization (C), a reactive diluent (D), and a compound having an epoxy group! The photosensitive resin composition which can be alkali-developed according to the present invention has excellent cellophane resistance, heat resistance or adhesion, and resistance to plugging, selective exposure, development, and local hardening. A hardened film having excellent electroless tin plating resistance and electroless plating property, which is excellent in various properties such as chemical properties and electrical properties. Hereinafter, a resin composition which can be alkali-developed according to the present invention will be described in detail. First, the present invention The mixing ratio of the carboxyl group-containing photosensitive resin (A) constituting the photosensitive composition capable of alkali development to the copolymerized resin (B) having a carboxyl group is preferably 90:10 to 3 0:70. More preferably The mixing ratio is 90: 10 to 50: 50. The ratio of (A) is 90: 1 〇 is higher, the wrinkle property is deteriorated, and conversely, the lower imaging performance is worse than 30: 70, so it is not desirable. Secondly, the The total of the two resins is 30 to 150 mgKOH/g, preferably 40 to 120 mg KO. When the acid oxime of the carboxyl group-containing photosensitive resin (A) and the two types of resin having a carboxyl group (B) is 30 mgKOH/g, the solubility in the aqueous alkali solution is deteriorated. The coating film is not like. In addition, when it is higher than 150 mgKOH/g, it does not have the impression of the exposure bar: A) The hair agent (E) has a mellow gold light-resistant resin, and when compared with the case, the acid値范合合更低更低更低更低更低更低 ( 合合合合合合合合合合合合合合合合合合合合合 (6) 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 monounsaturated 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 of two carboxyl groups is polymerized in the presence of a conventional esterification catalyst such as a phosphine, an alkali metal compound or an amine to form an epichlorohydrin on an alcoholic secondary hydroxyl group. Conventional aprotic polar solvents such as dimethyl hydrazine, N,N-dimethylformamide, N,N-dimethylacetamide, aromatic hydrocarbons such as toluene and xylene, and the like The reaction is carried out in the presence of an alkali metal hydroxide such as caustic soda in a solvent (the reaction amount of epichlorohydrin is arbitrarily selected in the 〇~i molar for 1 mol of hydroxyl groups). The polyfunctional epoxy compound (a) and the unsaturated group-containing monocarboxylic acid (b) are bonded to the epoxy group contained in the 1 molar complex epoxy compound at a ratio of 〜1.2 mol. a saturated monocarboxylic acid (b) 'and a non-polymerizable agent such as hydroquinone or oxygen in the presence or absence of an organic solvent, and a tertiary amine such as triethylamine or triethyl benzalkonium chloride In the presence of a reaction catalyst such as a quaternary ammonium salt, an imidazole compound such as 2-ethyl-4-methylimidazole or a phosphorus compound such as triphenylphosphine, it is usually reacted at about 80 to 140 ° C to obtain a reaction product. 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) (7) 1331700 (A). However, the amount of the polybasic acid anhydride (c) used in the reaction was adjusted so that the acid group of the produced carboxyl group-containing photosensitive resin (A) was 3 〇 50 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 amine such as triethylamine or a quaternary ammonium salt such as triethylbenzylammonium chloride or an imidazole compound such as 2-ethyl-4-methylimidazole or the like may be added as needed. A phosphorus compound such as phenylphosphine is used as a catalyst. 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, a bisphenol type diglycidyl ether Japanese epoxy resin (trade name) can be used, and the product name is "Yipikton (transliteration) YL-6056", bisxylenol type diglycidyl ether of Japanese epoxy Resin (stock) made under the trade name "Yipikton (译音)ΥΧ-4〇00", bisphenol type diepoxypropyl ether, manufactured by Sumitomo Chemical Industries Co., Ltd. Bisphenol oxime type epoxy resin such as ESA-011", "Sumi Epoxy ELA-115", or the product name "Yipigulong (transliteration) 8 3 0S" manufactured by Dainippon Ink Chemical Industry Co., Ltd. A bisphenol S-type epoxy resin or a bismuth S-type epoxy resin or a naphthalene-type diglycidyl ether, which is manufactured by Dainippon Ink Chemical Industry Co., Ltd. under the trade name "Yipigulong EXA15 14". The product name "Yipigulong HP-403 2 (D)" manufactured by the Ink Chemical Industry Co., Ltd. may be used alone or in combination of two or more. A dibasic acid having two carboxyl groups in one molecule, and 1,4-cyclohexanedicarboxylic acid, tetrahydrofurfuric acid, hexahydrophthalic acid, hexahydroisodecanoic acid, hexahydropyridinic acid or citric acid can be used. , isophthalic acid, citric acid, itaconic acid, succinic acid, adipic acid, muconic acid, sebacic acid, etc., in terms of ultraviolet light transmission and flexibility, -10- (8) (8) 1331700 Aliphatic or alicyclic dicarboxylic acid compounds are preferred. These 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 (meth) acrylate, hydroxybutyl (methyl) Acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, phenylepoxypropyl (meth)acrylate, An unsaturated dibasic acid anhydride adduct of a hydroxyl group-containing acrylate such as a methyl caprolactone adduct or the like. More preferably, it is acrylic acid and/or methacrylic acid. These unsaturated group-containing monocarboxylic acids may be used singly or in combination of two or more kinds. Further, in the present specification, the (meth) acrylate is a generic term for acrylate and methacrylate, and the other similar expressions are also the same. The polyvalent 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 resin (A), but the use of the polybasic acid anhydride (c) in the reaction The amount is adjusted within the range of 30 to 150 mg KOH/g (preferably 4 〇 to 12 〇 mgKOH/g) of the carboxyl group-containing photosensitive resin (A). When the acid hydrazide of the carboxyl group-containing photosensitive resin (A) is less than 30 mgKOH/g, the solubility in the alkaline aqueous solution is deteriorated, and the formed coating film is hard to develop. On the other hand, when it is larger than 150 mgKOH/g, it is not required to be exposed to the surface of the exposed portion depending on the exposure conditions. The reaction is carried out in the presence or absence of an organic solvent in the presence of a polymerization inhibitor such as hydroquinone or oxygen, -11 - (9) (9) 1331700, usually at about 50 to 130 °C. At this time, a tertiary amine, a quaternary salt, a bismuth compound, a phosphorus compound or the like may be added as a catalyst depending on the necessity. The above polybasic acid anhydride (c) is, for example, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, naramic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methyl An alicyclic dibasic acid anhydride such as endomethyltetrahydrophthalic anhydride or tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadecyl succinic anhydride, phthalic anhydride, trimellitic anhydride Or an aliphatic or aromatic polybasic acid anhydride. One type or two or more types can be used herein. Next, the 'copolymerized resin (B) having a carboxyl group is obtained by (d) a (meth)acrylic copolymer resin containing a carboxyl group, 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. (d) A carboxyl group-containing (meth)acrylic copolymer resin obtained by copolymerizing a (meth) acrylate with a compound having one unsaturated group and at least one carboxyl group in one molecule. a (meth)acrylic acid vinegar which comprises a carboxyl group-containing (meth)acrylic acid copolymerized resin (d), such as methyl (meth)acrylate, ethyl (meth)acrylate, or (meth)acrylic acid (meth)acrylic acid alkyl esters such as propyl ester, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, 2-hydroxyethyl (meth) acrylate, hydroxyl group a hydroxyl group-containing (meth) acrylate such as propyl (meth) acrylate, butyl butyl (meth) acrylate vinegar or caprolactone modified 2- mercaptoethyl (meth) acrylate Class, A-12-1331700 (ίο) oxydiethylene glycol (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, isooctyloxy diethylene glycol (meth) acrylate Ethylene glycol modification of ester, butoxy triethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, etc. (Meth) 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 carboxyl group in one molecule, a chain-extended modified unsaturated monocarboxylic acid (for example, β·carboxyl group) between acrylic acid methacrylic acid, an unsaturated group and a carboxylic acid Ethyl (meth) acrylate, 2-propenyl methoxyethyl succinic acid, 2-propenyl hydroxyethyl hexahydrophthalic acid, an unsaturated monocarboxylic acid having an ester bond modified by a lactone, 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, such as a glycidyl (meth) acrylate, α. -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) (1) (11) (11) 1331700 Next, a photopolymerization initiator (C) constituting the photocurable and 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-3-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-(Dimethylamino)·2-[(4-methylphenyl)methyl]-l-[4-(4-morpholinyl)phenyl]-1-butanone, N,N- Amino acetophenones such as dimethylamino acetophenone; 2-methyl hydrazine, 2-ethyl hydrazine, 2 - 3 - butyl hydrazine, 1- ruthenium chloride, 2-戊蒽醌蒽醌, 2-amino hydrazine, etc. a thioxanthone such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone or 2,4-diisopropylthioxanthone; Acetals such as acetophenone dimethyl acetal, benzyl dimethyl acetal, benzophenone, methyl benzophenone, 4,4'-dichlorobenzophenone, 4, 4 a benzophenone such as bis-diethylaminobenzophenone or 4-benzylidene-4'-methyldiphenyl sulfide; 2,4,6-trimethylbenzhydrazide The photopolymerization initiator may be used singly or in combination of two or more kinds thereof. The photopolymerization initiator (C) may be used alone or in combination of two or more. Ethyl N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, etc. A tertiary amine light sensitizer or photoinitiator. 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) 1331700 ( The total amount of A) and (B) is 1 part by mass (the same as the solid content, the same applies hereinafter), and is preferably 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 polyhydric alcohols 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 acid, hydrogenated bisphenol A diglycidyl ether or phenol phenolic Varnish epoxy resin (methyl) propylene acid -15- (13) (13) an epoxy group was 1,331,700 (meth) acrylate and the like, 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, Jippikton 828 and Yeppicton 834 manufactured by Nippon Epoxy Co., Ltd. , Yepiketon 1〇〇1, Yepiketon 10 04, Yeppei Dragon 840 made by Dainippon Ink Chemical Industry Co., Ltd., Yeppi Valley Dragon 8 50, Yeppi Valley Dragon 1 050, Yeppi Valley Long 2055, Dongdu Huacheng (share) system, Yabatonton (transliteration) YD-011, YD-013, YD-127, YD-128, Sumitomo Chemical Industry Co., Ltd. Simi Epoxy ESA-11, ESA Bisphenol A type epoxy resin such as -014, ELA-115, ELA-128 (all are trade names); Yepiketon YL903 made by Japan Epoxy Resin Co., Ltd., Dainippon Ink Chemical Industry Co., Ltd. Yepi Gulong 152, Yepi Gulong 165, Dongdu Huacheng (share) system, Yptonton YDB-400, YDB-500, Sumitomo Chemical Industry Co., Ltd., Simi Epoxy ESB-400, ESB- Brominated epoxy resin such as 700 (both are trade names); yuppieton 152, yipikton 154, large-16- (14) (14) 1331700 made by Japan Epoxy Resin Co., Ltd. Yep Valley Dragon N-73〇, Yeppi Valley Dragon N-770, Yeppi Valley Dragon N-865, Dongdu Huacheng (shares), Yebtonton YDCN-701, YDCN-704, EPPN-201, EOCN-1 025, EOCN-1 020, EOCN-104S 'RE-3 06, manufactured by Sumitomo Chemical Co., Ltd., Sumi Epoxy ESCN-195X, ESCN- manufactured by Sumitomo Chemical Industries Co., Ltd. Novolac type epoxy resin such as 220 (both are trade names); Yepugulong 83〇 made by Dainippon Ink Chemical Industry Co., Ltd., Yepiketon 807 made by Japan Epoxy Resin Co., Ltd., Dongdu Huacheng ) bisphenol F-type epoxy resin such as Yeptonton YDF-170, YDF-175, YDF-2004 (all are trade names), and Eptonton ST-2004, ST manufactured by Dongdu Chemical Co., Ltd. -2007, ST-3 0 00 (all are trade names), etc. Hydrogenated bisphenol A type epoxy resin; Japan Epoxy resin (share) made by Yepiketon 604, Dongdu Huacheng (share) made of Yepi Tengton YH-434, Sumitomo Chemical Industries Co., Ltd., Simi Epoxy ELM-1 20 (both trade names), etc., epoxy propylamine epoxy resin; Lai Xilu (transliteration) chemical industry (share) system West Roach Seton (transliteration) 2 02 1 (trade name) and other alicyclic epoxy resin; YL-93 made by Japan Epoxy Resin Co., Ltd. 3, EPPN-501 and EPPN-502 made by Nippon Chemical Co., Ltd. (all are trade names) Ethylene glycol type epoxy resin; bis-xylenol type or bisphenol such as YL-6056, YX-4 00 0, YL-6121 (all are trade names) made by Japan Epoxy Resin Co., Ltd. Type epoxy resin or a mixture of such; EBP S-2 00 made by Nippon Kayaku Co., Ltd., EPX-30 by Asahi Kasei Co., Ltd., EXA-1514 by Dainippon Ink Chemical Industry Co., Ltd. ( Bisphenol S type epoxy resin such as the product name; bisphenol a phenolic acid such as yuppicton 157S (trade name) made by Japan Epoxy Resin Co., Ltd. • 17- (15) (15) 1331700 Lacquer-type epoxy resin; tetraphenol-based ethane type epoxy resin such as yuppieton 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) manufactured by Nippon Oil & Fat Co., Ltd.: ZX-1 063 manufactured by Tohto Kasei Co., Ltd. Business Tetra-glycidyl propyl decyl ethane hydride resin, etc.; ESN-190, ESN-3 60 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA manufactured by Dainippon Ink Chemical Industry Co., Ltd. Naphthyl-containing epoxy resin such as -4750 and EXA-4700 (both are trade names); HP 72 00 and HP-72 00H (both are trade names) manufactured by Dainippon Ink Chemical Industry Co., Ltd. Epoxy resin of cyclopentadiene structure; epoxy methacrylate copolymerized epoxy resin such as CP-50S and CP-5 0M (all trade name) manufactured by 曰本油(股); 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 order to suppress the adhesion of the solder ball of the hardened coating film, the present invention requires -18-(16) (16) 1331700 to make the gloss of the cured coating film ASTM 60. It is then suppressed from 1 to 50. For this purpose, it is preferred to select cerium oxide containing cerium oxide powder, finely powdered cerium oxide, amorphous cerium oxide or the like. The amount of the inorganic chelating agent (F) to be added is 60 to 200 parts by mass, preferably 80 to 00 parts by mass of the photosensitive resin (A) and (B) having a carboxyl group. The proportion of 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 of 2E4MZ-AZINE, C11Z-AZINE, 2PHZ, etc., guanamine, benzoguanamine, guanamine, urea, urea derivative, etc. 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 desired, and a pigment such as a -19-(17) (17) 1331700 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 filled with a microporous portion of a printed circuit board on which a circuit is formed by printing. The sputum is a screen that can be selectively filled in the microporous portion, usually from a one-sided grave. 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) 1331700 coating method, and a roll coating method. When the coating is applied by the screen printing method, the steps and the steps of filling in the above-mentioned micropores may be omitted, and the micropores may be coated and filled. After coating, the volatile component contained in the composition is removed at a temperature of 60 to 90 ° C and dried to form a microporous dry coating film. At this point, the solvent in the micropores is extremely important for the selected volatile temperature and time. (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 the patterned light hood. The exposure light source usually uses low-pressure mercury. A lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a metal halide lamp, and the like. The amount of exposure of the light source to be exposed may be the weight average molecular weight of the binder polymer, the monomer ratio, the content, the type or content of the photopolymerizable compound, the type or content of the photopolymerization initiator, and the type of photopolymerization initiation aid. Or the content is appropriately selected. (3) Alkali development step The coating film after the exposure in the above step (2) was 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) 1331700. After development, it is usually dried. Water washing and (4) hardening step to heat-harden the coating film on the substrate which completes the above step (3)

熱硬化係抑制微孔中塗膜之硬化收縮，抑制驾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肖加熱硬化的方法。通常，適當選擇在60〜80°C下分鐘、在100〜120 °C下0〜40分鐘、然後在150〜 40〜90分鐘之溫度與時間使用。爲得充分的無電库性、無電解鍍金耐性時，使分段式硬化之條件在1 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、性，且具有耐熱性、密接性、電絕緣性等之各種转及無電解鍍錫耐性、無電解鍍金耐性優異的硬化塗 ;加熱予 i膜之滲 :式進行 30 〜60 1 6 0 〇C 下【鑛錫耐會產生空泡耐性，以膜》【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明’惟本發明不受下述實施例所限制。而且，於「份」及「％」沒有特別限定時，全部爲質量份 %。關本發下述中及質量 -22- (20) (20)1331700 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，加入羧酸當量 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828、環氧當量 189 g/當量）378份，在氮氣氣體環境中、攪拌、11〇 °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15 0°C，且使溫度保持於150°C，約反應90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9 5〜1 0 5 °C下加熱，慢慢地滴入丙烯酸72份，反應 16小時。使該反應生成物冷卻至80〜90°C，且加入四氫酞酸酐190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65 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828、環氧當量189g/當量）776份，在氮氣氣體環境中、攪拌、 -23- (21) (21)1331700 1 1 or下溶解。然後，添加三苯基膦〇·65份，且使反應容器內之溫度昇溫至150°C，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、二甲基亞礪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碾予以回收，使含有副生鹽與二甲基亞碾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24 5 g/當量之多官能環氧樹脂β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 24〇份，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16小時。使該反應生成物冷卻至80〜90 °C，且加入四氫酞酸酐129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 1〇〇 mgKOH/g。於下述中，該樹月旨溶液稱爲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7 0 0.0g加熱至11(TC，在3小時內滴入甲基丙烯酸270.0g、甲基丙 -24- (22) (22)1331700 烯酸甲酯153.0g、二丙二醇單甲醚294.0g、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）O) lO.Og之混合物，再於110°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1.5g，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95〜105°C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16小時。使該反應生成物冷卻至80〜90 °C，加入四氫酞酸酐60.1份’藉由紅外線吸光分析，直至沒有酸酐之吸收波峰（1780cnT1)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) 1331700 音）#15〇 96.4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，該樹月旨溶液稱爲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-680GW)，照射紫外線（曝光量500mJ/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(TCx3〇分鐘、11(rCx30 分鐘、160°Cx4 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 • 進行駿摺性、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- 1331700 24The thermosetting system performs segmental hardening for the purpose of suppressing the hardening shrinkage of the coating film in the micropores and suppressing the driving or cavitation. Segmented hardening allows temperature and time to be divided into two-stage or three-dimensional heat-hardening methods. Usually, it is suitably selected at 60 to 80 ° C for 1 minute, at 100 to 120 ° C for 0 to 40 minutes, and then at 150 to 40 to 90 minutes for temperature and time. In order to obtain sufficient electroless plating resistance and electroless gold plating resistance, it is preferable to shorten the condition of the segmentation hardening within the range of 1 void. According to the procedure described above, it is possible to form a hard coating having excellent plugging property, heat resistance, adhesion, electrical insulating properties, and the like, and excellent electroless tin plating resistance and electroless gold plating resistance; Membrane permeation: the formula is carried out at 30 to 60 1 6 0 〇C [the smelting resistance of the smelting resistance to the film, and the film] [Embodiment] The following examples are more specifically illustrated by the examples and comparative examples. 'The invention is not limited by the following examples. Further, when "parts" and "%" are not particularly limited, all are in parts by mass. The following is a medium and a mass of -22- (20) (20) 1331700. Synthesis Example 1 A carboxylic acid is added to a reaction vessel equipped with a gas introduction pipe, a stirring device, a cooling pipe, a thermometer, and a drip funnel for continuous dripping. 86 parts per gram of 1,4-cyclohexanedicarboxylic acid equivalent to 86 g/eq. and bisphenol A type epoxy resin (manufactured by Nippon Epoxy Resin Co., Ltd., yippicton 828, epoxy equivalent 189 g/eq) 378 The mixture was dissolved in a nitrogen gas atmosphere under stirring at 11 °C. Then, 3 parts of triphenylphosphine was added, and 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 equivalent of 464 g / equivalent. Oxygen compound. Then, the temperature in the flask was cooled to 40 ° C, and 3 parts of carbitol acetate was added, and dissolved by heating, and 0.46 parts of methylhydroquinone and 1.38 parts of triphenylphosphine were added, at 9 5 to 1 After heating at 0 ° C, 72 parts of acrylic acid was slowly added dropwise and reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C, and 190 parts of tetrahydrofurfuric anhydride was added and 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 inlet pipe, a stirring device, a cooling pipe, a thermometer, and an aqueous alkali metal hydroxide aqueous solution dropping funnel, a carboxylic acid equivalent of 65 g/eq. of itaconic acid was added. 130 parts and bisphenol A type epoxy resin (made by Nippon Epoxy Resin Co., Ltd., Jeep Picton 828, Epoxy equivalent 189 g/eq), 776 parts, stirred in a nitrogen atmosphere, -23- (21) (21) 1331700 1 1 or dissolved under. Then, 65 parts of triphenylphosphine ruthenium was added, and 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 equivalent of 443 g / equivalent. Oxygen compound. Then, the temperature in the flask was cooled to 40 ° C, and 1,800 parts of epichlorohydrin and 1,690 parts of dimethyl hydrazine were added, and the temperature was maintained at 45 ° C with stirring. Then, 364 parts of a 48% aqueous sodium hydroxide solution was continuously added dropwise over 60 minutes, and further reacted for 6 hours. After the reaction is completed, most of the excess epichlorohydrin and dimethyl sub-milling are distilled under reduced pressure to recover the reaction product containing the by-product salt and dimethyl sub-milling in methyl isobutyl ketone. Washed. After separating the organic solvent layer from the aqueous layer, methyl isobutyl ketone is distilled off from the organic solvent layer under reduced pressure to obtain a polyfunctional epoxy resin having an epoxy equivalent of 24 5 g/eq. 245 parts of epoxy resin was added to a flask equipped with a stirring device, a cooling tube and a thermometer, and 24 parts of carbitol acetate was added thereto, and dissolved by heating, and 0.46 parts of methylhydroquinone and 1.38 parts of triphenylphosphine were added. After heating at 95 to 105 ° C, 72 parts of acrylic acid was slowly added dropwise, and the reaction was carried out for 16 hours. The reaction product was cooled to 80 to 90 ° C, and 129 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. The obtained carboxyl group-containing photosensitive resin had a nonvolatile content of 65% and a solid content of strontium acetate of 1 〇〇 mgKOH/g. In the following, the tree-shaped 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 solvent of dipropylene glycol monomethyl ether 70 g was heated to 11 (TC, and methyl group was dropped in 3 hours. 270.0 g of acrylic acid, methylpropane-24-(22) (22) 1331700 methyl olefinate 153.0 g, dipropylene glycol monomethyl ether 294.0 g, and 3-butylperoxy-2-ethyl as a polymerization catalyst A mixture of octanoate (available from Nippon Oil Co., Ltd.), a mixture of 10% of O.Og, was further stirred at 110 ° C for 3 hours to deactivate the polymerization catalyst to prepare a copolymerized resin solution. After cooling, 3,4-epoxycyclohexyl methacrylate was added (Rai Silu Chemical Industry Co., Ltd., Seymour Rouma), 390.0 g of 'triphenylphosphine 5.0 g, hydroquinone 1.5 g of methyl ether 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 and a nonvolatile content of 45 wt%. The acid hydrate of the solid component is 70 mgKOH/g. In the following, the resin solution is referred to as B-1 varnish. Synthesis Example 4 In the reaction vessel of the meter, the agitator, the dropping funnel, and the reflux cooler, the cresol novolac type epoxy resin (Yupigulong N-680, manufactured by Dainippon Ink Chemical Industry Co., Ltd., epoxy equivalent = 2) was weighed. 10) 210 parts and 96.4 parts of carbitol ethylene glycol ester were heated and dissolved. Then, 0.1 part of hydroquinone as a polymerization inhibiting agent and 2.0 parts of triphenylphosphine as a reaction catalyst were added. The mixture was made at 95~ After heating at 105 ° C, 72 parts of acrylic acid was slowly added dropwise until the acid hydrazine was 3.0 mg KOH / g or less, and the reaction was carried out for about 16 hours. The reaction product was cooled to 80 to 90 ° C, and tetrahydrophthalic anhydride 60.1 was added. The fraction was analyzed by infrared light absorption until there was no absorption peak of the acid anhydride (1780cnT1). The reaction was carried out for about 6 hours. Into the reaction solution, the aromatic solvent, von Fluro, manufactured by Idemitsu Petrochemical Co., Ltd. was added. 23) 1331700 Sound) #15〇96.4 parts, which were 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 tree The monthly solution is called R-1 varnish. Examples 1 to 7 and ratio 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 tree|fat composition. The micro-holes of the patterned copper through-hole printed circuit board were sufficiently filled and printed by a vertical needle and screen printing method using a 90 mesh mesh screen formed with a pattern capable of filling the microporous portion. In addition, a 90 mesh mesh of polyester mesh was used, and the film was completely coated on both sides, and the film was dried by a hot air dryer at 70 ° C for 40 minutes. Then, a negative film having a light-resistance pattern was adhered to the coating film, and an ultraviolet ray exposure apparatus (type HMW-680GW, manufactured by Ougu (trans)) was used to irradiate ultraviolet rays (exposure amount: 500 mJ/cm 2 ). The image was developed by a spray pressure of 2.0 kg/cm 2 in a 1% aqueous potassium carbonate solution for 90 seconds to dissolve and remove the unexposed portion. Then, using a hot air dryer, 8 (TCx3 〇 minutes, 11 (rCx 30 minutes, 160 ° C x 40 minutes heat hardening 'production test substrate. The obtained test substrate having a hardened film' was tested by the following test methods and evaluation methods. Tests for folding, adhesion, solder heat resistance, solvent resistance, electroless plating, gold resistance, electroless tin plating resistance, and bubble resistance. The evaluation results of the above tests are shown in Table 2. -26- 1331700 twenty four

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〇〇〇〇 < X 卜寸 ο 〇〇〇〇〇 X 寸〇 Λ3 X 〇 X 〇〇〇寸〇 v〇〇〇〇〇〇〇寸寸〇 iTi 〇〇〇〇〇 <1 寸寸〇寸 <] 〇 < 〇〇〇 ΓΛ 寸〇辑 r〇〇〇〇〇〇 < 00 〇 CS 〇〇〇〇〇 < CN 〇〇〇〇〇〇〇寸寸〇味蜘 m * m a 鹱〇 iH 鹪鹪 v〇坦 m 菌蘅毖毖 m Μ #1 m m 键瓣 ϋ 蜒 m 铂 it m #: 摧 -28- (26) (26)1331700 於上述表2中各特性試驗試驗之評估方法，如下所述。 (1)雛摺性：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JIS D 0202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。〇：10 0/100完全沒有剝離者。 △ : 1 00/100中有稍許十字切割部分被剝離者。 X: 0/100〜90/100產生剝離者。 (3) 焊接耐熱性：以JIS C 6481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1〇秒鐘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)1331700 △: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3μπι、金爲Ο.〇3μπι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，且有電鑛潛入情形者。 (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+軟性蝕刻+硫酸處理），使用市售的無電解鍍錫液，以電鍍厚度Ιμηι之條件（70°C、12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) (28)1331700 〇：在微孔5 Ο 0個孔中’沒有剝離情形者。 △:在微孔500個孔中產生1 〇個以下剝離情形者。 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，6(Γ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’以及無電解鑛錫耐性、無電解鍍金耐性優異的可以鹼現象之感光性樹脂組成物。〇〇〇〇< X 寸 inch 〇〇〇〇〇X inch 〇Λ3 X 〇X 〇〇〇 inch 〇v〇〇〇〇〇〇〇 inch inch 〇iTi 〇〇〇〇〇<1 inch inch inch<1 inch inch inch<1 inch inch inch ;] 〇< 〇〇〇ΓΛ inch〇 r〇〇〇〇〇〇< 00 〇CS 〇〇〇〇〇< CN 〇〇〇〇〇〇〇 inch inch 蜘味虫m * ma 鹱〇iH 鹪鹪v〇坦m 蘅毖毖m Μ#1 mm key ϋ 蜒m platinum it m #: -28-28- (26) (26) 1331700 The evaluation methods of the test tests for each characteristic in Table 2 above, as follows Said. (1) Fragmentation property: In the above test substrate production step, the peeling of the negative film after exposure was evaluated visually and based on the following criteria. 〇: There is no wrinkle on the film. △: There is only a slight wrinkle on the film. X: The skin is completely wrinkled. (2) Adhesiveness: A checkerboard-shaped cross cut was applied to the hardened film of the test substrate based on the test method of JIS D 0202, and then the following conditions were used to evaluate the peeling after peeling off by the glass tape. 〇: 10 0/100 has no peeling at all. △ : There is a slight peel cut in 1 00/100. X: 0/100~90/100 produces a peeler. (3) Solder heat resistance: The test substrate was immersed in a solder bath at 260 ° C for 3 times, 3 times or less, using the rosin-based flux and the non-washing flux, based on the test method of JIS C 6481. The baseline assesses changes in the membrane. 〇: There is no abnormality such as peeling on the hardened film. △: Only slightly discolored on the hardened film. X: There are cases of floating and peeling 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 to confirm the state of the cured film. The evaluation criteria are as follows. 〇: There is no discoloration or whitening on the hardened film. -29- (27) (27) 1331700 △: There is a slight discoloration on the hardened film. X: There is a discoloration such as peeling or whitening on the hardened film. (5) Electroless gold plating resistance: The hardened film of the test substrate is made of a commercially available electroless nickel liquid or an electroless gold plating solution, and the thickness of the nickel plating is 3 μm in a temperature of 85 to 90 ° C. Electroless plating was performed at 3 μm, and the discoloration and peeling state of the hardened film were evaluated by 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 case where the electric ore is infiltrated. (6) Electroless tin plating resistance: pre-treating the hardened film of the above test substrate (acid degreasing + soft etching + sulfuric acid treatment), using a commercially available electroless tin plating solution, and plating the thickness Ιμηι (70 ° C , 12 minutes) electroless tin plating treatment. 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, and there are those who are immersed in electroplating. (7) Cavitation resistance: The test substrate was subjected to a welding correction process by a leveling machine, and after peeling off the tape, the peeling state of the film in the micropore portion was confirmed. -30- (28) (28) 1331700 〇: In the 5 holes of the micropores, there is no peeling. △: One or less peeling cases were generated in 500 pores 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 test substrate was measured for a gloss of 60° (gloss 値) using a micro-lighting machine (manufactured by Bizom). Further, 6 (the glossiness of Γ 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. From the above description, it can be seen that the plugging property and the bubble resistance can be formed by the present invention. 'There are various properties such as heat resistance, adhesion, and electrical properties', and an alkali-sensitive photosensitive resin composition excellent in electroless tin-resistance and electroless gold plating resistance.

-31 --31 -

Claims

1331700 ||~ —————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————— A resin composition characterized by containing (A) a polybasic acid anhydride in a reaction product of a polyfunctional epoxy compound (a) represented by the following general formula (I) and a monocarboxylic acid (b) containing an unsaturated group ( c) a carboxyl group-containing photosensitive resin obtained by the reaction, (B) (d) a carboxyl group-containing (meth)acrylic copolymer resin, and (e) an oxirane ring and an ethyl group in one molecule. a compound having a residue, a (C) photopolymerization initiator, (D) a reactive diluent, and (E) a compound having an epoxy group, which is a residue of a compound of a saturated group, is formed by a compound having an epoxy group; CHj-

—CH 广CH—CH 广0—X_ •CHr \J •••a·· (I) (In the formula, X is an aromatic ring having two epoxy acrylate aromatic epoxy resins in one molecule. The residue, lanthanide means a glycidyl group and/or a hydrogen atom 'Ζ is a residue of an aliphatic or aromatic dibasic acid, and ρ means an integer of 1 i to 20). 2. The photosensitive resin composition which can be alkali-developed according to the first aspect of the patent application, wherein the copolymerized resin (B) having a carboxyl group is (d) a (meth)acrylic group having a carboxyl group A polymerized resin having a carboxyl group obtained by reacting a compound having an alicyclic epoxy group and an ethylenically unsaturated group in 1 molecule with 1,331,700. 3. The photosensitive resin composition which can be alkali-developed according to the first aspect of the patent application, wherein the ratio of the carboxyl group-containing photosensitive resin (A) to the carboxyl group-containing copolymer resin (B) is 90: 10~ 50: 50. 4. The photosensitive resin composition which can be alkali-developed as in the first aspect of the patent application, wherein the photosensitive resin (A) having a carboxyl group and the copolymerized resin having a carboxyl group are contained in a total amount of 1 part by weight. The amount of the photopolymerization initiator (C) to be in the range of 1 to 30 parts by mass, and the amount of the reactive diluent (D) to be in the range of 5 to 40 parts by mass, which has an epoxy group The compounding amount of the compound (E) is in the range of 10 to 70 parts by mass. 5. A photosensitive resin composition which can be alkali-developed as in the first aspect of the patent application, wherein the photosensitive resin (A) and (B) containing a carboxyl group in a total amount of 1 part by mass are re- It contains 50 to 200 parts by mass of an inorganic chelating agent (F). 6. The photosensitive resin composition which can be alkali-developed as in the fifth aspect of the patent application, wherein the inorganic chelating agent (F) contains cerium oxide. 7. The photosensitive resin composition which can be alkali-developed according to any one of claims 1 to 6, wherein after the coating is dried, the active energy ray is irradiated, and after development, the coating film obtained by heat curing is cured. ASTM 60° is in the range of 1 to 60. 8. A printed circuit board characterized by forming a solder resist film which is coated with a photosensitive resin composition which can be alkali-developed according to any one of claims 1 to 6. After drying, the live -2- 1331700 performance line irradiation, and the heat-hardened result after development.