TW201134840A

TW201134840A - Curable composition, cured material therefrom, and use thereof

Info

Publication number: TW201134840A
Application number: TW099140399A
Authority: TW
Inventors: Yoshihiro Miki; Masahiro Tsuchiya; Keita Harashima; In-Jung Yang; Momoko Takai
Original assignee: Tamura Seisakusho Kk
Priority date: 2009-11-30
Filing date: 2010-11-23
Publication date: 2011-10-16
Also published as: TWI488869B; WO2011065228A1; JPWO2011065228A1; JP5667080B2

Abstract

Provided is a novel curable composition for manufacturing a cured film that has a variety of uses. Said curable composition is characterized by containing: a compound (A) with a molecular weight between 500 and 5000, each molecule of which contains two or more unsaturated groups but does not contain any carboxy groups; a photopolymerization initiator (B); a reactive diluent (C), each molecule of which contains two or more unsaturated groups; and a compound (D), each molecule of which contains at least one amino group or imino group.

Description

201134840 六、發明說明：【發明所屬之技術領域】本發明關於一種新穎的硬化性組成物，進一歩詳細而言，關於一種製造印刷電路板所使用的阻焊劑或標記油墨等所使用的硬化性組成物、其硬化物及其用途。【先前技術】過去以來，液狀顯像型阻焊劑油墨組成物被使用在一部分民生用印刷電路板，以及絕大部分產業用印刷電路板這些用途上。使用液狀顯像型阻焊劑組成物的時候，藉由照射紫外線然後顯像而形成影像，以熱及照光完工硬化（正式硬化），能夠製造出高精密度、高密度印刷電路板。就光阻墨組成物的具體例子而言，已有文獻揭示出一種光阻墨組成物，係由酚醛型環氧樹脂，以及在含不飽和基單羧酸之反應生成物附加酸酐而成的含羧基感光性樹脂、光聚合起始劑、稀釋劑及環氧樹脂所構成（參照專利文獻1 )。然而，專利文獻1所記載的阻焊劑油墨組成物，爲了防止在使用之前含羧基的感光性樹脂與環氧樹脂發生反應而製成二液型，會有必須在剛要使用之前加以混合的問題點。另外，近來以印刷電路板之製造步驟的高效率化爲目的，而提出了以噴墨印刷機描繪阻焊劑圖案。就噴墨印刷機所使用的阻焊劑油墨組成物而言，在專 201134840 利文獻2中揭示了一種硬化性組成物，由於包含了含烯丙基之二醯亞胺化合物，以及雙馬來醯亞胺化合物、稀釋劑，因此黏度低並且操作性、保存安定性、耐熱性、耐藥品性、無電解鍍金耐性優異。另外，在專利文獻3中揭示了一種樹脂組成物，係由於包含了含烯丙基的二醯亞胺化合物、雙馬來醯亞胺化合物、使平均粒徑5至1 0 Onm的二氧化矽或氧化鋁微粒子分散於稀釋劑而成的分散液，以及稀釋劑，因此黏度低並且耐熱性及重塗性優異（參照專利文獻3)。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開昭61-243869號公報 [專利文獻2] PCT/JP2006/300279號公報 [專利文獻3]日本特開2008-37898號公報【發明內容】 [發明所欲解決之課題] 本發明所欲解決之課題，係提供一種硬化性組成物，能夠在各種用途方面提供具有優異性能的硬化物。 [用於解決課題之方法] 本發明人發現藉由以下（1 )〜（丨2 )所關連之構成 ’可解決上述課題，而完成了本發明。 -6 - ⑧ 201134840 (1 ) 一種硬化性組成物，其特徵爲含有：在分子中不具有羧基而具有2個以上不飽和基，且分子量5 00〜 5000之化合物（A );光聚合起始劑（B ):在分子中具有2個以上不飽和基之反應性稀釋劑（C);在分子中具有胺基或亞胺基至少一個以上之化合物（D )。前述化 (2 )如（1 )所記載之硬化性組成物，其中合物（A)係下述一般式（i)所表示之化合物，201134840 VI. Description of the Invention: [Technical Field] The present invention relates to a novel hardenable composition, and more particularly to a hardenability used for a solder resist or a marking ink used for manufacturing a printed circuit board. A composition, a cured product thereof, and use thereof. [Prior Art] In the past, a liquid-developing type solder resist ink composition has been used for a part of a consumer printed circuit board, and most industrial printed circuit boards. When a liquid-developing type solder resist composition is used, an image is formed by irradiation with ultraviolet rays and development, and heat and illumination are completed and hardened (formally hardened), whereby a high-precision, high-density printed circuit board can be manufactured. As a specific example of the resist ink composition, there has been disclosed a photoresist ink composition which is composed of a novolac type epoxy resin and an acid anhydride added to a reaction product containing an unsaturated monocarboxylic acid. A carboxyl group-containing photosensitive resin, a photopolymerization initiator, a diluent, and an epoxy resin are formed (see Patent Document 1). However, in the solder resist ink composition described in Patent Document 1, in order to prevent the photosensitive resin containing a carboxyl group from reacting with the epoxy resin before use to form a two-liquid type, there is a problem that it is necessary to mix it just before use. point. Further, recently, in order to increase the efficiency of the manufacturing steps of printed circuit boards, it has been proposed to draw a solder resist pattern by an ink jet printer. In the case of a solder resist ink composition used in an ink jet printer, a hardenable composition is disclosed in Japanese Patent No. 201134840, which contains an allyl-containing bis-imine compound and a double-malay The imine compound and the diluent have low viscosity, and are excellent in workability, storage stability, heat resistance, chemical resistance, and electroless gold plating resistance. Further, Patent Document 3 discloses a resin composition which comprises an allyl-containing diquinone imine compound, a bismaleimide compound, and an cerium oxide having an average particle diameter of 5 to 10 Onm. Further, the dispersion in which the alumina fine particles are dispersed in the diluent and the diluent are low in viscosity and excellent in heat resistance and recoatability (see Patent Document 3). [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. No. 2008-37898. [Problem to be Solved by the Invention] The object of the present invention is to provide a curable composition capable of providing a cured product having excellent properties in various applications. [Means for Solving the Problem] The present inventors have found that the above problems can be solved by the following configuration of (1) to (丨2), and the present invention has been completed. -6 - 8 201134840 (1) A curable composition comprising: a compound (A) having a molecular weight of from 500 to 5,000 having no carboxyl group in the molecule and having two or more unsaturated groups; The agent (B): a reactive diluent (C) having two or more unsaturated groups in the molecule; and at least one compound (D) having an amine group or an imine group in the molecule. (2) The curable composition according to (1), wherein the compound (A) is a compound represented by the following general formula (i),

[式（i)中’ R。表示- CH2-或- CH2〇-R01-; R1意指甲基或 (0 氫’虛線表示可爲雙鍵的鍵結處；G表示下述一般式（ia )、（ib )或（ic )所表示之2價或3價基；m係對應於 G之價數之數字；ROi表示碳數2〜1〇之分支或直鏈狀伸院基' 【化2】 201134840 (式（ia)中，R2〜r4各自獨立，表示氫原子或甲基）【化3】[In the formula (i) 'R. Represents -CH2- or -CH2〇-R01-; R1 means methyl or (0 hydrogen 'dashed line indicates a bond which can be a double bond; G means the following general formula (ia), (ib) or (ic) The two-valent or three-valent base represented; m is a number corresponding to the valence of G; ROi is a branch of a carbon number of 2 to 1 或 or a linear chain of the base [Chemical 2] 201134840 (in the formula (ia) , R2~r4 are independent of each other, indicating a hydrogen atom or a methyl group.

(ib) (式（ib)中，R5及R6各自獨立，意指氫原子或甲基）【化4】(ib) (in the formula (ib), R5 and R6 are each independently, meaning a hydrogen atom or a methyl group) [Chemical 4]

(式（ic)中，p意指2〜5之整數）]。 (3 )如（1 )所記載之硬化性組成物，其中，前述化合物（A )係含烯丙基之二醯亞胺化合物。 (4 )如（1 )〜（3 )任一者所記載之硬化性組成物，其中，前述反應性稀釋劑（C)含有下述一般式（ii) 所表示之三環癸二醇二（甲基）丙烯酸酯，【化2】(in the formula (ic), p means an integer of 2 to 5)]. (3) The curable composition according to (1), wherein the compound (A) is an allyl-containing bis-imine compound. (4) The curable composition according to any one of (1) to (3), wherein the reactive diluent (C) contains a tricyclic decanediol II represented by the following general formula (ii) ( Methyl) acrylate, [Chemical 2]

(式中，R7及r8各自獨立，意指甲基或氫；η及m各自獨立，意指〇〜5之整數）。 (5 )如（1 )〜（4 )任一項所記載之硬化性組成物 -8- ⑧ 201134840 ，其中，前述反應性稀釋劑（c )係含有由二乙二醇二（甲基）丙烯酸酯、二季戊四醇二（甲基）丙烯酸酯、二季戊四醇三（甲基）丙稀酸醋、二季戊四醇四（甲基）丙嫌酸酯、二季戊四醇五（甲基）丙烯酸酯及二季戊四醇六（甲基）丙烯酸酯所構成之群中所選出之一種以上。 (6 )如（1 )〜（5 )任一者所記載之硬化性組成物，其中，前述化合物（D )係三嗪系化合物。 (7 )如（6 )所記載之硬化性組成物，其中，前述三嗪系化合物係三聚氰胺、三聚氰胺衍生物或Ν’-第三丁基-Ν -環丙基-6-(甲硫基）-1,3,5·三嗪-2,4-二胺。 (8 )如（1 )〜（8 )任一項所記載之硬化性組成物，其係阻焊劑油墨用。 (9 )如（8 )所記載之硬化性組成物，其係用於噴墨法中的阻焊劑油墨，在25 °C的黏度爲200mPa . s以下。 (1 0 ) —種硬化物，係如（1 )〜（9 )任一項所記載之硬化性組成物之硬化物。 (1 η —種印刷電路板，係使用如（1 〇)所記載之硬化物。 (12)—種反射片，其係具有進一步含有氧化鈦的由如（Ο〜（7 )任一者所記載之硬化性組成物之硬化物所產生的被膜。 [發明之效果] 依據本發明，可提供一種硬化性組成物，可形成具有 -9 - 201134840 優異特性的硬化物。【實施方式】以下，就本發明的實施形態詳細地說明。 [硬化性組成物] 化合物（A) 就化合物（A)而言’只要不具有羧基而具有2個以上不飽和基、分子量（對於以單體爲結構單元的高分子化合物而言，是指重a平均分子量，在本發明中相同）在 5 0 0 0以下，則並未受到限制，而宜使用含烯丙基之二醯亞胺化合物。就含烯丙基之二醯亞胺化合物之具體例而言，並未特別受到限制，而可適合使用下述式（i i i )所表示之化合物【化3】(wherein R7 and r8 are each independently, meaning methyl or hydrogen; and η and m are each independently, meaning an integer of 〇~5). (5) The curable composition of any one of (1) to (4), wherein the reactive diluent (c) contains diethylene glycol di(meth)acrylic acid. Ester, dipentaerythritol di(meth) acrylate, dipentaerythritol tris(meth) acrylate vinegar, dipentaerythritol tetrakis(methyl) propyl acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa One or more selected from the group consisting of methyl acrylates. (6) The curable composition according to any one of (1) to (5), wherein the compound (D) is a triazine-based compound. (7) The curable composition according to (6), wherein the triazine-based compound is melamine, a melamine derivative or Ν'-tert-butyl-fluorene-cyclopropyl-6-(methylthio). -1,3,5·triazine-2,4-diamine. (8) The curable composition according to any one of (1) to (8), which is used for a solder resist ink. (9) The curable composition according to (8), which is used for the solder resist ink in the inkjet method, has a viscosity at 25 ° C of 200 mPa·s or less. (10) The hardened material is a cured product of the curable composition according to any one of (1) to (9). (1 η - A printed circuit board is a cured product as described in (1). (12) A reflection sheet having a further containing titanium oxide, such as (Ο~(7) [Effects of the Invention] According to the present invention, it is possible to provide a curable composition which can form a cured product having excellent characteristics of -9 to 201134840. [Embodiment] The embodiment of the present invention is described in detail. [Curable composition] The compound (A) has two or more unsaturated groups and a molecular weight as long as it does not have a carboxyl group (for a monomer as a structural unit) In the case of a polymer compound, it means that the weight average molecular weight is the same as in the present invention), and it is not limited, and it is preferable to use an allyl group-containing imine compound. The specific example of the propylene diimine compound is not particularly limited, and a compound represented by the following formula (iii) can be suitably used.

(iii) 此處，在一般式（iii)中，R9意指伸焼基、亞芳基或亞芳烷基。就該等基團的碳數而言，一般爲丨〜^^。此種基團較具體而言，可列舉-(CH2)n-所表示之直鍵狀伸垸基（π=1〜18之整數’宜爲n=6) ’或下述式所表示 -10- ⑧ (iv) 201134840 之基，【化4】(iii) Here, in the general formula (iii), R9 means an exoendyl group, an arylene group or an aralkylene group. In terms of the carbon number of the groups, it is generally 丨~^^. More specifically, such a group may be a linear bond-extension group represented by -(CH2)n- (an integer of π = 1 to 18 is preferably n = 6) ' or a formula represented by the following formula -10 - 8 (iv) 201134840 basis, [Chem. 4]

H2H2

C - (v) 另外還可使用由本發明人所提出的下述一般式（i) 所表示之新穎化合物’以作爲含烯丙基之二醯亞胺化合物C - (v) In addition, the novel compound represented by the following general formula (i) proposed by the present inventors can also be used as the allyl-containing bis-imine compound

[式（i)中’ R0表示- CH2-或·CH2O-R01-; R1意指甲基或氫：虛線表示可爲雙鍵的鍵結處；G表示下述一般式（ia )、（ib )或（i c )所表示之2價或3價基；m係對應於 G之價數之數字；R01表不碳數2〜10之分支或直鏈狀伸烷基。另外’在虛線鍵結處爲雙鍵的情況下，係以3處全爲雙鍵爲佳。 -11 - 201134840 lit 2][In the formula (i), R0 represents -CH2- or ·CH2O-R01-; R1 means methyl or hydrogen: the dotted line indicates a bond which may be a double bond; G represents the following general formula (ia), (ib Or a divalent or trivalent group represented by (ic); m is a number corresponding to the valence of G; R01 represents a branched or linear alkyl group having a carbon number of 2 to 10. Further, in the case where the dotted key is a double bond, it is preferable that all three are double bonds. -11 - 201134840 lit 2]

οο

(式（ia)中，R2〜R4各自獨立，表示氫原子或甲基）【化3】 R5 R6(In the formula (ia), R2 to R4 are each independently and represent a hydrogen atom or a methyl group.) [Chemical 3] R5 R6

(ic) (式（ic)中，p意指2〜5之整數）]。另外，在上述一般式（i〇〜（ic )中，與波浪線交叉的鍵結，表示（i )式中G與N原子間之鍵結。由式中明顯可知，一般式（i)的N原子在氧原子或羰基的鄰位、間位或對位任一者皆可，而宜爲對位。一般式（i )所表示之化合物，如下述實施例所詳細 ⑧ -12- 201134840 三胺衍生敘述般，可由一般式（vii)〜（viii)所表示之而得，【化5】(ic) (in the formula (ic), p means an integer of 2 to 5)]. Further, in the above general formula (i〇~(ic), the bond crossing the wavy line indicates the bond between G and N atoms in the formula (i). It is apparent from the formula that the general formula (i) The N atom may be in the ortho, meta or para position of the oxygen atom or the carbonyl group, and is preferably para. The compound represented by the general formula (i) is as detailed in the following examples. 8 -12- 201134840 The amine derivative can be represented by the general formula (vii) to (viii), which is represented by the general formula (vii) to (viii).

(vi)(vi)

(vii) 另外，一般式（vi )〜（viii )所表示之三述實施例所詳細敘述般’能夠以通常周知的化合始原料，經過周知的反應而合成出來。另外，若化合物（A )分子量的値低’則焊降低，因此以5 0 0以上爲佳。另外，化合物（A )的含量，係以相對於組而言的40〜95質量％爲佳，50〜85質量％更佳物（A )含量未達4〇質量％，則會有感光性降硬度降低的顧慮’若超過95質量％ ’則會有交、無法得到適當塗膜特性的顧慮。 -13- (viii) 胺，如下物作爲起接耐熱性成物全量 ° 若化合低、塗膜聯點降低 201134840 光聚合起始劑（B ) 就光聚合起始劑而言，適合使用藉由熱或活性能量射線照射而產生自由基的自由基聚合起始劑。就自由基聚合起始劑而言’可列舉例如安息香、安息香甲醚、安息香乙酸、安息香異丙醚等安息香與安息香烷醚類；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-—氣苯乙酮等苯乙酮類；2 -甲基- l- [4-(甲硫基）苯基]-2 -嗎啉基丙-1-酮、2 -苄基-2-二甲基胺基-1- (4 -嗎啉基苯基）丁 -1-酮、N，N-二甲基胺基苯乙酮等胺基苯乙酮類；2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、丨_氯蒽醌等蒽醌類；2,4-二甲基噻噸酮、2，4-二乙基噻噸酮、 2-氯噻噸酮、2,4-二異丙基噻噸酮等噻噸酮類；苯乙酮二甲基縮酮、苄基二甲基縮酮等縮酮類；二苯酮、4,4·-雙二乙基胺基二苯酮等二苯酮類或氧雜蔥酮類；2,4,6-三甲基苯甲醯基二苯膦氧化物，或2-三氯甲基-5-苯乙烯基-1，3,4-噁二唑、2-三氯甲基- 5-(對氰基苯乙烯基）-1，3,4_ 噁二唑等鹵甲基噁二唑系化合物；2,4-雙（三氯甲基）-6_ (對甲氧基-苯基乙烯基）-丨，3,5-三嗪、2,4-雙（三氯甲基 )-6-對甲氧基苯乙烯基-s-三嗪、2,4-雙（三氯甲基）_6_ (卜對二甲基胺基苯基-1，3-丁二烯基）-s-三嗪等鹵甲基-s-三嗪系化合物、2,4,6-三甲基苯甲醯基二苯膦氧化物、雙（2,4,6-三甲基苯甲醯基）-苯膦氧化物等苯甲醯基苯膦氧化物系化合物。另外’由於會有銅箔等金屬表面發生氧 •14- 201134840 化的顧慮，因此以不使用過氧化物爲佳。另外，在形成透明硬化膜的情況，爲了刃的硬化膜所特別適合使用光聚合起始劑，係酮系化合物，特別是下述一般式（I)所表示苯酮系光聚合起始劑。【化8】 Ο(vii) In addition, the three examples shown in the general formulas (vi) to (viii) can be synthesized by a well-known reaction using a generally known chemical starting material. Further, if the molecular weight of the compound (A) is low, the weld is lowered, so that it is preferably 500 or more. Further, the content of the compound (A) is preferably 40 to 95% by mass based on the group, and the content of the compound (A) of 50 to 85% by mass is less than 4% by mass, which may cause a decrease in photosensitivity. When the hardness is lowered, if it exceeds 95% by mass, there is a concern that the appropriate coating properties cannot be obtained. -13- (viii) Amine, the following is the total amount of the heat-resistant product. If the compound is low, the film joint point is lowered. 201134840 Photopolymerization initiator (B) For the photopolymerization initiator, it is suitable for use. A free radical polymerization initiator that generates heat by irradiation with heat or active energy rays. Examples of the radical polymerization initiator include benzoin and benzoin ethers such as benzoin, benzoin methyl ether, benzoin acetic acid, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-benzene Acetophenones such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-acetophenone, etc.; 2-methyl-l-[4-(methylsulfide) Phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, N,N -Amino acetophenones such as dimethylamino acetophenone; anthracene such as 2-methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl fluorene, and hydrazine chloropyrene; Thiophenones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; acetophenone II a ketal such as a methyl ketal or a benzyl dimethyl ketal; a benzophenone or an oxalyl ketone such as a benzophenone or a 4,4·-bisdiethylaminobenzophenone; 2,4 ,6-trimethylbenzimidyldiphenylphosphine oxide, or 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- Halomethyloxadiazoles such as p-cyanostyryl-1,3,4-oxadiazole Compound; 2,4-bis(trichloromethyl)-6-(p-methoxy-phenylvinyl)-indole, 3,5-triazine, 2,4-bis(trichloromethyl)-6- P-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl)_6_(b-p-dimethylaminophenyl-1,3-butadienyl)-s-triazine Isohalomethyl-s-triazine-based compound, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine A benzamidine phenylphosphine oxide compound such as an oxide. In addition, since there is a concern that oxygen is generated on a metal surface such as copper foil, it is preferable to use no peroxide. In the case of forming a transparent cured film, a photopolymerization initiator, a ketone compound, and a benzophenone photopolymerization initiator represented by the following general formula (I) are particularly preferably used. 【化8】 Ο

在式（Ο之中，R9係可經任意取代的· 式之芳香族基。就R9之具體例而言，可列_ 等。可作爲R9的取代基，可列舉氟、溴、描數1〜5之烷基、碳數1〜5之羥基烷氧基等。 R1C)及R11各自獨立，表示碳數1〜5之存倂表示碳數合計爲5〜1 0之環烷基。就此種α -羥基酮系光聚合起始劑的具體列舉2-羥基-2甲基-1-苯基丙-1-酮、2-羥基-基乙氧基）本基）-2 -甲基丙-1-嗣、1-經基環 2-羥基-1-{4-[4-(2-羥基-2-甲基丙醯基）-苄甲基丙-1-酮等。該等光聚合起始劑可單獨使用或混合兩種化合物（A )定爲1 〇〇質量份的情況，宜爲ϊ 、較佳爲2〜1 5質量份。若光聚合起始劑摻会量份，則會有感光性降低的顧慮，超過2 0 f 》成不會著色 α -羥烷基苯之α -羥院基環式或多環苯基及萘基等鹵素、碳 :基，或者合例而言，可 -(4- ( 2-羥己基苯酮、基]苯基}-2- :以上，在將〜2 0質量份量未達1質量份的情況 -15- 201134840 ，會引起塗膜特性降低，故不適合。反應性稀釋劑（C ) 就反應性稀釋劑（C )而言，只要是在分子中具有2 個以上不飽和基則並無特別限制，可使用通常周知者。較具體而言，可列舉1，3-丁二醇二（甲基）丙烯酸酯、1，5- 戊二醇二（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯、1，4-丁二醇二（甲基）丙烯酸酯、ΐ，6·己二醇二（甲基）丙烯酸酯、1,9-壬烯二醇二（甲基）丙烯酸酯、二乙二醇二（甲基）丙烯酸酯、三乙二醇二（甲基）丙烯酸酯、三羥甲基丙烷三（甲基）丙烯酸酯、三羥甲基丙烷三（甲基）丙烯酸酯、季戊四醇二（甲基）丙烯酸酯、季戊四醇三（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、二季戊四醇五（甲基）丙烯酸酯等一分子中具有兩個以上丙烯醯基及/或甲基丙烯醯基的化合物。另外，在本發明中，（甲基）丙烯酸酯意指丙烯酸酯及甲基丙烯酸酯之任一者或兩者皆可。另外，反應性稀釋劑（C)還可採用三環癸二醇二（甲基）丙烯酸酯，例如下述一般式（i i )所表示之化合物〇【化8】In the formula (R9), R9 is an aromatic group which may be optionally substituted. In the specific example of R9, _ may be listed. Examples of the substituent of R9 include fluorine, bromine, and trace number 1. An alkyl group of ～5, a hydroxyalkoxy group having a carbon number of 1 to 5, etc. R1C) and R11 each independently represent a carbon number of 1 to 5, and a cycloalkyl group having a carbon number of 5 to 10 in total. Specific examples of such an α-hydroxyketone photopolymerization initiator are 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-ethylethoxy)benzyl-2-methyl Prop-1-ylidene, 1-pyridyl 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropenyl)-benzylmethylpropan-1-one and the like. These photopolymerization initiators may be used singly or in combination of two compounds (A) in an amount of 1 part by mass, preferably ϊ, preferably 2 to 15 parts by mass. If the photopolymerization initiator is mixed in a part amount, there is a concern that the photosensitivity is lowered, and it is more than 20 f to form an α-hydroxyl-based or polycyclic phenyl group and naphthalene which does not color the α-hydroxyalkylbenzene. a halogen such as a group, a carbon group, or a combination, and -(4-(2-hydroxyhexyl benzophenone, yl)phenyl}-2-: or more, in an amount of not more than 1 part by mass of the 280 parts by mass In the case of -15-201134840, it is not suitable because the coating film properties are lowered. Reactive diluent (C) As far as the reactive diluent (C) is concerned, as long as it has two or more unsaturated groups in the molecule, In particular, a person who is generally known can be used. More specifically, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, neopentyl glycol can be cited. Di(meth)acrylate, 1,4-butanediol di(meth)acrylate, anthracene, 6·hexanediol di(meth)acrylate, 1,9-decenediol di(methyl) Acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylol Alkane tris(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol five ( a compound having two or more acryl fluorenyl groups and/or methacryl fluorenyl groups in one molecule such as methacrylate. Further, in the present invention, (meth) acrylate means acrylate and methacrylate. In addition, the reactive diluent (C) may also be a tricyclodecanol di(meth) acrylate such as the compound represented by the following general formula (ii). 】

⑤ 201134840 此處，式中，R7及R8各自獨立，意指甲基或璧及m各自獨立，意指0〜5(宜爲0〜3)之整數》該等反應性稀釋劑可單獨使用或混合兩種以上，化合物（A)爲100質量份的情況，其合計量宜爲5〜質量份，較佳爲1 〇〜1 50質量份。若反應性稀釋劑（摻合量未達5質量份，則會有感光性變低的顧慮，在 2 00質量份的情況，會同時有發生耐熱性降低的顧慮不適合。另外，噴墨法所使用的阻焊劑油墨在採用硬化性物的情況，爲了防止滲透發生，並確保足夠的精密度必須將黏度定在200mPa· s以下（宜爲1〇〜150mPa. ，因此必須藉由反應性稀釋劑（C )適當地調整黏度情況下，亦可倂用在分子中具有1個不飽和基的單官體，此種物質較具體而言，可列舉（甲基）丙烯酸乙酯、東亞合成股份有限公司製的酚EO變性丙烯酸商品名M-102) 、N -丙嫌醯氧基乙基六氫酞醯亞胺（名M-140)、馬來醯亞胺丙烯酸酯（商品名M-145) 乙基己基EO變性丙烯酸酯（商品名M-120) 、2 -羥3 苯氧基丙基丙烯酸酯（商品名M-5700)、噁唑烷酮酸酯（商品名MT-1 000 )等。該等單官能單體適當的相對於化合物（A ) 1 0 0質量份而言，合計爲4 0〜1 5 量份，更適合爲40〜120質量份。化合物（D ) 在以 ^ 200 C) 超過，故組成，而 s ) 。此能單 2·羥酯（商品、2-i -3-丙烯含量 0質 -17- 201134840 就一而言，只例如三嗪 )所表不分子中具有至少1個以上胺基或亞胺基的化合物要是以往所周知者，則任一者皆可使用，可列舉系化合物。就三嗪系化合物而言，可列舉式（ix 之化合物。【化9】5 201134840 Here, in the formula, R7 and R8 are each independently, meaning that methyl or hydrazine and m are each independently, meaning 0 to 5 (preferably 0 to 3) integers. These reactive diluents may be used alone or When two or more compounds are mixed, and the compound (A) is 100 parts by mass, the total amount thereof is preferably 5 parts by mass, preferably 1 〇 to 150 parts by mass. When the amount of the reactive diluent is less than 5 parts by mass, the photosensitivity may be lowered, and in the case of 200 parts by mass, the heat resistance may be lowered at the same time. In the case of using a hardener, in order to prevent penetration, and to ensure sufficient precision, the viscosity must be set to 200 mPa·s or less (preferably 1 to 150 mPa.), so it is necessary to use reactive diluent. (C) In the case of appropriately adjusting the viscosity, a monolithic body having one unsaturated group in the molecule may be used, and more specifically, such a substance may be exemplified by ethyl (meth) acrylate and the East Asian synthetic stock. Company-made phenol EO denaturing acrylic trade name M-102), N-propyl decyloxyethyl hexahydroimide (name M-140), maleic imide acrylate (trade name M-145) Ethylhexyl EO denatured acrylate (trade name: M-120), 2-hydroxy 3 phenoxypropyl acrylate (trade name: M-5700), oxazolidinone ester (trade name: MT-1 000), and the like. The monofunctional monomers are appropriately combined with respect to 100 parts by mass of the compound (A). Calculated as 4 0 to 1 5 parts by weight, more suitably 40 to 120 parts by mass. Compound (D) is more than ^ 200 C), so composition, and s). This can be a monohydroxyl ester (commercially, 2-i-3-propene content 0 -9-201134840, for example, only triazine, for example) has at least one or more amine or imine groups in the molecule. Any compound can be used as long as it is known in the art, and examples thereof include a compound. Examples of the triazine-based compound include a compound of the formula (ix).

此處 (宜爲1 R15 、 R16 三丁基、該等例如R12 別互相獨市售的三限公司製 390」、 750LM」」等。另外 Ν'-第三丁，可歹IJ ί ，式中，R12意指- SR17 (但是R17意指碳數1〜5 〜3)之烷基）或-NRI8R19。另外’ R13、R14、、R18、R19分別互相獨立，表示氫、環丙基、第羥甲基或甲氧基甲基。之中，可適合使用三聚氰胺、三聚氰胺衍生物（爲-NR18R19; R13、R14、R15、R16、R18、R19 分立，爲氫、羥甲基或甲氧基甲基的化合物）。在聚瓿胺衍生物之中，可列舉例如三和化學股份有之「NIKALAC MW-30HM」、「NIKALAC MW-「NIKALAC MW-100LM」、「NIKALAC MX-、「NIKALAC MX-7 5 0」、「NIKALAC MX-002 ，就R 12爲-S R 17的化合物具體例而言，可使用基-1^-環丙基-6-(甲硫基）-1，3,5-三嗪-2,4-二胺 ^市售的 Chiba Japan股份有限公司製「 -18- ⑧ 201134840 IRGAGU ARD D 1 07 1」、「I R G A R O L 1 〇 5 1」等。從確保硬化速度的觀點看來，在一分子中具有至少1 個以上胺基或亞胺基的化合物摻合量的下限値，係以相對於化合物（A) 100質量份而言的0.2質量份爲佳，從提高耐變色性的觀點看來，係以1 ·〇質量份爲佳，從進一步提高焊接耐熱性的觀點看來，係以1 .5質量份爲特佳。另外，從硬化塗膜之耐水性的觀點看來，摻合量之上限値爲 1〇質量份，從提高保存安定性的觀點看來，係以3質量份爲特佳。其他成分本發明之組成物，進一步以提升密著性、硬度等特性爲目的，可因應必要使用硫酸鋇、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、雲母粉等通常周知的無機充塡劑。其使用量係以本發明之組成物中之0〜6 0重量爲佳，特佳爲5〜40重量％。進一步還可因應必要使用通常周知的添加劑類，如酞花青藍、酞花青綠、碘綠、雙偶氮黃、結晶紫、氧化鈦、碳黑、萘黑等通常周知的著色劑、氫醌、氫醌單甲醚、第二丁基兒茶酣、五倍子酌、吩噻嗪等周知慣用的聚合禁止劑·’石棉、Orben (商品名）、Bentοne (商品名）、蒙脫石等通常周知的增黏劑、聚矽氧系、氟系、高分子系等消泡劑及/或均勻劑；咪唑系、噻唑系、***系、矽烷偶合 -19 - 201134840 劑等密著性賦予劑。 [硬化物] 如上述方式所得到的本發明之硬化性組成物，例如在蝕刻貼銅層合板的銅箔所形成具有電路圖案的印刷電路板塗佈所希望的厚度，例如5〜1 00 v m的厚度。就噴墨式以外的塗佈手段而言，現在一般大多採用絲網印刷法進行全面印刷，而只要是可均勻地塗佈的塗佈手段，則任何手段皆能夠採用而不受限制。例如噴霧塗佈機、熱熔塗佈機、棒式塗佈機、塗佈器、刮刀塗佈機、刀式塗佈機、氣刀式塗佈機、淋幕式塗佈機、輥塗機、凹版塗佈機、平板印刷、浸塗機、刷毛塗佈法，其他通常的方法全部皆可使用〇塗佈後，使用LDI ( Laser Direct imaging )進行雷射直寫，或藉由活性能量射線進行光硬化步驟。在印刷電路板製造過程中，大多使用紫外線作爲活性能量射線。紫外線照射量大槪在10〜1 000mJ/cm2。接下來進行熱硬化步驟，例如以130〜170°C的熱風爐或遠紅外線爐等乾燥機等加熱例如20〜80分鐘，藉此可形成阻焊被膜。 [印刷電路板] 本發明所關連之印刷電路板，其特徵爲使用上述硬化物。此處，就印刷電路板而言，不含積體電路、電阻器、 -20- ⑧ 201134840 電容器等電子零件而只有基板的物品，以及實裝電子零件狀態下的物品皆包括在內。本發明之印刷電路板，可使用作爲家電製品、事務機器、汽車、電腦、工業用機器等各種電氣製品的零件。 [反射片] 在上述本發明實施形態例所關連之硬化性組成物中，進一步摻合既定量的金紅石型氧化鈦等氧化鈦，而製成白色組成物，將此白色硬化性組成物塗佈於片狀基材薄膜上 ’可得到反射片。例如將上述反射片配置於太陽能電池模組背側（亦即與受日光照射的表面相反的一側）的表面上，如此一來，太陽能電池模組的發電元件並未受到光照，穿透過太陽能電池模組的太陽光會因爲上述反射片而反射 ’由太陽能電池模組的背側再度回到太陽能電池模組內部 ’因此可提升太陽能電池模組的發電效率。另外，將反射片設置於太陽能電池模組背面的方法，可列舉例如使用黏著劑或黏接用膠帶直接貼合於太陽能電池模組背面的方法。另外’就氧化鈦的摻合量而言，係以相對於化合物（A )100質量份而言的30〜250質量份、或5〇〜1〇〇質量份 ’甚至以60〜80質量份的範圍爲佳。塗佈白色硬化性組成物的基材薄膜之材料，係並未特別受到限定，而可列舉例如聚醯亞胺、聚對苯二甲酸乙二酯（PET)、聚氟乙烯（PVF)、氟乙烯-丙烯共聚物（ FEP)、聚四氟乙烯（PTFE)、芳綸、聚醯胺-醯亞胺、 -21 - 201134840 環氧樹脂、聚醚醯亞胺、聚颯、聚萘二甲酸乙二酯（PEN )、液晶聚合物（LCP)等。將白色硬化性組成物塗佈於片狀基材薄膜上的方法並未特別受到限定，而可採用在[硬化物]一欄所說明的方法，或者例如以3%硫酸對於厚度40//m的聚對苯二甲酸乙二酯薄膜表面進行處理，將表面洗淨後，藉由絲網印刷等周知的印刷方法在洗淨後的表面塗佈既定厚度（例如硬化後膜厚成爲20〜23ym)的白色硬化性組成物的方法。白色硬化性組成物進行塗佈的部位，係在對向於太陽能電池模組背面的基材薄膜全部表面或大致全部的表面。接下來，藉由在130〜170 °C左右的溫度進行後硬化20〜80分鐘，可在片狀基材薄膜上形成目標的白色膜。 [實施例] 以下’藉由實施例對本發明作詳細說明，而本發明並不受該等實施例限制。另外在以下實驗中，重量平均分子量係以THF作爲移動相，並以聚苯乙烯作換算，而藉由 GPC進行測定（裝置名稱：HlC-9120 (東曹股份有限公司製）、管柱：TSK gel Super HZ2500、流速：〇.3mL/分鐘 '溶質濃度：10g/L、溫度：40°C、偵測器：RI)。 (1 )原料的準備方法 (1-1)化合物（A-1)之合成使作爲環氧樹脂的雙酣A型環氧樹脂（Japan Epoxy -22- ⑧ 201134840Here (preferably 1 R15, R16 tributyl, such as 390", 750LM", such as R12, which is sold separately from each other. In addition, Ν'-third, 歹IJ ί, R12 means -SR17 (but R17 means an alkyl group having 1 to 5 to 3 carbon atoms) or -NRI8R19. Further, 'R13, R14, R18 and R19 are each independently represent hydrogen, cyclopropyl, hydroxymethyl or methoxymethyl. Among them, a melamine or a melamine derivative (a compound in which -NR18R19; R13, R14, R15, R16, R18, and R19 is a hydrogen, a methylol group or a methoxymethyl group) can be suitably used. Among the polyamine derivatives, for example, "NIKALAC MW-30HM", "NIKALAC MW-"NIKALAC MW-100LM", "NIKALAC MX-, "NIKALAC MX-7 50", "NIKALAC MX-002, in the case of a compound in which R 12 is -SR 17, a group -1^-cyclopropyl-6-(methylthio)-1,3,5-triazine-2 can be used. 4--18-II 201134840 IRGAGU ARD D 1 07 1 and "IRGAROL 1 〇5 1" manufactured by Chiba Japan Co., Ltd., which is commercially available. The lower limit 掺 of the compounding amount of the compound having at least one amino group or imine group in one molecule is 0.2 parts by mass relative to 100 parts by mass of the compound (A) from the viewpoint of ensuring the curing rate. In the viewpoint of improving the discoloration resistance, it is preferably 1 part by mass, and more preferably 1.5 parts by mass from the viewpoint of further improving solder heat resistance. Further, from the viewpoint of water resistance of the cured coating film, the upper limit 値 of the blending amount is 1 〇 by mass, and it is particularly preferable to use 3 parts by mass from the viewpoint of improving storage stability. Other components The composition of the present invention is further used for the purpose of improving the properties such as adhesion and hardness, and it is necessary to use barium sulfate, barium titanate, cerium oxide powder, fine powdered cerium oxide, amorphous cerium oxide, talc, Commonly known inorganic fillers such as clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder. The amount thereof is preferably from 0 to 60% by weight, particularly preferably from 5 to 40% by weight, based on the composition of the present invention. Further, generally known additives such as phthalocyanine blue, phthalocyanine, iodine green, bisazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc., and hydroquinone, may also be used as necessary. , commonly known polymerization inhibitors such as hydroquinone monomethyl ether, second butyl catechin, gallnut, phenothiazine, etc., 'asbestos, Orben (trade name), Bentοne (trade name), montmorillonite, etc. are generally known. An antifoaming agent and/or a homogenizing agent such as a tackifier, a polyoxymethylene, a fluorine or a polymer; and an adhesion imparting agent such as an imidazole, a thiazole, a triazole or a decane coupling -19 - 201134840. [Cured product] The curable composition of the present invention obtained as described above is applied to a printed circuit board having a circuit pattern formed by etching a copper foil of a copper clad laminate, for example, to have a desired thickness, for example, 5 to 100 m thickness of. In the case of coating means other than the ink jet type, it is generally used for screen printing in general, and any means can be used without limitation as long as it is a coating means which can be uniformly applied. For example, spray coater, hot melt coater, bar coater, applicator, knife coater, knife coater, air knife coater, curtain coater, roll coater , gravure coater, lithography, dip coater, brush coating method, all other common methods can be used after laser coating, laser direct imaging using LDI (laser direct imaging), or by active energy ray A photohardening step is performed. In the manufacturing process of printed circuit boards, ultraviolet rays are mostly used as active energy rays. The ultraviolet radiation is large at 10 to 1 000 mJ/cm 2 . Next, a heat hardening step is carried out, for example, by heating in a dryer such as a hot air furnace or a far infrared ray furnace at 130 to 170 ° C for 20 to 80 minutes, whereby a solder resist film can be formed. [Printed Circuit Board] A printed circuit board to which the present invention relates is characterized in that the above-mentioned hardener is used. Here, in the case of a printed circuit board, an electronic component such as an integrated circuit, a resistor, a -20-8 201134840 capacitor, and the like, and only articles of the substrate, and articles in the state of the mounted electronic component are included. The printed circuit board of the present invention can be used as a component of various electrical products such as home electric appliances, business machines, automobiles, computers, and industrial equipment. [Reflecting sheet] In the curable composition according to the embodiment of the present invention, titanium oxide such as rutile-type titanium oxide is further blended to form a white composition, and the white curable composition is coated. A reflective sheet can be obtained by coating on a sheet-like substrate film. For example, the reflective sheet is disposed on the surface of the back side of the solar cell module (ie, the side opposite to the surface illuminated by the sunlight), so that the power generating element of the solar cell module is not exposed to light and penetrates the solar energy. The sunlight of the battery module will be reflected by the reflection sheet 'returning from the back side of the solar cell module to the inside of the solar cell module', thereby improving the power generation efficiency of the solar cell module. Further, a method of providing the reflecting sheet on the back surface of the solar cell module may be, for example, a method of directly bonding the back surface of the solar cell module using an adhesive or a bonding tape. In addition, the amount of the titanium oxide to be added is 30 to 250 parts by mass, or 5 to 1 part by mass, or even 60 to 80 parts by mass, per 100 parts by mass of the compound (A). The range is good. The material of the base film to which the white curable composition is applied is not particularly limited, and examples thereof include polyimine, polyethylene terephthalate (PET), polyvinyl fluoride (PVF), and fluorine. Ethylene-propylene copolymer (FEP), polytetrafluoroethylene (PTFE), aramid, polyamido-imide, -21 - 201134840 epoxy resin, polyether phthalimide, polyfluorene, polyethylene naphthalate Diester (PEN), liquid crystal polymer (LCP), and the like. The method of applying the white curable composition to the sheet-like base film is not particularly limited, and the method described in the column of [hardened material] may be employed, or for example, 3% sulfuric acid for thickness 40/m The surface of the polyethylene terephthalate film is treated, and after the surface is washed, a predetermined thickness is applied to the surface after washing by a known printing method such as screen printing (for example, the film thickness after hardening becomes 20 to 23 μm). A method of white curable composition. The portion to be coated with the white curable composition is on the entire surface or substantially the entire surface of the substrate film facing the back surface of the solar cell module. Next, by performing post-hardening at a temperature of about 130 to 170 ° C for 20 to 80 minutes, a target white film can be formed on the sheet-like base film. [Examples] The present invention is described in detail by the following examples, but the invention is not limited by the examples. In addition, in the following experiment, the weight average molecular weight was measured by GPC using THF as a mobile phase and converted to polystyrene (device name: HlC-9120 (manufactured by Tosoh Corporation), column: TSK Gel Super HZ2500, flow rate: 〇.3mL / min 'solute concentration: 10g / L, temperature: 40 ° C, detector: RI). (1) Preparation method of raw materials (1-1) Synthesis of compound (A-1) A bismuth A type epoxy resin as an epoxy resin (Japan Epoxy -22- 8 201134840

Resins股份有限公司 JER834) 24〇質量份溶於二乙二醇單***醋酸酯1 20質量份，於其中加入丙烯酸72質量份，在加熱回流條件下，藉由既定方法使其進行反應，得到相當於化合物（A )的合成樹脂1 (重量平均分子量500 (1-2)化合物（A-2)之合成 (1-2-1 )三胺化合物之合成加入1-[4-[1- ( 4-羥苯基）-1-甲基乙基]苯基]-1,1-雙 [4-羥苯基]乙烷（本州化學工業公司製trisP-PA) 42.5g( O.lmol )、對氯硝基苯50.4g(0.32mol)與碳酸鉀55.3g (〇.4mol )，在N-甲基吡咯烷酮150g溶劑中，在氮氣流下回流攪拌5小時，並使其進行反應。冷卻至室溫之後，藉由減壓過濾去除副產物無機鹽及殘留的碳酸鉀，得到三硝基體的N-甲基吡咯烷酮溶液。接下來，在具備攪拌機、溫度計、回流管與氮導入管的1 L四口燒瓶加入所得到三硝基體的N-甲基吡咯烷酮溶液與丙二醇單甲醚150g及5%鈀碳l.Og，將燒瓶內以氮氣置換之後，攪拌，同時昇溫至80〜85°C之後，緩慢滴入6 0 %聯胺水溶液5 0ml，將反應溫度調整成8 0〜9 5 °C，同時加熱攪拌5小時。其後以HP LC分析反應液，同時在確認了三硝基體的還原中間體的峰消失之後，使其停止反應。冷卻後，藉由減壓過濾去除反應液中的鈀碳，攪拌同時緩慢加入甲醇3 0 0 g及水6 0 0 g ’以減壓過瀘回收析出物 -23- 201134840 水洗之後真空乾燥’得到下述式（x)所表示之三胺化 62-5g (產率 92% ) 合物褐白色結晶。產量爲 [化1 0】Resins Co., Ltd. JER834) 24 parts by mass dissolved in diethylene glycol monoethyl ether acetate 20 parts by mass, 72 parts by mass of acrylic acid was added thereto, and the reaction was carried out by a predetermined method under heating under reflux to obtain a equivalent Synthesis of Compound (A) Synthetic Resin 1 (weight average molecular weight 500 (1-2) Compound (A-2) Synthesis (1-2-1) Triamine Compound Synthesis 1-[4-[1- ( 4 -Hydroxyphenyl)-1-methylethyl]phenyl]-1,1-bis[4-hydroxyphenyl]ethane (trisP-PA, manufactured by Honshu Chemical Industry Co., Ltd.) 42.5g (O.lmol), pair 50.4 g (0.32 mol) of chloronitrobenzene and 55.3 g (〇. 4 mol) of potassium carbonate were stirred under a nitrogen stream in a solvent of 150 g of N-methylpyrrolidone for 5 hours, and allowed to react. After cooling to room temperature The by-product inorganic salt and residual potassium carbonate were removed by filtration under reduced pressure to obtain a trinitro-form N-methylpyrrolidone solution. Next, a 1 L four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube was used. Adding the obtained N-nitropyridyl N-methylpyrrolidone solution to 150 g of propylene glycol monomethyl ether and 5% palladium carbon, 1.0 g of nitrogen in the flask After the exchange, the mixture was stirred and heated to 80 to 85 ° C, and then slowly dropped into 50 ml of a 60% aqueous hydrazine solution, and the reaction temperature was adjusted to 80 to 95 ° C while heating and stirring for 5 hours. Thereafter, HP was used. The reaction liquid was analyzed by LC, and after confirming that the peak of the reducing intermediate of the trinitro group disappeared, the reaction was stopped. After cooling, the palladium carbon in the reaction liquid was removed by filtration under reduced pressure, and methanol was slowly added while stirring. g and water 600 g "recovering precipitates under reduced pressure -23-201134840 After washing with water and vacuum drying", a triamid 62-5 g (yield 92%) represented by the following formula (x) was obtained. White crystal. The yield is [Chemical 1 0]

Η P L C 面積（％ ) 9 9 · 3 %、I η - N M R ( D M S 0 d - 6 ' T M S )<5 7.14~7.10(m、4H) 、6.94〜6.91(m、6H) ' 6.77 〜6.73 (m、12H) 、6.59 〜6,55 (m、6H) 、4.96( s、6H )、2.01 ( s、3H ) ' 1 .58 ( s ' 6H ) (1-2-2 )化合物（A2 )之合成在具備搅拌機、氮導入管、溫度計、回流管及Dean-Stark 分離器的 300ml 四口燒瓶加入氫化偏苯三甲酸酐（ H-TMAn-s、三菱 GAS 化學製）39.63g(0.2mol)，以及作爲溶劑的r-丁內酯30g’在10〜15°c的冷卻環境下攪拌，同時花费30分鐘滴入使（1-2-1 )所合成的三胺化合物46.5g(〇.〇67mol)溶於r-丁內酯7〇g的溶液’然後在室溫攪拌1小時’得到醯亞胺前驅物樹脂溶液。在所得到的醯亞胺前驅物樹脂溶液加入環戊基甲醚30g’並使氮氣 -24- ⑧ 201134840 流通，藉由共沸脫水除去所產生的水，同時在1 3 0 °c加熱攪拌2小時，進一步在1 5 (TC加熱攪拌2小時，末得到端具有羧基的醯亞胺化合物之r - 丁內酯溶液。接下來，加入甲基丙烯酸縮水甘油酯（BLEMMER GH，曰油製） 42.7g ( 0.3mol )，及甲氧基氫醌0 · 2 g作爲聚合禁止劑，三苯膦0.2g作爲反應觸媒，在燒瓶內使乾燥空氣流通，同時在9 0 °C加熱攪拌5小時後，進一步在1 〇〇 °C加熱攪拌 10小時，進行反應至固體成分酸價成爲2mgKOH/g以下，得到相當於化合物（A )而且構造如下述式（xi )之化合物之7-丁內酯溶液（分子量1665)。固體成分爲57% ，以GPC測得的重量平均分子量約2800。【化11】Η PLC area (%) 9 9 · 3 %, I η - NMR ( DMS 0 d - 6 ' TMS ) < 5 7.14~7.10 (m, 4H), 6.94~6.91 (m, 6H) ' 6.77 ~ 6.73 ( m, 12H), 6.59 to 6, 55 (m, 6H), 4.96 (s, 6H), 2.01 (s, 3H) '1 .58 (s '6H) (1-2-2) compound (A2) In a 300 ml four-necked flask equipped with a stirrer, a nitrogen introduction tube, a thermometer, a reflux tube, and a Dean-Stark separator, 39.63 g (0.2 mol) of hydrogenated trimellitic anhydride (H-TMAn-s, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added, and The r-butyrolactone 30 g' as a solvent was stirred in a cooling environment of 10 to 15 ° C, and it took 30 minutes to drip in 46.5 g of a triamine compound synthesized by (1-2-1) (〇.〇67 mol). A solution of 7 〇g of r-butyrolactone was then stirred at room temperature for 1 hour to obtain a quinone imine precursor resin solution. Adding 30 g of cyclopentyl methyl ether to the obtained yttrium imide precursor resin solution and allowing nitrogen gas to flow through -24 - 201134840, and removing the produced water by azeotropic dehydration while heating and stirring at 130 ° C 2 In an hour, further, the mixture was heated at 15 °C for 2 hours to obtain a r-butyrolactone solution of a quinone imine compound having a carboxyl group at the end. Next, glycidyl methacrylate (BLEMMER GH, manufactured by Oyster Sauce) was added. g (0.3mol), and methoxyhydroquinone 0 · 2 g as a polymerization inhibitor, 0.2 g of triphenylphosphine as a reaction catalyst, and the dry air was circulated in the flask while heating and stirring at 90 ° C for 5 hours. Further, the mixture was heated and stirred at 1 ° C for 10 hours, and the reaction was carried out until the acid value of the solid component became 2 mgKOH/g or less to obtain a 7-butyrolactone solution corresponding to the compound (A) and having a compound of the following formula (xi). (Molecular weight 1665). The solid content was 57%, and the weight average molecular weight measured by GPC was about 2800.

(1-3)化合物A3之合成 -25- 201134840 在具備攪拌機、氮導入管、溫度計、回流管及Dean-Stark 分離器的 500ml 四口燒瓶加入氫化偏苯三甲酸酐（ H-TMAn-s，三菱 GAS 化學製）2 3 7.8 g ( 1 _2mol )，及作爲溶劑的r-丁內酯540g，在10〜15 °C的冷卻環境下攪拌，同時花費30分鐘滴入使上述三胺化合物2 79.1 4g ( 0.4mol )溶於r -丁內酯60g的溶液，然後在室溫攪拌1 小時，得到醯亞胺前驅物樹脂溶液。在所得到的醯亞胺前驅物樹脂溶液加入環戊基甲醚l〇〇g，並使氮氣流通，藉由共沸脫水去除所產生的水，同時在1 3 0°c加熱攪拌2小時，進一步在1 50°C加熱攪拌2小時，得到末端具有羧基的醯亞胺化合物之r -丁內酯溶液。接下來，加入4-羥了基丙烯酸酯縮水甘油醚（4HBAGE，日本化成製）3 60.l8g (1.8 mol)，以及作爲聚合禁止劑的甲氧基氫醌3.0g、作爲反應觸媒的三苯膦1.5g，在燒瓶內使乾燥空氣流通，同時在90°C加熱攪拌5小時後，進一步在100°C加熱攪枠 10小時，進行反應至固體成分酸價成爲2mgKOH/g以丨，得到化合物A3的7 -丁內酯溶液（分子量1 83 8 )。自體成分爲53.5%，以GPC測得的重量平均分子量約24〇Q 。將合成反應流程圖揭示如下。 -26- ⑧ 201134840 【化1 2】 H2Ntx(1-3) Synthesis of Compound A3 - 201134840 Hydrogenated trimellitic anhydride (H-TMAn-s, Mitsubishi) was added to a 500 ml four-necked flask equipped with a stirrer, a nitrogen introduction tube, a thermometer, a reflux tube, and a Dean-Stark separator. GAS Chemical) 2 3 7.8 g (1 _2 mol), and 540 g of r-butyrolactone as a solvent, stirred under a cooling environment of 10 to 15 ° C, and dropped into the above-mentioned triamine compound 2 79.1 4 g in 30 minutes. (0.4 mol) was dissolved in a solution of 60 g of r-butyrolactone, followed by stirring at room temperature for 1 hour to obtain a quinone imine precursor resin solution. To the obtained quinone imine precursor resin solution, cyclopentyl methyl ether l〇〇g was added, and nitrogen gas was passed through, and the produced water was removed by azeotropic dehydration while heating and stirring at 130 ° C for 2 hours. Further, the mixture was heated and stirred at 150 ° C for 2 hours to obtain a r -butyrolactone solution of a quinone imine compound having a carboxyl group at the end. Next, 4-hydroxy acrylate glycidyl ether (4HBAGE, manufactured by Nippon Chemical Co., Ltd.) 3 60.18 g (1.8 mol), and 3.0 g of methoxyhydroquinone as a polymerization inhibitor, three as a reaction catalyst were added. 1.5 g of phenylphosphine was allowed to flow through a dry air in a flask, and the mixture was heated and stirred at 90 ° C for 5 hours, and further heated and stirred at 100 ° C for 10 hours to carry out a reaction until the acid value of the solid component became 2 mgKOH/g. 7-butyrolactone solution of compound A3 (molecular weight 1 83 8 ). The autogenous component was 53.5%, and the weight average molecular weight measured by GPC was about 24 〇Q. The synthetic reaction scheme is disclosed below. -26- 8 201134840 【化1 2】H2Ntx

XX ,ja ΤΑΡΡΑ C47H43N3O3 Exact Mass: 697.33 Mol,Wt.: 697.86 C, 80.89： H. 6.21； N. 6.0¾ O. 6.88XX ,ja ΤΑΡΡΑ C47H43N3O3 Exact Mass: 697.33 Mol,Wt.: 697.86 C, 80.89: H. 6.21; N. 6.03⁄4 O. 6.88

-〇K 〇-〇K 〇

CioHt g〇4 Exact Mass: 200.10 Md.Wt.: 200.23 C. 59.96: H. 8.05: 0,31.96CioHt g〇4 Exact Mass: 200.10 Md.Wt.: 200.23 C. 59.96: H. 8.05: 0,31.96

4HBAGE4HBAGE

(I-4)化合物A4之合成在具備攪拌機、氮導入管、溫度計、回流管及Dean-Stark 分離器的 500ml 四口燒瓶，加入氫化偏苯三甲酸酐 -27- 201134840 (H-TMAn-s、三菱 GAS 化學製）99.09g(0.5mol)，以及作爲溶劑的r-丁內酯18〇g，在10〜15 °C的冷卻環境下搅拌，同時花費30分鐘滴入使（2,2·雙[4- (4-胺基苯氧基）苯基]丙烷102.55g(0.25mol)溶於丁內酯30g的溶液，然後在室溫搅拌1小時，得到醯亞胺前驅物樹脂溶液。在所得到的醯亞胺前驅物樹脂溶液加入環戊基甲醚 5 〇 g ’並使氮氣流通，藉由共沸脫水去除所產生的水，同時在130°C加熱攪拌2小時，進一步在150°C加熱攪拌2 小時’得到末端具有羧基的醯亞胺化合物之7 -丁內酯溶液。接下來，加入甲基丙烯酸縮水甘油酯（BLEMMER GH ’日油製）106.888(〇.75111〇1)，以及作爲聚合禁止劑的甲氧基氫醌〇.5g、作爲反應觸媒的三苯膦〇.5g，使乾燥空氣流通於燒瓶內，同時在9 (TC加熱攪拌5小時後，進一步在100°C加熱攪拌1〇小時，進行反應至固體成分酸價成爲2mgKOH/g以下，得到化合物A4的7 -丁內酯溶液 (分子童1 05 5 )。固體成分爲6 2.5%，以GPC測得的重量平均分子約1 1 90。將合成反應流程圖揭示如下。 ⑧ 201134840 【化1 3】(I-4) Synthesis of Compound A4 In a 500 ml four-necked flask equipped with a stirrer, a nitrogen introduction tube, a thermometer, a reflux tube, and a Dean-Stark separator, hydrogenated trimellitic anhydride -27-201134840 (H-TMAn-s, Mitsubishi GAS Chemical Co., Ltd.) 99.09g (0.5mol), and as a solvent, r-butyrolactone 18〇g, stirred in a cooling environment of 10~15 °C, while taking 30 minutes to drip into (2,2·double [4-(4-Aminophenoxy)phenyl]propane 102.55 g (0.25 mol) of a solution of 30 g of butyrolactone, and then stirred at room temperature for 1 hour to obtain a quinone imine precursor resin solution. The obtained quinone imine precursor resin solution was added to cyclopentyl methyl ether 5 〇g ' and the nitrogen gas was passed, and the generated water was removed by azeotropic dehydration while heating and stirring at 130 ° C for 2 hours, further at 150 ° C. Heating and stirring for 2 hours to obtain a 7-butyrolactone solution of a quinone imine compound having a carboxyl group at the end. Next, glycidyl methacrylate (BLEMMER GH 'Nippon Oil Co., Ltd.) 106.888 (〇.75111〇1) was added, and Methoxyhydroquinone as a polymerization inhibiting agent. 5 g, triphenylphosphine ruthenium as a reaction catalyst. 5 g The dry air was circulated in the flask, and after stirring at 5 (TC for 5 hours, the mixture was further heated and stirred at 100 ° C for 1 hour, and the reaction was carried out until the acid value of the solid component became 2 mgKOH/g or less to obtain 7-butyl of the compound A4. A lactone solution (Molecular Child 1 05 5 ). The solid content is 6 2.5%, and the weight average molecular weight measured by GPC is about 1 1 90. The synthesis reaction scheme is disclosed as follows. 8 201134840 [Chem. 1 3]

26^2^226^2^2

BAPPBAPP

Exact Mass: 410.20 Md. Wt.: 410.51 C( 79.00; H, 6.38; N, 6.82： O, 7.79Exact Mass: 410.20 Md. Wt.: 410.51 C (79.00; H, 6.38; N, 6.82: O, 7.79

HOHO

CgH10O5CgH10O5

Exact Mass: 193.05 Mol. Wt: 198.17 Ct 54.55； H, 5.09； O, 40.37 H-TMAnExact Mass: 193.05 Mol. Wt: 198.17 Ct 54.55; H, 5.09; O, 40.37 H-TMAn

Mol. Wt.: 770.82 Ct 70.12； H, 5.49； H, 3.63； O, 20.76Mol. Wt.: 770.82 Ct 70.12; H, 5.49; H, 3.63; O, 20.76

GMA(GH) C7H10O3 Exact Mass: 142.06 Mol. Wt.： 142.15 C, 59.14; H, 7.09; O, 33.77GMA(GH) C7H10O3 Exact Mass: 142.06 Mol. Wt.: 142.15 C, 59.14; H, 7.09; O, 33.77

(1 -5 )化合物A 5之合成在具備攪拌機、氮導入管、溫度計、回流管及D e a n -Stark分離器的5 00ml四口燒瓶加入氫化偏苯三甲酸酐（ -29- 201134840 H-TMAn-s、三菱 GAS 化學製）99.09g(0.5mol)，以及作爲溶劑的r -丁內酯180g ’在10〜15°c冷卻環境下攪拌，同時，花費30分鐘滴入使三亞甲基雙（4-胺基苯甲酸酯）（CUA-4，IHARA 化學工業製）7 8.5 3 g ( 0 · 2 5 m ο 1 ) 溶於r -丁內酯2〇g的溶液’然後在室溫攪拌1小時，得到醯亞胺前驅物樹脂溶液。在所得到的醯亞胺前驅物樹脂溶液加入環戊基甲醚50g，使氮氣流通，藉由共沸脫水去除所產生的水，同時在1 3 0°C加熱攪拌2小時，進一步在 1 5 0°C加熱攪拌2小時，得到末端具有羧基的醯亞胺化合物之r-丁內酯溶液。接下來，甲基丙烯酸縮水甘油酯（ BLEMMER GH，日油製）106_88g(0.75mol)，以及加入作爲聚合禁止劑的甲氧基氫醌0.5g、作爲反應觸媒的三苯膦〇.5g，並使燒瓶內流通乾燥空氣，同時在90°C加熱攪拌5小時後，進一步在1 〇〇°C加熱搅拌1 〇小時’進行反應至固體成分酸價成爲2mgKOH/g以下，得到化合物A5 之r-丁內酯溶液（分子量95 8 )。固體成分爲57%，以 GPC測得的重量平均分子g約1 08 0。將合成反應流程圖揭示如下。 -30- ⑧ 201134840 h2n(1 -5) Synthesis of Compound A 5 Hydrogenated trimellitic anhydride was added to a 500 ml four-necked flask equipped with a stirrer, a nitrogen introduction tube, a thermometer, a reflux tube, and a Dean-Stark separator (-29-201134840 H-TMAn- s, Mitsubishi GAS Chemical Co., Ltd.) 99.09g (0.5mol), and r-butyrolactone as a solvent 180g 'stirred in a cooling environment of 10 to 15 ° C, while taking 30 minutes to drip into the trimethylene double (4 -Aminobenzoic acid ester) (CUA-4, manufactured by IHARA Chemical Industry Co., Ltd.) 7 8.5 3 g (0 · 2 5 m ο 1 ) A solution of 2 μg of r-butyrolactone is then stirred at room temperature 1 In an hour, a solution of the quinone imine precursor resin was obtained. 50 g of cyclopentyl methyl ether was added to the obtained quinone imine precursor resin solution, nitrogen gas was passed, and the produced water was removed by azeotropic dehydration while heating and stirring at 130 ° C for 2 hours, further at 15 The mixture was heated and stirred at 0 ° C for 2 hours to obtain a r-butyrolactone solution of a quinone imine compound having a carboxyl group at the terminal. Next, glycidyl methacrylate (BLEMMER GH, manufactured by Nippon Oil Co., Ltd.) 106-88 g (0.75 mol), and 0.5 g of methoxyhydroquinone as a polymerization inhibitor, and triphenylphosphine ruthenium as a reaction catalyst, 5 g, The mixture was heated and stirred at 90 ° C for 5 hours, and further heated and stirred at 1 ° C for 1 hour to carry out a reaction until the acid value of the solid component became 2 mgKOH/g or less to obtain a compound A5. - Butyrolactone solution (molecular weight 95 8 ). The solid content was 57%, and the weight average molecular weight G measured by GPC was about 1800. The synthetic reaction scheme is disclosed below. -30- 8 201134840 h2n

2 CUA4 c17h18n2o42 CUA4 c17h18n2o4

Exact Mass: 314.13 Mol. Wl.: 314.34 C, 64.96; H, 5.77; N, 8.91; 0. 20.36Exact Mass: 314.13 Mol. Wl.: 314.34 C, 64.96; H, 5.77; N, 8.91; 0. 20.36

CsHi〇〇5CsHi〇〇5

Exact Mass: 198.05 Mol.Wt.: 198.17 C, 54.55； H, 5.09; O, 40.37Exact Mass: 198.05 Mol.Wt.: 198.17 C, 54.55; H, 5.09; O, 40.37

Mol. Wt.: 674.65 C, 62.31; H, 5.08; N, 4.15; 0, 28.46Mol. Wt.: 674.65 C, 62.31; H, 5.08; N, 4.15; 0, 28.46

C7H10O3 Exact Mass: 142.06 Md. Wt.:142.15C7H10O3 Exact Mass: 142.06 Md. Wt.: 142.15

C, 59.14； H, 7.09:0, 33.77 HO OC, 59.14; H, 7.09:0, 33.77 HO O

C4gH54N2〇i0C4gH54N2〇i0

Exact Mass: 958.34 Mol. Wt.: 958.96 C, 61.37: H 5,68; N. 2.92: 0,30.03 (1 - 6 )比較化合物1 使作爲環氧樹脂的雙酣A型環氧樹脂（J a p a η E p o x y Resins股份有限公司JER8 3 4 ) 240質量份溶於二乙二醇單***醋酸酯1210質量份，於其中加入丙烯酸72質量份，在加熱回流條件下，藉由既定方法使其進行反應，接下來加入四氫苯二甲酸酐83質量份，藉由既定方法使其進 -31 - 201134840 行反應，得到在一分子中具有羧基且具有2個以上不飽和基的樹脂，其重量平均分子量爲500。 (1-7 )比較化合物2 使作爲環氧樹脂的雙酚A型環氧樹脂（Japan Epoxy Resins股份有限公司JER1 01 0 ) 400質量份溶於二乙二醇單***醋酸酯120質量份，於其中加入丙烯酸7.2質量份，在加熱回流的條件下，藉由既定方法使其進行反應，得到在一分子中不具有羧基而具有2個以上不飽和基的樹脂，其重量平均分子量爲5800。 (2 )評估測試片製作方法 (2 - 1 )實施例1〜7及比較例1〜5 以三輥機使表1所示重量比的各摻合物混合分散’調製出硬化性樹脂組成物。另外，硬化塗膜之製作步驟如同以下所述。表面處理：拋光硏磨塗膜膜厚：乾燥膜厚，20〜23/zm 塗佈：以棒式塗佈機進行塗佈 UV照射：光阻上，400mJ/cm2 ( ORC公司製HMW-68 0GW ) 加熱處理：150 °C，60分鐘（BOX爐內70分鐘） (2-2 )實施例8〜1 4及比較例6〜1 0 -32- ⑧ 201134840 以三輥機使表2所示重量比的各摻合物混合分散，調製出白色硬化性樹脂組成物。以3 %硫酸水溶液對於厚度 38ym的聚對苯二甲酸乙二酯薄膜（東麗製，「Lumirror 」）表面進行處理，將表面洗淨後，使乾燥膜厚成爲20 〜23 # m，以絲網印刷法將白色硬化性樹脂組成物塗佈於聚對苯二甲酸乙二酯薄膜其中一個表面全體，採用與上述相同的UV照射及加熱處理條件製作出硬化塗膜，以此作爲測試片。另外，關於反射率，聚對苯二甲酸乙二酯本身的劣化會伴隨著放置於加速測試的環境而發生，爲了去除其所造成的影響，以同樣方法在玻璃板（1 .2mm厚）上形成硬化塗膜，並且對其進行評估。 (2-3)實施例15〜30 以三輥機使表3所示重量比的各摻合物混合分散，調製出樹脂組成物。使用異丙醇對於厚度16;/m之聚對苯二甲酸乙二酯薄膜（UNITIKA製）的表面進行脫脂處理。接下來以棒式塗佈機將樹脂組成物塗佈於該薄膜，使乾燥膜厚成爲10〜15/zm，並照射500〜2000mJ/cm2 (燈光源：金屬鹵素燈）的UV。然後在120〜15(TC進行後硬化 60分鐘（BOX爐內70分鐘），製作出測試片。 (3 )評估方法 (3 -1 )黏度測定藉由音叉型振動式黏度計測定硬化性組成物之黏度。 -33- 201134840 測定裝置名稱：s V型黏度計（S V - 1 0 ) ，A & D股份有限公司製Exact Mass: 958.34 Mol. Wt.: 958.96 C, 61.37: H 5,68; N. 2.92: 0,30.03 (1 - 6 )Comparative Compound 1 A double bismuth A type epoxy resin (J apa) η E poxy Resins Co., Ltd. JER8 3 4 ) 240 parts by mass of 1210 parts by mass of diethylene glycol monoethyl ether acetate, 72 parts by mass of acrylic acid was added thereto, and reacted by a predetermined method under heating under reflux Then, 83 parts by mass of tetrahydrophthalic anhydride was added, and the reaction was carried out in the range of -31 - 201134840 by a predetermined method to obtain a resin having a carboxyl group in one molecule and having two or more unsaturated groups, and the weight average molecular weight thereof. Is 500. (1-7) Comparative Compound 2 400 parts by mass of a bisphenol A type epoxy resin (Japan Epoxy Resins Co., Ltd. JER1 01 0 ) as an epoxy resin was dissolved in 120 parts by mass of diethylene glycol monoethyl ether acetate, 7.2 parts by mass of acrylic acid was added thereto, and the mixture was reacted under heating under reflux to obtain a resin having no carboxyl group and having two or more unsaturated groups in one molecule, and the weight average molecular weight thereof was 5,800. (2) Evaluation test piece production method (2 - 1) Examples 1 to 7 and Comparative Examples 1 to 5 The mixture of the respective weight ratios shown in Table 1 was mixed and dispersed by a three-roller to prepare a curable resin composition. . Further, the steps of producing the cured coating film are as follows. Surface treatment: polishing honing coating film thickness: dry film thickness, 20~23/zm coating: coating with a bar coater UV irradiation: photoresist, 400mJ/cm2 (HMW-68 0GW made by ORC) Heat treatment: 150 ° C, 60 minutes (70 minutes in the BOX furnace) (2-2) Examples 8 to 14 and Comparative Examples 6 to 1 0 - 32 - 8 201134840 The weight shown in Table 2 was measured by a three-roller The blends were mixed and dispersed to prepare a white curable resin composition. The surface of a polyethylene terephthalate film ("Lumirror" manufactured by Toray Industries, Inc.) having a thickness of 38 μm was treated with a 3% sulfuric acid aqueous solution, and the surface was washed to have a dry film thickness of 20 to 23 #m. In the screen printing method, a white curable resin composition was applied to one surface of one of the polyethylene terephthalate films, and a cured film was produced by the same UV irradiation and heat treatment conditions as described above, and this was used as a test piece. In addition, regarding the reflectance, the deterioration of the polyethylene terephthalate itself occurs along with the environment placed in the accelerated test, and in order to remove the influence, the same method is applied to the glass plate (1.2 mm thick). A hard coat film was formed and evaluated. (2-3) Examples 15 to 30 The blends of the weight ratios shown in Table 3 were mixed and dispersed by a three-roll mill to prepare a resin composition. The surface of a polyethylene terephthalate film (manufactured by UNITIKA) having a thickness of 16;/m was subjected to degreasing treatment using isopropyl alcohol. Next, the resin composition was applied to the film by a bar coater to have a dry film thickness of 10 to 15 / zm, and irradiated with UV of 500 to 2000 mJ/cm 2 (light source: metal halide lamp). Then, at 120 to 15 (TC was post-hardened for 60 minutes (70 minutes in the BOX furnace), a test piece was produced. (3) Evaluation method (3 -1) Viscosity measurement The curable composition was measured by a tuning fork type vibrating viscometer. Viscosity -33- 201134840 Measuring device name: s V-type viscometer (SV - 1 0 ), manufactured by A & D Co., Ltd.

固有頻率：3 Ο Η z、測定溫度：2 5 °C (3-2)保存安定性（增黏率）以音叉型振動式黏度計對於樹脂組成物進行黏度測定 (25〇C )，置於5 0 °C恆溫槽7天之後，求得增黏率。將增黏率未達1.1評爲◎、1.1以上未達-1.2評爲〇、1_2以上未達_ 1 . 5評爲△、1.5以上g平爲X。 (3-3 )變色性評估將實施例1〜7及比較例1〜5的硬化塗膜在26(TC加熱5分鐘後，以目視評估變色。將沒有變色的情況評爲〇、將稍微觀察到變色的情況評爲△、將變黃的情況評爲X 。關於Ϊ!施例I 5〜3 0 ’在上述（2 - 3 )中，以目視對於經過後硬化的基板進行確認，同樣地進行評估。 (3-4)塗膜硬度依據】IS K-5600-5-4的測試方法，評估銅箔上硬化塗膜的鉛筆硬度。 (3 - 5 )焊接耐熱性焊接耐熱性係依據JIS C-64 8 1的測試方法，將測試片的硬化塗膜fe漬於260C焊接槽30秒鐘之後，以玻璃 -34- 201134840 紙膠帶進行剝離測試，將此定爲一個循環，重覆循環1〜 3次之後’以目視觀察塗膜狀態，按照以下基準進行評估〇 ◎:重覆3循環後，仍未觀察到塗膜發生變化。〇：重覆3循環後，觀察到塗膜發生很微小的變化。 △:重覆2循環後，觀察到塗膜發生變化。 X :重覆1循環後，觀察到塗膜發生剝離。 (3-6)絕緣特性絕緣特性係使用 IPC-TM-650之 IPC-SM840B B· 25test coupon 的梳狀電極，在 85°C 、85%R.H.施加 DC50V，測定加濕200小時後的絕緣電阻。 (3-7)反射率使用分光光度計U-3410(日立製作所股份有限公司製：φ 60mm積分球），對於被覆了硬化塗膜的測試片測定450nm的反射率。另外，「初期」意指評估測試片剛製作好的時候、製作出評估測試片之後，「加溫加濕後」是指在85t：、85%RH放置1 000小時後。 (3-8)透過率將樹脂組成物塗佈於石英玻璃（50x 50x 1 mm )，以（ 2-3)的條件使其硬化之後，依據JIS-K-7105、 JIS-K-7136，使用日立HITEC公司製U-3310分光光度計 -35- 201134840 ，對於硬化膜測定全光線透過率。 (3-9)霧度將樹脂組成物塗佈於石英玻璃（ 50x50xlmm)，以（ 2-3)的條件使其硬化之後，依據JIS-K-7105、 JIS-K-7136，使用日立HITEC公司製U-3310分光光度計對於硬化膜測定霧度。 (3 -1 0 )費折測試將以（2-3 )的條件形成硬化塗膜的測試片，藉由板金彎折機重覆進行180°的彎折數次，以目視及200倍光學顯微鏡觀察此時透明絕緣膜中龜裂的發生狀況，以未發生龜裂的彎折次數作爲評價。 (3 -1 1 )伸長率（％ ) 使用棒式塗佈機均勻地將樹脂組成物塗佈於PET薄膜，而使厚度成爲5〇vm±10//m，然後進行（2-3)的預乾燥以至後硬化的步驟，而形成硬化塗膜。接下來，將所製作出的硬化塗膜由PET薄膜（125 v m )剝離並切成既定大小，然後使用SHIMAZU公司製AUTOGRAPH (拉伸試驗機），以拉伸速度5mm/min的條件測定其伸長率。 (4 )實驗結果將各樹脂組成物（硬化物）之評估結果揭示於表1〜 -36- 201134840 3 表【1巡Natural frequency: 3 Ο Η z, measured temperature: 2 5 °C (3-2) Preservation stability (tackifying ratio) Viscosity measurement (25〇C) of resin composition by tuning fork type vibrating viscometer After 7 days at 50 °C, the viscosity increase rate was obtained. The viscosity increase rate is not as high as 1.1, ◎, 1.1 or less is not up to -1.2, 〇, 1_2 is not up to _1.5, △, 1.5 or more, g is X. (3-3) Evaluation of discoloration The cured coating films of Examples 1 to 7 and Comparative Examples 1 to 5 were visually evaluated after 26 minutes of TC heating for 5 minutes. The case where no discoloration was evaluated was evaluated as 〇, which was slightly observed. The case of discoloration was rated as Δ, and the case of yellowing was evaluated as X. Regarding Ϊ! Example I 5 to 3 0 'In the above (2 - 3), the substrate which was post-hardened was visually confirmed, and similarly (3-4) Coating hardness According to the test method of IS K-5600-5-4, the pencil hardness of the hardened coating film on the copper foil is evaluated. (3 - 5) Solder heat resistance Solder heat resistance is based on JIS For the test method of C-64 8 1 , after the hardened coating film of the test piece is stained in the 260C welding groove for 30 seconds, the peeling test is performed with the glass-34-201134840 paper tape, and this is determined as a cycle, and the cycle 1 is repeated. After ~3 times, the film was visually observed and evaluated according to the following criteria: ◎: After repeated 3 cycles, no change in the coating film was observed. 〇: After repeated 3 cycles, it was observed that the coating film was very small. Change: △: After repeated 2 cycles, a change in the coating film was observed. X: After repeating 1 cycle, view (3-6) Insulation characteristics Insulation characteristics were measured by using a comb electrode of IPC-TM840B B. 25 test coupon of IPC-TM-650, applying DC50V at 85 ° C and 85% RH, and measuring the humidification. Insulation resistance after 200 hours. (3-7) Reflectance A reflectance of 450 nm was measured for a test piece coated with a cured coating film using a spectrophotometer U-3410 (manufactured by Hitachi, Ltd.: φ 60 mm integrating sphere). In addition, "initial" means that after the evaluation test piece is just produced and the evaluation test piece is produced, "after warming and humidifying" means after placing it at 85t:, 85% RH for 1,000 hours. (3-8) After the resin composition was applied to quartz glass (50×50×1 mm) and cured by (2-3) conditions, U-made by Hitachi HITEC Co., Ltd. was used in accordance with JIS-K-7105 and JIS-K-7136. -3310 Spectrophotometer -35- 201134840, The total light transmittance is measured for the cured film. (3-9) Haze The resin composition is applied to quartz glass (50x50xlmm) and hardened under conditions of (2-3). Then, according to JIS-K-7105 and JIS-K-7136, U-3310 spectrophotometer manufactured by Hitachi HITEC Co., Ltd. was used. The cured film is measured for haze. (3 -1 0 ) Folding test The test piece of the hardened coating film is formed under the condition of (2-3), and the 180° bending is repeated several times by the sheet metal bending machine to The occurrence of cracks in the transparent insulating film at this time was observed by a visual observation and a 200-fold optical microscope, and the number of times of bending without occurrence of cracks was evaluated. (3 -1 1 ) Elongation (%) The resin composition was uniformly applied to a PET film by a bar coater to have a thickness of 5 〇 vm ± 10 / / m, and then (2-3) The step of pre-drying to post-hardening forms a hardened coating film. Next, the hardened coating film produced was peeled off from a PET film (125 vm ) and cut into a predetermined size, and then the elongation was measured at a tensile speed of 5 mm/min using an AUTOGRAPH (stretching tester) manufactured by SHIMAZU Co., Ltd. rate. (4) Experimental results The evaluation results of the respective resin compositions (hardened materials) are disclosed in Table 1 to -36-201134840 3 Tables [1 Tour

1比較例5| I 唧I 〇 S o (_ 250 1 X 〇 ◎ L比較例4! L伽—1 〇 S δ 〇 ID s 〇 ◎ < = X 5 |比較例3丨 ! 1〇〇 I 〇 S Μ in 宕 g ◎ ο < 1比較例2丨 § S S CM m s - - S ◎ 0 < § 1比較例ι| Β 〇 S S Μ tn o - I 200 | X ο 5 Ο ΙΟ 施例7| 〇〇 S S to o - 〇 ο 0 s ◎ cq ί實施例6| 〇〇 S S tn s - 〇 < 0 s ◎ rj 施例5| § V— 〇 S S C4 in - 〇 ◎ ο 吞 Ο CM 丨實施例4| 〇〇 s S CM o s ◎ ο m ◎ - 丨韻例3| S 〇 S S Μ iq s δ ◎ ο S ο t*» 1實施例2] 〇〇 S S u> s s ◎ 0 Ξ ◎ 3 丨麵例1丨〇〇 S S CM S s 1 150 I ο ο ο S | 化合物(Α1) 1 | 化合物(Α2) I | 比較化合物ί | [ ΒΑΝΙ—Μ *1 I I 比較化合物2 I | 光聚合起始劑*2 I W I® Π® 睞丨i 111 二季戊四醇六丙烯酸酯甲基丙烯酸2-羥乙酯 1 三聚氛胺 i MX-750LM *3 1 mOAQUARD D)071 | | 顔料M I | 體質顔料*5 I | 消泡劑*6 I m 吕验 m I 保存安定性 I I 變色性評估 ι 塗膜硬度 | 焊接耐熱性 I 絕緣電阻（xi〇UQ) I -37- 2011348401 Comparative Example 5| I 唧I 〇S o (_ 250 1 X 〇 ◎ L Comparative Example 4! L gamma-1 〇S δ 〇ID s 〇 ◎ < = X 5 | Comparative Example 3丨! 1〇〇I 〇S Μ in 宕g ◎ ο < 1Comparative Example 2丨§ SS CM ms - - S ◎ 0 < § 1 Comparative Example ι| Β 〇SS Μ tn o - I 200 | X ο 5 Ο ΙΟ Example 7 〇〇SS to o - 〇ο 0 s ◎ cq ί Example 6| 〇〇SS tn s - 〇< 0 s ◎ rj Example 5| § V— 〇SS C4 in - 〇◎ ο Ο Ο CM 丨Example 4| 〇〇s S CM os ◎ ο m ◎ - 丨例 Example 3| S 〇 SS Μ iq s δ ◎ ο S ο t*» 1 Example 2] 〇〇SS u> ss ◎ 0 Ξ ◎ 3 Example 1 丨〇〇 SS CM S s 1 150 I ο ο ο S | Compound (Α1) 1 | Compound (Α2) I | Comparative compound ί | [ ΒΑΝΙ-Μ *1 II Comparative compound 2 I | Photopolymerization Starting agent*2 IWI® Π® 丨i 111 Dipentaerythritol hexaacrylate 2-hydroxyethyl methacrylate 1 Trimeric amine i MX-750LM *3 1 mOAQUA RD D)071 | | Pigment MI | Body Color Pigment*5 I | Defoamer*6 I m Lum m I Preservation Stability II Discoloration Evaluation ι Film Hardness | Solder Heat Resistance I Insulation Resistance (xi〇UQ) I -37- 201134840

-38- ⑧ 201134840 Η施例30 8 〇 ΙΛ CM S 8 «Si Ο <§> 5 Ο ΛΛ ΓΟ 2〇〇苡施例29 8 〇 u> CM s CM 8 Csl <s> ο ΛΛ CD οο »« o CO ΪΪ施例28 8 〇 s δ CO csl <s> 5 <J SC Γ= 衫 o U? Η施例27 8 〇 ΙΟ CM s δ CsJ <s> 5 < 妄怀 o Κ R施例26 8 〇 csi s δ CM 〇〇 CSI <S> 5 < CO 衫 o 25 W施例25 8 〇 m CM s δ CSI A CM <s> 5 ο we CO 〇> β o Β施例24 8 〇 CSI s δ σ» esi <s> ο CO A wc β o S5 Η施例23 8 〇 to «si δ CSI m Φ 5 ο 1 »« o u> 苡施例22 8 〇 lO CM s δ CM <s> 5 ο wc CO 〇> «c o 0施例21 8 〇筘 s 8 CSJ <s> ο S5 σ> »c o ίο Π施例20 8 〇 ΙΛ CM s 8 CM <s> 吞 ο CO σ> β Π施例19 8 〇 ΙΑ CM s 8 CM 穿 5 ο ve 05 VC β CO Π施例18 8 〇 ΙΛ CM s 8 CM to to a> ο 筘 σ> ve >C 过施例17 8 〇 ΙΛ Csl s 8 Csi t/y CM e δ ο »e CO O) «« u Κ施例16 8 〇 vr> CM s δ Cs| CM CO <s> ο >e «Μ 洽苡施冽15 8 〇 u1» s 8 Csl a> Csl <s> 5 ο ss WK ο 化合物(Α2) 化合物(A3) 化合物(Α4) 化合物(Α5) EGECRYL9270 EGECRY13708 IR3AOURE184 DAROCUR1173 1RQACUR£2S29 IRQACURE127 IROACURE651 IRQACURE369 啪 ACURES07 KAYARADR-684 s GE-610 MX-760 | MX-708 MX-002 三聚氛胺黏度(raPa _ s)25t：保存安定性離硬度變色性透過率錤度 1 母折測試怦長率胺甲酸乙酯丙烯酸酯羥基烷銅類 cy KH礙 ffl 二乙二醇二丙讎醋_ 甲基丙烯酸 2·羥乙酯 liff li mg 丄1 * ZS8 sa > 2S 屮摊靼 1涅8 (Β)光聚合起始劑 (c)反應性稀釋劑理如 1| £還 m e -39- 201134840 式（iv)所表示之含烯丙基之二醯亞胺（九善石油化學公司製） *2: 2-甲基- ΐ·[4-(甲硫基）苯基]-2-嗎啉基丙-1-酮（ IRGACURE 907，Ciba Specialty Chemicals 公司製） *3 :三聚氰胺衍生物（MX-7 5 0LM，三和化學股份有限公司製） *4 :酞花青綠（LIONOL GREEN 2Y-301，東洋油墨製造股份有限公司製） *5 :二氧化矽（MIN-U-SIL 5，林化成股份有限公司製 ) *6 :消泡劑（KS-66，信越化學工業股份有限公司製） *7 :搖變性賦予劑（R_974，曰本Aerosil股份有限公司製） *8:2,4,6-三甲基苯甲醯基二苯膦氧化物（3?已丘0(：1；11£ TPO，日本SiberHegner股份有限公司製） *9 :雙（2,4,6-三甲基苯甲醯基）苯膦氧化物（ IRGACURE 819、Ciba Specialty Chemicals 股份有限公司製） EBECRYL3 708 ： Daicel Cytec股份有限公司製，二官能變性環氧丙烯酸酯、重量平均分子量1500 EBECRYL9270 ： Dai cel Cytec股份有限公司製，二官能胺甲酸乙酯丙烯酸酯，重量平均分子II 100 0 IRGACURE 1 84 : Ciba Specialty Chemicals 股份有限公司製，1-羥基環己基苯酮 -40- ⑧ 201134840 DAROCUR 1173: Ciba Specialty Chemicals 股份有限公司製，2_羥基-2-甲基-1-苯基丙-1-酮 IRGACURE 2959 : Ciba Specialty Chemicals 股份有限公司製，1-[4-( 2-羥基乙氧基）苯基]-2-羥基-2-甲基丙_ 1 -酮 IRGACURE 127 : Ciba Specialty Chemicals 股份有限公司製，2-羥基- l-{4-[4-(2-羥基-2-甲基丙醯基）-苄基]苯基}-2 -甲基丙-1-嗣 IRGACURE 651: Ciba Specialty Chemicals 股份有限公司製，苄基二甲基縮酮系光聚合起始劑（2,2·二甲氧基-1,2-二苯基乙-1-酮） IRGACURE 369: Ciba Specialty Chemicals 股份有限公司製，α -胺基酮系光聚合起始劑（2-苄基·2-二甲基胺基-1- ( 4-嗎咐基苯基）丁酮-1 ) ΜΧ708 :三聚氰胺衍生物，三和化學股份有限公司製 ΜΧ002 :三聚氰胺衍生物，三和化學股份有限公司製由表1明顯可知，本發明之硬化性組成物的保存安定性、變色性評估、焊接耐熱性任一者皆表現優異。另外，從實施例6的結果可知，由於保存安定性稍微有變差的傾向，因此就三聚氰胺的含量而言，係以2質量份左右爲適當。另外，本發明之硬化性組成物任一者的塗膜硬度皆爲 3 Η以上（宜爲4Η以上），絕緣電阻爲0 · 8 X 1 0 12 Ω以上， -41 - 201134840 而表現出良好的結果。特別針對於實施例2及實施例3之組成物’可知其評估項目任一者皆表現良好而優異》再者’由表2明顯可知，本發明之硬化性組成物之硬化物具有優異的反射率，塗膜硬度亦表現良好，因此亦適合作爲太陽能電池模組用的反射片。另外由表3還可知，實施例1 5〜3 0之硬化性組成物之硬化物’尤其是實施例1 5〜2 5之硬化性組成物之硬化物，會具有良好的透明性。 [產業上之可利用性] 本發明之硬化性組成物的保存安定性優異，其硬化後的塗膜具有足夠的硬度、焊接耐熱性、絕緣電阻，以及在進行焊接時等不易發生變色，由於具有這些優異特性，故爲有效的印刷電路板製造原料。另外，本發明之硬化性組成物之硬化物具有優異的反射率，塗膜硬度亦表現良好，因此亦適合作爲太陽能電池模組用的反射片。另外，由本發明之硬化性組成物產生的透明硬化物，適合於觸控面板電極基板等製造。 -42-38- 8 201134840 Η例30 8 〇ΙΛ CM S 8 «Si Ο <§> 5 Ο ΛΛ ΓΟ 2〇〇苡Example 29 8 〇u> CM s CM 8 Csl <s> ο ΛΛ CD Οο »« o CO ΪΪExample 28 8 〇s δ CO csl <s> 5 <J SC Γ= 衫o U? ΗExample 27 8 〇ΙΟ CM s δ CsJ <s> 5 < o Κ R Example 26 8 〇csi s δ CM 〇〇CSI <S> 5 < CO 衫 o 25 W Example 25 8 〇m CM s δ CSI A CM <s> 5 ο we CO 〇> β o ΒExample 24 8 〇CSI s δ σ» esi <s> ο CO A wc β o S5 ΗExample 23 8 〇to «si δ CSI m Φ 5 ο 1 »« o u> 苡 Example 22 8 〇lO CM s δ CM <s> 5 ο wc CO 〇> «co 0example 21 8 〇筘s 8 CSJ <s> ο S5 σ> »co ίο ΠExample 20 8 〇ΙΛ CM s 8 CM <s> οο CO σ> β ΠExample 19 8 〇ΙΑ CM s 8 CM wear 5 ο ve 05 VC β CO Example 18 8 〇ΙΛ CM s 8 CM to to a> ο 筘σ> ve >C Example 17 8 〇ΙΛ Csl s 8 Csi t/y CM e δ ο »e CO O) «« u Κ Example 16 8 〇vr> CM s δ Cs| CM CO <s> ο >e «Μ 苡苡 15 8 〇u1» s 8 Csl a> Csl <s> 5 ο ss WK ο Compound ( Α2) Compound (A3) Compound (Α4) Compound (Α5) EGECRYL9270 EGECRY13708 IR3AOURE184 DAROCUR1173 1RQACUR£2S29 IRQACURE127 IROACURE651 IRQACURE369 啪ACURES07 KAYARADR-684 s GE-610 MX-760 | MX-708 MX-002 Trimeric Amine Viscosity (raPa _ s)25t: Preservation stability, hardness, discoloration, transmittance, temperature, 1 degree, test, length, rate, urethane, acrylate, hydroxyalkane, copper, cy KH, ffl, diethylene glycol, dipropylene vinegar, methacrylic acid · Hydroxyethyl ester liff li mg 丄1 * ZS8 sa > 2S 屮 1 8 8 (Β) photopolymerization initiator (c) Reactive diluent such as 1| £ also me -39- 201134840 Formula (iv ) allyl-containing bis-imine (Hybrid Petroleum Chemical Co., Ltd.) 2: 2-methyl-indole-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one (IRGACURE 907, manufactured by Ciba Specialty Chemicals) *3: melamine derivative (MX- 7 5 0LM, manufactured by Sanwa Chemical Co., Ltd.) *4 : 酞花青绿 (LIONOL GREEN 2Y-301, manufactured by Toyo Ink Manufacturing Co., Ltd.) *5 : cerium oxide (MIN-U-SIL 5, Lin Huacheng Co., Ltd.) *6: Defoamer (KS-66, manufactured by Shin-Etsu Chemical Co., Ltd.) *7: Shake-denying agent (R_974, manufactured by Sakamoto Aerosil Co., Ltd.) *8:2,4,6- Trimethylbenzhydryldiphenylphosphine oxide (3? 丘丘0 (:1; 11 £ TPO, manufactured by Siber Hegner Co., Ltd., Japan) *9: bis(2,4,6-trimethylbenzhydrazide) Benzene phosphine oxide (IRGACURE 819, manufactured by Ciba Specialty Chemicals Co., Ltd.) EBECRYL3 708: Dicelyl epoxidized acrylate, manufactured by Daicel Cytec Co., Ltd., weight average molecular weight 1500 EBECRYL9270: manufactured by Daicel Cell Co., Ltd. Difunctional urethane acrylate, weight average molecule II 100 0 IRGACURE 1 84 : Ciba Specialty Manufactured by Chemicals Co., Ltd., 1-hydroxycyclohexyl benzophenone-40- 8 201134840 DAROCUR 1173: manufactured by Ciba Specialty Chemicals Co., Ltd., 2-hydroxy-2-methyl-1-phenylpropan-1-one IRGACURE 2959: Manufactured by Ciba Specialty Chemicals Co., Ltd., 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one IRGACURE 127 : manufactured by Ciba Specialty Chemicals Co., Ltd., 2 -hydroxy-l-{4-[4-(2-hydroxy-2-methylpropenyl)-benzyl]phenyl}-2-methylpropan-1-oxime IRGACURE 651: Ciba Specialty Chemicals Co., Ltd. Benzyl dimethyl ketal photopolymerization initiator (2,2·dimethoxy-1,2-diphenylethan-1-one) IRGACURE 369: manufactured by Ciba Specialty Chemicals Co., Ltd., α -aminoketone photopolymerization initiator (2-benzyl-2-methylamino-1-(4-ythylphenyl)butanone-1) ΜΧ708: melamine derivative, Sanwa Chemical Co., Ltd. Co., Ltd. ΜΧ 002: Melamine derivative, manufactured by Sanwa Chemical Co., Ltd. It is apparent from Table 1 that the storage stability and discoloration evaluation of the curable composition of the present invention Both of any one of soldering heat resistance performance is excellent. Further, from the results of Example 6, it is understood that the storage stability is slightly deteriorated, so that the content of melamine is preferably about 2 parts by mass. Further, the hardness of the coating film of any of the curable compositions of the present invention is 3 Å or more (preferably 4 Å or more), and the insulation resistance is 0 · 8 X 1 0 12 Ω or more, -41 - 201134840 and exhibits good hardness. result. Particularly, in the composition of Example 2 and Example 3, it is understood that any of the evaluation items is excellent and excellent. Further, as apparent from Table 2, the cured product of the curable composition of the present invention has excellent reflection. The rate and film hardness are also good, so it is also suitable as a reflection sheet for solar cell modules. Further, as is clear from Table 3, the cured product of the curable composition of Examples 15 to 30, especially the cured product of the curable composition of Examples 15 to 25, has good transparency. [Industrial Applicability] The curable composition of the present invention is excellent in storage stability, and the cured coating film has sufficient hardness, solder heat resistance, insulation resistance, and discoloration during soldering. With these excellent characteristics, it is an effective raw material for printed circuit board manufacturing. Further, since the cured product of the curable composition of the present invention has excellent reflectance and good hardness of the coating film, it is also suitable as a reflection sheet for a solar cell module. Further, the transparent cured product produced by the curable composition of the present invention is suitable for the production of a touch panel electrode substrate or the like. -42

Claims

201134840 七、申請專利範圍： 1 _ 一種硬化性組成物，其特徵爲含有：在分子中不具有羧基而具有2個以上不飽和基，且分子量5 0 0〜5 00 0 之化合物（A )、光聚合起始劑（B )、在分子中具有2個以上不飽和基之反應性稀釋劑（C )、與在分子中具有至少一個以上胺基或亞胺基之化合物（ 2 ·如申請專利範圍第1項之硬化性組成物，其中，前述化合物（A)係下述一般式（i)所表示之化合物，【化1】201134840 VII. Patent application scope: 1 _ A curable composition characterized by containing: a compound (A) having no carboxyl group in the molecule and having two or more unsaturated groups, and having a molecular weight of 50,000 to 50,000; a photopolymerization initiator (B), a reactive diluent (C) having two or more unsaturated groups in the molecule, and a compound having at least one amine group or imine group in the molecule (2) The curable composition of the first aspect, wherein the compound (A) is a compound represented by the following general formula (i);

[式（i)中’ R〇表示- CH2 -或- CH2O-R01-; R1意指甲基或氫’虛線表示可爲雙鍵的鍵結處；G表示下述一般式（U )、（ib )或（ic )所表示之2價或3價基；m係對應於 G之價數之數字；RM表示碳數2〜1〇之分支或直鏈狀伸烷基， -43- 201134840 【化2】[In the formula (i), 'R〇 represents -CH2 - or -CH2O-R01-; R1 means methyl or hydrogen'. The dotted line indicates a bond which can be a double bond; G represents the following general formula (U), ( Divalent or trivalent group represented by ib or (ic); m is a number corresponding to the valence of G; RM is a branch of a carbon number of 2 to 1 或 or a linear alkyl group, -43-201134840 2]

(式（ia)中，R2〜R4各自獨立，表示氫原子或甲基）【化3】(In the formula (ia), R2 to R4 are each independently and represent a hydrogen atom or a methyl group.

(式（ic)中，p意指2〜5之整數）]。 3. 如申請專利範圍第1項之硬化性組成物，其中，前述化合物（A )係含烯丙基之二醯亞胺化合物。 4. 如申請專利範圍第1〜3項中任一項之硬化性組成物，其中，前述反應性稀釋劑（C )含有下述一般式（ii -44- 201134840 )所表不之二環癸一醇二（甲基）丙嫌酸醋，【化2】(in the formula (ic), p means an integer of 2 to 5)]. 3. The sclerosing composition of claim 1, wherein the compound (A) is an allyl-containing bis-imine compound. 4. The curable composition according to any one of claims 1 to 3, wherein the reactive diluent (C) contains a bicyclic ring represented by the following general formula (ii-44-201134840). Mono-alcohol (methyl)-propyl sulphuric acid vinegar, [Chemical 2]

獨立，意指0〜5之整數）。 5.如申請專利範圍第1〜4項中任一項之硬化性組成物’其中，前述反應性稀釋劑（C )係含有由二乙二醇二 (甲基）丙烯酸酯、二季戊四醇二（甲基）丙烯酸酯、二季戊四醇三（甲基）丙烯酸酯、二季戊四醇四（甲基）丙烧酸酯、二季戊四醇五（甲基）丙烯酸酯及二季戊四醇六 (甲基）丙烯酸酯所構成之群中選出之一種以上。 6·如申請專利範圍第1〜5項中任一項之硬化性組成物’其中，前述化合物（D )係三嗪系化合物。 7. 如申請專利範圍第6項之硬化性組成物，其中，前述三嗪系化合物係三聚氰胺、三聚氰胺衍生物或Ν'-第二丁基-Ν -環丙基-6-(甲硫基）-1,3,5 -三曉-2,4 -二胺。 8. 如申請專利範圍第1〜8項中任一項之硬化性組成物，其係用於阻焊劑油墨。 9. 一種硬化性組成物，其特徵爲：如申請專利範圍第8項之硬化性組成物，係用於噴墨法中的阻焊劑油墨’ 在25°C的黏度爲200mPa . s以下。 10. 一種硬化物，其特徵爲：如申請專利範圍第1〜 -45- 201134840 9項中任一項之硬化性組成物之硬化物。 11. 一種印刷電路板，其特徵爲：使用如申請專利範圍第1 〇項之硬化物。 12. —種反射片，其特徵爲：具有進一步含有氧化鈦的由如申請專利範圍第1〜7項中任一項之硬化性組成物之硬化物所產生的被膜。 -46 201134840 四指定代表圖： (一）本案指定代表圖為：無 (二）本代表圖之元件符號簡單說明：無 201134840 五本案若有化學式時，請揭示最能顯示發明特徵的化學式：無Independent, meaning an integer from 0 to 5.) 5. The sclerosing composition of any one of claims 1 to 4 wherein the reactive diluent (C) contains diethylene glycol di(meth) acrylate or dipentaerythritol di ( Methyl)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(methyl)propionate, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate One or more selected from the group. 6. The curable composition according to any one of the first to fifth aspects of the invention, wherein the compound (D) is a triazine compound. 7. The sclerosing composition of claim 6, wherein the triazine compound is melamine, a melamine derivative or Ν'-second butyl-fluorene-cyclopropyl-6-(methylthio). -1,3,5 - Sanxiao-2,4-diamine. 8. The curable composition according to any one of claims 1 to 8, which is used for a solder resist ink. A curable composition characterized by having a curable composition as in the eighth aspect of the patent application, wherein the solder resist ink used in the ink jet method has a viscosity at 25 ° C of 200 mPa·s or less. A cured product characterized by a cured product of a curable composition according to any one of claims 1 to 45 to 2011. A printed circuit board characterized by using a cured product as in the first aspect of the patent application. A reflection sheet comprising: a film produced by a cured product of a curable composition according to any one of claims 1 to 7 further containing titanium oxide. -46 201134840 IV Designated representative map: (1) The representative representative of the case is: None (2) The symbol of the representative figure is simple: No 201134840 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None