TWI631169B - Curable resin composition - Google Patents

Curable resin composition Download PDF

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TWI631169B
TWI631169B TW103125380A TW103125380A TWI631169B TW I631169 B TWI631169 B TW I631169B TW 103125380 A TW103125380 A TW 103125380A TW 103125380 A TW103125380 A TW 103125380A TW I631169 B TWI631169 B TW I631169B
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component
group
carbon atoms
resin composition
curable resin
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TW201510051A (en
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齋藤雅子
神林孝明
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艾迪科股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Silicon Polymers (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

本發明提供一種給予被研削性良好且具有較高之耐熱耐光性之白色硬化物的硬化性樹脂組合物，具體而言，提供一種含有下述物質之硬化性樹脂組合物：作為(A)成分的通式(1)所表示之基及/或通式(2)所表示之基由自通式(3)~(7)中之任一者所表示之化合物中去除乙烯基所得之殘基連結而成的矽氧烷化合物、作為(B)成分之通式(8)所表示之鏈狀矽氧烷化合物、作為(C)成分之熱自由基產生劑、及作為(D)成分之無機填料。再者，通式之具體內容如本說明書所記載。 The present invention provides a curable resin composition which is imparted with a white cured product which is excellent in heat resistance and light resistance and which has high heat resistance and light resistance. Specifically, a curable resin composition containing the following substance is provided as the component (A). The group represented by the formula (1) and/or the group represented by the formula (2) is a residue obtained by removing a vinyl group from a compound represented by any one of the formulas (3) to (7). a linked siloxane compound, a chain siloxane compound represented by the formula (8) as the component (B), a thermal radical generator as the component (C), and an inorganic component as the component (D) filler. Furthermore, the specific contents of the general formula are as described in the present specification.

Description

硬化性樹脂組合物 Curable resin composition

本發明係關於一種聚矽氧烷系之硬化性樹脂組合物，關於一種可獲得具有較高之耐熱耐光性且具有良好之被研削性之硬化物的硬化性樹脂組合物。 The present invention relates to a polyoxyalkylene-based curable resin composition, and to a curable resin composition which can obtain a cured product having high heat resistance and light resistance and having good groundability.

業界需要發光二極體基板用反射塗佈材、液晶顯示裝置之背光單元所使用之反射塗佈材、太陽電池之聚光面板用反射塗佈材、或建築物之屋頂或屋頂平台或外壁所使用之反射塗佈材、照明器具所使用之反射塗佈材等具有耐熱耐光性即於曝露於高溫或能量較高之光下之環境下亦會保持較高之光反射率的反射塗佈材。 The industry needs a reflective coating material for a light-emitting diode substrate, a reflective coating material for a backlight unit of a liquid crystal display device, a reflective coating material for a concentrating panel for a solar cell, or a roof or roof terrace or outer wall of a building. A reflective coating material such as a reflective coating material used for a lighting fixture or a lighting fixture, which has heat resistance and light resistance, that is, a high light reflectance in an environment exposed to high temperature or high energy.

作為反射塗佈材用之硬化性樹脂組合物，已知有於環氧樹脂中填充有白色顏料者(例如參照專利文獻1及2)、於矽酮樹脂中填充有白色顏料者(例如參照專利文獻3~6)，但於環氧樹脂中填充有白色顏料者存在如下問題：耐熱耐光性並不充分，於長時間曝露於高溫或能量較高之光下之環境下緩慢地著色而光反射率下降，因此於要求較高之耐熱耐光性之領域中研究於矽酮樹脂中填充有白色顏料者。 As a curable resin composition for a reflective coating material, it is known that a white pigment is filled in an epoxy resin (for example, refer to Patent Documents 1 and 2), and a white pigment is filled in an anthrone resin (for example, a reference patent) Document 3~6), but the epoxy resin filled with white pigment has the following problems: heat resistance and light resistance are not sufficient, and it is slowly colored and the light reflectance is lowered under the environment exposed to high temperature or high energy for a long time. Therefore, it has been studied in the field of requiring high heat resistance and light resistance to be filled with a white pigment in an anthrone resin.

作為於基板上形成反射塗佈部分之方法，實施僅於反射塗佈部分塗佈硬化性樹脂組合物使其硬化之方法、塗佈可實施光微影法之硬化性樹脂組合物而曝光、顯影之方法等。近年來，作為反射塗佈部分之形成方法，提出有於基板上塗佈硬化性樹脂組合物並硬化後研削去除不需要部分之方法(例如參照專利文獻7)，先前已知之矽酮樹脂系 之硬化物之被研削性並不充分，尋求可獲得被研削性良好之硬化物之硬化性樹脂組合物。 As a method of forming a reflective coating portion on a substrate, a method in which a curable resin composition is applied to a reflective coating portion and cured, and a curable resin composition capable of performing photolithography is applied to be exposed and developed. Method and so on. In recent years, as a method of forming a reflective coating portion, there has been proposed a method in which a curable resin composition is applied onto a substrate and cured, and then the unnecessary portion is removed by grinding (for example, see Patent Document 7). The machinable property of the cured product is not sufficient, and a curable resin composition capable of obtaining a cured product having good machinability is sought.

先前技術文獻 Prior technical literature 專利文獻 Patent literature

專利文獻1：日本專利特開2007-129173號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2007-129173

專利文獻2：日本專利特開2009-194222號公報 Patent Document 2: Japanese Patent Laid-Open Publication No. 2009-194222

專利文獻3：日本專利特開2010-229382號公報 Patent Document 3: Japanese Patent Laid-Open Publication No. 2010-229382

專利文獻4：日本專利特開2011-105869號公報 Patent Document 4: Japanese Patent Laid-Open No. 2011-105869

專利文獻5：日本專利特開2012-233035號公報 Patent Document 5: Japanese Patent Laid-Open Publication No. 2012-233035

專利文獻6：美國專利公開第2013/0075154號說明書 Patent Document 6: US Patent Publication No. 2013/0075154

專利文獻7：日本專利特開2012-253322號公報 Patent Document 7: Japanese Patent Laid-Open Publication No. 2012-253322

本發明之目的在於提供一種給予被研削性良好且具有較高之耐熱耐光性之白色硬化物的硬化性樹脂組合物。 An object of the present invention is to provide a curable resin composition which imparts a white cured product which is excellent in high heat resistance and light resistance and which is excellent in heat resistance and light resistance.

本發明者等人鑒於上述情況而潛心研究，結果達成本發明。即本發明係關於一種含有下述物質之硬化性樹脂組合物：作為(A)成分的下述通式(1)所表示之基及/或下述通式(2)所表示之基由自下述通式(3)~(7)中之任一者所表示之化合物中去除乙烯基所得之殘基連結而成的矽氧烷化合物、作為(B)成分之下述通式(8)所表示之鏈狀矽氧烷化合物、作為(C)成分之熱自由基產生劑、及作為(D)成分之無機填料。 The present inventors have diligently studied in view of the above circumstances, and as a result, have achieved the present invention. In other words, the present invention relates to a curable resin composition containing a group represented by the following formula (1) as the component (A) and/or a group represented by the following formula (2). a oxoxane compound obtained by linking a residue obtained by removing a vinyl group to a compound represented by any one of the following general formulae (3) to (7), and the following general formula (8) as a component (B) The chain halosiloxane compound, the thermal radical generator as the component (C), and the inorganic filler as the component (D).

(式中，R1表示碳數1~4之烷基或碳數6~10之芳基，a表示2~5之數。其中，R1可為全部相同之基，亦可為不同之基) (wherein R 1 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and a represents a number of 2 to 5. wherein R 1 may be all the same groups or may be different groups. )

(式中，b表示a-b+1成為0~4之數之2~6之數，R1及a與上述通式(1)同義) (where b represents a number of 2 to 6 in which a-b+1 becomes 0 to 4, and R 1 and a are synonymous with the above formula (1))

(式中，c表示1或2之數) (where c is the number of 1 or 2)

(式中，d表示1或2之數) (where d is the number of 1 or 2)

(式中，R2表示碳數1~4之烷基、縮水甘油基或烯丙基) (wherein R 2 represents an alkyl group having a carbon number of 1 to 4, a glycidyl group or an allyl group)

(式中，R3~R5各自獨立地表示碳數1~4之烷基或碳數6~10之芳基，e表示1或2之數，f及g各自獨立地表示0~6之數) (wherein R 3 to R 5 each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and e represents a number of 1 or 2, and f and g each independently represent 0 to 6 number)

(式中，R6及R7各自獨立地表示碳數1~4之烷基或碳數6~10之芳基) (wherein R 6 and R 7 each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms)

(式中，R8及R9各自獨立地表示碳數1~4之烷基，R10表示碳數6~10之芳基，R11表示碳數1~4之烷基或碳數6~10之芳基，h及j為將通式(8)所表示之鏈狀矽氧烷化合物之質量平均分子量設為1000~100萬之數) (wherein R 8 and R 9 each independently represent an alkyl group having 1 to 4 carbon atoms, R 10 represents an aryl group having 6 to 10 carbon atoms, and R 11 represents an alkyl group having 1 to 4 carbon atoms or a carbon number of 6~ The aryl group of 10, h and j are the mass average molecular weight of the chain siloxane compound represented by the formula (8) of 1,000 to 1,000,000.

本發明之效果在於提供一種給予被研削性良好且具有較高之耐熱耐光性之白色硬化物的硬化性樹脂組合物。 An effect of the present invention is to provide a curable resin composition which imparts a white cured product which is excellent in high heat resistance and light resistance and which is excellent in heat resistance and light resistance.

<(A)成分> <(A) component>

首先，對作為本發明之(A)成分的下述通式(1)所表示之基及/或下述通式(2)所表示之基由自上述通式(3)~(7)中之任一者所表示之化合物中去除乙烯基所得之殘基連結而成的矽氧烷化合物進行說明。 First, the group represented by the following formula (1) which is the component (A) of the present invention and/or the group represented by the following formula (2) are derived from the above formula (3) to (7). The oxoxane compound in which the residue obtained by removing the vinyl group in the compound represented by any of the compounds is bonded will be described.

於上述通式(1)中，R1表示碳數1~4之烷基或碳數6~10之芳基。其中，R1可為完全相同之基，亦可為不同之基。作為碳原子數1~4之烷基，例如可列舉：甲基、乙基、丙基、異丙基、丁基、第二丁基、異丁基、第三丁基等。作為碳數6~10之芳基，例如可列舉：苯基、乙基苯基、甲苯基、異丙苯基、二甲苯基、偽枯烯基(pseudocumenyl)、基、第三丁基苯基、苯乙基等。作為R1，就耐熱性提昇之方面而言，較佳為甲基、苯基，最佳為甲基。 In the above formula (1), R 1 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Wherein, R 1 may be the same group or may be a different group. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, an isobutyl group, and a tert-butyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, an ethylphenyl group, a tolyl group, a cumyl group, a xylyl group, and a pseudo-cumenyl group. Base, tert-butylphenyl, phenethyl and the like. R 1 is preferably a methyl group or a phenyl group in terms of heat resistance improvement, and is preferably a methyl group.

於上述通式(1)中，a表示2~5之數，就工業原料之獲取較容易之方面而言，a較佳為2~4之數，更佳為2~3之數，最佳為3之數。 In the above formula (1), a represents a number of 2 to 5, and in terms of easy acquisition of industrial raw materials, a is preferably 2 to 4, more preferably 2 to 3, and most preferably For the number three.

於上述通式(2)中，b表示a-b+1成為0~4之數之2~6之數，R1及a與上述通式(1)同義。 In the above formula (2), b represents a number of 2 to 6 in which a-b+1 is 0 to 4, and R 1 and a are synonymous with the above formula (1).

本發明之(A)成分係上述通式(1)所表示之基及/或上述通式(2)所表示之基由自上述通式(3)~(7)中之任一者所表示之化合物中去除乙烯基所得之殘基連結而成的矽氧烷化合物。上述通式(3)~(7)所表示之化合物均為於1分子中具有2個或3個乙烯基之化合物。 The component (A) of the present invention is a group represented by the above formula (1) and/or a group represented by the above formula (2) is represented by any one of the above formulas (3) to (7). A siloxane compound in which a residue obtained by removing a vinyl group is bonded to a compound. The compounds represented by the above formulas (3) to (7) are all compounds having two or three vinyl groups in one molecule.

上述通式(3)所表示之化合物為於1分子中具有2個或3個乙烯基之化合物。於上述通式(3)中，c表示1或2之數。作為c為1之數之通式(3) 所表示之化合物，可列舉：1,2-二乙烯基苯、1,3-二乙烯基苯、1,4-二乙烯基苯。作為c為2之數之通式(3)所表示之化合物，可列舉：1,2,4-三乙烯基苯、1,3,5-三乙烯基苯。 The compound represented by the above formula (3) is a compound having two or three vinyl groups in one molecule. In the above formula (3), c represents the number of 1 or 2. As a formula in which c is 1 (3) The compound to be represented includes 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene. Examples of the compound represented by the formula (3) wherein c is 2 are 1,2,4-trivinylbenzene and 1,3,5-trivinylbenzene.

上述通式(4)所表示之化合物為於1分子中具有2個或3個乙烯基之化合物。於上述通式(4)中，d表示1或2。作為d為1之數之上述通式(4)所表示之化合物，可列舉：1,2-二乙烯基環己烷、1,3-二乙烯基環己烷、1,4-二乙烯基環己烷。作為d為2之數之上述通式(4)所表示之化合物，可列舉：1,2,4-三乙烯基環己烷、1,3,5-三乙烯基環己烷。 The compound represented by the above formula (4) is a compound having two or three vinyl groups in one molecule. In the above formula (4), d represents 1 or 2. The compound represented by the above formula (4) wherein d is 1 may, for example, be 1,2-divinylcyclohexane, 1,3-divinylcyclohexane or 1,4-divinyl. Cyclohexane. The compound represented by the above formula (4) wherein d is 2 may, for example, be 1,2,4-trivinylcyclohexane or 1,3,5-trivinylcyclohexane.

上述通式(5)所表示之化合物為於1分子中具有2個或3個乙烯基之化合物。於上述通式(5)中，R2表示碳數1~4之烷基、縮水甘油基或烯丙基。作為R2，較佳為甲基、乙基、縮水甘油基、烯丙基。於上述通式(5)所表示之化合物之中，作為較佳之化合物，可列舉：異氰脲酸1,3-二烯丙基-5-甲酯、異氰脲酸1,3-二烯丙基-5-乙酯、異氰脲酸1,3-二烯丙基-5-縮水甘油酯、異氰脲酸1,3,5-三烯丙酯等。 The compound represented by the above formula (5) is a compound having two or three vinyl groups in one molecule. In the above formula (5), R 2 represents an alkyl group having a carbon number of 1 to 4, a glycidyl group or an allyl group. R 2 is preferably a methyl group, an ethyl group, a glycidyl group or an allyl group. Among the compounds represented by the above formula (5), preferred examples of the compound include 1,3-diallyl-5-methyl isocyanurate and 1,3-diene isocyanurate. Propyl-5-ethyl ester, 1,3-diallyl-5-glycidyl isocyanurate, 1,3,5-triallyl isocyanurate, and the like.

上述通式(6)所表示之化合物為於1分子中具有2個或3個乙烯基之化合物。於上述通式(6)中，R6及R7各自獨立地表示碳數1~4之烷基或碳數6~10之芳基。作為碳數1~4之烷基及碳數6~10之芳基，可列舉由上述通式(1)之R1所例示之基等，就耐熱性良好而言，較佳為甲基、乙基、丙基、苯基，進而較佳為甲基、乙基、苯基，最佳為甲基。e表示1或2之數，f及g各自獨立地表示0~6之數。 The compound represented by the above formula (6) is a compound having two or three vinyl groups in one molecule. In the above formula (6), R 6 and R 7 each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. The aryl group having a carbon number of 1 to 4 and the aryl group having 6 to 10 carbon atoms is exemplified by the group represented by R 1 of the above formula (1), and is preferably a methyl group in terms of good heat resistance. Ethyl, propyl, phenyl, more preferably methyl, ethyl or phenyl, most preferably methyl. e represents the number of 1 or 2, and f and g each independently represent the number of 0-6.

於e為1之數之上述通式(6)所表示之化合物之中，作為較佳之化合物，可列舉：二甲基二乙烯基矽烷、二乙基二乙烯基矽烷、二苯基二乙烯基矽烷、1,1,3,3-四甲基-1,3-二乙烯基二矽氧烷、1,1,3,3-四乙基-1,3-二乙烯基二矽氧烷、1,1,3,3-四苯基-1,3-二乙烯基二矽氧烷、1,1,5,5-四甲基-3,3-二苯基-1,5-二乙烯基三矽氧烷、1,1,7,7-四甲基- 3,3,5,5-四苯基-1,7-二乙烯基三矽氧烷等，較佳為二甲基二乙烯基矽烷、二乙基二乙烯基矽烷、二苯基二乙烯基矽烷，進而較佳為1,1,3,3-四甲基-1,3-二乙烯基二矽氧烷。於e為2之數之上述通式(6)所表示之化合物之中，作為較佳之化合物，可列舉：甲基三乙烯基矽烷、乙基三乙烯基矽烷、苯基三乙烯基矽烷、1,1,3,5,5-五甲基-1,3,5-三乙烯基三矽氧烷、1,1,5,5-四甲基-3-苯基-1,3,5-三乙烯基三矽氧烷、三(二甲基乙烯基矽烷氧基)甲基矽烷、三(二甲基乙烯基矽烷氧基)苯基矽烷等。 Among the compounds represented by the above formula (6) wherein e is 1 , preferred examples of the compound include dimethyldivinyl decane, diethyl divinyl decane, and diphenyl divinyl group. Decane, 1,1,3,3-tetramethyl-1,3-divinyldioxane, 1,1,3,3-tetraethyl-1,3-divinyldioxane, 1,1,3,3-tetraphenyl-1,3-divinyldioxane, 1,1,5,5-tetramethyl-3,3-diphenyl-1,5-diethylene Trioxane, 1,1,7,7-tetramethyl- 3,3,5,5-tetraphenyl-1,7-divinyltrioxane, etc., preferably dimethyldivinyl decane, diethyldivinyl decane, diphenyldivinyl The decane is further preferably 1,1,3,3-tetramethyl-1,3-divinyldioxane. Among the compounds represented by the above formula (6) wherein e is 2, preferred examples of the compound include methyl trivinyl decane, ethyl trivinyl decane, and phenyl trivinyl decane; , 1,3,5,5-pentamethyl-1,3,5-trivinyltrioxane, 1,1,5,5-tetramethyl-3-phenyl-1,3,5- Trivinyltrioxane, tris(dimethylvinylnonyloxy)methylnonane, tris(dimethylvinyldecyloxy)phenyldecane, and the like.

上述通式(7)所表示之化合物為於1分子中具有2個乙烯基之化合物。於上述通式(7)中，R6及R7各自獨立地表示碳數1~4之烷基或碳數6~10之芳基。作為碳數1~4之烷基及碳數6~10之芳基，可列舉由上述通式(1)之R1所例示之基等，就耐熱性良好而言，較佳為甲基、乙基、丙基、苯基，進而較佳為甲基、乙基、苯基，最佳為甲基。於上述通式(7)所表示之化合物之中，作為較佳之化合物，可列舉：1,2-雙(二甲基乙烯基矽烷基)苯、1,3-雙(二甲基乙烯基矽烷基)苯、1,4-雙(二甲基乙烯基矽烷基)苯、1,2-雙(二乙基乙烯基矽烷基)苯、1,3-雙(二乙基乙烯基矽烷基)苯、1,4-雙(二乙基乙烯基矽烷基)苯等，較佳為1,2-雙(二甲基乙烯基矽烷基)苯、1,4-雙(二甲基乙烯基矽烷基)苯，進而較佳為1,4-雙(二甲基乙烯基矽烷基)苯。 The compound represented by the above formula (7) is a compound having two vinyl groups in one molecule. In the above formula (7), R 6 and R 7 each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. The aryl group having a carbon number of 1 to 4 and the aryl group having 6 to 10 carbon atoms is exemplified by the group represented by R 1 of the above formula (1), and is preferably a methyl group in terms of good heat resistance. Ethyl, propyl, phenyl, more preferably methyl, ethyl or phenyl, most preferably methyl. Among the compounds represented by the above formula (7), preferred examples of the compound include 1,2-bis(dimethylvinyldecyl)benzene and 1,3-bis(dimethylvinylnonane). Benzo, 1,4-bis(dimethylvinyldecyl)benzene, 1,2-bis(diethylvinyldecyl)benzene, 1,3-bis(diethylvinyldecyl) Benzene, 1,4-bis(diethylvinyldecyl)benzene, etc., preferably 1,2-bis(dimethylvinyldecyl)benzene, 1,4-bis(dimethylvinyldecane) Benzo) is further preferably 1,4-bis(dimethylvinyldecyl)benzene.

自上述通式(3)~(7)所表示之化合物中去除乙烯基所得之殘基之中，就處理性之方面而言，較佳為於1分子中具有2個乙烯基之化合物之殘基，就原料獲取之容易性與反應性而言，較佳為上述通式(3)或上述通式(4)所表示之化合物之殘基。 Among the residues obtained by removing a vinyl group from the compounds represented by the above formulas (3) to (7), in terms of handleability, it is preferably a residue of a compound having two vinyl groups in one molecule. The base is preferably a residue of the compound represented by the above formula (3) or the above formula (4) in terms of ease of availability of the raw material and reactivity.

關於(A)成分之分子量，就耐熱性及處理性之方面而言，以質量平均分子量計較佳為5000~20萬，進而較佳為5000~15萬，最佳為1萬~10萬。再者，於本發明中，所謂質量平均分子量，意指以四氫呋 喃作為溶劑進行GPC(Gel Permeation Chromatography，凝膠層析法)分析之情形時之聚苯乙烯換算之質量平均分子量。 The molecular weight of the component (A) is preferably from 5,000 to 200,000, more preferably from 5,000 to 150,000, and most preferably from 10,000 to 100,000, in terms of heat resistance and handleability. Further, in the present invention, the mass average molecular weight means tetrahydrofuran. The mass average molecular weight in terms of polystyrene in the case of GPC (Gel Permeation Chromatography) analysis as a solvent.

(A)成分可藉由使下述通式(1a)所表示之環狀矽氧烷化合物之SiH基與上述通式(3)~(7)所表示之化合物之乙烯基進行矽氫化反應而獲得。 The component (A) can be subjected to a hydrogenation reaction of a SiH group of a cyclic siloxane compound represented by the following formula (1a) with a vinyl group of a compound represented by the above formula (3) to (7). obtain.

(式中，R1及a與通式(1)同義) (wherein R 1 and a are synonymous with the general formula (1))

該矽氫化反應較佳為使用觸媒進行，作為矽氫化觸媒，例如可列舉：鉑系觸媒、鈀系觸媒、銠系觸媒等。作為鉑系觸媒，例如可列舉：氯鉑酸、氯鉑酸與醇、醛、酮等之錯合物、鉑-烯烴錯合物、鉑-羰基乙烯基甲基錯合物(Ossko觸媒)、鉑-二乙烯基四甲基二矽氧烷錯合物(Karstedt觸媒)、鉑-環乙烯基甲基矽氧烷錯合物、鉑-辛醛錯合物、鉑-膦錯合物(例如Pt[P(C6H5)3]4、PtCl[P(C6H5)3]3、Pt[P(C4H9)3)4]、鉑-亞磷酸酯錯合物(例如Pt[P(OC6H5)3]4)、Pt[P(OC4H9)3]4)、二羰基二氯鉑等。作為鈀系觸媒或銠系觸媒，例如可列舉含有鈀原子或銠原子代替上述鉑系觸媒之鉑原子之化合物。該等可使用1種，亦可併用2種以上。作為矽氫化觸媒，就反應性之方面而言，較佳為鉑系觸媒，進而較佳為鉑-二乙烯基四甲基二矽氧烷錯合物及鉑-羰基乙烯基甲基錯合物，最佳為鉑-羰基乙烯基甲基錯合物。又，關於觸媒之使用量，就反應性之方面而言，較佳為各原料之合計量之5質量%以下，進而較佳為0.0001~1.0質量%，最佳為0.001 ~0.1質量%。矽氫化之反應條件並無特別限定，只要使用上述觸媒於先前公知之條件下進行即可，就反應速度之方面而言，較佳為於室溫(25℃)~130℃下進行，亦可於反應時使用甲苯、己烷、甲基異丁基酮、環己烷、丙二醇單甲醚乙酸酯等先前公知之溶劑。 The rhodium hydrogenation reaction is preferably carried out using a catalyst. Examples of the rhodium hydrogenation catalyst include a platinum-based catalyst, a palladium-based catalyst, and a rhodium-based catalyst. Examples of the platinum-based catalyst include a complex of chloroplatinic acid, chloroplatinic acid and an alcohol, an aldehyde, a ketone, a platinum-olefin complex, and a platinum-carbonylvinylmethyl complex (Ossko catalyst). ), platinum-divinyltetramethyldioxane complex (Karstedt catalyst), platinum-cyclovinylmethyl oxime complex, platinum-octanal complex, platinum-phosphine complex (for example, Pt[P(C 6 H 5 ) 3 ] 4 , PtCl[P(C 6 H 5 ) 3 ] 3 , Pt[P(C 4 H 9 ) 3 ) 4 ], platinum-phosphite (for example, Pt[P(OC 6 H 5 ) 3 ] 4 ), Pt[P(OC 4 H 9 ) 3 ] 4 ), dicarbonyldichloroplatinum or the like. Examples of the palladium-based catalyst or the ruthenium-based catalyst include a compound containing a palladium atom or a ruthenium atom in place of the platinum atom of the platinum-based catalyst. These may be used alone or in combination of two or more. As the ruthenium hydrogenation catalyst, a platinum-based catalyst is preferred from the viewpoint of reactivity, and further preferably a platinum-divinyltetramethyldioxane complex and a platinum-carbonylvinylmethyl group. The compound is preferably a platinum-carbonylvinylmethyl complex. In addition, the amount of the catalyst to be used is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass, and most preferably 0.001 to 0.1% by mass, based on the total amount of the respective raw materials. The reaction conditions for hydrogenation of hydrazine are not particularly limited, and may be carried out under previously known conditions using the above-mentioned catalyst. From the viewpoint of the reaction rate, it is preferably carried out at room temperature (25 ° C) to 130 ° C. A previously known solvent such as toluene, hexane, methyl isobutyl ketone, cyclohexane or propylene glycol monomethyl ether acetate can be used for the reaction.

於本反應中，通常獲得作為主成分之具有上述通式(1)所表示之基與上述通式(2)所表示之基之化合物。於選擇性地獲得僅具有上述通式(1)所表示之基之化合物之情形時，只要非常過量地使用上述通式(3)~(7)所表示之化合物使其與上述通式(1a)所表示之環狀矽氧烷化合物反應，反應結束後去除過量之上述通式(3)~(7)所表示之化合物即可。 In the present reaction, a compound having a group represented by the above formula (1) and a group represented by the above formula (2) as a main component is usually obtained. In the case of selectively obtaining a compound having only the group represented by the above formula (1), the compound represented by the above formula (3) to (7) is used in a very large excess to make it conform to the above formula (1a). The cyclic oxirane compound represented by the reaction is carried out, and after the completion of the reaction, the excess compound represented by the above formula (3) to (7) may be removed.

繼而，對作為(B)成分之上述通式(8)所表示之鏈狀矽氧烷化合物進行說明。於上述通式(8)中，R8及R9各自獨立地表示碳數1~4之烷基，R10表示碳數6~10之芳基，R11表示碳數1~4之烷基或碳數6~10之芳基。作為碳數1~4之烷基及碳數6~10之芳基，可列舉由上述通式(1)之R1所例示之基等。 Next, the chain siloxane compound represented by the above formula (8) as the component (B) will be described. In the above formula (8), R 8 and R 9 each independently represent an alkyl group having 1 to 4 carbon atoms, R 10 represents an aryl group having 6 to 10 carbon atoms, and R 11 represents an alkyl group having 1 to 4 carbon atoms. Or an aryl group having a carbon number of 6 to 10. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified by R 1 of the above formula (1).

作為R8及R9，就耐熱性良好而言，較佳為甲基、乙基，進而較佳為甲基。作為R10，就耐熱性良好而言，較佳為苯基。作為R11，就耐熱性之方面而言，較佳為碳數6~10之芳基，進而較佳為苯基，就可撓性之方面而言，較佳為碳數1~4之烷基，進而較佳為甲基、乙基，最佳為甲基。 R 8 and R 9 are preferably a methyl group or an ethyl group, and more preferably a methyl group, in terms of good heat resistance. R 10 is preferably a phenyl group in terms of good heat resistance. R 11 is preferably an aryl group having 6 to 10 carbon atoms, more preferably a phenyl group, in terms of heat resistance, and preferably an alkyl group having 1 to 4 carbon atoms in terms of flexibility. The group is further preferably a methyl group or an ethyl group, and most preferably a methyl group.

於上述通式(8)中，h及j為將上述通式(8)所表示之鏈狀矽氧烷化合物之質量平均分子量設為3000~100萬之數。於上述通式(8)所表示之鏈狀矽氧烷化合物之質量平均分子量小於3000之情形時，耐熱性較低，於大於100萬之情形時，黏度變高而處理性下降。上述通式(8)所表示之鏈狀矽氧烷化合物之質量平均分子量較佳為5000~5萬，進而較佳為8000~2萬。 In the above formula (8), h and j are those in which the mass average molecular weight of the chain siloxane compound represented by the above formula (8) is 3,000 to 1,000,000. When the mass average molecular weight of the chain siloxane compound represented by the above formula (8) is less than 3,000, the heat resistance is low, and when it is more than 1,000,000, the viscosity is high and the handleability is lowered. The chain-shaped oxirane compound represented by the above formula (8) preferably has a mass average molecular weight of 5,000 to 50,000, more preferably 8,000 to 20,000.

於上述通式(8)中，關於碳數1~4之烷基與碳數6~10之芳基之比率，就耐熱性之方面而言，較佳為碳數6~10之芳基較多者。因此，於R11為碳數1~4之烷基之情形時，h：j較佳為95：5~0：100，進而較佳為90：10~0：100，最佳為50：50~0：100。另一方面，於R11為碳數6~10之芳基之情形時，於h：j之j之比率過多之情形時，就存在可撓性下降之情況而言，h：j較佳為100：0~50：50，進而較佳為98：2~65：35，最佳為95：5~70：30。 In the above formula (8), the ratio of the alkyl group having 1 to 4 carbon atoms to the aryl group having 6 to 10 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms in terms of heat resistance. More. Therefore, when R 11 is an alkyl group having 1 to 4 carbon atoms, h:j is preferably 95:5 to 0:100, more preferably 90:10 to 0:100, and most preferably 50:50. ~0:100. On the other hand, when R 11 is an aryl group having 6 to 10 carbon atoms, when the ratio of j of h:j is too large, in the case where the flexibility is lowered, h:j is preferably 100:0~50:50, further preferably 98:2~65:35, and most preferably 95:5~70:30.

於本發明之硬化性樹脂組合物中，關於SiH基相對於乙烯基之比，就硬化性及被研削性之方面而言，以莫耳比計較佳為0.5~10，進而較佳為0.9~5，最佳為1~3。(A)成分與(B)成分之調配量只要基於該乙烯基與SiH基之比而決定即可。 In the curable resin composition of the present invention, the ratio of the SiH group to the vinyl group is preferably from 0.5 to 10, more preferably from 0.9 to 0.5 in terms of hardenability and groundability. 5, the best is 1~3. The blending amount of the component (A) and the component (B) may be determined based on the ratio of the vinyl group to the SiH group.

繼而，對作為(C)成分之熱自由基產生劑進行說明。於本發明中，所謂熱自由基產生劑，意指藉由加熱而產生自由基之化合物。自(C)成分產生之自由基發揮使鍵結於SiH基或矽原子之甲基(Si-CH3基)活化，並與鍵結於乙烯基或矽原子之甲基反應的功能。作為熱自由基產生劑，例如可列舉：二異丁醯過氧化物、過氧化新癸酸異丙苯酯、過氧化新癸酸3-羥基-1,1-二甲基丁酯、過氧化二碳酸二丙酯、過氧化二碳酸二異丙酯、過氧化二碳酸二-第三丁酯、過氧化新癸酸1,1,3,3,-四甲基丁基酯、過氧化二碳酸雙(4-第三丁基環己基)酯、過氧化二碳酸雙(2-乙基己基)酯、過氧化新癸酸第三己酯、過氧化新癸酸第三丁酯、過氧化新庚酸第三丁酯、過氧化特戊酸第三庚酯、過氧化特戊酸第三丁酯、過氧化特戊酸第三庚酯、雙(3,5,5-三甲基己醯基)過氧化物、二-十二醯基過氧化物、過氧化2-乙基己酸-1,1,3,3,-四甲基丁基酯、二琥珀酸過氧化物、過氧化2-乙基-己酸-1,1,3,3-四甲基丁基酯、過氧化2-乙基己酸第三戊基酯、過氧化2-乙基己酸第三丁基酯、1,1-二(過氧化第三己基)環己烷、1,1-二(過氧化第三丁基)環己烷、1,1-二 (過氧化第三戊基)環己烷、2,2-雙(4,4-二(過氧化第三丁基)環己基丙烷、過氧化異丙基單碳酸第三己基酯、過氧化異丙基碳酸第三戊基酯、過氧化正辛酸第三戊酯、第三丁基過氧化順丁烯二酸、1,1-二(過氧化第三丁基)環己烷、過氧化-3,5,5-三甲基己酸第三丁酯、過氧化月桂酸第三丁酯、過氧化異丙基單己酸第三丁基酯、過氧化-2-乙基己基碳酸第三戊基酯、過氧化-2-乙基己基單己酸第三丁基酯、過氧化苯甲酸第三己酯、過氧化乙酸第三戊酯、2,5-二甲基-2,5-二(過氧化苯甲醯基)己烷、過氧化乙酸第三丁酯、2,2-二(過氧化第三丁基)丁烷、過氧化苯甲酸第三丁酯、4,4-二(過氧化第三丁基)戊酸丁酯、3,3-二(過氧化第三丁基)丁酸乙酯、雙(2-第三丁基過氧化異丙基)苯、二異丙基過氧化物、二-第三己基過氧化物、2,5二甲基2,5二(過氧化第三丁基)己烷、二-第三丁基過氧化物、過氧化異丁酸第三丁酯、2,5-二甲基-2,5-二(過氧化第三丁基)己烷等有機過氧化物系熱自由基產生劑； 2,2'-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2-甲基丁腈)、1,1'-偶氮雙(環己基-1-甲腈)、2,2'-偶氮雙(N-(2-丙烯基)-2-甲基丙醯胺)、1-((1-氰基-1-甲基乙基)偶氮)甲醯胺、2,2'-偶氮雙(N-丁基-2-甲基丙醯胺)、2,2'-偶氮雙(N-環己基-2-甲基丙醯胺)、2,2'-偶氮雙異丁腈等偶氮化合物系熱自由基產生劑等。 Next, the thermal radical generating agent as the component (C) will be described. In the present invention, the term "thermal radical generating agent" means a compound which generates a radical by heating. The radical generated from the component (C) functions to activate a methyl group (Si-CH 3 group) bonded to the SiH group or the ruthenium atom, and reacts with a methyl group bonded to a vinyl group or a ruthenium atom. Examples of the thermal radical generating agent include diisobutyl hydrazine peroxide, cumene peroxy neodecanoate, 3-hydroxy-1,1-dimethylbutyl peroxy neodecanoate, and peroxidation. Dipropyl dicarbonate, diisopropyl peroxydicarbonate, di-t-butyl peroxydicarbonate, 1,1,3,3,-tetramethylbutyl peroxydecanoate, peroxide Bis(4-tert-butylcyclohexyl) carbonate, bis(2-ethylhexyl) peroxydicarbonate, trihexyl peroxy neodecanoate, tert-butyl peroxy neodecanoate, peroxidation Tert-butyl heptanoate, third heptyl peroxypivalate, tert-butyl peroxypivalate, third heptyl peroxypivalate, bis(3,5,5-trimethylhexyl) Mercapto) peroxide, di-dodecyl peroxide, 2-ethylhexanoic acid-1,1,3,3,-tetramethylbutyl ester, disuccinic acid peroxide, Oxidation of 2-ethyl-hexanoic acid-1,1,3,3-tetramethylbutyl ester, 3-pentyl peroxy 2-ethylhexanoate, tert-butyl 2-ethylhexanoate peroxide Ester, 1,1-di(trihexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(peroxidized third pentylene) Base) cyclohexane, 2,2-bis(4,4-di(t-butylperoxide)cyclohexylpropane, hexyl isopropyl monocarbonate, third pentyl isopropyl carbonate Base ester, third amyl peroxyoctanoate, tert-butyl peroxy maleic acid, 1,1-di(t-butylperoxy)cyclohexane, peroxy-3,5,5- Tert-butyl trimethylhexanoate, tert-butyl peroxy laurate, tert-butyl peroxy isopropyl monohexanoate, third amyl peroxy-2-ethylhexyl carbonate, peroxidation Tert-butyl 2-ethylhexyl monohexanoate, third hexyl peroxybenzoate, third amyl acetate, 2,5-dimethyl-2,5-di (peroxybenzoate) Mercapto) hexane, tert-butyl peroxyacetate, 2,2-di(t-butylperoxy)butane, tert-butyl peroxybenzoate, 4,4-di(peroxidized third) Butyl pentanoate, 3,3-di(t-butylperoxy)butyrate, bis(2-tert-butylperoxyisopropyl)benzene, diisopropyl peroxide, two - a third hexyl peroxide, 2,5-dimethyl 2,5-di(t-butylperoxy)hexane, di-tert-butyl peroxide, peroxidation Organic peroxide-based thermal radical generator such as acid tert-butyl ester or 2,5-dimethyl-2,5-di(t-butylperoxy)hexane; 2,2'-azobis ( 4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2 , 2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexyl-1-carbonitrile), 2,2'-azobis(N-(2-propenyl) )-2-methylpropionamide), 1-((1-cyano-1-methylethyl)azo)carbamamine, 2,2'-azobis(N-butyl-2- Thermal radical generation of azo compounds such as methyl propylamine, 2,2'-azobis(N-cyclohexyl-2-methylpropionamide), 2,2'-azobisisobutyronitrile Agents, etc.

作為(C)成分，就防止本發明之硬化性樹脂組合物之製造時之異常反應或保存穩定性之方面而言，較佳為半衰期溫度較高之化合物，於半衰期溫度過高之化合物之情形時，本發明之硬化性樹脂組合物之硬化溫度變高，作業性變差。因此，作為(C)成分，較佳為1分鐘半衰期溫度為130~250℃、尤其是150~200℃之化合物。 The component (C) is preferably a compound having a high half-life temperature and a compound having a high half-life temperature in terms of preventing an abnormal reaction or storage stability at the time of production of the curable resin composition of the present invention. When the curable resin composition of the present invention has a high curing temperature, workability is deteriorated. Therefore, as the component (C), a compound having a one-minute half-life temperature of 130 to 250 ° C, particularly 150 to 200 ° C is preferable.

作為1分鐘半衰期溫度為150~200℃之有機過氧化物系熱自由基 產生劑，可列舉：1,1-二(過氧化第三丁基)環己烷、1,1-二(過氧化第三戊基)環己烷、2,2-雙(4,4-二(過氧化第三丁基)環己基丙烷、過氧化異丙基單碳酸第三己基酯、過氧化異丙基碳酸第三戊酯、過氧化正辛酸第三戊酯、過氧化第三丁基順丁烯二酸、1,1-二(過氧化第三丁基)環己烷、過氧化-3,5,5-三甲基己酸第三丁基酯、過氧化月桂酸第三丁酯、過氧化異丙基單己酸第三丁基酯、過氧化-2-乙基己基碳酸第三戊酯、過氧化-2-乙基己基單己酸第三丁酯、過氧化苯甲酸第三己酯、過氧化乙酸第三戊酯、2,5-二甲基-2,5-二(過氧化苯甲醯基)己烷、過氧化乙酸第三丁酯、2,2-二(過氧化第三丁基)丁烷、過氧化苯甲酸第三丁酯、4,4-二(過氧化第三丁基)戊酸丁酯、3,3-二(過氧化第三丁基)丁酸乙酯、雙(2-過氧化第三丁基異丙基)苯、二異丙基過氧化物、二-第三己基過氧化物、2,5二甲基2,5二(過氧化第三丁基)己烷、二-第三丁基過氧化物、過氧化異丁酸第三丁酯、2,5-二甲基-2,5-二(過氧化第三丁基)己烷。 Organic peroxide-based thermal radicals with a 1-minute half-life temperature of 150-200 ° C The generating agent may, for example, be a 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(triethoxyperoxy)cyclohexane, 2,2-bis (4,4-) Di(t-butylperoxide)cyclohexylpropane, hexyl isopropyl monocarbonate, third amyl isopropyl peroxide, third amyl peroxyoctanoate, tributyl sulfoxide Butenedioic acid, 1,1-di(t-butylperoxy)cyclohexane, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butylperoxy laurate , tert-butyl isopropyl monohexanoate, third amyl peroxy-2-ethylhexyl carbonate, tert-butyl peroxy-2-ethylhexyl monohexanoate, benzoic acid Trihexyl ester, third amyl acetate, 2,5-dimethyl-2,5-di(benzylidene peroxide)hexane, tert-butyl peroxyacetate, 2,2-di ( Tert-butyl peroxy)butane, tert-butyl peroxybenzoate, butyl 4,4-di(t-butylperoxy)pentanoate, 3,3-di(t-butylperoxide) Ethyl butyrate, bis(2-butylperoxyisopropyl)benzene, diisopropyl peroxide, di-tert-hexyl peroxide, 2,5-dimethyl Base 2,5 2 (t-butylperoxy)hexane, di-tert-butyl peroxide, tert-butyl peroxyisobutyrate, 2,5-dimethyl-2,5-di ( Tributyl butyl peroxide.

作為1分鐘半衰期溫度為150~200℃之偶氮化合物系熱自由基產生劑，可列舉：2,2'-偶氮雙(N-(2-丙烯基)-2-甲基丙醯胺)、1-((1-氰基-1-甲基乙基)偶氮)甲醯胺、2,2'-偶氮雙(N-丁基-2-甲基丙醯胺)、2,2'-偶氮雙(N-環己基-2-甲基丙醯胺)。 Examples of the azo compound-based thermal radical generator having a one-minute half-life temperature of 150 to 200 ° C include 2,2'-azobis(N-(2-propenyl)-2-methylpropionamide). , 1-((1-cyano-1-methylethyl)azo)carbamamine, 2,2'-azobis(N-butyl-2-methylpropanamide), 2,2 '-Azobis(N-cyclohexyl-2-methylpropanamide).

(C)成分之調配量根據(C)成分之種類或硬化溫度而有所不同，若過少，則本發明之硬化性樹脂組合物之硬化變不充分，又，若過多，則存在不僅無法獲得與調配量相稱之增量效果，反而對硬化物之物性造成不良影響之情況，因此相對於(A)成分與(B)成分之合計量100質量份，較佳為0.001~5質量份，更佳為0.05~3質量份，進而較佳為0.1~2質量份，最佳為0.1~1.5質量份。 The amount of the component (C) is different depending on the type of the component (C) or the curing temperature. When the amount is too small, the curing of the curable resin composition of the present invention is insufficient, and if it is too large, it is not only impossible to obtain. The incremental effect commensurate with the blending amount adversely affects the physical properties of the cured product. Therefore, it is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of the components (A) and (B). It is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, most preferably 0.1 to 1.5 parts by mass.

繼而，對作為(D)成分之上述無機填料進行說明。於本發明中，無機填料分為白色無機顏料與無機填充材，所謂白色無機顏料，係指 於可見區域不具有特定之吸收且折射率較大之無機填料，所謂無機填充材，意指除白色無機顏料以外之無機填料。作為白色無機顏料，可列舉：氧化鈦、鈦酸鉀、鈦酸鈣、鈦酸鋇、氧化鋯、氧化鋅、氧化鎂、氧化銻、氧化鍶、氧化鈮、氧化鈹、氮化硼、硫化鋅、硫酸鋇等。又，作為無機填充材，可列舉：熔融二氧化矽、熔融球狀二氧化矽、結晶性二氧化矽、膠體二氧化矽、煙熏二氧化矽、二氧化矽凝膠等二氧化矽類；氧化鋁、氧化鐵、三氧化銻、氮化矽、氮化鋁、氮化硼、碳化矽、碳酸鈣、矽酸鈣、碳酸鎂、碳酸鋇、雲母、蒙脫石、高嶺土、滑石、石墨、碳黑等。作為白色無機顏料，就光反射率之方面而言，較佳為氧化鈦。氧化鈦就結晶構造而言分類為金紅石型、銳鈦礦型、板鈦礦型，就硬化物之熱穩定性或光穩定性之方面而言，較佳為金紅石型。作為無機填充材，就本發明之樹脂組合物之流動性與硬化物之被研削性之方面而言，較佳為二氧化碳。無機填料可僅使用1種，亦可將2種以上組合使用。於在反射塗佈材用途中使用本發明之樹脂組合物之情形時，較佳為使用白色無機顏料作為(D)成分製成白色硬化性樹脂組合物。 Next, the above inorganic filler as the component (D) will be described. In the present invention, the inorganic filler is classified into a white inorganic pigment and an inorganic filler, and the so-called white inorganic pigment refers to An inorganic filler which does not have a specific absorption in the visible region and has a large refractive index, and an inorganic filler refers to an inorganic filler other than the white inorganic pigment. Examples of the white inorganic pigment include titanium oxide, potassium titanate, calcium titanate, barium titanate, zirconium oxide, zinc oxide, magnesium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, boron nitride, and zinc sulfide. , barium sulfate and the like. Further, examples of the inorganic filler include cerium oxide such as molten cerium oxide, molten spherical cerium oxide, crystalline cerium oxide, colloidal cerium oxide, smoked cerium oxide, and cerium oxide gel; Alumina, iron oxide, antimony trioxide, antimony nitride, aluminum nitride, boron nitride, niobium carbide, calcium carbonate, calcium niobate, magnesium carbonate, barium carbonate, mica, montmorillonite, kaolin, talc, graphite, Carbon black and so on. As the white inorganic pigment, titanium oxide is preferred in terms of light reflectance. Titanium oxide is classified into a rutile type, an anatase type, and a brookite type in terms of a crystal structure, and is preferably a rutile type in terms of thermal stability or light stability of the cured product. The inorganic filler is preferably carbon dioxide in terms of the fluidity of the resin composition of the present invention and the groundability of the cured product. The inorganic filler may be used alone or in combination of two or more. In the case where the resin composition of the present invention is used in the use of a reflective coating material, it is preferred to use a white inorganic pigment as the component (D) to prepare a white curable resin composition.

關於(D)成分之無機填料之粒徑，就被研削性之方面而言，以平均粒徑計較佳為0.01~5μm，更佳為0.05~3μm，最佳為0.1~1μm。再者，平均粒徑可以藉由雷射光繞射法所得之粒度分佈測定中之質量平均值D50(或中值粒徑)之形式而求出。 The particle diameter of the inorganic filler of the component (D) is preferably from 0.01 to 5 μm, more preferably from 0.05 to 3 μm, most preferably from 0.1 to 1 μm, in terms of the grinding property. Further, the average particle diameter can be obtained by the mass average value D 50 (or median diameter) in the particle size distribution measurement by the laser light diffraction method.

又，關於(D)成分之調配量，就被研削性之方面而言，較佳為相對於本發明之組合物(其中，(D)成分除外)100質量份為40~500質量份，進而較佳為60~300質量份。 In addition, the blending amount of the component (D) is preferably 40 to 500 parts by mass based on 100 parts by mass of the composition of the present invention (excluding the component (D)). It is preferably 60 to 300 parts by mass.

關於本發明之硬化性樹脂組合物，就提昇交聯密度從而提昇硬化物之被研削性之方面而言，較佳為進而含有作為(E)成分之下述通式(9)所表示之矽氧烷化合物。 In the curable resin composition of the present invention, in order to increase the crosslink density and improve the groundability of the cured product, it is preferable to further contain the following formula (9) as the component (E). Oxyalkane compound.

(式中，R12及R13各自獨立地表示碳數6~10之芳基，k表示1~5之數) (wherein R 12 and R 13 each independently represent an aryl group having 6 to 10 carbon atoms, and k represents a number of 1 to 5)

於上述通式(9)中，R12及R13各自獨立地表示碳數6~10之芳基。作為碳數6~10之芳基，可列舉由通式(1)之R1所例示之碳數6~10之芳基。作為R12及R13，就被研削性之提昇效果較高而言，較佳為苯基。k表示1~5之數，就被研削性之提昇效果較高而言，較佳為1~2之數，進而較佳為1之數。於通式(9)所表示之鏈狀矽氧烷化合物之中，作為較佳之化合物，可列舉：1,1,5,5-四甲基-3,3-二苯基-1,5-二乙烯基三矽氧烷、1,1,7,7-四甲基-3,3,5,5-四苯基-1,7-二乙烯基三矽氧烷等。 In the above formula (9), R 12 and R 13 each independently represent an aryl group having 6 to 10 carbon atoms. Examples of the aryl group having 6 to 10 carbon atoms include an aryl group having 6 to 10 carbon atoms exemplified by R 1 of the formula (1). R 12 and R 13 are preferably a phenyl group because of the high effect of improving the grinding property. k represents a number of 1 to 5, and is preferably a number of 1 to 2, and more preferably 1 in terms of a higher effect of improving the grinding property. Among the chain siloxane compounds represented by the formula (9), preferred compounds are 1,1,5,5-tetramethyl-3,3-diphenyl-1,5- Divinyltrioxane, 1,1,7,7-tetramethyl-3,3,5,5-tetraphenyl-1,7-divinyltrioxane, and the like.

於作為本發明之(E)成分之上述通式(9)所表示之矽氧烷化合物之調配量過少之情形時，被研削性之提昇效果並不充分，又，於過多之情形時，交聯密度過度提昇，反而存在被研削性下降之情形，(E)成分之調配量較佳為相對於(A)成分100質量份為20~80質量份，進而較佳為30~70質量份。於調配(E)成分之情形時，只要基於上述乙烯基與SiH基之比決定(B)成分之量即可。 When the amount of the oxoxane compound represented by the above formula (9) which is the component (E) of the present invention is too small, the effect of improving the grinding property is insufficient, and in the case of too much, When the joint density is excessively increased, the amount of the component (E) is preferably 20 to 80 parts by mass, and more preferably 30 to 70 parts by mass, based on 100 parts by mass of the component (A). In the case of blending the component (E), the amount of the component (B) may be determined based on the ratio of the vinyl group to the SiH group.

關於本發明之硬化性樹脂組合物，就提昇硬化物與基材之密接性而言，較佳為進而含有具有異三聚氰酸結構之化合物。作為具有異三聚氰酸結構之化合物，例如除上述通式(5)所表示之化合物以外，可列舉：異三聚氰酸、1,3,5-三縮水甘油基異三聚氰酸、1-烯丙基- 3,5-二縮水甘油基異三聚氰酸、三(2-羥基乙基)異三聚氰酸、三(2,3-二羥基丙基)異三聚氰酸等。 The curable resin composition of the present invention preferably further contains a compound having an isomeric isocyanate structure in order to improve the adhesion between the cured product and the substrate. Examples of the compound having an isomeric cyanuric acid structure include, for example, isomeric cyanuric acid and 1,3,5-triglycidyl isocyanuric acid, in addition to the compound represented by the above formula (5). 1-allyl- 3,5-diglycidyl isocyanuric acid, tris(2-hydroxyethyl)isocyanuric acid, tris(2,3-dihydroxypropyl)isocyanuric acid, and the like.

本發明之硬化性樹脂組合物除此以外，可於無損本發明之目的及效果之範圍內添加抗氧化劑、紫外線吸收劑、脫模劑、抗靜電劑、鉑系矽氫化觸媒、硬化延遲劑、偶合劑、阻燃劑、有機溶劑等。 In addition to the curable resin composition of the present invention, an antioxidant, an ultraviolet absorber, a mold release agent, an antistatic agent, a platinum-based hydrogenation catalyst, and a hardening retarder may be added to the extent that the object and effect of the present invention are not impaired. , coupling agents, flame retardants, organic solvents, and the like.

本發明之硬化性樹脂組合物之流動性優異，可於塗佈於基板等對象物後加熱使其硬化。作為將本發明之硬化性樹脂組合物塗佈於對象材料之方法，例如可列舉：旋轉塗佈法、浸漬塗佈法、刮塗法、輥式塗佈法、噴塗法、狹縫式塗佈法、網版印刷法等。 The curable resin composition of the present invention is excellent in fluidity, and can be heated and cured after being applied to an object such as a substrate. Examples of the method of applying the curable resin composition of the present invention to a target material include a spin coating method, a dip coating method, a knife coating method, a roll coating method, a spray coating method, and a slit coating method. Law, screen printing method, etc.

本發明之硬化性樹脂組合物可藉由進行加熱而使其硬化，從而可製成硬化物。該硬化反應根據(C)成分之種類而有所不同，就作業性之方面而言，較佳為80~350℃，更佳為100~250℃。硬化時間較佳為2~120分鐘，更佳為20~60分鐘。 The curable resin composition of the present invention can be cured by heating to form a cured product. The hardening reaction varies depending on the type of the component (C), and is preferably from 80 to 350 ° C, more preferably from 100 to 250 ° C in terms of workability. The hardening time is preferably from 2 to 120 minutes, more preferably from 20 to 60 minutes.

本發明之硬化性樹脂組合物之硬化物之耐熱性、耐光性、耐龜裂性、著色性等各種物性優異，例如可用作密封材、模具材、塗佈材、絕緣材、反射材，尤其是可較佳地用作LED(Light Emitting Diode，發光二極管)等發光元件之反射材。 The cured product of the curable resin composition of the present invention is excellent in various physical properties such as heat resistance, light resistance, crack resistance, and coloring property, and can be used, for example, as a sealing material, a mold material, a coating material, an insulating material, and a reflective material. In particular, it can be preferably used as a reflective material for a light-emitting element such as an LED (Light Emitting Diode).

又，本發明之硬化性樹脂組合物之硬化物之被研削性優異，因此可藉由如下方法等進行研削：使用具有於旋轉板之半徑方向配置有複數個金剛石製等之硬質刀之硬質旋轉刀之研削裝置的方法，或使用砂磨機、砂帶、研磨機、平面研削盤、硬質研磨粒成形品等之方法。關於本發明之硬化性樹脂組合物之硬化物，若使用研削裝置，則使該硬質旋轉刀一面旋轉一面沿著被固定支持之佈線基板之上表面移動，藉此可使上表面平坦化。又，作為研磨之方法，可列舉藉由砂帶、拋光研磨等而輕輕地研磨之方法。 Moreover, since the cured product of the curable resin composition of the present invention is excellent in the machinability, it can be ground by the following method: a hard rotation having a hard knife having a plurality of diamonds or the like disposed in the radial direction of the rotating plate is used. A method of grinding a knife, or a method using a sand mill, a belt, a grinder, a plane grinding disc, a hard abrasive pellet, or the like. In the cured product of the curable resin composition of the present invention, when the grinding device is used, the hard rotating blade is moved along the upper surface of the fixed supporting wiring substrate while rotating, whereby the upper surface can be flattened. Further, as a method of polishing, a method of gently grinding by a belt, polishing, or the like can be mentioned.

實施例 Example

以下，藉由實施例進一步說明本發明，但本發明並不受該等實施例限定。再者，只要無特別限定，則實施例中之「份」或「%」係以質量為基準者。 Hereinafter, the present invention will be further illustrated by the examples, but the present invention is not limited by the examples. Further, the "parts" or "%" in the examples are based on mass unless otherwise specified.

[合成例1](A)成分：化合物A1之合成 [Synthesis Example 1] Component (A): Synthesis of Compound A1

於具備氮氣導入管、溫度計、冷卻管及攪拌裝置之反應容器中添加2,4,6,8-四甲基環四矽氧烷48.0g(0.20mol)、二乙烯基苯26.0g(0.20mol)、作為觸媒之鉑-二乙烯基四甲基二矽氧烷錯合物0.002g及作為溶劑之甲苯150g，於105℃下反應2小時。其後，於70℃下將溶劑減壓蒸餾去除而獲得化合物A1。化合物A1之藉由GPC(Gel Permeation Chromatograph，凝膠滲透層析)分析求出之重量平均分子量為10,000，藉由H-NMR(Nuclear Magnetic Resonance，核磁共振)分析求出之每1g之SiH基之含量為5.40mmol。 2,4,6,8-tetramethylcyclotetraoxane 48.0 g (0.20 mol) and divinylbenzene 26.0 g (0.20 mol) were added to a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, a cooling tube and a stirring device. ), 0.002 g of a platinum-divinyltetramethyldioxane complex as a catalyst and 150 g of toluene as a solvent were reacted at 105 ° C for 2 hours. Thereafter, the solvent was distilled off under reduced pressure at 70 ° C to obtain Compound A1. The weight average molecular weight of the compound A1 determined by GPC (Gel Permeation Chromatograph) analysis was 10,000, and each 1 g of SiH group was determined by H-NMR (Nuclear Magnetic Resonance) analysis. The content was 5.40 mmol.

[合成例2](A)成分：化合物A2之合成 [Synthesis Example 2] Component (A): Synthesis of Compound A2

除將1,4-二乙烯基苯之調配量自26.0g(0.20mol)變更為18.2g(0.14mol)以外，進行與合成例1相同之操作，而獲得化合物A2。化合物A2之藉由GPC分析求出之重量平均分子量為14000，藉由H-NMR分析求出之每1g之SiH基之含量為7.85mmol。 The same procedure as in Synthesis Example 1 was carried out except that the amount of the 1,4-divinylbenzene was changed from 26.0 g (0.20 mol) to 18.2 g (0.14 mol) to obtain the compound A2. The weight average molecular weight of the compound A2 determined by GPC analysis was 14,000, and the content per 1 g of the SiH group determined by H-NMR analysis was 7.85 mmol.

[合成例3](A)成分：化合物A3之合成 [Synthesis Example 3] Component (A): Synthesis of Compound A3

除使用1,4-雙(二甲基乙烯基矽烷基)苯49.3g(0.20mol)代替1,4-二乙烯基苯26.0g(0.20mol)以外，進行與合成例1相同之操作，而獲得化合物A3。化合物A3之藉由GPC分析求出之重量平均分子量為10,000，藉由H-NMR分析求出之每1g之SiH基之含量為2.27mmol。 The same operation as in Synthesis Example 1 was carried out except that 49.3 g (0.20 mol) of 1,4-bis(dimethylvinyldecyl)benzene was used instead of 26.0 g (0.20 mol) of 1,4-divinylbenzene. Compound A3 was obtained. The weight average molecular weight of the compound A3 determined by GPC analysis was 10,000, and the content per 1 g of the SiH group determined by H-NMR analysis was 2.27 mmol.

[合成例4](A)成分：化合物A4之合成 [Synthesis Example 4] (A) component: Synthesis of Compound A4

除使用異氰脲酸1,3,5-三烯丙酯29.9g(0.12mol)代替1,4-二乙烯基苯26.0g(0.20mol)以外，進行與合成例1相同之操作，而獲得化合物A3。化合物A3之藉由GPC分析求出之重量平均分子量為8,000，藉由 H-NMR分析求出之每1g之SiH基之含量為5.65mmol。 Except that 29.9 g (0.12 mol Compound A3. The weight average molecular weight of the compound A3 determined by GPC analysis is 8,000. The content per 1 g of the SiH group determined by H-NMR analysis was 5.65 mmol.

[合成例5](F)成分：化合物F2之合成 [Synthesis Example 5] (F) component: Synthesis of compound F2

依據WO2011/155459號公報之合成例1之方法(1/10之比例)，使用苯基三甲氧基矽烷19.8g(0.1mol)、乙烯基三甲氧基矽烷7.4g(0.05mol)、甲基三甲氧基矽烷6.8g(0.05mol)及二甲基二甲氧基矽烷3.0g(0.025mol)而獲得含矽之聚合物之化合物F2(乙烯基含量：1.05mmol/g)。 According to the method of Synthesis Example 1 (1/10 ratio) of WO2011/155459, phenyltrimethoxydecane 19.8 g (0.1 mol), vinyltrimethoxydecane 7.4 g (0.05 mol), methyltrimethyl group were used. 6.8 g (0.05 mol) of oxoxane and 3.0 g (0.025 mol) of dimethyldimethoxydecane were used to obtain a compound F2 (vinyl content: 1.05 mmol/g) of a ruthenium-containing polymer.

[實施例1~8及比較例1~6]硬化性樹脂組合物之製備及評價 [Examples 1 to 8 and Comparative Examples 1 to 6] Preparation and Evaluation of Curable Resin Composition

使用以上之合成例中獲得之各化合物及下述化合物，以[表1]所示之組成調配(A)成分~(F)成分等，而獲得本發明及比較用之硬化性樹脂組合物。分別利用以下所示之方法對所獲得之硬化性樹脂組合物進行肖氏硬度、總反射率、被研削性及密接性之評價。 Using the respective compounds obtained in the above Synthesis Examples and the following compounds, the components (A) to (F) are blended in the composition shown in [Table 1] to obtain the curable resin composition of the present invention and comparative use. The obtained curable resin composition was evaluated for Shore hardness, total reflectance, groundability, and adhesion by the methods described below.

<硬化性樹脂組合物之其他原料> <Other raw materials of curable resin composition>

(B)成分 (B) component

化合物B1： Compound B1:

(乙烯基含量：0.173mmol/g) (Vinyl content: 0.173 mmol/g)

化合物B2： Compound B2:

(乙烯基含量：0.177mmol/g) (Vinyl content: 0.177 mmol/g)

(C)成分 (C) component

C1：2,5-二甲基-2,5-二(過氧化第三丁基)己烷 C1: 2,5-dimethyl-2,5-di(t-butylperoxy)hexane

(D)成分 (D) component

D1：金紅石型氧化鈦(平均粒徑0.25μm) D1: rutile type titanium oxide (average particle size 0.25 μm)

D2：球狀二氧化碳(平均粒徑5μm) D2: spherical carbon dioxide (average particle size 5 μm)

D3：氧化鋅(平均粒徑10μm) D3: zinc oxide (average particle size 10 μm)

(E)成分 (E) component

化合物E1：1,1,5,5-四甲基-3,3-二苯基-1,5-二乙烯基三矽氧烷 (乙烯基含量：5.20mmol/g) Compound E1:1,1,5,5-tetramethyl-3,3-diphenyl-1,5-divinyltrioxane (Vinyl content: 5.20 mmol/g)

混合物E2：1,1,5,5-四甲基-3,3-二苯基-1,5-二乙烯基三矽氧烷與1,1,7,7-四甲基-3,3,5,5-四苯基-1,7-二乙烯基三矽氧烷之質量比為2：1的混合物(乙烯基含量：5.00mmol/g) Mixture E2: 1,1,5,5-tetramethyl-3,3-diphenyl-1,5-divinyltrioxane with 1,1,7,7-tetramethyl-3,3 a mixture of 5,5-tetraphenyl-1,7-divinyltrioxane in a mass ratio of 2:1 (vinyl content: 5.00 mmol/g)

(F)其他 (F) other

F1：鉑-二乙烯基四甲基二矽氧烷錯合物 F1: platinum-divinyltetramethyldioxane complex

F3：2,4,6,8-四甲基-2,4,6,8-四乙烯基環四矽氧烷(乙烯基含量：2.09mmol/g) F3: 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetraoxane (vinyl content: 2.09 mmol/g)

F4：丙二醇單甲醚乙酸酯(用作溶劑) F4: propylene glycol monomethyl ether acetate (used as a solvent)

<肖氏硬度> <Shore hardness>

[試驗片之製作] [Production of test piece]

於直徑10cm之玻璃培養皿中以硬化後之厚度成為10mm之方式流入實施例1~8或比較例1~5之硬化性樹脂組合物，於150℃之恆溫槽中硬化1小時，將硬化物自容器取出而製備試驗片。 The curable resin composition of Examples 1 to 8 or Comparative Examples 1 to 5 was poured into a glass petri dish having a diameter of 10 cm so as to have a thickness of 10 mm after hardening, and hardened in a thermostat at 150 ° C for 1 hour to cure the cured product. A test piece was prepared by taking out from the container.

[硬度測定方法] [Method of measuring hardness]

依據JIS Z2246(肖氏硬度試驗-試驗方法)測定肖氏硬度。將結果示於[表2]。 The Shore hardness was measured in accordance with JIS Z2246 (Shore hardness test - test method). The results are shown in [Table 2].

<總反射率> <Total reflectance>

利用紫外可見分光光度計對肖氏硬度之測定所使用之試驗片測定300~800nm下之總反射率。再者，測定係使用積分球。將結果示於[表2]。 The total reflectance at 300 to 800 nm was measured using a UV-visible spectrophotometer for the test piece used for the measurement of Shore hardness. Furthermore, the measurement system uses an integrating sphere. The results are shown in [Table 2].

<被研削性> <grinding>

[試驗片之製作] [Production of test piece]

使用棒式塗佈機於以寬度1mm、長度20mm、間隔1mm形成有5條銅線圖案之玻璃環氧基板上以膜厚成為100μm之方式塗佈實施例1~8及比較例1~5之硬化性組合物。將該基板於150℃之恆溫槽中加熱1小時藉此製備試驗片。 Coatings of Examples 1 to 8 and Comparative Examples 1 to 5 were applied to a glass epoxy substrate having five copper wire patterns formed by a bar coater at a width of 1 mm, a length of 20 mm, and a gap of 1 mm so as to have a film thickness of 100 μm. A curable composition. The test piece was prepared by heating the substrate in a thermostat at 150 ° C for 1 hour.

[被研削性評價方法] [Planting evaluation method]

利用P220之研磨紙研磨試驗片之表面直至露出銅線圖案，藉由銅線圖案附近之樹脂部之狀態並藉由下述基準評價被研削性。將結果 示於[表2]。 The surface of the test piece was polished with a polishing paper of P220 until the copper wire pattern was exposed, and the ground property was evaluated by the state of the resin portion in the vicinity of the copper wire pattern by the following criteria. Will result Shown in [Table 2].

．評價基準 . Evaluation basis

○：未見到凹部，被研削性優異。 ○: No concave portion was observed, and the grinding property was excellent.

△：略微見到凹部，被研削性稍差。 △: The concave portion was slightly observed, and the grinding property was slightly inferior.

×：凹部較多，被研削性較差。 ×: There are many concave portions, and the grinding property is poor.

<密接性> <Adhesiveness>

[試驗片之製作] [Production of test piece]

使用棒式塗佈機於寬度50mm、長度100mm及厚度0.3mm之銅板上以膜厚成為100μm之方式塗佈實施例1~8及比較例1~5之硬化性組合物後，於150℃之恆溫槽中加熱1小時，藉此製備試驗片。將結果示於[表2]。 The curable compositions of Examples 1 to 8 and Comparative Examples 1 to 5 were applied to a copper plate having a width of 50 mm, a length of 100 mm, and a thickness of 0.3 mm by a bar coater at a film thickness of 100 μm, and then at 150 ° C. The test piece was prepared by heating in a thermostat for 1 hour. The results are shown in [Table 2].

[密接性評價方法] [Adhesive evaluation method]

於試驗片之硬化膜之中央部分以1mm間隔添加縱6條、橫6條之格子狀交叉切割。將該試驗片壓抵於外徑140mm之硬質氯乙烯管使交叉切割部分彎曲，藉由有無交叉切割部分之剝離等，並藉由下述基準評價密接性。將結果示於[表2]。 In the central portion of the cured film of the test piece, six vertical and six horizontal cross-cuts were added at intervals of 1 mm. The test piece was pressed against a hard vinyl chloride tube having an outer diameter of 140 mm to bend the cross-cut portion, and the adhesion was evaluated by the following criteria with or without peeling of the cross-cut portion. The results are shown in [Table 2].

．評價基準 . Evaluation basis

○：未見到剝離，密接性優異。 ○: No peeling was observed, and the adhesion was excellent.

△：於1~10個部位見到剝離，密接性稍差。 △: Peeling was observed in 1 to 10 places, and the adhesion was slightly inferior.

×：於11個部位以上見到剝離，密接性較差。 ×: Peeling was observed at 11 or more places, and the adhesion was poor.

Claims (4)

一種硬化性樹脂組合物，其含有：作為(A)成分的下述通式(1)所表示之基及/或下述通式(2)所表示之基由自下述通式(6)及(7)中之任一者所表示之化合物中去除乙烯基所得之殘基連結而成的矽氧烷化合物、作為(B)成分之下述通式(8)所表示之鏈狀矽氧烷化合物、作為(C)成分之熱自由基產生劑、及作為(D)成分之無機填料，其中SiH基相對於乙烯基之比，以莫耳比計為0.5~10，相對於(A)成分與(B)成分之合計量100質量份，(C)成分之調配量為0.001~5質量份，相對於(A)成分、(B)成分與(C)成分之合計量100質量份，(D)成分之調配量為40~500質量份， (式中，R1表示碳數1~4之烷基或碳數6~10之芳基，a表示2~5之數；其中，R1可為全部相同之基，亦可為不同之基) (式中，b表示a-b+1成為0~4之數之2~6之數，R1及a與上述 通式(1)同義) (式中，R3~R5各自獨立地表示碳數1~4之烷基或碳數6~10之芳基，e表示1或2之數，f及g各自獨立地表示0~6之數) (式中R6及R7各自獨立地表示碳數1~4之烷基或碳數6~10之芳基) (式中，R8及R9各自獨立地表示碳數1~4之烷基，R10表示碳數6~10之芳基，R11表示碳數1~4之烷基或碳數6~10之芳基，h及j為將通式(8)所表示之鏈狀矽氧烷化合物之質量平均分子量設為1000~100萬之數)。 A curable resin composition containing a group represented by the following formula (1) as the component (A) and/or a group represented by the following formula (2) derived from the following formula (6) And a oxoxane compound obtained by linking a residue obtained by removing a vinyl group to a compound represented by any one of the above (7), and a chain oxime represented by the following formula (8) as a component (B) An alkane compound, a thermal radical generator as the component (C), and an inorganic filler as the component (D), wherein the ratio of the SiH group to the vinyl group is 0.5 to 10 in terms of a molar ratio, relative to (A) 100 parts by mass of the total amount of the component (B), and the amount of the component (C) is 0.001 to 5 parts by mass, and 100 parts by mass based on the total amount of the component (A) and the component (B) and the component (C). The amount of the component (D) is 40 to 500 parts by mass. (wherein R 1 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and a represents a number of 2 to 5; wherein R 1 may be all the same groups or may be different groups. ) (where b represents a number of 2 to 6 in which a-b+1 becomes 0 to 4, and R 1 and a are synonymous with the above formula (1)) (wherein R 3 to R 5 each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and e represents a number of 1 or 2, and f and g each independently represent 0 to 6 number) (wherein R 6 and R 7 each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms) (wherein R 8 and R 9 each independently represent an alkyl group having 1 to 4 carbon atoms, R 10 represents an aryl group having 6 to 10 carbon atoms, and R 11 represents an alkyl group having 1 to 4 carbon atoms or a carbon number of 6~ The aryl group of 10, h and j are the mass average molecular weight of the chain siloxane compound represented by the formula (8) of 1,000 to 1,000,000. 如請求項1之硬化性樹脂組合物，其進而含有作為(E)成分之下述通式(9)所表示之矽氧烷化合物， (式中，R12及R13各自獨立地表示碳數6~10之芳基，k表示1~5之數)。 The curable resin composition of claim 1, further comprising a oxoxane compound represented by the following formula (9) as the component (E), (wherein R 12 and R 13 each independently represent an aryl group having 6 to 10 carbon atoms, and k represents a number of 1 to 5). 如請求項1或2之硬化性樹脂組合物，其中作為(D)成分之無機填料為白色無機顏料。 The curable resin composition of claim 1 or 2, wherein the inorganic filler as the component (D) is a white inorganic pigment. 一種反射塗佈材，其係將如請求項3之硬化性樹脂組合物硬化所得者。 A reflective coating material obtained by hardening the curable resin composition of claim 3.
TW103125380A 2013-07-24 2014-07-24 Curable resin composition TWI631169B (en)

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