TW201605934A - Organopolysiloxane and method of producing thereof - Google Patents

Organopolysiloxane and method of producing thereof Download PDF

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TW201605934A
TW201605934A TW104119855A TW104119855A TW201605934A TW 201605934 A TW201605934 A TW 201605934A TW 104119855 A TW104119855 A TW 104119855A TW 104119855 A TW104119855 A TW 104119855A TW 201605934 A TW201605934 A TW 201605934A
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organopolyoxane
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森田好次
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道康寧東麗股份有限公司
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Abstract

An organopolysiloxane represented by the average unit formula: (R1SiO3/2)a(R1 2R2SiO1/2)b(O1/2SiR1 2R3-X-R3R1 2SiO1/2)c (R1 is a C1-12 alkyl group, C6-20 aryl group, or C7-20 aralkyl group; R2 is a C2-12 alkenyl group; R3 is a C2-12 alkylene group; however, at least 10 mol% of the total of R1-R3 is C6-20 aryl groups; X is a siloxy group or silphenylene group; a is a number of 0.65-0.90, b is a number of 0.04-0.29, c is a number of 0.01-0.07, and a + b + c = 1.00) in which organopolysiloxane resin blocks are linked by the abovementioned siloxy groups or silphenylene groups. This organopolysiloxane has a high refractive index, high transparency, and excellent handling properties.

Description

有機聚矽氧烷及其製造方法 Organic polyoxyalkylene and manufacturing method thereof

本發明係關於一種有機聚矽氧烷樹脂嵌段由矽烷氧基或矽伸苯基連結之新穎之有機聚矽氧烷、及其製造方法。 The present invention relates to a novel organopolyoxane in which an organopolyoxane resin block is bonded by a decyloxy group or a fluorenylphenyl group, and a process for producing the same.

專利文獻1~3中記載有如下之有機聚矽氧烷：其包含通式：-(R2SiO)m-(式中，R為不具有不飽和脂肪族鍵之未經取代或經取代之一價烴基，m為1以上之整數)所表示之直鏈狀有機聚矽氧烷嵌段；及包含通式：R'3SiO1/2(式中，R'為未經取代或經取代之一價烴基、烷氧基、或羥基)所表示之M單元、及式：SiO4/2所表示之Q單元及/或式：R'SiO3/2(式中，R'與上述相同)所表示之T單元，且全部R'之至少2個為烯基的有機聚矽氧烷樹脂嵌段。 Patent Documents 1 to 3 disclose organic polyoxoxanes containing the formula: -(R 2 SiO) m - (wherein R is unsubstituted or substituted without an unsaturated aliphatic bond) a linear organopolyoxane block represented by a monovalent hydrocarbon group, m is an integer of 1 or more; and a general formula: R' 3 SiO 1/2 (wherein R' is unsubstituted or substituted M unit represented by a monovalent hydrocarbon group, alkoxy group, or a hydroxyl group, and a Q unit represented by SiO 4/2 and/or a formula: R'SiO 3/2 (wherein R' is the same as above The T unit represented by the above, and at least two of all R' are an alkenyl organopolysiloxane resin block.

專利文獻1~3中不關心高折射率、高透明性之有機聚矽氧烷。又，專利文獻1~3中存在如下問題：為了將乙烯基二有機氯矽烷(M單元源)、有機三氯矽烷(T單元源)及/或四氯矽烷(Q單元源)、及式：Cl(R2SiO)m-1SiR2Cl(式中，R、m與上述相同)所表示之α,ω-二氯二有機聚矽氧烷共水解並聚合而製備有機聚矽氧烷，由於各自之水解性能相異，故而較難控制有機聚矽氧烷之分子結構，將直鏈狀二有機聚矽氧烷嵌段引入有機聚矽氧烷樹脂嵌段中，無法生成上述有機聚矽氧烷樹脂嵌段由上述直鏈狀二有機聚矽氧烷嵌段連結而成的有機聚矽氧烷， 或作為α,ω-二氯二有機聚矽氧烷之水解物的α,ω-羥基二有機聚矽氧烷彼此發生縮聚合，而生成不與有機聚矽氧烷樹脂嵌段鍵結之未反應之二有機聚矽氧烷。 Patent Documents 1 to 3 do not care about organic polyoxyalkylene having high refractive index and high transparency. Further, in Patent Documents 1 to 3, there are problems in that vinyl diorganochlorosilane (M unit source), organic trichlorodecane (T unit source), and/or tetrachlorodecane (Q unit source), and the formula are as follows: An organopolyoxane is prepared by co-hydrolyzing and polymerizing α,ω-dichlorodiorganopolysiloxane represented by Cl(R 2 SiO) m-1 SiR 2 Cl (wherein R and m are the same as above). Since the respective hydrolysis properties are different, it is difficult to control the molecular structure of the organopolyoxane, and the linear diorganopolyoxyalkylene block is introduced into the organopolyoxane resin block, and the above organic polyfluorene cannot be formed. An organopolysiloxane having a block of a linear diorganopolyoxyalkylene block as described above, or an α,ω- as a hydrolyzate of α,ω-dichlorodiorganopolyoxyalkylene oxide The hydroxydiorganopolyoxyalkylenes are polycondensed with each other to form an unreacted diorganopolyoxyalkylene which is not bonded to the block of the organopolyoxane resin.

另一方面，專利文獻4中記載有溶劑可溶性之有機聚矽氧烷，其係一分子中至少具有2個烯基之有機聚矽氧烷樹脂與分子鏈兩末端經鍵結於矽原子之氫原子封阻之直鏈狀二有機聚矽氧烷進行矽氫化反應而成者。然而，存在藉此所獲得之有機聚矽氧烷之折射率或透明性較低、或黏稠且操作作業性較差之問題。 On the other hand, Patent Document 4 describes a solvent-soluble organic polyoxane which is an organic polydecane resin having at least two alkenyl groups in one molecule and hydrogen bonded to a ruthenium atom at both ends of the molecular chain. Atomically blocked linear diorganopolyoxyalkylene is a hydrogenation reaction. However, there is a problem in that the obtained organic polysiloxane has a low refractive index or transparency, or is viscous and has poor workability.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開2007-063538號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-063538

[專利文獻2]日本專利特開2010-106243號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-106243

[專利文獻3]日本專利特開2012-041428號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2012-041428

[專利文獻4]日本專利特開2009-242627號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-242627

本發明之目的在於提供一種有機聚矽氧烷樹脂嵌段由矽烷氧基或矽伸苯基連結而成、且折射率高、透明性高、操作性良好之有機聚矽氧烷、及其製造方法。 An object of the present invention is to provide an organopolysiloxane having a high refractive index, high transparency, and good handleability, which is obtained by linking a polyalkylene oxide resin block to a decyloxy group or a fluorenylphenyl group, and a process for producing the same. method.

本發明之有機聚矽氧烷之特徵在於：其係平均單元式：(R1SiO3/2)a(R1 2R2SiO1/2)b(O1/2SiR1 2R3-X-R3R1 2SiO1/2)c{式中，R1為相同或不同之碳數1~12之烷基、碳數6~20之芳基、或碳數7~20之芳烷基，R2為碳數2~12之烯基，R3為相同或不同之碳數2~12之伸烷基，其中，R1~R3之合計之至少10莫耳%為碳數6~20之芳基，X為通式(I)：-SiR4 2O(R4 2SiO)nSiR4 2- The organopolyoxane of the present invention is characterized in that it has an average unit formula: (R 1 SiO 3/2 ) a (R 1 2 R 2 SiO 1/2 ) b (O 1/2 SiR 1 2 R 3 - XR 3 R 1 2 SiO 1/2 ) c {wherein, R 1 is the same or different alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms , R 2 is an alkenyl group having 2 to 12 carbon atoms, and R 3 is an alkylene group having the same or different carbon number of 2 to 12, wherein at least 10 mol% of the total of R 1 to R 3 is a carbon number of 6~ 20 aryl, X is of the formula (I): -SiR 4 2 O(R 4 2 SiO) n SiR 4 2 -

(式中，R4為相同或不同之碳數1~12之烷基、碳數6~20之芳基、或碳數7~20之芳烷基，n為0~5之整數)所表示之矽烷氧基、或通式(II)：-SiR4 2-C6H4-SiR4 2- (wherein R 4 is the same or different alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and n is an integer of 0 to 5) Alkoxy group, or formula (II): -SiR 4 2 -C 6 H 4 -SiR 4 2 -

(式中，R4與上述相同)所表示之矽伸苯基，a為0.65~0.90之數，b為0.04~0.29之數，c為0.01~0.07之數，且，a+b+c=1.00}所表示，包含式：R1SiO3/2所表示之矽氧烷單元及式：R1 2R2SiO1/2所表示之矽氧烷單元及式：R1 2R3SiO1/2所表示之矽氧烷單元之有機聚矽氧烷樹脂嵌段(式中，R1、R2、及R3與上述相同)經由式中之R3而由上述矽烷氧基或上述矽伸苯基連結。 (wherein R 4 is the same as above) is a phenyl group, a is a number from 0.65 to 0.90, b is a number from 0.04 to 0.29, c is a number from 0.01 to 0.07, and a+b+c= Included by 1.00}, the oxime unit represented by the formula: R 1 SiO 3/2 and the oxime unit represented by the formula: R 1 2 R 2 SiO 1/2 and the formula: R 1 2 R 3 SiO 1 silicon siloxane units of / 2 indicates the siloxane silicone organopolysiloxane resin block (in the formula, R 1, R 2, and R 3 are as defined above) in the formula via R 3 and by the above silicon or silicon-alkoxy Stretch phenyl link.

較佳為，平均單元式中，R2為乙烯基，R3為伸乙基，又，較佳為，通式(I)中，於R4全部為碳數1~12之烷基之情形時，n為0。 Preferably, in the average unit formula, R 2 is a vinyl group, R 3 is an exoethyl group, and further preferably, in the formula (I), all of R 4 are an alkyl group having 1 to 12 carbon atoms. When n is 0.

本發明之有機聚矽氧烷之製造方法之特徵在於：其係使(A)平均單元式：(R1SiO3/2)d(R1 2R2SiO1/2)e The method for producing an organopolyoxane of the present invention is characterized in that (A) is an average unit formula: (R 1 SiO 3/2 ) d (R 1 2 R 2 SiO 1/2)e

(式中，R1為相同或不同之碳數1~12之烷基、碳數6~20之芳基、或碳數7~20之芳烷基，R2為碳數2~12之烯基，其中，R1及R2之合計之至少10莫耳%為碳數6~20之芳基，d為0.65~0.90之數，e為0.10~0.35之數，且，d+e=1.00)所表示之有機聚矽氧烷樹脂與(B)(B-1)通式：HR4 2SiO(R4 2SiO)nSiR4 2H (wherein R 1 is the same or different alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms; and R 2 is an alkene having 2 to 12 carbon atoms; a base wherein at least 10 mol% of the total of R 1 and R 2 is an aryl group having 6 to 20 carbon atoms, d is a number from 0.65 to 0.90, and e is a number from 0.10 to 0.35, and d + e = 1.00 ) The organic polydecane resin and (B) (B-1) represented by the formula: HR 4 2 SiO(R 4 2 SiO) n SiR 4 2 H

(式中，R4為相同或不同之碳數1~12之烷基、碳數6~20之芳基、或碳數7~20之芳烷基，n為0~5之整數)所表示之二有機矽氧烷或(B-2)通式：HR4 2Si-C6H4-SiR4 2H (wherein R 4 is the same or different alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and n is an integer of 0 to 5) Bis organic oxane or (B-2) formula: HR 4 2 Si-C 6 H 4 -SiR 4 2 H

(式中，R4與上述相同)所表示之雙矽烷基苯進行矽氫化反應而成。 The formula wherein (in the formula, R 4 is the same as above) is carried out by hydrogenation of a dinonylalkylbenzene.

較佳為(A)成分中之R2為乙烯基，又，較佳為於(B-1)成分中之R4全部為碳數1~12之烷基之情形時，n為0。 It is preferable that R 2 in the component (A) is a vinyl group, and it is preferable that n is 0 when all of R 4 in the component (B-1) are an alkyl group having 1 to 12 carbon atoms.

本發明之有機聚矽氧烷係有機聚矽氧烷樹脂嵌段由矽烷氧基或矽伸苯基連結而成、且折射率高、透明性高之有機聚矽氧烷。又，本發明之製造方法具有可高效率地製造此種新穎之有機聚矽氧烷之特徵。 The organopolyoxyalkylene-based organopolyoxane resin block of the present invention is an organopolysiloxane having a high refractive index and high transparency, which is obtained by linking a decyloxy group or a fluorenylphenyl group. Further, the production method of the present invention has the feature of efficiently producing such a novel organopolyoxane.

首先，對本發明之有機聚矽氧烷進行詳細說明。 First, the organopolyoxane of the present invention will be described in detail.

本有機聚矽氧烷係平均單元式：(R1SiO3/2)a(R1 2R2SiO1/2)b(O1/2SiR1 2R3-X-R3R1 2SiO1/2)c所表示。 The organic polysiloxane is an average unit: (R 1 SiO 3/2 ) a (R 1 2 R 2 SiO 1/2 ) b (O 1/2 SiR 1 2 R 3 -XR 3 R 1 2 SiO 1 /2 ) c is indicated.

式中，R1為相同或不同之碳數1~12之烷基、碳數6~20之芳基、或碳數7~20之芳烷基。具體而言，可例示：甲基、乙基、丙基、異丙基、丁基、異丁基、第三丁基、戊基、新戊基、己基、環己基、辛基、壬基、癸基等烷基；苯基、甲苯基、二甲苯基、萘基等芳基；苄基、苯乙基、苯丙基等芳烷基。再者，R1~R3之合計之至少10莫耳%為碳數6~20之芳基，較佳為苯基。其原因在於：可提高本有機聚矽氧烷之折射率。再者，式：R1SiO3/2所表示之矽氧烷單元中之R1較佳為碳數6~20之芳基，尤佳為苯基。 In the formula, R 1 is the same or different alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Specifically, it may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a cyclohexyl group, an octyl group or a decyl group. An alkyl group such as fluorenyl; an aryl group such as a phenyl group, a tolyl group, a xylyl group or a naphthyl group; an aralkyl group such as a benzyl group, a phenethyl group or a phenylpropyl group. Further, at least 10 mol% of the total of R 1 to R 3 is an aryl group having 6 to 20 carbon atoms, preferably a phenyl group. The reason for this is that the refractive index of the present organopolyoxyalkylene can be increased. Further, the formula: R 1 SiO 3/2 siloxane units represented by Si the sum of carbon atoms R 1 is preferably an aryl group of 6 to 20, and particularly preferably a phenyl group.

式中，R2為碳數2~12之烯基。具體而言，可例示：乙烯基、烯丙基、異丙烯基、丁烯基、戊烯基、己烯基、環己烯基、辛烯基，較佳 為乙烯基。 In the formula, R 2 is an alkenyl group having 2 to 12 carbon atoms. Specifically, a vinyl group, an allyl group, an isopropenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclohexenyl group, or an octenyl group is preferable, and a vinyl group is preferable.

式中，R3為相同或不同之碳數2~12之伸烷基。具體而言，可例示：伸乙基、伸丙基、異伸丙基、伸丁基、伸戊基、伸己基、伸環己基、伸辛基，較佳為伸乙基。 In the formula, R 3 is the same or different alkylene group having 2 to 12 carbon atoms. Specifically, an ethyl group, a propyl group, an exo-propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, and an octyl group are preferably exemplified, and an ethyl group is preferably extended.

式中，X為通式(I)：-SiR4 2O(R4 2SiO)nSiR4 2- Wherein X is of the formula (I): -SiR 4 2 O(R 4 2 SiO) n SiR 4 2 -

所表示之矽烷氧基、或通式(II)：-SiR4 2-C6H4-SiR4 2- The decyloxy group represented by the formula or the general formula (II): -SiR 4 2 -C 6 H 4 -SiR 4 2 -

所表示之矽伸苯基。 The indicated phenylene.

式中，R4為相同或不同之碳數1~6之烷基、碳數6~20之芳基、或碳數7~20之芳烷基。具體而言，可例示與上述R1相同之基。再者，通式(I)中，式中之全部R4之至少10莫耳%較佳為碳數6~20之芳基，尤佳為苯基。其原因在於：可進而提高本有機聚矽氧烷之折射率或穿透率。 In the formula, R 4 is the same or different alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Specifically, the same group as the above R 1 can be exemplified. Further, in the formula (I), at least 10 mol% of all R 4 in the formula is preferably an aryl group having 6 to 20 carbon atoms, and particularly preferably a phenyl group. The reason for this is that the refractive index or transmittance of the present organopolyoxyalkylene can be further increased.

式中，n為0~5之範圍內之整數，較佳為0~4之範圍內之整數，進而較佳為0~3之範圍內之整數。其原因在於：若n為上述範圍內之整數，則可不降低本有機聚矽氧烷之折射率而提高其穿透率。再者，較佳為通式(I)中，於式中之R4全部為碳數1~12之烷基之情形時，n為0。 In the formula, n is an integer in the range of 0 to 5, preferably an integer in the range of 0 to 4, and further preferably an integer in the range of 0 to 3. The reason for this is that if n is an integer within the above range, the refractive index of the organic polyoxyalkylene can be increased without lowering the refractive index. Further, in the case of the formula (I), when all of R 4 in the formula are an alkyl group having 1 to 12 carbon atoms, n is 0.

式中，a為0.65~0.90之範圍內之數，b為0.04~0.29之範圍內之數，c為0.01~0.07之範圍內之數，且，a+b+c=1.00。其原因在於：若a為上述範圍之下限以上，則可提高本有機聚矽氧烷中之有機聚矽氧烷樹脂嵌段之熱熔性等熱特性，另一方面，若為上述範圍之上限以下，則可提高本有機聚矽氧烷對有機溶劑之溶解性，可提高其操作性。又，原因在於：若b為上述範圍之下限以上，則可藉由利用含有鍵結於矽原子之氫原子之有機聚矽氧烷所進行之矽氫化反應使本有機聚矽氧烷硬化，另一方面，若為上述範圍之上限以下，則可提高本有機聚矽氧烷中之有機聚矽氧烷樹脂嵌段之熱熔性等熱特性。又，原因在於：若c 為上述範圍內，則可提高本有機聚矽氧烷中之有機聚矽氧烷樹脂嵌段之熱熔性等熱特性，另一方面，若為上述範圍之上限以下，則可提高本有機聚矽氧烷之操作性。 In the formula, a is a number in the range of 0.65 to 0.90, b is a number in the range of 0.04 to 0.29, c is a number in the range of 0.01 to 0.07, and a+b+c=1.00. The reason is that when a is at least the lower limit of the above range, the thermal characteristics such as the hot melt property of the organopolyoxane resin block in the organopolysiloxane can be improved, and the upper limit of the above range is Hereinafter, the solubility of the organic polyoxane in an organic solvent can be improved, and the workability can be improved. Further, the reason is that if b is at least the lower limit of the above range, the organopolyoxyalkylene can be hardened by a hydrogenation reaction using an organopolysiloxane having a hydrogen atom bonded to a halogen atom, and On the other hand, when it is at most the upper limit of the above range, thermal properties such as hot meltability of the organopolyoxane resin block in the organic polysiloxane can be improved. Again, the reason is: if c In the above range, the thermal properties such as the hot melt property of the organopolyoxane resin block in the organic polysiloxane can be improved. On the other hand, if it is at most the upper limit of the above range, the organic polymerization can be improved. The operability of the oxirane.

此般之本有機聚矽氧烷之特徵在於：包含式：R1SiO3/2所表示之矽氧烷單元及式：R1 2R2SiO1/2所表示之矽氧烷單元及式：R1 2R3SiO1/2所表示之矽氧烷單元之有機聚矽氧烷樹脂嵌段(式中，R1、R2、及R3與上述相同)係經由式中之R3而由上述矽烷氧基或上述矽伸苯基連結。 The organic polyoxyalkylene is generally characterized by comprising: a fluorinated alkane unit represented by the formula: R 1 SiO 3/2 and a fluorinated alkane unit represented by the formula: R 1 2 R 2 SiO 1/2 : an organopolyoxyalkylene resin block of a decane unit represented by R 1 2 R 3 SiO 1/2 (wherein R 1 , R 2 , and R 3 are the same as defined above) via R 3 in the formula Further, it is bonded by the above decyloxy group or the above-mentioned phenylene group.

又，本有機聚矽氧烷之可見光(589nm)之折射率(25℃)並無限定，較佳為1.50以上。其原因在於：本有機聚矽氧烷可適用於高折射率之光學材料。 Further, the refractive index (25 ° C) of the visible light (589 nm) of the organic polysiloxane is not limited, and is preferably 1.50 or more. The reason for this is that the present organopolysiloxane can be applied to an optical material having a high refractive index.

其次，對本發明之有機聚矽氧烷之製造方法進行詳細說明。 Next, the method for producing the organopolyoxane of the present invention will be described in detail.

(A)成分係平均單元式：(R1SiO3/2)d(R1 2R2SiO1/2)e所表示之有機聚矽氧烷樹脂，為用於形成有機聚矽氧烷樹脂嵌段之原料。 (A) component is an average unit: (R 1 SiO 3/2 ) d (R 1 2 R 2 SiO 1/2 ) e is an organopolysiloxane resin for forming an organic polyoxyalkylene resin. The raw material of the block.

式中，R1為相同或不同之碳數1~6之烷基、碳數6~20之芳基、或碳數7~20之芳烷基，可例示與上述相同之基。再者，(A)成分中之R1與R2之合計之至少10莫耳%較佳為碳數6~20之芳基，尤佳為苯基。其原因在於：可提高所獲得之有機聚矽氧烷之折射率，可提高透明性，提高操作性。再者，式：R1SiO3/2所表示之矽氧烷單元中之R1較佳為碳數6~20之芳基，尤佳為苯基。 In the formula, R 1 is the same or different alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and the same groups as described above can be exemplified. Further, at least 10 mol% of the total of R 1 and R 2 in the component (A) is preferably an aryl group having 6 to 20 carbon atoms, and particularly preferably a phenyl group. The reason for this is that the refractive index of the obtained organic polyoxyalkylene can be increased, transparency can be improved, and workability can be improved. Further, the formula: R 1 SiO 3/2 siloxane units represented by Si the sum of carbon atoms R 1 is preferably an aryl group of 6 to 20, and particularly preferably a phenyl group.

式中，R2為碳數2~12之烯基，可例示與上述相同之基，較佳為乙烯基。再者，(A)成分於一分子中至少具有2個烯基，其含量係R1與R2之合計之0.1~40莫耳%、較佳為0.5~40莫耳%、尤佳為1~30莫耳%之範圍內。其原因在於：若(A)成分中之烯基之含量為上述範圍內，則可充分進行與(B)成分之矽氫化反應，且可使烯基殘存於所獲得之有機聚 矽氧烷中。 In the formula, R 2 is an alkenyl group having 2 to 12 carbon atoms, and the same groups as described above are exemplified, and a vinyl group is preferred. Further, the component (A) has at least two alkenyl groups in one molecule, and the content thereof is 0.1 to 40 mol%, preferably 0.5 to 40 mol%, particularly preferably 1 in total of R 1 and R 2 . ~30% of the range of moles. The reason for this is that when the content of the alkenyl group in the component (A) is within the above range, the hydrogenation reaction with the component (B) can be sufficiently carried out, and the alkenyl group can remain in the obtained organopolyoxane. .

式中，d為0.65~0.90之範圍內之數，e為0.10~0.35之範圍內之數，且，d+e=1.00。其原因在於：若d為上述範圍之下限以上，則可提昇所獲得之有機聚矽氧烷中之有機聚矽氧烷樹脂嵌段之熱熔性等熱特性，另一方面，若d為上述範圍之上限以下，則可提高所獲得之有機聚矽氧烷對有機溶劑之溶解性，可提高其操作性。又，若e為上述範圍之下限以上，則可使烯基殘存於所獲得之有機聚矽氧烷，使之可進行利用含有鍵結於矽原子之氫原子之有機聚矽氧烷所進行之矽氫化反應，另一方面，若e為上述範圍之上限以下，則可提昇所獲得之有機聚矽氧烷中之有機聚矽氧烷樹脂嵌段之熱熔性等熱特性。 In the formula, d is a number in the range of 0.65 to 0.90, e is a number in the range of 0.10 to 0.35, and d + e = 1.00. The reason for this is that if d is at least the lower limit of the above range, thermal properties such as hot meltability of the organopolyoxane resin block in the obtained organopolyoxane can be improved, and if d is the above Below the upper limit of the range, the solubility of the obtained organic polyoxane in an organic solvent can be improved, and the workability can be improved. Further, when e is at least the lower limit of the above range, an alkenyl group may remain in the obtained organopolyoxane, and it can be carried out by using an organopolyoxane having a hydrogen atom bonded to a ruthenium atom. In the hydrogenation reaction, on the other hand, when e is at most the upper limit of the above range, thermal properties such as hot meltability of the organopolyoxane resin block in the obtained organic polysiloxane can be improved.

此種(A)成分之於25℃下之性狀並無限定，例如25℃下為固體狀或黏度為10mPa．s以上之液狀。 The trait of the component (A) at 25 ° C is not limited, for example, it is solid at 25 ° C or the viscosity is 10 mPa. Liquid above s.

(B)成分係用於連結上述有機聚矽氧烷樹脂之原料，為(B-1)通式：HR4 2SiO(R4 2SiO)nSiR4 2H所表示之二有機矽氧烷或(B-2)通式：HR4 2Si-C6H4-SiR4 2H所表示之雙矽烷基苯。 The component (B) is a raw material for linking the above organopolyoxane resin, and is a compound of the formula (B-1): HR 4 2 SiO(R 4 2 SiO) n SiR 4 2 H Or (B-2) Formula: bis 4 alkyl group represented by HR 4 2 Si-C 6 H 4 -SiR 4 2 H.

式中，R4為相同或不同之碳數1~6之烷基、碳數6~20之芳基、或碳數7~20之芳烷基，可例示與上述R1相同之基。再者，(B-1)成分中，式中之全部R4之至少10莫耳%較佳為碳數6~20之芳基，尤佳為苯基。其原因在於：可進而提高所獲得之有機聚矽氧烷之折射率或穿透率。 In the formula, R 4 is the same or different alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and the same group as the above R 1 can be exemplified. Further, in the component (B-1), at least 10 mol% of all R 4 in the formula is preferably an aryl group having 6 to 20 carbon atoms, and particularly preferably a phenyl group. The reason for this is that the refractive index or transmittance of the obtained organopolyoxane can be further increased.

式中，n為0~5之範圍內之整數，較佳為0~4之範圍內之整數，尤佳為0~3之範圍內之整數。其原因在於：若n為上述範圍內之整數，則可不降低所獲得之有機聚矽氧烷之折射率而提高其穿透率。再者，(B-1)成分中，較佳為於式中之R4全部為碳數1~12之烷基之情形時，n為0。 In the formula, n is an integer in the range of 0 to 5, preferably an integer in the range of 0 to 4, and particularly preferably an integer in the range of 0 to 3. The reason for this is that if n is an integer within the above range, the transmittance of the obtained organopolyoxane can be increased without lowering the refractive index. Further, in the component (B-1), it is preferred that when R 4 in the formula is an alkyl group having 1 to 12 carbon atoms, n is 0.

作為(B-1)成分，可例示如下之二有機矽氧烷：H(CH3)2SiOSi(CH3)2H As the component (B-1), the following two organooxanes can be exemplified: H(CH 3 ) 2 SiOSi(CH 3 ) 2 H

H(CH3)(C6H5)SiOSi(CH3)(C6H5)H H(CH 3 )(C 6 H 5 )SiOSi(CH 3 )(C 6 H 5 )H

H(CH3)2SiO[(CH3)2SiO]Si(CH3)2H H(CH 3 ) 2 SiO[(CH 3 ) 2 SiO]Si(CH 3 ) 2 H

H(CH3)2SiO[(CH3)(C6H5)SiO]Si(CH3)2H H(CH 3 ) 2 SiO[(CH 3 )(C 6 H 5 )SiO]Si(CH 3 ) 2 H

H(CH3)2SiO[(C6H5)2SiO]Si(CH3)2H H(CH 3 ) 2 SiO[(C 6 H 5 ) 2 SiO]Si(CH 3 ) 2 H

H(CH3)(C6H5)SiO[(CH3)2SiO]Si(CH3)(C6H5)H H(CH 3 )(C 6 H 5 )SiO[(CH 3 ) 2 SiO]Si(CH 3 )(C 6 H 5 )H

又，作為(B-2)成分，可例示如下之雙矽烷基苯：H(CH3)2Si-C6H4-Si(CH3)2H Further, as the component (B-2), the following dinonylalkylbenzene can be exemplified: H(CH 3 ) 2 Si-C 6 H 4 -Si(CH 3 ) 2 H

H(CH3)(C6H5)Si-C6H4-Si(CH3)(C6H5)H H(CH 3 )(C 6 H 5 )Si-C 6 H 4 -Si(CH 3 )(C 6 H 5 )H

H(C6H5)2Si-C6H4-Si(C6H5)2H H(C 6 H 5 ) 2 Si-C 6 H 4 -Si(C 6 H 5 ) 2 H

本發明之製造方法中，(B)成分之添加量並無限定，較佳為相對於(A)成分中之烯基1莫耳，本成分中之鍵結於矽原子之氫原子成為未達0.8莫耳之量，進而較佳為成為0.05~0.7莫耳之範圍內之量，進而較佳為成為0.1~0.6莫耳之範圍內之量，尤佳為成為0.2~0.5莫耳之範圍內之量。其原因在於：可抑制所獲得之有機聚矽氧烷之凝膠化，使烯基殘存。 In the production method of the present invention, the amount of the component (B) to be added is not limited, and it is preferably the same as the alkenyl group 1 in the component (A), and the hydrogen atom bonded to the ruthenium atom in the component is not reached. The amount of 0.8 moles is more preferably in the range of 0.05 to 0.7 moles, more preferably in the range of 0.1 to 0.6 moles, and particularly preferably in the range of 0.2 to 0.5 moles. The amount. The reason for this is that the gelation of the obtained organic polyoxyalkylene can be suppressed, and the alkenyl group remains.

用於促進上述反應之矽氫化反應用觸媒並無限定，可例示：鉑系觸媒、銠系觸媒、鈀系觸媒。尤其，就可顯著促進矽氫化反應而言，較佳為鉑系觸媒。作為該鉑系觸媒，可例示：鉑細粉末、氯鉑酸、氯鉑酸之醇溶液、鉑-烯基矽氧烷錯合物、鉑-烯烴錯合物、鉑-羰基錯合物，尤其鉑-烯基矽氧烷錯合物較佳。作為該烯基矽氧烷，可例示：1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷、1,3,5,7-四甲基-1,3,5,7-四乙烯基環四矽氧烷、將該等烯基矽氧烷之甲基之一部分以乙基、苯基等基取代而得之烯基矽氧烷、將該等烯基矽氧烷之乙烯基以烯丙基、己烯基等基取代而得之烯基矽氧烷。 The catalyst for the hydrogenation reaction for promoting the above reaction is not limited, and examples thereof include a platinum-based catalyst, a ruthenium-based catalyst, and a palladium-based catalyst. In particular, in the case of remarkably promoting the hydrogenation reaction, a platinum-based catalyst is preferred. Examples of the platinum-based catalyst include platinum fine powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum-alkenyl alkane complex, a platinum-olefin complex, and a platinum-carbonyl complex. In particular, a platinum-alkenyl alkoxylate complex is preferred. As the alkenyl decane, 1,3-divinyl-1,1,3,3-tetramethyldioxane and 1,3,5,7-tetramethyl-1,3 can be exemplified. , 5,7-tetravinylcyclotetraoxane, an alkenyl alkane obtained by substituting a part of a methyl group of the alkenyl alkoxysilane with a group such as an ethyl group or a phenyl group, the alkenyl group An alkenyl alkane obtained by substituting a vinyl group of a decane with a group such as an allyl group or a hexenyl group.

上述製備方法中之矽氫化反應用觸媒之添加量並無限定，例如，相對於(A)成分與(B)成分之合計量，觸媒金屬以質量單位計較佳為成為0.01~1,000ppm之範圍內之量，尤佳為成為0.1~500ppm之範圍內之量。其原因在於：若矽氫化反應用觸媒之添加量為上述範圍之下限以上，則可充分促進矽氫化反應，另一方面，若矽氫化反應用觸媒之添加量為上述範圍之上限以下，則變得難以產生對所獲得之有機聚矽氧烷著色等問題。 The amount of the catalyst for the hydrogenation reaction in the above-mentioned production method is not limited. For example, the catalyst metal is preferably 0.01 to 1,000 ppm by mass based on the total amount of the component (A) and the component (B). The amount in the range is particularly preferably in the range of 0.1 to 500 ppm. The reason for this is that if the amount of the catalyst for the hydrogenation reaction is at least the lower limit of the above range, the rhodium hydrogenation reaction can be sufficiently promoted, and if the amount of the catalyst for the rhodium hydrogenation reaction is less than the upper limit of the above range, Then, it becomes difficult to cause problems such as coloring of the obtained organic polyoxane.

上述製備方法中之反應條件並無限定，可藉由加熱而促進反應。又，該反應系中，於使用甲苯、二甲苯等芳香族系溶劑；庚烷、己烷等脂肪族系溶劑等溶劑之情形時，反應溫度較佳為溶劑之回流溫度，於不使用有機溶劑之情形時，反應溫度較佳為200℃以下。再者，該反應中，藉由使用有機溶劑，可降低反應系之黏度，同時可自反應系利用共沸等將水脫去。 The reaction conditions in the above production method are not limited, and the reaction can be promoted by heating. In the reaction system, when an aromatic solvent such as toluene or xylene or a solvent such as an aliphatic solvent such as heptane or hexane is used, the reaction temperature is preferably the reflux temperature of the solvent, and the organic solvent is not used. In the case of the case, the reaction temperature is preferably 200 ° C or lower. Further, in the reaction, by using an organic solvent, the viscosity of the reaction system can be lowered, and water can be removed from the reaction system by azeotropy or the like.

藉此所獲得之有機聚矽氧烷係有機聚矽氧烷樹脂嵌段由矽烷氧基或矽伸苯基連結，可溶於甲苯、二甲苯等芳香族系溶劑；庚烷、己烷等脂肪族系溶劑等溶劑。其於25℃下之性狀並無特別限定，可例示液狀、黏稠之液狀、固體狀。 The organopolysiloxane-based organopolyoxane resin block obtained by this is linked by a decyloxy group or a fluorenylphenyl group, and is soluble in an aromatic solvent such as toluene or xylene; or a fat such as heptane or hexane. A solvent such as a family solvent. The properties at 25 ° C are not particularly limited, and examples thereof include a liquid form, a viscous liquid form, and a solid form.

本發明之有機聚矽氧烷於分子中含有烯基，故而可藉由含有鍵結於矽原子之氫原子之有機聚矽氧烷、及矽氫化反應用觸媒，而進行硬化，並製成形成具有適度之彈性模數之硬化物之硬化性有機聚矽氧烷組合物。 Since the organopolysiloxane of the present invention contains an alkenyl group in the molecule, it can be hardened by forming an organic polyoxane having a hydrogen atom bonded to a halogen atom and a catalyst for hydrogenation reaction. A curable organopolyoxane composition having a moderate modulus of elasticity.

作為該含有鍵結於矽原子之氫原子之有機聚矽氧烷，由平均組成式：R5 fHgSiO(4-f-g)/2所表示。式中，R5為不具有脂肪族不飽和鍵之一價烴基，可例示與上述R1相同之基。又，式中，f及g為滿足0.7≦f≦2.1、0.001≦g≦1.0、 且0.8≦f+g≦2.6，較佳為0.8≦f≦2、0.01≦g≦1、1≦f+g≦2.4之正數。 The organic polyoxosiloxane containing a hydrogen atom bonded to a halogen atom is represented by an average composition formula: R 5 f H g SiO (4-fg)/2 . In the formula, R 5 is a monovalent hydrocarbon group having no aliphatic unsaturated bond, and the same group as the above R 1 can be exemplified. Further, in the formula, f and g satisfy 0.7≦f≦2.1, 0.001≦g≦1.0, and 0.8≦f+g≦2.6, preferably 0.8≦f≦2, 0.01≦g≦1, 1≦f+ A positive number of g≦2.4.

該有機聚矽氧烷之分子結構並無特別限定，可例示直鏈狀、一部分具有支鏈之直鏈狀、支鏈狀、環狀、立體網狀結構，較佳為一部分具有支鏈之直鏈狀、支鏈狀、立體網狀結構。此種有機聚矽氧烷之於25℃下之性狀為固體狀或液狀，較佳為於25℃下之黏度為10,000mPa．s以下，更佳為0.1~5,000mPa．s之範圍內，尤佳為0.5~1,000mPa．s之範圍內。 The molecular structure of the organopolysiloxane is not particularly limited, and examples thereof include a linear chain, a part of a linear, branched, cyclic, or three-dimensional network having a branch, and preferably a part having a straight chain. Chain, branched, three-dimensional network structure. The organic polyoxyalkylene has a solid or liquid property at 25 ° C, preferably a viscosity of 10,000 mPa at 25 ° C. s or less, more preferably 0.1 to 5,000 mPa. Within the range of s, especially preferably 0.5~1,000mPa. Within the scope of s.

作為此種有機聚矽氧烷，可例示：三甲基矽烷氧基封阻分子鏈兩末端之甲基氫聚矽氧烷、三甲基矽烷氧基封阻分子鏈兩末端之二甲基矽氧烷-甲基氫矽氧烷共聚物、二甲基氫矽烷氧基封阻分子鏈兩末端之二甲基聚矽氧烷、二甲基氫矽烷氧基封阻分子鏈兩末端之二甲基矽氧烷-甲基氫矽氧烷共聚物、三甲基矽烷氧基封阻分子鏈兩末端之甲基氫矽氧烷-二苯基矽氧烷共聚物、三甲基矽烷氧基封阻分子鏈兩末端之甲基氫矽氧烷-二苯基矽氧烷-二甲基矽氧烷共聚物、包含(CH3)2HSiO1/2單元與SiO4/2單元之共聚物、包含(CH3)2HSiO1/2單元與SiO4/2單元與(C6H5)SiO3/2單元之共聚物。 As such an organic polyoxane, a methyl methacrylate polyoxyalkylene at both ends of the molecular chain of the trimethyl decyloxy group is blocked, and a dimethyl hydrazine at both ends of the molecular chain of the trimethyl decyloxy group is blocked. An oxane-methylhydroquinone copolymer, a dimethylhydroquinoloxy group blocking the dimethylpolyoxane at both ends of the molecular chain, and a dimethylhydroquinoloxy group blocking the dimethyl group at both ends of the molecular chain a hydrazine-methylhydroperoxane copolymer, a methyl hydrooxane-diphenyl fluorene copolymer at both ends of a molecular chain of a trimethyl decyloxy group, and a trimethyl decyloxy group a copolymer of methylhydroquinoxane-diphenyloxirane-dimethyloxane at both ends of the molecular chain, a copolymer comprising (CH 3 ) 2 HSiO 1/2 unit and SiO 4/2 unit, A copolymer comprising (CH 3 ) 2 HSiO 1/2 units and SiO 4/2 units and (C 6 H 5 )SiO 3/2 units.

上述組合物中，關於有機聚矽氧烷之含量，相對於本發明之有機聚矽氧烷中之烯基1莫耳，為鍵結於矽原子之氫原子成為0.1~10莫耳、較佳為0.1~5莫耳、尤佳為0.5~5莫耳之範圍內之量。其原因在於：若有機聚矽氧烷之含量未達上述範圍之下限，則所獲得之組合物並不充分硬化，另一方面，若超過上述範圍之上限，則有所獲得之硬化物之機械特性降低之虞。 In the above composition, the content of the organopolyoxane is 0.1 to 10 moles, more preferably 0.1 to 10 moles, per mole of the hydrogen atom bonded to the ruthenium atom in the organopolysiloxane of the present invention. It is in the range of 0.1 to 5 moles, and more preferably 0.5 to 5 moles. The reason for this is that if the content of the organopolyoxane is less than the lower limit of the above range, the obtained composition is not sufficiently cured, and on the other hand, if it exceeds the upper limit of the above range, the obtained cured product is mechanically obtained. The feature is reduced.

矽氫化反應用觸媒係用於促進上述組合物之利用矽氫化反應所進行之交聯反應的觸媒，可例示如上所述之矽氫化反應用觸媒。上述組合物中，矽氫化反應用觸媒之含量為觸媒量，具體而言，相對於上 述組合物，該觸媒中之觸媒金屬以重量單位計較佳為成為0.01~1000ppm之範圍內之量，尤佳為成為0.1~500ppm之範圍內之量。其原因在於：若矽氫化反應用觸媒之含量未達上述範圍之下限，則有本組合物並不充分硬化之傾向，另一方面，若超過上述範圍之上限，則有產生對所獲得之硬化物著色等問題之虞。 The catalyst for hydrogenation reaction is used as a catalyst for promoting the crosslinking reaction by the hydrogenation reaction of the above composition, and the catalyst for hydrogenation reaction as described above can be exemplified. In the above composition, the content of the catalyst for the hydrogenation reaction of the rhodium is the amount of the catalyst, specifically, relative to the upper In the composition, the catalytic metal in the catalyst is preferably in an amount of from 0.01 to 1000 ppm by weight, and particularly preferably in an amount of from 0.1 to 500 ppm. The reason for this is that if the content of the catalyst for the hydrogenation reaction does not reach the lower limit of the above range, the composition tends not to be sufficiently cured. On the other hand, if the upper limit of the above range is exceeded, the obtained The problem of hardening coloring and other issues.

又，於上述組合物中，作為其他任意之成分，亦可含有：3-甲基-1-丁炔-3-醇、3,5-二甲基-1-己炔-3-醇、苯基丁炔醇等炔醇；3-甲基-3-戊烯-1-炔、3,5-二甲基-3-己烯-1-炔等烯炔化合物；1,3,5,7-四甲基-1,3,5,7-四乙烯基環四矽氧烷、1,3,5,7-四甲基-1,3,5,7-四己烯基環四矽氧烷、苯并***等反應抑制劑。該反應抑制劑之含量並無限定，相對於上述組合物100重量份，較佳為0.0001~5重量份之範圍內。 Further, in the above composition, as other optional components, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and benzene may be contained. Alkynyl alcohols such as butylbutynol; alkenyl compounds such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexene-1-yne; 1,3,5,7 -tetramethyl-1,3,5,7-tetravinylcyclotetraoxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrazepine Reaction inhibitors such as alkane and benzotriazole. The content of the reaction inhibitor is not limited, and is preferably in the range of 0.0001 to 5 parts by weight based on 100 parts by weight of the above composition.

進而，於上述組合物中，亦可含有用於提高其接著性之接著賦予劑。作為該接著賦予劑，較佳為一分子中具有至少1個鍵結於矽原子之烷氧基的有機矽化合物。作為該烷氧基，可例示：甲氧基、乙氧基、丙氧基、丁氧基、甲氧基乙氧基，尤佳為甲氧基。又，作為該有機矽化合物之鍵結於矽原子之烷氧基以外之基，可例示：上述烷基、上述烯基、上述芳基、上述芳烷基、上述鹵化烷基等經取代或未經取代之一價烴基；3-縮水甘油氧基丙基、4-縮水甘油氧基丁基等縮水甘油氧基烷基；2-(3,4-環氧環己基)乙基、3-(3,4-環氧環己基)丙基等環氧環己基烷基；4-環氧乙烷基丁基、8-環氧乙烷基辛基等環氧乙烷基烷基等含環氧基之一價有機基；3-甲基丙烯醯氧基丙基等含丙烯醯基之一價有機基；氫原子。較佳為該有機矽化合物含有烯基或鍵結於矽原子之氫原子。又，就對各種基材可賦予良好之接著性而言，較佳為該有機矽化合物係一分子中含有至少1個含環氧基之一價有機基者。 Further, the composition may further contain an adhesion-imparting agent for improving the adhesion. As the adhesion-imparting agent, an organic ruthenium compound having at least one alkoxy group bonded to a ruthenium atom in one molecule is preferable. The alkoxy group may, for example, be a methoxy group, an ethoxy group, a propoxy group, a butoxy group or a methoxyethoxy group, and more preferably a methoxy group. Further, the group other than the alkoxy group bonded to the ruthenium atom of the organic ruthenium compound may, for example, be substituted or not, such as the above alkyl group, the above alkenyl group, the above aryl group, the above aralkyl group, or the above halogenated alkyl group. Substituting a monovalent hydrocarbon group; a glycidoxyoxy group such as 3-glycidoxypropyl or 4-glycidoxybutyl; 2-(3,4-epoxycyclohexyl)ethyl, 3-( Epoxycyclohexylalkyl group such as 3,4-epoxycyclohexyl)propyl; epoxy group such as 4-oxiranylbutyl group, 8-oxiranyloctyl group, etc. One-valent organic group; one-valent organic group containing propylene fluorenyl group such as 3-methylpropenyloxypropyl group; hydrogen atom. Preferably, the organic ruthenium compound contains an alkenyl group or a hydrogen atom bonded to a ruthenium atom. Further, in order to impart good adhesion to various substrates, it is preferred that the organic ruthenium compound contains at least one monovalent organic group containing an epoxy group in one molecule.

作為此種有機矽化合物，可例示：有機矽烷化合物、有機矽氧烷低聚物。作為該有機矽氧烷低聚物之分子結構，可例示：直鏈狀、一 部分具有支鏈之直鏈狀、支鏈狀、環狀、網狀，尤佳為直鏈狀、支鏈狀、網狀。作為此種有機矽化合物，可例示：3-縮水甘油氧基丙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷等矽烷化合物；一分子中含有烯基或鍵結於矽原子之氫原子、及鍵結於矽原子之烷氧基各至少1個之矽氧烷化合物、含有至少1個鍵結於矽原子之烷氧基之矽烷化合物或矽氧烷化合物與一分子中含有鍵結矽原子之羥基及烯基各至少1個之矽氧烷化合物的混合物；式： Examples of such an organic ruthenium compound include an organic decane compound and an organic siloxane oxide oligomer. The molecular structure of the organic siloxane oxide oligomer is exemplified by a linear chain, a part of a linear chain having a branch, a branch, a ring, or a network, and more preferably a linear or branched chain. Mesh. As such an organic phosphonium compound, 3-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-methylpropenyloxy group can be exemplified. a decane compound such as propyltrimethoxydecane; a oxoxane compound containing at least one of an alkenyl group or a hydrogen atom bonded to a ruthenium atom and an alkoxy group bonded to a ruthenium atom in one molecule, and at least one a mixture of a decane compound or a oxoxane compound bonded to an alkoxy group of a halogen atom and at least one of a hydroxyl group and an alkenyl group having a bonded ruthenium atom in one molecule;

(式中，k、m、及p為正數)所表示之矽氧烷化合物；式： (wherein, k, m, and p are positive numbers) represented by a oxoxane compound;

(式中，k、m、p、及q為正數)所表示之矽氧烷化合物。 The formula (wherein k, m, p, and q are positive numbers) represents a oxoxane compound.

該接著賦予劑較佳為低黏度液狀，其黏度並無限定，較佳為於25℃下為1~500mPa．s之範圍內。又，於上述組合物中，該接著賦予劑之含量並無限定，相對於上述組合物之合計100重量份，較佳為0.01~10重量份之範圍內。 The adhesion-imparting agent is preferably a low-viscosity liquid, and the viscosity thereof is not limited, and is preferably 1 to 500 mPa at 25 ° C. Within the scope of s. Further, in the above composition, the content of the adhesion-imparting agent is not limited, and is preferably in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the total of the composition.

又，於上述組合物中，只要無損本發明之目的，則作為其他任意 之成分，亦可含有：二氧化矽、玻璃、氧化鋁、氧化鋅等無機質填充劑；聚甲基丙烯酸酯樹脂等有機樹脂細粉末；耐熱劑、染料、顏料、阻燃性賦予劑、溶劑等。 Further, in the above composition, as long as the object of the present invention is not impaired, The component may further contain: an inorganic filler such as cerium oxide, glass, aluminum oxide or zinc oxide; a fine powder of an organic resin such as a polymethacrylate resin; a heat-resistant agent, a dye, a pigment, a flame retardant imparting agent, a solvent, etc. .

上述組合物係藉由室溫或加熱而進行硬化，為了使之迅速硬化較佳為進行加熱。作為該加熱溫度，較佳為50~250℃之範圍內。藉此所獲得之硬化物為橡膠狀，尤其是硬質之橡膠狀，或具有可撓性之樹脂狀。 The above composition is cured by room temperature or heating, and heating is preferably carried out in order to rapidly harden it. The heating temperature is preferably in the range of 50 to 250 °C. The cured product obtained thereby is in the form of a rubber, in particular, a hard rubber or a resin having flexibility.

[實施例] [Examples]

利用實施例對本發明之有機聚矽氧烷及其製造方法進行詳細說明。 The organic polyoxyalkylene of the present invention and a method for producing the same will be described in detail by way of examples.

[實施例1] [Example 1]

於反應容器中投入甲苯107.98g、質量平均分子量為1,560之平均單元式：(C6H5SiO3/2)0.75[(CH3)2(CH2=CH)SiO1/2]0.25所表示之有機聚矽氧烷樹脂之58.6質量%甲苯溶液204.84g、及式：H(CH3)2SiOSi(CH3)2H所表示之二矽氧烷3.37g(相對於上述有機聚矽氧烷樹脂中之乙烯基1莫耳，本成分中之鍵結於矽原子之氫原子成為0.2莫耳之量)，以112℃進行共沸脫水後，冷卻至室溫。繼而，添加鉑之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物(本錯合物中之鉑金屬相對於上述有機聚矽氧烷樹脂與上述二矽氧烷之合計量以質量單位計為5ppm之量)，以111℃之甲苯回流溫度反應1.7小時。其後，藉由1mmHg、117℃之加熱減壓而蒸餾去除甲苯，而獲得折射率1.5395、於50℃~100℃發生熔融而成為透明液體、於室溫下為白色之固體。可知，該固體係平均單元式：(C6H5SiO3/2)0.77[(CH3)2(CH2=CH)SiO1/2]0.20[O1/2Si(CH3)2-C2H4-(CH3)2SiO(CH3)2Si-C2H4-(CH3)2SiO1/2]0.03 所表示，且包含式：C6H5SiO3/2所表示之矽氧烷單元及式：(CH3)2(CH2=CH)SiO1/2所表示之矽氧烷單元及式：(CH3)2(-C2H4)SiO1/2所表示之矽氧烷單元的有機聚矽氧烷樹脂嵌段由式：-(CH3)2SiO(CH3)2Si-所表示之矽烷氧基連結而成的有機聚矽氧烷。 The reaction vessel was charged with 107.98 g of toluene and a mass average molecular weight of 1,560. The average unit formula: (C 6 H 5 SiO 3/2 ) 0.75 [(CH 3 ) 2 (CH 2 =CH)SiO 1/2 ] 0.25 The organic polyfluorene oxide resin has a 58.6 mass% toluene solution of 204.84 g, and the formula: H(CH 3 ) 2 SiOSi(CH 3 ) 2 H represents dioxane 3.37 g (relative to the above organopolyoxane) The vinyl group 1 mol in the resin, the hydrogen atom bonded to the ruthenium atom in the present component was 0.2 mol, and was azeotropically dehydrated at 112 ° C, and then cooled to room temperature. Then, a platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex (the platinum metal in the present complex is compared with the above organopolyoxyalkylene resin and the above) The total amount of dioxane was 5 ppm by mass unit, and the reaction was carried out at a reflux temperature of toluene of 111 ° C for 1.7 hours. Thereafter, toluene was distilled off by heating under reduced pressure of 1 mmHg and 117 ° C to obtain a solid having a refractive index of 1.5395, which was melted at 50 ° C to 100 ° C to be a transparent liquid, and was white at room temperature. It can be seen that the solid system has an average unit formula: (C 6 H 5 SiO 3/2 ) 0.77 [(CH 3 ) 2 (CH 2 =CH)SiO 1/2 ] 0.20 [O 1/2 Si(CH 3 ) 2 - C 2 H 4 —(CH 3 ) 2 SiO(CH 3 ) 2 Si—C 2 H 4 —(CH 3 ) 2 SiO 1/2 ] is represented by 0.03 and contains the formula: C 6 H 5 SiO 3/2 a oxoxane unit represented by the formula: (CH 3 ) 2 (CH 2 =CH) SiO 1/2 represented by a oxoxane unit and a formula: (CH 3 ) 2 (-C 2 H 4 )SiO 1/2 The organopolyoxane resin block of the oxoxane unit represented by the formula is an organopolyoxane in which a decyloxy group represented by the formula: -(CH 3 ) 2 SiO(CH 3 ) 2 Si- is bonded.

[實施例2] [Embodiment 2]

於反應容器中投入甲苯102.4g、質量平均分子量為1,560之平均單元式：(C6H5SiO3/2)0.75[(CH3)2(CH2=CH)SiO1/2]0.25所表示之有機聚矽氧烷樹脂之58.6質量%甲苯溶液204.97g、及式：H(CH3)2SiO(C6H5)2SiOSi(CH3)2H所表示之三矽氧烷16.67g(相對於上述有機聚矽氧烷樹脂中之乙烯基1莫耳，本成分中之鍵結於矽原子之氫原子成為0.4莫耳之量)，以113℃進行共沸脫水後，冷卻至室溫。繼而，添加鉑之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物(本錯合物中之鉑金屬相對於上述有機聚矽氧烷樹脂與上述三矽氧烷之合計量以質量單位計成為5ppm之量)，以111℃之甲苯回流溫度反應2小時。其後，冷卻至室溫，混合活性碳9.0g後，利用玻璃過濾器進行過濾。藉由對濾液以30~40mmHg、95~105℃進行加熱減壓而蒸餾去除甲苯，獲得折射率1.5422、於50℃~100℃發生熔融而成為透明液體、室溫下為白色之固體。可知，該固體係由平均單元式：(C6H5SiO3/2)0.80[(CH3)2(CH2=CH)SiO1/2]0.15[O1/2Si(CH3)2-C2H4-(CH3)2SiO(C6H5)2SiO(CH3)2Si-C2H4-(CH3)2SiO1/2]0.05所表示，且包含式：C6H5SiO3/2所表示之矽氧烷單元及式：(CH3)2(CH2=CH)SiO1/2所表示之矽氧烷單元及式：(CH3)2(-C2H4)SiO1/2所表示之矽氧烷單元之有機聚矽氧烷樹脂嵌段由式： -(CH3)2SiO(C6H5)2SiO(CH3)2Si-所表示之矽烷氧基連結而成的有機聚矽氧烷。 The reaction unit was charged with 102.4 g of toluene and a mass average molecular weight of 1,560. The average unit formula: (C 6 H 5 SiO 3/2 ) 0.75 [(CH 3 ) 2 (CH 2 =CH)SiO 1/2 ] 0.25 204.97 g of a 58.6 mass% toluene solution of the organopolysiloxane resin, and 16.67 g of a trioxane represented by H(CH 3 ) 2 SiO(C 6 H 5 ) 2 SiOSi(CH 3 ) 2 H ( It is azeotropically dehydrated at 113 ° C and then cooled to room temperature with respect to the vinyl 1 mol in the above organopolysiloxane resin, the hydrogen atom bonded to the ruthenium atom in the present component is 0.4 mol. . Then, a platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex (the platinum metal in the present complex is compared with the above organopolyoxyalkylene resin and the above) The total amount of trioxane was 5 ppm in mass units, and the reaction was carried out at a reflux temperature of toluene of 111 ° C for 2 hours. Thereafter, the mixture was cooled to room temperature, and 9.0 g of activated carbon was mixed, followed by filtration using a glass filter. Toluene was distilled off by heating and depressurizing the filtrate at 30 to 40 mmHg and 95 to 105 ° C to obtain a solid having a refractive index of 1.5422, melting at 50 to 100 ° C to form a transparent liquid, and white at room temperature. It can be seen that the solid system is of the average unit formula: (C 6 H 5 SiO 3/2 ) 0.80 [(CH 3 ) 2 (CH 2 =CH)SiO 1/2 ] 0.15 [O 1/2 Si(CH 3 ) 2 -C 2 H 4 -(CH 3 ) 2 SiO(C 6 H 5 ) 2 SiO(CH 3 ) 2 Si-C 2 H 4 -(CH 3 ) 2 SiO 1/2 ] 0.05 , and contains: a oxoxane unit represented by C 6 H 5 SiO 3/2 and a oxime unit represented by the formula: (CH 3 ) 2 (CH 2 =CH)SiO 1/2 and a formula: (CH 3 ) 2 (- The organopolyoxane resin block of the oxirane unit represented by C 2 H 4 )SiO 1/2 is represented by the formula: -(CH 3 ) 2 SiO(C 6 H 5 ) 2 SiO(CH 3 ) 2 Si- The organopolyoxane in which the decyloxy groups are bonded.

[實施例3] [Example 3]

於反應容器中投入甲苯74.23g、質量平均分子量為1,560之平均單元式：(C6H5SiO3/2)0.75[(CH3)2(CH2=CH)SiO1/2]0.25所表示之有機聚矽氧烷樹脂之58.6質量%甲苯溶液170.65g、平均式：H(CH3)2SiO[(C6H5)2SiO]2.5Si(CH3)2H所表示之二有機聚矽氧烷13.34g(相對於上述有機聚矽氧烷樹脂中之乙烯基1莫耳，本成分中之鍵結於矽原子之氫原子成為0.2莫耳之量)，以114℃進行共沸脫水後，冷卻至室溫。繼而，添加鉑之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物(本錯合物中之鉑金屬相對於上述有機聚矽氧烷樹脂與上述二有機聚矽氧烷之合計量以質量單位計成為5ppm之量)，以112℃之甲苯回流溫度反應1.8小時。其後，冷卻至室溫，混合活性碳9.0g後，利用玻璃過濾器進行過濾。藉由對濾液以30~40mmHg、95~105℃進行加熱減壓而蒸餾去除甲苯，獲得折射率1.5462、於50℃~100℃發生熔融而成為透明液體、室溫下為白色之固體。可知，該固體係平均單元式：(C6H5SiO3/2)0.77[(CH3)2(CH2=CH)SiO1/2]0.20[O1/2Si(CH3)2-C2H4-(CH3)2SiO[(C6H5)2SiO]2.5(CH3)2Si-C2H4-(CH3)2SiO1/2]0.03所表示，且包含式：C6H5SiO3/2所表示之矽氧烷單元及式：(CH3)2(CH2=CH)SiO1/2所表示之矽氧烷單元及式：(CH3)2(-C2H4)SiO1/2所表示之矽氧烷單元之有機聚矽氧烷樹脂嵌段由式：-(CH3)2SiO[(C6H5)2SiO]2.5(CH3)2Si-所表示之矽烷氧基連結而成的有機聚矽氧烷。 Into the reaction vessel, 74.23 g of toluene and an average molecular weight of 1,560 were introduced: (C 6 H 5 SiO 3/2 ) 0.75 [(CH 3 ) 2 (CH 2 =CH)SiO 1/2 ] 0.25 The organic polyfluorene oxide resin has a 58.6 mass% toluene solution of 170.65 g, and an average formula: H(CH 3 ) 2 SiO[(C 6 H 5 ) 2 SiO] 2.5 Si(CH 3 ) 2 H 13.34 g of a decane (relative to the vinyl 1 mol in the above organopolysiloxane resin, the hydrogen atom bonded to the ruthenium atom in the composition is 0.2 mol), and azeotropically dehydrated at 114 ° C After that, it was cooled to room temperature. Then, a platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex (the platinum metal in the present complex is compared with the above organopolyoxyalkylene resin and the above) The total amount of the diorganopolyoxyalkylene oxide was 5 ppm in terms of mass units, and the reaction was carried out at a reflux temperature of toluene of 112 ° C for 1.8 hours. Thereafter, the mixture was cooled to room temperature, and 9.0 g of activated carbon was mixed, followed by filtration using a glass filter. Toluene was distilled off by heating and depressurizing the filtrate at 30 to 40 mmHg and 95 to 105 ° C to obtain a solid having a refractive index of 1.5462, melting at 50 to 100 ° C to form a transparent liquid, and white at room temperature. Understood, the solid system average unit formula: (C 6 H 5 SiO 3/2 ) 0.77 [(CH 3) 2 (CH 2 = CH) SiO 1/2] 0.20 [O 1/2 Si (CH 3) 2 - C 2 H 4 -(CH 3 ) 2 SiO[(C 6 H 5 ) 2 SiO] 2.5 (CH 3 ) 2 Si-C 2 H 4 -(CH 3 ) 2 SiO 1/2 ] 0.03 , and includes The oxime unit represented by C 6 H 5 SiO 3/2 and the oxime unit represented by the formula: (CH 3 ) 2 (CH 2 =CH)SiO 1/2 and the formula: (CH 3 ) 2 (-C 2 H 4 ) The organopolyoxyalkylene resin block of the oxoxane unit represented by SiO 1/2 is of the formula: -(CH 3 ) 2 SiO[(C 6 H 5 ) 2 SiO] 2.5 (CH 3 ) An organopolyoxane in which a decyloxy group represented by 2 Si- is bonded.

[實施例4] [Example 4]

於反應容器中投入甲苯149.67g、質量平均分子量為1,560之平均單元式：(C6H5SiO3/2)0.75[(CH3)2(CH2=CH)SiO1/2]0.25所表示之有機聚矽氧烷樹脂之58.6質量%甲苯溶液204.8g、式：H(CH3)2Si-C6H4-Si(CH3)2H所表示之雙(二甲基矽烷基)苯9.79g(相對於上述有機聚矽氧烷樹脂中之烯基1莫耳，本成分中之鍵結於矽原子之氫原子成為0.4莫耳之量)，以113℃進行共沸脫水後，冷卻至室溫。繼而，添加鉑之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物(本錯合物中之鉑金屬相對於上述有機聚矽氧烷樹脂與上述雙(二甲基矽烷基)苯之合計量以質量單位計成為5ppm之量)，以112℃之甲苯回流溫度反應2.6小時。其後，冷卻至室溫，混合活性碳9.6g後，利用玻璃過濾器進行過濾。對濾液以30~40mmHg、95~105℃進行加熱減壓，蒸餾去除甲苯，而獲得折射率1.5438、於50℃~100℃發生熔融而成為透明液體、室溫下為白色之固體。可知，該固體係平均單元式：(C6H5SiO3/2)0.79[(CH3)2(CH2=CH)SiO1/2]0.16[O1/2Si(CH3)2-C2H4-(CH3)2Si-C6H4-Si(CH3)2-C2H4-(CH3)2SiO1/2]0.05所表示，且包含式：C6H5SiO3/2所表示之矽氧烷單元及式：(CH3)2(CH2=CH)SiO1/2所表示之矽氧烷單元及式：(CH3)2(-C2H4)SiO1/2所表示之矽氧烷單元之有機聚矽氧烷樹脂嵌段由式：-(CH3)2Si-C6H4-Si(CH3)2-所表示之矽伸苯基連結而成的有機聚矽氧烷。 Into the reaction vessel, 149.67 g of toluene and a mass average molecular weight of 1,560 were introduced: (C 6 H 5 SiO 3/2 ) 0.75 [(CH 3 ) 2 (CH 2 =CH)SiO 1/2 ] 0.25 a 58.6 mass% toluene solution of an organic polyoxymethane resin, 204.8 g, of the formula: H(CH 3 ) 2 Si-C 6 H 4 -Si(CH 3 ) 2 H represented by bis(dimethylalkylalkyl)benzene 9.79 g (relative to the alkenyl group 1 mol in the above organopolysiloxane resin, the hydrogen atom bonded to the ruthenium atom in the present component is 0.4 mol), and azeotropically dehydrated at 113 ° C, followed by cooling To room temperature. Then, a platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex (the platinum metal in the present complex is compared with the above organopolyoxyalkylene resin and the above) The total amount of bis(dimethylalkylalkyl)benzene was 5 ppm by mass unit, and the reaction was carried out at a reflux temperature of toluene of 112 ° C for 2.6 hours. Thereafter, the mixture was cooled to room temperature, and 9.6 g of activated carbon was mixed, followed by filtration using a glass filter. The filtrate was heated and decompressed at 30 to 40 mmHg and 95 to 105 ° C, and toluene was distilled off to obtain a solid having a refractive index of 1.5438, melting at 50 to 100 ° C to form a transparent liquid, and white at room temperature. It can be seen that the solid system has an average unit formula: (C 6 H 5 SiO 3/2 ) 0.79 [(CH 3 ) 2 (CH 2 =CH)SiO 1/2 ] 0.16 [O 1/2 Si(CH 3 ) 2 - C 2 H 4 -(CH 3 ) 2 Si-C 6 H 4 -Si(CH 3 ) 2 -C 2 H 4 -(CH 3 ) 2 SiO 1/2 ] 0.05 , and contains: C 6 H 5 a siloxane unit represented by SiO 3/2 and a oxime unit represented by the formula: (CH 3 ) 2 (CH 2 =CH)SiO 1/2 and a formula: (CH 3 ) 2 (-C 2 H 4 ) The organopolyoxane resin block of the oxirane unit represented by SiO 1/2 is represented by the formula: -(CH 3 ) 2 Si-C 6 H 4 -Si(CH 3 ) 2 - An organic polyoxyalkylene linked by a phenyl group.

[實施例5] [Example 5]

於反應容器中投入甲苯52.83g、質量平均分子量為1,500之平均單元式：(C6H5SiO3/2)0.80[(CH3)2(CH2=CH)SiO1/2]0.20 所表示之有機聚矽氧烷樹脂之54.2質量%甲苯溶液221.50g、及式：H(CH3)2SiOSi(CH3)2H所表示之二矽氧烷3.37g(相對於上述有機聚矽氧烷樹脂中之乙烯基1莫耳，本成分中之鍵結於矽原子之氫原子成為0.4莫耳之量)，以113℃進行共沸脫水後，冷卻至室溫。繼而，添加鉑之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物(本錯合物中之鉑金屬相對於上述有機聚矽氧烷樹脂與上述二矽氧烷之合計量以質量單位計成為5ppm之量)，以113℃之甲苯回流溫度反應1小時。其後，藉由以30~40mmHg、100℃進行加熱減壓而蒸餾去除甲苯，獲得折射率1.5436、於50℃~100℃發生熔融而成為透明液體、室溫下為白色之固體。可知，該固體係平均單元式：(C6H5SiO3/2)0.82[(CH3)2(CH2=CH)SiO1/2]0.15[O1/2Si(CH3)2-C2H4-(CH3)2SiO(CH3)2Si-C2H4-(CH3)2SiO1/2]0.03所表示，且包含式：C6H5SiO3/2所表示之矽氧烷單元及式：(CH3)2(CH2=CH)SiO1/2所表示之矽氧烷單元及式：(CH3)2(-C2H4)SiO1/2所表示之矽氧烷單元之有機聚矽氧烷樹脂嵌段由式：-(CH3)2SiO(CH3)2Si-所表示之矽烷氧基連結而成的有機聚矽氧烷。 The reaction vessel was charged with 52.83 g of toluene and an average unit mass of 1,500 mass average molecular weight: (C 6 H 5 SiO 3/2 ) 0.80 [(CH 3 ) 2 (CH 2 =CH)SiO 1/2 ] 0.20 221.50 g of a 54.2% by mass toluene solution of the organopolysiloxane resin, and 3.37 g of a dioxane represented by H(CH 3 ) 2 SiOSi(CH 3 ) 2 H (relative to the above organopolyoxane) The vinyl group 1 mol in the resin, the hydrogen atom bonded to the ruthenium atom in the present component was 0.4 mol, and was azeotropically dehydrated at 113 ° C, and then cooled to room temperature. Then, a platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex (the platinum metal in the present complex is compared with the above organopolyoxyalkylene resin and the above) The total amount of dioxane was 5 ppm in mass units, and the reaction was carried out at a reflux temperature of toluene of 113 ° C for 1 hour. Then, toluene was distilled off by heating and decompressing at 30 to 40 mmHg and 100 ° C to obtain a solid having a refractive index of 1.5436, melting at 50 to 100 ° C to form a transparent liquid, and white at room temperature. It can be seen that the solid system has an average unit formula: (C 6 H 5 SiO 3/2 ) 0.82 [(CH 3 ) 2 (CH 2 =CH)SiO 1/2 ] 0.15 [O 1/2 Si(CH 3 ) 2 - C 2 H 4 —(CH 3 ) 2 SiO(CH 3 ) 2 Si—C 2 H 4 —(CH 3 ) 2 SiO 1/2 ] is represented by 0.03 and contains the formula: C 6 H 5 SiO 3/2 a oxoxane unit represented by the formula: (CH 3 ) 2 (CH 2 =CH) SiO 1/2 represented by a oxoxane unit and a formula: (CH 3 ) 2 (-C 2 H 4 )SiO 1/2 The organopolyoxane resin block of the oxoxane unit represented by the formula is an organopolyoxane in which a decyloxy group represented by the formula: -(CH 3 ) 2 SiO(CH 3 ) 2 Si- is bonded.

[實施例6] [Embodiment 6]

於反應容器中投入甲苯74.23g、質量平均分子量為1,560之平均單元式：(C6H5SiO3/2)0.75[(CH3)2(CH2=CH)SiO1/2]0.25所表示之有機聚矽氧烷樹脂之58.6質量%甲苯溶液170.60g、及式：H(CH3)2SiO[(C6H5)2SiO]2.5Si(CH3)2H所表示之二有機聚矽氧烷26.50g(相對於上述有機聚矽氧烷樹脂中之乙烯基1莫耳，本成分中之鍵結於矽原子之氫原子成為0.4莫耳之量)，以113℃進行共沸脫水後，冷卻至室溫。繼而，添加鉑之1,3-二乙烯基 -1,1,3,3-四甲基二矽氧烷錯合物(本錯合物中之鉑金屬相對於上述有機聚矽氧烷樹脂與上述二有機聚矽氧烷之合計量以質量單位計成為5ppm之量)，以112℃之甲苯回流反應12小時。其後，冷卻至室溫，混合活性碳12.0g後，利用玻璃過濾器進行過濾。藉由對濾液以30~40mmHg、95~105℃進行加熱減壓而蒸餾去除甲苯，獲得折射率1.5490、於50℃~100℃發生熔融而成為透明液體、室溫下為白色之固體。可知，該固體係平均單元式：(C6H5SiO3/2)0.79[(CH3)2(CH2=CH)SiO1/2]0.16[O1/2Si(CH3)2-C2H4-(CH3)2SiO[(C6H5)2SiO]2.5(CH3)2Si-C2H4-(CH3)2SiO1/2]0.05所表示，且包含式：C6H5SiO3/2所表示之矽氧烷單元及式：(CH3)2(CH2=CH)SiO1/2所表示之矽氧烷單元及式：(CH3)2(-C2H4)SiO1/2所表示之矽氧烷單元之有機聚矽氧烷樹脂嵌段由式：-(CH3)2SiO[(C6H5)2SiO]2.5(CH3)2Si-所表示之矽烷氧基連結而成的有機聚矽氧烷。 Into the reaction vessel, 74.23 g of toluene and an average molecular weight of 1,560 were introduced: (C 6 H 5 SiO 3/2 ) 0.75 [(CH 3 ) 2 (CH 2 =CH)SiO 1/2 ] 0.25 The organic polyfluorene oxide resin has a 58.6 mass% toluene solution of 170.60 g, and the formula: H(CH 3 ) 2 SiO[(C 6 H 5 ) 2 SiO] 2.5 Si(CH 3 ) 2 H 26.50 g of a decane (relative to the vinyl 1 mol in the above organopolysiloxane resin, the hydrogen atom bonded to the ruthenium atom in the present component is 0.4 mol), and azeotropically dehydrated at 113 ° C After that, it was cooled to room temperature. Then, a platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex (the platinum metal in the present complex is compared with the above organopolyoxyalkylene resin and the above) The total amount of the diorganopolyoxyalkylene oxide was 5 ppm in terms of mass units, and the reaction was refluxed at 112 ° C for 12 hours. Thereafter, the mixture was cooled to room temperature, and 12.0 g of activated carbon was mixed, followed by filtration using a glass filter. Toluene was distilled off by heating and depressurizing the filtrate at 30 to 40 mmHg and 95 to 105 ° C to obtain a solid having a refractive index of 1.5490, melting at 50 to 100 ° C to form a transparent liquid, and white at room temperature. It can be seen that the solid system has an average unit formula: (C 6 H 5 SiO 3/2 ) 0.79 [(CH 3 ) 2 (CH 2 =CH)SiO 1/2 ] 0.16 [O 1/2 Si(CH 3 ) 2 - C 2 H 4 -(CH 3 ) 2 SiO[(C 6 H 5 ) 2 SiO] 2.5 (CH 3 ) 2 Si-C 2 H 4 -(CH 3 ) 2 SiO 1/2 ] 0.05 , and includes The oxime unit represented by C 6 H 5 SiO 3/2 and the oxime unit represented by the formula: (CH 3 ) 2 (CH 2 =CH)SiO 1/2 and the formula: (CH 3 ) 2 (-C 2 H 4 ) The organopolyoxyalkylene resin block of the oxoxane unit represented by SiO 1/2 is of the formula: -(CH 3 ) 2 SiO[(C 6 H 5 ) 2 SiO] 2.5 (CH 3 ) An organopolyoxane in which a decyloxy group represented by 2 Si- is bonded.

[產業上之可利用性] [Industrial availability]

本發明之有機聚矽氧烷係有機聚矽氧烷樹脂嵌段由矽烷氧基或矽伸苯基連結而成、且折射率高、透明性高、操作性良好之有機聚矽氧烷，藉由加熱而進行熔融，可利用分子中之烯基進行矽氫化反應，故而可用作電氣、電子用之接著劑、灌封劑、保護塗佈劑、底部填充劑，尤其就硬化物之透光率較高而言，適宜作為光學用途之半導體元件之接著劑、灌封劑、保護塗佈劑、底部填充劑。 The organopolyoxyalkylene-based organopolyoxane resin block of the present invention is an organopolysiloxane having a high refractive index, high transparency, and good handleability, which is obtained by linking a decyloxy group or a fluorenylphenyl group. It is melted by heating, and can be used for the hydrogenation reaction of an alkenyl group in a molecule, so that it can be used as an adhesive for electric and electronic materials, a potting agent, a protective coating agent, an underfill, and especially a light-transmitting agent. In the case of a higher rate, it is suitable as an adhesive for a semiconductor component for optical use, a potting agent, a protective coating agent, and an underfill.

Claims (8)

一種有機聚矽氧烷，其係平均單元式：(R1SiO3/2)a(R1 2R2SiO1/2)b(O1/2SiR1 2R3-X-R3R1 2SiO1/2)c{式中，R1為相同或不同之碳數1~12之烷基、碳數6~20之芳基、或碳數7~20之芳烷基，R2為碳數2~12之烯基，R3為相同或不同之碳數2~12之伸烷基，其中，R1~R3之合計之至少10莫耳%為碳數6~20之芳基，X為通式(I)：-SiR4 2O(R4 2SiO)nSiR4 2-(式中，R4為相同或不同之碳數1~12之烷基、碳數6~20之芳基、或碳數7~20之芳烷基，n為0~5之整數)所表示之矽烷氧基，或通式(II)：-SiR4 2-C6H4-SiR4 2-(式中，R4與上述相同)所表示之矽伸苯基，a為0.65~0.90之數，b為0.04~0.29之數，c為0.01~0.07之數，且，a+b+c=1.00}所表示，且包含式：R1SiO3/2所表示之矽氧烷單元及式：R1 2R2SiO1/2所表示之矽氧烷單元及式：R1 2R3SiO1/2所表示之矽氧烷單元之有機聚矽氧烷樹脂嵌段(式中，R1、R2、及R3與上述相同)經由式中之R3而由上述矽烷氧基或上述矽伸苯基連結。 An organopolymethoxyalkane having an average unit formula: (R 1 SiO 3/2 ) a (R 1 2 R 2 SiO 1/2 ) b (O 1/2 SiR 1 2 R 3 -XR 3 R 1 2 SiO 1/2 ) c { wherein R 1 is the same or different alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R 2 is carbon The alkenyl group having 2 to 12, R 3 being the same or different alkylene group having 2 to 12 carbon atoms, wherein at least 10 mol% of the total of R 1 to R 3 is an aryl group having 6 to 20 carbon atoms. X is a general formula (I): -SiR 4 2 O(R 4 2 SiO) n SiR 4 2 - (wherein R 4 is the same or different alkyl group having 1 to 12 carbon atoms, and the carbon number is 6 to 20 An aryl group, or an aralkyl group having 7 to 20 carbon atoms, n is an integer represented by 0 to 5, or a formula (II): -SiR 4 2 -C 6 H 4 -SiR 4 2 - (wherein R 4 is the same as above) is a phenyl group, a is a number from 0.65 to 0.90, b is a number from 0.04 to 0.29, c is a number from 0.01 to 0.07, and a+b+c= Included by 1.00}, and include a formula: a oxoxane unit represented by R 1 SiO 3/2 and a fluorinated alkane unit represented by the formula: R 1 2 R 2 SiO 1/2 and a formula: R 1 2 R 3 SiO An organopolyoxyalkylene resin block of 1/2 represented by a siloxane unit (wherein R 1 , R 2 , and R 3 is the same as above) and is bonded to the above decyloxy group or the above-mentioned phenylene group through R 3 in the formula. 如請求項1之有機聚矽氧烷，其中平均單元式中，R2為乙烯基，R3為伸乙基。 The organopolyoxane of claim 1, wherein in the average unit formula, R 2 is a vinyl group and R 3 is an exoethyl group. 如請求項1或2之有機聚矽氧烷，其中通式(I)中，於R4全部為碳數1~12之烷基之情形時，n為0。 The organopolyoxane of claim 1 or 2, wherein in the case of the formula (I), when all of R 4 are an alkyl group having 1 to 12 carbon atoms, n is 0. 如請求項1或2之有機聚矽氧烷，其中可見光(589nm)之折射率(25℃)為1.50以上。 The organopolyoxane of claim 1 or 2, wherein the visible light (589 nm) has a refractive index (25 ° C) of 1.50 or more. 如請求項3之有機聚矽氧烷，其中可見光(589nm)之折射率(25℃)為1.50以上。 The organopolyoxane of claim 3, wherein the visible light (589 nm) has a refractive index (25 ° C) of 1.50 or more. 一種如請求項1之有機聚矽氧烷之製造方法，其係使(A)平均單元式：(R1SiO3/2)d(R1 2R2SiO1/2)e(式中，R1為相同或不同之碳數1~12之烷基、碳數6~20之芳基、或碳數7~20之芳烷基，R2為碳數2~12之烯基，其中，R1與R2之合計之至少10莫耳%為碳數6~20之芳基，d為0.65~0.90之數，e為0.10~0.35之數，且，d+e=1.00)所表示之有機聚矽氧烷樹脂與(B)(B-1)通式：HR4 2SiO(R4 2SiO)nSiR4 2H(式中，R4為相同或不同之碳數1~12之烷基、碳數6~20之芳基、或碳數7~20之芳烷基，n為0~5之整數)所表示之二有機矽氧烷或(B-2)通式：HR4 2Si-C6H4-SiR4 2H(式中，R4與上述相同)所表示之雙矽烷基苯進行矽氫化反應而成。 A method for producing an organopolyoxane according to claim 1, which comprises (A) an average unit formula: (R 1 SiO 3/2 ) d (R 1 2 R 2 SiO 1/2 ) e (wherein R 1 is the same or different alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R 2 is an alkenyl group having 2 to 12 carbon atoms, wherein At least 10 mol% of the total of R 1 and R 2 is an aryl group having 6 to 20 carbon atoms, d is a number of 0.65 to 0.90, e is a number of 0.10 to 0.35, and d + e = 1.00) The organic polydecane resin and (B) (B-1) have the formula: HR 4 2 SiO(R 4 2 SiO) n SiR 4 2 H (wherein R 4 is the same or different carbon number 1 to 12) An alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, n is an integer of 0 to 5, or a compound of the formula (B-2): HR 4 2 is a hydrogenation reaction of a dinonylalkylbenzene represented by Si-C 6 H 4 -SiR 4 2 H (wherein R 4 is the same as defined above). 如請求項6之有機聚矽氧烷之製造方法，其中(A)成分中之R2為乙烯基。 The method for producing an organopolyoxane according to claim 6, wherein R 2 in the component (A) is a vinyl group. 如請求項6或7之有機聚矽氧烷之製造方法，其中於(B-1)成分中之R4全部為碳數1~12之烷基之情形時，n為0。 The method for producing an organopolyoxane according to claim 6 or 7, wherein, in the case where all of R 4 in the component (B-1) are an alkyl group having 1 to 12 carbon atoms, n is 0.
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* Cited by examiner, † Cited by third party
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Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6689859B2 (en) * 2002-03-05 2004-02-10 Dow Corning Corporation High fracture toughness hydrosilyation cured silicone resin
US6646039B2 (en) * 2002-03-05 2003-11-11 Dow Corning Corporation Hydrosilyation cured silicone resin containing colloidal silica and a process for producing the same
JP4908736B2 (en) * 2003-10-01 2012-04-04 東レ・ダウコーニング株式会社 Curable organopolysiloxane composition and semiconductor device
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JP5972512B2 (en) * 2008-06-18 2016-08-17 東レ・ダウコーニング株式会社 Curable organopolysiloxane composition and semiconductor device
JP5667740B2 (en) * 2008-06-18 2015-02-12 東レ・ダウコーニング株式会社 Curable organopolysiloxane composition and semiconductor device
US20150299543A1 (en) * 2012-12-07 2015-10-22 Dow Corning Toray Co., Ltd. Curable Silicone Composition And Optical Semiconductor Device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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