TWI389981B - Room temperature hardened organopolysiloxane composition - Google Patents
Room temperature hardened organopolysiloxane composition Download PDFInfo
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本發明係有關適用於建築用、電氣．電子零件之黏著、密封所使用之材料的脫酮型變色少之室溫硬化性有機聚矽氧組成物。 The invention relates to the application for construction and electrical. A room temperature curable organopolyfluorene composition having less deketalized discoloration of a material used for adhesion and sealing of electronic parts.
建築用磚縫(masonry joint)之密封、濾器周邊部密封、電氣．電子零件之黏著．密封等中，由其耐氣候性、耐熱性、電氣特性及作業性面多半使用室溫硬化性有機聚矽氧烷組成物。近年來，為提昇建築物之工業設計性，做為建築用密封材料使用時，特別受重視完成後之外觀。惟，脫酮型之室溫硬化性有機聚矽氧烷組成物有致命性之經時間性導致外觀泛黃變色之問題，特別是缺乏做為建築用密封材料之實用性。 Seal of masonry joint for construction, seal around the filter, electrical. Adhesive of electronic parts. In the sealing or the like, a room temperature curable organopolyoxane composition is mostly used for weather resistance, heat resistance, electrical properties, and workability. In recent years, in order to improve the industrial design of buildings, when used as a sealing material for construction, the appearance after completion is particularly emphasized. However, the deketone type room temperature curable organopolyoxane composition has a fatal time-dependent appearance of yellowing discoloration, and in particular, lacks practicality as a building sealing material.
有關先前技術亦被揭示有即使於高溫高濕下外加電壓時仍不降低絕緣值之耐電蝕性良好之組成物(專利文獻1：日本特開2003-012927號公報)、添加第1級胺化合物後可提昇組成物之深部硬化性之組成物(專利文獻2：日本專利第2841155號公報)，經由添加具有SH基之矽氧烷與增感劑之紫外線硬化性組成物(專利文獻3：日本特開昭62-96562號公報、專利文獻4：日本特開昭62-197453號公報、專利文獻5：日本特開昭63-10632號公報、專利文獻6：日本特開昭63-189460號公報等)等， 可提昇特殊性能之技術者，惟，其中完全未提及經時間性變色之相關對策，另外如：做為建築用密封材料，特別是無塵室用者，如：依經由基板表面吸附-加熱解吸法(對於聚矽氧晶圓之吸附試驗)(JACA，No.34)之測定由硬化物所生成之低分子聚矽氧及有機物質量少之組成物(專利文獻7：日本特開2003-183505號公報)之例，惟其中亦未提及組成物經時間之變色對策等。 In the related art, a composition having excellent corrosion resistance which does not lower the insulation value even when a voltage is applied under high temperature and high humidity is disclosed (Patent Document 1: JP-A-2003-012927), and a first-stage amine compound is added. After that, the composition of the deep-hardening property of the composition can be improved (Patent Document 2: Japanese Patent No. 2841155), and an ultraviolet curable composition containing a SH group-containing oxime and a sensitizer (Patent Document 3: Japan) JP-A-62-96562, JP-A-62-197453, JP-A-63-197453, JP-A-63-196, 460, and JP-A-63-189460 and many more, A technician who can improve special performance, but there is no mention of countermeasures related to temporal discoloration, and another example: as a sealing material for construction, especially for clean room users, such as: adsorption-heating via substrate surface Desorption method (adsorption test for polyfluorene oxide wafers) (JACA, No. 34) The composition of low molecular weight polyfluorene and organic matter produced by hardened materials is measured (Patent Document 7: JP-A-2003- In the case of 183505, there is no mention of countermeasures for the discoloration of the composition over time.
[專利文獻1]日本特開2003-012927號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-012927
[專利文獻2]日本專利第2841155號公報 [Patent Document 2] Japanese Patent No. 2841155
[專利文獻3]日本特開昭62-96562號公報 [Patent Document 3] Japanese Laid-Open Patent Publication No. 62-96562
[專利文獻4]日本特開昭62-197453號公報 [Patent Document 4] Japanese Laid-Open Patent Publication No. 62-197453
[專利文獻5]日本特開昭63-10632號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 63-10632
[專利文獻6]日本特開昭63-189460號公報 [Patent Document 6] JP-A-63-189460
[專利文獻7]日本特開2003-183505號公報 [Patent Document 7] Japanese Patent Laid-Open Publication No. 2003-183505
本發明係鑑於上述情況所完成者，提供一種於硬化前後，經時組成物未出現泛黃變色，適用於建築用密封材料電氣．電子零件之黏著．密封之材料的室溫硬化性有機聚矽氧組成物為其目的。 The present invention is made in view of the above circumstances, and provides a yellowing discoloration of the composition over time before and after hardening, and is suitable for electrical insulation materials for construction. Adhesive of electronic parts. The room temperature hardening organopolyfluorene composition of the sealed material is for its purpose.
本發明者為達成上述目的，對於先前未被探討之經時間性變色問題進行精密研討後結果，發現經時之變色原因係於製造時組成物中含微量之酮化合物、及經時後組成物中所生成之酮化合物與含有1級胺之化合物反應後，所生 成之酮亞胺化合物被氧化後呈黃色~褐色物質之新的發現。因此，使用不含1級胺基之矽烷化合物及其部份水解物後，討論滿足黏著特性等之組成物之結果發現經時之組成物無泛黃變色，本組成物為極適於建築用之密封材料、電氣．電子零件用之黏著劑．密封材料者，進而完成本發明。 In order to achieve the above object, the inventors of the present invention conducted a detailed study on the problem of temporal discoloration which has not been previously investigated, and found that the cause of discoloration over time is a trace amount of a ketone compound and a composition after time. The ketone compound formed in the reaction with the compound containing the amine of the first grade The ketone imine compound is oxidized to a new yellow-brown substance. Therefore, after using a decane compound having no amine group 1 and a partial hydrolyzate thereof, the composition satisfying the adhesive property or the like is discussed as a result of finding that the composition over time has no yellowing discoloration, and the composition is highly suitable for construction. Sealing material, electrical. Adhesive for electronic parts. The sealing material is used to complete the present invention.
因此，本發明之特徵係提供一種含有(A)分子鏈末端被羥基、烷氧基、或烯氧基所封端之二有機聚矽氧烷：100質量份、(B)具有一般式(1)
(式中，R1、R2分別為氫原子或取代或非取代之一價烴基)所示基之矽烷化合物或其部份水解物：0.5~30質量份、(C)1分子中不含1級胺基，較佳者為至少含有1種二級或三級胺基之(B)成份以外的矽烷化合物或其部份水解物：0.1~30質量份之變色少之室溫硬化性有機聚矽氧烷組成物。 a decane compound or a partial hydrolyzate thereof (wherein R 1 and R 2 are each a hydrogen atom or a substituted or unsubstituted one-valent hydrocarbon group): 0.5 to 30 parts by mass, and (C) 1 molecule is not contained a primary amine group, preferably a decane compound other than the component (B) having at least one secondary or tertiary amine group or a partial hydrolyzate thereof: 0.1 to 30 parts by mass of a room temperature hardening organic substance having less discoloration Polyoxane composition.
此時，更佳者為含有(D)具有下述一般式(2)
(式中，R3、R4分別為氫原子或1價烴基。) (wherein R 3 and R 4 are each a hydrogen atom or a monovalent hydrocarbon group.)
之1價基之有機矽化合物或其部份水解物：0.01~10質量份。 The monovalent organic hydrazine compound or a partial hydrolyzate thereof: 0.01 to 10 parts by mass.
又，含有1~100質量份之表面經疏水化處理之燻矽、或含有1~100質量份之表面以選自脂肪酸、脂肪酸酯、及烴之表面處理劑所處理之碳酸鈣者宜。 Further, it is preferred that the surface contains 1 to 100 parts by mass of the hydrophobized smoked sputum or the surface of the calcium carbonate treated with a surface treatment agent selected from the group consisting of fatty acids, fatty acid esters, and hydrocarbons in an amount of from 1 to 100 parts by mass.
本發明可取得經時間性變色少、黏著性佳之室溫硬化性有機聚矽氧烷組成物，除最適於建築用密封材料之外，亦適用於電氣、電子零件用之黏著劑，亦可廣泛用於對於各種基材之密封劑、塗層劑。 The invention can obtain a room-temperature hardening organopolyoxane composition with less time-changing and good adhesion, and is suitable for adhesives for electrical and electronic parts, and is also widely applicable to sealing materials for building materials. It is used as a sealant and coating agent for various substrates.
本發明室溫硬化性有機聚矽氧烷組成物中，(A)成份之二有機聚矽氧烷係做為此組成物主要聚合物使用之。做為二有機聚矽氧烷者，只要分子鏈末端以羥基、碳數1~6之烷氧基或碳數2~6之烯氧基所封端者即可，而，平均組成式：R5aSiO(4-a)/2(其中，R5為取代或非取代之一價烴基，a為1.90~2.05之正數。)所示之分子鏈末端被羥基、烷氧基或烯氧基所封端者宜。做為R5者以碳數1~10，特別是1~8為宜，具體例如：甲基、乙基、丙基、丁基等之烷基、乙烯基、烯丙基等烯基、苯基、甲苯基等芳基、苄基、2-苯基乙基等之芳烷基、或此等部份或全部氫原子被鹵素原子等取代之氯甲基、3,3,3-三氟丙基等例 。做為此二有機聚矽氧烷者如下式所示者宜。 In the room temperature curable organopolyoxane composition of the present invention, the diorganopolysiloxane of the component (A) is used as the main polymer of the composition. As the diorganopolyoxyalkylene, as long as the end of the molecular chain is terminated by a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms or an alkenyloxy group having 2 to 6 carbon atoms, the average composition formula: R 5 aSiO (4-a)/2 (wherein R 5 is a substituted or unsubstituted one-valent hydrocarbon group, a is a positive number of 1.90 to 2.05.) The molecular chain terminal is represented by a hydroxyl group, an alkoxy group or an alkenyloxy group. The sealer should be suitable. As R 5 , carbon number is 1 to 10, especially 1 to 8. Specifically, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, an alkenyl group such as a vinyl group or an allyl group, or a benzene group. An aryl group such as an aryl group such as a benzyl group or a tolyl group, an aralkyl group such as a benzyl group or a 2-phenylethyl group, or a chloromethyl group or a 3,3,3-trifluoro group in which some or all of the hydrogen atoms are replaced by a halogen atom or the like. Examples of propyl and the like. It is preferred that the two organopolyoxyalkylenes are as shown in the following formula.
(式中，R5如上所述者。m係可將此二有機聚矽氧烷之25℃中將黏度做成25~1,000,000mPa．s之數。) (In the formula, R5 is as described above. The m system can make the viscosity of the diorganopolyoxyalkylene at 25 ° C to 25 to 1,000,000 mPa·s.)
具體而言，可例示下述式之二有機聚矽氧烷。 Specifically, an organic polyoxane of the following formula can be exemplified.
(式中，m、n、k為正的整數，m及n+k係此二有機聚矽氧烷於25℃之黏度為25~1,000,000mPa．s之數。Me代表甲基、Ph代表苯基、Vi代表乙烯基。) (wherein m, n, and k are positive integers, and m and n+k are the number of the diorganopolyoxyalkylene having a viscosity of 25 to 1,000,000 mPa·s at 25 ° C. Me represents a methyl group, and Ph represents a benzene. Base, Vi stands for vinyl.)
另外，組成物之硬化物顯示良好之橡膠彈性體，為做為且良好機械強度時，此(A)成份於25℃之黏度為25~1,000,000mPa．s，特別以100~1,000,000mPa．s者佳，較佳者為200~300,000mPa．s，更佳者為300~100,000mPa．s。 In addition, the cured product of the composition exhibits a good rubber elastomer. When used as a good mechanical strength, the viscosity of the component (A) at 25 ° C is 25 to 1,000,000 mPa. s, especially 100~1,000,000mPa. s is better, preferably 200~300,000mPa. s, the better is 300~100,000mPa. s.
又，(B)成份係具有一般式(1)所示基之矽烷化合物或其部份水解物者。 Further, the component (B) is a decane compound having a group represented by the general formula (1) or a partial hydrolyzate thereof.
其中，R1、R2分別為氫原子或取代或非取代之一價烴基，做為1價烴基例者以碳數1~10，特別是1~8者為宜，可與上述R5相同之示例。 Wherein, R 1 and R 2 are each a hydrogen atom or a substituted or unsubstituted one-valent hydrocarbon group; and as a monovalent hydrocarbon group, those having a carbon number of 1 to 10, particularly 1 to 8, are preferably the same as the above R 5 . An example of this.
此(B)成份之矽烷化合物或其部份水解物係本組成物硬化後賦與橡膠彈性體之必要成份者。 The decane compound of the component (B) or a partial hydrolyzate thereof is a component which is imparted to the rubber elastomer after the composition is cured.
做為(B)成份之矽烷化合物或其部份水解物者，以下述一般式(3)
(R1、R2如上所述，R6係與R5為相同之碳數1~10，特別為1~8之1價烴基，X為3或4。) (R 1 and R 2 are as described above, and R 6 and R 5 are the same carbon number 1 to 10, particularly 1 to 8 monovalent hydrocarbon group, and X is 3 or 4.)
所示之矽烷化合物或其部份水解物者宜，如：四異丙烯氧基矽烷、甲基三異丙烯氧基矽烷、乙烯三異丙烯氧基矽烷、苯基三異丙烯氧基矽烷、二甲基二異丙氧基矽烷或其部份水解物之例。 The decane compound or a partial hydrolyzate thereof is preferably, for example, tetraisopropoxy decane, methyl triisopropoxy decane, ethylene triisopropoxy decane, phenyl triisopropoxy decane, and An example of methyl diisopropoxydecane or a partial hydrolyzate thereof.
該(B)成份之量為每(A)成份100質量份為0.5~30質量份，較佳者為1~15質量份。對於(A)成份100質量份未達0.5質量份時，則硬化物將無法顯現足夠之機械性強度，反之，超出30質量份進行配合後，則將降低硬化後之橡膠強度，而不易取得目的之橡膠彈性體，亦不利經濟面。 The amount of the component (B) is 0.5 to 30 parts by mass, preferably 1 to 15 parts by mass per 100 parts by mass of the component (A). When 100 parts by mass of the component (A) is less than 0.5 part by mass, the cured product will not exhibit sufficient mechanical strength, and if it exceeds 30 parts by mass, the rubber strength after hardening will be lowered, and the purpose of the hardening is not easy. The rubber elastomer is also uneconomical.
又，(C)成份為本發明最重要之要素，1分子中不含1級胺基之(B)成份以外之矽烷化合物或其部份水解物。此(C)成份之矽烷化合物或其部份水解物係於本組 成物經時後不變色，硬化後為賦與良好黏著性之必要成份。 Further, the component (C) is the most important element of the present invention, and a decane compound other than the component (B) of the first-order amine group or a partial hydrolyzate thereof is not contained in one molecule. The decane compound of the component (C) or a partial hydrolyzate thereof is in this group The adult does not change color after the passage of time, and is hardened to be a necessary component for imparting good adhesion.
此(C)成份之例如：不含1級胺基之烷氧基之碳數為1~8之烷氧基矽烷(特別是三烷氧基矽烷)，含1級胺基之烷氧基之碳數1~8之烷氧基矽烷(特別是三烷氧基矽烷)與氯烷基三烷氧基矽烷等之具有氯原子之烷氧基矽烷(特別是三烷氧基矽烷)之脫鹽酸反應的加成物，含1級胺基之烷氧基碳數1~8之烷氧基矽烷(特別是三烷氧基矽烷)與含有環氧基之烷氧基之碳數1~8之烷氧基矽烷(特別是三烷氧基矽烷)之邁克耳加成物，此等部份水解物之例。 The component (C) is, for example, an alkoxy decane having 1 to 8 carbon atoms (particularly a trialkoxy decane) having an alkoxy group having no amine group of 1 degree, and an alkoxy group having a primary amino group. Dehydrochloric acid of alkoxy decane having a chlorine atom (especially a trialkoxy decane) having a carbon number of 1 to 8 (e.g., a trialkoxy decane) and a chloroalkyltrialkoxy decane The adduct of the reaction, the alkoxy decane having 1 to 8 carbon atoms of alkoxy group having a primary amino group (particularly a trialkoxy decane) and the alkoxy group having an epoxy group having 1 to 8 carbon atoms A Michaele adduct of an alkoxydecane (especially a trialkoxydecane), an example of such a partial hydrolyzate.
此時，(C)成份雖為不含1級胺基者，但由提昇黏著性之目的面視之，以含有2級胺基或3級胺基者宜。 In this case, although the component (C) is a group which does not contain a grade 1 amine group, it is preferable to have a grade 2 amine group or a grade 3 amine group from the viewpoint of improving adhesion.
做為(C)成份例者如：γ-環氧丙氧基丙基三甲氧基矽烷、γ-氫硫基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-丙烯醯氧基丙基三甲氧基矽烷、或其部份水解物等之不含胺基之矽烷化合物類、γ-胺基丙基三乙氧基矽烷1莫耳與氯丙基三甲氧基矽烷1莫耳之脫鹽酸反應之加成物、N-β(胺基乙基)γ-胺基丙基三甲氧基矽烷1莫耳與氯丙基三甲氧基矽烷1莫耳之脫鹽酸反應之加成物、γ-胺基丙基三乙氧基矽烷與γ-環氧丙氧基丙基三甲氧基矽烷之邁克耳加成物或其部份水解物等例。 As the component (C), for example, γ-glycidoxypropyltrimethoxydecane, γ-hydrothiopropyltrimethoxydecane, γ-methylpropenyloxypropyltrimethoxydecane , γ-acryloxypropyltrimethoxydecane, or a partial hydrolyzate thereof, an amine group-free decane compound, γ-aminopropyltriethoxydecane 1 molar and chloropropyltrimethyl Addition of oxydecane 1 molar dehydrochlorination reaction, N-β(aminoethyl)γ-aminopropyltrimethoxydecane 1 molar and chloropropyltrimethoxydecane 1 molar An adduct of a hydrochloric acid reaction, a Michaele addition of γ-aminopropyltriethoxydecane and γ-glycidoxypropyltrimethoxydecane, or a partial hydrolyzate thereof.
該(C)成份之量為每100質量份之(A)成份以0.1~30質量份，較佳為0.3~20質量份，特別是0.5~15質 量份為最佳。當對於100質量份之(A)成份未達0.1質量份時，則硬化物無法顯示充份之黏著性能，反之，超出30質量份配合後則降低硬化後之橡膠強度，而無法取得目的之橡膠彈性體，亦不利經濟面。 The amount of the component (C) is 0.1 to 30 parts by mass, preferably 0.3 to 20 parts by mass, particularly 0.5 to 15 parts per 100 parts by mass of the (A) component. The amount is optimal. When it is less than 0.1 part by mass for 100 parts by mass of the component (A), the cured product cannot exhibit sufficient adhesive properties, and if it exceeds 30 parts by mass, the rubber strength after hardening is lowered, and the rubber of interest cannot be obtained. Elastomers are also uneconomical.
本發明室溫硬化性有機聚矽氧烷組成物由其速硬化面觀之，更以含具有(D)成份之下述一般式(2)
(式中，R3、R4分別為氫原子或1價烴基。) (wherein R 3 and R 4 are each a hydrogen atom or a monovalent hydrocarbon group.)
所示之1價基之有機矽化合物或其部份水解物者為更佳。 The monovalent organic hydrazine compound or a partial hydrolyzate thereof shown is more preferred.
此時，做為R3、R4之1價烴基者以碳數1~10，特別是1~8者宜，與R5為相同示例者。又，上述一般式(2)之基經由任意基鍵結於矽原子均可，一般經由伸烷基或氧化烯基(oxyalkylene)鍵結於矽原子者宜。 In this case, the monovalent hydrocarbon group of R 3 and R 4 is preferably a carbon number of 1 to 10, particularly preferably 1 to 8, and is the same as R 5 . Further, the group of the above general formula (2) may be bonded to a ruthenium atom via an arbitrary bond, and is generally bonded to a ruthenium atom via an alkylene group or an oxyalkylene group.
做為(D)成份之有機矽化合物例者如：下述一般式(4)所示例者。 Examples of the organic hydrazine compound as the component (D) are as shown in the following general formula (4).
(R3、R4如上述，Q為碳數1~6之伸烷基或氧化烯基、R8為氫原子，碳數1~10，特別是碳數1~8之1價 烴基或-SOiR8b(OR9)3-b(b為0，1或2)、R9為氫原子或碳數1~10，特別是1~8之1價烴基，y為0~5之整數，z為0，1或2。) (R 3 and R 4 are as defined above, wherein Q is an alkylene group or an oxyalkylene group having 1 to 6 carbon atoms, R 8 is a hydrogen atom, and a carbon number is 1 to 10, particularly a monovalent hydrocarbon group having 1 to 8 carbon atoms or SOiR 8 b(OR 9 ) 3-b (b is 0, 1 or 2), R 9 is a hydrogen atom or a carbon number of 1 to 10, particularly a monovalent hydrocarbon group of 1 to 8, and y is an integer of 0 to 5, z is 0, 1 or 2.)
具體而言，如下式所示之例。又，下式中，Me為甲基、Et為乙基、Pr為丙基、Ph為苯基。 Specifically, it is an example shown by the following formula. Further, in the following formula, Me is a methyl group, Et is an ethyl group, Pr is a propyl group, and Ph is a phenyl group.
此等中由易於合成面視之，以下式所示之有機矽化合物為宜。 Among these, an organic ruthenium compound represented by the following formula is preferred from the viewpoint of easy synthesis.
[化9](Me2N)2C=N-(CH2)2-Si(OMe)3 (Me 2 N) 2 C=N-(CH 2 ) 2 -Si(OMe) 3
(D)成份之配合量對於100質量份之(A)成份為0.01~10重量份，特別以0.1~5重量份為更佳。當(D) 成份太多時則反應生成物將變色，恐亦不利經濟面。 The amount of the component (D) is preferably 0.01 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight, per 100 parts by mass of the component (A). When (D) When there are too many ingredients, the reaction product will change color, which may also be unfavorable to the economy.
本發明之組成物中為提昇聚矽氧橡膠彈性體之機械性質，可添加燻矽，特別是以有機矽化合物進行表面之硫水化處理之二氧化矽為更佳。燻矽之配合量對於(A)成份100質量份為1~100質量份，特別是3~50質量份為更佳。 In the composition of the present invention, in order to enhance the mechanical properties of the polyoxyethylene rubber elastomer, it is preferable to add smoked cockroaches, in particular, cerium oxide which is subjected to surface sulfidation treatment with an organic cerium compound. The amount of the smoked mash is preferably from 1 to 100 parts by mass, particularly from 3 to 50 parts by mass, per 100 parts by mass of the component (A).
更由為提昇黏著性及保存安定性面觀之，配合以選自脂肪酸、脂肪酸酯、及烴之表面處理劑進行表面處理之碳酸鈣者宜。此處理之碳酸鈣的配合量對於(A)成份100質量份為1~100質量份，特別以5~75質量份為更佳。 Further, it is preferable to use a calcium carbonate which is surface-treated with a surface treatment agent selected from the group consisting of fatty acids, fatty acid esters, and hydrocarbons in order to improve adhesion and maintain stability. The amount of the calcium carbonate to be treated is preferably from 1 to 100 parts by mass, particularly preferably from 5 to 75 parts by mass, per 100 parts by mass of the component (A).
又，亦可配合上述以外之填充劑，填充劑例如：沈降二氧化矽、矽藻土、氧化鐵、氧化鋅、氧化鈦等金屬氧化物、或此等表面經矽烷處理者、碳酸鈣、碳酸鎂、碳酸鋅等金屬碳酸鹽、石棉、玻璃絨、碳黑、微粉雲母、熔融粉末、聚苯乙烯、聚氯化乙烯、聚丙烯等合成樹脂粉末例。更為調節其物性之目的下，亦可任意添加賦予觸變性劑、耐熱性提昇劑、著色劑、賦予黏著性劑等。此等中又以添加賦予黏著性劑為較佳，做為賦予黏著性劑例者如：含胺基之矽烷偶合劑等矽烷偶合劑為例。賦予黏著性劑對於(A)成份100質量份較佳為0.1~10質量份，特別是0.5~5質量份為更佳。 Further, a filler other than the above may be blended, for example, a metal oxide such as precipitated cerium oxide, diatomaceous earth, iron oxide, zinc oxide or titanium oxide, or a surface treated with decane, calcium carbonate or carbonic acid. Examples of synthetic resin powders such as metal carbonates such as magnesium and zinc carbonate, asbestos, glass wool, carbon black, fine powder mica, molten powder, polystyrene, polyvinyl chloride, and polypropylene. Further, the thixotropic agent, the heat resistance improving agent, the coloring agent, the adhesive agent, and the like may be added arbitrarily for the purpose of adjusting the physical properties thereof. In this case, it is preferable to add an adhesive to be added, and as an example of a decane coupling agent such as an amine-containing decane coupling agent which imparts an adhesive agent. The adhesive agent is preferably 0.1 to 10 parts by mass, particularly preferably 0.5 to 5 parts by mass, per 100 parts by mass of the component (A).
做為先行技術用於此種組成物之縮合反應觸媒者為有機錫化合物，如：有效量之二丁錫二乙酸酯、二丁錫二辛酸酯、二丁錫二月桂酸酯、二丁錫二油酸酯、二苯錫二乙 酸酯、二丁錫氧化物、二丁錫二甲醇鹽、二丁基雙(三乙氧基矽氧基)錫、二丁錫苄基馬來酸酯等、有機酞化合物、四異丙氧基鈦、四丁氧基鈦、鈦雙乙醯丙酮配位基等，較佳者對於(A)成份100質量份為0.01~10質量份、特別以0.05~5質量份添加者均可。 As a prior art, the condensation reaction catalyst for such a composition is an organotin compound, such as an effective amount of dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin dilaurate, Dibutyltin dioleate, diphenyltin di Acid ester, dibutyltin oxide, dibutyltin dimethoxide, dibutyl bis(triethoxydecyloxy)tin, dibutyltinbenzyl maleate, organic ruthenium compound, titanium tetraisopropoxide The tetrabutoxytitanium, the titanium diacetone acetone ligand, and the like are preferably added in an amount of 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass, per 100 parts by mass of the component (A).
本發明之室溫硬化性有機聚矽氧烷組成物只要以捏合混合器、行星混合器等進行混合上述之(A)~(C)成份及其他成份即可，混合可1次進行元成，亦可分數次混合之，又(A)~(C)成份及其他成份於密閉、減壓下進行混合亦可。此時混合溫度以室溫至100℃者宜。 The room temperature curable organopolyoxane composition of the present invention may be obtained by mixing the above components (A) to (C) and other components by a kneading mixer, a planetary mixer or the like, and mixing may be carried out once. It can also be mixed in fractions, and the ingredients (A) to (C) and other ingredients can be mixed under closed pressure and reduced pressure. At this time, the mixing temperature is preferably from room temperature to 100 ° C.
如此取得之本發明組成物藉由濕氣硬化後做成聚矽氧橡膠。此橡膠彈性體具有聚矽氧橡膠之特徵的良好耐熱性、耐氣候性、低溫特性，因此可廣泛圍之實用化者。 The composition of the present invention thus obtained is cured by moisture to form a polyoxyxene rubber. Since this rubber elastic body has the characteristics of good heat resistance, weather resistance, and low temperature characteristics which are characteristic of polyoxyxene rubber, it can be widely used.
因此，本發明室溫硬化性有機聚矽氧烷組成物特別適用於建築用密封材料、電氣．電子用黏著．密封材料。 Therefore, the room temperature hardening organopolyoxane composition of the present invention is particularly suitable for use in building sealing materials, electrical. Electronic with adhesive. Sealing material.
以下，以實施例及比較例為例，進行本發明具體的說明，惟，本發明未受限於下述實施例者。另外，例中之份係代表質量份，又，黏度為25℃下旋轉黏度計之測定值。 Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples. In addition, the parts in the examples represent the parts by mass, and the viscosity is the measured value of the rotational viscometer at 25 °C.
使兩末端被羥基所封端，黏度為20,000mPa．s之二甲基聚矽氧烷85份與表面以二甲基二氯矽烷所處理之煙 霧狀二氧化矽15份均勻地混合而製造基劑混合物。再於該基劑混合物100份中配合苯基三異丙烯氧基矽烷6份、γ-四甲基胍基丙基三甲氧基矽烷0.5份、γ-環氧丙氧基丙基三甲氧基矽烷1份，於濕份阻斷、減壓下完全混合後，調製室溫硬化性有機聚矽氧烷組成物。 The ends are blocked by hydroxyl groups and have a viscosity of 20,000 mPa. 85 parts of s dimethyl polyoxane and smoke treated with dimethyldichloromethane on the surface The hazy cerium oxide 15 parts were uniformly mixed to prepare a base mixture. Further, in 100 parts of the base mixture, 6 parts of phenyltriisopropenyloxydecane, 0.5 part of γ-tetramethylmercaptopropyltrimethoxydecane, and γ-glycidoxypropyltrimethoxydecane were blended. One part was prepared by thoroughly blocking the mixture under moisture and under reduced pressure to prepare a room temperature curable organopolyoxane composition.
將實施例1之γ-環氧丙氧基丙基三甲氧基矽烷1份變更為N-β(胺基乙基)γ-胺基丙基三甲氧基矽烷1莫耳與氯丙基三甲氧基矽烷1莫耳之脫鹽酸反應的加成物2份之外，與實施例1同法調製組成物。 1 part of γ-glycidoxypropyltrimethoxydecane of Example 1 was changed to N-β(aminoethyl)γ-aminopropyltrimethoxydecane 1 molar and chloropropyltrimethoxy The composition was prepared in the same manner as in Example 1 except that the adduct of the dehydrochlorination reaction of the decane 1 molar was 2 parts.
兩末端被羥基所封端，黏度為5,000mPa．s之二甲基聚矽氧烷50份中均勻混合兩末端被二甲基矽氧基所封端，黏度為1,000mPa．s之二甲基聚矽氧烷10份、以脂肪酸酯處理表面之碳酸鈣70份，製造基劑混合物。再於該基劑混合物130份中添加苯基三異丙烯氧基矽烷8份、γ-四甲基胍基丙基三甲氧基矽烷0.5份、N-β(胺基乙基)γ-胺基丙基三甲氧基矽烷1莫耳與氯丙基三甲氧基矽烷1莫耳之脫鹽酸反應的加成物2莫耳，於濕份限斷、減壓下完全混合後，調製室溫硬化性有機聚矽氧烷組成物。 The two ends are terminated by hydroxyl groups and have a viscosity of 5,000 mPa. The 50 parts of s dimethyl polyoxane are uniformly mixed and the two ends are blocked by dimethyl methoxy group, and the viscosity is 1,000 mPa. 10 parts of dimethyl dimethyl siloxane and 70 parts of calcium carbonate on the surface were treated with a fatty acid ester to prepare a base mixture. Further, 8 parts of phenyltriisopropenyloxydecane, 0.5 part of γ-tetramethylmercaptopropyltrimethoxydecane, and N-β(aminoethyl)γ-amino group were added to 130 parts of the base mixture. The addition product of propyltrimethoxydecane 1 molar and chloropropyltrimethoxydecane 1 molar dehydrochlorination reaction 2 moles, after complete mixing under moisture limitation and reduced pressure, the room temperature hardening property is adjusted. Organic polyoxane composition.
將實施例3之N-β(胺基乙基)γ-胺基丙基三甲氧基矽烷1莫耳與氯丙基三甲氧基矽烷1莫耳之脫鹽酸反應的加成物2份變更為γ-胺基丙基三乙氧基矽烷與γ-環氧丙氧基丙基三甲氧基矽烷之邁克耳加成物2份之外，與實施例3同法調製組成物。 2 parts of the adduct of the N-β(aminoethyl)γ-aminopropyltrimethoxydecane 1 molar of Example 3 and the chloropropyltrimethoxydecane 1 molar dehydrochlorination reaction was changed to The composition was prepared in the same manner as in Example 3 except that the γ-aminopropyltriethoxydecane and the γ-glycidoxypropyltrimethoxydecane were added in two portions.
將實施例1之γ-環氧丙氧基丙基三甲氧基矽烷1份變更為N-β(胺基乙基)γ-胺基丙基三甲氧基矽烷1份之外，與實施例1同法調製組成物。 1 part of γ-glycidoxypropyltrimethoxy decane of Example 1 was changed to 1 part of N-β (aminoethyl) γ-aminopropyltrimethoxy decane, and Example 1 The composition is modulated by the same method.
將實施例3之N-β(胺基乙基)γ-胺基丙基三甲氧基矽烷1莫耳與氯丙基三甲氧基矽烷1莫耳之脫鹽酸反應之加成物2份變更為N-β(胺基乙基)γ-胺基丙基三甲氧基矽烷2份之外，與實施例3同法調製組成物。 2 parts of the addition product of the N-β(aminoethyl)γ-aminopropyltrimethoxydecane 1 molar of Example 3 and the chloropropyltrimethoxydecane 1 molar dehydrochlorination reaction was changed to The composition was prepared in the same manner as in Example 3 except that 2 parts of N-β(aminoethyl)γ-aminopropyltrimethoxydecane was used.
將該實施例及比較例之各室溫硬化性有機聚矽氧烷組成物呈小珠狀塗佈於鋁板上，於23±2℃、50±5%RH之環境下硬化7天後，藉由色差計測定簡易黏著性試驗(JIS-A-5758為基準)與硬化薄片之外觀。又，為確認經時間之變化，將組成物密閉保管於聚支架中，於23℃、50%RH、進行3個月後、6個月後、12個月後、及50℃，80%RH進行7天後，該簡易黏著試驗與色差測定，進行製造後與色差(△b)確認。其結果示於表1。 The room temperature curable organopolyoxane compositions of the examples and the comparative examples were applied to the aluminum plate in the form of beads, and hardened in an environment of 23±2° C. and 50±5% RH for 7 days. The appearance of the simple adhesion test (based on JIS-A-5758) and the cured sheet was measured by a color difference meter. Further, in order to confirm the change in the elapsed time, the composition was sealed and stored in a poly scaffold at 80 ° C, 50% RH, 3 months, 6 months, 12 months, and 50 ° C, 80% RH. After 7 days, the simple adhesion test and the color difference measurement were carried out, and the color difference (Δb) was confirmed after the production. The results are shown in Table 1.
本發明室溫硬化性有機聚矽氧烷組成物被證實經時間性變色極少，具良好黏著性。 The room temperature curable organopolyoxane composition of the present invention has been confirmed to have little temporal discoloration and good adhesion.
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