TW512162B - Zinc oxide-filled addition-curable silicone rubber compositions - Google Patents
Zinc oxide-filled addition-curable silicone rubber compositions Download PDFInfo
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512162 補見 Α7 Β7 五、發明説明(0 本發明係有關實用之塡充氧化鋅之加成反應硬化型聚 矽氧橡膠組成物及其硬化物者。 (請先閲讀背面之注意事項再填寫本頁) 先行技術中,聚矽氧橡膠組成物爲提昇硬化促進,硬 化物之耐熱性及電氣絕緣性等等而塡充氧化鋅乃公知者。 先行技術中,氧化鋅之塡充係於藉由有機過氧化物後交聯 硬化之可軋性(millable)型聚矽氧橡膠組成物,藉由縮聚 反應後交聯硬化之室溫硬化型(R T V )聚矽氧橡膠組成 物進行之,而未藉由附加反應後交聯硬化型之聚矽氧橡膠 組成物進行之。其理由係將氧化鋅塡充於加成反應硬化型 聚矽氧橡膠組成物後做爲交聯劑含於組成物中之有機氫聚 矽氧烷將與鹽基性之氧化鋅反應後產生氫氣,且,因產生 氫氣致使保存中之組成物出現發泡情形,導致收納此組成 物之容器內內壓上昇而容器破裂之危險性。 經濟部智慧財產局員工消費合作社印製 惟’加成反應硬化型聚矽氧橡膠組成物特別與縮聚反 應硬化型R T V聚矽氧組成物相異,無需做長時間硬化, 又密封高溫狀態下,不致會發生組成成份聚矽氧裂開之所 謂引起硫化返原(reversion )之情形,此亦爲其利點。因此 利用此優點,可期待藉由塡充氧化鋅提高其特性。 又,先行技術之加強硬化型聚矽氧橡膠組成物之硬化 物對於鎳、鋁、聚矽氧、銅等(特別是銅及氧化銅)之各 類金屬、半導體等之粘著性不足,因此亦極期待改良該粘 著性。 因此’本發明之目的係爲提供一保存中氫氣的產生量 較少,保存安定性佳,且’維持良好橡膠物性之同時,對於 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) -4- 經濟部智慧財產局員工消費合作社印製 512162 A7 __ B7_ 五、發明説明(2 ) 耐熱性、電氣絕緣性、各種金屬、半導體等粘著性良好之 硬化物之塡充氧化鋅加成反應硬化型聚矽氧橡膠組成物者 〇 本發明係提供選自(A) 1分子中至少含2個鏈烯基 之二有機聚矽氧烷,(B)結合矽原子之氫原子1分子中 至少含2個之有機氫聚矽氧烷,(C)鉑族金屬系催化劑 ,反(D )四烷氧基矽烷及四烷氧基矽烷之部份水解聚合 物所組成群中至少1種化合物上做表面處理之含氧化鋅粉 末組成之塡充氧化鋅加成反應硬化型聚矽氧組成物及該組 成物經硬化取得之硬化物者。 〔實施發明之形態〕 以下更詳細說明本發明。 (A )含鏈烯基之二有機聚矽氧烷 本發明所使用之含鏈烯基二有機聚矽氧烷係1分子中 至少含2個鍵矯基者’因此’ 一^般主鍵部份基本上由一> 有 機矽氧烷單位重覆組成者,同時,分子鏈兩末端以三有機 聚矽氧烷基封鎖之直鏈狀者,此於部份分子結構中含分枝 狀結構者亦可,或環狀物亦可。惟,由硬化物機械強度等 物性面觀之,以直鏈狀之二有機聚矽氧烷者爲佳。該鏈烯 基於分子鏈末端之矽原子或分子鏈途中之矽原子任一處結 合均可,或結合於此兩處者亦可,惟,由硬化物之物性等 面觀之,以至少結合於分子鏈兩末端之矽原子之鏈烯基者 爲較佳。做爲含此鏈烯基之二有機聚矽氧烷之代表例者如 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -5- I—J—*-------1------訂——ml (請先閱讀背面之注意事項再填寫本頁) 512162 A7 B7 五、發明説明(3 ) 下述〜般式(1 ) [化1 R1 X—|iOhSiO. R1 R1512162 Supplementary A7 B7 V. Description of the invention (0 The present invention is related to the practical use of the addition reaction hardened polysiloxane rubber composition and its hardened zinc oxide. (Please read the precautions on the back before filling in this Page) In the prior art, it is known that the silicone rubber composition is filled with zinc oxide to improve the hardening promotion, heat resistance and electrical insulation of the hardened material, etc. In the prior art, the zinc oxide is filled with The millable silicone rubber composition crosslinked and cured after the organic peroxide is carried out by the room temperature curing (RTV) silicone rubber composition which is crosslinked and cured after the polycondensation reaction. It is carried out by cross-linking and curing type silicone rubber composition after additional reaction. The reason is that zinc oxide is added to the addition reaction-hardening type silicone rubber composition as a crosslinking agent and contained in the composition. The organohydrogenpolysiloxane will generate hydrogen gas after reacting with the basic zinc oxide, and the generated composition will foam due to the generation of hydrogen gas, which will cause the internal pressure of the container containing the composition to rise and the container to break. Of Dangerous. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the addition reaction hardening silicone rubber composition is different from the polycondensation reaction hardening RTV silicone rubber composition, which does not need to be hardened for a long time, and it is sealed at high temperature. In the state, the so-called reversion is not caused by the cracking of the polysilicone, which is also a benefit. Therefore, using this advantage, it can be expected to improve its characteristics by filling with zinc oxide. The hardened product of the reinforced hardened silicone rubber composition of the prior art has insufficient adhesion to various metals and semiconductors such as nickel, aluminum, polysiloxane, and copper (especially copper and copper oxide). It is highly anticipated that the adhesion is improved. Therefore, the object of the present invention is to provide a method that generates less hydrogen during storage, has good storage stability, and maintains good rubber properties while applying Chinese national standards for this paper size ( CNS) Α4 specification (210X297 mm) -4- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 512162 A7 __ B7_ V. Description of the invention (2) Heat resistance, electrical Those with good adhesion, hardened materials such as various metals, semiconductors, etc. are those filled with zinc oxide addition reaction hardening type silicone rubber composition. The present invention provides a molecule selected from (A) containing at least two chains in one molecule Alkenyl bisorganopolysiloxane, (B) Organic silicon polysiloxane containing at least two hydrogen atoms in a molecule of silicon, (C) platinum group metal catalyst, trans (D) tetraalkoxy Silane-filled zinc oxide addition reaction hardening type polysiloxane composition containing zinc oxide powder as a surface treatment on at least one compound in a group consisting of partially hydrolyzed polymer of tetrasilane and tetraalkoxysilane, and the composition A hardened product obtained by curing a material. [Forms of Implementing the Invention] The present invention will be described in more detail below. (A) Alkenyl group-containing diorganopolysiloxane The alkenyl group-containing diorganopolysiloxane used in the present invention An alkane-based molecule containing at least two bond groups is 'so'. The general main bond portion is basically composed of one > organic siloxane units. At the same time, both ends of the molecular chain are composed of three organic polysiloxanes. Alkyl-blocked linear ones, which are contained in some molecular structures It may be a branched structure or a ring. However, from the physical properties such as the mechanical strength of the hardened material, a linear two-organic polysiloxane is preferred. The alkene can be bonded based on either the silicon atom at the end of the molecular chain or the silicon atom in the middle of the molecular chain, or it can be bonded to the two. However, from the physical properties of the hardened material, etc. Alkenyl groups of silicon atoms at both ends of the molecular chain are preferred. As a representative example of the two organic polysiloxanes containing this alkenyl group, if the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -5- I—J — * ------ -1 ------ Order——ml (Please read the precautions on the back before filling this page) 512162 A7 B7 V. Description of the invention (3) The following ~ general formula (1) [化 1 R1 X— | iOhSiO. R1 R1
JnlJnl
-SiO 4—Si—X (1) X R1 經濟部智慧財產局員工消費合作社印製 (式中’ R1爲單獨未含脂肪族不飽和鍵之非取代或 取代之1價烴基者,X爲鏈烯基,n爲〇或1以上之整數 ’ m爲〇或1以上之整數者。)所代表之二有機聚矽氧烷 示例者。 做爲一般式(1 )中R 1之不含脂肪族不飽和鍵之非 取代或取代之1價烴基之例如:甲基、乙基、丙基。、異 丙基、丁基、異丁基、第3 - 丁基、戊基、新戈基、己基 、庚基、辛基、壬基、癸基、月桂基等烷基;環戊基、環 己基、環庚基等之環烷基;苯基、甲苯基、二甲苯基、萘 基、聯苯基等之芳基;苄基、苯乙基、苯丙基、甲苄基等 之芳烷基;以及至少部份結合於此基之碳原子之氫原子爲 氟’氯’溴等齒原子,氰基等被取代基,例如:氯甲基、 2 -溴乙基、3 —氯丙基、3 3-三氟丙基、氯苯 基、Μ本基、氰乙基、3,3,4,4,5,5,6,6 ’ 6 -壬氟己基等例。此1價烴基中,代表碳原子數1〜 12 ’特別是1〜8者,以甲基、乙基、丙基、氯甲基、 溴乙基、3,3,3 -三氟丙基、氰乙基等碳原子數1〜 3之非取代或取代之烷基及苯基、氯苯基、氟苯基等葬取 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐) 6- 丨 ϊ -------^— (請先閲讀背面之注意事項再填寫本頁) 訂 512162 A7 B7 --—-----------— 五、發明説明(4 ) 代或取代之苯基者爲佳。 (請先閲讀背面之注意事項再填寫本頁) 一般式(1)中X之鏈烯基例如:乙烯基、烯丙基、 丙焴基、異丙烯基、丁燦基、己烯基、環己烯基等一般爲 碳原子數2〜8者,其中又以乙烯基、烯丙基等之低級鏈 烯基者爲較佳。 一般式(1)中,η爲0或1以上之整數,m爲〇或 1以上之整數者。又,η及m爲10Sn+mS 10,000之整數者佳,更理想者爲50^n+mS 2,〇〇〇 者,且 〇Sm/(n+m) SO · 2 之整數者 〇 又,含此鏈烯基之二有機聚矽氧烷者’以2 5 °C下粘 度爲10〜1 ,000,OOOcs t ,特別是100〜 500,000cst者佳。 (B)有機氫聚矽氧烷 經濟部智慧財產局員工消費合作社印製 本發明組成物所使用之有機氫聚矽氧烷係1分子中至 少含2個較佳者爲3個以上之結合於砍原子之氣原子(亦 即S i Η基)者,可爲直鏈狀、分枝狀、環狀、或3元網 狀結構之樹脂狀者均可。代表該有機氫聚矽氧烷之例如下 述平均組成式(2):-SiO 4—Si—X (1) X R1 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (where 'R1 is a non-substituted or substituted monovalent hydrocarbon group without an aliphatic unsaturated bond alone, X is a chain Alkenyl, n is an integer of 0 or more, and m is an integer of 0 or more.) Examples of two examples of organic polysiloxanes. Examples of the unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond in R 1 in the general formula (1) include methyl, ethyl, and propyl. , Isopropyl, butyl, isobutyl, 3-butyl, pentyl, neogyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl and other alkyl groups; cyclopentyl, cyclo Hexyl, cycloheptyl and other cycloalkyl groups; phenyl, tolyl, xylyl, naphthyl, biphenyl and other aryl groups; benzyl, phenethyl, phenylpropyl, methylbenzyl and other aralkyl groups And at least part of the carbon atoms bonded to this group are hydrogen atoms such as fluorine, chloro, bromine, and other substituted atoms, such as cyano, chloromethyl, 2-bromoethyl, and 3-chloropropyl. , 3 3-trifluoropropyl, chlorophenyl, Mbenzyl, cyanoethyl, 3,3,4,4,5,5,6,6'6-nonfluorohexyl and the like. In this monovalent hydrocarbon group, those having 1 to 12 carbon atoms, especially 1 to 8 are represented by methyl, ethyl, propyl, chloromethyl, bromoethyl, 3,3,3-trifluoropropyl, Non-substituted or substituted alkyl with 1 to 3 carbon atoms such as cyanoethyl, phenyl, chlorophenyl, and fluorophenyl, etc. This paper is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 6 -丨 ϊ ------- ^ — (Please read the notes on the back before filling out this page) Order 512162 A7 B7 ----------------- 5. Description of the invention (4 ) Substituted or substituted phenyl is preferred. (Please read the precautions on the back before filling this page) Alkenyl of X in general formula (1) For example: vinyl, allyl, propenyl, isopropenyl, butanyl, hexenyl, cyclohexene Basically, those having 2 to 8 carbon atoms are preferred, and lower alkenyl groups such as vinyl and allyl are preferred. In the general formula (1), η is an integer of 0 or more, and m is an integer of 0 or more. In addition, η and m are preferably an integer of 10Sn + mS 10,000, more preferably 50 ^ n + mS 2,000, and 〇Sm / (n + m) SO · 2 integer. The two organopolysiloxanes containing this alkenyl group have a viscosity of 10 to 1,000, 000 cs at 25 ° C, especially 100 to 500,000 cst. (B) Organic Hydrogen Siloxanes The Intellectual Property Bureau of the Ministry of Economic Affairs, Employees' Cooperatives, printed the organic hydrogen polysiloxanes used in the composition of the present invention to contain at least two, preferably three or more molecules. Those who cut the gas atom of the atom (that is, S i fluorenyl) may be linear, branched, cyclic, or resinous with a three-membered network structure. For example, the average composition formula (2) of the organic hydrogen polysiloxane is as follows:
Ha R2bS i 〇(4-a-b)/2 (2) (式中,R 2爲獨立之不含脂肪族不飽和鍵之非取代 本紙張尺度適用中國國家標準(CNS ) A4規格(21〇'〆297公釐) -7 - ^2162 A 7 B7 五、發明説明(5 ) 或取代之1價烴基者,a及b爲〇<a<2、0 . 8Sb S2且Ο · 8<a + bS3之數者,較佳者爲Ο · 02$ a^l、 1.5SbS2且1.8Sa+bS2.7之數 .者。)所代表之有機聚矽氧烷之例。 做爲式中,R 2之未含脂肪族不飽和鍵非取代或取代 之1價烴基之例者如該一般式(1 )之R 1所示之例者相 同,代表碳數1〜1 0,特別是1〜7者,較佳者爲甲基 等碳數1〜3之低級烷基、苯基、3,3,3 -三氟丙基 者。做爲該有機氫聚矽氧烷之例者如:1,1 ,3,3-四甲基二矽氧烷、1 ,3 ’ 5,7 —四甲基四環矽氧烷、 1,3,5,7,8-戊甲基戊環矽氧烷等之矽氧烷低聚 物;分子鏈兩末端二甲基砂氧院基封鎖甲基氫聚砂氧院、 分子鏈兩末端三甲基矽氧烷封鎖二甲基矽氧烷、甲基氫矽 氧烷共聚物,分子鏈兩末端矽醇基封鎖甲基氫聚矽氧烷、 分子鏈兩末端矽醇基封鎖二甲基矽氧烷•甲基氫矽氧烷共 聚物、分子鏈末端二甲基氫矽氧烷基封鎖二甲基聚矽氧烷 、分子鏈兩末端二甲基氫矽氧烷封鎖甲基氫聚矽氧烷、分 子鏈兩末端二甲基氫矽氧烷封鎖二甲基矽氧烷•甲基氫矽 氧烷共聚物等;R2 (H) S i 〇1/2單位與S i〇4/2 單位所組成,含任意之R 3 S i 0 i / 2單位、 R 2 ( H ) Si 〇 2/2 單位、R(H) Si 〇 2/2 單位、 (H) S i 〇3/2單位或RS i 〇3/2單位取得之聚矽氧 樹脂(惟,式中,R與該R 1所示之非取代或取代之1價 烴基者相同。)等例,更有下式: 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) _ 8 _ (請先閲讀背面之注意事項再填寫本頁) 、τ 經濟部智慧財產局員工消費合作社印製 512162 A7 B7 五、發明説明(6 【化2] .ch3 ch3 ch3 CH3 CH3 i 1 1 H—Si—〇一Si一O一Si —H H_si—〇—Si—Η 1 1 ch3 1 ch3 1 CH3 , 1 I . ? ? j * Η_si -〇—Si —H 1 1 ch3 ' ch3 H . H CH3 1 1 1 J CH3 CH3 , H—Si 一 1 -〇—Si—O· 1. 1 1 一3| —〇—si 一O一Si一〇 1 1 1 1 I 9h3 CH-, CsH5 CH3 CHn I CeHg CH3 等所示之例。 本發明組成物所使用之有機氫聚矽氧烷可以公知之方 法取得,選自如下述一般式: R 2 S i H C 1 及Ha R2bS i 〇 (4-ab) / 2 (2) (In the formula, R 2 is an independent non-substituted without aliphatic unsaturated bond. The paper size is applicable to Chinese National Standard (CNS) A4 specification (21〇'〆 297 mm) -7-^ 2162 A 7 B7 V. Description of the invention (5) or substituted monovalent hydrocarbon group, a and b are 0 < a < 2, 0.8Sb S2 and 0 · 8 < a + bS3 Among them, the preferred one is the number of 0. 02 $ a ^ l, 1.5SbS2, and 1.8Sa + bS2.7.) The example of the organopolysiloxane. In the formula, an example of an unsubstituted or substituted monovalent hydrocarbon group which does not contain an aliphatic unsaturated bond in R 2 is the same as the example shown by R 1 in the general formula (1), and represents a carbon number of 1 to 10. In particular, 1 to 7 are preferred, and lower alkyl groups having 1 to 3 carbon atoms such as methyl, phenyl, and 3,3,3-trifluoropropyl are preferred. Examples of the organohydrogenpolysiloxane include: 1,1,3,3-tetramethyldisilaxane, 1,3'5,7-tetramethyltetrasiloxane, 1,3 Siloxane oligomers such as 5,7,8-pentylmethylpentacyclosilane, etc .; dimethyl sand oxygen radicals at both ends of the molecular chain block the methyl hydrogen poly sand oxygen radicals, and tertiary methyl at both ends of the molecular chain Siloxane blocks dimethylsiloxane and methylhydrosiloxane copolymer, silanol groups at both ends of the molecular chain block methylhydropolysiloxanes, silanol groups at both ends of the molecular chain block dimethylsiloxanes Alkane • methylhydrosiloxane copolymer, dimethylhydrosiloxane blocked at the end of the molecular chain, dimethylpolysiloxane, dimethylhydrosiloxane blocked at the end of the molecular chain, methylhydropolysiloxane blocked Dimethyl hydrosiloxane blocked at both ends of the molecular chain dimethyl siloxane • methyl hydrosiloxane copolymer; etc .; R2 (H) S i 〇1 / 2 units and S i〇4 / 2 units Composition, including arbitrary R 3 S i 0 i / 2 units, R 2 (H) Si 〇 2/2 units, R (H) Si 〇 2/2 units, (H) S i 〇 3/2 units, or RS i 〇3 / 2 units of polysiloxane resin (however, in the formula, R and the R 1 Substituted or substituted monovalent hydrocarbon groups are the same.) For other examples, the following formulas are used: The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 8 _ (Please read the precautions on the back before filling in this Page), τ Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 512162 A7 B7 V. Description of the invention (6 [Chemical 2] .ch3 ch3 ch3 CH3 CH3 i 1 1 H—Si—〇—Si—O—Si—H H_si —〇—Si—Η 1 1 ch3 1 ch3 1 CH3, 1 I.?? J * Η_si -〇-Si —H 1 1 ch3 'ch3 H. H CH3 1 1 1 J CH3 CH3, H—Si-1- 〇—Si—O · 1. 1 1—3 | ———— O—Si—〇1 1 1 1 I 9h3 CH—, CsH5 CH3 CHn I CeHg CH3, etc. The examples shown are used in the composition of the present invention The organohydrogenpolysiloxane can be obtained by a known method, and is selected from the following general formula: R 2 S i HC 1 and
RR
S H C 1 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 (式中,R2與上述相同者。)至少1種之氯矽烷之 共同水解後或該氯砂院與選自下述一般式: (式中,R2與上述相同者。)之至少1種氯矽烷之 相互組合、共同水解後取得者。又,有機氫聚矽氧烷亦可 由共同水解後得聚矽氧烷之平衡化者。 成份(B )之使用量以成份(A)含鏈烯基之二有機 聚矽氧烷中之鏈烯基1莫耳時,結合於成份(B )之有機 氫聚矽氧烷中之矽原子之氫原子(即S i Η基)通常爲 0 . 5〜4莫耳之量,較佳者爲1〜2 . 5莫耳之量者。 C )鉑族金屬系催化劑SHC 1 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (where R2 is the same as above.) After co-hydrolysis of at least one chlorosilane or the chlorinated sand The compound is selected from the following general formula: (In the formula, R2 is the same as the above.) At least one chlorosilane is combined with each other and obtained by common hydrolysis. In addition, the organohydrogen polysiloxane can be co-hydrolyzed to obtain a polysiloxane balance. The amount of component (B) is based on the silicon atom in the organohydrogenpolysiloxane of component (B) when the content of component (A) is 1 mol of the alkenyl group in the organic polysiloxane containing alkenyl groups. The hydrogen atom (that is, the Si fluorenyl group) is usually in an amount of 0.5 to 4 moles, preferably in an amount of 1 to 2.5 moles. C) Platinum group metal catalyst
本發明所使用之鉑金屬系催化劑係爲促進成份(A 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -9- 512162 A7 _______B7 五、發明説明(7 ) (請先閲讀背面之注意事項再填寫本頁) 之鏈烯基與結合於成份(B )之矽原子之氫原子相互氫化 矽烷化反應(加成反應)之催化劑者,而做爲氫化矽烷化 反應所使用之催化劑例如公知之催化劑者。其具體例如: 鉑(含鉑黑)、铑、鈀等之鉑族金屬單體; H2PtCl4*nH2〇, H2PtCl6*nH2〇, NaHPtCl6*nH2〇、 ΚΗΡΐ0ΐ6·ηΗ20 、NaePtCle^nHeO. K2PtCl4*nH2〇 、P t C 1 4 · η Η 2 Ο , Ρ t C 1 2 . Na2HPtCl4*nH2〇。 經濟部智慧財產局員工消費合作社印製 (式中,h爲〇〜6之整數,較佳者爲0或6者。) 等之氯化鉑、氯鉑酸及氯鉑酸鹽;醇變性氯鉑酸(美國專 利第3,220,972號明細書參考者):氯鉑酸與烯 烴之絡合物(美國專利第3,1 5 9,6 0 1號明細書, 同第3 ,159 ,662號明細書,同第 3,7 7 5,4 5 2號明細書參考者);鉑黑、鈀等之鉑 族金屬擔載於鋁氧粉、二氧化矽、碳等載體上者;含铑一 烯烴絡合物;氯三(三苯基膦)铑(Geoffrey Wilkinson 崔化劑):氯鉑、氯鉑酸或氯鉑酸鹽與乙烯基矽氧烷者。 特別是與含乙烯基之環狀矽氧烷之絡合物者之例。 成份(C )之用量可以所謂之催化劑量者’一般以成 份(A)及成份(B)之合計量換算鉑族金屬重量爲 0 · 1 〜500ppm、特別以 0 · 5 〜200ppm者 (D )於四烷氧基矽烷及/或四烷氧基矽烷之部份水解縮 -10- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 512162 A7 B7 五、發明説明(8 ) 聚物上做表面處理後之氧化鋅粉末 (請先閱讀背面之注意事項再填寫本頁) 本發明所使用之氧化鋅粉末係於四烷^氧基矽烷及/或 四烷氧基矽烷部份水解縮聚物做面處理者。進行表面處理 後含氧化鋅之加成反應硬化型聚矽氧橡膠組成物中,因此 氧化鋅粉末之鹽基性而減低有機聚矽氧烷之去氫反應爲被 考量因素者。 因此,(D )成份於本發明組成物之保存中可防止起 泡之同時,防止收納該組成物於容器中內壓上昇之容器破 裂之慮,並且,可附與該組成物具耐熱性、電氣絕緣性等 特性者。 .①四烷氧基矽烷及/或四烷氧基矽烷部份水解縮聚物 本發明所使用之四烷氧基矽烷係如下述一般式=The platinum metal catalyst used in the present invention is a promoting component (A The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -9- 512162 A7 _______B7 V. Description of the invention (7) (Please read the back first (Notes to fill in this page again) The alkenyl group and the hydrogen atom of the silicon atom bound to the component (B) are used as catalysts for the hydrosilylation reaction (addition reaction), and used as the catalyst for the hydrosilylation reaction For example, well-known catalysts. Specific examples include platinum group metal monomers such as platinum (including platinum black), rhodium, and palladium; H2PtCl4 * nH2〇, H2PtCl6 * nH2〇, NaHPtCl6 * nH2〇, ΚΗΡΐ0ΐ6 · ηΗ20, NaePtCle ^ nHeO K2PtCl4 * nH2〇, P t C 1 4 · η Η 2 〇, P t C 1 2. Na2HPtCl4 * nH2〇. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (where h is an integer from 0 to 6, The preferred ones are 0 or 6.), such as platinum chloride, chloroplatinic acid, and chloroplatinate; alcohol-denatured chloroplatinic acid (reference book of US Patent No. 3,220,972): chloroplatinic acid and Complexes of olefins (Detailed US Patent No. 3,159,601 Book, as detailed in No. 3,159,662, and referenced in No. 3, 7 7 5, 4 5 2); platinum group metals such as platinum black and palladium are supported on aluminum oxide powder, silicon dioxide Carriers such as carbon and carbon; rhodium-olefin complexes; chlorotris (triphenylphosphine) rhodium (Geoffrey Wilkinson Cuihua agent): chloroplatin, chloroplatinic acid or chloroplatinate and vinylsiloxane In particular, it is an example of a complex with a vinyl-containing cyclic siloxane. The amount of the component (C) can be a so-called catalyst amount. Generally, platinum is converted by the total amount of the component (A) and the component (B). Group metals with a weight of 0. 1 to 500 ppm, especially 0. 5 to 200 ppm (D) are partially hydrolyzed in tetraalkoxysilanes and / or tetraalkoxysilanes. This paper size applies to Chinese national standards (CNS) A4 specification (210X297 mm) 512162 A7 B7 V. Description of the invention (8) Zinc oxide powder after surface treatment on the polymer (Please read the precautions on the back before filling this page) The oxidation used in the present invention Zinc powder is prepared by using tetraalkoxysilane and / or tetraalkoxysilane partially hydrolyzed polycondensate as surface treatment. After the surface treatment, the addition reaction hardening type silicone rubber composition containing zinc oxide is the factor to be considered because of the alkalinity of zinc oxide powder and reducing the dehydrogenation reaction of organic polysiloxane. Therefore, (D) The ingredients in the preservation of the composition of the present invention can prevent foaming, and prevent the container containing the composition from rising in the container from rising in internal pressure. Furthermore, the composition can have properties such as heat resistance and electrical insulation. By. .① Tetraalkoxysilane and / or tetraalkoxysilane partially hydrolyzed polycondensate. The tetraalkoxysilane used in the present invention is as follows:
Si (OR3) 4 經濟部智慧財產局員工消費合作社印製 (式中,R 3爲獨立之非取代或低級烷氧基取代之烷 基者。)所示者。做爲式中R 3之非取代或低級烷氧基取 代之烷基者如:甲基、乙基、丙基、異丙基、丁基、異丁 基、第3-丁基、戊基、新戊基、己基、庚基、辛基、壬 基、癸基、月桂基等,及甲氧基甲基、甲氧基乙基、乙氧 基甲基、乙氧基乙基等一般碳數爲1〜12較佳者爲1〜 6者。做爲該四烷氧基矽烷之部份水解縮聚物者如下式平 均組成。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) _ ” _ 512162 A7 B7 _ 五、發明説明(9 )Si (OR3) 4 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (where R 3 is an independent non-substituted or lower alkoxy-substituted alkyl group). As the unsubstituted or lower alkoxy substituted alkyl group of R 3 in the formula, such as: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 3-butyl, pentyl, Neopentyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, etc., and general carbon numbers such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl 1 to 12 are preferred, and 1 to 6 are preferred. The partially hydrolyzed polycondensate of the tetraalkoxysilane has an average composition as shown below. This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm) _ _ _ 512162 A7 B7 _ V. Description of the invention (9)
[(R3〇)3Si〇l/2]K[(R3〇)2Si〇2/2]L[(R3〇)Si〇3/2]M[Si〇4/2]N (請先閱讀背面之注意事項再填寫本頁) (式中,R3與上述相同者,K ’ L ’ Μ及N爲K + L + M+n=1,〇.〇〇2SKS1、O^L^O . 998 、〇SMS〇 · 998 及 OSN^O · 35 之數者。)所 代表者等示例,特別之代表例如下述一般式(3 ): R 3 0 - [ S i (OR3) 2 0 ) j - R 3 (3) (式中,R3與上述同,j爲1以上’ 一般爲2〜 1,000,較佳者爲3〜500之整數者。)所示者。 該四烷氧基矽烷及/或其剖份水解縮聚物之重量平均分子 量爲150〜100,000者佳。 ② 氧化鋅 經濟郎智慧財產局員工消費合作社印製 供與表面處理之氧化鋅粉末可使用公知者,而較理想 者以純度佳之J I S單種者爲宜。氧化鋅粉末之平均粒徑 通常以0 · 05〜10/zm者,可依其用途做適當選擇。 ③ 表面處理 做爲表面處理之方法者可使用公知的濕式處理法或乾 式處理法。做爲該表面處理方法之具體例者如:以適當溶 媒將該四烷氧基矽烷及/或四烷氧基矽烷之部份水解縮聚 物溶解或分散後,將該氧化鋅粉末加入此溶液或分散液中 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) .12- ' 512162 A7 B7 五、發明説明(1〇 ) (請先閲請背面之注意事項再填寫本頁) 混合後’加熱、乾燥之方法。該溶媒之例如:甲苯、二甲 本等等。做爲加熱、乾燥之條件者以8 0〜2 0 0 °C下做 〇 · 5〜1〇小時者宜。 又’另外之表面處理方法者如:氧化鋅粉末與四烷氧 基砂烷及/或四烷氧基矽烷之部份水解縮聚物加上至少一 部份之(A )成份(通常3 0重量%以上,特別爲5 0〜 1 〇 0重量% ) —起混合後,取得之混合物經加熱處理之 方法者。加熱條件以8 0〜2 0 0 t:下0 . 5〜1 0小時 者宜。 此種將氧化鋅粉末與四烷氧基矽烷及/或四烷氧基矽 烷之部份水解縮聚物與至少一部份之(A )成份混合後之 表面處理方法無需添加溶媒、乾燥工程,可直接用於製造 本發明時之各成份混合或混煉工程中,因此可有效節約能 源及縮短工程時間等優點。該四烷氧基矽烷及/或四烷氧 基矽烷之剖份水解縮聚物使用量可依其氧化鋅粉末之比表 面積、其他性狀而做適當調節,一般,1 0 0重量份之氧 化鋅粉末爲〇 · 1〜2 0重量份者佳。 經濟部智慧財產局員工消費合作社印製 藉由以上之表面處理於該氧化鋅粉末表面形成矽氧烷 被膜,而預防影響氧化鋅粉末之鹽基性。 該表面處理後之氧化鋅粉末使用量一般當成份(A ) 之含鏈烯基二有機聚矽氧烷1 0 0重量份時爲5〜3 0 0 重量份,較理想者爲1 0〜2 0 0重量份者。若用量太少 時,取得之硬化物耐熱性、電氣絕緣性則不足,反之,用 量太多時,則取得塡充氧化鋅加成反應硬化型聚矽氧橡膠 -13- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 512162 A7 B7 五、發明説明(11 ) 組成物之粘度上昇之後使得流動性變差。 (請先閲讀背面之注意事項再填寫本頁) 其他成份 本發明組成物除該成份(A )、 ( B )、 ( C )、( D )之外,因應所需可添加humid二氧化矽、humid二氧化 鈦等之補強性無機塡充劑;矽酸鈣、二氧化鈦、氧化第二 鐵、炭黑等非補強性無機塡充劑;硬化抑制劑(如:乙炔 醇等)等等。無機塡充劑之添加量通常當成份(A)〜( D)之合計量1 〇 〇重量時爲〇〜1 〇重量份者。 更且,爲提昇本發明組成物中組成物之粘著性之目的 下,除該成份(A )〜(D )之外,必要時亦可添加含環 氧基之聚矽氧烷化合物,酯矽氧烷化合物(亦即,結合於 矽原子之1價基全爲烷氧基或氫原子者,分子中不含矽-碳結合之有機矽氧烷化合物)者。此等矽氧烷化合物之添 加量通常爲成份(A)〜(D)合計量1 〇 〇重量份之〇 〜1 0重量份者。 經濟部智慧財產局員工消費合作社印製[(R3〇) 3Si〇l / 2] K [(R3〇) 2Si〇2 / 2] L [(R3〇) Si〇3 / 2] M [Si〇4 / 2] N (Please read the Please fill in this page again) (where R3 is the same as above, K'L'M and N are K + L + M + n = 1, 0.002SKS1, O ^ L ^ O. 998, 〇 SMS〇 · 998 and OSN ^ O · 35.) Representative examples, such as the following general formula (3): R 3 0-[S i (OR3) 2 0) j-R 3 (3) (wherein R3 is the same as above, j is 1 or more, generally 2 to 1,000, and preferably an integer of 3 to 500.) The weight average molecular weight of the tetraalkoxysilane and / or its split hydrolyzed polycondensate is preferably from 150 to 100,000. ② Zinc oxide The zinc oxide powder printed and surface-treated by the Employees' Cooperative Cooperative of the Economic and Intellectual Property Bureau can be used by publicly known persons, and the more ideal one is J I S with a high purity. The average particle size of zinc oxide powder is usually from 0.05 to 10 / zm, and it can be appropriately selected according to its application. ③ Surface treatment As the surface treatment method, a known wet treatment method or dry treatment method can be used. As a specific example of the surface treatment method, for example, after dissolving or dispersing the tetraalkoxysilane and / or a part of the hydrolyzed polycondensate of the tetraalkoxysilane with an appropriate solvent, the zinc oxide powder is added to the solution or The paper size in the dispersion is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). 12- '512162 A7 B7 V. Description of the invention (1〇) (Please read the notes on the back before filling this page) Mix After 'heating and drying method. Examples of the solvent include toluene, dimethylbenzene, and the like. For heating and drying conditions, it is recommended to do it at 80 ~ 200 ° C for 0 ~ 5 ~ 10 hours. Also 'other surface treatment methods such as: Partially hydrolyzed polycondensates of zinc oxide powder and tetraalkoxysarane and / or tetraalkoxysilane, plus at least a part of the (A) component (usually 30 weight % Or more, especially 50 to 100% by weight)-after mixing, the method of heating the obtained mixture. The heating conditions are 80 ~ 2 0 0 t: 0.5 ~ 10 hours. This surface treatment method in which zinc oxide powder is mixed with a tetraalkoxysilane and / or a partially hydrolyzed polycondensate of tetraalkoxysilane and at least a part of the component (A) does not require the addition of a solvent and a drying process. It is directly used in the mixing or kneading process of various ingredients when manufacturing the present invention, so it can effectively save energy and shorten engineering time. The used amount of the tetraalkoxysilane and / or the tetraalkoxysilane split hydrolyzed polycondensate can be appropriately adjusted according to the specific surface area and other properties of the zinc oxide powder. Generally, 100 parts by weight of zinc oxide powder It is preferably from 0.1 to 20 parts by weight. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The above surface treatment forms a siloxane film on the surface of the zinc oxide powder to prevent affecting the salinity of the zinc oxide powder. The amount of zinc oxide powder after the surface treatment is generally 5 to 3 0 0 parts by weight when the alkenyl-containing diorganopolysiloxane containing the component (A) is 100 parts by weight, and more preferably 10 to 2 0 0 parts by weight. If the amount is too small, the heat resistance and electrical insulation of the hardened material obtained will be insufficient. On the contrary, when the amount is too large, a zinc-filled zinc oxide addition-reaction-hardened silicone rubber will be obtained. 13- This paper is applicable to China. Standard (CNS) A4 specification (210X297 mm) 512162 A7 B7 V. Description of the invention (11) After the viscosity of the composition increases, the fluidity becomes worse. (Please read the notes on the back before filling this page) Other ingredients In addition to the ingredients (A), (B), (C), (D) of the composition of the present invention, humid silica, Reinforcing inorganic concrete fillers such as humidified titanium dioxide; non-reinforcing inorganic concrete fillers such as calcium silicate, titanium dioxide, second iron oxide, and carbon black; hardening inhibitors (such as acetylene alcohol, etc.), etc. The addition amount of the inorganic filler is usually 0 to 10 parts by weight when the total amount of the ingredients (A) to (D) is 100 parts by weight. Furthermore, for the purpose of improving the adhesiveness of the composition in the composition of the present invention, in addition to the ingredients (A) to (D), an epoxy group-containing polysiloxane compound or ester may be added if necessary. Siloxane compounds (that is, those in which the monovalent radicals bound to the silicon atom are all alkoxy or hydrogen atoms, and the molecule does not contain a silicon-carbon bonded organic siloxane compound). The addition amount of these siloxane compounds is usually one of the components (A) to (D) in a total amount of 100 to 10 parts by weight. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
塡充氧化鋅加成反應硬化型聚矽氧橡膠組成物及其硬化物 本發明組成物基本上由該成份(A )〜(D )及必要 時使用之添加成份所混合、混煉後取得者。惟,使用前與 一般硬化性聚矽氧橡膠組成物相同如:成份(A )、 ( C )及(D)與成份(A)及(B)之2液,將成份(A) 〜(D )分成2液,使用時將2液混合後使硬化成2液型 之組成物者亦可。另外,使用上述另種表面處理法取得之 -14- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 512162 Α7 Β7 "mini1丨|| uuuii-.....................................................................111111 ....................................................................................................................................................................................................................... ................. 〜 五、發明説明(12) (請先閲讀背面之注意事項再填寫本頁) 氧化鋅粉末與四烷氧基矽烷及/或四烷氧基矽烷部份水解 縮聚物以及(A )成份之至少部份與之混合物(加熱處埋 混合物)時,此做成1液與其他成份做成另一液之2液型 組成物者亦可。另外,混合(A )〜(D )各成份後,更 加入少量硬化抑制劑(如:乙炔醇等)等混合成所謂之1 液型組成物者亦可。 本發明硬化物藉由硬化該組成物後取得。硬化條件可 與公知之加成反應硬化型聚矽氧橡膠組成物相同,如常溫 下亦可充份硬化之必要加熱亦可。 塡充氧化鋅加成反應硬化型聚矽氧橡膠組成物之用途 本發明組成物做爲硬化物具良好橡膠物性(硬度、張 力強度、伸展性等),優異之耐熱性及電氣絕緣性以及各 種金屬或半導體,特別是銅及銅氧化物均具良好之粘著性 。可有效做爲電器、電子零件之絕緣體、半導體裝置之粘 著劑及保護塗佈劑、陶瓷製造劑等之使用。 經濟部智慧財產局員工消費合作社印製 〔實施例〕 實施例1 如下述一般式(4 )塡 Zinc oxide addition reaction hardening type silicone rubber composition and its hardened product The composition of the present invention is basically obtained by mixing and kneading the components (A) to (D) and additional components used when necessary . However, before use, it is the same as the general hardening silicone rubber composition. For example, the two components of the components (A), (C), and (D) and the components (A) and (B) are the components (A) to (D). ) Is divided into two liquids, and when used, two liquids are mixed to harden into a two-liquid composition. In addition, -14- obtained from the other surface treatment method mentioned above is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 512162 Α7 Β7 " mini1 丨 || ............ ........................................ ........... 111111 ............................ ........................................ ........................................ ........................................ ................................. V. Explanation of the invention ( 12) (Please read the notes on the back before filling this page) Zinc oxide powder and tetraalkoxysilane and / or tetraalkoxysilane partially hydrolyzed polycondensate and at least part of the (A) component mixed with ( When the mixture is buried under heating), it can also be made into a two-liquid composition with one fluid and other ingredients. In addition, after mixing the components (A) to (D), a small amount of a hardening inhibitor (such as acetylene alcohol, etc.) is further added to mix into a so-called one-liquid composition. The cured product of the present invention is obtained by curing the composition. The hardening conditions may be the same as those of the known addition-reaction hardening type silicone rubber composition, and it may be heated if necessary for sufficient hardening at room temperature.用途 Application of zinc oxide addition reaction hardening type silicone rubber composition The composition of the present invention has good rubber physical properties (hardness, tensile strength, stretchability, etc.) as a hardened material, excellent heat resistance and electrical insulation, and various Metals or semiconductors, especially copper and copper oxides, have good adhesion. It can be effectively used as insulators for electrical appliances, electronic parts, adhesives and protective coating agents for semiconductor devices, and ceramic manufacturing agents. Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [Example] Example 1 The general formula (4)
Vi(Me)2Si(OSiMe2)n〇Si(Me)2Vi ( 4 ) (式中,Me爲甲基、Vi爲乙烯基、η爲該式所示 -15- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 512162 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明(^ 之有機聚矽氧烷2 5 °C下粘度爲5,000 c S t之數者 。)所示之含乙烯基之直鏈狀有機聚矽氧烷9 0重量份, 該一般式(4)中,η爲25 °C下粘度100,0〇〇 c S t之數之直鏈狀有機聚矽氧烷1 〇重量份,j I s具 單種之純度之氧化鋅(平均粒徑:〇 · 3 μ m )(三井金 屬公司製)100重量份,以及三乙氧基矽烷2重量份於 3種根滾輥做混煉之後,以行星混合器更於1 6 0 °C下將 此混合物做3小時之混煉。於此混煉物中加入甲基氫聚砂 氧院〔結合於砂原子之氫原子(S i Η基)之含量: 〇 · 8莫耳/ 1 0 0 g〕2重量份及氯鉑酸之辛醇變性物 溶液(鉑含量:2重量% ) 0 · 〇 2重量%後攪拌之後, 取得硬化性聚矽氧橡膠組成物。以B型旋轉粘度計測定此 組成物之粘度(2 5 °C下之粘度,以下相同),爲2 7 5 P (泊)。 針對取得之組成物由下述方法測定萃取水電導度,氫 氣產生量、硬化物之橡膠物性(硬度、張力強度、伸展性 ),硬化物之電氣特性(體積電阻率)、硬化物之粘著性 、耐化物之耐熱性,另外觀察硬化物之起泡狀況。 萃取水電導度 將該組成物2 0重量份,特級甲苯4 〇重量份,以及 純水1 0 0重量份投入分液漏斗中,經1小時振搖後靜置 ,由此分取水相。再將分取之水電導度(# S / c m )以 電導儀測定之。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) (請先聞讀背面之注意事項再填寫本頁)Vi (Me) 2Si (OSiMe2) n〇Si (Me) 2Vi (4) (where Me is methyl, Vi is vinyl, and η are as shown in this formula. -15- This paper size applies to Chinese national standards (CNS ) A4 specification (210X297 mm) 512162 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (^ The organopolysiloxane at 25 ° C has a viscosity of 5,000 c S t. 90% by weight of the linear organopolysiloxane containing a vinyl group shown in ()). In the general formula (4), η is a linear form having a viscosity of 100, 000 cSt at 25 ° C. 10 parts by weight of organopolysiloxane, 100 parts by weight of zinc oxide (average particle size: 0.3 μm) (made by Mitsui Metals Co., Ltd.) with a single purity of j I s, and 2 parts by weight of triethoxysilane After mixing with 3 kinds of rollers, use a planetary mixer to mix the mixture for 3 hours at 160 ° C. To this mixture, add methyl hydrogen polysand oxygen institute [combination Content of hydrogen atom (S i fluorenyl) in sand atom: 0.8 mole / 100 g] 2 parts by weight and octanol modified solution of chloroplatinic acid (platinum content: 2% by weight) 0 · 〇 After 2% by weight After mixing, a curable silicone rubber composition was obtained. The viscosity of the composition (viscosity at 25 ° C, the same applies hereinafter) was measured with a B-type rotational viscometer, and was 2 7 5 P (poise). The composition measures the conductivity of the extracted water, the amount of hydrogen produced, the physical properties of the hardened rubber (hardness, tensile strength, elongation), the electrical characteristics (volume resistivity) of the hardened, the adhesion of the hardened, and the resistance The heat resistance of the compound was observed, and the foaming condition of the hardened product was also observed. The conductivity of the extracted water was 20 parts by weight of the composition, 40 parts by weight of special toluene, and 100 parts by weight of pure water. After shaking for an hour, it was allowed to stand still, so that the water phase was collected. The water conductivity (# S / cm) of the collected water was measured with a conductivity meter. The paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm) ) (Please read the notes on the back before filling this page)
-16- 512162-16- 512162
A7 B7 五、發明説明(^ Μ氣產生量 (請先閱讀背面之注意事項再填寫本頁) 該組成物5 g密封於5 0 0 J之head space bottle中, 室溫下放置4 8小時後,藉由氣體層析法測定該瓶內所產 生之氫氣量。硬化物之橡膠物性。 該組成物流入1 5 0 m m X 1 〇 〇 m m X 2 m m之模具 中,此真空脫泡後,1 5 0 °C下加熱4小時後,取得薄片 狀之硬化物。針對取得之硬化物測定以J I S K 6301爲基準之硬度、張力強度及伸展度。另外,利用 彈簧式硬度試驗器A型測定硬度。 硬化物之電氣特性 該組成物流入1 5 0 m m X 1 0 0 m m X 1 m m之模具 中,此經真空脫泡後,1 5 0 t下加熱4小時後.,取得薄 片狀硬化物。針對取得之硬化物以J I S c 2 1 2 3爲基準測定體積電阻率。 經濟部智慧財產局員工消費合作社印製 硬化物之耐熱性 與該橡膠物性測定所使用者相同之薄片狀硬化物於 2 5 0 t:下加熱2 4小時後之硬度及同溫度下4 8小時加 熱後之硬度以J I S K 6 3 0 1爲基準測定之(彈簧 式硬度試驗器A型者利用之)。 硬化物之粘著性 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -17- 512162 A7 B7 五、發明説明(15) 組成物流入1 5 Ommx 1 0 Ommx 1mm之鎳、 (請先閱讀背面之注意事項再填寫本頁) 鋁、聚矽氧、銅及酸腐蝕後之銅之各板上,此經真空脫泡 後,1 5 0 °C下加熱4小時後,取得薄片狀硬化物。針對 取得之硬化物利用微量勺〜由基板將此剝取時,觀察凝聚 破壞(硬化物之截面被破壞者)之剖份與界面剝落(硬化 物與基板之粘著界面被破壞者)之部份之比例(面積比) 評定粘著性。 〇:凝聚破壞率超迥8 0 %,具強固粘著性。 △:凝聚破壞率爲2 0〜8 0%者,具粘著性。 X :凝聚破壞率爲2 0 %以下,幾乎不具粘著性。 硬化物之起泡狀態 與該橡膠物性測定所用者相同之薄片狀硬化物以目測 觀察其起泡之有無。 實施例2 以四乙氧基矽烷之部份水解縮聚物(S i 0 2含量: 經濟部智慧財產局員工消費合作社印製 4 0重量%) 〔kolcode (公司)製’茼品名乙基聚砂酸 鹽4 0 T〕2重量份取代四乙氧基矽烷之外,與實施例 1同法取得聚矽氧橡膠組成物。以B型旋轉粘度計測定此 組成物之粘度爲2 3 3 P (泊)。 再針對取得組成物依實施例1所載方法進行各種功能 之測定。 -18- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 512162 Α7 Β7 五、發明説明(16 ) 實施例3 以四甲氧基矽烷之部份水解縮聚物〔重量平均分子量 (M w ) : 788〕2重量份取代四乙氧基矽烷之外,與 實施例1同法取得硬化性聚矽氧橡膠組成物。利用Β型旋 轉粘度計測定此組成物之粘度爲2 4 6 Ρ (泊)。 再針對取得組成物依實施例1所載之方法測定各種功 實施例4 將甲基氫聚砂氧院2重量份更改爲1重量份,且,含 下述環氧基之甲基氫聚矽氧烷: (請先閱讀背面之注意事項再填寫本頁) |-fCH2)3〇CH2CH -CH2 -Si—ΟΙ CH3 Η I -Si ΟΙ CH3 經濟部智慧財產局員工消費合作社印製 除添加1重量份以外與實施例1同法取得硬化性聚矽 氧橡膠組成物。以B型旋轉粘度計測定該組成物之粘度爲 2 6 Ο P (泊)。 再針對取得之組成物依實施例1所載方法測定各種功 比較例1 以下式 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公董) -19- 512162 A7 __________ B7_ 五、發明説明(17) (Me)3Si-[OS(Me)2]xNH[Si(Me)2〇]y-Si(Me)3 (請先閲讀背面之注意事項再填寫本頁) (式中,M. e爲甲基、X及y之平均x + y爲3 0之 數者。)之甲矽烷氧基矽胺烷化合物2 8重量份取代四乙 氧基矽烷除外與實施例1同法取得硬化性聚矽氧橡膠組成 物。以B型旋轉粘度計測定此組成物粘度爲1 5 5 P (泊 )° 再針對取得組成物依實施例1所載方法測定各種功能 比較例2 以3重量份之六甲基二矽胺烷取代四乙氧基政烷之外 ,與實施例1同法取得硬化性聚矽氧橡膠組成物。以B型 旋轉粘度計測定此組成物之粘度爲2 8 0 P (泊)。 再將取得之組成物依實施例1所載方法測定各種之功 能。 經濟部智慧財產局員工消費合作社印製 比較例3 以2重量份之三乙氧基甲基矽烷取代四乙氧基矽烷之 外與實施例1同法取得硬化性聚矽氧橡膠組成物。以B型 旋轉粘度計測定該混合物之粘度爲2 8 3 P (泊)。 再將取得之組成物,依實施例之方法測定其各種之功 能0 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) _ 2〇 - 512162 A7 ______ B7 五、發明説明(18 ) 比較例4 除未使用氧化鋅之外與實施例4同法取得硬化性聚砂 氧橡膠組成物。以B型旋轉粘度計測定此組成物之粘度爲 4 Ο P (泊)。 再將取得之組成物,依實施例1之取代測定其各種功 會b 。 以上結果示於表1及表2。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -21 - 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 512162 經濟部智慧財產局員工消費合作社印製 五 、發明説明(19) 【表1】 實施例1 實施例2 實施例3 實施例4 粘度(Ρ) 275 233 246 260 萃取水電導度(// s/cm) 2 2 2 2 氫氣產生量(// 1/g) 21 19 20 21 硬度(JIS-A) 49 47 47 48 張力強度(kgf/cm2 ) 52 45 50 50 伸展度(%) 155 140 145 150 體積電阻率(Ω cm) lx 1016 9x ΙΟ15 8x 1015 lx 1016 耐 250°C /24hr 57 57 57 56 熱 之硬度 性 250〇C /72hr 66 65 67 66 之硬度 發泡之有無 Μ ι te JIW M j i 接著性(150°C /4hr後) Ni 〇 o 〇 o A1 〇 〇 〇 〇 Si 〇 〇 o o Cu 〇 〇 o o Cu(酸腐蝕後) 〇 〇 〇 〇 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4規格(21〇Χ:297公釐) -22- 512162A7 B7 V. Description of the invention (^ Μ gas generation (please read the precautions on the back before filling in this page) 5 g of this composition is sealed in a head space bottle of 5 0 0 J, and left to stand at room temperature for 4 8 hours The amount of hydrogen generated in the bottle was determined by gas chromatography. The rubber physical properties of the hardened product. The composition was flowed into a mold of 150 mm X 100 mm X 2 mm. After this vacuum defoaming, 1 After heating at 50 ° C for 4 hours, a flaky hardened material was obtained. The obtained hardened material was measured for hardness, tensile strength, and elongation based on JISK 6301. In addition, the hardness was measured using a spring-type hardness tester type A. Electrical characteristics of the hardened material The composition is flowed into a mold of 150 mm X 100 mm X 1 mm. After being degassed in a vacuum, the composition is heated for 4 hours at 150 t to obtain a sheet-like hardened product. The obtained hardened product was measured for volume resistivity based on JIS c 2 1 2 3. The heat resistance of the printed hardened product printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs was the same as that of the user of the rubber physical property measurement. 0 t: Hard after heating for 24 hours And the hardness after heating for 48 hours at the same temperature is measured based on JISK 6 3 01 (used by spring-type hardness tester A). Adhesion of hardened material This paper applies Chinese national standard (CNS) A4 specification (210X297 mm) -17- 512162 A7 B7 V. Description of the invention (15) Composition of nickel in 1 Ommx 1 0 Ommx 1mm, (Please read the precautions on the back before filling this page) Aluminum, polysilicon Oxygen, copper, and acid-corroded copper plates were degassed in a vacuum and heated at 150 ° C for 4 hours to obtain a sheet-like hardened product. A small amount of spoon was used for the obtained hardened product. During this peeling, observe the ratio (area ratio) of the part of the cohesive failure (the cross section of the hardened object being destroyed) and the part of the interface peeling (the broken interface of the hardened object and the substrate), and evaluate the adhesion. 〇: Cohesive failure rate exceeding 80%, with strong adhesion. △: Cohesive failure rate of 20 to 80%, with adhesiveness. X: Cohesive failure rate of 20% or less, almost non-adhesive The foaming state of the hardened material is the same as that used for measuring the physical properties of the rubber. The flaky hardened product was visually observed for the presence or absence of blistering. Example 2 Partially hydrolyzed polycondensate of tetraethoxysilane (S i 0 2 content: 40% by weight printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs) A polysiloxane rubber composition was obtained in the same manner as in Example 1 except that [Kolcode (Company) 's product name ethyl polyoxalate 40 T]] was used in place of 2 parts by weight instead of tetraethoxysilane. The viscosity of this composition was measured with a B-type rotational viscometer to be 2 3 3 P (poise). Various functions were measured for the obtained composition according to the method described in Example 1. -18- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 512162 A7 B7 V. Description of the invention (16) Example 3 Partially hydrolyzed polycondensate with tetramethoxysilane [weight average molecular weight ( M w): 788] A curable polysiloxane rubber composition was obtained in the same manner as in Example 1 except that 2 parts by weight was substituted for tetraethoxysilane. The viscosity of this composition was measured by a B-type rotary viscometer to be 2 4 6 P (poise). Various functions were measured according to the method described in Example 1 for the obtained composition. Example 4 The 2 parts by weight of methyl hydrogen polysand oxygen institute was changed to 1 part by weight, and the methyl hydrogen polysilicon containing the following epoxy group was used. Oxane: (Please read the precautions on the back before filling in this page) | -fCH2) 3〇CH2CH -CH2 -Si—〇Ι CH3 Η I -Si 〇Ι CH3 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in addition to 1 weight A curable polysiloxane rubber composition was obtained in the same manner as in Example 1 except for the other parts. The viscosity of this composition was measured by a B-type rotational viscometer to be 2 6 0 P (poise). According to the obtained composition, various functions were measured according to the method described in Example 1. Comparative Example 1 The following formula is applicable to the Chinese National Standard (CNS) A4 specification (210X297 public director) -19- 512162 A7 __________ B7_ 5. Description of the invention ( 17) (Me) 3Si- [OS (Me) 2] xNH [Si (Me) 2〇] y-Si (Me) 3 (Please read the precautions on the back before filling this page) (where, M. e Except that the average x + y of methyl, X and y is 30.), except for 28 parts by weight of the silyloxysilamine compound instead of tetraethoxysilane. A hardening polymer was obtained in the same manner as in Example 1. Silicone rubber composition. The viscosity of this composition was measured with a B-type rotational viscometer to be 15 5 P (poise) °, and then various functions were measured according to the method described in Example 1 for the obtained composition. Comparative Example 2 3 parts by weight of hexamethyldisilazane A curable silicone rubber composition was obtained in the same manner as in Example 1 except that the tetraethoxyalkylene was replaced. The viscosity of this composition was measured by a B-type rotational viscometer to be 280 P (poise). The obtained composition was measured for various functions according to the method described in Example 1. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Comparative Example 3 A curable silicone rubber composition was obtained in the same manner as in Example 1 except that 2 parts by weight of triethoxymethylsilane was used instead of tetraethoxysilane. The viscosity of the mixture was measured using a B-type rotational viscometer to be 2 8 3 P (poise). The obtained composition will be used to determine its various functions according to the method of the example. 0 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 2〇- 512162 A7 ______ B7 V. Description of the invention (18) Comparative Example 4 A curable polysand rubber composition was obtained in the same manner as in Example 4 except that zinc oxide was not used. The viscosity of this composition was measured with a B-type rotational viscometer to be 4 Ο P (poise). Then, the obtained composition was measured for various functions b in place of Example 1. The above results are shown in Tables 1 and 2. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-21-This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 512162 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by a consumer cooperative V. Description of the invention (19) [Table 1] Example 1 Example 2 Example 3 Example 4 Viscosity (P) 275 233 246 260 Extraction water conductivity (// s / cm) 2 2 2 2 Amount of hydrogen produced (// 1 / g) 21 19 20 21 Hardness (JIS-A) 49 47 47 48 Tensile strength (kgf / cm2) 52 45 50 50 Elongation (%) 155 140 145 150 Volume resistivity (Ω cm ) lx 1016 9x ΙΟ15 8x 1015 lx 1016 resistance to 250 ° C / 24hr 57 57 57 56 heat hardness 250 ° C / 72hr 66 65 67 66 hardness foaming presence or absence Μ te JIW M ji adhesion / 4hr later) Ni 〇o 〇o A1 〇〇〇〇〇〇oooo Cu 〇〇oo Cu (after acid corrosion) 〇〇〇〇 (Please read the precautions on the back before filling out this page) This paper size applies to China National standard (CNS) A4 specification (21〇 ×: 297mm) -22- 512162
7 B 經濟部智慧財產局員工消費合作社印製 五、發明説明(2〇) 【表2】7 B Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of Invention (20) [Table 2]
比較例1 比較例2 比較例3 比較例4 粘度(P) 155 280 283 40 萃取水電導度(// s/cm) 2 3 3 2 氫氣產生量(// 1/g) 20 100 120 10 硬度(JIS-A) 35 47 47 19 張力強度(kgf/cm2 ) 20 51 50 5 伸展度(%) 160 170 150 200 體積電阻率(Ω cm) 5x 1015 7χ ΙΟ15 8χ 1015 7χ ΙΟ14 7Π 1 耐 250〇C /24hr 45 57 57 不可測 熱 之硬度 定裂化 性 之發生 250t: /72hr 55 69 69 同上 之硬度 發泡之有無 有 有 稍有 Μ 接著性(150°C /4hr後) Ni X X X 〇 A1 X X X 〇 Si Δ X Δ Ο Cu X X X X Cu(酸腐鈾後) X X X X (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -23- 512162 A7 _____B7_ 五、發明説明(21 ) 本發明儘管含氧化鋅,保存中幾乎未有氫氣產生,因 此可提供具保安定性優異之實用型塡充氧化鋅之加成反應 硬化型聚矽氧橡膠組成物。同時,該組成物不僅維持硬化 後良好之橡膠物性(硬度、張力強度、伸展度等;更顯示 優異之耐熱性及電氣絕緣性,且對於各種金屬、半導體等 ,特別是先行技術中粘著困難之銅、氧化銅均具有優異之 粘合性之硬化物者。 更且,本發明藉由氧化鋅之表面處理法可使組成物之 製造過程中,節約能源及縮短工程時間之優點。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -24- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Viscosity (P) 155 280 283 40 Conductivity of extracted water (// s / cm) 2 3 3 2 Hydrogen generation amount (// 1 / g) 20 100 120 10 Hardness (JIS-A) 35 47 47 19 Tensile strength (kgf / cm2) 20 51 50 5 Elongation (%) 160 170 150 200 Volume resistivity (Ω cm) 5x 1015 7χ ΙΟ15 8χ 1015 7χ ΙΟ14 7Π 1 250 ° C resistant / 24hr 45 57 57 Occurrence of non-measurable hardness and fixed cracking 250t: / 72hr 55 69 69 Identical hardness foaming with or without slight M adhesion (after 150 ° C / 4hr) Ni XXX 〇A1 XXX 〇 Si Δ X Δ 〇 Cu XXXX Cu (after acid rot uranium) XXXX (Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -23- 512162 A7 _____B7_ 5. Description of the invention (21) Although the present invention contains zinc oxide, almost no hydrogen is generated during storage, so it can provide a practical type of addition-reaction-hardened polysiloxane rubber with excellent security and qualitative properties. At the same time, the composition not only maintains good rubber properties (hardness, tensile strength, elongation, etc.) after hardening; it also shows excellent heat resistance and electrical insulation, and it is difficult to adhere to various metals, semiconductors, etc., especially in the prior art Copper and copper oxide are both hardened with excellent adhesion. Furthermore, the surface treatment method of zinc oxide in the present invention can save the energy and shorten the engineering time in the manufacturing process of the composition. (Please (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -24- This paper size applies to China National Standard (CNS) A4 (210X297 mm)
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102272231A (en) * | 2008-11-19 | 2011-12-07 | 陶氏康宁公司 | A silicone composition and a method for preparing the same |
CN102585757A (en) * | 2011-12-28 | 2012-07-18 | 烟台德邦科技有限公司 | Silica gel fin and preparation method thereof |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN102272231A (en) * | 2008-11-19 | 2011-12-07 | 陶氏康宁公司 | A silicone composition and a method for preparing the same |
CN102272231B (en) * | 2008-11-19 | 2013-10-30 | 陶氏康宁公司 | Silicone composition and method for preparing same |
CN102585757A (en) * | 2011-12-28 | 2012-07-18 | 烟台德邦科技有限公司 | Silica gel fin and preparation method thereof |
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