1374913 (1) 九、發明說明 【發明所屬之技術領域】 本發明係關於以有機聚矽氧烷爲主成分，藉由加成反 應硬化所得之聚矽氧橡膠之聚矽氧橡膠組成物，更詳細爲 ，經由硬化得到透明性優異之聚矽氧橡膠，該等聚矽氧橡 膠不僅安全，且隨時間的增加或高溫下不會有透明性降低 或產生變黃之加成硬化型聚矽氧橡膠組成物。 【先前技術】 聚矽氧橡膠，爲使耐熱性，耐寒性，電氣特性等有效 利用，在各式各樣的領域被廣泛利用。特別是加成反應硬 化型態的聚矽氧橡膠組成物由於不會如有機過氧化物硬化 般之因過氧化物的分解而產生副產物，在安全性上特別優 異，進而外觀良好（透明性），肌觸佳，加上耐久性優異等 ’在幼兒用玩具或食具，牙刷等，特別是奶瓶用奶嘴或嬰 兒用奶嘴（pacifier)等，更廣泛的使用在水中眼鏡，潛水鏡 (goggle) ’潛水用呼吸管等，廣泛地使用在潛水用品之成 形材料。又’由於離型性優異之故，作爲文化資產，美術 工藝品等的成型材料也被使用。 藉由加成反應硬化而賦予聚矽氧橡膠之組成物係在爲 基質聚合物之含鏈烯基的有谭聚矽氧烷，將爲交聯劑之有 機氫聚矽氧烷，與使兩者進行加成反應之觸媒混合時，在 常溫下也可進行反應’而終至形成膠狀物乃至硬化物。但 是，在該常溫下反應費時，生產大量的成型物時，並沒有 -4- (2) 1374913 效率。 因此，實際上該等成型物於大量生產時，由於加成硬 化型可軋（mi liable )聚矽氧橡膠組成物的壓縮成型或射 出成型，加成硬化型液狀聚矽氧橡膠組成物的射出成型， 在15〇°C〜220°C之所謂的高溫下，在數秒〜數分所謂的短 時間下成型爲一般。但是，此種加成硬化型的聚矽氧橡膠 成型品，在透明性優異方面，隨時間的增加會產生混濁及 g 變黃，特別是硬化或使用時在高溫下曝曬，透明性降低與 變黃最明顯。因此，在高溫下曝曬無損其透明性，又不會 產生變黃的透明聚矽氧橡膠成型品爲所期望。 _ 在日本特開平9-221597號公報（專利文獻1)中，爲防 止透明的聚矽氧橡膠變黃，則在含有聚有機矽氧烷，微粉 末狀二氧化矽充塡劑及觸媒量的硬化劑組成物上，配合微 量藍色或者黑色顏料被揭示。但是，同公報記載的實施例 組成物中，使用作爲硬化劑之有機過氧化物，因被該過氧 φ 化物的熱分解產生之自由基攻擊，而產生交聯之物。因此 ’關於透明性雖有記載，但關於安全性完全沒有觸及。再 者關於其用途’僅記載有鍵盤開關，而關於重視安全性之 奶嘴等的嬰幼兒用品或潛水用呼吸管等的潛水用品則完全 沒有記載。 日本特開2003 - 1 92 898號公報（專利文獻2)，記載有 在液狀加成硬化型聚有機矽氧烷組成物中添加呈現藍色〜 紫色或黑色之鈷化合物之方法，但是鈷化合物顯示有致癌 之疑之化合物’有安全方面的問題。實際上，鈷化合物雖 -5- (3) 1374913 然有例舉，但是沒有安全性方面的記載，而且亦無記載具 體用途例。 【專利文獻1】日本特開平9-221597號公報 【專利文獻2】日本特開2003 - 1 92898號公報 【發明內容】 [發明揭示] [發明欲解決課題] 本發明係鑒於上述事情，其目的爲提供不僅可維持聚 矽氧橡膠擁有之透明性，防止隨時間增加或溫度增加時的 _ 變黃，安全性更優異之聚矽氧橡膠所得加成硬化型聚矽氧 橡膠組成物。 〔解決課題之手段〕 本發明者’爲了達成上述目的，經一再戮力檢討的結 φ 果’首先發現在加成硬化型聚矽氧橡膠組成物上，藉由添 加含有群青之藍色顏料的特定量所得之硬化物，不但可維 持聚矽氧橡膠擁有之透明性，也可防止隨時間增加或温度 的增加產生變黃，可獲得安全性更優異之物，因此完成本 發明。 亦即，本發明係提供， (A)—分子中含有至少與2個矽原子結合的鏈烯基有 機聚矽氧烷100質量份’（B) —分子中含有至少與2個矽 原子結合的氫原子（Si-H基）有機氫聚砂氧院〇.2〜30質量 (4) (4)1374913 份’（C)由BET法之比表面積爲100 πί/g以上之煙燻二氧 化砂10〜40質量份，（D)含有群青（Ultra marine blue)之藍 色系顏料0.000 1〜0.01質量份，（E)加成反應觸媒觸媒， 爲主成分所成之加成硬化型聚矽氧橡膠組成物。 〔發明效果〕 本發明之加成硬化型聚矽氧橡膠組成物，該硬化物安 全’而且透明性佳，可以防止隨時間增加或溫度的增加之 透明性降低或變黃者。 〔.實施發明之最佳型態〕 本發明的加成硬化型聚矽氧橡膠組成物係以， (A) —分子中含有與至少2個矽原子結合之鏈烯基的 有機聚矽氧烷， (B) —分子中含有與至少2個矽原子結合之氫原子（Si-H基）的有機氫聚矽氧烷， (C) 由BET法所得比表面積爲100 rri/g以上之煙燻二 氧化矽， (D) 含有群青（Ultra marine blue)之藍色系顏料， (E) 加成反應觸媒 爲主成分所成者。 本發明的（A)成分，可以使用下述平均組成式（I)所示 之一分子中含有至少平均2個鏈烯基的有機聚矽氧烷。 (5)13749131374913 (1) EMBODIMENT OF THE INVENTION [Technical Field of the Invention] The present invention relates to a polyoxyxene rubber composition of a polyoxyxene rubber obtained by an addition reaction of an organopolysiloxane as a main component, and Specifically, a polyoxyxene rubber excellent in transparency is obtained by hardening, and the polyoxyxene rubber is not only safe, but also has an increase in transparency over time or a decrease in transparency at a high temperature or a yellowing addition hardening type polyoxygen Rubber composition. [Prior Art] Polyoxyxene rubber is widely used in various fields for its effective use in heat resistance, cold resistance, electrical properties, and the like. In particular, the addition-reactive-hardening type of the polyoxyxene rubber composition does not cause by-products due to decomposition of the peroxide as the organic peroxide is hardened, and is particularly excellent in safety and good in appearance (transparency). ), good muscle contact, excellent durability, etc. 'In children's toys or utensils, toothbrushes, etc., especially bottle nipples or baby pacifiers, etc., more widely used in water glasses, goggles (goggle ) 'Diving snorkels, etc., are widely used in the forming materials of diving equipment. In addition, as a cultural asset, molding materials such as art and crafts are also used. The composition of the polyoxyxene rubber which is imparted by the addition reaction hardening is an alkenyl group-containing organic polyhydroxane which is a crosslinking agent of the matrix polymer, and When the catalyst is subjected to the addition reaction, the reaction can be carried out at normal temperature to form a gel or a cured product. However, when the reaction is time-consuming at this normal temperature, there is no -4- (2) 1374913 efficiency when producing a large amount of the molded product. Therefore, in actuality, when the molded articles are mass-produced, the addition-hardening type liquid polyoxyethylene rubber composition is subjected to compression molding or injection molding of a composition-hardenable meltable (methicable) polyoxymethylene rubber composition. Injection molding is carried out at a so-called high temperature of 15 ° C to 220 ° C in a so-called short time of several seconds to several minutes. However, such an addition-curable polyoxyxene rubber molded article has excellent transparency, and turbidity and g yellowing occur with an increase in time, and particularly, it is exposed to high temperature at the time of hardening or use, and transparency is lowered and changed. Yellow is the most obvious. Therefore, it is desirable to expose a transparent polyoxyethylene rubber molded article which does not deteriorate its transparency at a high temperature and which does not cause yellowing. Japanese Patent Publication No. Hei 9-221597 (Patent Document 1), in order to prevent the transparent polyxanthene rubber from turning yellow, contains polyorganosiloxane, fine powdered cerium oxide chelating agent and amount of catalyst. The hardener composition is revealed with a trace amount of blue or black pigment. However, in the composition of the examples described in the publication, an organic peroxide as a curing agent is used, and a crosslinked product is generated by attack by a radical generated by thermal decomposition of the peroxygen compound. Therefore, although there is a description about transparency, there is no mention of safety. In addition, the use of the keyboard switch is not described in the following, and the diving products such as baby products such as pacifiers that are important for safety, and diving snorkels are not described at all. JP-A-2003-92 898 (Patent Document 2) discloses a method of adding a cobalt compound of blue to purple or black to a liquid addition-curable polyorganosiloxane composition, but a cobalt compound. It shows that there are safety problems with compounds that are suspected of carcinogenicity. Actually, although the cobalt compound is exemplified by -5-(3) 1374913, there is no description of safety, and no specific use example is described. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In order to provide a polysulfide rubber composition which is not only capable of maintaining the transparency possessed by the polyoxyethylene rubber, but also prevents the yellowing of the time and the temperature increase, and which is more excellent in safety, the addition-hardening type polyoxyxene rubber composition. [Means for Solving the Problem] The inventors of the present invention have found that, in order to achieve the above object, the results of repeated review have been found on the addition-hardening type polyoxo rubber composition by adding a blue pigment containing ultramarine blue. The cured product obtained in a specific amount not only maintains the transparency possessed by the polyoxyethylene rubber, but also prevents yellowing due to an increase in time or an increase in temperature, and can obtain a more excellent safety. Thus, the present invention has been completed. That is, the present invention provides, (A) - an alkenyl organopolyoxyalkylene having at least two deuterium atoms in the molecule, 100 parts by mass '(B) - having at least two deuterium atoms in the molecule Hydrogen atom (Si-H based) organohydrogen polyxanthine 〇. 2~30 mass (4) (4) 1374913 parts '(C) smoked silica sand with a specific surface area of 100 πί/g by BET method 10 to 40 parts by mass, (D) 0.000 1 to 0.01 parts by mass of a blue pigment containing ultramarine blue, (E) an addition reaction catalyst, and an addition hardening type which is a main component A silicone rubber composition. [Effect of the Invention] The addition-curable polyoxyxene rubber composition of the present invention has good transparency and good transparency, and can prevent a decrease in transparency or yellowing due to an increase in time or an increase in temperature. [Best Mode for Carrying Out the Invention] The addition-hardening polyxanthene rubber composition of the present invention is, (A) - an organopolyoxane having an alkenyl group bonded to at least two deuterium atoms in the molecule. (B) - an organic hydrogen polyoxyalkylene having a hydrogen atom (Si-H group) bonded to at least two deuterium atoms in the molecule, (C) a smoke having a specific surface area of 100 rri/g or more by the BET method Cerium dioxide, (D) Blue pigment containing ultramarine blue, (E) Addition reaction catalyst is the main component. In the component (A) of the present invention, an organopolyoxane having at least an average of two alkenyl groups in the molecule represented by the following average composition formula (I) can be used. (5) 1374913
R 1 aS i 0(4-a)/2 (I) 上述式（I)中，R〗爲互爲相同或異種的碳 佳爲1〜8的取代或非取代的一價烴基，a爲 佳爲1.8〜2.5的正數。 在此，與上述R1所示矽原子結合之取# —價烴基方面，可例舉甲基，乙基，丙基，晏 ，異丁基，三級丁基，戊基，新戊基，己基， 基，壬基，癸基等的烷基，苯基，甲苯基，二 基等的芳基，苄基，苯基乙基，苯基丙基等β 烯基，烯丙基，丙烯基，異丙烯基，丁烯基， 己烯基，辛烯基等的鏈烯基或|該等基的氫原 全部可以氟，溴，氯等的鹵原子，氰基等取# 甲基，氯丙基，溴乙基，三氟丙基，氰乙基等 8 0莫耳％以上以甲基爲佳。 又，R1中，至少2個，較佳爲2〜20個 10個鏈烯基爲必要（碳數2〜8者爲佳，更佳 佳爲乙烯基）。 此外，鏈烯基的含量爲，在有機聚1 l.〇xl(T6mol/g 〜l.〇xl0_3mol/g，特別是以 1. 〜5.〇xI(T4moI/g爲佳。鏈烯基的量若比l.Oxi 的話橡膠硬度會變得過低而成膠狀’又若比1 多的話交聯密度會變得過高而使橡膠變脆。 該鏈烯基與分子鏈末端的矽原子結合亦可 敦1〜1 0，較 1 .5 〜2.8，較 :或非取代的 I丙基，丁基 環己基，辛 :甲苯基，萘 J芳烷基，乙 己烯基，環 i子的一部或 :者，例如氯 €，全R1的 ，更佳爲2〜 爲2〜6，特 夕氧烷中以 0 X 1 0'5mo 1 /g 【0 ·6 m ο 1 / g 少 .〇χ 1 0*3mol/g ‘，與分子鏈 -8 - (6) (6)1374913 途中的砂原子結合亦可，與兩者結合亦優。該等有機聚砂 氧烷的構造有基本的直鏈狀構造，也有部分的分支鏈狀構 造，環狀構造等亦可。關於其分子量，在室溫（25 °c)下於 液狀乃至生橡膠狀下，平均聚合度以100〜20，000爲佳 ’更佳爲150〜10，000。平均聚合度不足1〇〇的話，無法 獲得充分的橡膠感，又若比20，000高的話，其成形加工 恐有變困難之虞。 本發明的（B)成分係，一分子中與至少2個與矽原子 結合之氫原子（Si-H基）之有機氫聚矽氧烷，分子中之SNH 基與該（A)成分中的矽原子結合之鏈烯基與氫單矽烷基藉 由.加成反應而交聯，係作爲組成物硬化用之硬化劑者。 該（B)成分的有機氫聚矽氧烷爲，下述平均組成式（II) R2bHcSiO(4-b-c)/2 (Π)所示 (式中，R2爲碳數1〜10的取代或非取代的一價烴基❶b 爲0.7〜2.1，c爲0.001〜1.0，而且b + c爲可滿足0.8〜 3.0之正數。），一分子中含有與至少2個，較佳爲3〜100 個，更佳爲3〜50個的矽原子結合之氫原子者可恰當使用 〇 在此，R2的一價烴基方面，可以例舉與所例示之Rl 一樣者，以沒有脂肪族不飽和基者爲佳。又’ b較佳爲 0.8〜2.0，c較佳爲0.01〜1.0，b + c較佳爲1.0〜2.5，有 機氫聚矽氧烷的分子構造爲直鏈狀，環狀，分支鏈狀，三 -9- (7) (7)1374913 次元網眼狀之任一種構造均可。此種情形下，一分子中矽 原子數（或聚合度）爲2〜300個，特別是4〜200個左右之 室溫（25 °C)下液狀者可恰當使用。此外，與砂原子結合之 氫原子可在分子鏈末端，分子鏈中間之任一位置均可，在 兩種位置也可。 上述（B)成分的有機氫聚矽氧烷具體言之可以例舉， 兩末端三甲基甲矽烷氧基閉鎖甲基氫聚矽氧烷，兩末端三 甲基甲矽烷氧基閉鎖二甲基矽氧烷•甲基氫矽氧烷共聚物 ，兩末端二甲基氫甲矽烷氧基閉鎖二甲基聚矽氧烷，兩末 端二甲基氫甲矽烷氧基閉鎖二甲基矽氧烷•甲基氫矽氧烷 共聚物，兩末端三甲基甲矽烷氧基閉鎖甲基氫矽氧烷•二 苯基矽氧烷共聚物，兩末端三甲基甲矽烷氧基閉鎖甲基氫 矽氧烷•二甲基矽氧烷共聚物，（CH3)2HSi01/2單位與 Si〇4/2單位所成之共聚物，（CH3)2HSi01/2單位與5丨04/2單 位與（C6H5)Si03/2單位所成共聚物等。 該有機氫聚矽氧烷的配合量爲，相對於（A)成分1〇〇 質量份爲〇·2〜30質量份，較佳爲0.3〜20質量份。有機 氫聚矽氧烷的配合量若不足0.2質量份會產生硬化不完全 之膠狀硬化物，又若超出30質量份同樣會產生硬化不完 全之膠狀硬化物。又，與上述有機聚矽氧烷的矽原子結合 之氫原子（Si-H基）與（Α)成分中的矽原子結合而成之鏈烯 基，其總量之莫耳比爲Si-H基/鏈烯基=0.8〜2.5，特別是 1.0〜2.3爲佳。該比率比〇.8小的話會形成交聯不完全， 恐有形成膠黏的（sticky )橡膠之虞，若比2.5大的話， -10- (8) 1374913 隨時間增加及溫度的增加，恐有變黃加強之虞。 本發明的（C)成分之煙燻（fumed )二氧化矽，爲賦予· 聚矽氧橡膠充分強度爲必須。煙燻二氧化矽由BET法所得 之比表面積爲100 πί/g以上，較佳爲150〜400 m2/g，更 佳爲150〜350m2/g。比表面積若比ΙΟΟπί/g小，不僅無法 獲得充分的強度，也會有成形物透明性降低的問題，若比 400 rri/g大的話，配合會變困難，還有變色之虞。 | 該等煙燻二氧化矽照樣使用亦無妨，以表面疏水化處 理劑予以處理後再使用，或與聚矽氧油捏合時添加表面處 理劑處理後再使用爲佳。該等表面處理劑有，烷基烷氧基 • 砍烷’烷基氯矽烷，烷基矽氮烷，矽烷偶合劑，鈦酸酯系 處理劑’脂肪酸酯等爲周知之物，可任意使用1種或2種 以上’同時或不同時機使用亦無妨。 又’該等煙燻二氧化矽的配合量爲相對於（A)成分100 質量份，爲10〜4〇質量份，較佳爲15〜35質量份。配合 φ 量若比10質量份少的話無法獲得充分的橡膠強度，又若 超出4〇質量份會有配合上的困難。 本發明的（D)成分含有群青之藍色系顏料，在本發明 隨時間或溫度的增加時防止變黃所必須者。群青在此化學 名爲「群青」，英語名爲「Ultra marine blue」，構造式 爲Na6Al6Si6〇24S4所示。在日本化審法i_22，FDA 21 CFH · 178 · 3970的分類裏，關於其安全性在 LD50(RatsandMice)，在 10，〇〇〇mg/kg<下，則完全沒有問 題。 •11- (9) (9)1374913 關於群青，其平均粒徑以〇·1〜20μπι爲佳，特別是 0.5〜ΙΟμηι爲佳。平均粒徑右比Ο.ίμηι小的話，會有配合 上的困難之情形，若20μηι以上不僅分散不完全，還有會 造成無法防止變黃效果之虞。 此外，本發明中，平均粒徑可藉由如雷射光繞射法求 得粒度分布測定中累積重量平均値（或median徑）等。 此外，藍色系顏料方面，群青以外尙有鈷藍，普魯士 藍（Iron blue)等的無機顏料，酞菁藍等的有機顏料。但是 ’鈷化合物有致癌性之疑，作爲潛水換氣裝置（snorkel ) 或哺乳瓶用奶嘴等含在口中之物方面並不佳。又，普魯士 藍等有機顏料，不僅耐熱性不完全，隨著加溫度的增加會 有變色的問題。因此，在與上述群青以外顏料之藍色系顏 料配合之情形，藍色系顏料中群青以外的顏料其配合比率 方面，0〜50質量％，特別是〇〜30質量％，尤其以〇〜1〇 質量％爲佳。 又’上述群青經過表面疏水化處理後再使用亦可。表 面處理劑方面，硬脂酸乙酯等的脂肪酸酯，三烷氧基乙烯 矽烷等的矽烷及矽烷系偶合劑，六甲基二矽氮烷等的矽氮 烷類，兩末端羥基矽氧烷等含有機官能基之矽氧烷類，八 甲基環四矽氧烷等的低分子聚矽氧，鈦酸酯等，若爲以二 氧化矽等之表面處理劑之周知之物則可無障礙地使用。此 外，關於表面處理劑的使用量及表面處理方法與二氧化矽 等的面處理相同，沒有特別的限制。 該等藍色系顏料的配合量方面，相對於（A)成分100 -12- (10) (10)1374913 質量份爲0.0001〜0.01質量份，較佳爲0.0002〜0.005質 量份。不足0.0001質量份，防止變黃之效果不充分，若 超出0.01質量份，藍色會過多，喪失其透明性。 在此，關於（d)成分的配合方法，照樣與組成物中配 合亦可，但微量配合會有分散不完全的可能性。所以，首 先將聚矽氧油（具體言之（A)成分及/或（B)成分）與藍色系顏 料，藍色系顏料以如0.5〜2質量％般地混合，儘可能以三 輥等予以強化分散後，配合於組成物中的方法爲佳。 (E)成分的加成反應觸媒方面，可以例舉鉑黑，氯化 鉑（IV)，氯鉑酸，氯鉑酸與1價醇的反應物，氯鉑酸與 烯烴類之錯合物，鈾雙乙醯乙酸酯等的鈾系觸媒，鈀系觸 媒，铑系觸媒等。此外，該加成反應觸媒的配合量可作爲 觸媒量，通常，作爲鉑族金屬相對於（A)成分，以0.5〜 l，000ppm，特別是1〜500ppm左右。 本發明的加成硬化型聚矽氧橡膠組成物中，其他的成 分在無損硬化橡膠的透明性下可因應需要任意配合沈澱二 氧化砂（Precipitated Silicas)，石英粉，砂藻土，碳酸 鈣般之充塡劑，碳黑，導電性鋅白（zinc white )，金屬 粉等之導電劑，含氮化合物或乙炔化合物，磷化合物，腈 化合物，竣酸醋，錫化合物，水銀化合物，硫化合物等之 氫單矽烷基化反應控制劑，氧化鐵，氧化铈般之耐熱劑， 二甲基聚矽氧油等的內部離型劑，賦予黏接性劑，賦予觸 變性（THIXOTROPIC)劑等。 本發明的加成硬化型聚矽氧橡膠組成物可以藉由使用 -13- (11) (11)1374913 捏合器’行星式混合器等一般的混合攪拌器，捏合器等將 上述各成分予以均勻混合調製。 又’本發明之加成硬化型聚矽氧橡膠組成物的硬化條 件方面’與周知的加成反應硬化型聚矽氧橡膠組成物相同 ’例如在常溫下也可完全硬化，但亦可因應需要加熱，該 情形，在8 0〜2 5 0 °C，特別是1 2 0〜2 2 0 °C下3秒〜1 0分鐘 ’特別以5秒〜3分鐘的加熱可以硬化。 如此所得本發明之加成硬化型聚矽氧橡膠組成物的硬 化物（聚矽氧橡膠）藉由霧度計（Suga試驗機公司製）測定， 其全光線透過率爲7 0 %以上，特別是7 5 %以上，總之以 8 0%以上爲佳。全光線透過率不足7 0%的話，不適合用於 潛水用品，游泳用品或嬰幼兒用品。 在上限1 00%時，變得過於透明而產生變黃的情形， 所以可以在90%以下，特別是85%以下。 本發明之加成硬化型聚矽氧橡膠組成物的硬化物，由 於安全，透明性優異，而且隨時間增加或高溫下也不會有 透明性降低和變黃的產生，特別是由於該優異外觀與安全 性，可以適合用於幼兒用玩具或食器，牙刷，奶瓶用奶嘴 ，嬰兒用奶嘴等的嬰幼兒用品或水中眼鏡，潛水鏡帶，潛 水換氣裝置（snorkel )零件等的潛水，游泳用品等。 【實施方式】 [實施例] 以實施例及比較例具體說明本發明如下，本發明不受 -14 - (12) (12)1374913 下述實施例的限制。此外，在下述例子中，部表示質量份 ’比表面積表示以B E T吸附法測定而得之値，平均粒徑表 示由雷射光繞射法以粒度分布測定裝置由測定累積重量平 均値（D5Q)所得之値。 [實施例1] 將兩末端以二甲基乙烯甲矽烷氧基所閉鎖之平均聚合 度750之二甲基聚矽氧烷（1)60份，比表面積爲3 00 iri/g 之煙燻二氧化矽（曰本Aerosil公司製，Aerosil 300)30份 ’六甲基二矽氮烷6份，水1.5份在室溫（25 °C)下混合30 分鐘後，加溫到1 5 0 °C，繼續3小時的攪拌冷卻後，再加 入二甲基聚矽氧烷（1)20份，繼續30分鐘的攪拌，產生聚 矽氧橡膠基質。 在該聚矽氧橡膠基質110份，加入兩末端以二甲基乙 烯甲矽烷氧基所閉鎖之平均聚合度250的二甲基聚矽氧烷 (2)20份，繼續30分鐘的攪拌後，作爲交聯劑係兩末端及 側鏈有Si-H基之甲基氫聚矽氧烷（3)[聚合度17，Si-H基 量0.0050mol/g]1.6份[Si-H基/鏈烯基=1.6]，作爲反應控 制劑之乙炔基環己醇0.10份，添加下述所示群青糊（A)0.4 份，繼續15分鐘的攪拌，獲得聚矽氧橡膠組成物。 在該聚矽氧橡膠組成物100份混合鉑觸媒（Pt濃度 1%)0.1份，以150°C /10分之壓製固化（press cure )獲得 厚度10mm的橡膠硬化物。關於該l〇mm厚的橡膠薄片， 藉由霧度計（Suga試驗機公司製）測定其全光線透過率所得 -15- (13) (13)1374913 的結果記載於表1。進而，於初期，關於在屋外放置3個 月所得者及在150 °C的烤箱放置1週所得者，其黃色之變 化度由目視觀察，結果如表1所示。 *群青糊（A):二甲基聚矽氧烷（1)99.5份+群青No.2000( 第一化成工業公司製，平均粒子徑：約ΙμΓη)0.5份予以混合 ，以通過三輥2次所得者 [實施例2] 兩末端以二甲基乙烯甲矽烷氧基閉鎖平均聚合度500 之二甲基聚矽氧烷（4)60份，比表面積200 rri/g之煙燻二 氧化砂（日本Aerosil公司製，Aerosil200)40份，六甲基二 矽氮烷5份，水1.0份在室溫（2 5 °C)下混合30分鐘後，加 溫至1 50°C，繼續3小時攪拌冷卻後，添加二甲基聚矽氧 烷（4)20份，再繼續攪拌30分鐘，獲得聚矽氧橡膠基質。 在該聚矽氧橡膠基質120份上，添加兩末端以三甲基 甲矽烷氧基閉鎖，側鏈有乙烯基平均聚合度3 00之二甲基 聚矽氧烷（5)[乙烯基含量0.0003 8mol/g] 20份，作爲交聯 劑之甲基氫聚矽氧烷（6)[聚合度 50，Si-H 基量 0.0068mol/g] 1.75份 [Si-H基/鏈烯基=1.0]，作爲反應控 制劑之乙炔基環己醇0.05份，並添加實施例1的群青糊 (Α)0·2份，繼續30分鐘的攪拌，獲得聚矽氧橡膠組成物 〇 在該聚矽氧橡膠組成物100份與鉑觸媒（Pt濃度 份混合後，以150°c /10分的壓製固化，獲得l〇mm -16- (14) (14)1374913 的橡膠硬化物。與實施例1 —樣’就全光線透過率，及初 期，在屋外放置3個月，在150 °C的烤箱放置1週所得者 ，其黃色變化度由目視觀察之，結果如表1所示。 [實施例3] 在分子鏈兩末端以三甲基甲砂燒氧基閉鎖，側鏈有乙 烯基聚合度約8，00 0的生橡膠狀有機聚矽氧烷（7)[乙烯基 含量0.000088mol/g]100份上’加上比表面積200 m2/g之 煙燻二氧化矽（日本Aerosil公司製，Aerosil 200)40份， 及作爲分散劑之二甲基二甲氧基矽烷8份，六甲基二矽氮 烷1份，水2份，予以平均的捏合，在15 0 °C下經過4小 時熱處理後，以二輥釋解，予以可塑化獲得聚矽氧橡膠混 合物。 在該聚矽氧橡膠混合物1 4 0份上，添加作爲交聯劑之 實施例1中的甲基氫聚矽氧烷（3)3.5份[Si-H基/鏈烯基 = 2.0] ·，作爲反應控制劑之乙炔基環己醇〇_〇5份，下述所 示群青糊（B )0.2份，並以二輥配合，獲得聚矽氧橡膠組成 物。 在該聚矽氧橡膠組成物100份上，再配合鉑觸媒（Pt 濃度1 °/〇) 0 .1份，在1 5 0 °C /1 0分之壓製固化下，獲得厚度 10 mm的橡膠硬化物。與實施例1 —樣，就全光線透過率 ，及初期，在屋外放置3個月，在150 °C的烤箱內放置1 週所得者，其黃色變化度以目視觀察’結果如表1所示。 *群青糊（B):二甲基聚矽氧烷（1)99.5份+表面以聚矽氧 -17- (15) (15)1374913 處理之群青AP-205(第一化成工業公司製，平均粒子徑：約 1μιη)0.5份，予以混合後，經2次通過三輥所得者 [比較例1] 將實施例1的二甲基聚矽氧烷（1)60份，比表面積300 irf/g之煙燻二氧化矽（日本 Aerosil公司製，Aerosil 3 0 0)3 0份，六甲基二矽氮烷6份，水1 .5份在室溫（25 °C ) 下混合3 0分鐘後，加溫至1 5 0 °C ’繼續3小時的攪拌’冷 卻後，加上二甲基聚矽氧烷（1)20份，繼續30分鐘的攪拌 ，獲得聚矽氧橡膠基質。 在該聚矽氧橡膠基質份上，加入實施例1的二甲 基聚矽氧烷（2)20份，繼續30分鐘的攪拌後，加入作爲交 聯劑之實施例1的甲基氫聚矽氧烷（3)1 .6份[Si-H基/鏈烯 基=1 .6]，作爲反應控制劑之乙炔基環己醇0.10份，繼續 15分鐘的攪拌，獲得聚矽氧橡膠組成物。 該聚矽氧橡膠組成物1〇〇份與鉑觸媒（Pt濃度1%)0.1 份混合後，再1 5 0 °C /〗0分的壓製固化下，獲得厚度1 0mm 的橡膠硬化物。與實施例1 —樣，就全光線透過率，及初 期，在屋外放置3個月，在150 °C的烤箱內放置1週所得 者，其黃色變化度以目視觀察，結果如表1所示。 [實施例4] 將實施例2的二甲基聚矽氧烷（4)60份，比表面積200 rri/g之煙燻二氧化矽（日本Aerosil公司製，Aerosil200)40 -18 - (16) 1374913 份，六甲基二矽氮烷5份，水丨·0份在室溫（25 °C )30 混合後，加溫至1 50°C ’繼續3小時的攪拌’冷卻後 加二甲基聚矽氧烷（4)20份，繼續30分鐘的攪拌，獲 矽氧橡膠基質。 在該聚矽氧橡膠基質120份上，添加實施例2的 基聚矽氧烷（5)[乙烯基含量〇.〇〇〇38mol/g]20份，作爲 劑之甲基氫聚矽氧烷（6)4.20份[5丨-11基/鏈烯基=2.4] 爲反應控制劑之乙炔基環己醇〇.〇5份，實施例1的 糊（A) 0.2份，繼續30分鐘的攪拌，獲得聚矽氧橡膠 物。 將該聚矽氧橡膠組成物100份與鉑觸媒（Pt 1%)0·1份混合後，以150°c/10分之壓製固化，獲得 10mm的橡膠硬化物。與實施例1 —樣，就全光線透 ，及初期，在屋外放置3個月，在15(TC的烤箱內放 週所得者，其黃色變化度以目視觀察，結果如表1所5 [比較例2] 在實施例3的生橡膠狀有機聚矽氧烷（7)i〇〇份上 加比表面積200 m2/g之煙燻二氧化矽（日本Aerosil公 ，Aerosil 200)40份’及作爲分散劑之二甲基二甲氧 烷8份’六甲基二矽氮烷1玲，水2份，予以平均地 ，經過1 5 0 °C 4小時的熱處理後，以二輥釋解，予以 化獲得聚矽氧橡膠混合物。 在該聚矽氧橡膠混合物1 4 0份上，添加作爲交聯 分鐘 ，添 得聚 二甲 交聯 ，作 群青 組成 濃度 厚度 過率 置 1 ，添 司製 基矽 捏合 可塑 劑之 -19- (17) (17)1374913 實施例1的甲基氫聚矽氧烷（3)3.5份[Si-H基/鏈烯基= 2.0] ’作爲反應控制劑的乙炔基環己醇〇.〇5份，下述所示普 魯，士藍糊（C )0.1份，以二輥配合，獲得聚矽氧橡膠組成物 〇 將該聚矽氧橡膠組成物100份再配合以鉑觸媒（Pt濃 度份，在15(TC/10分壓製固化，獲得厚度10mm 橡膠硬化物。，與實施例1—樣，就全光線透過率，及初 期’在屋外放置3個月，在1 5 0 °C的烤箱內放置1週所得 者，其黃色變化度以目視觀察之結果如表1所示。 *普魯士藍糊（C):二甲基聚矽氧烷（1)99.5份+平均粒子 徑.0.2μπι的普魯士藍（Iron Blue)0.5份予以混合後，通過 三輥2次所得者。 [比較例3 ] 除了不配合群青糊（A)0.2份以外，其他則與實施例4 一樣來調製聚矽氧橡膠組成物’與實施例1 —樣’其全光 線透過率，及初期，在屋外放置3個月’在15 0°C的烤箱 內放置1週所得者，其黃色變化度以目視觀察之結果如表 1所示。 -20- (18)1374913 [表ΠR 1 aS i 0(4-a)/2 (I) In the above formula (I), R is a substituted or unsubstituted monovalent hydrocarbon group which is preferably the same or different carbon and is preferably 1 to 8 carbon, and a is preferably A positive number of 1.8 to 2.5. Here, as the valence hydrocarbon group bonded to the above-mentioned ruthenium atom represented by R1, a methyl group, an ethyl group, a propyl group, a hydrazine group, an isobutyl group, a tertiary butyl group, a pentyl group, a neopentyl group, a hexyl group may be mentioned. An alkyl group of a group, a fluorenyl group, a fluorenyl group, an aryl group such as a phenyl group, a tolyl group or a diyl group, a β-alkenyl group such as a benzyl group, a phenylethyl group or a phenylpropyl group, an allyl group or a propylene group. An alkenyl group such as isopropenyl group, butenyl group, hexenyl group or octenyl group; or a hydrogen atom of such a group may be a halogen atom such as fluorine, bromine or chlorine, or a cyano group; More preferably, the methyl group, the bromoethyl group, the trifluoropropyl group, the cyanoethyl group and the like are preferably more than 80% by mole. Further, in R1, at least two, preferably 2 to 20, 10 alkenyl groups are necessary (preferably having 2 to 8 carbon atoms, more preferably vinyl). In addition, the content of the alkenyl group is, in the organic poly 1 l. 〇 xl (T6mol / g ~ l. 〇 x l0_3mol / g, especially in the range of 1. ~ 5. 〇 xI (T4moI / g is preferred. Alkenyl If the amount is l.Oxi, the rubber hardness will become too low to form a gelatinous shape. If it is more than 1, the crosslink density will become too high and the rubber will become brittle. The alkenyl group and the ruthenium atom at the end of the molecular chain. Combination can also be 1~1 0, compared to 1.5 to 2.8, compared with: or unsubstituted I propyl, butylcyclohexyl, octyl: tolyl, naphthalene J aralkyl, ethylhexenyl, ring i One or: one, such as chlorine, all R1, more preferably 2~2~6, 0 X 1 0'5mo 1 /g [0 · 6 m ο 1 / g less. 〇χ 1 0*3mol/g ', combined with the sand atom of the molecular chain-8 - (6) (6) 1374913, and the combination of the two is also excellent. The structure of these organic polyoxanes is basic. The linear structure may also have a partial branched chain structure, a ring structure, etc. Regarding the molecular weight thereof, the average polymerization degree is 100 to 20 at room temperature (25 ° C) in the form of liquid or even raw rubber. 000 is better 'better than 150 to 10,000. Average degree of polymerization If it is one foot, a sufficient rubbery feeling cannot be obtained, and if it is higher than 20,000, the forming process may become difficult. The component (B) of the present invention is at least two in one molecule. An organic hydrogen polyoxyalkylene atom of an atom-bonded hydrogen atom (Si-H group), an alkenyl group in which a SNH group in a molecule is bonded to a ruthenium atom in the (A) component, and a hydrogen mono-alkyl group are subjected to an addition reaction. The cross-linking is used as a hardening agent for curing the composition. The organic hydrogen polyoxyalkylene of the component (B) is represented by the following average composition formula (II) R2bHcSiO(4-bc)/2 (Π) (wherein R2 is a substituted or unsubstituted monovalent hydrocarbon group 碳b having a carbon number of 1 to 10 of 0.7 to 2.1, c is 0.001 to 1.0, and b + c is a positive number which satisfies 0.8 to 3.0.), in one molecule The hydrogen atom containing at least 2, preferably 3 to 100, more preferably 3 to 50, ruthenium atoms may be suitably used. Here, the monovalent hydrocarbon group of R2 may be exemplified and exemplified. Rl is the same as those having no aliphatic unsaturated group. Further, 'b is preferably 0.8 to 2.0, c is preferably 0.01 to 1.0, and b + c is preferably 1.0 to 2.5. The molecular structure of the hydrogen polyoxyalkylene is linear, cyclic, branched, and any of the three--9-(7) (7) 1374913-dimensional meshes can be constructed. In this case, one molecule The number of cesium atoms (or degree of polymerization) is 2 to 300, and particularly, the liquid at room temperature (25 ° C) of about 4 to 200 may be suitably used. Further, the hydrogen atom bonded to the sand atom may be in the molecular chain. The end, either in the middle of the molecular chain, can be used in two positions. The organic hydrogen polyoxyalkylene of the above component (B) can be specifically exemplified by a two-terminal trimethylmethaneoxy group blocking methyl hydrogen polyoxyalkylene, and a terminal trimethylmethane alkoxy group blocking dimethyl group. a decane/methylhydroquinone copolymer, a two-terminal dimethylhydroformaloxy group blocking dimethyl polyoxane, and a two-terminal dimethylhydroformaloxy group blocking dimethyloxane. Methylhydroquinone copolymer, two-terminal trimethylmethane alkoxy-blocked methylhydroquinone-diphenyl decane copolymer, two-terminal trimethylmethane oxide-locked methylhydroquinone Alkyl dimethyl decane copolymer, copolymer of (CH3)2HSi01/2 unit and Si〇4/2 unit, (CH3)2HSi01/2 unit and 5丨04/2 unit and (C6H5)Si03 /2 units of copolymers, etc. The amount of the organohydrogenpolyoxane to be added is from 2 to 30 parts by mass, preferably from 0.3 to 20 parts by mass, per part by mass of the component (A). When the amount of the organohydrogenpolysiloxane is less than 0.2 part by mass, a gel-like hardened material which is incompletely hardened may be produced, and if it exceeds 30 parts by mass, a hardened incomplete gelatinous product may be produced. Further, the alkenyl group in which the hydrogen atom (Si-H group) bonded to the ruthenium atom of the above organopolysiloxane is bonded to the ruthenium atom in the (Α) component has a molar ratio of Si-H. The base/alkenyl group is 0.8 to 2.5, particularly preferably 1.0 to 2.3. If the ratio is smaller than 〇.8, the cross-linking will be incomplete, and there is a fear of forming a sticky rubber. If it is larger than 2.5, -10-(8) 1374913 increases with time and the temperature increases. There are yellowing and strengthening. The fumed cerium oxide of the component (C) of the present invention is essential for imparting sufficient strength to the polyoxyxene rubber. The smoked ceria has a specific surface area obtained by the BET method of 100 π ί / g or more, preferably 150 to 400 m 2 /g, more preferably 150 to 350 m 2 /g. When the specific surface area is smaller than ΙΟΟπί/g, not only is it impossible to obtain sufficient strength, but also the transparency of the molded article is lowered. If it is larger than 400 rri/g, the mixing becomes difficult and there is a discoloration. The smoked ruthenium dioxide may also be used as it is, after being treated with a surface hydrophobizing agent, or when it is kneaded with a polyoxyphthalic acid oil, it is preferably treated by adding a surface treatment agent. The surface treatment agents are, for example, alkyl alkoxy • cetane 'alkyl chloro decane, alkyl decazane, decane coupling agent, titanate-based treatment agent 'fatty acid ester, etc., which can be used arbitrarily. One or two or more 'use it at the same time or at different times. Further, the amount of the smoked cerium oxide to be added is 10 to 4 parts by mass, preferably 15 to 35 parts by mass, per 100 parts by mass of the component (A). If the amount of φ is less than 10 parts by mass, sufficient rubber strength cannot be obtained, and if it exceeds 4 parts by mass, there is a difficulty in blending. The component (D) of the present invention contains ultramarine blue pigment, which is necessary for preventing yellowing in the present invention as time or temperature increases. In this chemistry, the group is called "Qingqing", the English name is "Ultra marine blue", and the structure is Na6Al6Si6〇24S4. In the classification of Japanese chemistries i_22, FDA 21 CFH · 178 · 3970, there is no problem with the safety of LD50 (RatsandMice) at 10, 〇〇〇mg/kg < • 11- (9) (9) 1374913 For ultramarine, the average particle size is preferably 〇1~20μπι, especially 0.5~ΙΟμηι. If the average particle diameter is smaller than Ο.ίμηι, there will be difficulties in matching. If 20μηι or more is not only incompletely dispersed, it will also prevent the yellowing effect. Further, in the present invention, the average particle diameter can be obtained by, for example, a laser light diffraction method to obtain a cumulative weight average enthalpy (or median diameter) in the particle size distribution measurement. Further, in the case of the blue pigment, an inorganic pigment such as cobalt blue, Iron blue or the like, or an organic pigment such as phthalocyanine blue is used in the group. However, the 'cobalt compound is suspected of being carcinogenic, and it is not preferable as a snorkel or a nipple for a feeding bottle. Further, organic pigments such as Prussian blue are not only incomplete in heat resistance, but also have a problem of discoloration as the temperature increases. Therefore, in the case of blending with the blue pigment of the pigment other than the ultramarine blue, the blending ratio of the pigment other than the ultramarine blue pigment in the blue pigment is 0 to 50% by mass, particularly 〇 to 30% by mass, particularly 〇~1. 〇% by mass is preferred. Further, the above-mentioned ultramarine may be used after being subjected to surface hydrophobic treatment. Examples of the surface treatment agent include fatty acid esters such as ethyl stearate, decane and decane coupling agents such as trialkoxyvinyl decane, and decazanes such as hexamethyldiazepine. a low molecular weight polyoxane such as an alkyl functional group or a low molecular weight polyoxane such as octamethylcyclotetraoxane, a titanate or the like, which is known as a surface treatment agent such as cerium oxide. Use without barriers. Further, the amount of the surface treatment agent used and the surface treatment method are the same as those of the surface treatment such as cerium oxide, and are not particularly limited. The blending amount of the blue pigments is 0.0001 to 0.01 parts by mass, preferably 0.0002 to 0.005 parts by mass, based on 100 parts by weight of (A) component 100 -12-(10) (10) 1374913 parts by mass. When the amount is less than 0.0001 parts by mass, the effect of preventing yellowing is insufficient, and if it exceeds 0.01 parts by mass, the blue color is excessive and the transparency is lost. Here, the method of blending the component (d) may be carried out in combination with the composition, but the amount of the mixture may be incompletely dispersed. Therefore, first, the polyoxygenated oil (specifically, the component (A) and/or the component (B)) is mixed with the blue pigment and the blue pigment in a ratio of, for example, 0.5 to 2% by mass, as much as possible by three rolls. After the dispersion is strengthened, the method of blending in the composition is preferred. The addition reaction catalyst of the component (E) may, for example, be platinum black, platinum (IV) chloride, chloroplatinic acid, a reaction product of chloroplatinic acid with a monovalent alcohol, or a complex of chloroplatinic acid and an olefin. , uranium-based catalysts such as uranyl diacetamidine acetate, palladium-based catalysts, and lanthanide catalysts. Further, the amount of the addition reaction catalyst may be used as the amount of the catalyst. Usually, the platinum group metal is from 0.5 to 1,000 ppm, particularly from 1 to 500 ppm, based on the component (A). In the addition-hardening polyoxyxene rubber composition of the present invention, other components may be optionally blended with precipitated silica sand (Precipitated Silicas), quartz powder, diatomaceous earth, calcium carbonate in accordance with the transparency of the non-destructive hardening rubber. Filling agent, carbon black, conductive zinc white (zinc white), conductive powder such as metal powder, nitrogen-containing compound or acetylene compound, phosphorus compound, nitrile compound, citric acid vinegar, tin compound, mercury compound, sulfur compound, etc. The hydrogen monoterpene alkylation reaction controlling agent, an iron oxide, a cerium oxide-like heat-resistant agent, an internal release agent such as dimethylpolyphthalic acid oil, an adhesive agent, and a thixotropic agent (THIXOTROPIC). The addition-hardening type polyoxyxene rubber composition of the present invention can be uniformly obtained by using a general mixer such as a-13-(11) (11) 1374913 kneader 'planetary mixer, a kneader or the like. Mixed modulation. Further, the curing condition of the addition-hardening polyxanthene rubber composition of the present invention is the same as that of the well-known addition reaction-curable polyoxo rubber composition. For example, it can be completely cured at room temperature, but it can also be used as needed. Heating, in this case, at 8 0 to 2 50 ° C, especially 1 2 0 to 2 2 ° ° C for 3 seconds ~ 1 0 minutes 'Specially 5 seconds ~ 3 minutes of heating can be hardened. The cured product (polyoxymethylene rubber) of the addition-hardening type polyoxo rubber composition of the present invention is measured by a haze meter (manufactured by Suga Test Instruments Co., Ltd.), and the total light transmittance is 70% or more. It is more than 7 5 %, and in general it is better than 80%. If the total light transmittance is less than 70%, it is not suitable for diving equipment, swimming supplies or baby products. When the upper limit is 100%, it becomes too transparent to cause yellowing, so it may be 90% or less, particularly 85% or less. The cured product of the addition-hardening type polyoxyxene rubber composition of the present invention is excellent in transparency and transparency, and does not have a decrease in transparency and yellowing with an increase in time or at a high temperature, particularly due to the excellent appearance. And safety, it can be suitable for children's toys or food, toothbrushes, bottle nipples, baby pacifiers, baby products or water glasses, goggles, diving snorkel parts, diving, swimming supplies Wait. [Embodiment] [Examples] The present invention will be specifically described by way of Examples and Comparative Examples. The present invention is not limited by the following examples of -14 - (12) (12) 1374913. Further, in the following examples, the portion indicates the mass portion 'the specific surface area indicates the measurement by the BET adsorption method, and the average particle diameter indicates the cumulative weight average 値 (D5Q) obtained by the laser light diffraction method by the particle size distribution measuring device. After that. [Example 1] 60 parts of dimethylpolyoxane (1) having an average degree of polymerization of 750 blocked by dimethylvinylformyloxy group at both ends, and a smoked surface having a specific surface area of 300 iri/g Cerium oxide (Aerosil 300, manufactured by Acer, Aursil 300) 30 parts of 'hexamethyldioxane 6 parts, 1.5 parts of water mixed at room temperature (25 ° C) for 30 minutes, heated to 150 ° C After 3 hours of stirring and cooling, 20 parts of dimethyl polyoxane (1) was further added, and stirring was continued for 30 minutes to produce a polyoxymethylene rubber matrix. In 110 parts of the polyoxyethylene rubber matrix, 20 parts of dimethyl polyoxyalkylene (2) having an average degree of polymerization of 250 blocked by dimethylvinylformyloxy groups at both ends was added, and after stirring for 30 minutes, As a cross-linking agent, a methylhydropolysiloxane (3) having a Si-H group at both ends and a side chain [degree of polymerization 17, Si-H group amount: 0.0050 mol/g] 1.6 parts [Si-H group/chain Alkenyl = 1.6], 0.10 part of ethynylcyclohexanol as a reaction controlling agent, 0.4 parts of the green paste (A) shown below was added, and stirring was continued for 15 minutes to obtain a polyoxymethylene rubber composition. To the 100 parts of the polyoxyethylene rubber composition, 0.1 part of a platinum catalyst (Pt concentration: 1%) was mixed, and press cured at 150 ° C / 10 to obtain a rubber cured product having a thickness of 10 mm. The results of -15-(13)(13)1374913 obtained by measuring the total light transmittance of the rubber sheet having a thickness of 100 mm by a haze meter (manufactured by Suga Test Instruments Co., Ltd.) are shown in Table 1. Further, in the initial stage, the degree of change in yellow was observed by visual observation of those who had been placed outside the house for three months and those who had been placed in an oven at 150 ° C for one week. The results are shown in Table 1. *Group green paste (A): dimethyl polyoxyalkylene (1) 99.5 parts + ultramarine blue No. 2000 (manufactured by Daiei Kasei Co., Ltd., average particle diameter: about ΙμΓη) 0.5 parts were mixed to pass three rolls twice The obtained person [Example 2] 60 parts of dimethylpolyoxane (4) having an average polymerization degree of 500 dimethyl dimethyl decyloxy groups at both ends, and a smoked silica sand having a specific surface area of 200 rri/g ( Made from Japan Aerosil Co., Ltd., Aerosil 200), 5 parts of hexamethyldioxane, 1.0 part of water, mixed at room temperature (25 ° C) for 30 minutes, then warmed to 150 ° C, and continued for 3 hours. After cooling, 20 parts of dimethyl polyoxane (4) was added, and stirring was continued for further 30 minutes to obtain a polyoxymethylene rubber matrix. On the 120 parts of the polyoxyethylene rubber matrix, two ends were added with trimethylmethaneoxyl group, and the side chain had a vinyl group having a vinyl group average degree of polymerization of 30,000 (5) [vinyl content 0.0003 8 mol/g] 20 parts, methylhydrogenpolyoxane as a crosslinking agent (6) [degree of polymerization 50, Si-H group amount: 0.0068 mol/g] 1.75 parts [Si-H group/alkenyl group = 1.0 ], 0.05 part of ethynylcyclohexanol as a reaction controlling agent, and adding 0.2 part of the ultramarine paste (Α) of Example 1, and stirring was continued for 30 minutes to obtain a polyxanthoxy rubber composition in the polyfluorene oxide. 100 parts of the rubber composition and a platinum catalyst (Pt concentration parts were mixed and cured by pressing at 150 ° C/10 minutes to obtain a rubber cured product of 10 mm -16 - (14) (14) 1374913. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results of the whole light transmittance and the initial period were 3 months after being placed outside the house and placed in an oven at 150 °C for one week. 3] At the two ends of the molecular chain, the trimethylmethane is alkoxy blocked, and the side chain has a raw rubbery organopolyoxane with a vinyl polymerization degree of about 8.0 (7) [vinyl content 0.000 088 mol/g] 100 parts of a smoked cerium oxide (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 200 m2/g, 40 parts, and 8 parts of dimethyldimethoxy decane as a dispersing agent. 1 part of hexamethyldioxane, 2 parts of water, kneaded on average, heat-treated at 150 ° C for 4 hours, and then disintegrated in two rolls to obtain plasticized polyoxo rubber mixture. To 140 parts of the oxygen-oxygen rubber mixture, 3.5 parts of methylhydrogen polyoxane (3) in Example 1 as a crosslinking agent was added [Si-H group/alkenyl group = 2.0], as reaction control 5 parts of ethynylcyclohexanol oxime 〇 〇, 0.2 parts of the green paste (B) shown below, and mixed with two rolls to obtain a polyoxyxene rubber composition. On the 100 parts of the polyoxyethylene rubber composition And with platinum catalyst (Pt concentration 1 ° / 〇) 0.1 parts, at 150 ° C / 10 ° press curing, obtain a rubber hardened material with a thickness of 10 mm. As in the case of Example 1, For the total light transmittance, and initially, placed outside the house for 3 months, and placed in an oven at 150 °C for 1 week, the yellowness of the change is visually observed. The results are shown in Table 1. * Green paste (B): dimethyl polyoxyalkylene (1) 99.5 parts + ultramarine AP-205 treated with polyfluorene-17-(15) (15) 1374913 (manufactured by Daisei Kogyo Co., Ltd., Average particle diameter: about 1 μm) 0.5 parts, after mixing, two passes through three rolls [Comparative Example 1] 60 parts of the dimethyl polyoxyalkylene (1) of Example 1, a specific surface area of 300 irf / g of smoked cerium oxide (Aerosil 300 manufactured by Aerosil, Japan) 30 parts, 6 parts of hexamethyldioxane, and 1.5 parts of water mixed at room temperature (25 ° C) for 30 minutes Thereafter, the mixture was heated to 150 ° C and continued for 3 hours of stirring. After cooling, 20 parts of dimethyl polyoxyalkylene (1) was added, and stirring was continued for 30 minutes to obtain a polyoxymethylene rubber matrix. To the polyoxyethylene rubber matrix component, 20 parts of the dimethyl polyoxane (2) of Example 1 was added, and after stirring for 30 minutes, the methyl hydrogen polycondensate of Example 1 as a crosslinking agent was added. Oxygenane (3) 1.6 parts [Si-H group / alkenyl group = 1.6], 0.10 parts of ethynylcyclohexanol as a reaction controlling agent, stirring for 15 minutes to obtain a polyoxyxene rubber composition . One part of the polyoxyethylene rubber composition was mixed with 0.1 part of a platinum catalyst (Pt concentration: 1%), and then pressed and solidified at 150 ° C / 0 ° to obtain a rubber cured product having a thickness of 10 mm. In the same manner as in the first embodiment, the total light transmittance and the initial stage were placed outside the house for 3 months, and the result was placed in an oven at 150 ° C for one week. The yellowness of the change was visually observed. The results are shown in Table 1. . [Example 4] 60 parts of dimethylpolysiloxane (4) of Example 2, smoked cerium oxide (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 200 rri/g 40 -18 - (16) 1374913 parts, 5 parts of hexamethyldioxane, hydrazine · 0 parts mixed at room temperature (25 °C) 30, warmed to 1 50 ° C 'Continue for 3 hours of stirring' after cooling, add dimethyl 20 parts of polyoxyalkylene (4) was stirred for 30 minutes to obtain a silicone rubber matrix. To 120 parts of the polyoxyxylene rubber matrix, 20 parts of the polyoxyalkylene oxide (5) of Example 2 [vinyl content 〇.〇〇〇38 mol/g] was added as a methyl methoxide polyoxane (6) 4.20 parts [5丨-11-yl/alkenyl=2.4] is a reaction control agent of ethynylcyclohexanol oxime. 5 parts, 0.2 part of the paste (A) of Example 1, and stirring was continued for 30 minutes. , obtaining a polyoxymethylene rubber. 100 parts of this polyoxyethylene rubber composition and 0.1 part of platinum catalyst (Pt 1%) were mixed, and it solidified by 150 degree/10/10, and the hardening of the rubber of 10 mm was obtained. As in Example 1, the whole light was allowed to pass through, and at the beginning, it was placed outside the house for 3 months, and in the 15 (TC oven), the yellowness was visually observed. The results are shown in Table 1 [Comparative Example 2] A smoked cerium oxide (Japan Aerosil, Aerosil 200) having a specific surface area of 200 m 2 /g was added to the raw rubbery organopolyoxane (7) i part of Example 3, and 40 parts were used as Dispersing agent dimethyl dimethoxyl 8 parts of 'hexamethyldiazane alkane 1 ling, 2 parts of water, averaged, after heat treatment at 150 ° C for 4 hours, released by two rolls, The polyxanthene rubber mixture was obtained. On the 140 parts of the polyoxyxene rubber mixture, as a crosslinking minute, a polydimethyl crosslink was added, and the concentration of the ultramarine component was set to 1 and the thickness of the mixture was set to 1. Kneading plasticizer -19-(17) (17) 1374913 Methylhydrogen polyoxyalkylene (3) of Example 1 3.5 parts [Si-H group/alkenyl group = 2.0] 'Ethynyl group as a reaction controlling agent 5 parts of cyclohexanol oxime. 普, the following shows Prolu, Shilan paste (C) 0.1 parts, and is mixed with two rolls to obtain a polyxanthoxy rubber composition. 100 parts of the rubber composition was further blended with a platinum catalyst (Pt concentration part, and cured at 15 (TC/10 minutes to obtain a 10 mm thick rubber cured product. As in Example 1, the total light transmittance, and the initial stage) After being placed outside the house for 3 months and placed in an oven at 150 ° C for 1 week, the yellowness of the change was visually observed as shown in Table 1. *Prussian blue paste (C): dimethyl polyfluorene 99.5 parts of oxane (1) + 0.5 parts of an average particle diameter of 0.2 μm of Iron Blue, which was mixed, and passed through three rolls twice. [Comparative Example 3] In addition to not supporting the ultramarine paste (A) 0.2 parts Other than the fourth embodiment, the polyoxyethylene rubber composition was prepared in the same manner as in Example 1 and its entire light transmittance was initially placed in the oven for 3 months 'placed in an oven at 150 ° C. The results of visual observation of the yellowness of the one-week gain are shown in Table 1. -20- (18) 1374913 [Former Π
實施例1 實施例2 實施例3 實施例4 比較例1 比較例2 比較例3 全光線透過率(％) 87 84 82 83 87 81 83 初期 ◎ ◎ ◎ ◎ 〇 ◎ 〇 外觀 屋外3個月 ◎ ◎ ◎ ◎ △ ◎ Δ 150 °C xl 週 〇 ◎ ◎ 〇 △ △ XExample 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Total light transmittance (%) 87 84 82 83 87 81 83 Initial ◎ ◎ ◎ ◎ 〇 ◎ 〇 Exterior appearance 3 months ◎ ◎ ◎ ◎ △ ◎ Δ 150 °C xl 〇 ◎ ◎ 〇 △ △ X
變黃之判定 ◎:不變黃 〇：僅稍變黃 〇：有變黃 X:變黃強烈Judging yellowing ◎: No yellowing 〇: Only slightly yellowing 〇: There is yellowing X: Yellowing is strong
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