1330647 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關濕式二氧化矽所成之透明橡膠用塡充材 料及透明橡膠者。更詳細者係有關做爲透明橡膠之塡充材 料使用時，其使用性良好，且具有透明橡膠之透明性及耐 摩損性均良好之濕式二氧化矽所成之透明橡膠用塡充材料 及含此之透明橡膠者。 【先前技術】 透明橡膠係以具有高度透明性之未硫化橡膠，例如： S-SBR (溶液聚合型苯乙烯丁二烯橡膠）、BR (丁二烯橡 膠）爲主成份，其中調配補強用之塡充材料構成之高透明 性硫化橡膠，被期待做爲附與創造性之材料、機能性材料 之各種用途。 做爲透明橡膠用途之一者爲鞋底之用途。該用途中透 明橡膠做爲鞋底某部份使用後附與創造性之用途爲極普遍 者，近來，嘗試藉由透明橡膠構成整個鞋底使用者。此時 ，透明橡膠不僅被要求透明性，亦期待其耐摩損性、耐滑 動性等之機械性能者。 以往，附與上述機械性能於透明橡膠之塡充材料，由 分散性，透明性的觀點，而使用乾式二氧化矽，惟以乾式 二氧化矽做爲塡充材料使用之透明橡膠，因該乾式二氧化 矽造成製品價格之上昇，特別做爲鞋底用途等之一般用途 之使用有其經濟面的困難點。 (2) (2)1330647 鑑於此狀況，硏究使用以價格低於乾式二氧化矽之濕 式二氧化矽做爲透明橡膠用塡充材。惟，做爲透明橡膠所 使用之BR、S-SBR等橡膠成份，特別是BR相較於一般 濕式二氧化矽做爲塡充材料使用之其他橡膠其支撐極弱， 混谏時不易剪切，因此，以濕式二氧化矽做爲塡充材料使 用時，無法充份分散濕式二氧化矽，所取得之透明橡膠其 透明性明顯降低，產生無商品價値之問題點。且，透明橡 膠之耐摩損性等橡膠強度亦極不理想。 爲解決上述問題之方法爲考量藉由使濕式二氧化矽進 行極細粉碎後，提昇於橡膠中之分散性方法者，惟，粉碎 務必大型裝置與需要大量勞力，不僅經濟面不佳，因礙於 濕式二氧化矽之高度凝聚性而無法取得理想之效果。且， 微粉化後，產生粉體使用性變差之問題。 【發明內容】 本發明目的係爲提供一種由濕式二氧化矽所構成，具 有容易使用之較大粒徑，可藉由低剪切高度分散於橡膠中 ’其結果得到透明性高，且耐摩損性、耐滑動性等機械性 能優異之透明橡膠的透明橡膠用塡充材料者。 本發明之其他目的係提供含有本發明之透明橡膠用塡 充材料，且具有上述特性之透明橡膠用塡充材料。 本發明之其他目的及優點如下述說明。 本發明者爲解決上述課題進行精密硏討後結果發現， 濕式二氧化矽之吸油量對比表面積之比高於以往一般橡膠 -6- (3) 1330647 用塡充材料所使用之濕式二氧化矽，調整 式二氧化矽可降低二氧化矽粒子間之凝聚 橡膠成份混練時之分散性，以及藉由調整 濕式二氧化矽平均粒徑後，可提高使用性 不易造成剪切，與該橡膠成份混練時更能 其結果取得透明性佳，且，附與該機械特 ，進而完成本發明。 亦即，本發明之特徵係由比表面積爲 吸油量（V;CC/100g)與比表面積（S; m2/ 爲1.05以上，且平均粒徑爲5〜10 μιη之 成之透明橡膠用塡充材料。 本發明之透明橡膠用塡充材料係於公 造中做爲塡充材料之使用，提供該透明橡 與機械特性。 〔發明實施之形態〕 (透明橡膠） 本發明中 > 透明橡藤係指以透明未硫 述S-SBR及BR (丁二烯橡膠）爲主成份 混合IR (異戊二烯橡膠）等的橡膠中調 硫化促進劑，及必要時更配合防止老化劑 之橡膠用藥品，進行硫化取得之橡膠的慣 透明之未硫化橡膠係具有依據JIS-2mm薄片中所測定之硫化後總光線透光率 爲特定範圍之濕 性，明顯提昇與 爲特定範圍之該 ，同時，混練時 縮小到達粒徑， 性之透明橡膠者 100~250m2/g， g )之比（V/S ) 濕式二氧化矽所 知之透明橡膠製 膠優異之透明性 化橡膠，例如前 ，其中必要時， 配合塡充材料， 、活性劑等公知 用名。 (-7105，於厚度 爲80%以上之高 (4) (4)1330647 度透明性》此等透明未硫化橡膠起因於S-SBR及BR等， 因此，支撐性比NR等一般橡膠來得弱，混合時具有不易 剪切之特性。 透明之未硫化橡膠之具體例，較佳爲BR、S-SBR及 IR之組合，以及BR與S-SBR之組合。又，由上述BR、 S-SBR及IR所成之透明未硫化橡膠中，各橡膠成份之配 合比例爲對於65〜75 重量份BR時，S-SBR 15〜35 重量 份及〇〜10重量份之IR(BR、S-SBR及IR總計爲100 重量份者）爲佳。 (透明橡膠用塡充材料之特徵） 本發明之透明橡膠用塡充材料係做爲上述透明橡膠之 塡充材料使用者，滿足比表面積爲1〇〇~250 m2/g，吸油量 (V; cc/lOOg )與比表面積（S; m2/g )之比（V/S )爲 1.05以上，且平均粒徑爲5〜ΙΟμιη之濕式二氧化矽。 當濕式二氧化矽之比表面積未達100 m2/g時，與橡 膠混練後所到達之粒徑（以下稱最終到達粒徑）不夠小， 取得之透明橡膠之透明性降低。 另外，當濕式二氧化矽之比表面積超出250 m2/g時 ，二氧化矽粒子之凝聚性增大，結果很難於橡膠中得到充 份之分散性。因此，所得之透明橡膠之透明性降低。 本發明中比表面積係如後述實施例所示，係指bet 比表面積。 該濕式二氧化矽比表面積只要於上述範圍者時，無特 -8- (5) (5)1330647 別限定，一般以150〜200 m2/g者爲特別理想者。 又，濕式二氧化矽之吸油量（V; cc/lOOg)與比表面 積（S; m2/g)之比（V /S)爲未達1.05時，與橡膠混練 時之粉碎性、分散性低，無法充分降低最終到達粒徑，其 結果難以取得具良好透明性之透明橡膠。 該濕式二氧化矽之V/S只要在上述範圍者時，即無特 別限定’一般較佳爲I·1以上，更佳爲〜1·5。 更且，本發明之透明橡膠用塡充材料中，濕式二氧化 矽之平均粒徑爲開始混練時之平均粒徑。該平均粒徑超出 10 μιη時，即使具有滿足該V /S爲1.05以上之良好粉碎 性、分散性，與不易剪切之透明橡膠混練中’仍不易充分 降低最終到達粒徑.，難以取得高度透明性之透明橡膠° 而濕式二氧化矽之平均粒徑小於5 μιη之濕式二氧化 矽不僅使用性差，且製造需費許多勞力。 (透明橡膠用塡充材料之理想物性） 構成本發明之透明橡膠用塡充材料之濕式二氧化砂只 要滿足上述條件者，並無特別限定，一般以具有下記特性 者爲佳。 (1 ) 吸油量爲100〜300 cc/100g，特別以160 〜2 50c c/100g之濕式二氧化矽爲佳。吸油量於上記範圔者 時，二氧化矽之構造更爲鬆動’其結果可更提昇椽膠中之 分散性。 (2) 鐵雜質量被調整爲〇_〇2重量％以下’特別是 -9- (6) (6)1330647 0.001〜0.01重量％之濕式二氧化矽爲佳。 當鐵雜質量爲該範圍內者，可降低透明橡膠之黑點、 變黃。 降低該鐵雜質量於後述製造方法中’強化洗滌’’防 止由製造步驟中鐵雜質混入於濕式二氧化矽。 (3) 細孔容積爲2.5 cc/100g以上，特別爲2.6-3.0 CC/100g之濕式二氧化矽爲佳。 (4) 以5 g/1 〇〇ml濃度分散於蒸餾水中所測定之 pH爲6~7.5之濕式二氧化矽者爲宜。 調整濕式二氧化矽之PH爲上記範圍’可縮短配合此 二氧化矽，進行硫化後取得透明橡膠時之硫化時間。藉此 可防止構成透明橡膠之橡膠於長時間高溫曝露’因橡膠分 解產生微量雜質，抑制橡膠製品著色，同時因縮短硫化時 間而可提昇生產性》 (5) 未通過45 μιη網篩之粗粉量爲0~0.01重量％ 之濕式二氧化矽者較佳。 調整粗粉量於該範圍，可充份提高取得之透明橡膠之 透明性及機械特性。 (透明橡膠用塡充材料之製造方法） 本發明之透明橡膠用塡充材料之具有上述特性的濕式 二氧化矽的製造方法並未特別限定，代表性製造方法例如 有下述方法》 濕式二氧化砂之析出反應係例如反應砍酸驗水溶液與 -10- (7) (7)1330647 酸水溶液同時添加於預先調整濃度之矽酸鹼水溶液後，使 二氧化矽析出，較佳爲90~150分鐘，更佳爲100~140 分鐘結束反應的方法。 特別推薦於上述同時添加之途中，暫時停止矽酸鹼與 硫酸之添加，維持溫度，同時僅進行攪拌之操作（中斷） 的方法。 此被推薦之方法係藉由同時添加矽酸鹼與酸，前述濕 式二氧化矽之比表面積被控制，又藉由如上述調整反應完 成時間，前述濕式二氧化矽之V /S被控制。又，藉由調 整此等反應條件，亦可適當調整先前之粉體特性中之比表 面積、吸油量、細孔容積之特性値。 矽酸鹼係以矽酸鈉爲代表。又，酸可使用硫酸。矽酸 鹼水溶液之濃度以 5〜30g/100cc爲宜，酸之濃度較佳爲 20〜2 5g/100cc。上述矽酸鹼水溶液與酸水溶液係指使兩者 幾乎相同量者同時添加。中斷係於上述同時添加30〜50% 後，中斷15〜30分鐘較佳。上述反應溫度以87〜95 °C爲 佳。 又，上述反應所得之濕式二氧化矽係反應後，進行充 份洗滌，成爲上述鐵含量爲佳。此時之洗滌標準係使反應 副產物之硫酸鹼的量爲所取得之二氧化矽以5g/100ml濃 度分散於蒸餾水後所測定之導電度爲45 # S以下者。 另外，此時做爲洗淨所使用之水者其導電度以2 Ms 以下之過濾水·離子交換水者宜。藉由該洗滌後，硫酸鹼 被去除之，同時亦去除其他微量之金屬鹽，如上述於透明 -11 - (8) (8)1330647 橡膠中著色被抑制之。 洗滌後濕式二氧化矽之乾燥中，以採用不易引起乾燥 收縮之乾燥方法充份保持V /S者宜。具體而言，藉由噴 霧乾燥器降低漿料濃度後進行乾燥之方法例者。特別使漿 料濃度爲5〜10重量％進行乾燥者其效果最佳。 本發明中以上述方法取得之濕式二氧化矽粒子約爲 80〜100 μιη之粒徑者。此以一般粉碎機及必要時組合分 級機後，調整爲該粒徑之範圍者。 乾燥後之配管等中使用鐵後將導致鐵銹等混入製品後 產生製品之黑點，因此，於SUS等中做爲材質配管等之 製品中鐵雜質量以0.02重量％以下者宜。 (透明橡膠之製造方法） 於上述透明之未硫化橡膠中配合本發明透明之橡膠用 塡充材料後製造透明橡膠時，其配合量並未特別受限。一 般，爲充份發揮所取得透明橡膠之耐摩損性、耐滑動性等 機械性能時，針對1 〇 〇 重量份透明之未硫化橡膠以 20〜50重量份，較佳者爲25〜40重量份之比例者。 配合時可使用公知之方法，如：密閃式混練機、揑合 器、開放滾輥等者。 此時，硫化促進劑，必要時所添加之其他橡膠用藥品 亦可同時與上述透明橡膠用塡充材料進行配合之，而，於 配合後再配合該塡充材料者爲較佳者。該透明橡膠用塡充 材料之配合後，構成透明橡膠用塡充材料之濕式二氧化矽 -12- (9) (9)1330647 粒子被分散至不易吸附橡膠用藥之粒徑爲止，因此，藉由 配合之後的橡膠用藥品後，於透明未硫化橡膠中可更均勻 分散該橡膠用藥品者。 另外，濕式二氧化矽於必要時亦可以公知之矽烷偶合 劑進行處理。 上述成份所配合之透明未硫化橡膠組成物係以任意形 狀成型後，藉由硫化轉換成透明橡膠者。此硫化條件爲公 知條件下即可，無特別限定。一般如：140〜170 °C之溫 度下，進行3〜10分鐘者。 如此取得透明橡膠之透明性以其透明性特別良好之 S-SBR、BR做爲主成份之透明未硫化橡膠做爲橡膠成份 使用時，不論以濕式二氧化矽做爲塡充材料使用，依ns-K-7105爲基準，於厚度2mm之薄片中所測定之全光線透 光率爲70 %以上，多半爲70〜85 %者，不同情況下亦有高 達90%以上者。 如此，藉由本發明提供一種以S-SBR及/或BR做爲 主成份之1〇〇重量份橡膠成份及濕式二氧化矽所成之 20〜50 重量份塡充材料相互配合物所成者，再於厚度 2mm之薄片中所測定全光線透光率爲70%以上者爲其特徵 之透明橡膠者。 本 Ln 1 惟 之 示 例 施 實 以 明 發 本 明 說 遵 具 更 1 爲 式3 , 方例下 施施以 -13- (10) (10)1330647 發明未受限於此等實施例者。 又，本明細書中各物性、試驗係由以下方法進行者。 (1 ) 比表面積 簡易型氮吸附法之BET法中藉由1點法進行求出。 (2 ) 吸油量 依JIS K5101爲基準進行測定。 (3 ) 平均粒徑 於甲醇溶液中添加少量樣品後，以超音波分散機60 W ，3 0分鐘進行分散。 將該溶液以庫爾特計數器法粒度分佈測定器（ BECKMAN COULTER INS 製 TA-II 型）利用 50 " m，或 2 0 0 β m之口徑進行測定之。 (4 ) 鐵雜質量 測取一定量之樣品後’成型之後’預先作成檢量線， 於螢光X線測定裝置進行測定。 (5 ) 細孔容積 藉由CARLO ERBA公司製之水銀壓入法以細孔徑分 佈測定器孔率計2 0 0 0型進行測定之。1330647 (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a retanning material for transparent rubber and a transparent rubber formed by wet cerium oxide. More specifically, it is a transparent rubber slinger made of wet cerium oxide which is excellent in usability when it is used as a squeezing material for transparent rubber, and has a transparent rubber and a good anti-wear property. Those who have this transparent rubber. [Prior Art] The transparent rubber is made of an unvulcanized rubber having high transparency, such as S-SBR (solution polymerization type styrene butadiene rubber) and BR (butadiene rubber) as main components. Highly transparent vulcanized rubber composed of a filler material is expected to be used for various purposes including creative materials and functional materials. One of the uses for transparent rubber is the use of the sole. In this application, it is extremely common to use transparent rubber as a part of the sole for use with creative use. Recently, attempts have been made to make the entire sole user by transparent rubber. In this case, the transparent rubber is not only required to have transparency, but also is expected to have mechanical properties such as abrasion resistance and slip resistance. In the past, the above-mentioned mechanically-adhesive material for transparent rubber is used, and from the viewpoint of dispersibility and transparency, dry cerium oxide is used, but dry cerium oxide is used as a retanning material. The increase in the price of products caused by cerium oxide, especially for the general use of soles and the like, has its economic difficulties. (2) (2) 1330647 In view of this situation, the use of wet cerium oxide at a lower price than dry cerium oxide is used as a retort for transparent rubber. However, the rubber components such as BR and S-SBR used as transparent rubber, especially BR, are weaker than other rubbers used as the filling material for general wet cerium oxide, and are not easily sheared when mixed. Therefore, when wet cerium oxide is used as the cerium material, the wet cerium oxide cannot be sufficiently dispersed, and the transparency of the obtained transparent rubber is remarkably lowered, resulting in a problem that there is no commercial price. Moreover, the rubber strength such as the abrasion resistance of the transparent rubber is also extremely unsatisfactory. In order to solve the above problems, it is considered that the method of improving the dispersibility in the rubber by extremely finely pulverizing the wet cerium oxide, but smashing the large-scale device and requiring a large amount of labor, is not only economically unsatisfactory, The high cohesion of wet cerium oxide does not achieve the desired effect. Further, after the micronization, there is a problem that the usability of the powder is deteriorated. SUMMARY OF THE INVENTION An object of the present invention is to provide a wet yttria which has a large particle size which is easy to use and which can be dispersed in a rubber by a low shear height, which results in high transparency and resistance to abrasion. A transparent rubber transparent rubber material which is excellent in mechanical properties such as loss and slidability. Another object of the present invention is to provide an entangled material for a transparent rubber comprising the enamel material for a transparent rubber of the present invention and having the above characteristics. Other objects and advantages of the present invention are as described below. The inventors of the present invention have found that the ratio of the oil absorption to the surface area of the wet cerium oxide is higher than that of the conventional rubber -6-(3) 1330647.矽, the adjusted cerium oxide can reduce the dispersibility during mixing of the condensed rubber components between the cerium oxide particles, and by adjusting the average particle size of the wet cerium oxide, the usability can be improved and the shearing is not easy, and the rubber When the components are kneaded, the results are more excellent in transparency, and the mechanical properties are attached to complete the present invention. That is, the present invention is characterized by a conductive material for a transparent rubber having a specific surface area of oil absorption (V; CC/100 g) and a specific surface area (S; m2/ of 1.05 or more and an average particle diameter of 5 to 10 μm). The decorative material for transparent rubber of the present invention is used as a filling material in the art of manufacture, and provides the transparent rubber and mechanical properties. [Form of the invention] (Transparent rubber) In the present invention > Transparent Oakvine refers to a vulcanization accelerator for mixing rubber such as IR (isoprene rubber) with a transparent non-sulfur S-SBR and BR (butadiene rubber) as a main component, and a rubber compound for preventing an aging agent, if necessary, The conventionally transparent unvulcanized rubber of the rubber obtained by vulcanization has a specific range of wettability according to the total light transmittance after vulcanization measured in the JIS-2mm sheet, and is obviously improved to a specific range, and is reduced at the time of kneading. Reaching the particle size, the transparent rubber is 100~250m2/g, g) ratio (V/S). The transparent rubber rubber known as wet cerium oxide is excellent in transparency rubber, for example, before, if necessary, Cooperating with filling materials , Known by the name of active agent. (-7105, the thickness is 80% or more high (4) (4) 1330647 degrees transparency. These transparent unvulcanized rubbers are caused by S-SBR and BR, etc. Therefore, the supportability is weaker than that of general rubber such as NR. Specific examples of the transparent unvulcanized rubber are preferably a combination of BR, S-SBR and IR, and a combination of BR and S-SBR. Further, by the above BR, S-SBR and IR In the transparent unvulcanized rubber, the mixing ratio of each rubber component is 15 to 35 parts by weight of S-SBR and 〇 to 10 parts by weight of IR for 65 to 75 parts by weight of BR (BR, S-SBR and IR total 100) (Part of the weight). (Characteristics of the reinforcing material for the transparent rubber) The decorative material for the transparent rubber of the present invention is used as the user of the above-mentioned transparent rubber, and satisfies the specific surface area of 1 〇〇 to 250 m 2 / g, the ratio of the oil absorption (V; cc / lOOg) to the specific surface area (S; m2 / g) (V / S) is 1.05 or more, and the average particle diameter is 5 ~ ΙΟ μιη wet cerium dioxide. When the specific surface area of cerium oxide is less than 100 m2/g, the particle size (hereinafter referred to as the final particle size) reached after mixing with the rubber is not sufficiently small. Further, when the specific surface area of the wet cerium oxide exceeds 250 m 2 /g, the cohesiveness of the cerium oxide particles increases, and as a result, it is difficult to obtain sufficient dispersibility in the rubber. The transparency of the obtained transparent rubber is lowered. In the present invention, the specific surface area is a bet specific surface area as shown in the following examples. When the specific surface area of the wet ceria is in the above range, there is no special - 8 - ( 5) (5) 1330647 is not limited, generally 150~200 m2/g is particularly ideal. Also, the oil absorption of wet ceria (V; cc / lOOg) and specific surface area (S; m2 / g) When the ratio (V / S) is less than 1.05, the pulverizability and dispersibility at the time of kneading with the rubber are low, and the final particle diameter cannot be sufficiently lowered, and as a result, it is difficult to obtain a transparent rubber having good transparency. When the V/S is in the above range, it is not particularly limited. Generally, it is preferably I·1 or more, and more preferably 〜1·5. Further, in the decorative material for a transparent rubber of the present invention, wet type The average particle size of cerium oxide is the average particle diameter at the start of mixing. When the particle diameter exceeds 10 μm, even if it has a good pulverizability and dispersibility satisfying the V / S of 1.05 or more, it is difficult to sufficiently reduce the final particle diameter in the kneading with the transparent rubber which is not easily sheared, and it is difficult to achieve high transparency. The transparent rubber ° and the wet cerium oxide having an average particle diameter of less than 5 μm are not only inferior in useability, but also require a lot of labor for manufacturing. (Ideal physical properties of the fused material for transparent rubber) constitute the transparent of the present invention. The wet silica sand of the rubber filler is not particularly limited as long as the above conditions are satisfied, and it is generally preferred to have the following characteristics. (1) The oil absorption is 100 to 300 cc/100 g, and particularly preferably 160 to 2 50 c c/100 g of wet cerium oxide. When the oil absorption is in the above, the structure of the cerium oxide is looser. The result is that the dispersibility in the silicone rubber is further improved. (2) The iron content is adjusted to 〇_〇2% by weight or less. Specifically, -9-(6) (6) 1330647 0.001 to 0.01% by weight of wet cerium oxide is preferred. When the iron impurity mass is within this range, the black spots and yellowing of the transparent rubber can be lowered. The iron content is reduced in the "strengthening washing" in the production method described later to prevent the iron impurities from being mixed into the wet cerium oxide in the production step. (3) The pore volume is 2.5 cc/100 g or more, and particularly 2.6-3.0 CC/100 g of wet cerium oxide is preferred. (4) It is preferred to use a wet cerium oxide having a pH of 6 to 7.5, which is dispersed in distilled water at a concentration of 5 g/1 〇〇ml. Adjusting the pH of the wet ceria to the above range can shorten the vulcanization time when the transparent rubber is obtained by vulcanization after the ceria is added. Therefore, the rubber constituting the transparent rubber can be prevented from being exposed to high temperature for a long time, and a small amount of impurities are generated due to decomposition of the rubber, and the coloration of the rubber product is suppressed, and the productivity can be improved by shortening the vulcanization time. (5) The coarse powder which has not passed through the 45 μm mesh sieve A wet cerium oxide in an amount of from 0 to 0.01% by weight is preferred. Adjusting the amount of coarse powder in this range can sufficiently improve the transparency and mechanical properties of the obtained transparent rubber. (Manufacturing Method of Filling Material for Transparent Rubber) The method for producing the wet cerium oxide having the above characteristics of the entangled material for a transparent rubber of the present invention is not particularly limited, and a typical production method includes, for example, the following method: The precipitation reaction of the silica sand, for example, the reaction chopping acid aqueous solution and the 10-(7) (7) 1330647 acid aqueous solution are simultaneously added to the pre-adjusted concentration of the aqueous citric acid solution to precipitate the cerium oxide, preferably 90~. 150 minutes, more preferably 100 to 140 minutes to end the reaction. It is particularly recommended to temporarily stop the addition of citric acid and sulfuric acid, maintain the temperature, and perform only the stirring operation (interruption) on the way of the above-mentioned simultaneous addition. The recommended method is to simultaneously control the specific surface area of the wet ceria by adding citric acid base and an acid, and by adjusting the reaction completion time as described above, the V / S of the wet ceria is controlled. . Further, by adjusting these reaction conditions, the characteristics of the specific surface area, the oil absorption amount, and the pore volume of the previous powder characteristics can be appropriately adjusted. The tannic acid base is represented by sodium citrate. Further, sulfuric acid can be used as the acid. The concentration of the aqueous citric acid solution is preferably 5 to 30 g/100 cc, and the concentration of the acid is preferably 20 to 2 5 g/100 cc. The above aqueous citric acid solution and aqueous acid solution mean that both of them are added in the same amount at the same time. The interruption is preferably 30 to 50% after the above addition, and the interruption is preferably 15 to 30 minutes. The above reaction temperature is preferably 87 to 95 °C. Further, after the wet cerium oxide obtained by the above reaction is reacted, it is preferably washed to obtain the above iron content. The washing standard at this time is such that the amount of the sulfate base of the reaction by-product is such that the obtained cerium oxide is dispersed in distilled water at a concentration of 5 g/100 ml and the conductivity is 45 or less. In addition, it is preferable that the water used for washing is a filtered water/ion exchange water having a conductivity of 2 Ms or less. By this washing, the sulfate base is removed, and other traces of the metal salt are also removed, as the above coloring is inhibited in the transparent -11 - (8) (8) 1330647 rubber. In the drying of the wet cerium oxide after washing, it is preferable to sufficiently maintain the V / S by a drying method which does not easily cause drying shrinkage. Specifically, a method in which the slurry concentration is lowered by a spray dryer and then dried is carried out. In particular, the effect of drying the slurry at a concentration of 5 to 10% by weight is optimal. In the present invention, the wet cerium oxide particles obtained by the above method have a particle diameter of about 80 to 100 μm. This is adjusted to the range of the particle size after the general pulverizer and, if necessary, the combination of the grading machines. When iron is used in the pipe after drying, etc., the black spot of the product is caused by the rust or the like being mixed into the product. Therefore, the product having a material such as SUS or the like is preferably 0.02% by weight or less. (Manufacturing Method of Transparent Rubber) When the transparent rubber is produced by blending the transparent rubber entangled material of the present invention with the transparent unvulcanized rubber, the amount of the transparent rubber is not particularly limited. In general, in order to fully exhibit the mechanical properties such as abrasion resistance and slidability of the obtained transparent rubber, it is preferably 20 to 50 parts by weight, preferably 25 to 40 parts by weight, based on 1 part by weight of the transparent unvulcanized rubber. Proportion. A well-known method can be used for the cooperation, such as a compact flash mixer, a kneader, an open roller, and the like. In this case, the vulcanization accelerator, if necessary, other rubber chemicals may be blended with the above-mentioned transparent rubber reinforcing material, and it is preferred to mix the reinforcing material after the compounding. After the transparent rubber is blended with the chelating material, the wet cerium oxide-12-(9)(9)1330647 particles constituting the entangled material for the transparent rubber are dispersed until the particle size of the rubber is not easily adsorbed, so After the rubber product is blended, the rubber drug can be more uniformly dispersed in the transparent unvulcanized rubber. Further, the wet cerium oxide may be treated by a known decane coupling agent as occasion demands. The transparent unvulcanized rubber composition to which the above components are combined is formed into an arbitrary shape and then converted into a transparent rubber by vulcanization. The vulcanization conditions are not particularly limited as long as they are under known conditions. Generally, for example, a temperature of 140 to 170 ° C is carried out for 3 to 10 minutes. When the transparency of the transparent rubber is obtained, the transparent unvulcanized rubber containing S-SBR and BR as the main component, which is particularly excellent in transparency, is used as the rubber component, regardless of whether the wet cerium oxide is used as the chelating material, Based on the K-7105, the total light transmittance measured in a sheet having a thickness of 2 mm is 70% or more, and most of them are 70 to 85%, and in some cases, it is as high as 90% or more. Thus, the present invention provides a composite of 1 to 2 parts by weight of a rubber component containing S-SBR and/or BR as a main component and 20 to 50 parts by weight of a composite material of wet cerium oxide. And a transparent rubber having a total light transmittance of 70% or more as measured in a sheet having a thickness of 2 mm. The present invention is not limited to the embodiments of the present invention. The invention is not limited to the embodiments. The invention is not limited to the embodiments. In addition, the physical properties and the test system in this detailed book are carried out by the following methods. (1) Specific surface area The BET method of the simple nitrogen adsorption method was determined by a one-point method. (2) Oil absorption The measurement is based on JIS K5101. (3) Average particle diameter A small amount of a sample was added to a methanol solution, and then dispersed by an ultrasonic disperser at 60 W for 30 minutes. This solution was measured by a Coulter counter method particle size distribution analyzer (Model TA-II manufactured by BECKMAN COULTER INS) using a diameter of 50 " m, or 200 μm. (4) Iron mass After a certain amount of sample was measured, it was prepared as a calibration curve in advance, and was measured by a fluorescent X-ray measuring apparatus. (5) The pore volume was measured by a mercury indentation method manufactured by CARLO ERBA Co., Ltd., using a pore size distribution measuring apparatus porosimeter type 2000.
(6 ) 濕式二氧化矽之PH 於100ml蒸餾水（吸漬一晚以上者）中加入5g試料 進行攪拌5分鐘後’靜置1〇分鐘之後’讀取pH計之 指示値。 (7) 45 以上之粗粉量 於乙烯袋中置入1kg試料’充份以蒸餾水濕潤後， -14- (11) (11)1330647 於裝設45 //m網舖之microwashable中將此獎料溶液少 量分批投入。此篩直接置入乾燥機於105 r下進行約半 曰的乾燥，測定殘留於此篩之粗粉量。 C 8) 導電度 於100ml蒸餾水（吸漬1晚以上者）中，加入5g試 料進行攪拌5分鐘後，靜置10分鐘，由導電度計讀取 指示値。 (9 ) 透明橡膠之各物性 藉由下記實施例，比較例所示方法作成試驗片後，供 於以下之測定。 ①透明椽膠之透明性 利用約2mm厚度所成型之薄片，依JIS-K-7105爲基 準進行測定於厚度2mm薄片所測得之全光線透光率後， 依表1所5階段進行評定之。 表1 評定 全光線透光率 5 7 0%以上 4 60%以上、70%以下 3 50%以上、60%以下 2 30%以上、50%以下 1 3 0%以下 ②透明橡膠之耐摩損性 利用Acron摩損機，依JIS-K-6264爲基準進行測定 之。 -15- (12) (12)1330647 ③透明橡膠之黃變 利用約2mm厚度所成型之薄片，該薄片下方鋪上白 色紙以目測進行評定是否黃變。評定結果以完全未出現黃 變者爲5，明顯出現黃變狀態者爲1之5個級數做成評定 者。 〔實施例1〕 於lm3反應槽中投入180L之水及7L之矽酸鈉溶液 (市販矽酸鈉溶液：Si02/Na20 = 3.32)，攪拌同時調整水 溶液溫度爲92 °C。再使液溫維持於92 °C，同時使同濃 度之矽酸鈉溶液以3.1L/分鐘，22%硫酸以0.49L/分鐘之 比例下40分鐘內進行投入。其中，暫時中斷矽酸鈉及硫 酸之投入，保持溫度於90 °C同時攪拌30分鐘。30分 鐘後，再度開始投入矽酸鈉及硫酸，最後以1〇5分鐘進 行添加矽酸鈉及硫酸。 然後，停止投入矽酸鈉，添加硫酸至反應液PH呈 3.5爲止，完成反應。再利用壓濾機充份過濾此反應液至 製品傳導度呈41 爲止，水洗後，乾燥濾餅，更進行 粉碎、分級後，取得表2所示之濕式二氧化矽。 上述方法所取得之濕式二氧化矽爲重量份硫化 後全光線透光率79%之市販透明未硫化橡膠（BR; 70重 量份/S-SBR; 25重量份/IR 5重量份）之30重量份的 比例進行配合後，以揑合器進行混練之。再於該取得組成 -16 - (13) (13)1330647 物中進行配合硫化促進劑、老化防止劑後，更進行混練後 ，於溫度1 60 °C下進行硫化9分鐘後，取得透明橡膠。 所取得透明橡膠之各物性示於表3。 〔實施例2〕 於lm3反應槽中預先投入180L水及7L矽酸鈉溶液 (市販矽酸鈉溶液：Si02/Na20 = 3.32 )，攪拌之同時調整 水溶液溫度爲92 t。再使液溫保持於89 °C之同時，使 同濃度之矽酸鈉溶液以3.1L/分鐘，22%硫酸以0.49L/分 鐘之比例於115分鐘內進行投入，其中投入以連續性進 行之。 隨後停止投入矽酸鈉後，添加硫酸至反應液PH呈 3.3爲止完成反應。 再利用濾壓機與實施例1同法充份過濾此反應液後’ 進行水洗之。再乾燥濾餅，更進行粉碎、分級後，取得表 2所示之濕式二氧化矽。 利用此取得之濕式二氧化矽，與實施例1同法製造透 明橡膠。 所取得透明橡膠各物性示於表3 ° 〔實施例3〕 於lm3反應槽中，預先投入180L水及6L矽酸鈉溶 液（市販矽酸鈉：Si02/Na2〇 = 3.29 )，攪拌之同時調整水 溶液溫度爲92 °C。再使液溫保持95它之同時’使同濃 -17- (14) (14)1330647 度之矽酸鈉溶液以3.8L/分鐘，21%硫酸以0.49L/分鐘之 比例4〇分鐘內進行投入。其中，暫時中斷矽酸鈉及硫酸 之投入，維持溫度爲95 °C，同時進行攪拌60分鐘。60 分鐘後，再度開始進行矽酸鈉及硫酸之投入，最後以總共 130分鐘添加矽酸鈉及硫酸。 然後，停止投入矽酸鈉，添加硫酸至反應液pH呈 3.5爲止，完成反應。再利用濾壓機充份過濾此反應液使 製品之傳導度呈36 //S爲止，進行水洗後，乾燥濾餅， 更進行粉碎、分級，取得表2所示之濕式二氧化矽。 利用此取得之濕式二氧化矽，與實施例1同法製造透 明橡膠。 所取得透明橡膠之各物性如表3所示。 〔實施例4〕 於lm3反應槽中，預先投入180L水及7L矽酸鈉溶 液（市販之矽酸鈉溶液：Si02/Na20 = 3.3 6 )，攪拌之同時 調整水溶液溫度爲84 °C。再保持液溫於84 °C下同時， 同濃度之矽酸鈉溶液以3.0L/分鐘，22%硫酸以0.50L/分 鐘之比例下40分鐘內進行投入。其中，暫時中斷矽酸鈉 及硫酸之投入，保持溫度於84 °C之同時，進行攪拌15 分鐘。15分鐘後，再度開始進行矽酸鈉及硫酸之投入， 最後以共90分鐘添加矽酸鈉及硫酸。 之後，停止投入矽酸鈉，添加硫酸至反應液pH呈 3.5爲止完成反應。再使此反應液以濾壓機充份過濾至製 -18 - (15) 1330647 品傳導度呈45 //S爲止，水洗後乾燥濾餅，更進行粉碎 、分級，取得表2所示之濕式二氧化矽。 使用此取得之濕式二氧化矽，與實施例1同法製造透 明橡膠。 取得透明橡膠之各物性如表3所示。 〔實施例5〕(6) PH of wet cerium oxide 5 g of the sample was added to 100 ml of distilled water (for one night or more of suction), and the mixture was stirred for 5 minutes and then left to stand for 1 minute to read the indicator of the pH meter. (7) The amount of coarse powder above 45 is placed in a vinyl bag and 1 kg sample is placed. 'Fullly wet with distilled water, -14- (11) (11) 1330647 This prize is given in a microwashable equipped with 45 //m net shop. The feed solution was injected in small portions in batches. The sieve was placed in a dryer directly at 105 r for about half a liter of drying, and the amount of coarse powder remaining on the sieve was measured. C 8) Conductivity In 100 ml of distilled water (for one night or more of suction), 5 g of the sample was added and stirred for 5 minutes, and then allowed to stand for 10 minutes, and the indicator 读取 was read by a conductivity meter. (9) Physical properties of the transparent rubber The test piece was prepared by the following method and the method shown in the comparative example, and was subjected to the following measurement. 1Transparency of transparent silicone The sheet formed by the thickness of about 2 mm is measured according to JIS-K-7105, and the total light transmittance measured by the sheet having a thickness of 2 mm is evaluated according to the 5 stages of Table 1. . Table 1 Evaluation of total light transmittance 570% or more 4 60% or more, 70% or less 3 50% or more, 60% or less 2 30% or more, 50% or less and 1130% or less 2 Acron damage machine is measured based on JIS-K-6264. -15- (12) (12) 1330647 3 Yellowing of transparent rubber A sheet formed by a thickness of about 2 mm was coated with white paper under the sheet to visually evaluate whether it was yellow. The results of the evaluation were 5 in the case where no yellowing occurred at all, and 5 in the number of yellowing states. [Example 1] 180 L of water and 7 L of sodium citrate solution (a commercial sodium citrate solution: SiO 2 / Na 20 = 3.32) were placed in a lm 3 reaction tank, and the temperature of the water solution was adjusted to 92 ° C while stirring. The liquid temperature was maintained at 92 ° C while the sodium citrate solution of the same concentration was introduced at a ratio of 3.1 L/min and 22% sulfuric acid at a rate of 0.49 L/min for 40 minutes. Among them, the input of sodium citrate and sulfuric acid was temporarily interrupted, and the temperature was maintained at 90 ° C while stirring for 30 minutes. After 30 minutes, sodium citrate and sulfuric acid were again charged, and sodium citrate and sulfuric acid were added in 1 to 5 minutes. Then, the sodium citrate was stopped, and sulfuric acid was added until the pH of the reaction solution was 3.5, and the reaction was completed. Further, the reaction mixture was filtered through a filter press until the product had a conductivity of 41. After washing with water, the cake was dried, and further pulverized and classified to obtain wet cerium oxide shown in Table 2. The wet cerium oxide obtained by the above method is 30 parts by weight of a commercially available transparent unvulcanized rubber (BR; 70 parts by weight/S-SBR; 25 parts by weight/IR 5 parts by weight) of a total light transmittance of 79% by weight after vulcanization. After mixing the proportions, the kneader is used for kneading. Further, after the composition of -16 - (13) (13) 1330647 was obtained, a vulcanization accelerator and an anti-aging agent were blended, and after kneading, the vulcanization was carried out at a temperature of 1 60 ° C for 9 minutes, and then a transparent rubber was obtained. The physical properties of the obtained transparent rubber are shown in Table 3. [Example 2] 180 L of water and 7 L of sodium citrate solution (sodium citrate solution: SiO 2 /Na20 = 3.32) were previously charged in a lm3 reaction tank, and the temperature of the aqueous solution was adjusted to 92 t while stirring. Then, while maintaining the liquid temperature at 89 ° C, the sodium citrate solution of the same concentration was input in a ratio of 3.1 L/min and 22% sulfuric acid at a rate of 0.49 L/min in 115 minutes, wherein the input was carried out in a continuous manner. . After the sodium citrate was stopped, the reaction was completed by adding sulfuric acid until the pH of the reaction solution was 3.3. Then, the reaction liquid was sufficiently filtered by the same method as in Example 1 using a filter press, and then washed with water. The filter cake was further dried, further pulverized and classified, and the wet cerium oxide shown in Table 2 was obtained. Using the wet cerium oxide thus obtained, a transparent rubber was produced in the same manner as in Example 1. The physical properties of the obtained transparent rubber are shown in Table 3 ° [Example 3] In the lm3 reaction tank, 180 L of water and 6 L of sodium citrate solution (sodium citrate: SiO 2 /Na 2 〇 = 3.29) were charged in advance, and the mixture was adjusted while stirring. The aqueous solution temperature was 92 °C. Then, the liquid temperature was maintained at 95 while it was made to make the sodium citrate solution of the same concentration -17-(14) (14) 1330647 degrees at 3.8 L/min, and 21% sulfuric acid at a ratio of 0.49 L/min for 4 〇 minutes. Invest. Among them, the input of sodium citrate and sulfuric acid was temporarily interrupted, and the temperature was maintained at 95 ° C while stirring for 60 minutes. After 60 minutes, the sodium citrate and sulfuric acid were started again, and sodium citrate and sulfuric acid were added for a total of 130 minutes. Then, the sodium citrate was stopped, and sulfuric acid was added until the pH of the reaction solution was 3.5, and the reaction was completed. Further, the reaction liquid was filtered through a filter press to have a conductivity of 36 //S. After washing with water, the cake was dried, pulverized and classified, and wet cerium oxide shown in Table 2 was obtained. Using the wet cerium oxide thus obtained, a transparent rubber was produced in the same manner as in Example 1. The physical properties of the obtained transparent rubber are shown in Table 3. [Example 4] In a lm3 reaction tank, 180 L of water and 7 L of sodium citrate solution (a commercially available sodium citrate solution: SiO 2 /Na 20 = 3.3 6 ) were charged in advance, and the temperature of the aqueous solution was adjusted to 84 ° C while stirring. While maintaining the liquid temperature at 84 ° C, the same concentration of sodium citrate solution was introduced at a rate of 3.0 L/min and 22% sulfuric acid at a rate of 0.50 L/min for 40 minutes. Among them, the input of sodium citrate and sulfuric acid was temporarily interrupted, and the mixture was stirred for 15 minutes while maintaining the temperature at 84 °C. After 15 minutes, the input of sodium citrate and sulfuric acid was started again, and sodium citrate and sulfuric acid were added for a total of 90 minutes. Thereafter, the sodium citrate was stopped, and sulfuric acid was added until the pH of the reaction solution was 3.5 to complete the reaction. The reaction solution was filtered in a filter press until the conductivity of the product was -18 - (15) 1330647. The conductivity was 45 // S. After washing with water, the cake was dried and pulverized and classified to obtain the wetness shown in Table 2. Cerium oxide. Using the wet cerium oxide thus obtained, a transparent rubber was produced in the same manner as in Example 1. The physical properties of the obtained transparent rubber are shown in Table 3. [Example 5]
於lm3反應槽中預先投入180L水及7L矽酸鈉溶液 (市販之矽酸鈉溶液：Si02/Na2 0 = 3.32 )，攪拌之同時調 整水溶液溫度爲90 °C »再保持液溫90 °C下同時使同濃 度之矽酸鈉以3.1L/分鐘，22%硫酸以0.49L/分鐘之比例 40分鐘內進行投入。其中，暫時中斷矽酸鈉及硫酸之投 入，保持溫度爲90 t下同時進行攪拌30分鐘。30分 鐘後，再度投入矽酸鈉及硫酸，最後以共計1 1 〇分鐘添 加矽酸鈉及硫酸。180 L of water and 7 L of sodium citrate solution (sodium citrate solution: SiO 2 /Na 2 0 = 3.32) were preliminarily charged in the lm3 reaction tank, and the temperature of the aqueous solution was adjusted to 90 ° C while stirring. The temperature was maintained at 90 ° C. At the same time, the same concentration of sodium citrate was introduced in a ratio of 3.1 L/min and 22% sulfuric acid at a ratio of 0.49 L/min for 40 minutes. Among them, the injection of sodium citrate and sulfuric acid was temporarily interrupted, and stirring was carried out for 30 minutes while maintaining the temperature at 90 t. After 30 minutes, sodium citrate and sulfuric acid were again charged, and sodium citrate and sulfuric acid were added for a total of 11 minutes.
然後，停止投入矽酸鈉，添加硫酸至反應液pH呈 4.1爲止，完成反應。再利用濾壓器充份過濾此反應液使 製品之傳導度呈40 //S爲止，水洗後，乾燥濾餅，更進 行粉碎、分級後，取得表2所示之濕式二氧化矽。 利用此取得之濕式二氧化矽，與實施例1同法製造透 明橡膠。 所取得透明橡膠之各物性如表3所示。 〔實施例6〕 -19- (16) 1330647 於lm3反應槽中，預先投入180L水及 市販矽酸鈉溶液：Si02/Na20 = 3_32)，攪拌 溶液溫度爲90 °C。再保持液溫於90 t之 之矽酸鈉溶液以3.1 L/分鐘，22%硫酸以0, 例下總時間1 20分鐘進行添加矽酸鈉及硫 持液溫之同時進行攪拌30分鐘。 隨後，停止投入矽酸鈉，添加硫酸至j 2.9後完成反應。再利用濾壓機充份進行此 、水洗後，乾燥濾餅後，更進行粉碎、分級 示之濕式二氧化矽。 利用此取得之濕式二氧化矽與實施例1 橡膠。 所取得透明橡膠之各物性示於表3。 〔比較例1〕 實施例1之反應中，使反應溫度於8 5 暫時中斷投入矽酸鈉及硫酸後，再度投入矽 此第2次投與時間爲120分鐘進行者，最 160分鐘投入矽酸鈉及硫酸後，完成反應。 反應結束後，與實施例1同法進行水洗 碎之後，取得表2所示之濕式二氧化矽。 使用此取得之濕式二氧化矽與實施例1 橡膠。 所取得透明橡膠之各物性如表3所示。 7L矽酸鈉（ 之同時調整水 同時，同濃度 4 9L/分鐘之比 酸。之後，保 泛應液pH呈 反應液之過濾 ，取得表2所 同法製造透明 °C下進行之， 酸鈉及硫酸而 後，總時間以 '乾燥後，粉 同法製造透明 -20- (17) (17)1330647 〔比較例2〕 實施例1之反應中，反應溫度於85 °C下進行之，暫 時中斷矽酸鈉及硫酸後，再度進行矽酸鈉及硫酸，而此第 2次投入時間爲3 5分鐘進行者，最後總時間以75分鐘 投入矽酸鈉及硫酸後完成反應。 反應結束後，與實施例1同法進行水洗、乾燥後，粉 碎之後，取得表2所示之濕式二氧化矽。 利用此取得之濕式二氧化矽後，與實施例1同法製造 透明橡膠。 所取得透明橡膠之各物性如表3 m示。 〔比較例3〕 實施例2中進行乾燥後粉碎、分級時，調整此粉碎、 分級條件後，取得具表2所示之平均粒徑的濕式二氧化矽 〇 利用此取得之濕式二氧化矽後，與實施例1同法製造 透明橡膠。 所取得透明橡膠之各物性如表3所示。 (18)1330647 比較例3 as 00 VO 产·Η 0.01 2.61 寸 v〇 <0.01 比較例2 η (Ν 〇\ 0.70 0.01 2.77 ON vd <0.02 比較例1 00 寸 vd Ο 1.57 I 0.01 2.14 寸 in <0.01 實施例6 〇> m 210 1.07 0.01 2.55 i ο ι> <0.01 實施例5 〇〇 r-H 200 1.07 0.01 2.43 cn <0.01 實施例4 宕 CN 〇\ Ο 1.09 0.01 2.96 卜 ν〇 <0.01 實施例3 宕 y Η ON od ο 1.42 0.01 2.32 τ—^ 實施例2 α\ ΟΟ r-Ή 5 220 v〇 0.01 2.72 ΟΟ -1 ί <0.01 實施例1 ΟΟ oo 210 1.10 1 0.01 I 2.64 m VD <0.01 比表面積 (m2/g)_ 平均粒徑 (μη〇_ 吸油量 (cc/100g) ν/s比 鐵不純物量 (重量％) 細孔容積 (cc/100g) Ο. 篩殘量 (重量％) 蟀狀1丨Jli与给 -22- (19)1330647 比較例3 0.32 16.7 〇 寸 比較例2 寸 0.44 17.2 490 m 比較例1 cn 0.56 15.4 -1 430 寸 實施例6 0.29 21.1 Ο s 實施例5 m 0.21 24.2 ο 實施例4 1 0.27 21.3 _1 uo 實施例3 0.28 17.6 實施例2 0.23 20.5 610 in 實施例1 0.22 19.0 560 透明性 耐摩損性 Μ_ 張力強度 (MPa) 延伸度 (%)_ 變黃性 透明 橡膠 各物 性 -23- (20) 1330647 〔實施例7、8〕 實施例1中將透明未硫化橡膠之組成做成表4所示之 組成之外，與實施例1同法取得透明橡膠。 所取得透明橡膠之各物性如表5所示。 表4 橡膠 成分（重量份） 全光線透光率 (%) BR S-SBR IR 實施例7 70 20 10 80 實施例8 70 30 - 82 表5 實施例7 實施例8 透明橡膠 各物性 透明性 5 5 耐摩損性（c c) 0.19 0.24 張力強度（MPa) 2 1.0 20.4 延伸度（％ ) 580 630 變黃性 4 5 〔實施例9〕 實施例1中，針對透明未硫化橡膠之濕式二氧化矽添 加量爲100重量份該未硫化橡膠之35重量份之外，與 實施例1同法取得透明橡膠。 針對取得透明橡膠進行評定透明性結果爲5，耐摩損 性爲0.16cc、張力強度爲26.7Pa、延伸度爲520%、黃變 性爲5者。 〔發明效果〕 -24- (21) (21)1330647 由以上說明證明本發明透明橡膠用塡充材料配合透明 未硫化橡膠後，進行混練時，不管濕式二氧化矽’即使少 許剪切仍呈良好分散性，可使最終到達粒徑呈極小者。因 此，使用此取得之透明橡膠可有效發揮具有明顯良好透明 性者。 如此，含有濕式二氧化矽之同時，達成高度透明性之 透明橡膠係藉由本發明最初揭示者。 又，藉由該塡充材料之高度分散性亦可充份發揮耐摩 損性、耐滑動性等機械性能者。 另外’本發明該透明橡膠藉由其良好透明性與橡膠特 性於鞋底、桌墊等創意性被期待之用途上，爲理想使用者 。且’該用途中，爲更提昇透明橡膠之創意性，亦可含顏 料、染料等著色劑、微細金屬箔、珠子等裝飾用塡充劑等 者。 -25-Then, the sodium citrate was stopped, and sulfuric acid was added until the pH of the reaction solution was 4.1, and the reaction was completed. Further, the reaction liquid was filtered through a filter to make the product have a conductivity of 40 //S. After washing with water, the cake was dried, and further pulverized and classified to obtain wet cerium oxide shown in Table 2. Using the wet cerium oxide thus obtained, a transparent rubber was produced in the same manner as in Example 1. The physical properties of the obtained transparent rubber are shown in Table 3. [Example 6] -19- (16) 1330647 In the lm3 reaction tank, 180 L of water and a sodium citrate solution: SiO 2 /Na 20 = 3 - 32 were charged in advance, and the temperature of the stirring solution was 90 °C. Further, the sodium citrate solution having a liquid temperature of 90 t was stirred at a rate of 3.1 L/min, 22% sulfuric acid at 0, and the total time was 1 20 minutes, and sodium citrate and sulfur were added while stirring for 30 minutes. Subsequently, the sodium citrate was stopped and the reaction was completed after adding sulfuric acid to j 2.9. After the filter cake was sufficiently washed with a filter press and dried, the cake was dried and pulverized and classified into wet cerium oxide. The wet cerium oxide obtained in this manner was used as the rubber of Example 1. The physical properties of the obtained transparent rubber are shown in Table 3. [Comparative Example 1] In the reaction of Example 1, the reaction temperature was temporarily interrupted by the introduction of sodium citrate and sulfuric acid at 8 5, and then the second administration time was 120 minutes, and the citric acid was put in the first 160 minutes. After sodium and sulfuric acid, the reaction is completed. After completion of the reaction, the mixture was washed with water in the same manner as in Example 1 to obtain wet cerium oxide shown in Table 2. The wet cerium oxide obtained in this manner was used as in Example 1 rubber. The physical properties of the obtained transparent rubber are shown in Table 3. 7L sodium citrate (simultaneously adjust the water at the same time, the same concentration of 49 L / min ratio of acid. After that, the pH of the protective solution is filtered by the reaction solution, and the same method as in Table 2 is used to make the transparent °C, sodium And sulfuric acid, the total time is 'after drying, the powder is produced in the same manner as the transparent -20- (17) (17) 1330647 [Comparative Example 2] In the reaction of Example 1, the reaction temperature is carried out at 85 ° C, temporarily interrupted After sodium citrate and sulfuric acid, sodium citrate and sulfuric acid are again used, and the second input time is 35 minutes. The final total time is 75 minutes into sodium citrate and sulfuric acid to complete the reaction. Example 1 was washed with water and dried in the same manner, and after pulverization, the wet cerium oxide shown in Table 2 was obtained. Using the wet cerium oxide obtained here, a transparent rubber was produced in the same manner as in Example 1. The physical properties of the rubber are shown in Table 3 m. [Comparative Example 3] In the case of drying and pulverization and classification in Example 2, the pulverization and classification conditions were adjusted, and then the wet-type dioxide having the average particle diameter shown in Table 2 was obtained.矽〇Using the obtained wet cerium oxide A transparent rubber was produced in the same manner as in Example 1. The physical properties of the obtained transparent rubber are shown in Table 3. (18) 1330647 Comparative Example 3 as 00 VO Production·Η 0.01 2.61 inch v〇<0.01 Comparative Example 2 η (Ν 〇 \ 0.70 0.01 2.77 ON vd < 0.02 Comparative Example 1 00 inch vd Ο 1.57 I 0.01 2.14 inch in <0.01 Example 6 〇> m 210 1.07 0.01 2.55 i ο ι><0.01 Example 5 〇〇rH 200 1.07 0.01 2.43 cn <0.01 Example 4 宕CN 〇\ Ο 1.09 0.01 2.96 卜ν〇<0.01 Example 3 宕y Η ON od ο 1.42 0.01 2.32 τ—^ Example 2 α\ ΟΟ r-Ή 5 220 v〇0.01 2.72 ΟΟ -1 ί <0.01 Example 1 ΟΟ oo 210 1.10 1 0.01 I 2.64 m VD <0.01 Specific surface area (m2/g) _ Average particle size (μη〇_ oil absorption (cc/100g) ν/s ratio of iron impurity (% by weight) Pore volume (cc/100g) Ο. Sieve residue (% by weight) 蟀1丨Jli and -22- (19)1330647 Comparative example 3 0.32 16.7 〇 Example 2 inch 0.44 17.2 490 m Comparative Example 1 cn 0.56 15.4 -1 430 inch Example 6 0.29 21.1 Ο s Example 5 m 0.21 24.2 ο Example 4 1 0.27 21 .3 _1 uo Example 3 0.28 17.6 Example 2 0.23 20.5 610 in Example 1 0.22 19.0 560 Transparency and abrasion resistance Μ Tension strength (MPa) Elongation (%) _ Yellowing transparent rubber various physical properties -23- ( 20) 1330647 [Examples 7 and 8] A transparent rubber was obtained in the same manner as in Example 1 except that the composition of the transparent unvulcanized rubber was made into the composition shown in Table 4 in Example 1. The physical properties of the obtained transparent rubber are shown in Table 5. Table 4 Rubber component (parts by weight) Total light transmittance (%) BR S-SBR IR Example 7 70 20 10 80 Example 8 70 30 - 82 Table 5 Example 7 Example 8 Transparent rubber physical transparency 5 5 abrasion resistance (cc) 0.19 0.24 tensile strength (MPa) 2 1.0 20.4 elongation (%) 580 630 yellowing property 4 5 [Example 9] In Example 1, the addition of wet non-vulcanized rubber to wet cerium oxide A transparent rubber was obtained in the same manner as in Example 1 except that the amount was 100 parts by weight of the unvulcanized rubber. The transparency of the obtained transparent rubber was 5, and the abrasion resistance was 0.16 cc, the tensile strength was 26.7 Pa, the elongation was 520%, and the yellowing property was 5. [Effect of the Invention] -24- (21) (21) 1330647 From the above description, it is proved that the entangled material for transparent rubber of the present invention is blended with a transparent unvulcanized rubber, and the kneaded cerium oxide is excellent even if it is slightly sheared. Dispersibility allows the final particle size to be extremely small. Therefore, the transparent rubber obtained by this use can effectively exhibit a person with apparently good transparency. Thus, a transparent rubber which achieves high transparency while containing wet cerium oxide is originally disclosed by the present invention. Further, the mechanical properties such as abrasion resistance and sliding resistance can be sufficiently exhibited by the high dispersibility of the entangled material. Further, the transparent rubber of the present invention is an ideal user for its intended use in terms of its excellent transparency and rubber properties, such as soles and table mats. Further, in this application, in order to enhance the creativity of the transparent rubber, it is also possible to contain a coloring agent such as a pigment or a dye, a fine metal foil, a decorative filler such as a bead, and the like. -25-