JP2004292219A - Surface-treated silica and rubber composition containing it - Google Patents
Surface-treated silica and rubber composition containing it Download PDFInfo
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- JP2004292219A JP2004292219A JP2003085425A JP2003085425A JP2004292219A JP 2004292219 A JP2004292219 A JP 2004292219A JP 2003085425 A JP2003085425 A JP 2003085425A JP 2003085425 A JP2003085425 A JP 2003085425A JP 2004292219 A JP2004292219 A JP 2004292219A
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- silica
- titanium dioxide
- rubber
- treated silica
- rubber composition
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 37
- 229920001971 elastomer Polymers 0.000 title claims abstract description 28
- 239000005060 rubber Substances 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 title claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 25
- 238000004381 surface treatment Methods 0.000 claims abstract description 5
- 239000011164 primary particle Substances 0.000 claims abstract description 4
- 230000032683 aging Effects 0.000 abstract description 8
- 230000002787 reinforcement Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WWIXJFPDYYVXLE-UHFFFAOYSA-N octadecanoic acid;tungsten Chemical compound [W].CCCCCCCCCCCCCCCCCC(O)=O WWIXJFPDYYVXLE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は表面処理されたシリカ及びそれを含むゴム組成物に関し、更に詳しくはゴムに対する補強性を増大させた表面処理シリカ及びそれを含むゴム組成物に関する。
【０００２】
【従来の技術】
種々の目的で、シランカップリング剤やその他の処理剤でシリカを処理することは知られているが（例えば特許文献１参照）、ナノスケールの二酸化チタンでシリカ表面を処理することは知られていない。
【０００３】
【特許文献１】
特開１９９４−２４８１１６号公報
【０００４】
【発明が解決しようとする課題】
従って、本発明は、ゴムの補強用として使用されるシリカの補強性を増大させて、ゴムの強度及び耐熱老化性を改良することができる表面処理されたシリカを提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明に従えば、二酸化チタンで表面処理してなる表面処理シリカが提供される。
【０００６】
本発明に従えば、また、上記表面処理シリカを配合してなるゴム組成物が提供される。
【０００７】
【発明の実施の形態】
本発明者らは、二酸化チタンはアルコキシシランとシリカとの反応を促進させる働きがあることに着目し、シリカ表面を二酸化チタンで処理することにより、シリカの補強性が増大することを見出し、本発明をするに至った。
【０００８】
本発明に係る表面処理シリカはゴム用として使用することができる任意のシリカを二酸化チタン、特にナノスケールの二酸化チタン（例えば一次粒径が５０ｎｍ以下、好ましくは１〜３０ｎｍ）で表面処理することによって得ることができる。
【０００９】
本発明に従ったシリカの表面処理に使用される二酸化チタンは特に限定はないが、一次粒径の小さいもの（例えば５０ｎｍ以下、更に好ましくは１〜３０ｎｍ）が好ましい。このようなものは、例えばテイカ（株）より市販されている。粉体のもの、水に細かく分散されたものがあり、それぞれＡＭＴ−６００、ＴＫＳ−２０３などが知られている。また、シリカ表面で、二酸化チタンを直接生成させることも可能である。
【００１０】
本発明に従ってシリカの表面を二酸化チタンで処理する方法及び条件には特に限定はないが、例えば以下のようにして処理することができる。
本発明に使用されるシリカは、水ガラスと硫酸により水を溶媒として製造される、いわゆる湿式シリカである。湿式シリカの製造後、洗浄、乾燥前に、二酸化チタンの水懸濁液（例えばテイカ（株）のＴＫＳ−２０３）を所定量添加、攪拌後、二酸化チタン処理シリカを得ることができる。また、乾燥された湿式シリカに有機チタン化合物を用いて処理した後、加水分解縮合して、シリカ表面に二酸化チタンを析出させる方法があげられる。有機チタン化合物としては、例えばテトラアルコキシチタン、チタンアシレート、チタンキレートの３群のものなどが使用できる。
【００１１】
本発明に従って二酸化チタン、特にナノスケール二酸化チタンで表面処理されたシリカはシリカの表面に二酸化チタンが点在した状態をしており、この二酸化チタンの処理量は、シリカ重量に対し、０．０５〜３重量％であるのが好ましく、０．１〜２重量％が更に好ましい。この二酸化チタンの量が少な過ぎると二酸化チタンのアルコキシシランとシリカとの反応促進作用が十分でなくなるおそれがあり、逆に多過ぎると加硫ゴムの物性が低下するおそれがある。
【００１２】
本発明においてゴム組成物に配合するゴムとしては、例えばタイヤ用原料ゴムとして使用することができる任意のジエン系ゴムを含み、かかる代表的なジエン系ゴムとしては、天然ゴム（ＮＲ）、ポリイソプレンゴム（ＩＲ）、各種ポリブタジエンゴム（ＢＲ）、各種スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、エチレン−プロピレン−ジエン三元共重合体ゴム（ＥＰＤＭ）などをあげることができる。これは単独又は任意のブレンドとして使用することができる。
【００１３】
本発明に係るゴム組成物には、前記した必須成分に加えて、カーボンブラックなどの補強剤（フィラー）、加硫又は架橋剤、加硫又は架橋促進剤、各種オイル、老化防止剤、可塑性剤などのタイヤ用、その他一般ゴム用に一般的に配合されている各種添加剤を配合することができ、かかる配合物は一般的な方法で混練、加硫して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量も本発明の目的に反しない限り、従来の一般的な配合量とすることができる。本発明によれば、伸びの低下を来たすことなく、高強度で耐熱老化性に優れたゴム組成物が得られるので、タイヤトレッド、サイドウォール用ゴム組成物として有用である。
【００１４】
【実施例】
以下、実施例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことはいうまでもない。
【００１５】
実施例１〜２及び比較例１
サンプルの調製
表Ｉに示す配合（重量部）において、加硫促進剤と硫黄を除く成分を１．８リットルの密閉型ミキサーで３〜５分間混練し、１６５±５℃に達したときに放出してマスターバッチを得た。このマスターバッチに加硫促進剤と硫黄を８インチのオープンロール混練し、ゴム組成物を得た。
得られたゴム組成物を１５×１５×０．２ｃｍおよびランボーン試験片用の金型中で１６０℃で３０分間プレス加硫して目的とする試験片を調製し、加硫物性、即ち老化前後（老化条件：８０℃オーブンにて９６時間放置後）の引張特性並びにｔａｎδ及び耐摩耗性を評価した。結果を表Ｉに示す。なお、老化後の値のカッコ内の数字は老化前の値に対するパーセント表示である。
【００１６】
各例において得られた組成物の加硫物性の試験方法は以下の通りである。
引張り特性：ダンベル状３号形ダンベルにて、２ｍｍ厚の加硫ゴムシートを打ち抜き、１００％モジュラス（Ｍ１００）、３００％モジュラス（Ｍ３００）、破断引張り強度（ＴＢ）及び破断伸び（ＥＢ）を、それぞれ、ＪＩＳ Ｋ６２５１に準拠して測定した。
【００１７】
ｔａｎδ：２ｍｍ厚の加硫ゴムシートから幅５ｍｍ×厚さ２ｍｍ×長さ２０ｍｍの短冊状試験片を打ち抜き、粘弾性スペクトロメーター（東洋精機（株）製）を用いて温度−１０℃、０℃及び６０℃、初期歪１０％、動的歪±２％、周波数２０Ｈｚの条件で測定した値である。−１０℃および０℃におけるｔａｎδ値は、タイヤのウエットスキッド抵抗と相関し、この値が大きい程、ウエット路でのブレーキング性能が良い。６０℃におけるｔａｎδ値は、タイヤの転がり抵抗と相関し、この値が小さい程、低燃費である。
【００１８】
摩耗一連ランボーン：ランボーン摩耗試験機を用いてＪＩＳ Ｋ６２６４に準拠し、直径６３．５ｍｍ、厚さ５ｍｍ円盤状試験片で、荷重１５Ｎ、スリップ率５０％、試験温度２０℃の条件にて測定した。（基準サンプルの摩耗量）×１００／（試料の摩耗量）を指数として表示した。指数値が大きいほど耐摩耗性は良好である。
【００１９】
【表１】
表Ｉの脚注
＊１ ：日本ゼオン製 Ｎｉｐｏｌ １７１２ スチレン量２３．５重量％、油展量３７．５ｐｈｒ（ゴム１００重量部に対しオイル３７．５重量部）
＊２ ：日本シリカ工業製 ニップシールＬＰ
＊３ ：二酸化チタンにて０．４重量％湿式処理したニップシールＬＰ
＊４ ：二酸化チタンにて２重量％湿式処理したニップシールＬＰ
＊５ ：正同化学製 亜鉛華３号
＊６ ：日本油脂製 ビーズステアリン酸 桐
＊７ ：日本モンサント製 サントフレックス１３
＊８ ：Ｄｅｇｕｓｓａ製 Ｓｉ６９
＊９ ：昭和シエル石油製 デゾレックス３号
＊１０ ：軽井沢精練所製 油処理硫黄
＊１１ ：大内新興化学製 ノクセラーＣＺ−Ｇ
【００２１】
【発明の効果】
以上の通り、シリカ表面を二酸化チタンで表面処理したシリカを補強剤としてゴムに配合することにより、伸びが低下せず、高強度のゴム物性が得られ、また優れた耐熱老化性を得ることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a surface-treated silica and a rubber composition containing the same, and more particularly, to a surface-treated silica having an enhanced reinforcing property to rubber and a rubber composition containing the same.
[0002]
[Prior art]
Although it is known to treat silica with a silane coupling agent or another treating agent for various purposes (for example, see Patent Document 1), it is known to treat a silica surface with nanoscale titanium dioxide. Absent.
[0003]
[Patent Document 1]
JP-A-1994-248116
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a surface-treated silica capable of increasing the reinforcing property of silica used for reinforcing rubber and improving the strength and heat aging resistance of rubber.
[0005]
[Means for Solving the Problems]
According to the present invention, there is provided a surface-treated silica obtained by performing a surface treatment with titanium dioxide.
[0006]
According to the present invention, there is also provided a rubber composition containing the surface-treated silica.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
The present inventors have noticed that titanium dioxide has a function of accelerating the reaction between alkoxysilane and silica, and found that treating the silica surface with titanium dioxide increases the reinforcing properties of silica. Invented the invention.
[0008]
The surface-treated silica according to the present invention is obtained by subjecting any silica that can be used for rubber to a surface treatment with titanium dioxide, particularly nanoscale titanium dioxide (for example, having a primary particle size of 50 nm or less, preferably 1 to 30 nm). Obtainable.
[0009]
The titanium dioxide used for the surface treatment of the silica according to the present invention is not particularly limited, but those having a small primary particle size (for example, 50 nm or less, more preferably 1 to 30 nm) are preferred. Such a product is commercially available, for example, from Teika Corporation. There are powder and finely dispersed in water, and AMT-600, TKS-203 and the like are known, respectively. It is also possible to generate titanium dioxide directly on the silica surface.
[0010]
The method and conditions for treating the surface of the silica with titanium dioxide according to the present invention are not particularly limited, and for example, the treatment can be performed as follows.
The silica used in the present invention is a so-called wet silica produced by using water as a solvent with water glass and sulfuric acid. After the production of the wet silica, before washing and drying, a predetermined amount of an aqueous suspension of titanium dioxide (for example, TKS-203 of Teika Co., Ltd.) is added, and after stirring, the titanium dioxide-treated silica can be obtained. Further, a method of treating a dried wet silica with an organic titanium compound, followed by hydrolysis and condensation to precipitate titanium dioxide on the silica surface may be mentioned. As the organic titanium compound, for example, three groups of tetraalkoxy titanium, titanium acylate, and titanium chelate can be used.
[0011]
The silica surface-treated with titanium dioxide, particularly nanoscale titanium dioxide, according to the present invention has a state in which titanium dioxide is scattered on the surface of silica, and the treatment amount of the titanium dioxide is 0.05% based on the weight of silica. It is preferably from 3 to 3% by weight, more preferably from 0.1 to 2% by weight. If the amount of titanium dioxide is too small, the reaction promoting action of the titanium dioxide with the alkoxysilane and silica may not be sufficient, while if too large, the physical properties of the vulcanized rubber may be reduced.
[0012]
In the present invention, the rubber compounded in the rubber composition includes, for example, any diene rubber which can be used as a raw material rubber for tires, and typical diene rubbers include natural rubber (NR) and polyisoprene. Rubber (IR), various polybutadiene rubbers (BR), various styrene-butadiene copolymer rubbers (SBR), ethylene-propylene-diene terpolymer rubbers (EPDM), and the like. It can be used alone or as any blend.
[0013]
In the rubber composition according to the present invention, in addition to the essential components described above, a reinforcing agent (filler) such as carbon black, a vulcanizing or crosslinking agent, a vulcanizing or crosslinking accelerator, various oils, an antioxidant, and a plasticizer Various additives that are generally compounded for tires such as tires and other general rubbers can be compounded, and such compounds are kneaded and vulcanized into compositions by general methods, and vulcanized or crosslinked. Can be used to The compounding amounts of these additives can also be conventional general compounding amounts, as long as they do not contradict the object of the present invention. According to the present invention, a rubber composition having high strength and excellent heat aging resistance can be obtained without a decrease in elongation, and thus is useful as a rubber composition for tire treads and sidewalls.
[0014]
【Example】
Hereinafter, the present invention will be further described with reference to Examples, but it goes without saying that the scope of the present invention is not limited to these Examples.
[0015]
Examples 1 and 2 and Comparative Example 1
Preparation of sample In the composition (parts by weight) shown in Table I, the components other than the vulcanization accelerator and sulfur were kneaded with a 1.8-liter closed mixer for 3 to 5 minutes to reach 165 ± 5 ° C. When released, a masterbatch was obtained. This master batch was kneaded with an 8-inch open roll with a vulcanization accelerator and sulfur to obtain a rubber composition.
The obtained rubber composition was press-vulcanized at 160 ° C. for 30 minutes in a mold for 15 × 15 × 0.2 cm and Lambourn test pieces to prepare a target test piece, and the vulcanization properties, that is, before and after aging (Aging conditions: after standing in an oven at 80 ° C. for 96 hours), tensile properties, tan δ and abrasion resistance were evaluated. The results are shown in Table I. The numbers in parentheses of the values after aging are percentages with respect to the values before aging.
[0016]
The method for testing the vulcanizate properties of the composition obtained in each example is as follows.
Tensile properties: A 2 mm thick vulcanized rubber sheet was punched out with a dumbbell-shaped No. 3 dumbbell, and 100% modulus (M100), 300% modulus (M300), tensile strength at break (TB) and elongation at break (EB) were determined. Each was measured according to JIS K6251.
[0017]
tan δ: A rectangular test piece of 5 mm wide × 2 mm thick × 20 mm long was punched out from a vulcanized rubber sheet having a thickness of 2 mm, and was subjected to a temperature of −10 ° C. and 0 ° C. using a viscoelastic spectrometer (manufactured by Toyo Seiki Co., Ltd.). And 60 ° C., an initial strain of 10%, a dynamic strain of ± 2%, and a frequency of 20 Hz. The tan δ values at −10 ° C. and 0 ° C. correlate with the wet skid resistance of the tire, and the larger the value, the better the braking performance on a wet road. The tan δ value at 60 ° C. correlates with the rolling resistance of the tire, and the smaller the value, the lower the fuel consumption.
[0018]
Abrasion series Lambourn: Measured using a Lambourn abrasion tester in accordance with JIS K6264, using a disc-shaped test piece having a diameter of 63.5 mm and a thickness of 5 mm under the conditions of a load of 15 N, a slip rate of 50%, and a test temperature of 20 ° C. (Abrasion amount of reference sample) × 100 / (abrasion amount of sample) was displayed as an index. The larger the index value, the better the wear resistance.
[0019]
[Table 1]
Table I footnotes
* 1 : Nipol 1712 manufactured by Nippon Zeon Co., Ltd. 23.5% by weight of styrene, 37.5 phr of oil extension (37.5 parts by weight of oil per 100 parts by weight of rubber)
* 2 : Nip Seal LP manufactured by Nippon Silica Kogyo
* 3 : Nip seal LP wet treated with 0.4% by weight of titanium dioxide
* 4 : Nip seal LP wet treated with 2% by weight of titanium dioxide
* 5 : Zinc flower No. 3 manufactured by Shodo Chemical
* 6 : Tungsten stearic acid made by NOF Corporation
* 7 : Santoflex 13 manufactured by Monsanto Japan
* 8 : Si69 manufactured by Degussa
* 9 : Showa Ciel's Desolex 3
* 10 : Oil-treated sulfur manufactured by Karuizawa Seirensho
* 11 : Noxeller CZ-G manufactured by Ouchi Shinko Chemical
[0021]
【The invention's effect】
As described above, by adding silica whose surface is treated with titanium dioxide to a rubber as a reinforcing agent, rubber does not decrease in elongation, high strength rubber properties can be obtained, and excellent heat aging resistance can be obtained. it can.
Claims (4)
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| JP2003085425A JP2004292219A (en) | 2003-03-26 | 2003-03-26 | Surface-treated silica and rubber composition containing it |
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| JP2003085425A JP2004292219A (en) | 2003-03-26 | 2003-03-26 | Surface-treated silica and rubber composition containing it |
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| JP2004292219A true JP2004292219A (en) | 2004-10-21 |
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| JP2003085425A Pending JP2004292219A (en) | 2003-03-26 | 2003-03-26 | Surface-treated silica and rubber composition containing it |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008526577A (en) * | 2005-01-14 | 2008-07-24 | 株式会社ブリヂストン | Tire composition having improved silica reinforcement and vulcanizate thereof |
| EP1997850A3 (en) * | 2007-05-31 | 2009-07-29 | The Goodyear Tire & Rubber Company | Elastomers containing surface metalated siliceous fillers |
| KR101242534B1 (en) | 2011-08-16 | 2013-03-12 | 전남대학교산학협력단 | Surface modification methods of titania added into silica-reinforced SBR compounds to enhance their dynamic properties |
| WO2019187587A1 (en) * | 2018-03-30 | 2019-10-03 | 太陽インキ製造株式会社 | Curable resin composition, dry film, cured object, layered structure, and electronic component |
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| JPH06127932A (en) * | 1992-10-21 | 1994-05-10 | Asahi Glass Co Ltd | Silica supporting metal oxide and method for producing the same |
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| JP2003001117A (en) * | 2001-06-22 | 2003-01-07 | Toshiba Ceramics Co Ltd | Photocatalytic particles and method for producing the same |
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| JPH02160608A (en) * | 1988-12-12 | 1990-06-20 | Hitachi Maxell Ltd | Surface-modification of powder, powder, aggregate and composition composed thereof |
| JPH06127932A (en) * | 1992-10-21 | 1994-05-10 | Asahi Glass Co Ltd | Silica supporting metal oxide and method for producing the same |
| JPH1072210A (en) * | 1996-04-22 | 1998-03-17 | Merck Patent Gmbh | Coated sio2 particles |
| JPH1160231A (en) * | 1997-06-13 | 1999-03-02 | Mizusawa Ind Chem Ltd | Amorphous silica particles having double structure, production method and use thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008526577A (en) * | 2005-01-14 | 2008-07-24 | 株式会社ブリヂストン | Tire composition having improved silica reinforcement and vulcanizate thereof |
| EP1997850A3 (en) * | 2007-05-31 | 2009-07-29 | The Goodyear Tire & Rubber Company | Elastomers containing surface metalated siliceous fillers |
| US7943693B2 (en) | 2007-05-31 | 2011-05-17 | The Goodyear Tire & Rubber Company | Elastomers containing surface metalated siliceous fillers |
| KR101242534B1 (en) | 2011-08-16 | 2013-03-12 | 전남대학교산학협력단 | Surface modification methods of titania added into silica-reinforced SBR compounds to enhance their dynamic properties |
| WO2013025041A3 (en) * | 2011-08-16 | 2013-05-30 | 전남대학교 산학협력단 | Surface treatment method of titania additives for improving dynamic properties of silica reinforced sbr rubber compound |
| WO2019187587A1 (en) * | 2018-03-30 | 2019-10-03 | 太陽インキ製造株式会社 | Curable resin composition, dry film, cured object, layered structure, and electronic component |
| CN111918933A (en) * | 2018-03-30 | 2020-11-10 | 太阳油墨制造株式会社 | Curable resin composition, dry film, cured product, laminated structure, and electronic component |
| JPWO2019187587A1 (en) * | 2018-03-30 | 2021-04-22 | 太陽インキ製造株式会社 | Curable resin compositions, dry films, cured products, laminated structures, and electronic components |
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