TW201625727A - Method for preparing a silica-filled rubber composition and the composition - Google Patents
Method for preparing a silica-filled rubber composition and the composition Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
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- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
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- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
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Abstract
Description
本發明是關於二氧化矽填料和橡膠的製造方法及其組成物。其是一種二氧化矽填充橡膠組成物的製造方法及其組成物,該製造方法將二氧化矽的漿料和乳化狀的橡膠混合,並進行共凝固且乾燥,而含有二氧化矽填充劑。藉由將本發明之二氧化矽填充橡膠組成物進行加硫,以輪胎胎面、胎面基部、胎體、外胎側面、胎唇部分等輪胎用途為首,能夠使用在防振橡膠、皮帶、軟管之其他的工業品等用途。 The present invention relates to a method for producing a cerium oxide filler and a rubber, and a composition thereof. It is a method for producing a ruthenium dioxide-filled rubber composition and a composition thereof, which comprises mixing a slurry of cerium oxide and an emulsified rubber, co-coagulation and drying, and containing a cerium oxide filler. By sulphurizing the cerium oxide-filled rubber composition of the present invention, it can be used for tire applications such as tire tread, tread base, carcass, tire side surface, and bead portion, and can be used in anti-vibration rubber, belt, and soft. Other industrial products and other uses.
從省資源、省能源的立場而言,對輪胎尋求低燃料消耗性能的需求正在年年增加。作為低燃料消耗輪胎的製造方法,有人提案了一種利用將二氧化矽作為填充劑而成之橡膠組成物。然而,在二氧化矽的調配中,矽烷偶合劑為必要,為了使用此試劑,橡膠混煉的溫度條件有了限制。並且在調配輪胎用橡膠時,由於相較於碳黑,二氧化矽更難以分散,故有著混煉步驟數較多,成本變高的問題。(非專利文獻1和2) From the standpoint of resource saving and energy saving, the demand for tires to seek low fuel consumption performance is increasing year by year. As a method for producing a low fuel consumption tire, a rubber composition obtained by using cerium oxide as a filler has been proposed. However, in the preparation of cerium oxide, a decane coupling agent is necessary, and in order to use this reagent, the temperature condition of rubber mixing is limited. Further, when rubber for tires is blended, since cerium oxide is more difficult to disperse than carbon black, there are problems in that the number of kneading steps is large and the cost is high. (Non-Patent Documents 1 and 2)
本發明提供一種方法,其藉由預先將乳化狀態的共軛二烯系橡膠、具有胺基或亞胺基之聚合物的水溶液、及二氧化矽進行混合、接觸,使橡膠和二氧化矽的共凝固變得容易,而能夠製造出一種粒徑適合於乾燥之二氧化矽填充橡膠組成物。 The present invention provides a method of mixing and contacting a conjugated diene rubber in an emulsified state, an aqueous solution of a polymer having an amine group or an imine group, and cerium oxide to cause rubber and cerium oxide. Co-coagulation becomes easy, and a ruthenium dioxide-filled rubber composition having a particle size suitable for drying can be produced.
專利文獻1:日本特公昭38-26765號公報 Patent Document 1: Japanese Patent Publication No. Sho 38-26765
專利文獻2:日本特開昭63-051435號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. SHO 63-051435
專利文獻3:日本特開2005-105154號公報 Patent Document 3: Japanese Laid-Open Patent Publication No. 2005-105154
非專利文獻1:日本橡膠協會誌,71(9),588(1998) Non-Patent Document 1: Japan Rubber Association, 71 (9), 588 (1998)
非專利文獻2:日本橡膠協會誌,74(2),64(2001) Non-Patent Document 2: Japan Rubber Association, 74(2), 64 (2001)
作為從二氧化矽和乳化狀態的橡膠來製造出二氧化矽填充橡膠組成物的方法,已知有一種方法,該方法將兩者混合並利用噴霧乾燥來使分散介質也就是水蒸發而得到粉末狀的二氧化矽和橡膠的組成物(專利文獻1)。但是,在此方法中,為了使大量的水蒸發,需要許多熱能。因此並不適合於大規模的工業生產。又,在此方法中,由於為了要使乳液的水直接汽化,而在包含了作為橡膠組成物所不需要的鹽和界面活性劑等的情況下進行乾燥,故會有加硫時的橡膠性能低劣的情形。 As a method for producing a cerium oxide-filled rubber composition from cerium oxide and a rubber in an emulsified state, a method is known in which a mixture of the two is used and spray-drying is used to evaporate a dispersion medium, that is, water to obtain a powder. A composition of cerium oxide and rubber (Patent Document 1). However, in this method, in order to evaporate a large amount of water, much heat energy is required. Therefore, it is not suitable for large-scale industrial production. Further, in this method, since the water of the emulsion is directly vaporized and dried in the case where the salt and the surfactant which are not required as the rubber composition are contained, the rubber property in the case of vulcanization may occur. Poor situation.
也已知一種方法,該方法在乳化狀態的橡膠和二氧化矽中,加入陽離子聚合物或非離子性聚合物,並進一步加入鹽及酸,而將橡膠和二氧化矽之組成物凝固、乾燥,來製造出粉末狀的二氧化矽填充橡膠組成物(專利文獻2)。但是,在此方法,二氧化矽填充橡膠組成物會變成粉末狀,若使用一般橡膠製造所使用的帶式乾燥機要讓它乾燥時,會有粒徑小的橡膠組成物從皮帶上脫落而無法乾燥的不良情況。為了要大量乾燥二氧化矽填充橡膠組成物,尋求一種二氧化矽填充橡膠組成物,其可獲得具有從5mm到15mm左右的粒徑的橡膠組成物,該橡膠組成物適合於一般的乾燥設備。 There is also known a method of adding a cationic polymer or a nonionic polymer to an emulsified rubber and cerium oxide, and further adding a salt and an acid, and solidifying and drying the composition of the rubber and cerium oxide. A powdery cerium oxide-filled rubber composition was produced (Patent Document 2). However, in this method, the ruthenium dioxide-filled rubber composition becomes a powder, and if a belt dryer used in general rubber production is used to dry it, a rubber composition having a small particle size is detached from the belt. Bad conditions that cannot be dried. In order to dry the ceria-filled rubber composition in a large amount, a ceria-filled rubber composition is sought which can obtain a rubber composition having a particle diameter of from about 5 mm to about 15 mm, which is suitable for general drying equipment.
又,也已知一種二氧化矽填充橡膠組成物的製造方法,該方法將陽離子性聚合物添加到乳化狀態的橡膠和二氧化矽中,且藉由鹽及酸而凝固並進行乾燥。但是,利用此方法所獲得的橡膠,由於複合橡膠(compounded rubber)會在貯藏中或在加硫步驟以前的加工作業中引起早期加硫,而引發製品無法加工的過早硫化(scorch),故必須選擇特定的交聯劑(專利文獻3)。利用此方法所獲得的二氧化矽填充橡膠組成物,由於交聯劑受到限制,當作為橡膠來利用時的橡膠物性和加工時的條件等也被制約因而不佳。 Further, a method for producing a ruthenium dioxide-filled rubber composition is known, which comprises adding a cationic polymer to an emulsified rubber and cerium oxide, and solidifying and drying by a salt and an acid. However, the rubber obtained by this method, because the compounded rubber causes early vulcanization during storage or in the processing operation before the vulcanization step, and causes premature vulcanization of the product, A specific crosslinking agent must be selected (Patent Document 3). The cerium oxide-filled rubber composition obtained by this method is limited by the crosslinking agent, and the rubber physical properties and the conditions at the time of processing when used as a rubber are also restricted, which is not preferable.
本發明之目的在於提供一種二氧化矽填充橡膠組成物的製造方法,其適合於橡膠在工業上大量生產,並製造出容易凝固和乾燥的二氧化矽填充橡膠組成物,該製造方法不需要藉由沒效率的噴霧式乾燥機所實行的乾燥,且不會變成粉末狀的二氧化矽和橡膠組成物,成為適當尺寸的顆粒而易於工業上的製造。 An object of the present invention is to provide a method for producing a ruthenium dioxide-filled rubber composition which is suitable for mass production of rubber in the industry and which produces a ruthenium dioxide-filled rubber composition which is easily solidified and dried, and the production method does not need to be borrowed. It is dried by an inefficient spray dryer and does not become a powdery cerium oxide and a rubber composition, and becomes an appropriately sized granule, which is easy to industrially manufacture.
在本發明中,在將乳化狀態的橡膠(a)和水分散二氧化矽漿料(b)混合並進行共凝固、乾燥,來製造二氧化矽填充橡膠組成物時,利用預先使水分散二氧化矽漿料(b),與乳化狀共軛二烯系橡膠(c)和具有胺基或亞胺基之聚合物的水溶液(d)混合、接觸,橡膠和具有胺基之聚合物將二氧化矽的表面進行改質,乳化狀態的橡膠(a)和二氧化矽的共凝固變得容易,凝固時的橡膠也不是粉末狀而能成為顆粒狀的橡膠。因為這樣,乾燥步驟也能夠使用帶式乾燥機等各種乾燥機來進行乾燥,能以低成本製造二氧化矽填充橡膠組成物。又,在製造而成的二氧化矽填充橡膠組成物中添加交聯劑或交聯助劑進行加硫時,也沒有為了防止過早硫化而使用特定的交聯劑等的限制。 In the present invention, when the rubber (a) in an emulsified state and the water-dispersed ceria slurry (b) are mixed, co-coagulated, and dried to produce a ceria-filled rubber composition, the water is dispersed in advance. The cerium oxide slurry (b) is mixed and contacted with the emulsified conjugated diene rubber (c) and the aqueous solution (d) having an amine group or an imine group, and the rubber and the polymer having an amine group will be The surface of the cerium oxide is modified, and co-coagulation of the rubber (a) and cerium oxide in an emulsified state is facilitated, and the rubber at the time of solidification is not powdery and can be a granular rubber. In this way, the drying step can be carried out by using various dryers such as a belt dryer, and the ruthenium dioxide-filled rubber composition can be produced at low cost. Further, when a crosslinking agent or a crosslinking assistant is added to the produced cerium oxide-filled rubber composition to carry out vulcanization, there is no limitation in that a specific crosslinking agent or the like is used in order to prevent premature vulcanization.
亦即,本發明是關於以下內容: That is, the present invention relates to the following:
[1]一種二氧化矽填充橡膠組成物的製造方法,其在將乳化狀態的橡膠(a)和水分散二氧化矽漿料(b)混合並進行共凝固、乾燥,來製造二氧化矽填充橡膠組成物時, 預先使水分散二氧化矽漿料(b),與乳化狀共軛二烯系橡膠(c)和具有胺基或亞胺基之聚合物的水溶液(d)混合、接觸後,與乳化狀態的橡膠(a)進行共凝固;其中,該乳化狀共軛二烯系橡膠(c)的換算固體含量,其相對於水分散二氧化矽漿料(b)中的二氧化矽固體含量100份,為0.1份到20份;該具有胺基或亞胺基之聚合物的水溶液(d)的換算固體含量,其相對於水分散二氧化矽漿料(b)中的二氧化矽固體含量100份,為0.1份到5份。 [1] A method for producing a ruthenium dioxide-filled rubber composition, which comprises mixing a rubber (a) in an emulsified state and a water-dispersed cerium oxide slurry (b), co-coagulation, and drying to produce a cerium oxide filling When the rubber composition The water-dispersed cerium oxide slurry (b) is mixed with the emulsified conjugated diene rubber (c) and the aqueous solution (d) having an amine group or an imine group in advance, and then contacted with the emulsified state. The rubber (a) is co-coagulated; wherein the emulsified conjugated diene rubber (c) has a conversion solid content of 100 parts by weight relative to the solid content of cerium oxide in the water-dispersed cerium oxide slurry (b). 0.1 parts to 20 parts; the converted solid content of the aqueous solution (d) of the polymer having an amine group or an imine group, which is 100 parts by weight relative to the solid content of cerium oxide in the water-dispersed cerium oxide slurry (b) , from 0.1 parts to 5 parts.
[2]如[1]所述之二氧化矽填充橡膠組成物的製造方法,其中,乳化狀共軛二烯系橡膠(c)是包含了含胺基之共軛二烯系聚合物、含羥基之共軛二烯系聚合物、含環氧基之共軛二烯系聚合物、及含烷氧矽烷基之共軛二烯系聚合物中的至少一種而成之共軛二烯系聚合物。 [2] The method for producing a ruthenium dioxide-filled rubber composition according to the above [1], wherein the emulsified conjugated diene rubber (c) is a conjugated diene polymer containing an amine group, and Conjugated diene polymerization of at least one of a conjugated diene polymer having a hydroxyl group, a conjugated diene polymer containing an epoxy group, and a conjugated diene polymer containing an alkoxyalkyl group Things.
[3]如[1]或[2]所述之二氧化矽填充橡膠組成物的製造方法,其中,具有胺基或亞胺基之聚合物的水溶液(d)中的該聚合物,是將伸乙亞胺、二烯丙基二甲胺、二烯丙基甲胺、脒、雙氰胺、具有胺基之丙烯酸酯、具有胺基之甲基丙烯酸酯、及乙烯吡啶中的至少一種聚合而成之同元聚合物或共聚物;或是具有胺基或亞胺基的天然水溶性高分子化合物。 [3] The method for producing a ruthenium dioxide-filled rubber composition according to [1] or [2], wherein the polymer in the aqueous solution (d) of the polymer having an amine group or an imine group is At least one polymerization of ethyleneimine, diallyldimethylamine, diallylmethylamine, hydrazine, dicyandiamide, an acrylate having an amine group, a methacrylate having an amine group, and vinylpyridine a homopolymer or copolymer; or a natural water-soluble polymer compound having an amine group or an imine group.
[4]如[1]~[3]所述之二氧化矽填充橡膠組成物的製造方法,其中,於水分散二氧化矽漿料(b)中,平均粒徑100μm以上的二氧化矽粒子未達5%。 [4] The method for producing a ruthenium dioxide-filled rubber composition according to [1] to [3], wherein, in the water-dispersed cerium oxide slurry (b), the oxidizing agent having an average particle diameter of 100 μm or more The bismuth particles are less than 5%.
[5]一種二氧化矽填充橡膠組成物,其是利用如[1]~[4]所述之製造方法而製造出來。 [5] A ruthenium dioxide-filled rubber composition produced by the production method according to [1] to [4].
[6]一種輪胎用橡膠,是將如[5]所述之二氧化矽填充橡膠組成物進行加硫、成形而成。 [6] A rubber for a tire obtained by vulcanizing and molding a cerium oxide-filled rubber composition as described in [5].
只要根據本發明之製造方法,預先利用乳化狀共軛二烯系橡膠、及具有胺基或亞胺基之聚合物的水溶液來對水分散二氧化矽進行處理,就能夠得到一種二氧化矽填充橡膠組成物,其共凝固率高,並成為適當尺寸的顆粒。又,由此二氧化矽填充橡膠組成物,可得到一種加硫橡膠物性、機械性強度、耐磨損性優異且低發熱性的加硫橡膠。藉由本發明而獲得之二氧化矽填充橡膠組成物是特別適合於輪胎的橡膠組成物。又,本發明之組成物在加硫時,亦沒有交聯劑相關的限制。 According to the production method of the present invention, water-dispersed cerium oxide is previously treated with an aqueous solution of an emulsified conjugated diene rubber and a polymer having an amine group or an imine group, whereby a cerium oxide filling can be obtained. The rubber composition has a high co-solidification rate and becomes an appropriately sized particle. Further, by filling the rubber composition with the cerium oxide, a vulcanized rubber having excellent physical properties, mechanical strength, and abrasion resistance and low heat build-up of the vulcanized rubber can be obtained. The cerium oxide-filled rubber composition obtained by the present invention is a rubber composition particularly suitable for a tire. Further, when the composition of the present invention is vulcanized, there is no restriction related to the crosslinking agent.
作為本發明之乳化狀態的橡膠(a)並沒有特別限制,但可舉出天然橡膠乳液、合成天然橡膠乳液、苯乙烯丁二烯共聚合橡膠乳液、苯乙烯異戊二烯共聚合橡膠乳液、丙烯腈丁二烯共聚合橡膠乳液、氯丁二烯橡膠乳液。在此等之中,較佳為天然橡膠乳液和苯乙烯丁二烯共聚合橡膠乳液。 The rubber (a) in the emulsified state of the present invention is not particularly limited, and examples thereof include a natural rubber emulsion, a synthetic natural rubber emulsion, a styrene butadiene copolymerized rubber emulsion, and a styrene isoprene copolymer rubber emulsion. Acrylonitrile butadiene copolymerized rubber emulsion, chloroprene rubber emulsion. Among these, a natural rubber emulsion and a styrene butadiene copolymerized rubber emulsion are preferred.
作為水分散二氧化矽漿料(b),使用合成後照原樣的水分散二氧化矽漿料、或未曾經過乾燥的二氧化 矽餅(silica cake)進行製備而成之水分散二氧化矽漿料,因為高分散性而較佳。亦可使用在乾燥二氧化矽中加入鹼來將pH作成8以上並使之再分散而成之二氧化矽漿料、在水玻璃中加入酸而析出之二氧化矽漿料、或水玻璃。照原樣地使用水玻璃時,與乳化狀態的特定橡膠乳液混合之後,能藉由加酸使之析出而利用。 As the water-dispersed cerium oxide slurry (b), a water-dispersed cerium oxide slurry which is synthesized as it is, or a non-drying oxidizing agent is used. A water-dispersed cerium oxide slurry prepared by a silica cake is preferred because of high dispersibility. A cerium oxide slurry obtained by adding a base to dry cerium oxide to have a pH of 8 or more and redispersing it, a cerium oxide slurry which is precipitated by adding an acid to water glass, or water glass can also be used. When water glass is used as it is, it mixes with the specific rubber emulsion in an emulsified state, and can be utilized by precipitation by acid addition.
作為水分散二氧化矽漿料(b)的比例,相對於乳化狀態的橡膠(a)的固體含量100份,水分散二氧化矽漿料(b)的固體含量為10份到150份。水分散二氧化矽漿料(b)的固體含量未達10份的話,無法期待作為二氧化矽所產生的橡膠補強效果。又,若超過150份,由於作為二氧化矽填充橡膠組成物會變硬,凝固時的顆粒的粒徑亦會變細而不佳。 As a ratio of the water-dispersed cerium oxide slurry (b), the solid content of the water-dispersed cerium oxide slurry (b) is from 10 parts to 150 parts with respect to 100 parts by weight of the rubber (a) in an emulsified state. When the solid content of the water-dispersed cerium oxide slurry (b) is less than 10 parts, the rubber reinforcing effect by cerium oxide cannot be expected. In addition, when it exceeds 150 parts, the rubber composition is hardened as a cerium oxide filling material, and the particle diameter of the particles at the time of solidification is also fine.
作為乳化狀共軛二烯系橡膠(c),可舉出由含胺基之共軛二烯系聚合物、含羥基之共軛二烯系聚合物、含環氧基之共軛二烯系聚合物、及含烷氧矽烷基之共軛二烯系聚合物選擇出來之共軛二烯系聚合物。與這些共軛二烯系聚合物進行共聚合之含胺基之單體、含羥基之單體、含環氧基之單體或含烷氧矽烷基之單體的量,較佳是共聚物的整體量的0.1%到10%(單體重量比)。若是未達0.1%則效果低,若超過10%則橡膠的柔軟性降低且加硫橡膠的發熱變大,橡膠物性降低。 Examples of the emulsified conjugated diene rubber (c) include an amine group-containing conjugated diene polymer, a hydroxyl group-containing conjugated diene polymer, and an epoxy group-containing conjugated diene system. A conjugated diene polymer selected from the group consisting of a polymer and an alkoxyalkyl group-containing conjugated diene polymer. The amount of the amine group-containing monomer, the hydroxyl group-containing monomer, the epoxy group-containing monomer or the alkoxyalkyl group-containing monomer copolymerized with these conjugated diene polymers is preferably a copolymer The overall amount is from 0.1% to 10% (monomer weight ratio). If it is less than 0.1%, the effect is low, and if it exceeds 10%, the softness of the rubber is lowered, and the heat generation of the vulcanized rubber is increased, and the rubber physical properties are lowered.
乳化狀共軛二烯系橡膠(c)的平均分子量,較佳為10萬以上。作為較佳的共軛二烯單體,可舉出丁二烯和異戊二烯。 The average molecular weight of the emulsified conjugated diene rubber (c) is preferably 100,000 or more. Preferred examples of the conjugated diene monomer include butadiene and isoprene.
作為含胺基之共軛二烯系聚合物,可舉出丁二烯、異戊二烯、具有胺基之單體之共聚物。 The conjugated diene polymer containing an amine group may, for example, be a copolymer of butadiene, isoprene or a monomer having an amine group.
作為具有胺基之單體,有含第1級胺基之單體、含第2級胺基之單體、及含第3級胺基之單體。作為含第1級胺基之單體,例如可舉出:對胺基苯乙烯、(甲基)丙烯酸胺甲酯、(甲基)丙烯酸胺乙酯、(甲基)丙烯酸胺丙酯、(甲基)丙烯酸胺丁酯等。 Examples of the monomer having an amine group include a monomer having a first-stage amine group, a monomer having a second-order amine group, and a monomer having a third-order amine group. Examples of the monomer having a first-stage amine group include p-aminostyrene, amine methyl (meth)acrylate, amine ethyl (meth)acrylate, and amine propyl (meth)acrylate. Aminobutyl methacrylate or the like.
作為含第2級胺基之單體,可舉出:N-甲基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N-羥甲基丙烯醯胺、及N-(4-苯胺基苯基)甲基丙烯醯胺等之N-單取代(甲基)丙烯醯胺類等。 Examples of the monomer having a second-order amine group include N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-methylol acrylamide, and N. N-monosubstituted (meth) acrylamide such as -(4-anilinophenyl)methacrylamide.
作為含第3級胺基之單體,例如可舉出:N,N-二取代胺烷基(甲基)丙烯酸酯、N,N-二取代胺烷基(甲基)丙烯醯胺、N,N-二取代胺基芳香族乙烯化合物、具有吡啶基之單體等。 Examples of the monomer having a third-order amine group include N,N-disubstituted amine alkyl (meth) acrylate, N,N-disubstituted amine alkyl (meth) acrylamide, and N. An N-disubstituted amino aromatic vinyl compound, a monomer having a pyridyl group, and the like.
作為N,N-二取代胺基(甲基)丙烯酸酯,例如可舉出:N,N-二甲基胺甲基(甲基)丙烯酸酯、N,N-二甲基胺乙基(甲基)丙烯酸酯、N,N-二甲基胺丙基(甲基)丙烯酸酯、N,N-二甲基胺丁基(甲基)丙烯酸酯、N,N-二乙基胺乙基(甲基)丙烯酸酯、N,N-二乙基胺丙基(甲基)丙烯酸酯、N,N-二乙基胺丁基(甲基)丙烯酸酯、 N-甲基-N-乙基胺乙基(甲基)丙烯酸酯、N,N-二丙基胺乙基(甲基)丙烯酸酯、N,N-二丁基胺乙基(甲基)丙烯酸酯、N,N-二丁基胺丙基(甲基)丙烯酸酯、N,N-二丁基胺丁基(甲基)丙烯酸酯、N,N-二己基胺乙基(甲基)丙烯酸酯、N,N-二辛基胺乙基(甲基)丙烯酸酯等。在此等之中,較佳為N,N-二甲基胺乙基(甲基)丙烯酸酯、N,N-二乙基胺乙基(甲基)丙烯酸酯、及N,N-二丙基胺乙基(甲基)丙烯酸酯。 Examples of the N,N-disubstituted amino (meth) acrylate include N,N-dimethylaminomethyl (meth) acrylate and N,N-dimethylaminoethyl (A). Acrylate, N,N-dimethylaminopropyl (meth) acrylate, N,N-dimethylaminobutyl butyl (meth) acrylate, N,N-diethylaminoethyl ( Methyl) acrylate, N,N-diethylaminopropyl (meth) acrylate, N,N-diethylamine butyl (meth) acrylate, N-methyl-N-ethylamine ethyl (meth) acrylate, N,N-dipropylamine ethyl (meth) acrylate, N,N-dibutylamine ethyl (methyl) Acrylate, N,N-dibutylaminopropyl (meth) acrylate, N,N-dibutylamine butyl (meth) acrylate, N,N-dihexylamine ethyl (methyl) Acrylate, N,N-dioctylamine ethyl (meth) acrylate, and the like. Among these, N,N-dimethylaminoethyl (meth) acrylate, N,N-diethylamine ethyl (meth) acrylate, and N,N-dipropyl are preferred. Aminoethyl (meth) acrylate.
作為N,N-二取代胺基芳香族乙烯化合物,例如可舉出:N,N-二甲基胺乙基苯乙烯、N,N-二乙基胺乙基苯乙烯、N,N-二丙基胺乙基苯乙烯、N,N-二辛基胺乙基苯乙烯等。 Examples of the N,N-disubstituted amino-based aromatic vinyl compound include N,N-dimethylaminoethylstyrene, N,N-diethylamineethylstyrene, and N,N-di Propylamine ethyl styrene, N,N-dioctylamine ethyl styrene, and the like.
作為具有吡啶基之單體,例如可舉出:2-乙烯吡啶、4-乙烯吡啶、5-甲基-2-乙烯吡啶、5-乙基-2-乙烯吡啶等。在此等之中,較佳為2-乙烯吡啶、4-乙烯吡啶及此等之混合物。 Examples of the monomer having a pyridyl group include 2-vinylpyridine, 4-vinylpyridine, 5-methyl-2-vinylpyridine, and 5-ethyl-2-vinylpyridine. Among these, 2-vinylpyridine, 4-vinylpyridine, and mixtures thereof are preferred.
這些含胺基之單體,能夠分別單獨、或是組合2種以上來使用。 These amine group-containing monomers can be used singly or in combination of two or more kinds.
作為具有羥基之單體,是1分子中至少具有1個第1級、第2級或第3級羥基之單體。作為含羥基之單體的具體例,例如可舉出:羥甲基(甲基)丙烯酸酯、2-羥乙基(甲基)丙烯酸酯、2-羥丙基(甲基)丙烯酸酯、3-羥丙基(甲基)丙烯酸酯、3-氯-2-羥丙基(甲基)丙烯酸酯、3-苯氧基-2-羥丙基(甲基)丙烯酸酯、甘油單 (甲基)丙烯酸酯、羥丁基(甲基)丙烯酸酯、2-氯-3-羥丙基(甲基)丙烯酸酯、羥己基(甲基)丙烯酸酯、羥辛基(甲基)丙烯酸酯、羥甲基(甲基)丙烯醯胺、2-羥丙基(甲基)丙烯醯胺、3-羥丙基(甲基)丙烯醯胺、二-(乙二醇)伊康酸酯、二-(丙二醇)伊康酸酯、雙(2-羥丙基)伊康酸酯、雙(2-羥乙基)伊康酸酯、雙(2-羥乙基)富馬酸酯、雙(2-羥乙基)蘋果酸酯、2-羥乙基乙烯醚、羥甲基乙烯酮、烯丙醇等。在此等之中,較佳為羥甲基(甲基)丙烯酸酯、2-羥乙基(甲基)丙烯酸酯、2-羥丙基(甲基)丙烯酸酯、3-羥丙基(甲基)丙烯酸酯、3-苯氧基-2-羥丙基(甲基)丙烯酸酯、甘油單(甲基)丙烯酸酯、羥丁基(甲基)丙烯酸酯、羥己基(甲基)丙烯酸酯、羥辛基(甲基)丙烯酸酯、2-羥丙基(甲基)丙烯醯胺、及3-羥丙基(甲基)丙烯醯胺等。 The monomer having a hydroxyl group is a monomer having at least one first-stage, second-order or third-order hydroxyl group in one molecule. Specific examples of the hydroxyl group-containing monomer include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3 -Hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, glycerol (Meth) acrylate, hydroxybutyl (meth) acrylate, 2-chloro-3-hydroxypropyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate Ester, hydroxymethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide, 3-hydroxypropyl (meth) acrylamide, bis-(ethylene glycol) itaconate , di-(propylene glycol) itaconate, bis(2-hydroxypropyl)iscanate, bis(2-hydroxyethyl)concanate, bis(2-hydroxyethyl)fumarate, Bis(2-hydroxyethyl) malate, 2-hydroxyethyl vinyl ether, methylol ketene, allyl alcohol, and the like. Among these, preferred are hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (A) Acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate And hydroxyoctyl (meth) acrylate, 2-hydroxypropyl (meth) acrylamide, and 3-hydroxypropyl (meth) acrylamide.
這些具有羥基之單體,能夠分別單獨、或是組合2種以上來使用。 These monomers having a hydroxyl group can be used singly or in combination of two or more kinds.
含環氧基之單體,是1分子中至少具有1個環氧基之單體。作為含環氧基之單體,例如可舉出:(甲基)丙烯酸縮水甘油酯、3,4-環氧基丁基(甲基)丙烯酸酯、3,4-氧基環己基(甲基)丙烯酸酯、4-羥丁基丙烯酸酯縮水甘油醚、N-縮水甘油(甲基)丙烯醯胺、乙烯基縮水甘油醚、烯丙基縮水甘油醚、2-甲基烯丙基縮水甘油醚、3,4-環氧基-1-丁烯、3,4-環氧基-1-甲基-1-丁烯、3,4-環氧基-1-戊烯、3,4-環氧基-3-甲基-1-戊烯、5,6- 環氧基-1-己烯、一氧化乙烯環己烯、苯乙烯-p-縮水甘油醚、N-[4-(2,3-環氧基-1-側氧-3-苯丙烷-1-基)苯基]甲基丙烯醯胺等。其中,較佳為(甲基)丙烯酸縮水甘油酯。這些含環氧基之單體,能夠分別單獨、或是組合2種以上來使用。 The epoxy group-containing monomer is a monomer having at least one epoxy group in one molecule. Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-oxycyclohexyl (methyl). Acrylate, 4-hydroxybutyl acrylate glycidyl ether, N-glycidyl (meth) acrylamide, vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether , 3,4-epoxy-1-butene, 3,4-epoxy-1-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-ring Oxy-3-methyl-1-pentene, 5,6- Epoxy-1-hexene, ethylene oxide cyclohexene, styrene-p-glycidyl ether, N-[4-(2,3-epoxy-1-oxo-3-phenylpropane-1 -yl)phenyl]methacrylamide or the like. Among them, glycidyl (meth)acrylate is preferred. These epoxy group-containing monomers can be used singly or in combination of two or more kinds.
含烷氧矽烷基之單體,是1分子中至少具有1個烷氧矽烷基之單體。作為含烷氧矽烷基之單體,例如可舉出:(甲基)丙烯醯氧基甲基三甲氧基矽烷、(甲基)丙烯醯氧基甲基三乙氧基矽烷、β-(甲基)丙烯醯氧基乙基三甲氧基矽烷、β-(甲基)丙烯醯氧基乙基三乙氧基矽烷、γ-(甲基)丙烯醯氧基丙基三甲氧基矽烷、γ-(甲基)丙烯醯氧基丙基三乙氧基矽烷、γ-(甲基)丙烯醯氧基丙基三丙氧基矽烷、γ-(甲基)丙烯醯氧基丙基三丁氧基矽烷、γ-(甲基)丙烯醯氧基丙基甲基二甲氧基矽烷、γ-(甲基)丙烯醯氧基丙基乙基二甲氧基矽烷、γ-(甲基)丙烯醯氧基丙基己基二甲氧基矽烷、β-丙烯醯氧基乙基氧基甲基三甲氧基矽烷、γ-(β-丙烯醯氧基乙基氧基)丙基三甲氧基矽烷、γ-(γ-甲基丙烯醯氧基丙基氧基)丙基三甲氧基矽烷、乙烯基三正丁氧基矽烷、乙烯基三-三級丁氧基矽烷、乙烯基三-二級丁氧基矽烷、乙烯基三異丙氧基矽烷等。在此等之中,較佳為γ-(甲基)丙烯醯氧基丙基三乙氧基矽烷、γ-(甲基)丙烯醯氧基丙基三丙氧基矽烷、γ-(甲基)丙烯醯氧基丙基三丁氧基矽烷、γ-(β-丙烯醯氧基乙基氧基)丙基三 丁氧基矽烷、γ-(γ-甲基丙烯醯氧基丙基氧基)丙基三丁氧基矽烷、及乙烯基烷氧矽烷類;更佳為γ-(甲基)丙烯醯氧基丙基三丙氧基矽烷、γ-(甲基)丙烯醯氧基丙基三丁氧基矽烷、及乙烯基三-三級丁氧基矽烷。這些含烷氧矽烷基之單體,能夠分別單獨、或是組合2種以上來使用。 The alkoxyalkyl group-containing monomer is a monomer having at least one alkoxyalkyl group in one molecule. Examples of the alkoxyalkyl group-containing monomer include (meth)acryloxymethyltrimethoxydecane, (meth)acryloxymethyltriethoxydecane, and β-(A). Base) propylene methoxyethyl trimethoxy decane, β-(meth) propylene methoxyethyl triethoxy decane, γ-(meth) propylene methoxy propyl trimethoxy decane, γ- (Meth)acryloxypropyltriethoxydecane, γ-(meth)acryloxypropyltripropoxydecane, γ-(meth)acryloxypropyltributoxy矽, γ-(meth) propylene methoxy propyl methyl dimethoxy decane, γ-(methyl) propylene methoxy propyl ethyl dimethoxy decane, γ-(methyl) propylene oxime Oxypropyl propyl dimethoxy decane, β-propylene methoxyethyloxymethyl trimethoxy decane, γ-(β-propylene methoxyethyloxy) propyl trimethoxy decane, γ -(γ-Methyl propylene methoxypropyloxy) propyl trimethoxy decane, vinyl tri-n-butoxy decane, vinyl tri-tertiary butoxy decane, vinyl tri- or 2-butoxy Base decane, vinyl triisopropoxy decane, and the like. Among these, γ-(meth)acryloxypropyltriethoxydecane, γ-(meth)acryloxypropyltripropoxydecane, γ-(methyl group) are preferred. ) acryloxypropyl tributoxy decane, γ-(β-propylene methoxyethyloxy) propyl three Butoxy oxane, γ-(γ-methacryloxypropyloxy)propyl tributoxy decane, and vinyl alkoxy oxane; more preferably γ-(meth) propylene fluorenyloxy Propyltripropoxydecane, γ-(meth)acryloxypropyl tributoxydecane, and vinyl tri-tertiary butoxydecane. These alkoxyalkylene group-containing monomers can be used singly or in combination of two or more kinds.
作為具有胺基或亞胺基之聚合物的水溶液(d)的聚合物,共軛二烯系共聚物被屏除在外。作為適合的聚合物,可舉出將伸乙亞胺、乙烯胺、二烯丙基二甲胺、二烯丙基甲胺、脒、雙氰胺、具有胺基之丙烯酸酯、具有胺基之甲基丙烯酸酯及乙烯吡啶中的至少一種聚合而成之同元聚合物、或與其他單體之共聚物。 As the polymer of the aqueous solution (d) having an amine group or an imine group, the conjugated diene copolymer is screened off. Examples of suitable polymers include ethylene diamine, vinylamine, diallyldimethylamine, diallylmethylamine, hydrazine, dicyandiamide, an acrylate having an amine group, and an amine group. a homopolymer polymerized by at least one of methacrylate and vinyl pyridine or a copolymer with other monomers.
作為具體之例,就伸乙亞胺系的聚合物而言,可舉出日本ZEON股份有限公司的「EPOMIN」(註冊商標);就脒系與具有胺基之丙烯酸酯之共聚物、或具有胺基之甲基丙烯酸酯系聚合物而言,可舉出HYMO股份有限公司的「Himoloc ZP、MP、MS系列」(註冊商標)。就二烯丙基二甲胺、二烯丙基甲胺系的聚合物而言,可舉出NITTOBO MEDICAL股份有限公司的「PAS」(註冊商標)的系列;就雙氰胺系聚合物而言,可舉出雙氰胺-聚烯烴聚胺系聚縮合物、或雙氰胺-甲醛聚縮合物。當然,這些聚合物並不限定於特定的製造商產品。 Specific examples of the ethyleneimine-based polymer include "EPOMIN" (registered trademark) of Japan ZEON Co., Ltd.; a copolymer of an anthracene and an acrylate having an amine group, or The "metholoc ZP, MP, MS series" (registered trademark) of HYMO Co., Ltd. is mentioned as an amino group methacrylate type polymer. Examples of the polymer of diallyldimethylamine and diallylamine are "PAS" (registered trademark) series of NITTOBO MEDICAL Co., Ltd.; Examples thereof include a dicyandiamide-polyolefin polyamine polycondensate or a dicyandiamide-formaldehyde polycondensate. Of course, these polymers are not limited to a particular manufacturer's product.
又,亦能使用具有胺基或亞胺基之天然水溶性高分子化合物。例如可舉出膠、明膠、膠原胜肽、酪蛋白、幾丁聚糖等,任一種都可以使用市售物。 Further, a natural water-soluble polymer compound having an amine group or an imine group can also be used. For example, a gel, gelatin, collagen peptide, casein, chitosan, etc. can be mentioned, and a commercial item can be used for either.
作為具體之例,就明膠而言是Nippi股份有限公司的牛鹼處理明膠ST1(註冊商標)或豬酸處理明膠AP-30(註冊商標);就膠原胜肽而言是Nippi股份有限公司的膠原胜肽FCP-AK-G(註冊商標)或Gelita Sol系列之LDA aggl(註冊商標)、Nacalai Tesque股份有限公司的酪蛋白(牛奶製造)(註冊商標)、明治Food Materia股份有限公司的明治FM膠原蛋白、三愛製藥股份有限公司的三愛幾丁聚糖(註冊商標)等。當然,這些天然水溶性高分子化合物並不限定於特定之製造商產品。 As a specific example, in the case of gelatin, it is a nicotine-treated gelatin ST1 (registered trademark) of Nippi Co., Ltd. or a porcine acid-treated gelatin AP-30 (registered trademark); in the case of a collagen peptide, it is a collagen of Nippi Co., Ltd. Peptide FCP-AK-G (registered trademark) or LDA aggl (registered trademark) of Gelita Sol series, casein (milk manufacturing) of Nacalai Tesque Co., Ltd. (registered trademark), Meiji FM collagen of Meiji Food Materia Co., Ltd. Protein, Sanai Chitosan (registered trademark) of Sanai Pharmaceutical Co., Ltd., etc. Of course, these natural water-soluble polymer compounds are not limited to a specific manufacturer's product.
一種二氧化矽填充橡膠組成物的製造方法,是在將乳化狀態的橡膠(a)和水分散二氧化矽漿料(b)混合並進行共凝固、乾燥,來製造二氧化矽填充橡膠組成物時,預先使水分散二氧化矽漿料(b)與乳化狀共軛二烯系橡膠(c)和具有胺基或亞胺基之聚合物的水溶液(d)混合、接觸後,與乳化狀態的橡膠(a)進行共凝固。藉由預先利用乳化狀共軛二烯系橡膠(c)和具有胺基或亞胺基之聚合物的水溶液(d)來處理水分散二氧化矽漿料(b)的表面,使與乳化狀態的橡膠(a)的共凝固變得容易,且漿料中的二氧化矽、乳液中的橡膠粒子,確實地成為二氧化矽填充橡膠組成物。二氧化矽和橡膠的回收率 提升,所生成之二氧化矽和橡膠的顆粒的粒徑也能調整到適合利用帶式乾燥機等來進行乾燥。 A method for producing a cerium oxide-filled rubber composition by mixing an emulsified rubber (a) and a water-dispersed cerium oxide slurry (b), co-coagulation, and drying to produce a cerium oxide-filled rubber composition At the same time, the water-dispersed cerium oxide slurry (b) is mixed with and contacted with the emulsified conjugated diene rubber (c) and the aqueous solution (d) having an amine group or an imine group, and then emulsified. The rubber (a) is co-coagulated. The surface of the water-dispersed ceria slurry (b) is treated with an emulsified state by using an aqueous solution (d) of an emulsified conjugated diene rubber (c) and a polymer having an amine group or an imine group in advance. The co-coagulation of the rubber (a) is easy, and the ceria in the slurry and the rubber particles in the emulsion are surely a ceria-filled rubber composition. Recovery of cerium oxide and rubber The particle size of the produced cerium oxide and rubber particles can be adjusted to be suitable for drying by a belt dryer or the like.
作為利用乳化狀共軛二烯系橡膠(c)和具有胺基或亞胺基之聚合物的水溶液(d)來處理水分散二氧化矽漿料(b)的表面的方法,從作業效率等的觀點而言,較佳是在水分散二氧化矽漿料(b)中添加乳化狀共軛二烯系橡膠(c),之後再添加具有胺基或亞胺基之聚合物的水溶液(d)的順序。當然,亦可改變添加的順序,或(c)和(d)幾乎同時添加。 A method of treating the surface of the water-dispersed ceria slurry (b) with an aqueous solution (d) of an emulsified conjugated diene rubber (c) and a polymer having an amine group or an imine group, from work efficiency, etc. In view of the above, it is preferred to add an emulsified conjugated diene rubber (c) to the water-dispersed cerium oxide slurry (b), followed by adding an aqueous solution of an amine group or an imine group (d) )order of. Of course, the order of addition can also be changed, or (c) and (d) can be added almost simultaneously.
作為將水分散二氧化矽漿料(b)和乳化狀共軛二烯系橡膠(c)、與具有胺基或亞胺基之聚合物的水溶液(d)進行混合、接觸的方法,有藉由攪拌葉片所實行的混合或施加由均質混合機所產生的高剪切力的混合方法。水分散二氧化矽漿料(b)的粒徑小時,藉由攪拌葉片所實行的混合就已經足夠,但稍微粗的水分散二氧化矽漿料(b)的時候是併用高剪切力的均質混合機為佳。 As a method of mixing and contacting the water-dispersed ceria slurry (b), the emulsified conjugated diene rubber (c), and the aqueous solution (d) having a polymer having an amine group or an imine group, there is a method of borrowing A mixing method performed by agitating blades or applying a high shear force generated by a homomixer. When the particle size of the water-dispersed cerium oxide slurry (b) is small, the mixing by the stirring blade is sufficient, but the slightly coarse water-dispersed cerium oxide slurry (b) is combined with high shear force. A homomixer is preferred.
作為水分散二氧化矽漿料(b)的平均粒徑,較佳為20μm以下,並且100μm以上的二氧化矽粒子較佳為5%以下。若100μm以上的二氧化矽粒子超過5%,由於會發生加硫橡膠的機械物性的低落而不佳。 The average particle diameter of the water-dispersed ceria slurry (b) is preferably 20 μm or less, and the ceria particles of 100 μm or more are preferably 5% or less. If the cerium oxide particles of 100 μm or more exceed 5%, the mechanical properties of the vulcanized rubber may be lowered.
二氧化矽(b)和乳化狀共軛二烯系橡膠(c)、具有胺基或亞胺基之聚合物的水溶液(d)的比例,相對於乾燥狀態的二氧化矽100重量份,將乳化狀共軛二烯系橡膠(c)以固體含量換算是使用0.1重量份到20重量份; 將具有胺基或亞胺基之聚合物的水溶液(d)相對於乾燥二氧化矽100重量份,以固體含量換算是使用0.1重量份到5重量份。 The ratio of the cerium oxide (b) and the emulsified conjugated diene rubber (c), the aqueous solution (d) of the polymer having an amine group or an imine group, relative to 100 parts by weight of the cerium oxide in a dry state, The emulsified conjugated diene rubber (c) is used in an amount of 0.1 parts by weight to 20 parts by weight in terms of solid content; The aqueous solution (d) of the polymer having an amine group or an imine group is used in an amount of from 0.1 part by weight to 5 parts by weight per 100 parts by weight of the dry cerium oxide.
另外,本說明書中的「份」全都是「重量份」,以下將「重量份」以「份」簡稱。 In addition, the "parts" in this specification are all "parts by weight", and the "parts by weight" is abbreviated as "parts" below.
乳化狀共軛二烯系橡膠(c)的量,以固體含量換算,若比0.1份還要少,則凝固時的顆粒的粒徑會變細,若比20份還要多,則加硫時的橡膠物性會降低。 When the amount of the emulsified conjugated diene rubber (c) is less than 0.1 part, the particle size of the particles during solidification becomes finer, and if more than 20 parts, sulfur is added. The rubber properties will be reduced.
具有胺基或亞胺基之聚合物的水溶液(d)的量,以固體含量換算,若比0.1份還要少,則與乳化狀態的橡膠(a)進行共凝固時的二氧化矽回收率會降低。又,具有胺基或亞胺基之聚合物的水溶液(d)的量,以固體含量換算,若比5份還要多,則在加硫時會有引起過早硫化的情況。 The amount of the aqueous solution (d) of the polymer having an amine group or an imine group is less than 0.1 part, and the amount of the cerium oxide recovered when co-coagulated with the rubber (a) in an emulsified state. Will decrease. Further, the amount of the aqueous solution (d) having a polymer of an amine group or an imine group is more than 5 parts in terms of the solid content, and may cause premature vulcanization during vulcanization.
作為使乳化狀態的橡膠(a)、與預先已混合、接觸之水分散二氧化矽、乳化共軛二烯系橡膠、具有胺基或亞胺基之聚合物的混合物混合並進行共凝固的方式,可為批次式亦可為連續式。兩者的混合,能夠先利用藉由一般的攪拌葉片所實行的混合來簡單混合,接著藉由添加食鹽等之鹽及稀硫酸等之酸來進行共凝固。 A method in which a rubber (a) in an emulsified state is mixed with a mixture of a water-dispersed cerium oxide, an emulsified conjugated diene rubber, and an amine group or an imine group polymer which have been previously mixed and brought into contact, and co-coagulated. It can be batch or continuous. The mixing of the two can be carried out by simple mixing by mixing by a general stirring blade, followed by co-coagulation by adding a salt such as salt or an acid such as dilute sulfuric acid.
共凝固時添加的食鹽,較佳為盡可能少加,最佳為只用酸來使之凝固。又,共凝固時的溫度較佳為50到60℃。又,共凝固後,較佳是利用水來將顆粒洗淨並去除橡膠中所包含的肥皂、鹽或酸等。 The salt to be added during co-coagulation is preferably added as little as possible, and it is preferred to use only an acid to solidify it. Further, the temperature at the time of co-coagulation is preferably from 50 to 60 °C. Further, after co-coagulation, it is preferred to use water to wash the particles and remove soap, salt or acid contained in the rubber.
在本發明之製造方法,由於有將具有胺基或亞胺基之聚合物的水溶液(d)進行混合、接觸,故藉由微量食鹽的添加,也有共凝固會進展,洗淨處理亦變得容易的優點。 In the production method of the present invention, since the aqueous solution (d) having a polymer having an amine group or an imine group is mixed and contacted, co-coagulation progresses due to the addition of a small amount of salt, and the washing treatment also becomes Easy advantage.
藉由共凝固而產生的顆粒的粒徑,是以成為5mm到15mm的方式來調節攪拌和pH值。顆粒的粒徑若變細則從狹縫脫落的顆粒數量會變多而不佳。又,若比15mm還要大則乾燥會不夠充分而不佳。 The particle size of the particles produced by co-coagulation is adjusted so that the stirring and pH are 5 mm to 15 mm. If the particle size of the particles is changed, the number of particles falling off the slit may become insufficient. Also, if it is larger than 15mm, the drying will be insufficient and not good.
在連續方式的共凝固中,與批次方式的共凝固相比,粒形的分布會變廣。PH值較佳為4到7,在4以下則因酸所致之設備的腐蝕或生成之顆粒的粒徑變細而不佳。 In the continuous mode of co-coagulation, the distribution of the grain shape becomes wider than the co-coagulation of the batch mode. The pH is preferably from 4 to 7, and if it is 4 or less, the corrosion of the device due to the acid or the particle size of the resulting particles may become fine.
顆粒的乾燥,有像是帶式乾燥機般地對顆粒吹送熱風來乾燥的方法;像是微波照射乾燥器或機械式的壓搾機、伸幅器或加熱輥般地利用機械性剪切力、熱和壓力來使之乾燥的方法。任何一種乾燥方法皆可,又亦可為像是在帶式乾燥機之後設置加熱輥的併用設備。 Drying of the granules, such as a belt dryer, blowing hot air to the granules for drying; such as a microwave irradiation dryer or a mechanical press, a stretcher or a heated roll, utilizing mechanical shearing force, Heat and pressure to dry it. Any drying method can be used, and it can also be a combined device such as a heating roller after the belt dryer.
藉由將在本發明之二氧化矽填充橡膠組成物中,添加了其他固形橡膠、碳黑等填充劑、油等塑化劑、矽烷偶合劑、加硫助劑或加硫劑而成之橡膠組成物,進行混煉、成形、加硫,能夠成為優異的加硫橡膠。 By adding the rubber composition such as solid rubber or carbon black to the cerium oxide-filled rubber composition of the present invention, a rubber such as a plasticizer such as oil, a decane coupling agent, a vulcanization aid or a vulcanizing agent is added. The composition is kneaded, formed, and vulcanized, and can be an excellent vulcanized rubber.
作為其他固形橡膠,可舉出溶液聚合苯乙烯丁二烯橡膠、丁二烯橡膠、天然橡膠、合成天然橡膠、丙烯腈丁二烯橡膠、氯丁二烯橡膠、乙烯丙烯橡膠等。 Examples of the other solid rubber include solution-polymerized styrene butadiene rubber, butadiene rubber, natural rubber, synthetic natural rubber, acrylonitrile butadiene rubber, chloroprene rubber, and ethylene propylene rubber.
在本發明之二氧化矽填充橡膠組成物中添加交聯劑等而成之橡膠組成物,以輪胎胎面、胎面基部、胎體、外胎側面、胎唇部分等之輪胎用途為首,也能夠使用在防振橡膠、皮帶、軟管之其他的工業品等用途上,但特別適合使用在輪胎胎面用橡膠上。 A rubber composition obtained by adding a crosslinking agent or the like to the cerium oxide-filled rubber composition of the present invention can be used for tire applications such as a tire tread, a tread base, a carcass, a tire side surface, and a bead portion. It is used in applications such as anti-vibration rubber, belts, and hoses, but it is particularly suitable for use on rubber for tire treads.
藉由在本發明之二氧化矽填充橡膠組成物中添加碳黑,能夠改善橡膠的抗靜電性能或機械性質。作為添加的碳黑,例如能夠使用爐法碳黑、乙炔黑、熱裂碳黑、槽法碳黑、及石墨等。在此等之中,特佳為爐法碳黑,作為其具體例,可舉出SAF、ISAF、ISAF-HS、ISAF-LS、IISAF-HS、HAF、HAF-HS、HAF-LS、FEF等品級。這些碳黑,能夠分別單獨、或是組合2種以上來使用。 By adding carbon black to the cerium oxide filling rubber composition of the present invention, the antistatic property or mechanical property of the rubber can be improved. As the carbon black to be added, for example, furnace black, acetylene black, thermal black, channel black, graphite, or the like can be used. Among these, the furnace carbon black is particularly preferable, and specific examples thereof include SAF, ISAF, ISAF-HS, ISAF-LS, IISAF-HS, HAF, HAF-HS, HAF-LS, FEF, and the like. level. These carbon blacks can be used singly or in combination of two or more.
相對於二氧化矽填充橡膠組成物的橡膠成分100份,碳黑的添加量為1~50份,較佳為3~30份。藉由添加碳黑,能夠提升橡膠組成物的抗靜電性能和耐候性能等。添加量若到50份以上則由於組成物的發熱變大,作為交聯橡膠的動態特性會降低而不佳。 The carbon black is added in an amount of from 1 to 50 parts, preferably from 3 to 30 parts, per 100 parts of the rubber component of the cerium oxide-filled rubber composition. By adding carbon black, the antistatic property and weather resistance of the rubber composition can be improved. When the amount is 50 parts or more, the heat generation of the composition becomes large, and the dynamic properties of the crosslinked rubber are lowered.
藉由在本發明之二氧化矽填充橡膠組成物中添加油等塑化劑,能夠輕易進行成形加工。作為添加之油等塑化劑,能夠使用於橡膠工業中一般被使用的填充油(extender oil),可舉出石蠟系填充油、芳香族系填充油、環烷系填充油或液狀橡膠等。 By adding a plasticizer such as oil to the cerium oxide-filled rubber composition of the present invention, the molding process can be easily performed. As a plasticizer such as an oil to be added, an extender oil which is generally used in the rubber industry can be used, and examples thereof include a paraffin-based extender oil, an aromatic filler oil, a naphthenic filler oil, or a liquid rubber. .
填充油的流動點,較佳為-20~50℃,更佳為-10~30℃。只要在此範圍,可獲得易於伸展,且拉伸特性和低發熱性之平衡性優異的橡膠組成物。填充油之合適的芳香碳含量(CA%,庫爾茲分析法),較佳為20%以上,更佳為25%以上,又,填充油之合適的石蠟碳含量(CP%),較佳為55%以下,更佳為45%。若CA%太小,或CP%太大,則拉伸特性會變得不充分。填充油之中的多環芳香族系化合物的含量,較佳為未達3%。此含量,是藉由IP346法(英國石油學會(The Institute of Petroleum)之檢查方法)來測定。 The flow point of the filling oil is preferably -20 to 50 ° C, more preferably -10 to 30 ° C. Within this range, a rubber composition which is easy to stretch and has excellent balance between tensile properties and low heat build-up property can be obtained. A suitable aromatic carbon content (CA%, Kurz analysis) of the extender oil, preferably 20% or more, more preferably 25% or more, and a suitable paraffin carbon content (CP%) of the extender oil, preferably It is 55% or less, more preferably 45%. If CA% is too small, or CP% is too large, the tensile properties may become insufficient. The content of the polycyclic aromatic compound in the extender oil is preferably less than 3%. This content is determined by the IP346 method (the inspection method of The Institute of Petroleum).
作為塑化劑,除了填充油以外,也能夠使用液狀橡膠。作為液狀橡膠,可舉出液狀聚異戊二烯橡膠、羧基改性液狀聚異戊二烯橡膠、液狀聚丁二烯橡膠、羧基改性液狀聚丁二烯橡膠、羥基改性液狀聚丁二烯橡膠、液狀丙烯腈丁二烯共聚合橡膠、液狀苯乙烯丁二烯共聚合橡膠、液狀苯乙烯異戊二烯共聚合橡膠等。 As the plasticizer, a liquid rubber can be used in addition to the filling oil. Examples of the liquid rubber include liquid polyisoprene rubber, carboxyl modified liquid polyisoprene rubber, liquid polybutadiene rubber, carboxyl modified liquid polybutadiene rubber, and hydroxyl group modification. Liquid polybutadiene rubber, liquid acrylonitrile butadiene copolymerized rubber, liquid styrene butadiene copolymerized rubber, liquid styrene isoprene copolymerized rubber, and the like.
相對於二氧化矽填充橡膠組成物的橡膠成分100份,塑化劑的含量較佳為1~50份,更佳為3~30份。塑化劑的含量若在此範圍,則調配了二氧化矽的調配物黏度為適度。 The content of the plasticizer is preferably from 1 to 50 parts, more preferably from 3 to 30 parts, per 100 parts by weight of the rubber component of the cerium oxide-filled rubber composition. If the content of the plasticizer is within this range, the viscosity of the formulation in which the cerium oxide is formulated is moderate.
藉由在本發明之二氧化矽填充橡膠組成物中添加矽烷偶合劑,能夠改善橡膠的機械性質或耐久性能。作為添加之偶合劑,可舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、γ-縮水甘油氧基丙基甲氧基矽烷、γ- 甲基丙烯醯氧基丙基甲氧基矽烷、γ-胺丙基甲氧基矽烷、N-β(胺乙基)γ-胺丙基甲氧基矽烷、N-苯基-γ-胺丙基甲氧基矽烷、γ-巰基丙基甲氧基矽烷、四硫化雙(γ-三乙氧基矽烷基丙基)、二硫化雙(γ-三乙氧基矽烷基丙基)、三乙氧基矽烷基丙基異氰酸酯、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-(聚乙烯胺基)-丙基三甲氧基矽烷、N-β-(胺乙基)-γ-胺丙基三甲氧基矽烷、N’-乙烯基苄基-N-三甲氧基矽烷基丙基乙二胺鹽等矽烷偶合劑。這些可單獨使用,亦可組合2種以上來使用。 By adding a decane coupling agent to the cerium oxide filling rubber composition of the present invention, the mechanical properties or durability of the rubber can be improved. As the coupling agent to be added, vinyl trimethoxy decane, vinyl triethoxy decane, γ-glycidoxypropyl methoxy decane, γ- may be mentioned. Methyl propylene methoxypropyl methoxy decane, γ-aminopropyl methoxy decane, N-β (aminoethyl) γ-aminopropyl methoxy decane, N-phenyl-γ-amine C Methoxy decane, γ-mercaptopropyl methoxy decane, bis(γ-triethoxydecylpropyl) tetrasulfide, bis(γ-triethoxydecylpropyl) disulfide, triethyl Oxyalkyl propyl isocyanate, vinyl triethoxy decane, vinyl trimethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, γ-methyl propylene methoxy propyl methyl Dimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-(polyvinylamino)-propyltrimethoxydecane, N- A decane coupling agent such as β-(aminoethyl)-γ-aminopropyltrimethoxydecane or N'-vinylbenzyl-N-trimethoxydecylpropylethylenediamine salt. These may be used alone or in combination of two or more.
在本發明之二氧化矽填充橡膠組成物中所添加的交聯劑和交聯助劑,能夠使用於膠調配數據手冊(日刊工業新聞發行,1987年4月)之NR、SBR、NBR、IR及BR的項目中所例示的交聯劑或交聯助劑。 The crosslinking agent and crosslinking assistant added to the cerium oxide filling rubber composition of the present invention can be used in the NR, SBR, NBR, IR of the glue dispensing data sheet (Nikkei Industry News Release, April 1987). And the crosslinking agent or crosslinking assistant exemplified in the BR project.
作為具體的交聯劑,可舉出:硫黃、金屬氧化物、4,4’-二硫嗎啉、多硫甲硫碳醯胺(thiuram polysulfide)、2-(嗎啉基)苯并噻唑、有機化氧化物、苯醌二肟、烷基酚樹脂、胺化合物,在這些之中最佳為硫黃。 Specific examples of the crosslinking agent include sulfur, metal oxide, 4,4'-dithiomorpholine, thiuram polysulfide, and 2-(morpholinyl)benzothiazole. An organic oxide, a benzoquinone, an alkylphenol resin, or an amine compound, among which sulfur is preferred.
具體的交聯助劑可舉出:硬脂酸、氧化鋅、胍化合物、硫脲化合物、噻唑化合物、亞磺醯胺化合物、甲硫碳醯胺 (thiuram)化合物、二硫胺甲酸鹽、黃原酸鹽化合物、聚乙二醇等。 Specific crosslinking aids include stearic acid, zinc oxide, cerium compounds, thiourea compounds, thiazole compounds, sulfinamide compounds, and methyl carbamide. (thiuram) compound, dithiocarbamate, xanthate compound, polyethylene glycol, and the like.
本發明之橡膠組成物,能夠使用輥機、密閉混合機等混煉機進行混煉。成形加工後,進行加硫,以輪胎胎面、胎面基部、胎體、外胎側面、胎唇部分等之輪胎用途為首,也能夠使用在防振橡膠、皮帶、軟管之其他的工業品等用途,但特別適合使用在輪胎胎面用橡膠上。 The rubber composition of the present invention can be kneaded by using a kneader such as a roll mill or a closed mixer. After the forming process, the vulcanization is carried out, and the tires such as the tire tread, the tread base, the carcass, the side surface of the tire, and the bead portion are used, and other industrial products such as anti-vibration rubber, belts, and hoses can be used. Use, but especially suitable for use on rubber for tire tread.
本發明之充氣輪胎,是使用本發明之橡膠組成物並藉由一般的方法所製造而成。又,視其需要,如同上述般,含有各種藥品之本發明之橡膠組成物在未加硫的階段擠壓成胎面用構件進行加工,在輪胎成形機上藉由一般的方法黏貼而成形,成形為生輪胎(green tire)。將此生輪胎在加硫機中進行加熱加壓,而獲得輪胎。如此進行而獲得之本發明的充氣輪胎,在低燃料消耗性、破壞特性及耐磨損性上優異,而且因為該橡膠組成物的加工性良好,所以在生產性上也優異。 The pneumatic tire of the present invention is produced by using a rubber composition of the present invention by a general method. Further, depending on the necessity, the rubber composition of the present invention containing various chemicals is extruded into a tread member at a stage where no sulfur is added, and is formed by being adhered to a tire molding machine by a general method. Formed into a green tire. The raw tire was heated and pressurized in a vulcanizer to obtain a tire. The pneumatic tire of the present invention obtained in this manner is excellent in low fuel consumption, fracture characteristics, and abrasion resistance, and is excellent in productivity because of good workability of the rubber composition.
為了更具體地說明本發明,於以下舉出實施例及比較例來說明,但本發明並不限定於這些實施例。另外,實施例及比較例中的各種物性,是藉由下列之方法來測定。又,「份」為「重量份」。 In order to explain the present invention more specifically, the following examples and comparative examples are described, but the present invention is not limited to these examples. In addition, various physical properties in the examples and comparative examples were measured by the following methods. Also, "parts" are "parts by weight".
(1)二氧化矽的一次粒徑 (1) Primary particle size of cerium oxide
藉由穿透式電子顯微鏡來測定。 It was measured by a transmission electron microscope.
(2)比表面積-藉由氮氣吸附法所實行的比表面積(SBET)之測定 (2) Specific surface area - Determination of specific surface area (SBET) by nitrogen adsorption method
將濕式二氧化矽餅放入乾燥器(120℃)進行乾燥後,使用Micromeritics公司製造的ASAP 2010(型號)來測定氮氣吸附量,並採用相對壓0.2中的1點法的值。 The wet ceria cake was placed in a desiccator (120 ° C) and dried, and then the amount of nitrogen adsorption was measured using ASAP 2010 (model) manufactured by Micromeritics Co., Ltd., and the value of the one-point method in the relative pressure of 0.2 was used.
(3)共聚物中的苯乙烯單位量:依照JIS K6383(折射率法)來測定。 (3) Styrene unit amount in the copolymer: Measured in accordance with JIS K6383 (refractive index method).
(4)二氧化矽含有率 (4) Ceria content
將含有二氧化矽之橡膠組成物於500℃進行燃燒,從殘留灰分求出二氧化矽量。 The rubber composition containing cerium oxide was burned at 500 ° C, and the amount of cerium oxide was determined from the residual ash.
(5)300%模數、拉伸強度、伸展 (5) 300% modulus, tensile strength, stretching
依照JIS K6253之拉伸應力試驗法來測定。 It was measured in accordance with the tensile stress test method of JIS K6253.
(6)耐磨損性 (6) Wear resistance
使用亞克朗式磨損試驗機(Akron abrasion tester),顯示出預摩擦1000次後的重量和正式摩擦1000次後的重量的減量。減量越少者耐磨損性越優異。 Using an Akron abrasion tester, the weight after 1000 rubs and the weight loss after 1000 rubs were shown. The smaller the amount of reduction, the more excellent the abrasion resistance.
在附有攪拌機之耐壓反應器中加入水1260g、歧化松香酸鉀33g、萘磺酸-甲醛縮合物的鈉鹽0.7g、氯化鉀3.5g、四乙烯戊胺0.7g、苯乙烯161g、丁二烯504g及第三級十二基硫醇1.7g。 In a pressure-resistant reactor equipped with a stirrer, 1260 g of water, 33 g of disproportionated potassium rosinate, 0.7 g of sodium salt of a naphthalenesulfonic acid-formaldehyde condensate, 3.5 g of potassium chloride, 0.7 g of tetraethylenepentylamine, and 161 g of styrene were added. 504 g of butadiene and 1.7 g of tertiary dodecyl mercaptan.
溫度下降到5℃為止後,注入異丙苯過氧化氫1.4g和苯乙烯35g開始聚合。 After the temperature was lowered to 5 ° C, 1.4 g of cumene hydroperoxide and 35 g of styrene were injected to initiate polymerization.
在每一定時間內取出一部分水溶液,測定固體含量,求出聚合轉化率。 A part of the aqueous solution was taken out every certain period of time, and the solid content was measured to determine the polymerization conversion ratio.
聚合轉化率若達約60%,就注入35g的二甲基二硫胺甲酸鈉10%水溶液,停止聚合。對聚合而成的SBR乳液吹入蒸氣來驅逐出未反應單體,作為試驗用SBR乳液,將固體含量濃度設在20%。分子量Mw為37萬,Mw/Mn=3.8,結合苯乙烯量22.8%,慕尼黏度50,SBR乳膠的粒徑為100nm。 When the polymerization conversion ratio is about 60%, 35 g of a 10% aqueous solution of sodium dimethyldithiocarbamate is injected to terminate the polymerization. The polymerized SBR emulsion was blown with steam to drive off unreacted monomers, and the test SBR emulsion was set to have a solid content concentration of 20%. The molecular weight Mw was 370,000, Mw/Mn was 3.8, the bound styrene amount was 22.8%, the Mooney viscosity was 50, and the SBR latex had a particle diameter of 100 nm.
在附有攪拌機之耐壓反應器中加入水1260g、歧化松香酸鉀33g、萘磺酸甲醛縮合物的鈉鹽0.7g、氯化鉀3.5g、四乙烯戊胺0.7g、苯乙烯161g、丁二烯504g、甲基丙烯酸二甲基胺乙酯10g及第三級十二基硫醇1.7g。 In a pressure-resistant reactor equipped with a stirrer, 1260 g of water, 33 g of disproportionated potassium rosinate, 0.7 g of sodium salt of a naphthalenesulfonic acid formaldehyde condensate, 3.5 g of potassium chloride, 0.7 g of tetraethylenepentylamine, 161 g of styrene, and butyl were added. 504 g of a diene, 10 g of dimethylaminoethyl methacrylate, and 1.7 g of a tertiary dodecyl mercaptan.
溫度下降到5℃為止後,注入異丙苯過氧化氫1.4g和苯乙烯35g開始聚合。 After the temperature was lowered to 5 ° C, 1.4 g of cumene hydroperoxide and 35 g of styrene were injected to initiate polymerization.
在每一定時間內取出一部分水溶液,測定固體含量,求出聚合轉化率。 A part of the aqueous solution was taken out every certain period of time, and the solid content was measured to determine the polymerization conversion ratio.
6.5小時後,聚合轉化率達約60%,注入35g的二甲基二硫胺甲酸鈉10%水溶液,停止聚合。對聚合而成的SBR乳液吹入蒸氣將未反應單體去除,將橡膠成分濃度設在20%。分子量Mw為28萬,Mw/Mn=3.5,結合苯乙烯量22.5%,慕尼黏度35,SBR乳膠的粒徑為90nm。 After 6.5 hours, the polymerization conversion rate was about 60%, and 35 g of a 10% aqueous solution of sodium dimethyldithiocarbamate was injected to terminate the polymerization. The unreacted monomer was removed by blowing steam into the polymerized SBR emulsion, and the rubber component concentration was set to 20%. The molecular weight Mw was 280,000, Mw/Mn was 3.5, the bound styrene amount was 22.5%, the Mooney viscosity was 35, and the SBR latex had a particle diameter of 90 nm.
在附有溫度調節機之1m3不銹鋼製反應容器中加入矽酸鈉水溶液(SiO2濃度:10g/L,莫耳比:SiO2/Na2O=3.41)230L,昇溫至85℃。其次,花費120分鐘來同時加入22重量%硫酸73L和矽酸鈉水溶液(SiO2濃度:90g/L,莫耳比:SiO2/Na2O=3.41)440L。10分鐘熟成後,花費15分鐘加入22重量%硫酸16L。上述反應是將反應液溫度維持在85℃,經常一邊攪拌反應液來進行,最終獲得了反應液之pH值為3.2的二氧化矽漿料。將此二氧化矽漿料用壓濾機進行水洗、過濾,獲得二氧化矽固體含量為20%的二氧化矽餅。 To a 1 m 3 stainless steel reaction vessel equipped with a temperature adjuster, 230 L of an aqueous solution of sodium citrate (SiO 2 concentration: 10 g/L, molar ratio: SiO 2 /Na 2 O = 3.41) was added, and the temperature was raised to 85 °C. Next, it took 120 minutes to simultaneously add 440 L of 22 wt% sulfuric acid 73 L and sodium citrate aqueous solution (SiO 2 concentration: 90 g/L, molar ratio: SiO 2 /Na 2 O = 3.41). After 10 minutes of ripening, it took 15 minutes to add 22% by weight of sulfuric acid 16L. In the above reaction, the temperature of the reaction liquid was maintained at 85 ° C, and the reaction liquid was often stirred while stirring, and finally a cerium oxide slurry having a pH of 3.2 in the reaction liquid was obtained. This cerium oxide slurry was washed with a filter press and filtered to obtain a cerium oxide cake having a cerium oxide solid content of 20%.
將所獲得的一部分濕式二氧化矽餅進行乾燥而獲得之二氧化矽粉末的BET比表面積(SBET)為200m2/g,一次粒徑為15nm而二次粒徑為10μm。100μm以上的粒子未達1%。 The cerium oxide powder obtained by drying a part of the obtained wet cerium oxide cake had a BET specific surface area (SBET) of 200 m 2 /g, a primary particle diameter of 15 nm, and a secondary particle diameter of 10 μm. Particles above 100 μm are less than 1%.
在二氧化矽固體含量為20%的二氧化矽餅1000g中添加水1000g,在二氧化矽濃度成為10%的二氧化矽分散液中添加50g的含胺基之SBR乳液(固體含量濃度20%),利用均質混合機攪拌5分鐘,添加60g的10%地氯化二烯丙基二甲胺聚合物水溶液(PAS-H-5S),再攪拌5分鐘。 1000 g of water is added to 1000 g of cerium oxide cake having a solid content of cerium oxide, and 50 g of an amino group-containing SBR emulsion is added to a cerium oxide dispersion having a cerium oxide concentration of 10% (solid content concentration: 20%) The mixture was stirred for 5 minutes by a homomixer, and 60 g of a 10% aqueous solution of diallyldimethylamine polymer (PAS-H-5S) was added thereto, followed by stirring for 5 minutes.
在此二氧化矽-含胺基之SBR乳液-氯化二烯丙基二甲胺聚合物水溶液中,添加SBR乳液(固體含量濃度20%)1818g並攪拌,加溫至60℃後添加10%稀硫酸使pH值至6.2,生成SBR橡膠和二氧化矽的共凝固物。用水洗淨三次,於105℃進行乾燥。 In this cerium oxide-amino group-containing SBR emulsion-diallyldimethylamine polymer aqueous solution, 1818 g of SBR emulsion (solid content concentration 20%) was added and stirred, and after heating to 60 ° C, 10% was added. Dilute sulfuric acid brought the pH to 6.2 to form a co-coagulum of SBR rubber and cerium oxide. It was washed three times with water and dried at 105 °C.
所生成的顆粒的平均粒徑為8mm,100%的二氧化矽隨著橡膠一起凝固了。 The resulting particles had an average particle diameter of 8 mm, and 100% of the ceria was solidified together with the rubber.
將實施例1的含胺基之SBR乳液改為100g,將氯化二烯丙基二甲胺聚合物水溶液(PAS-H-5S)改為20g來實施。 The amine group-containing SBR emulsion of Example 1 was changed to 100 g, and the aqueous diallyldimethylamine polymer solution (PAS-H-5S) was changed to 20 g.
所生成的顆粒的平均粒徑為12mm,98%的二氧化矽隨著橡膠一起凝固了。 The resulting particles had an average particle diameter of 12 mm, and 98% of the ceria was solidified together with the rubber.
將實施例1的含胺基之SBR乳液改為20g,將10%聚伸乙亞胺(EPOMIN SP200)水溶液設為100g來實施。 The amine group-containing SBR emulsion of Example 1 was changed to 20 g, and the 10% polyethylenimine (EPOMIN SP200) aqueous solution was set to 100 g.
所生成的顆粒的平均粒徑為5mm,98%的二氧化矽隨著橡膠一起凝固了。 The resulting particles had an average particle diameter of 5 mm, and 98% of the ceria was solidified together with the rubber.
將含胺基之SBR乳液之製造例的甲基丙烯酸二甲基胺乙酯10g替換為甲基丙烯酸縮水甘油酯10g,製造出含縮水甘油基之SBR乳液。又,作為二氧化矽水分散體, 是使用將市售二氧化矽VN3懸浮於水中者,該市售二氧化矽VN3,其經乾燥之BET比表面積(SBET)為210m2/g,一次粒徑為15nm,二次粒徑為10μm。二氧化矽的固體含量與實施例1同樣地設在20%。 10 g of dimethyl methacrylate methacrylate of the production example of the amine group-containing SBR emulsion was replaced with 10 g of glycidyl methacrylate to produce a glycidyl group-containing SBR emulsion. Further, as the aqueous dispersion of cerium oxide, the commercially available cerium oxide VN3 is suspended in water, and the commercially available cerium oxide VN3 has a dried BET specific surface area (SBET) of 210 m 2 /g, primary granules. The diameter was 15 nm, and the secondary particle diameter was 10 μm. The solid content of cerium oxide was set to 20% in the same manner as in Example 1.
將實施例1的含胺基之SBR乳液替換為含縮水甘油基之SBR乳液,並且,利用聚脒共聚物處理二氧化矽後,將二氧化矽和SBR橡膠進行共凝固。 The amine group-containing SBR emulsion of Example 1 was replaced with a glycidyl group-containing SBR emulsion, and after the cerium oxide was treated with the polyfluorene copolymer, the cerium oxide and the SBR rubber were co-coagulated.
所生成的顆粒的平均粒徑為9mm,99%的二氧化矽隨著橡膠一起凝固了。 The resulting particles had an average particle diameter of 9 mm, and 99% of the ceria was solidified together with the rubber.
將實施例1的SBR乳液替換為固體含量20%的天然橡膠乳液,與實施例1同樣地處理。 The SBR emulsion of Example 1 was replaced with a natural rubber emulsion having a solid content of 20%, and treated in the same manner as in Example 1.
所生成的顆粒的平均粒徑為11mm,99%的二氧化矽隨著橡膠一起凝固了。 The resulting particles had an average particle diameter of 11 mm, and 99% of the ceria was solidified together with the rubber.
將二氧化矽餅之製造例的二氧化矽餅於150℃進行乾燥,成為粉末二氧化矽後,在其粉末二氧化矽中再度添加水作成二氧化矽漿料。此二氧化矽漿料的平均粒徑為40μm而100μm以上的粒子含有11%。使用此二氧化矽,與實施例1同樣地和SBR橡膠實施共凝固。 The cerium oxide cake of the production example of the cerium oxide cake was dried at 150 ° C to obtain powdered cerium oxide, and then water was further added to the powdered cerium oxide to form a cerium oxide slurry. The cerium oxide slurry has an average particle diameter of 40 μm and particles of 100 μm or more contain 11%. Using this cerium oxide, co-coagulation was carried out with the SBR rubber in the same manner as in Example 1.
所生成的顆粒的平均粒徑為13mm,98%的二氧化矽隨著橡膠一起凝固了。 The resulting particles had an average particle diameter of 13 mm, and 98% of the ceria was solidified together with the rubber.
代替實施例1的10%氯化二烯丙基二甲胺聚合物水溶液,而是改成10%明膠(豬酸處理明膠Nippi股份有限公司製造的AP-30(商品名稱))水溶液60g來實施。 Instead of the 10% aqueous solution of 10% chlorinated diallyldimethylamine polymer of Example 1, it was changed to 60 g of 10% gelatin (AP-30 (trade name) manufactured by porcine acid-treated gelatin Nippi Co., Ltd.) aqueous solution. .
所生成的顆粒的平均粒徑為12mm,95%的二氧化矽隨著橡膠一起凝固了。 The resulting particles had an average particle diameter of 12 mm, and 95% of the ceria was solidified together with the rubber.
將實施例4的聚脒共聚物(Himoloc ZP-700)改為10%明膠(牛鹼處理明膠Nippi股份有限公司製造的ST1(商品名稱))水溶液60g來實施。 The polyfluorene copolymer (Himoloc ZP-700) of Example 4 was changed to 60 g of an aqueous solution of 10% gelatin (ST1 (trade name) manufactured by Bovine Gelatin Nippi Co., Ltd.).
所生成的顆粒的平均粒徑為8mm,94%的二氧化矽隨著橡膠一起凝固了。 The resulting particles had an average particle diameter of 8 mm, and 94% of the ceria was solidified together with the rubber.
不使用實施例1的10%之氯化二烯丙基二甲胺聚合物水溶液(PAS-H-5S),亦即,不使用處理二氧化矽之(d)成分來實施。在二氧化矽-含胺基之SBR乳液水溶液中,添加SBR乳液1818g並攪拌,然後添加100g溶有氯化鈣7.2g的水,並加溫至60℃後添加10%稀硫酸使pH值至6時,生成SBR橡膠和二氧化矽的共凝固物。用水洗淨三次,於105℃進行乾燥。 The 10% aqueous diallyldimethyl dimethylamine polymer solution (PAS-H-5S) of Example 1 was not used, that is, it was carried out without using the component (d) for treating cerium oxide. In an aqueous solution of cerium oxide-amine-containing SBR emulsion, 1818 g of SBR emulsion was added and stirred, then 100 g of water containing 7.2 g of calcium chloride was added, and after heating to 60 ° C, 10% dilute sulfuric acid was added to adjust the pH to At 6 o'clock, a co-coagulated material of SBR rubber and cerium oxide was formed. It was washed three times with water and dried at 105 °C.
所生成的顆粒的平均粒徑為20mm,53%的二氧化矽隨著橡膠一起凝固了。生成顆粒的粒徑大而難以乾燥,花 費了約2倍的實施例1的乾燥時間。又,二氧化矽約有一半沒有共凝固,而從回收篩網脫落了。 The resulting particles had an average particle diameter of 20 mm, and 53% of the ceria was solidified together with the rubber. The particle size of the resulting particles is large and difficult to dry, flowers The drying time of Example 1 was about 2 times. Also, about half of the cerium oxide did not co-coagulate and fell off the recycling screen.
於表1彙整了將乳化狀態的橡膠當作100份時,各自的組成比與共凝固結果。 In Table 1, when the rubber in an emulsified state was taken as 100 parts, the respective composition ratios and co-coagulation results were obtained.
B-1:在二氧化矽餅之製造例所製造出來的二氧化矽 B-1: cerium oxide produced in the production example of cerium oxide cake
B-2:將市售乾燥二氧化矽再漿化而成之二氧化矽 B-2: cerium oxide formed by re-slurrying commercially available dry cerium oxide
B-3:包含11%的粒徑100μm以上之二氧化矽 B-3: Containing 11% of cerium oxide having a particle diameter of 100 μm or more
C-1:含胺基之SBR乳液 C-1: ABR-containing SBR emulsion
C-2:含縮水甘油基之乳液 C-2: emulsion containing glycidyl group
D-1:氯化二烯丙基二甲胺聚合物(PAS-H-5S)NITTOBO MEDICAL股份有限公司 D-1: Diallyldimethylamine polymer (PAS-H-5S) NITTOBO MEDICAL Co., Ltd.
D-2:聚伸乙亞胺(EPOMIN SP-200)日本ZEON股份有限公司 D-2: Polyethylenimine (EPOMIN SP-200) Japan ZEON Co., Ltd.
D-3:聚脒共聚物(Himoloc ZP-700)HYMO股份有限公司 D-3: Polyfluorene Copolymer (Himoloc ZP-700) HYMO Co., Ltd.
D-4:明膠(豬酸處理明膠AP-30)Nippi股份有限公司製造 D-4: gelatin (porcine acid treated gelatin AP-30) manufactured by Nippi Co., Ltd.
D-5:明膠(牛鹼處理明膠ST1)Nippi股份有限公司製造 D-5: Gelatin (Carnitine Treatment Gelatin ST1) manufactured by Nippi Co., Ltd.
在各實施例(使用天然橡膠的實施例5除外)和比較例1所獲得之二氧化矽填充SBR橡膠中,添加矽烷偶合劑、聚乙二醇、碳黑、芳香族油、氧化鋅、硬脂酸、抗老化劑、硫化促進劑及硫黃,依照表2的混煉調配表進行混煉,以160℃的壓製機進行加硫來製備加硫橡膠,並評估物性。 In each of the examples (except for Example 5 using natural rubber) and the ceria-filled SBR rubber obtained in Comparative Example 1, a decane coupling agent, polyethylene glycol, carbon black, aromatic oil, zinc oxide, and hard were added. The fatty acid, the anti-aging agent, the vulcanization accelerator and the sulfur were kneaded according to the mixing schedule of Table 2, and sulfurized rubber was prepared by a 160 ° C press to prepare a vulcanized rubber, and the physical properties were evaluated.
另外,在使用實施例2、3、4、6所獲得之二氧化矽填充橡膠組成物之各加硫橡膠例2、3、4、5中,於上述的混煉時,補充共凝固時所脫落的二氧化矽(55重量份的1%至2%)之等量的二氧化矽微細粉體來實施上述的混煉。 Further, in each of the vulcanized rubber examples 2, 3, 4, and 5 using the cerium oxide-filled rubber composition obtained in Examples 2, 3, 4, and 6, in the above kneading, the co-coagulation was supplemented. The above-mentioned kneading was carried out by dropping an equal amount of fine ceria powder of ruthenium dioxide (55 parts by weight of 1% to 2%).
又,於比較例1所獲得之二氧化矽填充SBR橡膠中,在實施上述的混煉時,補充共凝固時所脫落的二氧化矽(55重量份的47%)之等量的二氧化矽微細粉體來進行混煉。 Further, in the cerium oxide-filled SBR rubber obtained in Comparative Example 1, when the above kneading was carried out, the same amount of cerium oxide (55% by weight of 47%) which was detached during co-coagulation was supplemented. Fine powder is used for kneading.
各混煉操作是如以下所述來實施。 Each kneading operation was carried out as described below.
在東洋精機製造的實驗室混煉擠出班布瑞密閉式混煉機(labo plastomill Banbury mixer)B-600(型號)中,依照表2的混煉調配表,以相對於橡膠(a)100重量份,二氧化矽(b)成為55重量份的方式,加入合計為364g的二氧化矽填充SBR組成物、與有脫落補充量時所追加的二氧化矽,亦即,以橡膠(a)235g和二氧化矽(b)129g的合計量為364g的方式加入。並且添加四硫化雙〔γ-(三乙氧基矽烷基)丙基〕作為矽烷偶合劑、碳黑(N339)、抗老化劑6C(N-苯基-N-(1,3-二甲基丁基)-對苯二胺)、硬脂酸、氧化鋅、芳香系油、聚乙二醇,進行混煉3分鐘。 In the laboratory blending and extrusion of the Labo plastomill Banbury mixer B-600 (model) manufactured by Toyo Seiki, according to the mixing schedule of Table 2, relative to the rubber (a) 100 The bismuth dioxide (b) is added in an amount of 55 parts by weight, and a total of 364 g of cerium oxide is added to fill the SBR composition, and cerium oxide added when the amount of detachment is added, that is, rubber (a) 235 g and cerium oxide (b) 129 g were added in a total amount of 364 g. And adding bis [γ-(triethoxydecyl)propyl] tetrasulfide as a decane coupling agent, carbon black (N339), anti-aging agent 6C (N-phenyl-N-(1,3-dimethyl) Butyl)-p-phenylenediamine, stearic acid, zinc oxide, aromatic oil, and polyethylene glycol were kneaded for 3 minutes.
從班布瑞密閉式混煉機B-600取出混煉橡膠,以輥機添加硫黃和硫化促進劑之NOCCELER CZ(N-環己基-2-苯并噻唑基亞磺醯胺)和NOCCELER D(二苯胍)。如此進行而獲得二氧化矽填充SBR橡膠複合物。 The rubber was taken out from the Bamburi Closed Mixer B-600, and the NOCCELER CZ (N-cyclohexyl-2-benzothiazolylsulfinamide) and NOCCELER D were added to the roller machine with sulfur and vulcanization accelerator. (diphenyl hydrazine). This was carried out to obtain a cerium oxide-filled SBR rubber composite.
將所獲得的二氧化矽填充SBR橡膠複合物於160℃加硫20分鐘之後,測定機械物性和亞克朗磨損。 The mechanical properties and the Akron wear were measured after the obtained cerium oxide-filled SBR rubber composite was sulfurized at 160 ° C for 20 minutes.
而且,為了比較二氧化矽之乾摻橡膠組成物的加硫橡膠物性而製備了加硫橡膠來作為比較加硫橡膠例2。具體 而言,將235g SBR1502和129g二氧化矽VN3,合計為364g,利用實驗室混煉擠出班布瑞密閉式混煉機B-600進行乾摻後,與加硫橡膠例1同樣地添加矽烷偶合劑、聚乙二醇、碳黑、芳香族油、氧化鋅、硬脂酸、抗老化劑、硫化促進劑及硫黃,進行混煉並以160℃的壓製機進行加硫。 Further, in order to compare the physical properties of the vulcanized rubber of the dry-blended rubber composition of cerium oxide, a vulcanized rubber was prepared as a comparative vulcanized rubber example 2. specific In the same manner, 235 g of SBR1502 and 129 g of cerium oxide VN3 were added in a total amount of 364 g, and dry blending was carried out by a laboratory kneading extrusion Banbury internal mixer B-600, and then decane was added in the same manner as in the sulfurized rubber example 1. The coupling agent, polyethylene glycol, carbon black, aromatic oil, zinc oxide, stearic acid, anti-aging agent, vulcanization accelerator and sulfur were kneaded and sulfurized by a 160 ° C press.
於表3顯示拉伸物性的結果。使用了實施例之二氧化矽填充SBR而成之加硫橡膠例,其斷裂時的拉伸強度不論哪一個都高於比較加硫橡膠例2,亞克朗磨損量亦少,拉伸特性和耐磨損性優異。由此可知,根據本發明所製造的源自濕式法之二氧化矽和橡膠的組成物,具有比乾摻的橡膠組成物還優異的加硫物性。又,成為低燃料消耗性能的指標之黏彈特性,也就是60℃的tanδ的值,低於比較加硫橡膠例1和比較加硫橡膠例2。這可以說是行駛時的發熱小、省燃料性能優異的橡膠。 Table 3 shows the results of tensile physical properties. In the case of the vulcanized rubber obtained by filling the SBR with the cerium oxide of the example, the tensile strength at the time of the fracture is higher than that of the comparative vulcanized rubber example 2, the amount of the Akron wear is small, the tensile property and the resistance are Excellent wear. From this, it is understood that the composition derived from the wet method of cerium oxide and rubber produced according to the present invention has a sulfur-adding property superior to that of the dry-blended rubber composition. Further, the viscoelastic property which is an indicator of low fuel consumption performance, that is, the value of tan δ at 60 ° C, is lower than that of the comparative vulcanized rubber example 1 and the comparative vulcanized rubber example 2. This can be said to be a rubber that has low heat generation during driving and has excellent fuel economy.
在本發明,藉由預先利用乳化狀共軛二烯系橡膠及具有胺基或亞胺基之聚合物的水溶液來處理水分散二氧化矽,能夠作成共凝固率高、適當尺寸的顆粒。又,可獲得一種不只在加硫橡膠物性,在機械強度和磨損也優異且低發熱性的加硫橡膠。根據本發明而獲得之二氧化矽填充橡膠組成物,是適合於輪胎的橡膠組成物。 In the present invention, by dissolving the water-dispersed cerium oxide in advance using an aqueous solution of an emulsified conjugated diene rubber and a polymer having an amine group or an imine group, it is possible to form particles having a high co-solidification ratio and an appropriate size. Further, it is possible to obtain a vulcanized rubber which is excellent not only in mechanical properties of vulcanized rubber but also in mechanical strength and abrasion and low in heat build-up. The cerium oxide-filled rubber composition obtained according to the present invention is a rubber composition suitable for a tire.
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