WO2013125415A1 - Silica-containing modified natural rubber latex, silica-containing modified natural rubber material, and method for producing same - Google Patents

Silica-containing modified natural rubber latex, silica-containing modified natural rubber material, and method for producing same Download PDF

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WO2013125415A1
WO2013125415A1 PCT/JP2013/053420 JP2013053420W WO2013125415A1 WO 2013125415 A1 WO2013125415 A1 WO 2013125415A1 JP 2013053420 W JP2013053420 W JP 2013053420W WO 2013125415 A1 WO2013125415 A1 WO 2013125415A1
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natural rubber
silica
containing modified
modified natural
latex
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PCT/JP2013/053420
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French (fr)
Japanese (ja)
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昭雄 間瀬
脇坂　治
河原　成元
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東海ゴム工業株式会社
国立大学法人長岡技術科学大学
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Priority to JP2014500674A priority Critical patent/JP5738468B2/en
Publication of WO2013125415A1 publication Critical patent/WO2013125415A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/25—Incorporating silicon atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F253/00—Macromolecular compounds obtained by polymerising monomers on to natural rubbers or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • the present invention relates to a silica-containing modified natural rubber latex, a silica-containing modified natural rubber material, and a method for producing the same, which can produce a rubber product having high strength by utilizing the reinforcing property of silica.
  • Natural rubber has excellent properties such as high tensile strength and low heat generation due to vibration. For this reason, natural rubber is used as a raw material for tires, vibration-proof members and the like.
  • carbon black, silica, and the like are blended as a natural rubber reinforcing material.
  • Silica is a naturally derived material and is present in large quantities. Further, the product is not colored black as in the case where carbon black is blended. However, the surface of silica is covered with hydrophilic silanol groups.
  • natural rubber is hydrophobic. Therefore, when silica is kneaded with natural rubber, the affinity between the two is low, and peeling tends to occur at the interface between the natural rubber and silica. Thereby, there existed a problem that sufficient reinforcement was not acquired.
  • Patent Documents 1 and 2 disclose a method of blending silica particles treated with a silane coupling agent into natural rubber.
  • Patent Document 3 discloses a method in which a diene rubber latex is modified with a silane coupling agent, an alkoxysilane compound is added, and silica particles are generated and dispersed by a sol-gel method.
  • the affinity for natural rubber is improved by treating the silica surface with a silane coupling agent.
  • the rubber composition before vulcanization and the surface-treated silica are kneaded by a Banbury mixer or the like.
  • Silica tends to aggregate due to hydrogen bonding of the remaining silanol groups.
  • it is difficult to uniformly disperse silica in the rubber material and there is a limit to the improvement of the reinforcing property.
  • the rubber component may be deteriorated.
  • since heat is generated during kneading it is difficult to control the reaction.
  • silica particles are generated and dispersed in a liquid (modified diene rubber latex). Specifically, first, a diene rubber latex and a silane coupling agent are reacted to graft bond the silane coupling agent to the rubber particles. Next, an alkoxysilane compound is added to the diene rubber latex modified with the silane coupling agent to produce and disperse silica particles in the latex.
  • a silane coupling agent is bonded to the rubber particles in advance.
  • the reaction is a two-stage reaction: (1) generation of silica particles by a sol-gel reaction, and (2) reaction of the generated silica particles and a silane coupling agent grafted to rubber particles. is required. For this reason, it is difficult to react with the silane coupling agent in a state where the generated silica particles are uniformly dispersed. Therefore, as in the above kneading method, the dispersibility of the silica particles is not sufficient. It is also difficult to reliably bond all the generated silica particles to rubber particles. There is also a possibility that unreacted alkoxysilane compounds may remain around the rubber particles. Therefore, even in the rubber material obtained by the method described in Patent Document 3, the reinforcing property is not sufficient.
  • the present invention has been made in view of such circumstances, and a silica-containing modified natural rubber capable of producing a rubber product having a high strength by combining silica with natural rubber particles in a uniformly dispersed state. It is an object of the present invention to provide a latex, silica-containing modified natural rubber material and a method for producing the same.
  • the silica-containing modified natural rubber latex of the present invention is obtained by adding a vinyl monomer having an alkoxysilane to the natural rubber latex and graft copolymerizing the vinyl monomer with natural rubber particles. It is obtained by producing silica by hydrolysis and condensation of the alkoxysilane.
  • alkoxysilane means a structure in which 1 to 3 alkoxy groups (—OR, R: alkyl group) are bonded to a silicon atom.
  • the vinyl monomer means a monomer having a vinyl structure.
  • the vinyl structure includes a mode in which the hydrogen atom of the vinyl group is substituted with a substituent such as a methyl group (—CH 3 ) (—C (CH 3 ) ⁇ CH 2 ). Including.
  • the vinyl monomer having alkoxysilane is grafted to natural rubber particles by the vinyl structure.
  • silica is produced by hydrolysis and condensation of the grafted vinyl monomer alkoxysilane.
  • the silica-containing modified natural rubber latex of the present invention is produced by a one-step reaction in which a natural rubber latex is reacted with a vinyl monomer having an alkoxysilane. That is, it is not necessary to treat the natural rubber latex with a silane coupling agent in advance. Further, the produced silica is surely bound to the natural rubber particles as a part of the grafted vinyl monomer. For this reason, silica hardly peels from the natural rubber particles, and the reinforcing effect is high.
  • silica is less likely to agglomerate than when silica is kneaded with natural rubber or when silica is reacted and bonded to natural rubber that has been subjected to silane coupling treatment. For this reason, silica can be uniformly dispersed around the natural rubber particles. Therefore, the rubber material obtained from the silica-containing modified natural rubber latex of the present invention has few silica agglomerates. That is, since the breaking base point is reduced, the strength is greatly improved. Moreover, when the dispersibility of silica improves, the surface area of silica increases. Thereby, a reinforcement property improves.
  • the silica-containing modified natural rubber material of the present invention is obtained by solidifying the silica-containing modified natural rubber latex of the present invention, and the natural rubber particles are formed on a matrix composed of the silica-containing graft chain. It is characterized by being distributed.
  • the silica-containing modified natural rubber material of the present invention has a nanomatrix structure in which natural rubber particles are dispersed in a matrix formed from a graft copolymerized vinyl monomer (graft chain).
  • the graft chain surrounds the natural rubber particles.
  • the graft chain contains the produced silica. That is, fine silica particles are dispersed and bonded around the natural rubber particles. For this reason, the tensile strength of the silica-containing modified natural rubber material of the present invention is larger than that of a conventional natural rubber material simply kneaded with silica. Therefore, the silica-containing modified natural rubber material of the present invention is suitable for the production of various rubber products that require strength.
  • the method for producing a silica-containing modified natural rubber material of the present invention comprises adding a vinyl monomer having an alkoxysilane and a polymerization initiator to natural rubber latex and graft copolymerizing the vinyl monomer to natural rubber particles. And a graft copolymerization step of generating silica by hydrolysis and condensation of the alkoxysilane, and a drying step of drying the obtained latex.
  • the vinyl monomer having alkoxysilane is grafted to the natural rubber particles, and the alkoxysilane of the vinyl monomer is hydrolyzed and condensed, so that silica Is generated.
  • the produced silica is reliably bonded to the natural rubber particles in a state of being uniformly dispersed around the natural rubber particles. Therefore, a silica-containing modified natural rubber material having high strength can be produced by drying the obtained latex.
  • the particle diameter of the silica produced can be adjusted by adjusting the stirring speed during the reaction, the pH of the natural rubber latex, and the like. For example, when the particle diameter of silica is small, the surface area of silica increases. Thereby, a reinforcement point increases. Therefore, the reinforcing property can be improved with a smaller amount of silica. Moreover, since it reacts in a liquid (natural rubber latex), it can be made to react at low temperature rather than the case of a kneading
  • the reaction may be a one-step reaction in which a natural rubber latex is reacted with a vinyl monomer having an alkoxysilane. Therefore, a manufacturing process can be reduced compared with the method of the said patent document 3 which requires a two-step reaction. That is, according to the production method of the present invention, the silica-containing modified natural rubber material of the present invention can be produced more simply and at low cost.
  • the TEM photograph of the rubber material of Example 2 is shown (magnification: 10,000 times).
  • An enlarged TEM photograph of the rubber material is shown (magnification: 30,000 times).
  • silica-containing modified natural rubber latex the silica-containing modified natural rubber material of the present invention, and the production method thereof will be described in detail.
  • silica-containing modified natural rubber latex As a natural rubber latex, a latex of deproteinized natural rubber from which protein has been removed can be used in addition to natural rubber. When deproteinized natural rubber is used, the reaction rate in graft copolymerization can be improved.
  • the natural rubber for example, field latex, latex processed by adding ammonia to field latex (high ammonia latex), or the like may be used.
  • Various known methods can be employed for deproteinization of natural rubber. For example, (i) a method of degrading a protein by adding a proteolytic enzyme or bacteria to natural rubber latex (see JP-A-6-56902), and (ii) natural rubber latex with a surfactant such as soap.
  • a protein denaturant selected from the group consisting of the urea compound represented by the following general formula (1) and NaClO is added to natural rubber latex to modify the protein in the latex For example, a method of removing after the removal (see Japanese Patent Application Laid-Open No.
  • RNHCONH 2 (1) [In the formula (1), R is H and an alkyl group having 1 to 5 carbon atoms.]
  • the vinyl monomer having alkoxysilane one having an alkoxysilane at one end of the main chain and a vinyl structure at the other end is desirable. In this case, the alkoxysilane and the vinyl structure may be directly bonded, and a carbon chain (which may contain an oxygen atom), an aromatic ring, or the like is interposed between the alkoxysilane and the vinyl structure. Also good.
  • the silica-containing modified natural rubber material of the present invention is obtained by solidifying the silica-containing modified natural rubber latex. Solidification may be performed by drying the silica-containing modified natural rubber latex. For example, the silica-containing modified natural rubber latex may be applied to the substrate surface, or the coating film obtained by immersing the substrate in the silica-containing modified natural rubber latex may be dried by heating.
  • the vinyl monomer (graft chain) graft copolymerized with the natural rubber particles forms a matrix.
  • the matrix consisting of graft chains contains the produced silica and surrounds the natural rubber particles. That is, the silica-containing modified natural rubber material of the present invention has a nanomatrix structure in which natural rubber particles are dispersed in a matrix composed of a graft chain containing silica.
  • the particle diameter of silica in the matrix is desirably 150 nm or less. It is more preferable that it is 100 nm or less.
  • the silica particle size is desirably 10 nm or more as a range in which the alkoxysilane hydrolysis and condensation reaction can be controlled. It is more preferable that it is 15 nm or more.
  • the particle diameter of silica for example, the length of the longest part of silica in an image observed with a transmission electron microscope (TEM) may be adopted.
  • the method for producing a silica-containing modified natural rubber material of the present invention includes a graft copolymerization step and a drying step. Hereinafter, each process is demonstrated in order.
  • Graft copolymerization step In this step, a vinyl monomer having an alkoxysilane and a polymerization initiator are added to natural rubber latex to graft copolymerize the vinyl monomer to natural rubber particles. This is a step of producing silica by hydrolysis and condensation.
  • the vinyl monomer having natural rubber latex and alkoxysilane is as described above.
  • the rubber content (dry rubber mass, hereinafter the same) concentration of natural rubber latex is not particularly limited. If the rubber concentration is too low, the amount of rubber material obtained is small, which is not economical. On the other hand, when the rubber concentration is too high, the rubber component in the latex becomes unstable. For this reason, aggregation of rubber particles tends to occur, and it becomes difficult to cause the graft copolymerization reaction to proceed uniformly.
  • the rubber concentration is desirably 10% by mass or more and 60% by mass or less.
  • the addition amount of the vinyl monomer having alkoxysilane (hereinafter simply referred to as “vinyl monomer” as appropriate) is preferably 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the rubber content in the natural rubber latex. .
  • the addition amount of the vinyl monomer is less than 5 parts by mass, a desired reinforcing effect cannot be obtained. More preferably, it is 10 parts by mass or more.
  • the addition amount of the vinyl monomer exceeds 60 parts by mass, the viscoelasticity inherent to natural rubber may be inhibited. More preferably, it is 30 parts by mass or less.
  • polymerization initiator examples include potassium persulfate (KPS), ammonium persulfate (APS), benzoyl peroxide (BPO), hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide (TBHPO), and di-tert.
  • KPS potassium persulfate
  • APS ammonium persulfate
  • BPO benzoyl peroxide
  • hydrogen peroxide cumene hydroperoxide
  • tert-butyl hydroperoxide THCPO
  • di-tert di-tert.
  • -Peroxides such as butyl peroxide and 2,2-azobisisobutyronitrile. From the viewpoint of lowering the polymerization temperature, a redox polymerization initiator may be used.
  • Examples of the reducing agent combined with the peroxide as a redox polymerization initiator include tetraethylenepentamine (TEPA), mercaptans, acidic sodium sulfite, reducing metal ions, ascorbic acid, and the like.
  • suitable combinations as redox-based polymerizable initiators include TBHPO and TEPA, hydrogen peroxide and Fe 2+ salt, KPS and sodium acid sulfite, and the like.
  • the addition amount of the polymerization initiator is preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the rubber content in the natural rubber latex.
  • the pH of the natural rubber latex is not particularly limited. For example, a pH of about 8 to 10 is suitable.
  • An emulsifier may be added in advance to the natural rubber latex.
  • any of various known anionic surfactants, nonionic surfactants, and cationic surfactants can be used.
  • the anionic surfactant include carboxylic acid type, sulfonic acid type, and sulfuric acid ester type.
  • nonionic surfactants include polyoxyalkylene ethers and polyhydric alcohol fatty acid esters.
  • the cationic surfactant include alkylamine salt type and imidazolinium salt type.
  • an anionic surfactant such as sodium dodecyl sulfate is suitable.
  • This step may be performed by adding a vinyl monomer having an alkoxysilane and a polymerization initiator to natural rubber latex and stirring at room temperature for about 0.5 to 12 hours.
  • the vinyl monomer is graft copolymerized with the natural rubber particles, and silica is generated by hydrolysis and condensation of the alkoxysilane.
  • the produced silica is bonded to the natural rubber particles as a part of the graft-bonded vinyl monomer in a state of being dispersed around the natural rubber particles.
  • a silica-containing modified natural rubber latex is produced.
  • This step is a step of drying the silica-containing modified natural rubber latex obtained in the previous graft copolymerization step.
  • the method for drying the latex is not particularly limited. For example, what is necessary is just to dry by apply
  • the drying temperature is preferably about 50 to 200 ° C. from the viewpoint of efficiently removing moisture in consideration of deterioration of rubber due to heat. In this way, a silica-containing modified natural rubber material is produced.
  • the latex after the proteolytic treatment was centrifuged at a rotational speed of 8000 rpm for 45 minutes. Then, the separated cream of the upper layer was redispersed in an aqueous SDS solution and stirred at a rotational speed of 300 rpm for 30 minutes. Such centrifugation and redispersion were repeated three times to produce a deproteinized natural rubber latex.
  • the concentration of the SDS aqueous solution used for redispersion was 1% by mass for the first time, 0.5% by mass for the second time, and 0.1% by mass for the third time.
  • Example 1 ⁇ Manufacture of silica-containing modified natural rubber latex and silica-containing modified natural rubber material> [Example 1] First, 200 g of deproteinized natural rubber latex prepared with a rubber concentration of 20% by mass is placed in a stainless steel container and subjected to nitrogen replacement for 1 hour while stirring at 30 ° C. at a rotation speed of 200 rpm. The dissolved oxygen was removed. Next, 0.238 g of a polymerization initiator TBHPO and 0.500 g of TEPA were added to the latex at room temperature. Further, 8 g of 3-methacryloxypropyltrimethoxysilane (MPTMS) was added dropwise and stirred for 2 hours to carry out graft copolymerization.
  • MPTMS 3-methacryloxypropyltrimethoxysilane
  • silica-containing modified natural rubber latex was produced.
  • the obtained latex was transferred to a petri dish and dried at 50 ° C. to produce a sheet-like silica-containing modified natural rubber material having a thickness of 1 mm.
  • the produced silica-containing modified natural rubber material is referred to as the rubber material of Example 1.
  • Example 2 A rubber material of Example 2 was produced in the same manner as in Example 1 except that vinyltriethoxysilane (BTES) was added dropwise instead of MPTMS.
  • BTES vinyltriethoxysilane
  • Example 3 A rubber material of Example 3 was produced in the same manner as in Example 1 except that p-styryltrimethoxysilane was added dropwise instead of MPTMS.
  • FIG. 1 shows a TEM photograph of the rubber material of Example 2 (magnification: 10,000 times).
  • FIG. 2 shows an enlarged TEM photograph of the rubber material (magnification: 30,000 times).
  • a matrix layer containing silica particles black portion was observed around the natural rubber particles (white portion). That is, it was confirmed that the rubber material of Example 2 had a nanomatrix structure in which natural rubber particles were dispersed in a matrix composed of a graft chain containing silica. Further, as shown in an enlarged view in FIG. 2, large particles having a particle size of about 150 nm and small particles having a particle size of about 20 nm were confirmed as silica. In the TEM photographs of the rubber materials of Examples 1 and 3, a matrix layer containing silica particles was observed around the natural rubber particles as in the rubber material of Example 2.
  • the tensile strengths of the rubber materials of Examples 1 to 3 were significantly larger than the tensile strength of the deproteinized natural rubber. From the above, it was confirmed that the silica-containing modified natural rubber latex of the present invention and the silica-containing modified natural rubber material obtained by drying the latex have high strength. Moreover, according to the manufacturing method of this invention, it was confirmed that a silica containing modified natural rubber material with a large intensity
  • the silica-containing modified natural rubber latex of the present invention and the silica-containing modified natural rubber material obtained by drying it, a rubber product having high strength can be produced. Therefore, the silica-containing modified natural rubber latex and the silica-containing modified natural rubber material of the present invention are useful as raw materials for tires, vibration-insulating rubber members, etc., as an alternative material for synthetic rubber.

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Abstract

Provided are: a silica-containing modified natural rubber latex that can produce a rubber product having high strength; a silica-containing modified natural rubber material; and a method for producing same. The silica-containing modified natural rubber latex is produced by adding a vinyl monomer having an alkoxysilane to a natural rubber latex, causing graft co-polymerization of the vinyl monomer to natural rubber particles, and generating silica by means of the hydrolysis and condensation of the alkoxysilane. The silica-containing modified natural rubber material is produced by solidifying the silica-containing modified natural rubber latex. The silica-containing modified natural rubber material results from the natural rubber particles being dispersed in a matrix comprising graft chains containing the generated silica.

Description

シリカ含有改質天然ゴムラテックス、シリカ含有改質天然ゴム材料およびその製造方法Silica-containing modified natural rubber latex, silica-containing modified natural rubber material and method for producing the same
　本発明は、シリカの補強性を利用して強度の大きなゴム製品を製造可能な、シリカ含有改質天然ゴムラテックス、シリカ含有改質天然ゴム材料およびその製造方法に関する。 The present invention relates to a silica-containing modified natural rubber latex, a silica-containing modified natural rubber material, and a method for producing the same, which can produce a rubber product having high strength by utilizing the reinforcing property of silica.
　天然ゴムは、引張り強さが大きく、振動による発熱が少ない等の優れた性質を有する。このため、天然ゴムは、タイヤ、防振部材等の原料として用いられている。製品特性を向上させるため、天然ゴムの補強材として、カーボンブラック、シリカ等が配合される。シリカは、天然由来の材料であり、多量に存在する。また、カーボンブラックを配合した場合のように、製品が黒く着色されることもない。しかし、シリカの表面は、親水性のシラノール基で覆われている。一方、天然ゴムは疎水性を有する。したがって、天然ゴムにシリカを混練した場合、両者の親和性が低く、天然ゴムとシリカとの界面で剥離が生じやすい。これにより、充分な補強性が得られないという問題があった。 Natural rubber has excellent properties such as high tensile strength and low heat generation due to vibration. For this reason, natural rubber is used as a raw material for tires, vibration-proof members and the like. In order to improve product characteristics, carbon black, silica, and the like are blended as a natural rubber reinforcing material. Silica is a naturally derived material and is present in large quantities. Further, the product is not colored black as in the case where carbon black is blended. However, the surface of silica is covered with hydrophilic silanol groups. On the other hand, natural rubber is hydrophobic. Therefore, when silica is kneaded with natural rubber, the affinity between the two is low, and peeling tends to occur at the interface between the natural rubber and silica. Thereby, there existed a problem that sufficient reinforcement was not acquired.
　この問題の解決策として、シランカップリング剤により処理したシリカ粒子を、天然ゴムに配合する方法が知られている（例えば、特許文献１、２参照）。また、特許文献３には、ジエンゴムラテックスをシランカップリング剤により改質処理した後に、アルコキシシラン化合物を添加して、ゾルゲル法によりシリカ粒子を生成、分散させる方法が開示されている。 As a solution to this problem, a method of blending silica particles treated with a silane coupling agent into natural rubber is known (see, for example, Patent Documents 1 and 2). Patent Document 3 discloses a method in which a diene rubber latex is modified with a silane coupling agent, an alkoxysilane compound is added, and silica particles are generated and dispersed by a sol-gel method.
特開２０１１－１７４０３４号公報JP 2011-174034 A 特開２００８－７７７０号公報JP 2008-7770 A 特開平９－１７６３８５号公報JP-A-9-176385
　シリカの表面をシランカップリング剤で処理することにより、天然ゴムに対する親和性は向上する。しかしながら、特許文献１、２に記載されているように、加硫前のゴム組成物と、表面処理されたシリカと、はバンバリーミキサー等により混練される。シリカは、残存するシラノール基の水素結合により凝集しやすい。このため、従来の混練法では、ゴム材料中にシリカを均一に分散させることが難しく、補強性の向上には限界がある。また、表面処理されたシリカとゴム組成物との反応を進行させるためには、１２０℃以上の温度で混練する必要がある。しかし、高温下で長時間混練すると、ゴム成分が劣化するおそれがある。また、混練中に熱が発生するため、反応の制御も難しい。 The affinity for natural rubber is improved by treating the silica surface with a silane coupling agent. However, as described in Patent Documents 1 and 2, the rubber composition before vulcanization and the surface-treated silica are kneaded by a Banbury mixer or the like. Silica tends to aggregate due to hydrogen bonding of the remaining silanol groups. For this reason, in the conventional kneading method, it is difficult to uniformly disperse silica in the rubber material, and there is a limit to the improvement of the reinforcing property. Further, in order to proceed the reaction between the surface-treated silica and the rubber composition, it is necessary to knead at a temperature of 120 ° C. or higher. However, when kneaded for a long time at a high temperature, the rubber component may be deteriorated. Also, since heat is generated during kneading, it is difficult to control the reaction.
　一方、特許文献３に記載された方法においては、液（改質ジエンゴムラテックス）中にてシリカ粒子を生成し分散させる。具体的には、まず、ジエンゴムラテックスとシランカップリング剤とを反応させて、ゴム粒子にシランカップリング剤をグラフト結合させる。次に、シランカップリング剤で改質されたジエンゴムラテックスに、アルコキシシラン化合物を添加して、ラテックス中にシリカ粒子を生成し分散させる。このように、特許文献３に記載された方法においては、生成したシリカ粒子とゴム粒子との親和性を改善するために、予めゴム粒子にシランカップリング剤を結合させている。 On the other hand, in the method described in Patent Document 3, silica particles are generated and dispersed in a liquid (modified diene rubber latex). Specifically, first, a diene rubber latex and a silane coupling agent are reacted to graft bond the silane coupling agent to the rubber particles. Next, an alkoxysilane compound is added to the diene rubber latex modified with the silane coupling agent to produce and disperse silica particles in the latex. Thus, in the method described in Patent Document 3, in order to improve the affinity between the generated silica particles and rubber particles, a silane coupling agent is bonded to the rubber particles in advance.
　特許文献３に記載された方法においては、（１）ゾルゲル反応によるシリカ粒子の生成、（２）生成したシリカ粒子とゴム粒子にグラフト結合されたシランカップリング剤との反応、という二段階の反応が必要である。このため、生成したシリカ粒子を均一に分散させた状態で、シランカップリング剤と反応させることは難しい。よって、上記混練法と同様に、シリカ粒子の分散性は充分ではない。また、生成したシリカ粒子の全てを、ゴム粒子と確実に結合させることも難しい。未反応のアルコキシシラン化合物が、ゴム粒子の周りに残存するおそれもある。したがって、特許文献３に記載された方法により得られたゴム材料においても、補強性は充分とはいえない。 In the method described in Patent Document 3, the reaction is a two-stage reaction: (1) generation of silica particles by a sol-gel reaction, and (2) reaction of the generated silica particles and a silane coupling agent grafted to rubber particles. is required. For this reason, it is difficult to react with the silane coupling agent in a state where the generated silica particles are uniformly dispersed. Therefore, as in the above kneading method, the dispersibility of the silica particles is not sufficient. It is also difficult to reliably bond all the generated silica particles to rubber particles. There is also a possibility that unreacted alkoxysilane compounds may remain around the rubber particles. Therefore, even in the rubber material obtained by the method described in Patent Document 3, the reinforcing property is not sufficient.
　本発明は、このような実情に鑑みてなされたものであり、シリカを均一に分散した状態で天然ゴム粒子と結合させることにより、強度の大きなゴム製品を製造可能な、シリカ含有改質天然ゴムラテックス、シリカ含有改質天然ゴム材料およびその製造方法を提供することを課題とする。 The present invention has been made in view of such circumstances, and a silica-containing modified natural rubber capable of producing a rubber product having a high strength by combining silica with natural rubber particles in a uniformly dispersed state. It is an object of the present invention to provide a latex, silica-containing modified natural rubber material and a method for producing the same.
　（１）上記課題を解決するため、本発明のシリカ含有改質天然ゴムラテックスは、天然ゴムラテックスにアルコキシシランを有するビニルモノマーを添加して、天然ゴム粒子に該ビニルモノマーをグラフト共重合させると共に、該アルコキシシランの加水分解および縮合によりシリカを生成させることにより得られることを特徴とする。 (1) In order to solve the above problems, the silica-containing modified natural rubber latex of the present invention is obtained by adding a vinyl monomer having an alkoxysilane to the natural rubber latex and graft copolymerizing the vinyl monomer with natural rubber particles. It is obtained by producing silica by hydrolysis and condensation of the alkoxysilane.
　天然ゴムラテックスとしては、天然ゴムの他、蛋白質を除去した脱蛋白質化天然ゴムのラテックスを使用することができる。本明細書において、アルコキシシランとは、ケイ素原子に１～３個のアルコキシ基（－ＯＲ、Ｒ：アルキル基）が結合した構造を意味する。また、ビニルモノマーとは、ビニル構造を有するモノマーを意味する。ビニル構造は、ビニル基（－ＣＨ＝ＣＨ２）の他、ビニル基の水素原子がメチル基（－ＣＨ３）等の置換基で置換された態様（－Ｃ（ＣＨ３）＝ＣＨ２）を含む。 As natural rubber latex, latex of deproteinized natural rubber from which protein has been removed can be used in addition to natural rubber. In the present specification, alkoxysilane means a structure in which 1 to 3 alkoxy groups (—OR, R: alkyl group) are bonded to a silicon atom. The vinyl monomer means a monomer having a vinyl structure. In addition to the vinyl group (—CH═CH 2 ), the vinyl structure includes a mode in which the hydrogen atom of the vinyl group is substituted with a substituent such as a methyl group (—CH 3 ) (—C (CH 3 ) ═CH 2 ). Including.
　アルコキシシランを有するビニルモノマーは、ビニル構造により天然ゴム粒子にグラフト結合される。同時に、グラフト結合されたビニルモノマーのアルコキシシランが加水分解および縮合することにより、シリカが生成される。このように、本発明のシリカ含有改質天然ゴムラテックスは、天然ゴムラテックスに、アルコキシシランを有するビニルモノマーを反応させるという一段階の反応により、製造される。つまり、天然ゴムラテックスを、予めシランカップリング剤により処理しておく必要はない。また、生成されたシリカは、グラフト結合された当該ビニルモノマーの一部として、確実に天然ゴム粒子に結合される。このため、シリカが天然ゴム粒子から剥離しにくく、補強効果が高い。また、天然ゴムにシリカを混練したり、シランカップリング処理した天然ゴムにシリカを反応させて結合させる場合と比較して、シリカが凝集しにくい。このため、天然ゴム粒子の周りに、シリカを均一に分散させることができる。したがって、本発明のシリカ含有改質天然ゴムラテックスから得られるゴム材料においては、シリカの凝集塊が少ない。つまり、破断基点が少なくなるため、強度が大幅に向上する。また、シリカの分散性が向上すると、シリカの表面積が大きくなる。これにより、補強性が向上する。 The vinyl monomer having alkoxysilane is grafted to natural rubber particles by the vinyl structure. At the same time, silica is produced by hydrolysis and condensation of the grafted vinyl monomer alkoxysilane. Thus, the silica-containing modified natural rubber latex of the present invention is produced by a one-step reaction in which a natural rubber latex is reacted with a vinyl monomer having an alkoxysilane. That is, it is not necessary to treat the natural rubber latex with a silane coupling agent in advance. Further, the produced silica is surely bound to the natural rubber particles as a part of the grafted vinyl monomer. For this reason, silica hardly peels from the natural rubber particles, and the reinforcing effect is high. In addition, silica is less likely to agglomerate than when silica is kneaded with natural rubber or when silica is reacted and bonded to natural rubber that has been subjected to silane coupling treatment. For this reason, silica can be uniformly dispersed around the natural rubber particles. Therefore, the rubber material obtained from the silica-containing modified natural rubber latex of the present invention has few silica agglomerates. That is, since the breaking base point is reduced, the strength is greatly improved. Moreover, when the dispersibility of silica improves, the surface area of silica increases. Thereby, a reinforcement property improves.
　（２）また、本発明のシリカ含有改質天然ゴム材料は、上記本発明のシリカ含有改質天然ゴムラテックスを固形化して得られ、前記シリカを含むグラフト鎖からなるマトリックスに前記天然ゴム粒子が分散されてなることを特徴とする。 (2) Further, the silica-containing modified natural rubber material of the present invention is obtained by solidifying the silica-containing modified natural rubber latex of the present invention, and the natural rubber particles are formed on a matrix composed of the silica-containing graft chain. It is characterized by being distributed.
　本発明のシリカ含有改質天然ゴム材料は、グラフト共重合したビニルモノマー（グラフト鎖）から形成されるマトリックスに、天然ゴム粒子が分散されたナノマトリックス構造を有する。グラフト鎖は、天然ゴム粒子の周りを囲んでいる。グラフト鎖は、生成したシリカを含む。すなわち、微細なシリカ粒子が、天然ゴム粒子の周りに分散して結合している。このため、本発明のシリカ含有改質天然ゴム材料の引張強さは、単にシリカを混練した従来の天然ゴム材料と比較して、大きい。したがって、本発明のシリカ含有改質天然ゴム材料は、強度を必要とする種々のゴム製品の製造に好適である。 The silica-containing modified natural rubber material of the present invention has a nanomatrix structure in which natural rubber particles are dispersed in a matrix formed from a graft copolymerized vinyl monomer (graft chain). The graft chain surrounds the natural rubber particles. The graft chain contains the produced silica. That is, fine silica particles are dispersed and bonded around the natural rubber particles. For this reason, the tensile strength of the silica-containing modified natural rubber material of the present invention is larger than that of a conventional natural rubber material simply kneaded with silica. Therefore, the silica-containing modified natural rubber material of the present invention is suitable for the production of various rubber products that require strength.
　（３）本発明のシリカ含有改質天然ゴム材料の製造方法は、天然ゴムラテックスに、アルコキシシランを有するビニルモノマーと重合開始剤とを添加して、天然ゴム粒子に該ビニルモノマーをグラフト共重合させると共に、該アルコキシシランの加水分解および縮合によりシリカを生成させるグラフト共重合工程と、得られたラテックスを乾燥する乾燥工程と、を有することを特徴とする。 (3) The method for producing a silica-containing modified natural rubber material of the present invention comprises adding a vinyl monomer having an alkoxysilane and a polymerization initiator to natural rubber latex and graft copolymerizing the vinyl monomer to natural rubber particles. And a graft copolymerization step of generating silica by hydrolysis and condensation of the alkoxysilane, and a drying step of drying the obtained latex.
　上記（１）において説明したように、グラフト共重合工程においては、アルコキシシランを有するビニルモノマーが天然ゴム粒子にグラフト結合されると共に、当該ビニルモノマーのアルコキシシランが加水分解および縮合することにより、シリカが生成される。生成されたシリカは、天然ゴム粒子の周りに均一に分散した状態で、確実に天然ゴム粒子に結合される。したがって、得られたラテックスを乾燥することにより、強度が大きなシリカ含有改質天然ゴム材料を製造することができる。 As described in (1) above, in the graft copolymerization step, the vinyl monomer having alkoxysilane is grafted to the natural rubber particles, and the alkoxysilane of the vinyl monomer is hydrolyzed and condensed, so that silica Is generated. The produced silica is reliably bonded to the natural rubber particles in a state of being uniformly dispersed around the natural rubber particles. Therefore, a silica-containing modified natural rubber material having high strength can be produced by drying the obtained latex.
　また、グラフト共重合工程において、反応時の撹拌速度、天然ゴムラテックスのｐＨ等を調整することにより、生成するシリカの粒子径を調整することができる。例えば、シリカの粒子径が小さいと、シリカの表面積が大きくなる。これにより、補強点が多くなる。したがって、より少量のシリカで、補強性を向上させることができる。また、液（天然ゴムラテックス）中で反応させるため、混練法の場合よりも低温で反応させることができる。このため、ゴム成分が劣化しにくく、反応率も高い。 In the graft copolymerization step, the particle diameter of the silica produced can be adjusted by adjusting the stirring speed during the reaction, the pH of the natural rubber latex, and the like. For example, when the particle diameter of silica is small, the surface area of silica increases. Thereby, a reinforcement point increases. Therefore, the reinforcing property can be improved with a smaller amount of silica. Moreover, since it reacts in a liquid (natural rubber latex), it can be made to react at low temperature rather than the case of a kneading | mixing method. For this reason, the rubber component is hardly deteriorated and the reaction rate is high.
　本発明のシリカ含有改質天然ゴム材料の製造方法によると、天然ゴムラテックスに、アルコキシシランを有するビニルモノマーを反応させるという一段階の反応でよい。したがって、二段階の反応が必要な上記特許文献３の方法と比較して、製造工程を削減することができる。すなわち、本発明の製造方法によると、より簡便かつ低コストに、上記本発明のシリカ含有改質天然ゴム材料を製造することができる。 According to the method for producing a silica-containing modified natural rubber material of the present invention, the reaction may be a one-step reaction in which a natural rubber latex is reacted with a vinyl monomer having an alkoxysilane. Therefore, a manufacturing process can be reduced compared with the method of the said patent document 3 which requires a two-step reaction. That is, according to the production method of the present invention, the silica-containing modified natural rubber material of the present invention can be produced more simply and at low cost.
実施例２のゴム材料のＴＥＭ写真を示す（倍率：１０，０００倍）。The TEM photograph of the rubber material of Example 2 is shown (magnification: 10,000 times). 同ゴム材料の拡大ＴＥＭ写真を示す（倍率：３０，０００倍）。An enlarged TEM photograph of the rubber material is shown (magnification: 30,000 times).
　以下、本発明のシリカ含有改質天然ゴムラテックス、シリカ含有改質天然ゴム材料およびその製造方法について、それぞれ詳細に説明する。 Hereinafter, the silica-containing modified natural rubber latex, the silica-containing modified natural rubber material of the present invention, and the production method thereof will be described in detail.
　＜シリカ含有改質天然ゴムラテックス＞
　本発明のシリカ含有改質天然ゴムラテックスの製造においては、天然ゴムラテックスとして、天然ゴムの他、蛋白質を除去した脱蛋白質化天然ゴムのラテックスを使用することができる。脱蛋白質化天然ゴムを使用すると、グラフト共重合における反応率を向上させることができる。 <Silica-containing modified natural rubber latex>
In the production of the silica-containing modified natural rubber latex of the present invention, as a natural rubber latex, a latex of deproteinized natural rubber from which protein has been removed can be used in addition to natural rubber. When deproteinized natural rubber is used, the reaction rate in graft copolymerization can be improved.
　天然ゴムとしては、例えば、フィールドラテックス、フィールドラテックスにアンモニアを加えて処理されたラテックス（ハイアンモニアラテックス）等を使用すればよい。また、天然ゴムの脱蛋白質化は、種々の公知の方法を採用することができる。例えば、（ｉ）天然ゴムラテックスに、蛋白質分解酵素またはバクテリアを添加して蛋白質を分解させる方法（特開平６－５６９０２号公報参照）、（ｉｉ）天然ゴムラテックスを、石鹸等の界面活性剤により繰り返し洗浄する方法、（ｉｉｉ）天然ゴムラテックスに、次の一般式（１）で表される尿素系化合物およびＮａＣｌＯからなる群から選択された蛋白質変性剤を添加し、ラテックス中の蛋白質を変性処理した後に除去する方法（特開２００４－９９６９６号公報参照）等が挙げられる。
ＲＮＨＣＯＮＨ２　・・・（１）
[（式（１）中、ＲはＨ、炭素数１～５のアルキル基である。]
　アルコキシシランを有するビニルモノマーとしては、主鎖の一端にアルコキシシランを、他端にビニル構造を有するものが望ましい。この場合、アルコキシシランとビニル構造とは直接結合していてもよく、アルコキシシランとビニル構造との間に、炭素鎖（酸素原子を含んでいてもよい）、芳香族環等が介在していてもよい。具体的には、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ｐ－スチリルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－アクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリエトキシシラン等が挙げられる。 As the natural rubber, for example, field latex, latex processed by adding ammonia to field latex (high ammonia latex), or the like may be used. Various known methods can be employed for deproteinization of natural rubber. For example, (i) a method of degrading a protein by adding a proteolytic enzyme or bacteria to natural rubber latex (see JP-A-6-56902), and (ii) natural rubber latex with a surfactant such as soap. (Iii) A protein denaturant selected from the group consisting of the urea compound represented by the following general formula (1) and NaClO is added to natural rubber latex to modify the protein in the latex For example, a method of removing after the removal (see Japanese Patent Application Laid-Open No. 2004-99696).
RNHCONH 2 (1)
[In the formula (1), R is H and an alkyl group having 1 to 5 carbon atoms.]
As the vinyl monomer having alkoxysilane, one having an alkoxysilane at one end of the main chain and a vinyl structure at the other end is desirable. In this case, the alkoxysilane and the vinyl structure may be directly bonded, and a carbon chain (which may contain an oxygen atom), an aromatic ring, or the like is interposed between the alkoxysilane and the vinyl structure. Also good. Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3 -Methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and the like.
　天然ゴムラテックスと、アルコキシシランを有するビニルモノマーと、の反応については、後のシリカ含有改質天然ゴム材料の製造方法の説明において、詳述する。 The reaction between the natural rubber latex and the vinyl monomer having alkoxysilane will be described in detail later in the description of the method for producing a silica-containing modified natural rubber material.
　＜シリカ含有改質天然ゴム材料＞
　本発明のシリカ含有改質天然ゴム材料は、上記シリカ含有改質天然ゴムラテックスを固形化して得られる。固形化は、シリカ含有改質天然ゴムラテックスを乾燥すればよい。例えば、シリカ含有改質天然ゴムラテックスを基材表面に塗布したり、基材をシリカ含有改質天然ゴムラテックスに浸漬して得られた塗膜を、加熱するなどして乾燥すればよい。得られたシリカ含有改質天然ゴム材料において、天然ゴム粒子にグラフト共重合したビニルモノマー（グラフト鎖）は、マトリックスを形成する。グラフト鎖からなるマトリックスは、生成したシリカを含み、天然ゴム粒子の周りを囲んでいる。すなわち、本発明のシリカ含有改質天然ゴム材料は、シリカを含むグラフト鎖からなるマトリックスに、天然ゴム粒子が分散されたナノマトリックス構造を有する。 <Silica-containing modified natural rubber material>
The silica-containing modified natural rubber material of the present invention is obtained by solidifying the silica-containing modified natural rubber latex. Solidification may be performed by drying the silica-containing modified natural rubber latex. For example, the silica-containing modified natural rubber latex may be applied to the substrate surface, or the coating film obtained by immersing the substrate in the silica-containing modified natural rubber latex may be dried by heating. In the obtained silica-containing modified natural rubber material, the vinyl monomer (graft chain) graft copolymerized with the natural rubber particles forms a matrix. The matrix consisting of graft chains contains the produced silica and surrounds the natural rubber particles. That is, the silica-containing modified natural rubber material of the present invention has a nanomatrix structure in which natural rubber particles are dispersed in a matrix composed of a graft chain containing silica.
　シリカの表面積を大きくして、補強効果を高めるという観点から、マトリックス中のシリカの粒子径は、１５０ｎｍ以下であることが望ましい。１００ｎｍ以下であるとより好適である。一方、アルコキシシランの加水分解および縮合反応の制御が可能な範囲として、シリカの粒子径は、１０ｎｍ以上であることが望ましい。１５ｎｍ以上であるとより好適である。シリカの粒子径としては、例えば、透過型電子顕微鏡（ＴＥＭ）により観察した画像において、シリカの最長部分の長さを採用すればよい。 From the viewpoint of increasing the surface area of silica and enhancing the reinforcing effect, the particle diameter of silica in the matrix is desirably 150 nm or less. It is more preferable that it is 100 nm or less. On the other hand, the silica particle size is desirably 10 nm or more as a range in which the alkoxysilane hydrolysis and condensation reaction can be controlled. It is more preferable that it is 15 nm or more. As the particle diameter of silica, for example, the length of the longest part of silica in an image observed with a transmission electron microscope (TEM) may be adopted.
　＜シリカ含有改質天然ゴム材料の製造方法＞
　本発明のシリカ含有改質天然ゴム材料の製造方法は、グラフト共重合工程と、乾燥工程と、を有する。以下、各工程について順に説明する。 <Method for producing silica-containing modified natural rubber material>
The method for producing a silica-containing modified natural rubber material of the present invention includes a graft copolymerization step and a drying step. Hereinafter, each process is demonstrated in order.
　（１）グラフト共重合工程
　本工程は、天然ゴムラテックスに、アルコキシシランを有するビニルモノマーと重合開始剤とを添加して、天然ゴム粒子に該ビニルモノマーをグラフト共重合させると共に、該アルコキシシランの加水分解および縮合によりシリカを生成させる工程である。 (1) Graft copolymerization step In this step, a vinyl monomer having an alkoxysilane and a polymerization initiator are added to natural rubber latex to graft copolymerize the vinyl monomer to natural rubber particles. This is a step of producing silica by hydrolysis and condensation.
　天然ゴムラテックス、およびアルコキシシランを有するビニルモノマーについては、上述した通りである。天然ゴムラテックスのゴム分（乾燥ゴム質量、以下同じ）濃度は、特に限定されない。ゴム分濃度が低すぎると、得られるゴム材料が少なくなり経済的ではない。反対に、ゴム分濃度が高すぎると、ラテックス中のゴム成分が不安定になる。このため、ゴム粒子同士の凝集が起きやすく、グラフト共重合反応を均一に進行させにくくなる。例えば、ゴム分濃度を、１０質量％以上６０質量％以下とすることが望ましい。 The vinyl monomer having natural rubber latex and alkoxysilane is as described above. The rubber content (dry rubber mass, hereinafter the same) concentration of natural rubber latex is not particularly limited. If the rubber concentration is too low, the amount of rubber material obtained is small, which is not economical. On the other hand, when the rubber concentration is too high, the rubber component in the latex becomes unstable. For this reason, aggregation of rubber particles tends to occur, and it becomes difficult to cause the graft copolymerization reaction to proceed uniformly. For example, the rubber concentration is desirably 10% by mass or more and 60% by mass or less.
　アルコキシシランを有するビニルモノマー（以下適宜、単に「ビニルモノマー」と称す）の添加量は、天然ゴムラテックス中のゴム分１００質量部に対して、５質量部以上６０質量部以下とすることが望ましい。ビニルモノマーの添加量が５質量部未満の場合には、所望の補強効果が得られない。１０質量部以上とするとより好適である。反対に、ビニルモノマーの添加量が６０質量部を超えると、本来天然ゴムが有する粘弾性が阻害されるおそれがある。３０質量部以下とするとより好適である。 The addition amount of the vinyl monomer having alkoxysilane (hereinafter simply referred to as “vinyl monomer” as appropriate) is preferably 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the rubber content in the natural rubber latex. . When the addition amount of the vinyl monomer is less than 5 parts by mass, a desired reinforcing effect cannot be obtained. More preferably, it is 10 parts by mass or more. On the other hand, when the addition amount of the vinyl monomer exceeds 60 parts by mass, the viscoelasticity inherent to natural rubber may be inhibited. More preferably, it is 30 parts by mass or less.
　重合開始剤としては、例えば、過硫酸カリウム（ＫＰＳ）、過硫酸アンモニウム（ＡＰＳ）、過酸化ベンゾイル（ＢＰＯ）、過酸化水素、クメンハイドロパーオキサイド、ｔｅｒｔ－ブチルハイドロパーオキサイド（ＴＢＨＰＯ）、ジ－ｔｅｒｔ－ブチルパーオキサイド、２，２－アゾビスイソブチロニトリル、等の過酸化物が挙げられる。重合温度を低くするという観点からは、レドックス系の重合開始剤を使用するとよい。レドックス系の重合開始剤として、過酸化物と組み合わされる還元剤には、例えば、テトラエチレンペンタミン（ＴＥＰＡ）、メルカプタン類、酸性亜硫酸ナトリウム、還元性金属イオン、アスコルビン酸等が挙げられる。レドックス系の重合性開始剤として好適な組み合わせ例としては、ＴＢＨＰＯとＴＥＰＡ、過酸化水素とＦｅ２＋塩、ＫＰＳと酸性亜硫酸ナトリウム等がある。重合開始剤の添加量は、天然ゴムラテックス中のゴム分１００質量部に対して０．１質量部以上５質量部以下とするとよい。 Examples of the polymerization initiator include potassium persulfate (KPS), ammonium persulfate (APS), benzoyl peroxide (BPO), hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide (TBHPO), and di-tert. -Peroxides such as butyl peroxide and 2,2-azobisisobutyronitrile. From the viewpoint of lowering the polymerization temperature, a redox polymerization initiator may be used. Examples of the reducing agent combined with the peroxide as a redox polymerization initiator include tetraethylenepentamine (TEPA), mercaptans, acidic sodium sulfite, reducing metal ions, ascorbic acid, and the like. Examples of suitable combinations as redox-based polymerizable initiators include TBHPO and TEPA, hydrogen peroxide and Fe 2+ salt, KPS and sodium acid sulfite, and the like. The addition amount of the polymerization initiator is preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the rubber content in the natural rubber latex.
　天然ゴムラテックスのｐＨは、特に限定されない。例えば、ｐＨ８～１０程度が好適である。天然ゴムラテックスには、予め乳化剤を加えておいてもよい。乳化剤としては、公知の種々のアニオン界面活性剤、ノニオン界面活性剤、カチオン界面活性剤のいずれも使用することができる。アニオン界面活性剤としては、カルボン酸系、スルホン酸系、硫酸エステル系等が挙げられる。ノニオン界面活性剤としては、ポリオキシアルキレンエーテル系、多価アルコール脂肪酸エステル系等が挙げられる。カチオン系界面活性剤としては、アルキルアミン塩型、イミダゾリニウム塩型等が挙げられる。例えば、ドデシル硫酸ナトリウム等のアニオン界面活性剤が好適である。 The pH of the natural rubber latex is not particularly limited. For example, a pH of about 8 to 10 is suitable. An emulsifier may be added in advance to the natural rubber latex. As the emulsifier, any of various known anionic surfactants, nonionic surfactants, and cationic surfactants can be used. Examples of the anionic surfactant include carboxylic acid type, sulfonic acid type, and sulfuric acid ester type. Examples of nonionic surfactants include polyoxyalkylene ethers and polyhydric alcohol fatty acid esters. Examples of the cationic surfactant include alkylamine salt type and imidazolinium salt type. For example, an anionic surfactant such as sodium dodecyl sulfate is suitable.
　本工程は、天然ゴムラテックスに、アルコキシシランを有するビニルモノマーと重合開始剤とを添加して、室温下で０．５～１２時間程度、攪拌して行えばよい。これにより、天然ゴム粒子にビニルモノマーがグラフト共重合されると共に、アルコキシシランの加水分解および縮合によりシリカが生成する。生成したシリカは、天然ゴム粒子の周りに分散した状態で、グラフト結合されたビニルモノマーの一部として天然ゴム粒子に結合される。本工程により、シリカ含有改質天然ゴムラテックスが製造される。 This step may be performed by adding a vinyl monomer having an alkoxysilane and a polymerization initiator to natural rubber latex and stirring at room temperature for about 0.5 to 12 hours. As a result, the vinyl monomer is graft copolymerized with the natural rubber particles, and silica is generated by hydrolysis and condensation of the alkoxysilane. The produced silica is bonded to the natural rubber particles as a part of the graft-bonded vinyl monomer in a state of being dispersed around the natural rubber particles. Through this step, a silica-containing modified natural rubber latex is produced.
　（２）乾燥工程
　本工程は、先のグラフト共重合工程にて得られたシリカ含有改質天然ゴムラテックスを、乾燥する工程である。ラテックスの乾燥方法は、特に限定されない。例えば、ラテックスを基材表面に塗布したり、基材をラテックスに浸漬して得られた塗膜を、加熱するなどして乾燥すればよい。乾燥時の温度は、熱によるゴムの劣化を考慮して、効率良く水分を除去するという観点から、５０～２００℃程度とすることが望ましい。このようにして、シリカ含有改質天然ゴム材料が製造される。 (2) Drying step This step is a step of drying the silica-containing modified natural rubber latex obtained in the previous graft copolymerization step. The method for drying the latex is not particularly limited. For example, what is necessary is just to dry by apply | coating latex to the base-material surface or heating the coating film obtained by immersing a base material in latex. The drying temperature is preferably about 50 to 200 ° C. from the viewpoint of efficiently removing moisture in consideration of deterioration of rubber due to heat. In this way, a silica-containing modified natural rubber material is produced.
　次に、実施例を挙げて本発明をより具体的に説明する。 Next, the present invention will be described more specifically with reference to examples.
　＜脱蛋白質化天然ゴムラテックスの製造＞
　天然ゴムラテックスとして、ゴールデンホープ社（マレーシア国）製のハイアンモニアラテックス（ゴム分濃度６０．２質量％、アンモニア分濃度０．７質量％）を使用した。まず、ハイアンモニアラテックスを、ゴム分濃度が３０質量％となるように希釈した。次に、希釈したラテックス１２００ｇに、ドデシル硫酸ナトリウム（ＳＤＳ：アニオン系界面活性剤）１．２ｇを添加して、ラテックスを安定させた。続いて、同ラテックスに、尿素１２ｇを添加して、室温で１０分間、回転速度２００ｒｐｍで攪拌することにより、蛋白質分解処理を行った。その後、蛋白質分解処理が完了したラテックスを、回転速度８０００ｒｐｍで４５分間、遠心分離した。そして、分離された上層のクリーム分を、ＳＤＳ水溶液に再分散して、回転速度３００ｒｐｍで３０分間撹拌した。このような遠心分離および再分散を、三回繰り返して、脱蛋白質化天然ゴムラテックスを製造した。なお、再分散に用いたＳＤＳ水溶液の濃度は、一回目１質量％、二回目０．５質量％、三回目０．１質量％とした。 <Production of deproteinized natural rubber latex>
As natural rubber latex, high ammonia latex (rubber content concentration 60.2 mass%, ammonia content concentration 0.7 mass%) manufactured by Golden Hope (Malaysia) was used. First, the high ammonia latex was diluted so that the rubber concentration was 30% by mass. Next, 1.2 g of sodium dodecyl sulfate (SDS: anionic surfactant) was added to 1200 g of the diluted latex to stabilize the latex. Subsequently, 12 g of urea was added to the latex, and the mixture was stirred at room temperature for 10 minutes at a rotation speed of 200 rpm to perform proteolytic treatment. Thereafter, the latex after the proteolytic treatment was centrifuged at a rotational speed of 8000 rpm for 45 minutes. Then, the separated cream of the upper layer was redispersed in an aqueous SDS solution and stirred at a rotational speed of 300 rpm for 30 minutes. Such centrifugation and redispersion were repeated three times to produce a deproteinized natural rubber latex. The concentration of the SDS aqueous solution used for redispersion was 1% by mass for the first time, 0.5% by mass for the second time, and 0.1% by mass for the third time.
　＜シリカ含有改質天然ゴムラテックスおよびシリカ含有改質天然ゴム材料の製造＞
　［実施例１］
　まず、ゴム分濃度が２０質量％に調製された脱蛋白質化天然ゴムラテックス２００ｇを、ステンレス製容器に入れ、３０℃で回転速度２００ｒｐｍで撹拌しながら、窒素置換を１時間行うことにより、ラテックス中の溶存酸素を除去した。次に、当該ラテックスに、室温下で、重合開始剤のＴＢＨＰＯ０．２３８ｇおよびＴＥＰＡ０．５００ｇを添加した。さらに、３－メタクリロキシプロピルトリメトキシシラン（ＭＰＴＭＳ）８ｇを滴下して、２時間攪拌することにより、グラフト共重合を行った。このようにして、シリカ含有改質天然ゴムラテックスを製造した。得られたラテックスをシャーレに移し、５０℃で乾燥して、厚さ１ｍｍのシート状のシリカ含有改質天然ゴム材料を製造した。製造したシリカ含有改質天然ゴム材料を、実施例１のゴム材料と称す。 <Manufacture of silica-containing modified natural rubber latex and silica-containing modified natural rubber material>
[Example 1]
First, 200 g of deproteinized natural rubber latex prepared with a rubber concentration of 20% by mass is placed in a stainless steel container and subjected to nitrogen replacement for 1 hour while stirring at 30 ° C. at a rotation speed of 200 rpm. The dissolved oxygen was removed. Next, 0.238 g of a polymerization initiator TBHPO and 0.500 g of TEPA were added to the latex at room temperature. Further, 8 g of 3-methacryloxypropyltrimethoxysilane (MPTMS) was added dropwise and stirred for 2 hours to carry out graft copolymerization. In this way, a silica-containing modified natural rubber latex was produced. The obtained latex was transferred to a petri dish and dried at 50 ° C. to produce a sheet-like silica-containing modified natural rubber material having a thickness of 1 mm. The produced silica-containing modified natural rubber material is referred to as the rubber material of Example 1.
　［実施例２］
　ＭＰＴＭＳに代えて、ビニルトリエトキシシラン（ＢＴＥＳ）を滴下した以外は、実施例１と同様にして、実施例２のゴム材料を製造した。 [Example 2]
A rubber material of Example 2 was produced in the same manner as in Example 1 except that vinyltriethoxysilane (BTES) was added dropwise instead of MPTMS.
　［実施例３］
　ＭＰＴＭＳに代えて、ｐ－スチリルトリメトキシシランを滴下した以外は、実施例１と同様にして、実施例３のゴム材料を製造した。 [Example 3]
A rubber material of Example 3 was produced in the same manner as in Example 1 except that p-styryltrimethoxysilane was added dropwise instead of MPTMS.
　＜ＴＥＭ観察＞
　実施例１～３のゴム材料を、ＴＥＭ（Ｈｉｔａｃｈｉ　Ｈ－８００、加速電圧２００ｋＶ）を用いて観察した。超薄切片は、ウルトラミクロトーム（Ｓｏｒｖａｌｌ　ＭＴ－６０００）を用いて、－９０℃で作製した。一例として、図１に、実施例２のゴム材料のＴＥＭ写真を示す（倍率：１０，０００倍）。図２に、同ゴム材料の拡大ＴＥＭ写真を示す（倍率：３０，０００倍）。 <TEM observation>
The rubber materials of Examples 1 to 3 were observed using TEM (Hitachi H-800, acceleration voltage 200 kV). Ultrathin sections were prepared at −90 ° C. using an ultramicrotome (Sorvall MT-6000). As an example, FIG. 1 shows a TEM photograph of the rubber material of Example 2 (magnification: 10,000 times). FIG. 2 shows an enlarged TEM photograph of the rubber material (magnification: 30,000 times).
　図１に示すように、天然ゴム粒子（白色部分）の周囲には、シリカ粒子（黒色部分）を含むマトリックス層が観察された。すなわち、実施例２のゴム材料は、シリカを含むグラフト鎖からなるマトリックスに、天然ゴム粒子が分散されたナノマトリックス構造を有することが、確認された。また、図２に拡大して示すように、シリカとして、粒子径が約１５０ｎｍの大粒子と、粒子径が約２０ｎｍの小粒子が確認された。なお、実施例１、３のゴム材料のＴＥＭ写真においても、実施例２のゴム材料と同様に、天然ゴム粒子の周囲にシリカ粒子を含むマトリックス層が観察された。 As shown in FIG. 1, a matrix layer containing silica particles (black portion) was observed around the natural rubber particles (white portion). That is, it was confirmed that the rubber material of Example 2 had a nanomatrix structure in which natural rubber particles were dispersed in a matrix composed of a graft chain containing silica. Further, as shown in an enlarged view in FIG. 2, large particles having a particle size of about 150 nm and small particles having a particle size of about 20 nm were confirmed as silica. In the TEM photographs of the rubber materials of Examples 1 and 3, a matrix layer containing silica particles was observed around the natural rubber particles as in the rubber material of Example 2.
　＜引張り特性＞
　実施例１～３のゴム材料について、引張強さ（ＴＳ）と切断時伸び（Ｅｂ）を測定した。これらの測定は、ＪＩＳ　Ｋ　６２５１（２０１０）に準じて行った。試験片としては、ダンベル状７号形を使用した。測定結果を、表１に示す。表１には、比較のため、原料の脱蛋白質化天然ゴムの引張強さと切断時伸びの値を、併せて示す。
Figure JPOXMLDOC01-appb-T000001
 <Tensile properties>
The rubber materials of Examples 1 to 3 were measured for tensile strength (TS) and elongation at break (E b ). These measurements were performed according to JIS K 6251 (2010). Dumbbell-shaped No. 7 was used as a test piece. The measurement results are shown in Table 1. For comparison, Table 1 also shows the tensile strength and the elongation at break of the raw material deproteinized natural rubber.
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、実施例１～３のゴム材料の引張強さは、脱蛋白質化天然ゴムの引張強さと比較して、大幅に大きくなった。以上より、本発明のシリカ含有改質天然ゴムラテックス、およびそれを乾燥して得られるシリカ含有改質天然ゴム材料は、大きな強度を有することが確認された。また、本発明の製造方法によると、強度の大きなシリカ含有改質天然ゴム材料を、容易に製造できることが確認された。 As shown in Table 1, the tensile strengths of the rubber materials of Examples 1 to 3 were significantly larger than the tensile strength of the deproteinized natural rubber. From the above, it was confirmed that the silica-containing modified natural rubber latex of the present invention and the silica-containing modified natural rubber material obtained by drying the latex have high strength. Moreover, according to the manufacturing method of this invention, it was confirmed that a silica containing modified natural rubber material with a large intensity | strength can be manufactured easily.
　本発明のシリカ含有改質天然ゴムラテックス、およびそれを乾燥して得られるシリカ含有改質天然ゴム材料によると、強度の大きなゴム製品を製造することができる。したがって、本発明のシリカ含有改質天然ゴムラテックスおよびシリカ含有改質天然ゴム材料は、合成ゴムの代替材料として、例えば、タイヤ、防振ゴム部材等の原料に有用である。 According to the silica-containing modified natural rubber latex of the present invention and the silica-containing modified natural rubber material obtained by drying it, a rubber product having high strength can be produced. Therefore, the silica-containing modified natural rubber latex and the silica-containing modified natural rubber material of the present invention are useful as raw materials for tires, vibration-insulating rubber members, etc., as an alternative material for synthetic rubber.

Claims (6)

  1. 　天然ゴムラテックスにアルコキシシランを有するビニルモノマーを添加して、天然ゴム粒子に該ビニルモノマーをグラフト共重合させると共に、該アルコキシシランの加水分解および縮合によりシリカを生成させることにより得られることを特徴とするシリカ含有改質天然ゴムラテックス。 It is obtained by adding a vinyl monomer having an alkoxysilane to natural rubber latex, graft-copolymerizing the vinyl monomer to natural rubber particles, and generating silica by hydrolysis and condensation of the alkoxysilane. Silica-containing modified natural rubber latex.
  2. 　前記アルコキシシランを有するビニルモノマーは、主鎖の一端にアルコキシシランを、他端にビニル構造を有する請求項１に記載のシリカ含有改質天然ゴムラテックス。 The silica-containing modified natural rubber latex according to claim 1, wherein the vinyl monomer having alkoxysilane has an alkoxysilane at one end of the main chain and a vinyl structure at the other end.
  3. 　請求項１または請求項２に記載のシリカ含有改質天然ゴムラテックスを固形化して得られ、前記シリカを含むグラフト鎖からなるマトリックスに前記天然ゴム粒子が分散されてなるシリカ含有改質天然ゴム材料。 A silica-containing modified natural rubber material obtained by solidifying the silica-containing modified natural rubber latex according to claim 1 or 2, wherein the natural rubber particles are dispersed in a matrix comprising a graft chain containing the silica. .
  4. 　前記シリカの粒子径は、１０ｎｍ以上１５０ｎｍ以下である請求項３に記載のシリカ含有改質天然ゴム材料。 The silica-containing modified natural rubber material according to claim 3, wherein a particle diameter of the silica is 10 nm or more and 150 nm or less.
  5. 　天然ゴムラテックスに、アルコキシシランを有するビニルモノマーと重合開始剤とを添加して、天然ゴム粒子に該ビニルモノマーをグラフト共重合させると共に、該アルコキシシランの加水分解および縮合によりシリカを生成させるグラフト共重合工程と、
    　得られたラテックスを乾燥する乾燥工程と、
    を有することを特徴とするシリカ含有改質天然ゴム材料の製造方法。     A vinyl monomer having an alkoxysilane and a polymerization initiator are added to natural rubber latex, and the vinyl monomer is graft-copolymerized to natural rubber particles. At the same time, a graft copolymer is produced that produces silica by hydrolysis and condensation of the alkoxysilane. A polymerization process;
    A drying step of drying the obtained latex;
    A method for producing a silica-containing modified natural rubber material characterized by comprising:
  6. 　前記アルコキシシランを有するビニルモノマーの添加量は、前記天然ゴムラテックスのゴム分１００質量部に対して５質量部以上６０質量部以下である請求項５に記載のシリカ含有改質天然ゴム材料の製造方法。 The production amount of the silica-containing modified natural rubber material according to claim 5, wherein the addition amount of the vinyl monomer having an alkoxysilane is 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the rubber content of the natural rubber latex. Method.
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JP2013170268A (en) * 2012-02-23 2013-09-02 Tokai Rubber Ind Ltd Vibration proof rubber composition and vibration proof rubber member
CN112778581A (en) * 2021-01-28 2021-05-11 中北大学 Low rolling resistance wet-skid modified natural rubber composite material and preparation method thereof
CN113845778A (en) * 2021-10-14 2021-12-28 胡海阔 High-elasticity wear-resistant polymer rubber and preparation method thereof
CN115157809A (en) * 2022-06-09 2022-10-11 科顺防水科技股份有限公司 Pre-laid waterproof coiled material and preparation method thereof
US11525023B2 (en) 2018-11-30 2022-12-13 Toyo Tire Corporation Modified diene polymer and method for producing same

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09176385A (en) * 1995-12-21 1997-07-08 Sumitomo Rubber Ind Ltd Rubber composition
JP2004359714A (en) * 2003-06-02 2004-12-24 Bridgestone Corp Modified natural rubber latex, modified natural rubber and method for producing the same
JP2005120178A (en) * 2003-10-15 2005-05-12 Yokohama Rubber Co Ltd:The Method of preparation of silica masterbatch
JP2006152156A (en) * 2004-11-30 2006-06-15 Bridgestone Corp Pneumatic tire
JP2006219618A (en) * 2005-02-14 2006-08-24 Bridgestone Corp Modified natural rubber masterbatch, method for producing the same, rubber composition and tire
JP2006225462A (en) * 2005-02-16 2006-08-31 Bridgestone Corp Modified natural rubber and rubber composition and tire using it
JP2007203903A (en) * 2006-02-02 2007-08-16 Bridgestone Corp Pneumatic tire for heavy load
WO2011138890A1 (en) * 2010-05-07 2011-11-10 横浜ゴム株式会社 Method for producing modified polymer

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09176385A (en) * 1995-12-21 1997-07-08 Sumitomo Rubber Ind Ltd Rubber composition
JP2004359714A (en) * 2003-06-02 2004-12-24 Bridgestone Corp Modified natural rubber latex, modified natural rubber and method for producing the same
JP2005120178A (en) * 2003-10-15 2005-05-12 Yokohama Rubber Co Ltd:The Method of preparation of silica masterbatch
JP2006152156A (en) * 2004-11-30 2006-06-15 Bridgestone Corp Pneumatic tire
JP2006219618A (en) * 2005-02-14 2006-08-24 Bridgestone Corp Modified natural rubber masterbatch, method for producing the same, rubber composition and tire
JP2006225462A (en) * 2005-02-16 2006-08-31 Bridgestone Corp Modified natural rubber and rubber composition and tire using it
JP2007203903A (en) * 2006-02-02 2007-08-16 Bridgestone Corp Pneumatic tire for heavy load
WO2011138890A1 (en) * 2010-05-07 2011-11-10 横浜ゴム株式会社 Method for producing modified polymer

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013170268A (en) * 2012-02-23 2013-09-02 Tokai Rubber Ind Ltd Vibration proof rubber composition and vibration proof rubber member
US11525023B2 (en) 2018-11-30 2022-12-13 Toyo Tire Corporation Modified diene polymer and method for producing same
CN112778581A (en) * 2021-01-28 2021-05-11 中北大学 Low rolling resistance wet-skid modified natural rubber composite material and preparation method thereof
CN112778581B (en) * 2021-01-28 2022-03-29 中北大学 Low rolling resistance wet-skid modified natural rubber composite material and preparation method thereof
CN113845778A (en) * 2021-10-14 2021-12-28 胡海阔 High-elasticity wear-resistant polymer rubber and preparation method thereof
CN115157809A (en) * 2022-06-09 2022-10-11 科顺防水科技股份有限公司 Pre-laid waterproof coiled material and preparation method thereof
CN115157809B (en) * 2022-06-09 2023-04-07 科顺防水科技股份有限公司 Pre-laid waterproof coiled material and preparation method thereof

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