WO2012073822A1 - Silice revêtue de résine, composition de caoutchouc et pneu - Google Patents

Silice revêtue de résine, composition de caoutchouc et pneu Download PDF

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Publication number
WO2012073822A1
WO2012073822A1 PCT/JP2011/077185 JP2011077185W WO2012073822A1 WO 2012073822 A1 WO2012073822 A1 WO 2012073822A1 JP 2011077185 W JP2011077185 W JP 2011077185W WO 2012073822 A1 WO2012073822 A1 WO 2012073822A1
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WIPO (PCT)
Prior art keywords
coating material
silica
resin
mass
tire
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PCT/JP2011/077185
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English (en)
Japanese (ja)
Inventor
正幸 齋藤
大久保　明浩
裕昭 斎藤
山崎　倫康
優紀 八木
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群栄化学工業株式会社
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Publication of WO2012073822A1 publication Critical patent/WO2012073822A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3063—Treatment with low-molecular organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3072—Treatment with macro-molecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to a resin-coated silica, a rubber composition containing the resin-coated silica, and a tire using the rubber composition.
  • a rubber composition in which carbon black is blended with rubber is used for the tire tread portion in order to impart wear resistance and reinforcement.
  • silica instead of carbon black
  • the balance between improved fuel economy and handling stability due to reduced rolling resistance of tires can be improved. Therefore, rubber compositions containing silica have been used (see Non-Patent Document 1).
  • the silica particles since the surface of the silica particles is covered with silanol groups, the silica particles tend to aggregate in the rubber and have poor dispersibility. As a result, there is a problem that silica particles and rubber are difficult to mix. In addition, it was difficult to obtain an effect of imparting hardness to the tire.
  • Patent Document 1 a method of surface-treating silica with a silane coupling agent containing a polysulfide structure has been disclosed (see Patent Document 1). Also disclosed are resin-coated silica in which silica is coated with a phenol resin obtained by reacting phenols and aldehydes in the presence of a catalyst, and a rubber composition containing rubber as an essential component (Patent Document 2). reference).
  • the resin-coated silica of the present invention is a resin-coated silica in which silica having a nitrogen adsorption specific surface area of 50 to 300 m 2 / g according to the BET method is sequentially coated with a first coating material and a second coating material,
  • the first coating material contains phenols
  • the second coating material contains (A) at least one of a novolac type phenol resin and a curing agent, and (B) a resol type phenol resin.
  • the first coating material preferably contains a curing agent.
  • the first coating material preferably contains a silane coupling agent.
  • the rubber composition of the present invention contains the resin-coated silica of the present invention and rubber.
  • the tire of the present invention is characterized in that the rubber composition of the present invention is used for a tire tread portion.
  • the present invention it is possible to provide a resin-coated silica having good kneadability with rubber and excellent hardness imparting effect.
  • the resin-coated silica of the present invention is obtained by sequentially coating silica having a nitrogen adsorption specific surface area of 50 to 300 m 2 / g by BET method with a first coating material and a second coating material.
  • silica used for the resin-coated silica of the present invention may be wet silica or dry silica. Of these, wet silica is preferred because of its higher reinforcing effect.
  • nitrogen adsorption specific surface area by BET method means that nitrogen gas is adsorbed on the surface of powder particles, and the amount of monomolecular adsorption is measured by the BET equation from the relationship between the pressure and the amount of adsorption at that time. The specific surface area required.
  • the nitrogen adsorption specific surface area of silica by the BET method is 50 to 300 m 2 / g, preferably 90 to 230 m 2 / g, and more preferably 115 to 215 m 2 / g.
  • the nitrogen adsorption specific surface area of silica is not less than the lower limit, the reinforcing effect on rubber is excellent.
  • the silica dispersibility in the rubber is excellent.
  • Silica may be used alone or in combination of two or more.
  • the first coating material contains phenols.
  • phenols refers to an aromatic hydroxy compound in which a hydrogen atom of an aromatic hydrocarbon nucleus is substituted with a hydroxy group.
  • Phenols include phenol, resorcin, cresol, xylenol, propylphenol, butylphenol, octylphenol, allylphenol, phenylphenol, bromophenol, bisphenol A, bisphenol F, cardanol, cashew nut shell oil, gallic acid, eugenol, urushiol, etc. Is mentioned.
  • cresol, allylphenol, cardanol, and cashew nut shell oil are preferable, and cresol and cardanol are more preferable because they are liquid and are easy to coat silica and are economically advantageous.
  • cresols ortho-cresol is preferable.
  • allylphenols orthoallylphenol is preferred.
  • Phenols may be used alone or in combination of two or more.
  • the content of phenols in the first coating material is 40% by mass or more and less than 100% by mass with respect to 100% by mass of the first coating material (excluding the solvent and the dispersion medium).
  • the silica coated with the first coating material can be easily coated with the second coating material.
  • the first coating material may contain components other than phenols.
  • the first coating material preferably contains a curing agent.
  • the “curing agent” refers to a compound that crosslinks by reacting with a hydrogen atom of a phenolic aromatic hydrocarbon nucleus or a phenolic hydroxyl group.
  • the curing agent examples include hexamethylenetetramine, hexamethoxymethylmelamine, paraformaldehyde, formaldehyde, glyoxal, trioxane, 4,4′-diaminodiphenylmethane, acetaldehyde ammonia, a resol type phenol resin, a urethane resin, and an epoxy resin.
  • hexamethylenetetramine, hexamethoxymethylmelamine, and 4,4′-diaminodiphenylmethane are preferable, and hexamethylenetetramine is particularly preferable because the curing reaction easily proceeds well.
  • curing agent may be used individually by 1 type, and may use 2 or more types together.
  • the content of the curing agent in the first coating material is preferably 0.5 to 50 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the phenols.
  • the content of the curing agent is not less than the preferred lower limit, the effect of integrating the first coating material and the second coating material is improved, and when the obtained rubber composition is used as a tire, a good hardness is obtained.
  • the steering stability is improved. On the other hand, even if the preferable upper limit is exceeded, the hardness imparting effect and the steering stability are not improved according to the increase. If it is less than or equal to the preferable upper limit value, the cost can be reduced.
  • the first coating material preferably contains a silane coupling agent.
  • the combined use of the silane coupling agent increases the affinity between silica and phenols, and increases the adhesion between silica and the first coating material.
  • silane coupling agents include aminosilanes such as 3-aminopropyltriethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ) Epoxy silane such as ethyltrimethoxysilane; Vinyl silane such as vinyltrimethoxysilane and vinyltriethoxysilane; Methacryloxysilane such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltriethoxysilane; p- Styrylsilane such as styryltrimethoxysilane; mercaptosilane such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; bis (triethoxysilylpropyl) tetras Such as Suruf
  • the silane coupling agent containing the polysulfide structure (sulfur atom) described in Patent Document 1 is expensive, and there is a problem in that it is expensive to obtain a tire.
  • a silane coupling agent is not essential. Even when a silane coupling agent is used, instead of using this silane coupling agent containing a sulfur atom, the adhesion between silica and the first coating material can be achieved by using the above-mentioned general silane coupling agent. The effect of improving the performance can be obtained, and the cost can be reduced.
  • the content of the silane coupling agent in the first coating material is preferably 5 to 700 parts by mass, more preferably 30 to 350 parts by mass with respect to 100 parts by mass of the phenols.
  • the content of the silane coupling agent is equal to or more than the preferred lower limit, the affinity between silica and phenols increases, and the adhesion between silica and the first coating material increases.
  • the content of the silane coupling agent is not more than the preferable upper limit value, strength as a rubber product such as breaking strength is not lowered.
  • the second coating material contains at least one of (A) a novolac type phenol resin and a curing agent, and (B) a resol type phenol resin. That is, the second coating material is either (A) a novolak type phenol resin and a curing agent, and (B) a resol type phenol resin, or (A) a novolac type phenol resin, a curing agent, and (B) a resole. Both types of phenolic resins are included.
  • Novolak-type phenolic resin and curing agent As the novolac-type phenolic resin, those obtained by reacting phenols and aldehydes in the presence of an acid catalyst are used. Moreover, the novolak-type phenol resin which modified
  • aldehydes refers to compounds having at least one hydrogen atom in the carbonyl group, that is, having a formyl group —CHO.
  • Phenols may be phenol, resorcin, cresol, xylenol, propylphenol, butylphenol, octylphenol, phenylphenol, bromophenol, bisphenol A, bisphenol F, cardanol, cashew nut shell oil, gallic acid, eugenol, urushiol, etc. it can.
  • the said phenols may be used individually by 1 type, and may use 2 or more types together.
  • aldehydes formaldehyde, paraformaldehyde, trioxane, glyoxal, benzaldehyde, salicylaldehyde, and the like can be used.
  • the aldehydes may be used alone or in combination of two or more. Among them, since it is easier to achieve both reduction in rolling resistance of the tire and driving stability of the vehicle when the tire is used, phenols are preferably phenol, cresol, cardanol, butylphenol, octylphenol, and bisphenol A, phenol, And cardanol is more preferred. As aldehydes, formaldehyde and paraformaldehyde are preferable, and formaldehyde is more preferable.
  • the acid catalyst examples include hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, succinic acid, butyric acid, lactic acid, benzenesulfonic acid, p-toluenesulfonic acid, boric acid, or a salt with a metal such as zinc chloride or zinc acetate.
  • the said acid catalyst may be used individually by 1 type, and may use 2 or more types together.
  • a novolak-type phenol resin may be used individually by 1 type, and may use 2 or more types together.
  • the second coating material contains (A) a novolak type phenol resin and a curing agent, and (B) does not contain a resol type phenol resin
  • the novolak type phenol resin in the second coating material (excluding the solvent and the dispersion medium)
  • the content of is preferably 30 to 99% by mass, more preferably 60 to 98% by mass, and still more preferably 70 to 95% by mass with respect to 100% by mass of the second coating material (excluding the solvent and dispersion medium).
  • the content of the novolac type phenol resin is equal to or more than the preferable lower limit value, the kneadability of silica with rubber is improved.
  • the content of the novolac type phenol resin is not more than the preferable upper limit value, physical properties as a rubber product such as breaking strength and hardness are not deteriorated.
  • curing agent in a component the thing similar to the hardening
  • hexamethylenetetramine, hexamethoxymethylmelamine, and 4,4′-diaminodiphenylmethane are more preferable, and hexamethylenetetramine is particularly preferable because the curing reaction easily proceeds well.
  • curing agent may be used individually by 1 type, and may use 2 or more types together.
  • the content of the curing agent in the second coating material is preferably 1 to 30 parts by mass and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the novolac type phenol resin.
  • the content of the curing agent is equal to or more than the preferred lower limit, the effect of imparting hardness to the vulcanized rubber composition is improved.
  • the preferable upper limit is exceeded, the tire hardness imparting effect corresponding to the increase and the improvement of the driving stability of the automobile are not observed. If it is less than or equal to the preferable upper limit value, the cost can be reduced.
  • Resol type phenol resin As the resol type phenol resin, a product obtained by reacting phenols and aldehydes in the presence of an alkali catalyst is used. In addition, a resol type phenol resin obtained by modifying a reaction product of a phenol and an aldehyde with cashew nut shell oil, tung oil, rosin or the like in the presence of an alkali catalyst can also be used. These resol type phenol resins are self-hardening. Examples of the phenols and aldehydes include the same phenols and aldehydes as those described above for the novolak type phenol resin.
  • phenol, cresol, cardanol, butylphenol, and octylphenol are preferred as phenols because phenol tires are more likely to have a reduction in rolling resistance and driving stability of the vehicle when used as a tire, and phenol and cardanol are preferred. More preferred.
  • aldehydes formaldehyde and paraformaldehyde are preferable, and formaldehyde is more preferable.
  • Alkali catalysts include alkali metal hydroxides such as sodium hydroxide and lithium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; ammonium hydroxide; diethylamine, triethylamine, and triethanol.
  • Examples include amines such as amines, ethylenediamine, and hexamethylenetetramine.
  • the said alkali catalyst may be used individually by 1 type, and may use 2 or more types together.
  • a resol type phenol resin may be used individually by 1 type, and may use 2 or more types together.
  • the second coating material contains (B) a resol type phenol resin and (A) a novolac type phenol resin and a curing agent
  • the resol type phenol resin in the second coating material (excluding the solvent and dispersion medium)
  • the content of is preferably 30 to 100% by mass, more preferably 70 to 100% by mass, and may be 100% by mass with respect to 100% by mass of the second coating material (excluding the solvent and dispersion medium).
  • the content of the resol type phenolic resin is equal to or more than the preferable lower limit value, the kneadability of silica with rubber is improved.
  • tires it is easy to achieve both a reduction in tire rolling resistance and driving stability of automobiles.
  • the second coating material includes (A) novolac type phenol resin and curing agent, (B) resol type phenol resin, melamine resin, urea resin, epoxy resin, urethane resin, alkyd resin, unsaturated polyester resin, Polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, ABS resin (acrylonitrile-butadiene-styrene copolymer), AS resin (acrylonitrile-styrene copolymer), acrylic resin, polyamide resin, polycarbonate resin, polyethylene terephthalate resin (C) resins such as polybutylene terephthalate resin, polyphenylene sulfide resin, polysulfone resin, and polyether sulfone resin may be used.
  • A novolac type phenol resin and curing agent
  • B resol type phenol resin, melamine resin, urea resin, epoxy resin, urethane resin, alkyd resin, unsaturated polyester
  • the mass ratio is not less than the preferred lower limit, the kneading property of silica to rubber is improved without deteriorating physical properties as a rubber product such as breaking strength and hardness.
  • the mass ratio is not less than the preferred lower limit, the kneading property of silica to rubber is improved without deteriorating physical properties as a rubber product such as breaking strength and hardness.
  • breaking strength and hardness when tires are used, it is easy to achieve both a reduction in tire rolling resistance and driving stability of automobiles.
  • the resin-coated silica of the present invention can be produced by sequentially coating the silica with a first coating material and a second coating material. Specifically, there is a method in which silica and a first coating material are mixed, and then a second coating material is added and mixed.
  • the coating amount of the first coating material is preferably such that the phenols contained in the coating material coated on silica are 0.5 to 50 parts by mass with respect to 100 parts by mass of silica.
  • the amount to be part is more preferable.
  • the larger the specific surface area of silica the greater the amount of the first coating material applied.
  • the phenols contained in the coating material have a preferable lower limit value or more, the polarity of the silica surface is easily reduced.
  • the silica coated with the first coating material can be easily coated with the second coating material.
  • it is not more than the preferred upper limit value it is easy to achieve both reduction in rolling resistance of the tire and steering stability of the vehicle when the tire is used.
  • the coating amount of the first coating material is 0 for the silane coupling agent contained in the coating material applied to silica to 100 parts by mass of silica.
  • the amount is preferably 3 to 20 parts by mass, and more preferably 1 to 10 parts by mass.
  • the silane coupling agent contained in the coating material has a preferable lower limit value or more, the adhesion between the silica and the first coating material tends to increase. On the other hand, even if it exceeds the preferable upper limit value, no improvement in the adhesion between the silica and the first coating material according to the increase is observed. If it is less than or equal to the preferable upper limit value, the cost can be reduced.
  • the coating amount of the second coating material is the same as that in the coating material applied to silica.
  • the novolac type phenolic resin contained in is preferably in an amount of 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of silica.
  • the novolac type phenol resin contained in the coating material is equal to or more than the preferable lower limit value, the kneadability of silica to rubber is improved.
  • the novolac type phenolic resin contained in the coating material has a preferable upper limit value or less, physical properties as a rubber product such as breaking strength and hardness are not deteriorated.
  • the amount of the novolac-type phenolic resin is within the above-mentioned preferable range, when the tire is used, it is easy to achieve both a reduction in rolling resistance of the tire and a driving stability of the automobile.
  • the coating amount of the second coating material is within the coating material applied to silica.
  • the amount of the resol type phenolic resin contained in is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of silica.
  • the resol type phenolic resin contained in the coating material has a preferable lower limit value or more, kneadability of silica with rubber is improved.
  • the resol type phenolic resin contained in the coating material has a preferable upper limit value or less, physical properties as a rubber product such as breaking strength and hardness are not deteriorated.
  • the amount of the resol type phenol resin is within the above-mentioned preferable range, it is easy to achieve both reduction in rolling resistance and steering stability when a tire is formed.
  • the coating amount of the second coating material is set in the coating material applied to silica.
  • the total amount of the novolac type phenol resin and the resol type phenol resin contained in is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of silica.
  • the total of the novolak-type phenol resin and the resol-type phenol resin contained in the coating material is equal to or more than the preferable lower limit value, the kneadability of silica to rubber is improved.
  • the total of the novolac type phenol resin and the resol type phenol resin contained in the coating material is not more than the preferable upper limit value, physical properties as a rubber product such as breaking strength and hardness are not deteriorated.
  • the total amount of the novolac type phenol resin and the resol type phenol resin is within the above-mentioned preferable range, when the tire is used, the reduction of the rolling resistance of the tire and the driving stability of the vehicle are easily compatible.
  • first coating material and the second coating material materials diluted or dispersed with an appropriate solvent or dispersion medium may be used as necessary.
  • solvent or dispersion medium water, methanol, acetone, methyl ethyl ketone, or the like can be used.
  • the silane coupling agent may be premixed with other components contained in the first coating material and mixed with silica, or the silane coupling agent May be mixed with silica alone, and then other components contained in the first coating material may be mixed.
  • apparatuses such as a batch mixer and a continuous mixer can be used. These devices may be used at room temperature or with heating as necessary.
  • the apparatus when a solid material is used for each coating material, it is preferable to use the apparatus after heating because the mixing operation can be easily performed.
  • the silica obtained after adding and mixing the second coating material may be dried by a known dryer or the like. What is necessary is just to determine the drying temperature and drying time in that case suitably by the solvent or dispersion medium to be used, the dilution amount of material, etc.
  • the phenols in the first coating material are phenol, resorcin, cresol, xylenol, propylphenol, butylphenol, octylphenol, allylphenol, phenylphenol, bromophenol, bisphenol A, bisphenol F, cardanol, cashew nut shell oil, gallic acid, eugenol And
  • the novolac type phenol resin and the curing agent in the second coating material the novolac type phenol resin is phenol, resorcin, cresol, xylenol, propyl.
  • Phenol, butylphenol, octylphenol, phenylphenol, bromophenol, bisphenol A, bisphenol F, cardanol, cashew At least one phenol selected from the group consisting of tschel oil, gallic acid, eugenol, and urushiol, and at least one aldehyde selected from the group consisting of formaldehyde, paraformaldehyde, trioxane, glyoxal, benzaldehyde, and salicylaldehyde
  • a catalyst such as hexamethylenetetramine, hexamethoxymethylmelamine, paraformaldehyde, formaldehyde, glyoxal, trioxane, 4,4'-diaminodiphenylmethane, acetaldehyde ammonia, resol type It is preferably at least one selected from the group consisting of phenolic resins, urethane resins,
  • at least one selected from the group consisting of aminosilanes such as 3-aminopropyltriethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane; 3-glycidoxypropyltrimethoxy as silane coupling agents; Silanes and epoxy silanes such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; Methacryloxy silanes such as tacryloxypropy
  • the phenols in the first coating material are phenol, resorcin, cresol, xylenol, propylphenol, butylphenol, octylphenol, allylphenol, phenylphenol, bromophenol, bisphenol A, bisphenol F, cardanol, cashew nut shell oil, gallic acid, eugenol
  • the resole type phenolic resin in the second coating material is phenol, resorcin, cresol, xylenol, propylphenol, butylphenol, octylphenol, phenylphenol, bromo Phenol, bisphenol A, bisphenol F, cardanol, cashew nut shell oil, gallic acid, eugenol, and Reaction of at least one phenol selected from the group consisting of luciol and at least one aldehyde selected from the group consisting of formaldehyde, paraformaldehyde, trioxane,
  • at least one selected from the group consisting of aminosilanes such as 3-aminopropyltriethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane; 3-glycidoxypropyltrimethoxy as silane coupling agents; Silanes and epoxy silanes such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; Methacryloxy silanes such as t
  • the phenols in the first coating material are phenol, resorcin, cresol, xylenol, propylphenol, butylphenol, octylphenol, allylphenol, phenylphenol, bromophenol, bisphenol A, bisphenol F, cardanol, cashew nut shell oil, gallic acid, eugenol And
  • the novolac type phenol resin and the curing agent in the second coating material the novolac type phenol resin is phenol, resorcin, cresol, xylenol, propyl.
  • Phenol, butylphenol, octylphenol, phenylphenol, bromophenol, bisphenol A, bisphenol F, cardanol, cashew At least one phenol selected from the group consisting of tschel oil, gallic acid, eugenol, and urushiol, and at least one aldehyde selected from the group consisting of formaldehyde, paraformaldehyde, trioxane, glyoxal, benzaldehyde, and salicylaldehyde
  • a catalyst such as hexamethylenetetramine, hexamethoxymethylmelamine, paraformaldehyde, formaldehyde, glyoxal, trioxane, 4,4'-diaminodiphenylmethane, acetaldehyde ammonia, resol type (B) resol type phenol resin in the second coating material, which is at least one selected from the group consisting
  • at least one selected from the group consisting of aminosilanes such as 3-aminopropyltriethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane; 3-glycidoxypropyltrimethoxy as silane coupling agents; Silanes and epoxy silanes such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; Methacryloxy silanes such as tacryloxypropy
  • the phenols in the first coating material are at least one selected from the group consisting of cresol, allylphenol, cardanol, and cashew nut shell oil, and (A) the novolac type phenol resin and the curing agent in the second coating material
  • the novolac type phenolic resin is an acid catalyst comprising at least one phenol selected from the group consisting of phenol, cresol, cardanol, butylphenol, octylphenol, and bisphenol A, and aldehydes of formaldehyde and / or paraformaldehyde.
  • the curing agent is at least one selected from the group consisting of hexamethylenetetramine, hexamethoxymethylmelamine, and 4,4′-diaminodiphenylmethane.
  • a curing agent for the first coating material hexamethylenetetramine, hexamethoxymethylmelamine, paraformaldehyde, formaldehyde, glyoxal, trioxane, 4,4'-diaminodiphenylmethane, acetaldehyde ammonia, resol type phenolic resin, urethane resin, and epoxy resin
  • at least one selected from the group consisting of aminosilanes such as 3-aminopropyltriethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane; 3-glycidoxypropyltrimethoxy as silane coupling agents; Silanes and epoxy silanes such as 2- (3,4-epoxycycl
  • the phenol in the first coating material is at least one selected from the group consisting of cresol, allylphenol, cardanol, and cashew nut shell oil
  • the resol type phenol resin in the second coating material is phenol
  • It is preferable that at least one phenol selected from the group consisting of cresol, cardanol, butylphenol, and octylphenol is reacted with aldehydes of formaldehyde and / or paraformaldehyde in the presence of an alkali catalyst.
  • at least one selected from the group consisting of aminosilanes such as 3-aminopropyltriethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane; 3-glycidoxypropyltrimethoxy as silane coupling agents; Silanes and epoxy silanes such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; Methacryloxy silanes such as tacryloxypropy
  • the phenols in the first coating material are at least one selected from the group consisting of cresol, allylphenol, cardanol, and cashew nut shell oil, and (A) the novolac type phenol resin and the curing agent in the second coating material
  • the novolac type phenolic resin is an acid catalyst comprising at least one phenol selected from the group consisting of phenol, cresol, cardanol, butylphenol, octylphenol, and bisphenol A, and aldehydes of formaldehyde and / or paraformaldehyde.
  • the reaction is preferably carried out under the following conditions.
  • at least one selected from the group consisting of aminosilanes such as 3-aminopropyltriethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane; 3-glycidoxypropyltrimethoxy as silane coupling agents; Silanes and epoxy silanes such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; Methacryloxy silanes such as tacryloxypropy
  • the phenol in the first coating material is cresol or cardanol
  • the novolac type phenol resin is phenol and / or cardanol and formaldehyde.
  • the curing agent is preferably hexamethylenetetramine or 4,4′-diaminodiphenylmethane. Hexamethylenetetramine may be added to the first coating material as a curing agent, and 3-aminopropyltriethoxysilane may be added as a silane coupling agent.
  • the phenols in the first coating material are cresol or cardanol
  • the (B) resol type phenol resin in the second coating material contains phenol and / or cardanol and formaldehyde in the presence of an alkali catalyst. It is preferable to have reacted. Hexamethylenetetramine may be added to the first coating material as a curing agent, and 3-aminopropyltriethoxysilane may be added as a silane coupling agent.
  • the phenols in the first coating material are cresol or cardanol, and among the (A) novolac type phenol resin and the curing agent in the second coating material, the novolac type phenol resin is phenol and / or cardanol.
  • the curing agent is hexamethylenetetramine, or 4,4′-diaminodiphenylmethane
  • (B) resol type phenolic resin is phenol or cardanol and formaldehyde Is preferably reacted in the presence of an alkali catalyst.
  • Hexamethylenetetramine may be added to the first coating material as a curing agent, and 3-aminopropyltriethoxysilane may be added as a silane coupling agent.
  • the rubber composition of the present invention contains the resin-coated silica of the present invention and a rubber.
  • the rubber include natural rubber; diene rubbers such as styrene butadiene rubber, polyisoprene rubber, polybutadiene rubber, and ethylene butadiene rubber.
  • the content of the resin-coated silica in the rubber composition is preferably 10 to 200 parts by weight and more preferably 30 to 150 parts by weight with respect to 100 parts by weight of the rubber.
  • the content of the resin-coated silica is not more than the preferable upper limit value, the resin-coated silica and the rubber are easily mixed well.
  • the content of the resin-coated silica is equal to or more than the preferable lower limit, the rolling resistance of the tire can be reduced when the tire is formed.
  • the content of the resin-coated silica is within the above-described preferable range, it is easy to achieve both reduction in rolling resistance of the tire and driving stability of the vehicle when the tire is used.
  • the rubber composition may contain components other than the resin-coated silica and rubber.
  • a reinforcing material such as carbon black, aluminum hydroxide, alumina, calcium carbonate, mica, and clay may be used in combination with the rubber composition. These reinforcing materials may be those whose surfaces are untreated or those whose surfaces are treated with a known silane coupling agent or the like.
  • the rubber composition includes a reinforcing resin such as a phenol resin; a curing agent such as hexamethylenetetramine and hexamethoxymethylmelamine; a rubber crosslinking agent such as sulfur and 4,4′-diaminodiphenylmethane; a vulcanization accelerator.
  • Compounding ingredients usually used in the rubber industry such as anti-aging agent, plasticizer, various oils, wax, stearic acid, and zinc oxide may be used.
  • a rubber composition in an unvulcanized state (unvulcanized rubber composition) is obtained by kneading resin-coated silica, rubber, and other compounding components as necessary with a device such as a Banbury mixer, a roll, or a kneader. Can be manufactured. Further, a rubber composition in a vulcanized state is prepared by filling an unvulcanized rubber composition in a predetermined mold and preferably performing a heat treatment (vulcanization) at 130 to 180 ° C. for 5 to 60 minutes. (Vulcanized rubber composition) is obtained.
  • the rubber composition of the present invention can be used for tires, belts, rubber crawlers, anti-vibration rubbers, hoses, mats, marine fences, and the like. Especially, it is suitable for tires and is particularly suitable for tire tread parts.
  • the tire of the present invention uses the rubber composition of the present invention in a tire tread portion.
  • a tire is manufactured by a usual method.
  • the rubber composition of the present invention processed in an unvulcanized state into a predetermined shape of a tire tread portion, and a rubber composition prepared for each member of a tire are in an unvulcanized state These are processed in a predetermined shape and bonded to each other by a tire molding machine to form a raw tire (unvulcanized state), which is then heated and pressurized in a vulcanizer.
  • the resin-coated silica of the present invention When producing an unvulcanized rubber composition, it is better to use the resin-coated silica of the present invention than to use a conventional silane coupling agent containing a polysulfide structure or silica surface-treated only with a phenol resin. The kneadability of silica with rubber is good. Further, the vulcanized rubber composition using the resin-coated silica of the present invention improves the fuel consumption and operation of the vehicle by reducing the rolling resistance of the tire, compared to the vulcanized rubber composition using the conventional surface-treated silica. Both stability and excellent hardness. These reasons are presumed as follows.
  • the silica is directly coated with the first coating material containing phenols.
  • Phenols have a hydrophilic phenolic hydroxyl group and a lipophilic phenyl group. And this hydrophilic phenolic hydroxyl group and the silanol group of the silica surface are couple
  • the polarity of the silica surface coated with the first coating material is lower than the polarity of the surface of the silica alone, and the adhesion between the silica and the second coating material is increased. It becomes easy to coat with a coating material.
  • the silica coating process can be easily performed without diluting with a solvent or the like.
  • the resin-coated silica of the present invention is further coated with a second coating material containing at least one of (B) a resol type phenol resin or (A) a novolak type phenol resin and a curing agent, which is a self-hardening resin. ing.
  • silica has the coating layer by the 1st and 2nd coating material, the viscosity at the time of kneading
  • the dispersibility of silica in the rubber is improved, thereby improving the fuel efficiency and handling of the vehicle due to the reduction in tire rolling resistance. Both stability is considered excellent.
  • the second coating material undergoes a curing reaction with the first coating material, and the first coating material and the second coating material are integrated to form silica and A resin coating layer having high adhesion is formed.
  • the second coating material is integrated with the rubber and the reinforcing resin that is blended as necessary to cause a curing reaction.
  • the resin-coated silica of the present invention is easy to produce as described above. Furthermore, the vulcanized rubber composition using the resin-coated silica of the present invention is superior in hardness and has the same breaking strength as the conventional vulcanized rubber composition using the surface-treated silica. It has sufficient strength as a rubber product. As described above, by using the resin-coated silica of the present invention as a tire raw material, it is possible to provide a tire that satisfies both environmental performance and safety.
  • the hardness (Shore A) of the vulcanized rubber composition was measured according to JIS K6253 using a type A durometer GS-719G manufactured by Teclock. It means that it is excellent in the hardness provision effect, so that the measured value of this hardness is high.
  • breaking strength With respect to the vulcanized rubber composition, the breaking strength (MPa) of a test piece having a dumbbell shape No. 3 was measured according to JIS K6251 using a strograph V10-C manufactured by Toyo Seiki. The higher the value of the breaking strength, the better the strength.
  • Orthocresol Orthocresol (trade name, manufactured by Nippon Steel Chemical Co., Ltd.).
  • Cardanol Cardanol (trade name, manufactured by Golden Cashew products pvt. Ltd.).
  • Silane coupling agent (1) 3-aminopropyltriethoxysilane KBE-903 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Novolac type phenolic resin (1) PS-6230 (trade name, manufactured by Gunei Chemical Industry Co., Ltd .; cardanol-phenol-formaldehyde resin, softening point 85 ° C.) in a 50% by mass methanol solution.
  • Novolac type phenol resin (2) PSK-2320 (trade name, manufactured by Gunei Chemical Industry Co., Ltd .; phenol-formaldehyde resin, softening point 90 ° C.) in a 50% by mass methanol solution.
  • Curing agent (1) 10% by mass aqueous solution of hexamethylenetetramine (manufactured by Mitsubishi Gas Chemical Company).
  • Curing agent (2) 4,4′-diaminodiphenylmethane, Sumicure M (trade name, manufactured by Sumitomo Chemical Co., Ltd.) in a 10% by mass methanol solution.
  • Resol type phenol resin PL-6507 (trade name, manufactured by Gunei Chemical Industry Co., Ltd .; cardanol-phenol-formaldehyde resin, methanol solution having a solid content of 50% by mass).
  • Silane coupling agent (2) 50% by mass methanol solution of bis (triethoxysilylpropyl) tetrasulfide KBE-846 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Silica (a1) to (a9) Surface-treated silica of Examples 1 to 5, 7, and 8 and Comparative Examples 1 to 2.
  • Silica (b1) The surface-treated silica of Example 6.
  • Stearic acid Sakura stearate (trade name, manufactured by NOF Corporation).
  • Zinc flower Zinc oxide (manufactured by Sakai Chemical Co., Ltd.).
  • Novolac type phenolic resin (3) PS-4569 (trade name, manufactured by Gunei Chemical Industry Co., Ltd .; cashew modified phenol-formaldehyde resin, melting point 72 ° C.).
  • Sulfur Sulfur (manufactured by Tsurumi Chemical Co., Ltd.).
  • Curing agent (1) 10% by mass aqueous solution of hexamethylenetetramine (manufactured by Mitsubishi Gas Chemical Company).
  • Vulcanization accelerator Noxeller NS-P (trade name, manufactured by Ouchi Shinsei Chemical Co., Ltd.).
  • each material was stirred and mixed to prepare surface-treated silica.
  • the blending amount of each material indicates the amount of the material itself (the amount as a solution when the material is a solution) with respect to 100 parts by mass of silica.
  • Example 1 2.7 parts by mass of cardanol was added to 100 parts by mass of silica (a), and the mixture was stirred and mixed with a Henschel mixer. Next, 12.6 parts by mass of the novolac-type phenol resin (1) (50% by mass methanol solution) and 9.0 parts by mass of the curing agent (1) (10% by mass aqueous solution) are added with stirring and mixed in a hot air dryer. The surface-treated silica (a1) was obtained by drying at 90 ° C. for 1 hour.
  • Example 2 To 100 parts by mass of silica (a), 4.5 parts by mass of ortho-cresol was added and mixed by stirring with a Henschel mixer. Next, 9.0 parts by mass of the novolac-type phenol resin (1) (50% by mass methanol solution) and 9.0 parts by mass of the curing agent (1) (10% by mass aqueous solution) are added with stirring and mixed in a hot air dryer. The surface-treated silica (a2) was obtained by drying at 90 ° C. for 1 hour.
  • Example 3 To 100 parts by mass of silica (a), 4.5 parts by mass of cardanol was added and stirred and mixed with a Henschel mixer. Next, 9.0 parts by mass of the novolak-type phenol resin (2) (50% by mass methanol solution) and 9.0 parts by mass of the curing agent (1) (10% by mass aqueous solution) are added with stirring and mixed in a hot air dryer. The surface-treated silica (a3) was obtained by drying at 90 ° C. for 1 hour.
  • Example 4 2.7 parts by mass of cardanol was added to 100 parts by mass of silica (a), and the mixture was stirred and mixed with a Henschel mixer. Next, 12.6 parts by mass of a resol type phenol resin (50% by mass methanol solution) was added, mixed by stirring, and dried by a hot air dryer at 90 ° C. for 1 hour to obtain surface-treated silica (a4). It was.
  • Example 5 To 100 parts by mass of silica (a), 2.0 parts by mass of the silane coupling agent (1) and 1.5 parts by mass of cardanol were added and stirred and mixed with a Henschel mixer. Next, 3.0 parts by mass of the novolac-type phenolic resin (1) (50% by mass methanol solution) and 3.0 parts by mass of the curing agent (1) (10% by mass aqueous solution) are added with stirring and mixed in a hot air dryer. The surface-treated silica (a5) was obtained by drying at 90 ° C. for 1 hour.
  • Example 6 Surface-treated silica (b1) was obtained in the same manner as in Example 5 except that the silica (a) was changed to silica (b).
  • Example 7 To 100 parts by mass of silica (a), 2.0 parts by mass of silane coupling agent (1), 4.5 parts by mass of cardanol, and 4.5 parts by mass of curing agent (1) (10% by mass aqueous solution) are added. The mixture was stirred and mixed with a Henschel mixer. Next, 9.0 parts by mass of the novolac-type phenolic resin (1) (50% by mass methanol solution) and 4.5 parts by mass of the curing agent (1) (10% by mass aqueous solution) were added with stirring and mixed in a hot air dryer. The surface-treated silica (a6) was obtained by drying at 90 ° C. for 1 hour.
  • Example 8 To 100 parts by mass of silica (a), 2.0 parts by mass of the silane coupling agent (1) and 4.5 parts by mass of cardanol were added and stirred and mixed with a Henschel mixer. Next, 9.0 parts by mass of novolac-type phenol resin (1) (50% by mass methanol solution), 4.5 parts by mass of curing agent (1) (10% by mass aqueous solution) and curing agent (2) (10% by mass methanol solution) ) 4.5 parts by mass was added, mixed with stirring, and dried in a hot air dryer at 90 ° C. for 1 hour to obtain surface-treated silica (a7).
  • novolac-type phenol resin (1) 50% by mass methanol solution
  • curing agent (1) 10% by mass aqueous solution
  • curing agent (2) 10% by mass methanol solution
  • each material was kneaded to prepare an unvulcanized rubber composition. Moreover, the unvulcanized rubber composition was heated in a mold to obtain a vulcanized rubber composition.
  • the blending amount of each material indicates the amount of the material itself (the amount as a solution when the material is a solution) with respect to 100 parts by mass of natural rubber.
  • Example 9 100 parts by weight of natural rubber, 85 parts by weight of silica (a1), 2 parts by weight of wax, 4 parts by weight of oil, 2 parts by weight of anti-aging agent, 4 parts by weight of stearic acid, 5 parts by weight of zinc white, 10 parts by mass of the novolac type phenol resin (3) was kneaded in a pressure kneader at 150 ° C. for 5 minutes. To the obtained kneaded product, 2.5 parts by mass of sulfur, 5 parts by mass of the curing agent (1) (10% by mass aqueous solution), and 1.5 parts by mass of the vulcanization accelerator were added. By kneading at 90 ° C. for 5 minutes, a sheet-like unvulcanized rubber composition was obtained.
  • the obtained unvulcanized rubber composition was put in a 150 mm ⁇ 150 mm ⁇ 2 mm mold and heated at 150 ° C. for 40 minutes to obtain a vulcanized rubber composition.
  • Example 10 to 16 Comparative Examples 3 to 4
  • a composition was obtained.
  • the curast minimum torque was determined for the unvulcanized rubber composition of each example by the above evaluation method. Further, the storage elastic modulus, tan ⁇ , hardness and breaking strength of the vulcanized rubber composition were measured. The results are shown in Table 2.
  • the unvulcanized rubber compositions of Examples 9 to 16 were compared with the unvulcanized rubber compositions of Comparative Examples 3 and 4 until the rubber composition was melted and vulcanized. From the fact that the value of the minimum torque is small, it can be seen that the kneadability at the time of producing the rubber composition is good.
  • the vulcanized rubber compositions of Examples 9 to 16 have a higher storage elastic modulus and a smaller tan ⁇ value than the vulcanized rubber compositions of Comparative Examples 3 and 4, and therefore, steering stability. It can be seen that the effect of improving the fuel efficiency of the automobile due to the reduction in tire rolling resistance is also high.
  • the vulcanized rubber compositions of Examples 9 to 16 have higher hardness values than the vulcanized rubber compositions of Comparative Examples 3 and 4, the surface-treated silica of Examples 1 to 8 was used. It can be seen that (resin-coated silica) is excellent in hardness imparting effect.
  • the vulcanized rubber compositions of Examples 9 to 16 have a breaking strength equal to or higher than the vulcanized rubber compositions of Comparative Examples 3 and 4, they have practically sufficient strength as rubber products. It can be said that.
  • the present invention it is possible to provide a resin-coated silica having good kneadability with rubber and excellent hardness imparting effect.

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  • Mechanical Engineering (AREA)
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Abstract

La présente invention concerne une silice revêtue de résine qui est obtenue par revêtement d'une silice qui présente une surface spécifique d'adsorption d'azote, telle que déterminée par une méthode BET, de 50 à 300 m2/g, successivement par une première matière de revêtement et une seconde matière de revêtement. La silice revêtue de résine est caractérisée en ce que la première matière de revêtement contient un phénol et la seconde matière de revêtement contient (A) une résine phénolique de type novolaque et un agent de durcissement et/ou (B) une résine phénolique de type résol. La présente invention permet de fournir : une silice revêtue de résine qui présente une bonne aptitude au malaxage avec un caoutchouc et un excellent effet de communication de dureté. L'invention concerne également une composition de caoutchouc et un pneu, chacun d'eux permettant un bon équilibre entre une stabilité de la direction et une amélioration dans le rendement du carburant d'un véhicule en raison de la diminution de la résistance au roulement des pneus.
PCT/JP2011/077185 2010-12-01 2011-11-25 Silice revêtue de résine, composition de caoutchouc et pneu WO2012073822A1 (fr)

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JP5867240B2 (ja) * 2012-03-30 2016-02-24 住友ベークライト株式会社 ゴム組成物
JP7427418B2 (ja) 2019-10-28 2024-02-05 Ｔｏｙｏ Ｔｉｒｅ株式会社 免震構造体用ゴム組成物および免震構造体

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JP2004099829A (ja) * 2002-09-12 2004-04-02 Toyota Motor Corp フィラー含有スラリー組成物
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JPH115874A (ja) * 1997-06-17 1999-01-12 Yokohama Rubber Co Ltd:The ゴム組成物
JP2002003652A (ja) * 2000-06-20 2002-01-09 Bridgestone Corp ゴム組成物及びそれを用いた空気入りタイヤ
JP2003292793A (ja) * 2002-04-01 2003-10-15 Asahi Kasei Corp 難燃組成物
JP2003292816A (ja) * 2002-04-01 2003-10-15 Asahi Kasei Corp 無機系機能付与剤
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JP2015048395A (ja) * 2013-08-30 2015-03-16 群栄化学工業株式会社 熱硬化性樹脂組成物及びレゾール型フェノール樹脂

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