Classifications

• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/548—Silicon-containing compounds containing sulfur
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • 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
• • 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
• • 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
  • C08C19/04—Oxidation
  • C08C19/06—Epoxidation
• • 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
  • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Definitions

• the present invention relates to a polymer composition, a rubber composition using the polymer composition, and a tire using the rubber composition. More specifically, the present invention relates to a polymer composition that provides a rubber composition that can be used for a tire member to improve the fuel efficiency of the tire and impart sufficient wear resistance and fracture resistance to the tire, The present invention relates to a rubber composition having the above properties using a polymer composition, and a tire using the rubber composition as a tire member.
• a rubber composition having a low tan ⁇ (hereinafter referred to as low loss property) and an excellent low heat generation property is required as a rubber composition used for tire treads and the like.
• low loss property a rubber composition having a low tan ⁇
• an excellent low heat generation property is required as a rubber composition used for tire treads and the like.
• an inorganic filler in the rubber composition is used. It is effective to improve the affinity with the rubber component.
• Patent Document 8 a partially hydrogenated diene liquid polymer having a terminal epoxidized hydroxyl group in the main chain is partially grafted with an anhydrous maleated styrene-ethylene-butylene-styrene copolymer, and then sensitized.
• a method for use in a pressure-sensitive adhesive formulation is disclosed.
• the molecular weight range of the epoxidized diene polymer is very low, and the host polymer used for the grafting reaction is main chain-modified, so that it is not a reaction involving the functional group of the coupling agent.
• a polymer is one into which more than one functional group has been introduced per molecule.
• Patent Document 1 a reaction in which an amine anti-aging agent is grafted and immobilized using a reaction between an epoxy group of a main chain epoxidized diene elastomer and a low molecular weight compound having an amine functional group has been reported (for example, non-binding).
• Patent Document 1 a reaction in which an amine anti-aging agent is grafted and immobilized using a reaction between an epoxy group of a main chain epoxidized diene elastomer and a low molecular weight compound having an amine functional group has been reported (for example, non-binding).
• Patent Document 1 a reaction in which an amine anti-aging agent is grafted and immobilized using a reaction between an epoxy group of a main chain epoxidized diene elastomer and a low molecular weight compound having an amine functional group has been reported (for example, non-binding).
• Patent Document 1 this technique is intended to suppress the migration by fixing the anti-aging agent to the
• the present invention has been made under such circumstances, and a rubber composition that can be used for a tire member to improve the low fuel consumption of the tire and to impart sufficient wear resistance and fracture resistance to the tire. It is an object of the present invention to provide a polymer composition that gives a product, a rubber composition having the above properties using the polymer composition, and a tire using the rubber composition.
• An elastomer having a reactive functional group on the main chain preferably an epoxidized diene-based elastomer, an inorganic filler, and a modified functional group having binding reactivity with respect to the reactive functional group on the main chain in the elastomer.
• the target polymer composition can be obtained by mixing a coupling agent having an average of 1 or less per molecule and having an affinity for the inorganic filler or having a functional group that chemically binds. I found. Furthermore, it discovered that the tire which has the said property was given by using the rubber composition containing the said polymer composition for a tire member. The present invention has been completed based on such findings.
• the present invention (1) (A) an elastomer having a reactive functional group on the main chain, (B) an inorganic filler, and (C) a reactive functional group on the main chain in the elastomer of component (A), It contains a coupling agent having an average of 1 or less modified functional groups having binding reactivity per molecule and having an affinity for the component (B) or having a functional group capable of chemically bonding.
• Polymer composition (2) The polymer composition as described in (1) above, wherein the mixture obtained by kneading the component (A) and the component (C) is blended with the component (B), (3) The polymer composition according to the above (1) or (2), wherein the reactive functional group on the main chain in the elastomer having a reactive functional group on the main chain of the component (A) is an epoxy group, (4) The polymer composition according to any one of the above (1) to (3), wherein the elastomer of component (A) is a diene elastomer, (5) The polymer composition according to the above (4), wherein the diene elastomer is epoxidized natural rubber, (6) The polymer composition according to the above (4), wherein the diene elastomer is an epoxidized styrene-butadiene copolymer rubber or an epoxidized block copolymer, (7) The polymer composition according to the above (6), wherein the epoxidized block
• a divalent hydrocarbon group of ⁇ 25, L 2 is a group having affinity for —Si (R b ) p (OR c ) q , —Si (R b ) r (OH) s or an inorganic filler;
• R b and R c are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms, p and r are each an integer of 0 to 2, and q and s are 1 to 3, respectively.
• the polymer composition as described in 9 above, wherein the compound having a structure represented by the general formula (2) is a compound having a structure represented by the following general formula (3).
• R 1 is a monovalent hydrocarbon group having 1 to 18 carbon atoms
• R 2 is a monovalent hydrocarbon group having 1 to 18 carbon atoms
• R d is a monovalent hydrocarbon group having 1 to 18 carbon atoms.
• Valent hydrocarbon group is a divalent hydrocarbon group having 2 to 10 carbon atoms that may contain a hetero atom in the chain, and L 1 is a reactive functional group on the main chain of component (A) , A functional group having a group having bonding reactivity, Z represents R 3 O— or —A 2 —L 3 , R 3 represents a monovalent hydrocarbon group having 1 to 18 carbon atoms, and A 2 represents a chain A divalent hydrocarbon group having 2 to 10 carbon atoms which may contain a hetero atom, L 3 is a functional group having a group having an affinity for an inorganic filler. ]
• the reactive functional group on the main chain of the component (A) is an epoxy group
• L 1 in the general formula (2) or the general formula (3) has an active hydrogen-containing group or an acid anhydride group.
• the active hydrogen-containing group is a carboxy group, a primary amino group, a secondary amino group, a hydroxy group, an acid amide group, an N-monosubstituted acid amide group, or a group in which these are protected with a hydrolyzable protecting group.
• the group having affinity for the inorganic filler is an isocyanate group, a silanol group, a primary amino group-containing group, or a secondary amino group.
• a rubber composition comprising the polymer composition according to any one of (1) to (13) above, (15) The above (14), wherein the content of the component (B) silica and / or the inorganic compound represented by the general formula (1) is 10 to 120 parts by mass with respect to 100 parts by mass of all rubber components.
• a tire comprising the rubber composition according to (16) and (16) the rubber composition according to (14) or (15) above as a tire member, Is to provide.
• a polymer composition that provides a rubber composition capable of improving the fuel efficiency of a tire and imparting sufficient abrasion resistance and fracture resistance to the tire, and the properties using the polymer composition are as follows.
• a rubber composition having the rubber composition and a tire using the rubber composition can be provided.
• the polymer composition of the present invention comprises (A) an elastomer having a reactive functional group on the main chain, (B) an inorganic filler, and (C) a reactive function on the main chain in the elastomer of component (A).
• a coupling agent having an average of 1 or less modified functional groups per molecule with respect to the group and having an affinity for the component (B) or a functional group that chemically binds It is characterized by that.
• the elastomer used as the component (A) has a reactive functional group on the main chain, and particularly as an elastomer before introducing the reactive functional group on the main chain.
• diene-based elastomers are preferable.
• natural rubber and synthetic diene-based rubbers such as polyisoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), Ethylene-propylene-diene rubber (EPDM), chloroprene rubber (CR), halogenated butyl rubber, acrylonitrile-butadiene rubber (NBR), etc.
• diene terpolymers such as styrene-butadiene-styrene ternary Polymer (SBS), styrene-isoprene-styrene terpolymer (SIS), etc.
• Rukoto can.
• natural rubber styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), and styrene-butadiene-styrene terpolymer (SBS) are preferable, and the polymer composition is used in the present invention.
• natural rubber, polybutadiene rubber (BR) and styrene-butadiene copolymer rubber (SBR) are more preferable, and natural rubber is particularly preferable.
• What was manufactured by solution polymerization or emulsion polymerization can be used for said SBR, for example, "JSR SL563", “JSR SL552", etc.
• JSR 1500 manufactured by JSR Corporation is on the market.
• SBS for example, “Tufprene Asaprene T” manufactured by Asahi Kasei Chemicals Corporation is marketed.
• component (A) epoxidized natural rubber (epoxidized NR), epoxidized polybutadiene rubber (epoxidized BR), epoxidized styrene-butadiene copolymer rubber (epoxidized SBR) And an epoxidized styrene-butadiene-styrene terpolymer (epoxidized SBS) are preferably used. These may be used singly or in combination of two or more.
• epoxidized NR epoxidized NR
• epoxidized BR epoxidized BR
• epoxidized SBR epoxidized NR
• the epoxy group content in these epoxidized diene elastomers is preferably 1 to 70 mol%, more preferably 5 to 65 mol%, from the viewpoint that the object of the present invention can be effectively achieved. Is more preferable.
• R is a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom or a methyl group.
• the method for epoxidizing the diene elastomer is not particularly limited, and examples thereof include a chlorohydrin method, a direct oxidation method, a hydrogen peroxide method, an alkyl hydroperoxide method, and a peracid method. Specifically, it is carried out using an organic peracid in an inert organic solvent such as benzene, chloroform, carbon tetrachloride or the like.
• the organic peracid for example, perbenzoic acid, peracetic acid, performic acid, perphthalic acid, perpropionic acid, trifluoroperacetic acid and the like can be used. Among these, from the viewpoint of availability and industrial use, Peracetic acid is preferred.
• Epoxidized NR for example, by reacting natural rubber latex with peracetic acid or a mixture of formic acid and H 2 O 2 under appropriate conditions, it does not contain unstable epoxy ring-opening reactants and has good reproducibility. Epoxidized NR can be obtained. Further, as commercially available products of epoxidized NR, specifically, for example, ENR-25 (epoxy group content: 25 mol%) and ENR-50 (epoxy group content: manufactured by Malaysian Rubber Board (MRB)) 50 mol%), ENR-60 (epoxy group content: 60 mol%), and the like.
• ENR-25 epoxy group content: 25 mol%)
• ENR-50 epoxy group content: manufactured by Malaysian Rubber Board (MRB)
• ENR-60 epoxy group content: 60 mol%)
• epoxy group content: 50 mol% means that 50% of the double bond of the natural rubber as the component (A) is epoxidized.
• the type of inorganic filler used as the component (B) is not particularly limited, and various inorganic fillers conventionally used in the plastic field, rubber field, and the like can be used.
• silica and / or an inorganic compound represented by the following general formula (3) as the inorganic filler as the component (B). Is particularly preferred.
• silica there is no restriction
• examples of the silica include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, and the like. The most prominent wet silica is preferred.
• a suitable inorganic filler other than silica is an inorganic compound represented by the following general formula (1).
• M is at least one metal oxide or metal hydroxide selected from Al, Mg, Ti, and Ca, x and y are both integers of 0 to 10, and x and y are both 0. In this case, it is at least one metal oxide or metal hydroxide selected from Al, Mg, Ti, and Ca.
• the inorganic compound represented by the general formula (1) include alumina (Al 2 O 3 ), magnesium hydroxide (Mg (OH) 2 ), magnesium oxide (MgO 2 ), and titanium white (TiO 2 ). titanium black (TiO 2n-1), talc (3MgO ⁇ 4SiO 2 ⁇ H 2 O), attapulgite (5MgO ⁇ 8SiO 2 ⁇ 9H 2 O), magnesium calcium silicate (CaMgSiO 4), magnesium silicate (MgSiO 3) Etc.
• the general formula (1) is preferably an inorganic compound or aluminum hydroxide represented by the following general formula (5).
• Al 2 O 3 .mSiO 2 .nH 2 O (5) In the formula (5), m is an integer of 1 to 4, and n is an integer of 0 to 4.
• Specific examples of the inorganic compound represented by the general formula (5) include clay (Al 2 O 3 .2SiO 2 ), kaolin (Al 2 O 3 .2SiO 2 .2H 2 O), pyrophyllite (Al 2 O 3 ⁇ 4SiO 2 ⁇ H 2 O), bentonite (Al 2 O 3 ⁇ 4SiO 2 ⁇ 2H 2 O) and the like.
• the aluminum hydroxide used by this invention also contains an alumina hydrate.
• Preferred inorganic compounds represented by the general formula (1) used in the present invention include clay (Al 2 O 3 .2SiO 2 ), aluminum hydroxide [Al (OH) 3 ], and alumina (Al 2 O 3 ). is there. Of these, aluminum hydroxide [Al (OH) 3 ] is particularly preferable.
• the inorganic compound represented by the general formula (1) has an average particle size of preferably 100 ⁇ m or less, and more preferably 1 to 90 ⁇ m. Particularly excellent wet performance (wet road surface performance) and on-ice performance (on-ice road surface) of the rubber composition by using the inorganic compound represented by the above general formula (1) having a larger average particle diameter as compared with silica. Performance).
• the inorganic filler used as the component (B) can be used alone or in admixture of two or more.
• (B) Fillers other than inorganic fillers in addition to the inorganic filler as the component (B), other fillers other than the inorganic filler may be used.
• Carbon black can be suitably used as a filler other than the inorganic filler.
• Carbon black is not particularly limited, and for example, SRF, GPF, FEF, HAF, ISAF, SAF and the like are used, iodine adsorption amount (IA) is 60 mg / g or more, and dibutyl phthalate oil absorption amount (DBP) is 80 ml / 100 g.
• the above carbon black is preferable.
• the improvement effect of grip performance and fracture resistance is increased, but HAF, N339, IISAF, ISAF, SAF, etc., which are excellent in wear resistance, are particularly preferable.
• the inorganic filler used as the component (B) is preferably 10 to 120 parts by weight, more preferably 20 to 120 parts, based on 100 parts by weight of the total polymer component, from the viewpoint of reinforcing properties and the effect of improving various properties thereby. It is blended in a proportion of part by mass, more preferably 20 to 100 parts by mass. (B) By making the quantity of the inorganic filler used as a component into the said range, it is excellent in factory workability
• the coupling agent used as the component (C) has one modified functional group having binding reactivity with respect to the reactive functional group on the main chain in the elastomer of the component (A) described above. It is a compound having an average of 1 or less per molecule and having an affinity for the inorganic filler of the component (B) or having a functional group chemically bonded.
• the number of the modified functional group is required to be 1 or less on average per molecule.
• component (A) elastomer usually has a plurality of reactive functional groups on the main chain, so that if there are a plurality of modified functional groups of the component (C) that react therewith, the crosslinking reaction proceeds. This is because gelation is likely to occur.
• the modified functional group in the coupling agent of the component (C) is a functional group capable of reacting with the epoxy group. Since it needs to be, it is preferably a functional group having an active hydrogen-containing group or an acid anhydride group.
• the active hydrogen-containing group include a carboxy group, a primary amino group, a secondary amino group (including a cyclic imino group), a hydroxy group, an acid amide group, an N-monosubstituted acid amide group, and a hydrolyzable protection thereof.
• Preferred examples include groups selected from groups protected by groups.
• the protected active hydrogen-containing group is a group that is converted into the active hydrogen-containing group by performing a modification reaction on the active terminal of the conjugated diene polymer and then performing a hydrolysis reaction, for example. I just need it.
• a trimethylsilyl group is mentioned as a protecting group for a primary amino group or a secondary amino group.
• preferred examples of the functional group having an acid anhydride group include a succinic anhydride residue.
• the component (C) as a functional group having an affinity with the inorganic filler of the component (B) or chemically bonded, for example, when the inorganic filler is silica, it is directly bonded to Si.
• Hydrocarbyloxy group or silicon group containing silanol group, isocyanate group containing group, primary amino group containing group, secondary amino group containing group, acyclic tertiary amino group containing group, cyclic tertiary amino group containing group, etc. Can be mentioned.
• Examples of the coupling agent of the component (C) having such a structure include compounds having a structure represented by the following general formula (2).
• L 1 is a functional group having a group having bonding reactivity with respect to the reactive functional group on the main chain of the component (A)
• Ra is a carbon number of 2 to 2 which may contain a hetero atom in the chain.
• 25 divalent hydrocarbon group L 2 has a group having an affinity for —Si (R b ) p (OR c ) q , —Si (R b ) r (OH) s or an inorganic filler.
• R b and R c are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms
• p and r are each an integer of 0 to 2
• q and s are each an integer of 1 to 3.
• the hetero atom means an atom other than a carbon atom, and an atom selected from a silicon atom, a nitrogen atom, an oxygen atom and a sulfur atom is preferable.
• “in the chain” includes not only on the main chain but also on the side chain.
• the compound having a structure represented by the general formula (2) used as a coupling agent of the component (C) according to the present invention is preferably a compound having a structure represented by the following general formula (3).
• R 1 is a monovalent hydrocarbon group having 1 to 18 carbon atoms
• R 2 is a monovalent hydrocarbon group having 1 to 18 carbon atoms
• R d is a monovalent hydrocarbon group having 1 to 18 carbon atoms.
• a 1 is a divalent hydrocarbon group having 2 to 10 carbon atoms that may contain a hetero atom in the chain
• L 1 is a reactive functional group on the main chain of the component (A)
• Z represents R 3 O— or —A 2 —L 3
• R 3 represents a monovalent hydrocarbon group having 1 to 18 carbon atoms
• a 2 represents a chain
• L 3 is a functional group having a group having an affinity for the inorganic filler.
• the monovalent hydrocarbon group having 1 to 18 carbon atoms represented by R 1 , R 2 and R d is, for example, an alkyl group having 1 to 18 carbon atoms or 2 to 18 carbon atoms.
• Alkenyl groups, aryl groups having 6 to 18 carbon atoms, aralkyl groups having 7 to 18 carbon atoms, and the like are examples of the monovalent hydrocarbon group having 1 to 18 carbon atoms represented by R 1 , R 2 and R d.
• those having 1 to 18 carbon atoms from the viewpoint of reactivity and performance of the coupling agent, those having 1 to 18 carbon atoms.
• An alkyl group is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable.
• the alkyl group may be linear, branched, or cyclic.
• methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert. -A butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, cyclopentyl groups, cyclohexyl groups and the like can be mentioned.
• an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group and an ethyl group are particularly preferable.
• the divalent hydrocarbon group having 2 to 10 carbon atoms which may contain a hetero atom in the chain represented by A 1 and A 2 is preferably an alkanediyl group having 2 to 10 carbon atoms, and having 2 to 6 carbon atoms. Alkanediyl groups are more preferred.
• the alkanediyl group having 2 to 6 carbon atoms may be linear or branched. For example, ethylene group, 1,3-propanediyl group, 1,2-propanediyl group, various butanediyl groups, various types A pentanediyl group, various hexanediyl groups and the like can be mentioned.
• linear ones such as ethylene group, 1,3-propanediyl group, 1,4-butanediyl group, 1,5-pentanediyl group 1,6-hexanediyl group and the like, and 1,3-propanediyl group is particularly preferable.
• alkanediyl groups may contain a heteroatom such as an ether bond (—O—), a sulfide bond (—S—), an ester bond (—COO—), etc. in the chain.
• L 1 is a functional group having a group having bonding reactivity with respect to the reactive functional group on the main chain of the component (A), and the reactive functional group on the main chain is an epoxy group
• L 1 is preferably a functional group having an active hydrogen-containing group or an acid anhydride group, for example.
• the active hydrogen-containing group and the acid anhydride group the above-mentioned groups are preferably exemplified.
• Z is R 3 O— or —A 2 —L 3 , and if only inorganic filler is blended and carbon black is not blended, affinity or chemical bond of the coupling agent to inorganic fillers such as silica From the viewpoint of properties, Z is preferably R 3 O—. R 3 is as described above. On the other hand, when carbon black is blended in addition to the inorganic filler, that is, in the case of a mixed system of silica and carbon black, Z is preferably -A 2 -L 3 .
• L 3 is a functional group having a group having an affinity for the inorganic filler. Examples of the affinity group include an isocyanate group, a silanol group, a primary amino group-containing group, and a secondary amino group.
• these functional groups isocyanate groups, primary amino group-containing groups, secondary amino group-containing groups, acyclic tertiary amino group-containing groups, and cyclic tertiary amino group-containing groups are also compatible with carbon black. Is preferable in a mixed system of silica and carbon black.
• the primary amino group and secondary amino group of the primary amino group-containing group and secondary amino group-containing group may be groups protected by a hydrolyzable protective group (for example, the above-mentioned trimethylsilyl group). .
• a 2 is as described above.
• L 1 is a functional group having an active hydrogen-containing group
• L 1 is a functional group having an active hydrogen-containing group
• examples of the coupling agent include 3- (trimethoxysilyl) propyl succinic anhydride, 3- (Triethoxysilyl) propyl succinic anhydride, 2- (trimethoxysilyl) ethyl succinic anhydride, 2- (triethoxysilyl) ethyl succinic anhydride and the like.
• examples of the group represented by -A 2 -L 3 include isocyanate group-containing groups such as 3-isocyanatopropyl group and 2-isocyanatoethyl group; N- (1,3- Dimethylbutylidene) -1-propanamine-3-yl group, N- (1-methylethylidene) -1-propanamine-3-yl group, N-ethylidene-1-propanamine-3-yl group, N- (1-methylpropylidene) -1-propanamine-3-yl group, N- (N, N-dimethylaminobenzylidene) -1-propanamine-3-yl group, N- (cyclohexylidene) -1- Acyclic tertiary amino group-containing group such as propanamine-3-yl group, 3-dimethylaminopropyl group, 2-dimethylaminoethyl group; 3- (4,5-dihydroimidazol
• Examples of the coupling agent represented by the general formula (3-b) include trimethoxysilane compounds, triethoxysilane compounds, and trimethoxysilyl exemplified as the coupling agent represented by the general formula (3-a).
• Examples include compounds in which one methoxy group and ethoxy group in trimethoxy and triethoxy in the group-containing compound and triethoxysilyl group-containing compound are replaced with various groups exemplified as the group represented by -A 2 -L 3. Can do.
• the aforementioned coupling agent of the component (C) may be used alone or in combination of two or more.
• the mixing method of the component (A) and the component (C) may be performed by mixing the component (A) and the component (C) by reaction in solution or reaction in latex, or by dry kneading. You may mix (A) component and (C) component.
• Dry kneading is particularly preferred from the standpoint of easy mixing, in which the inorganic filler of component (B) can be mixed in the same step after mixing component (A) and component (C).
• Inorganic filler of component is blended after mixing (A) component and (C) component, because (B) component inorganic filler and (A) component react. This is to prevent it.
• the bonding ratio of the component (C) to the component (A) is preferably 2 mol% or more, preferably 4 mol% or more, and more preferably 10 to 100 mol%.
• the modified functional groups may be self-condensed, and there is also a risk of volatilization of component (C). It is advantageous to perform dry kneading under conditions that promote the ring-opening reaction with the group.
• the temperature at the time of kneading is preferably room temperature to 180 ° C, more preferably 30 to 170 ° C, and further preferably 50 to 160 ° C.
• (A) Elastomer having a reactive functional group on the main chain as the component has an epoxy group as the reactive functional group on the main chain, while the modified functional group having the binding reactivity as the component (C) Is a primary amino group-containing modified functional group, the binding mode of the component (A) and the component (C) is, for example, as shown in the following formula (6).
• R 1 , R 2 , A 1 and Z in the formula (6) are the same as above, and R 4 is a hydrogen atom or a monovalent hydrocarbon having 1 to 10 carbon atoms which may contain a hetero atom in the chain. It is a group.
• the reaction product of the component (A) and the component (C) and the inorganic filler of the component (B) are completely reacted, the inorganic filler functions as a crosslinking point.
• the reaction is achieved, at least in part, during the subsequent vulcanization.
• bis (3-triethoxysilylpropyl) sulfide may be used in combination with the coupling agent of component (C). In this way, a vulcanized rubber composition in which the inorganic filler is highly dispersed can be obtained, and a tire with excellent loss resistance and improved fracture resistance and wear resistance can be obtained.
• the rubber composition of the present invention is characterized by including the above-described polymer composition of the present invention.
• rubber components other than the said (A) component can be mix
• the inorganic filler is silica and / or an inorganic compound represented by the general formula (1), and the content thereof is 10 to 120 with respect to 100 parts by mass of the total rubber components. Those having a mass part are preferred, and those having 20 to 120 parts by mass are more preferred.
• rubber component other than (A) component in the rubber composition of the present invention, for example, natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, ethylene- ⁇ -olefin copolymer rubber, ethylene- ⁇ -olefin- At least one selected from non-modified rubbers such as diene copolymer rubber, chloroprene rubber, halogenated butyl rubber, and a copolymer of styrene and isobutylene having a halogenated methyl group can be used.
• the proportion of the component (A) in the total rubber component is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more from the viewpoint of sufficiently achieving the effects of the present invention.
• silane coupling agent In the rubber composition of the present invention, when silica is used as the reinforcing inorganic filler, a silane coupling agent can be blended for the purpose of further improving the reinforcing property and low exothermic property.
• silane coupling agent examples include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis ( 2- (triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-di
• silane coupling agents may be used alone or in combination of two or more.
• the blending amount of the silane coupling agent varies depending on the type of the silane coupling agent and the like, but is preferably selected in the range of 1 to 20% by mass with respect to silica. If this amount is less than 1% by mass, the effect as a coupling agent is hardly exhibited, and if it exceeds 20% by mass, the rubber component may be gelled. From the viewpoint of the effect as a coupling agent and the prevention of gelation, a more preferable blending amount of this silane coupling agent is in the range of 5 to 15% by mass.
• the elastomer (A) and the coupling agent (C) are mixed in advance in the same manner as the preparation of the polymer composition described above, and then the inorganic filler (B) is added.
• the dry kneading is particularly preferred for the same reason.
• the reinforcing inorganic filler of the component (B) is added, and the object of the present invention is not impaired.
• various chemicals usually used in the rubber industry such as a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, an anti-scorching agent, zinc white, and stearic acid, can be contained.
• the vulcanizing agent include sulfur, and the amount used thereof is preferably 0.1 to 10.0 parts by weight, more preferably 1.0 to 5 parts by weight, based on 100 parts by weight of all rubber components. 0.0 part by mass. If the amount is less than 0.1 parts by mass, the rupture strength, wear resistance, and low heat build-up of the vulcanized rubber may be reduced. If the amount exceeds 10.0 parts by mass, rubber elasticity is lost.
• the vulcanization accelerator that can be used in the present invention is not particularly limited.
• M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl) Sulfenamide) and other guanidine vulcanization accelerators such as DPG (diphenylguanidine)
• DPG diphenylguanidine
• DPG diphenylguanidine
• the rubber composition of the present invention is obtained by kneading in the order as described above using a kneader such as an open kneader such as a roll, a closed kneader such as a Banbury mixer, and the like. It can be vulcanized after processing and applied to various rubber products. For example, it can be used for tire applications such as tire treads, under treads, carcass, sidewalls, and bead parts, vibration proof rubber, fenders, belts, hoses and other industrial products. It is suitably used as a tread rubber for tires for low fuel consumption, large tires, and high performance tires that have an excellent balance of heat generation, wear resistance, and breaking strength.
• a kneader such as an open kneader such as a roll, a closed kneader such as a Banbury mixer, and the like. It can be vulcanized after processing and applied to various rubber products. For example, it can be used for tire applications such as tire treads
• the tire of the present invention is characterized by using the above-described rubber composition of the present invention for a tire member.
• Preferred examples of the tire member include a tread, a base tread, and a sidewall, and the rubber composition of the present invention can be used for any of these, and it is particularly preferable to use the tread.
• a tire using the rubber composition of the present invention for a tread has low rolling resistance and excellent fuel efficiency, and excellent fracture resistance and wear resistance.
• gas with which the tire of the present invention is filled normal or air with a changed oxygen partial pressure, or an inert gas such as nitrogen is exemplified.
• the rubber composition of the present invention is used for a tread, for example, it is extruded on a tread member, and is pasted and molded by a usual method on a tire molding machine to form a raw tire.
• the green tire is heated and pressed in a vulcanizer to obtain a tire.
• Examples 1-2 and Comparative Example 1 Natural rubber and epoxidized natural rubber were used as the matrix rubber, and each rubber composition was prepared according to the formulation shown in Table 1.
• the epoxidized natural rubber and coupling agent-1 or coupling agent-2 are previously kneaded at a temperature of 145 ° C., then components other than the crosslinking system are added, and kneaded at a temperature of 150-151 ° C.
• a rubber composition was prepared by adding a crosslinking agent and kneading the mixture at 100 ° C. or lower. Each rubber composition was vulcanized at 160 ° C. for 15 minutes to obtain a vulcanized rubber, and the abrasion resistance and loss tangent (tan ⁇ ) of the vulcanized rubber were determined. The results are shown in Table 2.
• Epoxidized natural rubber Made by Malaysian rubber board (MRB), trade name “ENR-50” (epoxy group content 50 mol%) 2)
• Coupling agent-1 3- (triethoxysilyl) propyl succinic anhydride 3)
• Coupling agent-2 3-aminopropyltriethoxysilane 4)
• Product name “Nipsil AQ” registered by Tosoh Silica) Trademark)
• Aromatic oil “Aromax # 3” manufactured by Fuji Kosan Co., Ltd.
• the polymer composition of the present invention was excellent in wear resistance and low heat buildup. Then, by using the polymer composition of the present invention for a tire member, the fuel efficiency of the tire can be improved, and sufficient abrasion resistance and fracture resistance can be imparted to the tire.
• the polymer composition of the present invention can be used for a tire member to give a rubber composition that can improve the fuel efficiency of the tire and can impart sufficient wear resistance and fracture resistance to the tire.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Tires In General (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=43386596

Family Applications (1)

Country Status (5)

Cited By (1)

Families Citing this family (10)

Citations (16)

Family Cites Families (4)

• 2009
  • 2009-06-24 JP JP2009150067A patent/JP2011006548A/ja active Pending
• 2010
  • 2010-06-23 EP EP10792145.4A patent/EP2447318A4/en not_active Withdrawn
  • 2010-06-23 CN CN2010800322363A patent/CN102459448A/zh active Pending
  • 2010-06-23 US US13/380,783 patent/US20120157575A1/en not_active Abandoned
  • 2010-06-23 WO PCT/JP2010/060677 patent/WO2010150827A1/ja not_active Ceased

Patent Citations (16)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events