WO2017171458A1 - Composition de caoutchouc pour bande de roulement de pneu - Google Patents

Composition de caoutchouc pour bande de roulement de pneu Download PDF

Info

Publication number
WO2017171458A1
WO2017171458A1 PCT/KR2017/003532 KR2017003532W WO2017171458A1 WO 2017171458 A1 WO2017171458 A1 WO 2017171458A1 KR 2017003532 W KR2017003532 W KR 2017003532W WO 2017171458 A1 WO2017171458 A1 WO 2017171458A1
Authority
WO
WIPO (PCT)
Prior art keywords
silane
rubber composition
group
rubber
weight
Prior art date
Application number
PCT/KR2017/003532
Other languages
English (en)
Korean (ko)
Inventor
황재경
이제민
박준효
공원석
Original Assignee
코오롱인더스트리 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020170039166A external-priority patent/KR101995924B1/ko
Application filed by 코오롱인더스트리 주식회사 filed Critical 코오롱인더스트리 주식회사
Publication of WO2017171458A1 publication Critical patent/WO2017171458A1/fr

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/02—Polysilicates
    • 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 rubber composition for tire treads that can satisfy both grip force and rotational resistance at the same time.
  • the tire supports the load of the vehicle, mitigates the impact generated on the road, and delivers the power and braking power of the car engine to the road to maintain the movement of the car.
  • the tire energy consumption efficiency rating system measures the rolling resistance (friction force) and wet road braking force of tire products to improve energy consumption efficiency (fuel efficiency) in the vehicle driving stage. It is a scheme to encourage consumers to choose high-efficiency tires, just as they select energy-efficient electric refrigerators.
  • the tire energy consumption efficiency rating is classified into two types of fuel efficiency (efficiency) and safety.
  • efficiency fuel efficiency
  • safety safety. The lower the rolling resistance of the tire, the better the fuel efficiency, and the higher the braking force of the wet road, the higher the safety. .
  • Fuel efficiency is measured based on rolling resistance (RR) and refers to resistance generated while a round object such as a tire moves in a straight line at a constant speed in a plane.
  • RR rolling resistance
  • Wet Grip wet road braking force refers to the braking performance, the tire performance related to safety, and as the information on the accident of the vehicle is frequently encountered, the awareness of safety increases, which shows much interest in the braking performance of the vehicle. have.
  • the rubber composition of the tire tread is made of rubber, fillers and other additives, by changing their composition to adjust the physical properties required for the tire, that is, rotational resistance, durability, grip force and the like.
  • Rubber which is the main material of the tire tread rubber composition, deforms and recovers to its original state after a certain time. This is due to its elasticity, which is a property of rubber. Deterioration should be minimized.
  • Republic of Korea Patent No. 10-0227566 proposed that the use of carbon black and silica as a reinforcing material can significantly lower the rotational resistance
  • Republic of Korea Patent No. 10-1572106 to further lower the rotational resistance
  • silane A method of using vinyltris (2-methoxyethoxy) silane as a compound has been proposed.
  • Korean Laid-Open Patent No. 2016-0002044 discloses excellent grip performance under high-speed conditions by using a master batch containing styrene-butadiene rubber and pellet type plant resins such as sesame resin, sunflower resin, and coconut resin. And a composition showing wear resistance.
  • the grip force is a technique that allows the tire surface to closely adhere to the road surface, and it is advantageous if the tire elasticity is excellent.
  • the rolling resistance is advantageous as the adhesion to the road surface is lower, so that the rolling resistance and the grip force of the tire are opposite to each other. That is, tires with low rolling resistance may be advantageous in fuel efficiency but may have poor adhesion to the road when the road is wet.
  • Korean Patent Publication No. 2015-0024701 and US Patent No. 8,637,606 apply modified terpene phenolic resins having a high softening point together with silica, thereby improving the compatibility of phenols with synthetic rubbers. It is disclosed that the grip performance on a wet road surface can be improved by reducing the fluidity of the sheet without deteriorating the rolling resistance performance.
  • the Republic of Korea Patent No. 10-1591276 Tg is -50 to -40 °C
  • the pattern viscosity is 60 to 80 °C, including 20 to 50 parts by weight of epoxidized natural rubber having an epoxidation degree of 5 to 50 mol%, tires It has been proposed a rubber composition which can improve the wet road braking force of and can improve the durability performance with low rotational resistance performance or fuel economy performance without deterioration of abrasion resistance performance.
  • the present inventors pay attention to the properties of carbon black, silica and silane coupling agents used to improve physical properties in the rubber composition for tire tread, inorganic materials such as silica by using a material having high compatibility with Multidisciplinary research was carried out under the idea of increasing the dispersibility of.
  • an object of the present invention is to improve the grip force and at the same time lower the rising width of the rolling resistance known to the opposite physical properties, low fuel efficiency high performance tire tread that can satisfy the two properties of the grip force and rotation resistance required as a tire at the same time It is to provide a rubber composition.
  • the present invention provides a rubber composition for tire treads, comprising a silane-modified petroleum resin copolymerized with a petroleum resin monomer, and a silane compound represented by the following formula (1):
  • the petroleum resin monomer is characterized in that the olefin monomer having at least one ethylenically unsaturated group selected from mixed C5 fraction, mixed C9 fraction and dicyclopentadiene obtained from naphtha cracking.
  • the rubber composition for the tire tread is characterized in that it comprises a raw rubber, carbon black, silica, a silane coupling agent, a vulcanizing agent, and a vulcanization accelerator together with the silane-modified petroleum resin.
  • the rubber composition for tire treads according to the present invention improves the grip force (wet / dry) of the tire, lowers the rising width of the rotational resistance according to the improvement of the grip force, and simultaneously satisfies the two physical properties of the grip force and the rotational resistance required as a tire Low fuel efficiency, high performance tires can enhance product competitiveness.
  • the present invention improves the dry / wet grip of a tire and at the same time lowers the rise of rotational resistance, which is known to be the opposite of the physical properties, to satisfy the two properties of the tire and the grip force required as a tire. It provides a rubber composition for.
  • the grip force referred to herein includes both wet grip force and dry grip force.
  • the wet grip force refers to the grip force on the road surface wetted by snow or rain water
  • the dry grip force refers to the grip force on a general road surface state.
  • Good grip means that the tire and the road have high adhesion, which means good braking when cornering or stopping.
  • the rolling resistance refers to the ratio of the rolling resistance to the load applied to the tire, and in the present invention, the excellent rolling resistance characteristic means that the energy loss between the tire itself or the tire and the road surface is small or the rising width of the rolling resistance is high when the vehicle is driven. It means less.
  • the grip force and the rotational resistance are opposite to each other.
  • the rotational resistance is also increased to increase fuel economy.
  • the rubber composition for tire treads according to the present invention must satisfy the contradictory aspect of improving the fuel efficiency by reducing the rotational resistance while securing the braking property by increasing the grip force.
  • Rubber compositions used in tire treads include raw rubbers, reinforcing agents, silane coupling agents, vulcanizing agents, and vulcanizing accelerators, wherein silica is used together with carbon black as a reinforcing agent to increase rotational resistance and silane coupling to increase grip.
  • Use ring agent At this time, the rotational resistance and the grip force increase only when the silica and the silane coupling agent are uniformly mixed.
  • the carbon black, the silica and the silane coupling agent have inorganic properties, and Si (for the silica and the silane coupling agent)
  • Si for the silica and the silane coupling agent
  • the silane-modified petroleum resin proposed in the present invention means that the petroleum resin monomer and the silane compound are prepared by copolymerizing with each other.
  • the repeating unit composed of the petroleum resin monomer increases the hysteresis of the rubber composition for tire treads (energy loss per number of repeated deformations of the tire), thereby converting and absorbing external energy generated during tire braking into thermal energy to increase the grip force of the tire.
  • the repeating unit composed of the silane-based compound exhibits high compatibility with carbon black, silica, and a silane coupling agent, an inorganic filler used as a reinforcing agent in the rubber tread rubber composition due to the presence of Si, It is possible to secure the effect of increasing the dispersibility and lowering the rolling resistance obtained by the use of the above composition.
  • the petroleum resin monomer used in the production of the silane-modified petroleum resin proposed in the present invention is derived from naphtha cracking and includes at least one ethylenically unsaturated functional group which is a polymerizable functional group in a molecular structure.
  • the petroleum resin monomer may be a mixed C5 to C12 fraction, or a diolefin in a liquid phase, which may be put to practical use.
  • the mixed C5 fraction, a mixed C9 fraction, or a diolefin may be used.
  • Mixed C5 fractions include 1-pentene, 2-methyl-2-butene n-pentane, propadiene, dicyclopentadiene, piperylene, isoprene, cyclopentene, 1,3-pentadiene, and the like.
  • the petroleum resin monomers include diolefins, more preferably dicyclopentadiene.
  • the silane monomer copolymerized with such a petroleum resin monomer includes an ethylenically unsaturated functional group which is a polymerizable functional group in a molecular structure, and is preferably represented by the following Chemical Formula 1:
  • R 1 is hydrogen or methyl group
  • R 2 to R 4 are the same as or different from each other, hydrogen, C1 to C20 alkyl group, C3 to C12 cycloalkyl group, C1 to C12 alkoxy group, C2 to C12 An acyloxy group, a C6 to C30 aryloxy group, a C5 to C30 araloxy group, or a C1 to C20 amine group,
  • n is an integer from 1 to 12,
  • x and y are 0 or 1).
  • R 1 is hydrogen or a methyl group
  • R 2 to R 4 are the same as or different from each other, an alkyl group of C1 to C6, or an alkoxy group of C1 to C6, n is an integer of 1 to 6, x and y is 0 or 1.
  • Alkyl as used herein means a linear or branched saturated monovalent hydrocarbon moiety of 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms.
  • the alkyl group may be further substituted by the following substituents as well as unsubstituted.
  • alkyl groups include methyl, ethyl, propyl, 2-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, hexyl, dodecyl, and the like, and additionally substituted with halogen, fluoromethyl, difluoro Chloromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, iodomethyl, bromomethyl and the like.
  • cycloalkyl refers to a saturated or unsaturated non-aromatic monovalent monocyclic, bicyclic or tricyclic hydrocarbon moiety of 3 to 12 ring carbons, further defined by the following substituents. Can be substituted. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantyl, norbornyl (ie, bicyclo [2,2, 1] hept-5-enyl) etc. are mentioned.
  • alkoxy means a linear or branched saturated monovalent hydrocarbon moiety of 1 to 12, preferably 1 to 10, more preferably 1 to 6 carbon atoms.
  • the alkoxy group may be further substituted by the following substituents as well as unsubstituted.
  • Examples of the alkoxy group are methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy, ethoxy, dodecoxy and the like, and when substituted with halogen, fluoromethoxy, difluoromethoxy, tri Fluoromethoxy, chloromethoxy, dichloromethoxy, trichloromethoxy, iodomethoxy, bromomethoxy and the like.
  • acyloxy is a linear or branched hydrocarbon of 1 to 12, preferably 1 to 10 carbon atoms, such as acetoxy, ethanoloxy, propanoloxy, butanoloxy, pentanoloxy, Hexanoloxy, 2,2-dimethylpropanoloxy, 3,3-dimethylbutanoloxy and the like. These may be further substituted by certain substituents described below.
  • aryloxy includes the case where oxygen is contained in a monocyclic aryl group or a polycyclic aryl group.
  • An aryl group means an aromatic ring.
  • the "amine group” is not particularly limited in number of carbon atoms, but is preferably 1 to 30. Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, and 9-methyl-anthracenylamine group. , Diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group and the like, but are not limited thereto.
  • the substituted hydrogen is a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an amino group, a thio group, a methylthio group, an alkoxy group, a nitrile group, an aldehyde group, an epoxy group, an ether group, an ester group, an ester group , Carbonyl group, acetal group, ketone group, alkyl group, perfluoroalkyl group, cycloalkyl group, heterocycloalkyl group, allyl group, benzyl group, aryl group, heteroaryl group, derivatives thereof and combinations thereof Means replaced by one.
  • the silane-based compound of formula 1 is vinyltrimethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, triacetoxyvinylsilane, triphenylvinylsilane, tris (2-methoxyethoxy) vinylsilane, 3 -(Trimethoxysilyl) propyl methacrylate, ⁇ - (meth) acryloxypropyl trimethoxysilane and mixtures thereof, and one selected from the group consisting of vinyltrimethoxysilane. .
  • Silane-modified petroleum resins according to the present invention are prepared by copolymerization of petroleum resin monomers and silane compounds as described above. The copolymerization proceeds by addition reaction between the petroleum resin monomer and the double bond present in the silane compound.
  • the copolymerization may be used in various ways, it is not particularly limited in the present invention.
  • thermal polymerization, photopolymerization, ion polymerization, and radiation polymerization can be performed, and thermal polymerization can be preferably used.
  • the thermal polymerization is carried out by adding a petroleum resin monomer and a silane compound to the reactor, and then reacted for 0.5 to 10 hours, preferably 1 to 3 hours by applying heat of 150 to 300 °C, if necessary, can be applied pressure have.
  • Pressure application is carried out by mounting a separate pressure application device or by thermal polymerization in an autoclave. At this time, the pressure is carried out in the range of 20 to 25bar.
  • the range of reaction temperature, time and pressure during thermal polymerization is an optimal parameter for obtaining a petroleum resin that can satisfy both rotational resistance and grip force when applied to a rubber tread rubber composition.
  • the range of the reaction temperature, time and pressure is out of the range, an unreacted substance is present in the final product or the molecular weight of the petroleum resin is lowered.
  • due to side reactions or excessive increase in molecular weight when thermal polymerization is performed under excessive conditions it is not easy to secure satisfactory physical properties when applied to the rubber composition for tire tread of the final product.
  • the content ratio used in thermal polymerization of the petroleum resin monomer and the silane compound should be considered, and they are used in 50 to 95% by weight and 5 to 50% by weight, respectively.
  • the silane-based compound is involved in the softening point and degree of polymerization of the final silane-modified petroleum resin, and these properties decrease as the content thereof increases. Therefore, the silane-based compound is used in the above-mentioned range, preferably 10 to 25% by weight, more preferably 10 to 20% by weight.
  • the petroleum resin monomer and the silane-based compound have high reactivity, thereby eliminating the use of a thermal polymerization initiator during thermal polymerization, and a reaction solvent may be used if necessary.
  • Non-polymerizable solvents may be used as propane, butane, pentane, hexane, octane, decane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, dichloro Methane, chloroethane, dichloroethane, chlorobenzene and the like are used, preferably benzene, xylene, toluene, cyclohexane or a mixed solvent thereof can be used.
  • the reaction solvent may be used by diluting the final concentration of the reactant to 30 to 70% by weight.
  • the petroleum resin obtained after thermal polymerization is subjected to a general post-treatment process, for example, degassing and concentration to remove unreacted substances, side reaction products and the like to obtain a silane-modified resin to be prepared in the present invention.
  • a general post-treatment process for example, degassing and concentration to remove unreacted substances, side reaction products and the like to obtain a silane-modified resin to be prepared in the present invention.
  • the degassing process is a process for separating solid silane-modified petroleum resin, unreacted substances and side reaction products (eg oligomers) at high temperature and, if necessary, under high pressure.
  • the degassing process is directly related to the yield and softening point of the petroleum resin, and the higher the degassing temperature, the lower the yield and softening point.
  • the degassing process should be carried out under the condition that the yield and softening point do not decrease.
  • the present invention is carried out for 1 to 15 minutes in the temperature range of 200 to 280 °C, preferably 230 to 270 °C. If degassing is carried out at a temperature below the above, the purity of the silane-modified petroleum resin is lowered as mentioned above. On the contrary, if the degassing is carried out at the above temperature, the yield and the softening point are decreased, so Since adhesive force and cohesion force) fall, it uses suitably within the said range.
  • the silane-modified petroleum resin prepared through the above steps is a resin having a softening point of 70 to 150 ° C., preferably 90 to 130 ° C., measured according to STM E28, and a number average molecular weight (Mn) of 500 to 5000. resin having a range of g / mol.
  • the softening point and the molecular weight is a parameter that directly affects the grip force and the rolling resistance, and the high softening point and the molecular weight means that the hardness after curing is increased, which means that the rolling resistance may be lowered.
  • the softening point and low molecular weight means that the resin has flexibility, which means that the adhesion to the road surface may be increased and thus the grip force may be increased. In the present invention, it is possible to secure the optimum effect when having the above range.
  • the silane-modified petroleum resin according to the present invention has a proton content of silanes determined by 1 H-NMR of at least 1.7%, a proton content of silanes of at least 7%, and is analyzed by X-ray fluorescence spectroscopy. It is resin which Si weight fraction which is the weight ratio which a silicon (Si) element occupies among all the obtained elements is at least 0.3 wt%.
  • the silane-modified petroleum resin according to the present invention is a copolymer of an olefin-based compound represented by dicyclopentadiene and a silane-based compound, and includes a silane compound together with the adhesiveness of a conventional petroleum resin for tire treads.
  • the compatibility with the carbon black, silica, and silane coupling agents used in the rubber composition can be enhanced to further increase the tire physical properties (particularly, rotational resistance and grip force).
  • Such silane-modified petroleum resin is used in 1 to 30 parts by weight, preferably 5 to 15 parts by weight based on 100 parts by weight of the raw rubber. If the content is less than the above range, the effect of improving the rotational resistance and the grip force cannot be expected simultaneously. On the contrary, if the content exceeds the above range, the workability and the processability of reducing the viscosity of the rubber composition have to be redesigned to reduce the viscosity of the rubber composition. It may be lowered, which may cause deterioration of physical properties such as tensile strength and hardness of the final manufactured tire, so it is suitably used within the above range.
  • the rubber composition for tire treads was prepared including the composition described above, and the grip force and rotational resistance thereof were measured.
  • the grip force is involved in the brake braking property and is indicated by a loss factor (Tan ⁇ ) measured at a frequency of 10 to 100 Hz, 0 ° C, and 25 ° C by a dynamic viscoelastic test, and the larger the loss factor, the better the brake braking property is.
  • the excellent dry grip property means that the loss coefficient (Tan ⁇ ) measured at a frequency of 10 to 100 Hz and around 25 ° C. by the dynamic viscoelastic test of the rubber composition is large. By the dynamic viscoelastic test, the loss coefficient (Tan ⁇ ) measured at a frequency of 10 to 100 Hz and around 0 ° C is large.
  • Rotational resistance is shown by the loss coefficient (Tan delta) measured by the dynamic viscoelastic test of the rubber composition for tire treads about 10-100 Hz, 70 degreeC, and a smaller said loss coefficient improves rolling resistance characteristic.
  • the excellent rotational resistance characteristic means that the loss coefficient (Tan ⁇ ) measured at a frequency of 10 to 100 Hz and around 70 ° C by a dynamic viscoelastic test of the rubber composition for automobile tread is small.
  • the four measured values, Tg, Tan ⁇ (0 ° C.), Tan ⁇ (25 ° C.) and Tan ⁇ (70 ° C.) are moving in the same trend.
  • the rotational resistance (R / R, Tan ⁇ 70 ° C.) or wet grip force (Tan ⁇ 0 ° C.) should be improved while Tg is maintained at the same or similar level.
  • the direction in which the rotational resistance is lowered and the wet grip force is higher is preferable.
  • the rotational resistance and the wet grip force are complementary to each other, it is not easy to improve both of these properties. Therefore, it is most ideal to increase the wet grip force while the rotational resistance is substantially maintained or at least deteriorated.
  • the rubber composition for tire treads according to the present invention includes raw rubber, reinforcing agent, silane coupling agent, vulcanizing agent, and vulcanization accelerator as essential compositions in addition to the silane-modified petroleum resin.
  • the raw material rubber is not particularly limited as long as it has an olefinic double bond (carbon-carbon double bond), and natural rubber, synthetic rubber, or a mixture thereof can be used.
  • the raw rubber may be natural rubber, butadiene rubber, nitrile rubber, silicone rubber, isoprene rubber, styrene-butadiene rubber (SBR), isoprene-butadiene rubber, styrene-isoprene-butadiene rubber, acrylonitrile-butadiene rubber ( NBR), ethylene-propylene-diene rubber, halogenated butyl rubber, halogenated isoprene rubber, halogenated isobutylene copolymer, chloroprene rubber, butyl rubber and halogenated isobutylene-p-methylstyrene rubber It is preferable.
  • carbon black and silica are used as the reinforcing agent.
  • Carbon black obtains effects such as improvement of abrasion resistance, improvement of rotational resistance characteristics, prevention of cracking and cracking (ultraviolet rays deterioration) by ultraviolet rays.
  • the carbon black usable in the present invention is not particularly limited, and any carbon black may be used as long as it is commonly used in the field of tire treads.
  • carbon black such as farnes black, acetylene black, thermal black, channel black and graphite may be used.
  • physical properties such as particle diameter, pore volume, specific surface area, etc.
  • carbon black are not particularly limited, and various carbon blacks used in the rubber industry, for example, SAF, ISAF, HAF, FEF, GPF, SRF (all of which are abbreviations for carbon black classified in the ASTM specification D-1765-82a of the United States) and the like can be suitably used.
  • Such carbon black is preferably contained 5 to 50 parts by weight, preferably 50 to 65 parts by weight based on 100 parts by weight of the raw rubber.
  • the carbon black is an essential element for rubber compounding as a reinforcing filler. If the content is less than the above range, the effect of reinforcing is inferior. On the contrary, if the carbon black exceeds the above range, dispersion is difficult.
  • silica can be used without particular limitation what is used as a rubber reinforcing agent in the tire tread field, for example, dry method white carbon, wet method white carbon, synthetic silicate-based white carbon, colloidal silica, precipitated silica and the like.
  • the specific surface area of silica does not have a restriction
  • Such silica is preferably included in 30 to 80 parts by weight, preferably 50 to 65 parts by weight based on 100 parts by weight of the raw rubber. If the content is less than the above range, the rotational resistance is high and the fuel efficiency is lowered. On the contrary, if the content exceeds the above range, the grip force may be lowered. Therefore, it is suitably used within the above range.
  • the reinforcing agent in addition to the carbon black and silica, powders of minerals such as clay and talc, carbonates such as magnesium carbonate and calcium carbonate, alumina hydrates such as aluminum hydroxide and the like can be used.
  • Silane coupling agents are used to compound the silica.
  • silane coupling agent examples include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris ( ⁇ -methoxy-ethoxy) silane, ⁇ - (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 3 -Chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide , Bis (3-triethoxysilylpropyl) trisulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilyl Propyl) tetrasulfide, bis
  • the use amount of the silane coupling agent depends on the content of silica, and preferably 5 to 20 parts by weight based on 100 parts by weight of the raw rubber. If the content is less than the above range, it is difficult to uniformly mix silica, which may lower the physical properties of the tire tread. On the contrary, if the content exceeds the above range, the gelation of rubber may occur during the production of the tire tread. Use it appropriately.
  • the crosslinking agent can be used without particular limitation what is normally used for crosslinking of the rubber, and can be appropriately selected according to the rubber component and the isobutylene polymer.
  • a crosslinking agent For example, sulfur crosslinking agents, such as a sulfur, a morpholine disulfide, and an alkylphenol disulfide; Cyclohexanone peroxide, methyl acetoacetate peroxide, tert-butylperoxy isobutylate, tert-butylperoxybenzoate, benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, di-tert-butyl peroxide And organic peroxide crosslinking agents such as 1,3-bis (tert-butylperoxyisopropyl) benzene and the like.
  • the crosslinking agent is used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the raw rubber, and if the content is less than the above range, the crosslinking is insufficient, making it difficult to manufacture tires having desired physical properties (eg wear resistance), and vice versa. In this case, too, due to excessive crosslinking, the physical properties of the tire (eg, elasticity) are lowered, so it is appropriately used within the above range.
  • the rubber composition for automobile treads according to the present invention together with the crosslinking agent includes a vulcanization accelerator and a vulcanization aid. It does not specifically limit as a vulcanization accelerator and a vulcanization adjuvant, According to the rubber component, isobutylene-type polymer, and crosslinking agent which a rubber composition contains, it can select suitably and can use.
  • vulcanization represents the bridge
  • Thiuram type accelerators such as tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide, and tetraethyl thiuram disulfide
  • Thiazole type accelerators such as 2-mercaptobenzothiazole and dibenzothiazyl disulfide
  • Sulfenamide-based accelerators such as N-cyclohexyl-2-benzothiazylsulfenamide and N-oxydiethylene-2-benzothiazolylsulfenamide
  • Guanidine-based accelerators such as diphenylguanidine and diorthotriguanidine
  • aldehyde-amine accelerators such as n-butylaldehyde-aniline condensate and butylaldehyde-monobutylamine condensate
  • Aldehyde-ammonia-based accelerators such as hexamethylenetetramine
  • the content of such a vulcanization accelerator is preferably used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the raw rubber, in view of improving physical properties.
  • the vulcanization aid examples include metal oxides such as zinc oxide (zinc) and magnesium oxide; Metal hydroxides such as calcium hydroxide; Metal carbonates such as zinc carbonate and basic zinc carbonate; Fatty acids such as stearic acid and oleic acid; Aliphatic metal salts such as zinc stearate and magnesium stearate; Amines such as din-butylamine and dicyclohexylamine; Ethylene dimethacrylate, diallyl phthalate, N, N-m-phenylenedimaleimide, triallyl isocyanurate, trimethylolpropane trimethacrylate, and the like.
  • blending these vulcanization adjuvant you may use individually by 1 type or may use it in combination of 2 or more type.
  • the content of such vulcanization aid is preferably used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the raw rubber, in view of improving physical properties.
  • the rubber composition according to the present invention may also be used as one or two or more of various additives used in the field of the rubber industry, for example, an anti-aging agent, a vulcanization retardant, an annealing agent, a process oil, a plasticizer, etc. You may contain it. It is preferable that the compounding quantity of these additives is 0.1-10 weight part with respect to 100 weight part of rubber components.
  • the rubber composition for automobile treads comprising the composition as described above is made into a tire by a known method.
  • the rubber composition according to the present invention can be prepared by kneading each of the above components using a kneading machine such as a plastomill, a Banbury mixer, a roll, an internal mixer, or the like.
  • a kneading machine such as a plastomill, a Banbury mixer, a roll, an internal mixer, or the like.
  • the rubber composition produced by the above method can be used as a material constituting a tread portion (and a cap portion including the tread portion) in contact with the road surface.
  • an uncrosslinked molded body for a tire is produced by extrusion processing in accordance with the shape of the tire (specifically, the shape of the tread) in which the rubber composition is to be formed, and molding in a conventional manner on a tire molding machine.
  • a tire tread can be manufactured by heat-pressing this uncrosslinked molded object for tires in a vulcanizer, for example, and a tire tread and other parts can be manufactured, and a target tire can be manufactured.
  • the tires thus produced are excellent in mechanical properties (elasticity, wear resistance, hardness, tensile strength, modulus, etc.) to be used as tires.
  • the grip (wet / dry) is high, driving stability and brake braking of the vehicle is excellent, and the rotational resistance is low, it is possible to implement a low fuel consumption of the vehicle.
  • the rubber composition of this invention is suitable as a rubber composition for obtaining the tread of tires, such as a low fuel consumption tire and a high performance tire.
  • the reaction time was measured and reacted for 1 hour (in the reaction conditions, the reactor internal pressure was 20 to 25 bar).
  • the reaction was completed, it was cooled to room temperature. After cooling to 30 ° C. or lower, the internal pressure was depressurized, and the reactor was opened to obtain a polymer.
  • the polymer contained a solvent and an unreacted material in addition to the polymerized material, the polymer was removed. Specifically, the total amount of the polymer was put in a 1 L glass four-neck kettle, and vacuum was obtained at room temperature. The degree of vacuum was maintained at 10 torr, and when the vacuum was caught, the temperature was raised to 240 ° C with stirring. When the temperature reached 240 ° C., the concentration time began to be measured and maintained for 10 minutes. When the concentration was completed, the vacuum was released in that state to recover the molten resin powder therein.
  • a silane-modified petroleum resin was prepared in the same manner as in Preparation Example 1, except that degassing was performed at 260 ° C.
  • a silane-modified petroleum resin was prepared in the same manner as in Preparation Example 2 except that degassing was performed for 20 minutes.
  • Example 1 to 3 Comparative example 1 and 2: tires Tread Rubber composition
  • a rubber composition for tire treads was prepared using the silane or terpene phenol-modified petroleum resin prepared above.
  • a tire tread rubber composition was prepared in the composition of Table 2 below, and rubber specimens were prepared for physical property measurement.
  • Comparative Example 1 means a composition (Blank) not using a silane-modified petroleum resin
  • Comparative Example 2 means a composition using a petroleum resin prepared according to US Patent No. 8,637,606.
  • the rubber compositions of Examples 1 to 3 showed the same mechanical properties (modulus, tensile strength, elongation, hardness, etc.) compared to Comparative Examples 1 and 2.
  • Rheometer results measured with rubber rheometers, are parameters related to the rate of cure and the behavior of the rubber composition during process application, and are related to processability in tire manufacturing. At this time, if the value (T min , T max ) is too high or low, it is not easy to apply to the existing process, which means that a new process design is required.
  • T min , T max , Ts2 corch time
  • Tc2 time to 2% curing
  • Tc90 time to 90% curing
  • Abrasion resistance is a wear resistance by contact, which is a value that is considered when using a rubber product such as a tire in a dynamic state, and the rubber composition of Examples 1 to 3 exhibits a loss of about 4.7% or less. It can be seen that excellent.
  • the silane-modified petroleum resin proposed in the present invention can satisfactorily satisfy the physical properties required as a tire without affecting the workability even when added during the manufacture of a tire.
  • the loss coefficient (Tan ⁇ ) and glass transition temperature (Tg) related to grip force and rolling resistance were measured at 11 Hz by using Dynamic Mechanical Analysis (Model: TA-DMA Q800). 1 is shown. At this time, higher values of Tan ⁇ @ 0 ° C and Tan ⁇ @ 25 ° C mean better grip force, and lower values of Tan ⁇ @ 70 ° C mean better rotation resistance.
  • the numerical values of Tan ⁇ associated with the rotational resistance and the grip force presented in Table 4 are reliable data as a result of comparing the Tg values.
  • the peak value of Tan ⁇ is related to Tg.
  • the Tg value should be compared at almost the same level. It can be seen that the compositions of Examples and Comparative Examples have a Tg value in a nearly similar range.
  • the rubber composition for tire treads including the silane-modified petroleum resin according to the present invention secures an effect of simultaneously satisfying grip force and rotational resistance.
  • the rubber composition for tire treads according to the present invention is preferably applicable to the production of tire products with low fuel efficiency and high performance.

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)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)

Abstract

La présente invention concerne une composition de caoutchouc pour bande de roulement de pneu, capable de satisfaire simultanément à la fois des caractéristiques de force d'adhérence (humide/sec) et de résistance à la rotation grâce à l'utilisation d'une résine de pétrole modifiée par silane produite par la copolymérisation d'un monomère à base de résine de pétrole et d'un composé à base de silane.
PCT/KR2017/003532 2016-03-31 2017-03-31 Composition de caoutchouc pour bande de roulement de pneu WO2017171458A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20160039458 2016-03-31
KR10-2016-0039458 2016-03-31
KR1020170039166A KR101995924B1 (ko) 2016-03-31 2017-03-28 타이어 트레드용 고무 조성물
KR10-2017-0039166 2017-03-28

Publications (1)

Publication Number Publication Date
WO2017171458A1 true WO2017171458A1 (fr) 2017-10-05

Family

ID=59965018

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/003532 WO2017171458A1 (fr) 2016-03-31 2017-03-31 Composition de caoutchouc pour bande de roulement de pneu

Country Status (1)

Country Link
WO (1) WO2017171458A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100227566B1 (ko) * 1997-07-29 1999-11-01 홍건희 타이어 트레드용 고무 조성물
KR20130075445A (ko) * 2011-12-27 2013-07-05 한국타이어 주식회사 타이어 트레드용 고무 조성물 및 이를 이용하여 제조한 타이어
US8815995B2 (en) * 2007-03-29 2014-08-26 Compagnie Generale Des Etablissements Michelin Tire tread with resin
WO2015153058A1 (fr) * 2014-03-31 2015-10-08 Exxonmobil Chemical Patents Inc. Greffe radicalaire sur des résines fonctionnalisées pour pneus
WO2016018131A1 (fr) * 2014-08-01 2016-02-04 코오롱인더스트리 주식회사 Résine de pétrole durcissable et son procédé de préparation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100227566B1 (ko) * 1997-07-29 1999-11-01 홍건희 타이어 트레드용 고무 조성물
US8815995B2 (en) * 2007-03-29 2014-08-26 Compagnie Generale Des Etablissements Michelin Tire tread with resin
KR20130075445A (ko) * 2011-12-27 2013-07-05 한국타이어 주식회사 타이어 트레드용 고무 조성물 및 이를 이용하여 제조한 타이어
WO2015153058A1 (fr) * 2014-03-31 2015-10-08 Exxonmobil Chemical Patents Inc. Greffe radicalaire sur des résines fonctionnalisées pour pneus
WO2016018131A1 (fr) * 2014-08-01 2016-02-04 코오롱인더스트리 주식회사 Résine de pétrole durcissable et son procédé de préparation

Similar Documents

Publication Publication Date Title
WO2021125837A1 (fr) Résine de pétrole hydrogénée et composition de caoutchouc comprenant celle-ci
WO2018030645A1 (fr) Polymère diénique conjugué modifié, procédé pour sa préparation et composition à base de caoutchouc le contenant
CN1469898A (zh) 采用有机硅烷四硫化物二氧化硅偶合剂在高混合温度下混炼的二氧化硅增强橡胶
US20160237220A1 (en) Process for making elastomeric compositions comprising vinyl acetal polymers
WO2017078408A1 (fr) Composé d'organolithium, procédé de production d'un polymère à base de diène conjugué modifié l'utilisant, et polymère à base de diène conjugué modifié
WO2018062933A2 (fr) Composition pour bande de roulement de pneumatique comprenant une résine alternative à une huile de traitement
US9670341B2 (en) Rubber compositions comprising metal carboxylates and processes for making the same
KR102477254B1 (ko) 고무 조성물
WO2019045504A1 (fr) Composition de caoutchouc
KR101995924B1 (ko) 타이어 트레드용 고무 조성물
US11111338B2 (en) Terminal-functionalized polymer and related methods
WO2022108143A1 (fr) Composition de résine, son procédé de production et composition de caoutchouc la comprenant
WO2022108144A1 (fr) Composition de résine, son procédé de production et composition de revêtement la comprenant
WO2017171458A1 (fr) Composition de caoutchouc pour bande de roulement de pneu
US20180002497A1 (en) Elastomeric compositions comprising vinyl acetal polymers
WO2017105144A1 (fr) Procédé de préparation d'un polymère à base de diène conjugué modifié
JP2022542498A (ja) ゴム組成物
WO2018097517A1 (fr) Polymère à base de diène conjugué modifié et procédé de préparation de ce dernier
WO2018088711A1 (fr) Polymère à base de diène conjugué modifié et procédé de préparation de ce dernier
US20230220191A1 (en) Polymer composite, rubber composition, and tire
WO2016130880A1 (fr) Compositions élastomères comprenant des polymères de vinylacétal
US20170321045A1 (en) Elastomeric compositions comprising vinyl acetal polymers
WO2019018466A1 (fr) Compositions élastomériques contenant des polymères de vinylacétal
WO2018097480A1 (fr) Polymère à base de diène conjugué modifié et procédé de préparation de ce dernier
KR20130062706A (ko) 타이어 트레드용 고무 조성물 및 이를 이용하여 제조한 타이어

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17775882

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 17775882

Country of ref document: EP

Kind code of ref document: A1