JP5198746B2 - Rubber composition and pneumatic tire using the same - Google Patents

Description

  The present invention relates to a rubber composition and a pneumatic tire.

  Conventionally, aroma oils are generally used as plasticizers for tire rubber compositions, but aroma oils need to be replaced because of their carcinogenic problems, etc. Measures are being taken by tire companies in the direction of changing to various petroleum-derived oils (alternative aroma oils) having a structure. However, alternative aroma oils still rely on petroleum resources. Further, when petroleum oil is blended with a rubber composition containing natural rubber in particular, the rolling resistance of the tire increases (rolling resistance characteristics deteriorate), and the fuel efficiency tends to deteriorate. Even in oil, particularly in rubber compositions containing natural rubber, especially rubber compositions containing natural rubber and silica, performance is still good in filler dispersibility, wear resistance in tread applications and crack resistance in sidewall applications. There is room for improvement.

  In recent years, global environmental problems have become important, and new plasticizers that can replace petroleum-based oils have been demanded. Therefore, it is preferable to change to environmentally friendly vegetable oils. Patent Document 1 discloses a rubber composition containing vegetable oils such as soybean oil and palm oil. This is excellent from the viewpoint of considering the environment, but the abrasion resistance, filler dispersibility, and crack resistance are significantly inferior to those in the case of blending an aroma oil.

JP 2003-64222 A

  An object of the present invention is to provide a high-performance rubber composition and a pneumatic tire using the same, using a plasticizer derived from resources other than petroleum.

  The present invention relates to a rubber composition containing a rubber component containing 50% by weight or more of natural rubber and / or modified natural rubber, and a terpene (co) polymer having a number average molecular weight of 700 or less.

  The terpene (co) polymer is preferably hydrogenated.

  The present invention also relates to a pneumatic tire using the rubber composition.

  According to the present invention, a terpene (co) polymer having a number average molecular weight of 600 or less instead of petroleum oil as a rubber component containing 50% by weight or more of natural rubber and / or modified natural rubber and a plasticizer By containing, it is possible to provide a rubber composition having excellent processability, maintaining rubber hardness and excellent dispersibility of fillers (particularly white fillers such as silica).

  In particular, by using the rubber composition of the present invention for a tread, the wear resistance can be improved while maintaining wet grip performance and rolling resistance characteristics, and the rubber composition of the present invention is used for a sidewall. Thus, the crack resistance performance can be improved while maintaining the tear strength and rolling resistance characteristics.

Furthermore, terpene-based (co) polymers are generally non-petroleum resources, and by reducing raw materials derived from petroleum resources, it is possible to contribute to solving environmental problems such as global warming due to CO ₂ emissions.

  In addition, ozone resistance can be improved by using a hydrogenated terpene (co) polymer.

  The rubber composition of the present invention contains a rubber component and a terpene (co) polymer.

  The rubber component used in the present invention contains natural rubber (NR) and / or modified natural rubber.

  When the unmodified NR is contained, the content of the NR is preferably 85% by weight or less, and more preferably 80% by weight or less in the rubber component. When the content ratio of the NR exceeds 85% by weight, there is a tendency that problems occur in the resistance to flex crack growth and ozone resistance. In addition, when setting it as the rubber composition for treads, the content rate of this NR is preferable 80 weight% or less, and when setting it as the rubber composition for side walls, the content rate of this NR is preferable 15 to 85 weight%.

  Examples of the modified natural rubber include epoxidized natural rubber (ENR), episulfide natural rubber, hydrogenated natural rubber (H-NR), and the like. You may mix and use a seed | species or more. Among them, the terpene (co) polymer used in the present invention is effective for wear resistance, fatigue resistance and bending crack growth resistance for treads and sidewalls, and is environmentally friendly. Therefore, at least one rubber component selected from the group consisting of NR, ENR and H-NR is preferable, and the grip performance required for tread applications can be obtained. ENR is more preferred because it can create a moderately sized sea-island structure, improve resistance to flex crack growth, and can be obtained at a relatively low cost compared to other modified natural rubbers.

  As ENR, commercially available ENR may be used, or NR may be epoxidized. The method for epoxidizing NR is not particularly limited, and can be performed using a method such as a chlorohydrin method, a direct oxidation method, a hydrogen peroxide method, an alkyl hydroperoxide method, or a peracid method. Examples of the peracid method include a method of reacting NR with an organic peracid such as peracetic acid or performic acid.

  The epoxidation rate of ENR is preferably 3 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, and particularly preferably 15 mol% or more. If the epoxidation rate is less than 3 mol%, the effect of modification tends to be small. The epoxidation rate is preferably 80 mol% or less, and more preferably 60 mol% or less. When the epoxidation rate exceeds 80 mol%, the polymer tends to gel.

  When the modified natural rubber is contained, in the tread application, the content of the modified natural rubber is preferably 30% by weight or more, more preferably 50% by weight or more, and further preferably 60% by weight or more in the rubber component. If the content of the modified natural rubber is less than 30% by weight, the effect of improving the grip performance by blending the modified natural rubber tends to be insufficient. On the other hand, in the side wall application, the content of the modified natural rubber is preferably 15 to 85% by weight. For sidewall applications, by setting the content of the modified natural rubber within the above range, an appropriate sea-island structure can be formed with other rubbers such as NR, thereby improving crack resistance.

  The content of NR and / or modified natural rubber is 50% by weight or more in the rubber component, preferably 60% by weight or more, more preferably 75% by weight or more, and further preferably 85% by weight or more. If the content of NR and / or modified natural rubber is less than 50% by weight, the ratio of petroleum resources is high as a whole, and the characteristics of the present invention that are environmentally friendly are not exhibited, and compatibility with NR and modified natural rubber is achieved. However, the characteristics of a good terpene (co) polymer cannot be utilized.

The rubber component used in the present invention may contain rubber other than NR and modified natural rubber.
Rubber components other than NR and modified natural rubber include styrene butadiene rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), butyl rubber (IIR), ethylene propylene diene rubber (EPDM), acrylonitrile butadiene rubber (NBR). ), Chloroprene rubber (CR) and the like, and these rubber components may be used alone or in admixture of two or more. Of these, SBR and / or BR is preferable as the rubber other than NR and / or modified natural rubber.

  The bound styrene content of SBR is preferably 10% or more, and more preferably 15% or more. If the amount of bound styrene is less than 10%, sufficient grip performance tends to be difficult to obtain when used for treads. The amount of bound styrene is preferably 60% or less, and more preferably 50% or less. When the amount of bound styrene exceeds 60%, the wear resistance tends to deteriorate when used for treads.

  BR is preferably a high cis content BR in which 90% or more is a cis 1,4-bond. By blending the BR, flex crack growth resistance and aging resistance tend to be improved, particularly in tread applications for truck and bus tires and sidewall applications including passenger cars.

  When a rubber component other than NR and modified natural rubber is contained in the rubber composition of the present invention, the content of SBR and / or BR is preferably 50% by weight or less, more preferably 30% by weight or less in the rubber component. preferable. If the content of SBR and / or BR exceeds 50% by weight, the ratio of petroleum resources as a whole tends to be high, and it tends to be difficult to bring out the characteristics of the present invention in consideration of the environment. In particular, when the rubber composition of the present invention is used as a rubber composition for a sidewall, since SBR cannot usually be used, the BR content is preferably 50% by weight or less, more preferably 30% by weight or less. preferable.

  The terpene (co) polymers used in the present invention are dipentenes such as limonene, monoterpenes such as α-pinene, β-pinene, 3-carene, terpinolene and myrcene, and terpenes such as sesquiterpenes such as longifolene and caryophyllene. (Co) polymerized with a monomer as a monomer.

  The terpene (co) polymer can be a (co) polymer consisting only of a terpene monomer, or a (co) polymer using a terpene monomer and a monomer other than a terpene. it can.

  Examples of monomers other than terpenes include monomers other than naturally derived terpenes such as rosin, monomers derived from petroleum resources such as isoprene and phenol, and monomers derived from coal such as coumarone. Especially, it is preferable not to use the monomer derived from petroleum resources, and the monomer derived from coal from a viewpoint which considers an environment.

  The (co) polymerization amount of terpenes in the terpene (co) polymer is preferably 50% by weight or more, more preferably 70% by weight or more, and further preferably 80% by weight or more. When the (co) polymerization amount of the terpenes is less than 50% by weight, the effects of improving the dispersibility of the filler, improving the wear resistance, improving the crack resistance, and the like tend to be unfavorable from the viewpoint of environmental considerations. is there.

  The terpene (co) polymer is selected from the group consisting of α-pinene, β-pinene, limonene and terpinolene because of its high compatibility with modified natural rubber such as NR and ENR and synthetic rubber such as SBR. Terpenic (co) polymers obtained by (co) polymerizing one or more monomers are preferred, and terpene polymers obtained by (co) polymerizing β-pinene and / or limonene are more preferred. In particular, a terpene (co) polymer containing β-pinene as a main component has a glass transition temperature of −30 to −45 ° C., and is excellent in compatibility with NR, modified natural rubber, SBR, and the like. .

  In addition, the terpene (co) polymer used in the present invention is preferably subjected to a hydrogenation treatment in order to improve its heat aging resistance, weather resistance, ozone resistance and the like. In particular, in a rubber component system mainly composed of NR and modified natural rubber, ozone resistance can be improved, and improvement in accordance with social demands related to tire life can be achieved. In addition, when used as a side wall application, not only the ozone resistance is improved, but by adding hydrogen, the SP value can be reduced, the compatibility with NR, modified natural rubber, etc. can be increased, and the crack resistance is increased. Crack resistance such as growth and crack resistance can also be improved.

  When the terpene (co) polymer has a glass transition temperature (Tg), the Tg of the terpene (co) polymer is preferably −60 ° C. or higher, more preferably −50 ° C. or higher, and further −45 ° C. or higher. preferable. If the glass transition temperature is less than −60 ° C., the wet performance tends to be inferior. Tg is preferably −10 ° C. or lower, more preferably −15 ° C. or lower, and further preferably −20 ° C. or lower. When the glass transition temperature exceeds -10 ° C, it tends to be excessively hard or brittle at low temperatures.

  By having Tg as described above, it is close to Tg of modified natural rubber such as epoxidized natural rubber and Tg of SBR (generally −55 to −10 ° C.), so that terpene (co) polymer and rubber In this case, good compatibility can be obtained, and tan δ around 50 to 70 ° C. related to low fuel consumption can be reduced. Moreover, when used as a tread application, tan δ near 0 ° C. related to wet skid performance can be increased, and tan δ near 50 to 70 ° C. related to low fuel consumption can be reduced.

  The softening point of the terpene (co) polymer is preferably 30 ° C. or lower, and more preferably liquid at room temperature. When the softening point of the terpene (co) polymer exceeds 30 ° C., it tends to be excessively hard or brittle at low temperatures.

  The number average molecular weight (Mn) of the terpene (co) polymer is preferably 150 or more, more preferably 200 or more, and further preferably 250 or more. When Mn is less than 150, a monomer is included, and the monomer has a boiling point near the vulcanization temperature of the rubber, and tends to volatilize during the vulcanization to foam the rubber. Moreover, it reacts at the double bond of the terpene-based (co) polymer and tends to lack stability and heat aging resistance. Further, it becomes difficult to produce a terpene (co) polymer having a Tg within the above preferred range. Further, Mn is 700 or less, preferably 600 or less, more preferably 500 or less, and still more preferably 400 or less. When Mn exceeds 700, the viscosity increases, it becomes difficult to use as a plasticizer, and the hardness of the obtained rubber composition increases. In addition, the number average molecular weight here shows the molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC). In this invention, the dispersibility of fillers, such as a silica, can be improved by using a low molecular weight terpene type (co) polymer in this way. Thereby, higher wear resistance can also be obtained. Further, in the side wall application, crack resistance such as crack growth resistance and crack resistance is also improved.

  The hydrogenation rate of the terpene (co) polymer is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, and 90 mol based on the number of original double bonds. % Or more is particularly preferable, and 95 mol% or more is most preferable. When the hydrogenation rate of the terpene (co) polymer is less than 30 mol%, the effect of hydrogenation cannot be sufficiently obtained, and the remaining double bond may cause some reaction, and stability, heat aging resistance, Concerns may remain regarding ozone resistance, oxidation degradation resistance, and the like.

  The terpene (co) polymer satisfying the above conditions is excellent in compatibility with NR and modified natural rubber, thereby effectively plasticizing and giving more stable characteristics against heat aging and aging. The effect is obtained. Thereby, especially the synthetic rubber such as BR can be reduced, and the problem of reduction in crack resistance which becomes a problem when NR or modified natural rubber is the main component can be solved.

  The terpene (co) polymer used in the present invention is synthesized from paraffinic oil, naphthenic oil, aromatic (aromatic) oil, various alternative aroma oils, vegetable oils such as soybean oil and palm oil, and vegetable oils. You may use together with animal oils (fats), such as alcohol, fish oil, and beef tallow. The combination is selected from the group consisting of aroma oils in terms of low price, vegetable oils such as soybean oil and palm oil, alcohols synthesized from vegetable oils and animal oils (fats) such as fish oils from the viewpoint of environment. It is preferable to use together with 1 or more types. In particular, in a system containing more NR and modified natural rubber as rubber, by using a terpene (co) polymer and vegetable oil together, the rolling resistance is reduced without excessively increasing the hardness, Abrasion resistance can be improved.

  The iodine value of the vegetable oil used in the present invention is preferably 5 to 200, more preferably 30 to 150, and still more preferably 40 to 140. Those having an iodine value of less than 5 tend to be difficult to obtain at low cost. On the other hand, when the iodine value exceeds 200, tan δ and hardness increase, and heat aging characteristics tend to deteriorate.

  The content of the terpene (co) polymer is preferably 0.5 parts by weight or more, more preferably 1.5 parts by weight or more, still more preferably 2.5 parts by weight or more with respect to 100 parts by weight of the rubber component. Part by weight or more is particularly preferable. When the content of the terpene (co) polymer is less than 0.5 parts by weight, effects such as improvement in filler dispersibility, improvement in wear resistance, and improvement in crack resistance tend to be reduced. In addition, the content of the terpene (co) polymer is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, still more preferably 20 parts by weight or less, and particularly preferably 15 parts by weight or less. When the content of the terpene (co) polymer exceeds 50 parts by weight, the heat aging resistance tends to deteriorate. In addition, when setting it as the rubber composition for treads, 0.5-50 weight part is preferable and, as for content of a terpene type | system | group (co) polymer, 1.5-40 weight part is more preferable. Moreover, when setting it as the rubber composition for sidewalls, 0.5-20 weight part is preferable and, as for content of a terpene type | system | group (co) polymer, 1.5-15 weight part is more preferable.

  The rubber composition of this invention can mix | blend vegetable oil with a terpene type | system | group (co) polymer.

  When the terpene (co) polymer and the vegetable oil are used in combination, the content of the vegetable oil is preferably 2 to 40 parts by weight and more preferably 4 to 15 parts by weight with respect to 100 parts by weight of the rubber component. If the vegetable oil content is less than 2 parts by weight, the rubber hardness tends to be too high. Moreover, when content of vegetable oil exceeds 40 weight part, there exists a tendency for the intensity | strength of rubber | gum to fall too much.

  The rubber composition of the present invention preferably further contains an inorganic filler. Examples of the inorganic filler include carbon black, silica, calcium carbonate, sericite, alumina, magnesium carbonate, titanium oxide, clay, talc, magnesium oxide, and aluminum hydroxide. Above all, because it is environmentally friendly and the effects of terpene (co) polymers are likely to increase, silica, calcium carbonate, sericite, alumina, magnesium carbonate, titanium oxide, clay, talc, magnesium oxide, aluminum hydroxide In particular, silica is preferable in order to ensure rubber reinforcement by being used in combination with a low molecular weight terpene (co) polymer.

When silica is used as the inorganic filler, BET specific surface area of silica is preferably 20~600m ² / g, more preferably 40~500m ² / g, more preferably ranging from 50 to 450 ² / g. If the BET specific surface area of silica is less than 20 m ² / g, the reinforcing property tends to be inferior. Further, if the BET specific surface area of silica exceeds 600 m ² / g, the dispersibility is inferior and aggregation occurs, so that the physical properties tend to decrease.

  The content of the inorganic filler is preferably 5 parts by weight or more and more preferably 30 parts by weight or more with respect to 100 parts by weight of the rubber component. When the content of the inorganic filler is less than 5 parts by weight, there is a tendency that sufficient reinforcement cannot be secured. Moreover, 150 weight part or less is preferable, as for content of an inorganic filler, 120 weight part or less is more preferable, and 100 weight part or less is further more preferable. When the content of the inorganic filler exceeds 150 parts by weight, the workability tends to be inferior. In addition, when setting it as the rubber composition for treads, 30-150 weight part is preferable and, as for content of an inorganic filler, 50-120 weight part is more preferable. Moreover, when setting it as the rubber composition for sidewalls, 5-80 weight part is preferable, as for content of an inorganic filler, 15-65 weight part is more preferable, and 25-50 weight part is further more preferable.

  In the rubber composition of the present invention, a silane coupling agent, stearic acid, zinc oxide, anti-aging agent, wax and the like can be appropriately blended in addition to the rubber component, the terpene (co) polymer and the inorganic filler. .

  The rubber composition of the present invention is preferably a tire rubber composition. Particularly, as a rubber member in a tire, the volume and weight are large, silica dispersibility improvement, wear resistance improvement, and flex crack growth resistance. It is preferable to use it for treads and sidewalls from the viewpoint of taking advantage of improvement.

  The pneumatic tire of the present invention is produced by a usual method using the rubber composition of the present invention. That is, if necessary, the rubber composition of the present invention blended with the above-mentioned compounding agent is extruded in accordance with the shape of the tire tread or sidewall at an unvulcanized stage, and is used on a tire molding machine. An unvulcanized tire is formed by molding by the method. The unvulcanized tire is heated and pressurized in a vulcanizer to obtain the pneumatic tire of the present invention.

  Thus, by using the rubber composition of the present invention, the pneumatic tire of the present invention can be made into an eco-tire that can be environmentally friendly and can be prepared for a future reduction in the supply of petroleum resources. it can.

  EXAMPLES Although this invention is demonstrated in detail based on an Example, this invention is not limited only to these.

The chemicals used in Examples and Comparative Examples are shown below.
Styrene butadiene rubber (SBR): Nippon NS 116 manufactured by Nippon Zeon Co., Ltd. (solution polymerization SBR, styrene content: 21% by weight, glass transition temperature: −25 ° C.)
Natural rubber (NR): RSS # 3
Epoxidized natural rubber (ENR): ENR-25 manufactured by Guthrie Polymer sdn. Bhd (epoxidation rate: 25 mol%, glass transition temperature: −41 ° C.)
Silica: Ultrasil VN3 (BET specific surface area: 175 m ² / g) manufactured by Degussa Huls Co., Ltd.
Silane coupling agent: Si-69 (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by Degussa Huls Co., Ltd.
Soybean oil: Soybean white oil (S) manufactured by Nissin Oil Co., Ltd. (iodine value: 131, fatty acid component having 18 or more carbon atoms: 84.9% by weight)
Aroma oil: Process X-140 manufactured by Japan Energy Co., Ltd.
Terpene (co) polymer (1): Dimaron (number average molecular weight: 390, glass transition temperature: -38 ° C., no hydrogenation) manufactured by Yasuhara Chemical Co., Ltd.
Terpene (co) polymer (2): Dimalon hydrogenated product (manufactured by the following production method, hydrogenated product of terpene low polymer, number average molecular weight: 390, glass transition temperature: -38, manufactured by Yasuhara Chemical Co., Ltd. ° C, hydrogenation rate: 99 mol%)
Terpene (co) polymer (3): YS Polystar T30 hydrogenated product (manufactured by the following production method, hydrogenated terpene phenol copolymer, number average molecular weight: 540, softening point: manufactured by Yasuhara Chemical Co., Ltd. (30 ° C or less, hydrogenation rate: 99 mol%)
Terpene (co) polymer (4): YS resin LP hydrogenated product (manufactured by the following production method, hydrogenated aromatic-modified terpene copolymer, number average molecular weight: 640, glass, manufactured by Yasuhara Chemical Co., Ltd. (Transition temperature: -43 ° C, hydrogenation rate: 99 mol%)
Terpene resin: YS resin PX300N manufactured by Yasuhara Chemical Co., Ltd. (polymer of β-pinene, number average molecular weight: 2500, weight average molecular weight: 4800, softening point: 30 ° C., no hydrogenation)
Stearic acid: Tungsten zinc oxide manufactured by Nippon Oil & Fats Co., Ltd .: Zinc oxide type 2 anti-aging agent manufactured by Mitsui Mining & Smelting Co., Ltd .: NOCRACK 6C (N-1,3-dimethyl manufactured by Ouchi Shinsei Kagaku Co., Ltd.) Butyl-N′-phenyl-p-phenylenediamine)
Wax: Ozoace 0355 manufactured by Nippon Seiki Co., Ltd.
Sulfur: Sulfur powder vulcanization accelerator manufactured by Tsurumi Chemical Co., Ltd. BBS: Noxeller NS (Nt-butyl-2-benzothiazolylsulfenamide) manufactured by Ouchi Shinsei Chemical Co., Ltd.
Vulcanization accelerator DPG: Noxeller D (diphenylguanidine) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.

(Production of terpene (co) polymer (2))
1 to 5 g of N-103 (stabilized nickel powder) manufactured by JGC Chemical Co., Ltd. is added to 100 to 200 g of DIMARON manufactured by Yasuhara Chemical Co., Ltd., 200 to 200 under pressure with pure hydrogen of 30 kgf / cm ² gauge pressure. By stirring at 300 ° C. for 10 to 30 hours, a terpene (co) polymer (2) was produced.

(Production of terpene (co) polymer (3))
The terpene (co) polymer (3) is the same as the terpene (co) polymer (2) except that YS polystar T30 manufactured by Yasuhara Chemical is used instead of Yasuhara Chemical Co., Ltd. Manufactured.

(Production of terpene (co) polymer (4))
The terpene (co) polymer (4) is the same as the terpene (co) polymer (2) except that YS resin LP manufactured by Yasuhara Chemical is used instead of Yasuhara Chemical Co., Ltd. Manufactured.

Examples 1-8 and Comparative Examples 1-2
Using a 1.7-L Banbury mixer manufactured by Kobe Steel, Inc., the chemicals in the blending amount shown in Step 1 of Table 1 were added so that the filling rate would be 58%, and under the condition of a rotational speed of 80 rpm. The kneader was kneaded for 3 to 8 minutes until the indicated temperature of the kneader reached 140 ° C. Furthermore, once discharged, the kneaded product obtained in step 1 and the silica and silane coupling agent in the blending amounts shown in step 2 are added so that the filler is 58%, and the kneader display temperature is 140. It knead | mixed for 3 to 8 minutes until it became ° C.

  To the mixture obtained in step 2, sulfur of the blending amount shown in step 3 of Table 1 and vulcanization accelerators BBS and DPG are added and kneaded for 3 minutes at 50 ° C. using an open roll. Thus, an unvulcanized rubber composition was obtained. The rubber | gum of Examples 1-8 and Comparative Examples 1-2 by shape | molding the unvulcanized rubber composition obtained at the process 3 to a size required for each evaluation, and press-vulcanizing at 160 degreeC for 20 minutes. A composition was prepared.

Examples 9-16 and Comparative Examples 3-5
Using a 1.7-L Banbury mixer manufactured by Kobe Steel, Inc., the amount of chemicals shown in Step 1 of Table 2 was added so that the filling rate would be 58%, and under the conditions of a rotational speed of 80 rpm. The kneader was kneaded for 3 to 8 minutes until the indicated temperature of the kneader reached 140 ° C. Silica was added twice in step 1.

  To the mixture obtained in step 1, sulfur and the vulcanization accelerator BBS in the blending amounts shown in step 2 of Table 2 are added, and kneaded for 3 minutes at 50 ° C. using an open roll. An unvulcanized rubber composition was obtained. The rubbers of Examples 9 to 16 and Comparative Examples 3 to 5 were formed by molding the unvulcanized rubber composition obtained in Step 2 into a size necessary for each evaluation and press vulcanizing at 160 ° C. for 20 minutes. A composition was prepared.

Examples 17-28 and Comparative Examples 6-12
Using a 1.7 L Banbury mixer manufactured by Kobe Steel, Inc., the chemicals with the blending amounts shown in Step 1 in Tables 3 to 4 were added so that the filling rate would be 58%, and the conditions were 80 rpm. Below, it knead | mixed for 3 to 8 minutes until the display temperature of a kneader became 140 degreeC. Furthermore, once discharged, the kneaded product obtained in step 1 and the epoxidized natural rubber having the blending amount shown in step 2 are added so that the filling rate is 58%, and 1.7 L manufactured by Kobe Steel, Ltd. is added. Using a Banbury mixer, the mixture was kneaded for 3 minutes under the conditions of 70 ° C. and a rotational speed of 80 rpm to obtain a mixture.

  Then, the sulfur and vulcanization accelerator BBS of the blending amount shown in Step 3 are added to the mixture obtained in Step 2 and kneaded for 3 minutes under the condition of 50 ° C. using an open roll. A vulcanized rubber composition was obtained.

  The rubber compositions of Examples 17 to 28 and Comparative Examples 6 to 12 were formed by molding the unvulcanized rubber composition obtained in Step 3 into a size necessary for each evaluation and press vulcanizing at 160 ° C. for 20 minutes. A product was made.

  Using the unvulcanized rubber composition and the vulcanized rubber composition prepared above, the following measurements were performed.

  In each of the following measurements, the rolling resistance test, filler dispersion and hardness measurement were performed using the rubber compositions of Examples 1 to 28 and Comparative Examples 1 to 12, and the rubber composition before vulcanization was used for adhesion. Force measurements were made (Tables 1-4). Moreover, abrasion resistance and a wet skid test were done using the rubber composition of Examples 1-16 and Comparative Examples 1-5 (Tables 1-2), and the rubber of Examples 17-28 and Comparative Examples 6-9 Using the composition, a tear test, a demature flex crack growth test, and a constant elongation fatigue test were performed (Tables 3 to 4). In Table 1, Comparative Example 1 was used as the reference composition, in Table 2, Comparative Example 3 was used, and in Tables 3 to 4, Comparative Example 6 was used as the reference composition. Moreover, also about the ozone resistance test, it carried out in Examples 1-28 and Comparative Examples 1-12.

(Rolling resistance test)
A rubber slab sheet of 2 mm × 130 mm × 130 mm was prepared as a vulcanized rubber composition, a test piece for measurement was cut out from the rubber slab sheet, and the temperature was 70 ° C. using a viscoelastic spectrometer VES (manufactured by Iwamoto Seisakusho Co., Ltd.). Under the conditions of initial strain 10%, dynamic strain 2%, and frequency 10Hz, tan δ of each test rubber composition was measured, and the rolling resistance index of the standard blend was set to 100. displayed. The larger the index, the lower the rolling resistance and the better.
(Rolling resistance index) = (tan δ of reference blend / tan δ of each blend) × 100

(Dispersion of filler)
A rubber slab sheet of 2 mm × 130 mm × 130 mm was prepared as a vulcanized rubber composition, and a test piece for measurement was cut out from the rubber slab sheet, and it was applied to JIS K 6812 “Evaluation method for pigment dispersion or carbon dispersion of polyolefin pipes, joints and compounds”. Similarly, the silica agglomerates in the vulcanized rubber composition were counted, and the dispersion ratio (%) was calculated. The dispersion ratio of the reference blend was set to 100, and the dispersion ratio was indicated as an index. A larger filler dispersion index indicates that the filler is more dispersed and better.

(hardness)
Based on JIS K 6253 “Hardness test method of vulcanized rubber and thermoplastic rubber”, the hardness of the vulcanized rubber composition was measured using a type A durometer, and the rubber hardness index of the standard blend was set to 100, and the following calculation was performed. The rubber hardness was expressed as an index according to the formula. The greater the rubber hardness index, the greater the hardness. If this index deviates greatly from 100, it is not preferable.
(Rubber hardness index) = (Rubber hardness of each compound / Rubber hardness of standard compound) × 100

(Ozone resistance test)
Based on JIS K 6259 "Vulcanized rubber and thermoplastic rubber-Determination of ozone resistance", dynamic ozone deterioration test was conducted, reciprocating frequency 0.5 ± 0.025Hz, ozone concentration 50 ± 5pphm, test temperature Ozone resistance was evaluated by observing the state of cracks after testing for 48 hours under conditions of 40 ° C. and 20 ± 2% tensile strain. The evaluation method represented the number and size of cracks according to the method described in JIS. The alphabet (A, B, and C) indicates that A is a small number of cracks and C is a large number of cracks. The larger the number is, the larger the crack size is. Indicates that no cracks occurred.

(Adhesive force)
Using a PICMA / tack tester manufactured by Toyo Seiki Seisakusho, the adhesive strength [N] of the unvulcanized rubber composition at a temperature of 23 ° C. and a humidity of 55% under conditions of an ascending speed of 30 mm / min and a measurement time of 2.5 seconds. The adhesive strength index of the reference blend was set to 100, and the adhesive strength was displayed as an index according to the following formula. The larger the adhesion index, the greater the adhesion and the better.
(Adhesive strength index) = (Adhesive strength of each formulation / Adhesive strength of standard formulation) × 100

(Abrasion resistance)
Vulcanized rubber specimens for lamborn abrasion test obtained from each vulcanized rubber composition under the conditions of load load of 2.5 kg, temperature of 20 ° C., slip rate of 40%, test time of 2 minutes with a lamborn abrasion tester. The amount of volume loss of each blend was calculated, the wear resistance index of the reference blend was set to 100, and the wear resistance was indicated as an index by the following formula. The larger the wear resistance index, the better the wear resistance.
(Abrasion resistance index) = (volume loss amount of reference blend / volume loss amount of each blend) × 100

(Wet grip performance)
Using a Stanley portable skid tester, according to the method of ASTM E303-83, the maximum friction coefficient of each test rubber composition was measured, and the wet grip performance index of the reference compound was set to 100, and the index was calculated using the following formula. displayed. The larger the wet grip performance index, the better the wet grip performance.
(Wet grip performance index) = (Numerical value of each formulation / Numerical value of standard formulation) × 100

(Tear test)
According to JIS K6252 “Vulcanized Rubber and Thermoplastic Rubber—How to Obtain Tear Strength”, the tear strength (N / mm) was obtained by using an angle-shaped test piece without incision. Taking the strength index as 100, the tear strength index was calculated by the following formula. The larger the tear strength index, the greater the tear strength and the better.
(Tear strength index)
= (Tear strength of each formulation) / (Tear strength of Comparative Example 6) × 100

(Demach flex crack growth test)
According to JIS K6260 “Demach bending crack test method for vulcanized rubber and thermoplastic rubber”, cracks after 1 million tests were performed on samples of vulcanized rubber composition under conditions of a temperature of 23 ° C. and a relative humidity of 55%. The length or the number of times until the growth reaches 1 mm is measured, and the number of bendings until a 1 mm crack grows in the sample of the vulcanized rubber composition based on the obtained number of times and the crack length is commonly used. Expressed numerically. Incidentally, 70% and 110% represent the elongation ratio with respect to the length of the original vulcanized rubber composition sample, and the larger the common logarithm value, the more difficult the crack grows and the better the crack growth resistance. It shows that.

(Constant elongation fatigue test)
Using a No. 3 dumbbell, a constant strain repeated extension test was performed under the conditions of a maximum strain of 50% and a frequency of 5 Hz without introducing an initial crack. This was repeated 5,000,000 times, the fractured piece was marked with ×, the cracked or scratched mark was marked with Δ, and the broken one was marked with ◯.

  Test results are shown in Tables 1-4.

  By using a terpene (co) polymer having a number average molecular weight of 700 or less instead of vegetable oils such as aroma oil, alternative aroma oil, soybean oil and palm oil, the rolling resistance and hardness can be maintained, The dispersibility and adhesiveness of the filler could be improved. Furthermore, in Examples 1 to 16, wet skid characteristics can be maintained and wear resistance can be greatly improved, and in Examples 17 to 28, tear strength can be maintained and crack resistance can be improved. It was. In particular, in Examples 3 to 8, 11 to 16, and 20 to 28 using hydrogenated terpene (co) polymers, the ozone resistance could be improved.

Claims (5)

A terpene series (co-polymer) having a number average molecular weight of 700 or less and a glass transition temperature of −60 to −10 ° C. with respect to 100 parts by weight of a rubber component containing 85% by weight or more of natural rubber and / or epoxidized natural rubber. ) A rubber composition containing 0.5 to 50 parts by weight of a polymer . A terpene (co) polymer having a number average molecular weight of 700 or less and a softening point of 30 ° C. or less with respect to 100 parts by weight of a rubber component containing 85% by weight or more of natural rubber and / or epoxidized natural rubber. A rubber composition containing 0.5 to 50 parts by weight . The rubber composition according to claim 1 or 2, wherein the terpene (co) polymer is hydrogenated at an addition rate of 30 mol% or more. The rubber composition according to claim 1 or 2, wherein the terpene (co) polymer is hydrogenated at an addition rate of 95 mol% or more. A pneumatic tire using the rubber composition according to any one of claims 1 to 4 .