JP7056323B2 - Pneumatic tires - Google Patents

Description

The present invention relates to a pneumatic tire having a reinforcing layer.

Pneumatic tires have a reinforcing layer typified by a carcass layer, a breaker layer, a band layer, etc. In such a reinforcing layer, a steel cord or an organic fiber cord is coated with a rubber composition, and the reinforcing layer is press-vulcanized. And get it.

It is known that a cellulose fiber cord, which is an organic fiber, is used as a cord used for the reinforcing layer (Patent Document 1). However, although the cellulose fiber cord is effective from the viewpoint of utilization of recycled resources, it is not always good from the viewpoint of environmental load because carbon disulfide is used when producing the raw material.

On the other hand, polyethylene terephthalate fiber (PET fiber) does not use carbon disulfide at the time of production, so that it is good from the viewpoint of environmental load and has a feature of high strength.

Japanese Unexamined Patent Publication No. 2014-189212

However, PET fiber has a property of being temperature-dependent and easily generating heat. Therefore, when PET fiber is used as a cord used for a reinforcing layer of a tire, it is desired that the rubber composition covering the PET fiber has low heat generation. Further, it is desired that the rubber composition for coating the cord is excellent in bending fatigue resistance and adhesiveness as the original characteristics.

Under the above problems, the present invention provides a pneumatic tire including a reinforcing layer in which PET fibers are coated with a rubber composition having low heat generation, excellent bending fatigue resistance, and excellent adhesiveness. The purpose is.

As a result of diligent studies, the present inventor has made an organic fiber cord composed of PET fibers of the reinforcing layer into a rubber composition containing a rubber component and a predetermined liquid diene polymer in a pneumatic tire having a reinforcing layer. It was found that the above-mentioned problems could be solved by covering the tires, and further studies were carried out to complete the present invention.

That is, the present invention
[1] A pneumatic tire including a reinforcing layer formed by aligning organic fiber cords.
The organic fiber cord is composed of polyethylene terephthalate fiber.
The reinforcing layer is formed by coating an organic fiber cord with a rubber composition.
The rubber composition contains a rubber component and a liquid diene polymer.
A pneumatic tire having a number average molecular weight of 5000 or more and 100,000 or less of the liquid diene polymer.
[2] The liquid diene polymer is at least one selected from the group consisting of a liquid butadiene polymer, a liquid isoprene polymer, a liquid styrene butadiene copolymer, a liquid styrene isoprene copolymer and a liquid isoprene butadiene copolymer. There is a pneumatic tire according to the above [1],
[3] The pneumatic tire according to the above [1] or [2], wherein the content of the liquid diene polymer is 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component.
[4] The pneumatic tire according to any one of [1] to [3] above, wherein the rubber component contains 20 to 100% by mass of isoprene-based rubber and 0 to 80% by mass of styrene-butadiene rubber.
[5] The pneumatic tire according to any one of [1] to [4] above, wherein the reinforcing layer is at least one selected from the group consisting of a carcass layer, a breaker layer and a band layer.
Regarding.

According to the present invention, it is possible to provide a pneumatic tire including a reinforcing layer in which PET fibers are coated with a rubber composition having low heat generation, excellent bending fatigue resistance, and excellent adhesiveness. ..

This is an example of a partial cross-sectional view of a pneumatic tire.

One embodiment is a pneumatic tire including a reinforcing layer formed by aligning organic fiber cords, wherein the organic fiber cord is made of polyethylene terephthalate fiber, and the reinforcing layer is organic. The fiber cord is coated with a rubber composition (rubber composition for coating the cord), the rubber composition contains a rubber component and a liquid diene polymer, and the number average of the liquid diene polymers. It is a pneumatic tire having a molecular weight of 5000 or more and 100,000 or less.

Although not intended to be bound by theory, by using a predetermined liquid diene polymer, a rubber composition for cord coating having low heat generation, excellent bending fatigue resistance, and excellent adhesiveness can be obtained. The following can be considered as the mechanism. That is, in the present embodiment, the liquid diene polymer has a structure similar to that of the rubber constituting the rubber component as compared with the oil used for the same purpose, so that it is easy to mix with the oil. In addition, since it is a relatively small molecule, it can easily enter between the molecules of the rubber component. Therefore, it has a feature that it is easy to disperse in the rubber component without forming a sea-island state with the rubber component. Since the liquid diene polymer is cured by vulcanization, the network in the rubber is strengthened by curing the liquid diene polymer dispersed in the rubber component in this way, and the bending fatigue resistance and the adhesiveness are improved. It is presumed that the heat is improved and the heat generation is reduced by suppressing the movement of the molecular chain in the rubber. Further, since the liquid diene polymer has a lower glass transition temperature than oil, it is considered that this point also contributes to the reduction of heat generation property, bending fatigue resistance, and improvement of adhesiveness.

<Reinforcing layer>
In the present embodiment, the reinforcing layer is not particularly limited, and any reinforcing layer in the pneumatic tire may be used. FIG. 1 shows an example of a partial cross section of a pneumatic tire. Here, the carcass layer 4, the breaker layer 5, and the band layer 6 are typical reinforcing layers for pneumatic tires.

The reinforcing layer according to the present embodiment is configured by aligning a plurality of organic fiber cords and coating them with a coating rubber composition. As described above, the reinforcing layer according to the present embodiment may be any reinforcing layer in the pneumatic tire, but since it forms the basic skeleton of the pneumatic tire and occupies a large proportion in the tire. , The carcass layer is preferable.

<Organic fiber cord>
The organic fiber cord of the present embodiment is made of polyethylene terephthalate fiber (PET fiber) from the viewpoint of steering stability at high speed running.

From the viewpoint of sufficient durability, the organic fiber cord preferably has a breaking strength of 2.0 cN / dtex or more. Further, the organic fiber cord preferably has an intermediate elongation of 3.0% to 4.6% from the viewpoint of facilitating its production and improving rigidity and steering stability. Further, the organic fiber cord has a dimensional stability index of 5.0% to 9.0% from the viewpoint of facilitating its manufacture and stabilizing the tire width dimension at the time of post-cure inflation. preferable. Further, the organic fiber cord preferably has a twist coefficient of 2000 to 35000, preferably 20000 to 35000, from the viewpoint of sufficient fatigue resistance and rigidity. In the present specification, both the breaking strength and the intermediate elongation are values measured according to JIS L 1017. The intermediate elongation is a value under a 2.0 cN / dtex load. The dimensional stability index is the sum of the dry heat shrinkage rate and the above-mentioned intermediate elongation, and the dry heat shrinkage rate is a value measured according to JIS L 1017 under a temperature condition of 180 ° C. The twist coefficient is K according to the formula: K = T × D1 / 2 (where T is the number of top twists of the organic fiber cord (times / 10 cm) and D is the total fineness (dtex) of the organic fiber cord). It is a coefficient represented by. The twist coefficient can be set by adjusting the spinning speed when manufacturing the organic fiber cord. The total fineness of the organic fiber cord is not particularly limited, but is preferably set in the range of, for example, 1100 dtex to 3500 dtex, preferably 1100 to 3300 dtex. By setting the total fineness in such a range, it is possible to have a high level of strength. For the organic fiber cord, it is preferable that the difference between the elongation rate at the time of cutting in the tensile test and the elongation rate when a load of 70% of the tensile load at the time of cutting is applied is 11% to 16%. By setting the difference between the elongation rate at the time of cutting and the elongation rate under specific conditions in this way, high toughness can be ensured and trauma resistance can be improved.

<Rubber component>
As the rubber component of the rubber composition for coating the cord, any rubber component that can be usually used in this field can be preferably used, but it is preferable that the rubber component contains isoprene-based rubber. Examples of the isoprene-based rubber include natural rubber (NR), modified natural rubber, and isoprene rubber (IR). Of these, NR is preferable. NR also includes deproteinized natural rubber (DPNR) and high-purity natural rubber (HPNR), and the modified natural rubber includes epoxidized natural rubber (ENR), hydrogenated natural rubber (HNR), and grafted natural rubber. And so on. Further, as the NR, for example, SIR20, RSS # 3, TSR20 and the like, which are common in the tire industry, can be used. The isoprene-based rubber may be used alone or in combination of two or more.

The content of the isoprene-based rubber is preferably 20 to 100% by mass in 100% by mass of the rubber component from the viewpoint of heat generation suppressing effect and the like. The content of the isoprene-based rubber is more preferably 25% by mass or more, further preferably 30% by mass or more, still more preferably 35% by mass or more, still more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferable. Is 60% by mass or more. Further, the content of the isoprene-based rubber may be 100% by mass.

Examples of the rubber component other than the isoprene rubber include butadiene rubber (BR), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), diene rubber such as chloroprene rubber (CR), and butyl rubber (IIR). Of these, SBR and BR are preferable, and SBR is more preferable, from the viewpoints of reversion resistance, heat resistance, bending fatigue resistance, and the like. The rubber components other than the isoprene-based rubber may be used alone or in combination of two or more.

The BR is not particularly limited, and for example, BR1220 manufactured by Nippon Zeon Co., Ltd., BR150B manufactured by Ube Kosan Co., Ltd., etc., BR having a high cis content, VCR412 manufactured by Ube Kosan Co., Ltd., VCR617, etc. 1, BRs containing 2-syndiotactic polybutadiene crystals (SPB), BRs synthesized using Nd-based catalysts such as BUNA CB 25 and BUNA CB 24 manufactured by LANXESS, and the like, which are common in the tire industry, can be used. Further, a tin-modified butadiene rubber modified with a tin compound (tin-modified BR) can also be used.

The SBR is not particularly limited, and examples thereof include emulsion-polymerized styrene-butadiene rubber (E-SBR), solution-polymerized styrene-butadiene rubber (S-SBR), modified SBR modified with 3-aminopropyldimethylmethoxysilane, and the like. Among them, E-SBR is preferable because it has a large amount of high molecular weight polymer component and is excellent in elongation at break. As the SBR, for example, one manufactured by Sumitomo Chemical Co., Ltd. can be used.

From the viewpoint of processability, the styrene content of SBR is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, still more preferably 20% by mass or more. Further, the styrene content is preferably 50% by mass or less, more preferably 45% by mass or less, further preferably 40% by mass or less, further preferably 35% by mass or less, still more preferably 30% by mass or less, from the viewpoint of fuel efficiency. Especially preferable. The styrene content of SBR is calculated by H1 ^- NMR measurement.

When a rubber component other than isoprene-based rubber is used, the content in 100% by mass of the rubber component is preferably 0 to 80% by mass in 100% by mass of the rubber component from the viewpoint of heat generation suppressing effect and the like. The content of the rubber component is more preferably 75% by mass or less, further preferably 70% by mass or less, still more preferably 65% by mass or less, still more preferably 60% by mass or less. The content of the rubber component may be 0% by mass, or is preferably 5% by mass or more, preferably 10% by mass or more, preferably 20% by mass or more, and 30% by mass or more. It is preferable that it is 40% by mass or more.

Preferred combinations of rubbers constituting the rubber component include a rubber component containing isoprene-based rubber and styrene-butadiene rubber, and in particular, a rubber component consisting only of isoprene-based rubber and styrene-butadiene rubber is preferable.

<Liquid diene polymer>
The liquid diene polymer of the rubber composition for coating a cord has a number average molecular weight (Mn) of 5,000 (5,000) or more and 100,000 (100,000) or less. If Mn is less than 5000, bending fatigue resistance and the like cannot be sufficiently exhibited. On the other hand, when the molecular weight exceeds 100,000, the polymer becomes relatively high molecular weight, so that it becomes difficult for the liquid diene polymer to enter between the molecules of the rubber component, and a sufficient effect cannot be expected. Mn is preferably 5500 or more. Further, Mn is more preferably 90,000 or less, further preferably 80,000 or less. Here, Mn is a value measured by using a gel permeation chromatograph (GPC) and converted from standard polystyrene. The liquid diene polymer in the present specification is a diene polymer in a liquid state at room temperature (25 ° C.).

Examples of the liquid diene polymer include liquid butadiene polymer (liquid BR), liquid isoprene polymer (liquid IR), liquid styrene butadiene copolymer (liquid SBR), liquid styrene isoprene copolymer (liquid SIR) and liquid isoprene butadiene. Examples thereof include a copolymer (liquid IRBR). Of these, liquid BR, liquid IR, and liquid SBR are preferable. The liquid diene polymer may be used alone or in combination of two or more.

The liquid diene polymer may be hydrogenated or functionalized with a functional group such as a carboxy group. When the liquid diene polymer is a copolymer, it may be a random copolymer of each monomer or a block copolymer. Unless otherwise specified, the liquid diene polymer includes all of these.

As the liquid diene polymer, for example, any product sold by Kuraray Co., Ltd. under the trade name of Claprene (registered trademark) can be preferably used. More specifically, as the liquid BR, for example, LBR-302 (Mn: 5500), LBR-307 (Mn: 8000), LBR-305 (Mn: 26000), LBR-300 ^* (Mn: 45000), LBR- Examples thereof include 361 (Mn: 5500) and LBR-352 (Mn: 9000, vinyl content: 50 mol% or more). Examples of the liquid IR include KL-10 ^* (Mn: 10000), LIR-30 (Mn: 28000), LIR-50 (Mn: 54000) and the like. Examples of the liquid SBR include L-SBR-820 (Mn: 8500) and L-SBR-841 (Mn: 10000). Both L-SBR-820 and L-SBR-841 are random copolymers. Examples of the liquid SIR include LIR-310 (Mn: 32000). LIR-310 is a block copolymer. Examples of the liquid IRBR include LIR-390 (Mn: 48000). LIR-390 is a block copolymer. Examples of the hydrogenated liquid diene polymer include LIR-290 (Mn: 31000), which is a hydrogenated liquid IR. Examples of the carboxylated liquid diene polymer include LIR-410 (Mn: 30000) and LIR-403 (Mn: 34000), which are carboxylated liquid IRs.

When the liquid diene polymer is contained, the content with respect to 100 parts by mass of the rubber component is in the range of 0.1 to 20 parts by mass from the viewpoint of obtaining a suitable effect of the present embodiment. The content is preferably 1.5 parts by mass or more, more preferably 3.0 parts by mass or more, and further preferably 4.0 parts by mass or more. On the other hand, the content is preferably 18 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 12 parts by mass or less.

<Filler>
The rubber composition for coating the cord may contain a filler. As the filler, any of ordinary ones can be used, and examples of such a filler include carbon black and silica.

(Carbon black)
By containing carbon black, the rubber composition for coating can obtain better reinforcing properties, and can improve complex elastic modulus, low heat generation property, elongation at break, and durability in a well-balanced manner.

The nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably 40 m ² / g or more, more preferably 60 m ² / g or more, and 70 m ² / g or more, from the viewpoint of sufficient reinforcing property. Is more preferable. The carbon black N ₂ SA is preferably 125 m ² / g or less, more preferably 115 m ² / g or less, and more preferably 105 m, from the viewpoint of fuel efficiency, workability (sheet rollability), and the like. It is more preferably ² / g or less. The nitrogen adsorption specific surface area of carbon black is a value measured by the method A on page 7, JIS K 6217.

From the viewpoint of wear resistance, the amount of DBP oil absorbed by carbon black is preferably 50 ml / 100 g or more, more preferably 55 ml / 100 g or more, and even more preferably 60 ml / 100 g or more. Further, the DBP oil absorption amount is preferably 250 ml / 100 g or less, more preferably 200 ml / 100 g or less, further preferably 135 ml / 100 g or less, still more preferably 100 ml / 100 g or less, from the viewpoint of grip performance. The DBP oil absorption amount of carbon black is a value measured according to JIS K 6217-4: 2008.

From the viewpoint of sufficient reinforcing property, the content of carbon black is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and 25 parts by mass or more with respect to 100 parts by mass of the rubber component. It is more preferable to have. Further, the content of carbon black is preferably 55 parts by mass or less, preferably 50 parts by mass or less, from the viewpoints of low heat generation, elongation at break, workability (sheet rollability), durability and the like. More preferred.

(silica)
By containing silica, it can contribute to elongation at break and improvement of cord adhesiveness.

The silica is not particularly limited, and examples thereof include dry silica (silicic anhydride) and wet silica (hydrous silicic acid), but wet silica is preferable because it has many silanol groups.

The nitrogen adsorption specific surface area (N ₂ SA) of silica is preferably 80 m ² / g or more, more preferably 100 m ² / g or more, and 110 m ² in terms of elongation at break from the viewpoint of durability and the like. It is more preferably / g or more. Further, the N ₂ SA of silica is preferably 250 m ² / g or less, more preferably 235 m ² / g or less, and 220 m ² from the viewpoint of fuel efficiency, workability (sheet rollability) and the like. It is more preferably less than / g. The nitrogen adsorption specific surface area of silica is a value measured by the BET method according to ASTM D3037-81.

When the silica is contained, the content is preferably 5 parts by mass or more, and more preferably 7 parts by mass or more with respect to 100 parts by mass of the rubber component from the viewpoint of elongation at break, durability and the like. preferable. Further, the silica content is preferably 17 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 13 parts by mass or less from the viewpoint of dispersibility and complex elastic modulus E *. preferable.

When silica and carbon black are used in combination, the total content is preferably 30 parts by mass or more with respect to 100 parts by mass of the rubber component from the viewpoints of elongation at break, complex elastic modulus, dispersibility of the filler, and the like. It is more preferably 35 parts by mass or more. Further, the total content is preferably 60 parts by mass or less, more preferably 55 parts by mass or less, from the viewpoint of low heat generation, elongation at break and the like.

<Zinc oxide>
Zinc oxide can be contained in the rubber composition for coating the cord. As zinc oxide, any zinc oxide normally used in this field can be preferably used. The content of zinc oxide is preferably 2 parts by mass or more, and more preferably 2.5 parts by mass or more with respect to 100 parts by mass of the rubber component. On the other hand, the content of zinc oxide is preferably 10 parts by mass or less, and more preferably 8 parts by mass or less.

<Methylene donor>
The rubber composition for coating the cord may contain a methylene donor. As a result, the adhesiveness between the cord and the rubber can be further strengthened. Examples of the methylene donor include a partial condensate of hexamethoxymethylol melamine (HMMM) and a partial condensate of hexamethylol melamine pentamethyl ether (HMMPME). Of these, a partial condensate of HMMM is preferable because of its excellent reactivity.

The content of the methylene donor is preferably 0.05 parts by mass or more, more preferably 0.10 parts by mass or more, and 0.20 parts by mass with respect to 100 parts by mass of the diene rubber component from the viewpoint of improving the rigidity. More than a portion is more preferable. The content of the compound that provides the methylene group is preferably 0.5 parts by mass or less, more preferably 0.4 parts by mass or less, from the viewpoint of rigidity and low heat buildup.

<Other ingredients>
In addition to the above-mentioned components, the cord coating rubber composition includes compounding agents generally used in the production of rubber compositions, such as silane coupling agents, stearic acid, various antioxidants, oils, waxes, and vulcanizing agents. , Vulcanization accelerator and the like can be appropriately blended.

(Vulcanizing agent)
Sulfur can be preferably used as the vulcanizing agent. As the sulfur, powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur and the like can be used. The sulfur content is preferably 3.0 parts by mass or more, and more preferably 3.5 parts by mass or more with respect to 100 parts by mass of the rubber component from the viewpoint of sufficient wet and heat peeling resistance, durability and the like. The content is preferably 10.0 parts by mass or less, more preferably 6.0 parts by mass or less. The sulfur content means the sulfur content.

(Vulcanization accelerator)
As the vulcanization accelerator, any of those usually used in the field of the tire industry can be preferably used, and such vulcanization accelerators are guanidine-based, aldehyde-amine-based, and aldehyde-ammonia-based. , Thiazole-based, sulfenamide-based, thiourea-based, thiuram-based, dithiocarbamate-based, and zandate-based compounds. These vulcanization accelerators may be used alone or in combination of two or more. Among them, sulfenamide-based vulcanization accelerators [N-tert-butyl-2-benzothiazolyl sulfenamide (TBBS), N-cyclohexyl) are used from the viewpoint of dispersibility in rubber and stability of vulcanization material. -2-Benzothiazolyl sulfenamide (CBS), N, N-dicyclohexyl-2-benzothiazolylsulfenamide (DCBS), N, N-diisopropyl-2-benzothiazolesulfenamide, etc.], N-tert -Butyl-2-benzothiazolyl sulfenamide (TBSI), di-2-benzothiazolyl disulfide (DM) and the like are preferable, and TBBS, CBS, TBSI and DM are more preferable.

The content of the vulcanization accelerator is preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the rubber component, from the viewpoint of suitable crosslinking density, bending fatigue resistance and the like. .. The content of the vulcanization accelerator is preferably 2.0 parts by mass or less, more preferably 1.5 parts by mass or less.

<Rubber composition for cord coating>
The rubber composition for cord coating is produced by a general method. That is, it can be produced by a method of kneading each of the above components with a Banbury mixer, a kneader, an open roll, or the like, and then vulcanizing. In the kneading, it is preferable to first knead the components other than the vulcanizing agent and the vulcanization accelerator, and then add the vulcanizing agent and the vulcanization accelerator to the kneaded product and knead.

The cord coating rubber composition is used as a rubber composition for coating an organic fiber cord composed of PET fibers. Further, the composite obtained by coating the organic fiber cord with the rubber composition is used as a reinforcing layer for a pneumatic tire, for example, as a carcass layer, a breaker layer, a band layer and the like. Among them, it is preferable to use it for the carcass layer because it forms the basic skeleton of the pneumatic tire and occupies a large proportion in the tire.

<Pneumatic tires>
The pneumatic tire of the present embodiment is manufactured by a conventional method using an organic fiber cord composed of PET fibers and the rubber composition. That is, after the organic fiber cord is coated with the above rubber composition and molded into the shape of a tire member (for example, carcass) which is a reinforcing layer, the tire member is bonded to another tire member to form an unvulcanized tire. A pneumatic tire can be manufactured by molding and then vulcanizing the unvulcanized tire.

The pneumatic tire of the present embodiment is suitably used as a passenger car tire, a truck / bus tire, a motorcycle tire, a competition tire, and the like, and is particularly preferably used as a passenger car tire.

<Others>
In the present specification, when the numerical value range is expressed as "1 to 100 parts by mass", it means that the numerical values at both ends (in the above, "1" and "100") are included unless otherwise specified.

Although the present invention will be described based on examples, the present invention is not limited to the examples.

The various chemicals used in Examples and Comparative Examples are shown below.
NR: TSR20
SBR: SBR1502 manufactured by Sumitomo Chemical Co., Ltd. (styrene content: 23.5% by mass)
Carbon black: Show black N326 manufactured by Cabot Japan Co., Ltd. (N ₂ SA: 81 m ² / g, DBP oil absorption: 75 ml / 100 g)
Zinc oxide: Zinc oxide No. 3 manufactured by Mitsui Metal Mining Co., Ltd. Stearic acid: Stearic acid "Tsubaki" manufactured by NOF CORPORATION
Oil: Diana Process NH-70S manufactured by Idemitsu Kosan Co., Ltd.
Liquid diene polymer 1 (liquid BR): LBR-302 (Mn: 5500) manufactured by Kuraray Co., Ltd.
Liquid diene polymer 2 (liquid IR): LIR-50 (Mn: 54000) manufactured by Kuraray Co., Ltd.
Liquid diene polymer 3 (liquid SBR, random copolymer): L-SBR-841 (Mn: 10000) manufactured by Kuraray Co., Ltd.
Liquid diene polymer 4 (liquid SIR, block copolymer): LIR-310 (Mn: 32000) manufactured by Kuraray Co., Ltd.
Sulfur: Insoluble sulfur manufactured by Shikoku Chemicals Corporation, Mucron OT-20 (20% oil treatment)
Vulcanization accelerator: Noxeller NS (N-tert-butyl-2-benzothiazolylsulfenamide) manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.
Polyethylene terephthalate fiber (PET fiber): Polyethylene terephthalate fiber (cord structure (dtex): 1670T / 2, total fineness: 3340dtex, breaking strength: 5.0cN / dtex, intermediate elongation: 3.5%, dry heat shrinkage rate: 2.8%, dimensional stability index: 6.3%, twist coefficient: 2000, difference in elongation (elongation when a load of 70% of the elongation at cutting and the tensile load at cutting in the tensile test is applied) Difference from rate): 13.0%)

<Manufacturing of rubber composition>
According to the formulation shown in Table 1, a 1.7 L Banbury mixer is used to knead the ingredients other than sulfur and the vulcanization accelerator for 5 minutes under the condition of 150 ° C. to obtain a kneaded product. Next, sulfur and a vulcanization accelerator are added to the kneaded product and kneaded under the condition of 80 ° C. for 5 minutes using a twin-screw open roll to obtain an unvulcanized rubber composition. Subsequently, the unvulcanized rubber composition is press-vulcanized for 12 minutes under the condition of 170 ° C. to obtain a vulcanized rubber composition.

<Manufacturing of pneumatic tires>
The unvulcanized rubber composition is used to coat the aligned PET fibers to obtain an unvulcanized reinforcing layer. The unvulcanized reinforcing layer is used as a carcass layer and bonded to other tire members to form an unvulcanized tire, which is press-vulcanized for 35 minutes under the condition of 150 ° C. to manufacture a pneumatic tire.

<Evaluation>
By performing each of the following tests using the vulcanized rubber composition obtained above, each index shown in Table 1 or a value close thereto can be obtained.

(Bending fatigue resistance index)
It is performed according to the method of ISO6943 using a constant stress / constant strain fatigue tester (FT-3100) manufactured by Ueshima Seisakusho Co., Ltd. The test piece of dumbbell No. 3 made of the above vulcanized rubber composition was repeatedly subjected to a strain of 1 Hz and 30%, the number of times until the test piece broke was measured, and the measurement result was displayed in an exponential notation by the following formula. do. The larger the index, the higher the bending fatigue resistance and the better the durability.
(Bending fatigue resistance index) = {(number of times of each formulation) / (number of times of standard comparative example)} × 100

(Low fever index)
Using a viscoelastic spectrometer manufactured by Iwamoto Seisakusho Co., Ltd., the loss tangent tan δ of each vulcanized rubber composition at 70 ° C. was measured and measured under the conditions of frequency 10 Hz, initial strain 10% and kinetic strain 2%. The result is displayed as an index by the following formula. The larger the index, the less likely it is to generate heat.
(Low exothermic index) = {(tanδ of standard comparative example) / (tanδ of each formulation)} × 100

(Adhesion index)
A PET fiber cord-rubber complex in which PET fiber cords arranged at equal intervals are embedded in unvulcanized rubber is vulcanized at 160 ° C. for 20 minutes to prepare a test sample. The PET fiber cord is pulled out according to ASTM D-2229-93a, the pulling force at that time is measured, and the measurement result is displayed as an exponential notation by the following formula. The larger the index, the better the pull-out adhesiveness.
(Adhesiveness index) = {(Pulling force of each formulation) / (Pulling force of standard comparative example)} x 100

1 tread part 2 sidewall part 3 bead part 4 carcass layer 5 breaker layer 6 band layer

Claims (6)

A pneumatic tire that includes a reinforcing layer constructed by aligning organic fiber cords.
The organic fiber cord is composed of polyethylene terephthalate fiber.
The reinforcing layer is formed by coating an organic fiber cord with a rubber composition.
The rubber composition contains a rubber component and a liquid diene polymer.
The content of the liquid diene polymer is 0.1 to 4 parts by mass with respect to 100 parts by mass of the rubber component.
A pneumatic tire having a number average molecular weight of the liquid diene polymer of 5000 or more and 100,000 or less. Claimed that the liquid diene polymer is at least one selected from the group consisting of a liquid butadiene polymer, a liquid isoprene polymer, a liquid styrene butadiene copolymer, a liquid styrene isoprene copolymer and a liquid isoprene butadiene copolymer. Item 1. The pneumatic tire according to Item 1. The pneumatic tire according to claim 1 or 2, wherein the content of the liquid diene polymer is 1.5 to 4 parts by mass with respect to 100 parts by mass of the rubber component. The pneumatic tire according to any one of claims 1 to 3, wherein the rubber component contains 20 to 100% by mass of isoprene-based rubber and 0 to 80% by mass of styrene-butadiene rubber. The pneumatic tire according to any one of claims 1 to 4, wherein the reinforcing layer is at least one selected from the group consisting of a carcass layer, a breaker layer and a band layer. The pneumatic tire according to any one of claims 1 to 5, wherein the rubber composition contains 3.5 parts by mass or more of sulfur with respect to 100 parts by mass of the rubber component.

Images