JP2019077814A - Rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber composition excellent in vibration absorption, adhesiveness, adhesiveness, processability, and wet grip property when made into a tire because it is excellent in compatibility between a diene rubber and a cyclic organic compound. Further, the present invention provides a rubber composition that can be used for various purposes such as tires, anti-vibration rubbers, belts, hoses, footwear, adhesives, adhesive tapes and the like. SOLUTION: The rubber composition comprises at least 5 to 100 parts by weight of a cyclic organic compound with respect to 100 parts by weight of a diene rubber, and the cyclic organic compound is a fat containing an alicyclic group unit and an aromatic unit. A rubber composition, which is at least one cyclic organic compound selected from the group consisting of a ring group-aromatic compound, a fluorene compound, a tetralin compound and an adamantan compound. [Selection diagram] None

Description

  The present invention relates to a rubber composition, and is particularly excellent in compatibility between a diene rubber and a cyclic organic compound, and has vibration absorption, adhesiveness, adhesiveness, processability, and wet grip when used as a tire. It is expected to be excellent, and can be used in various applications such as tires, anti-vibration rubbers, belts, hoses, footwear, adhesives, adhesive tapes and the like.

  For the purpose of improving the physical properties and processability of rubber, it has been proposed to blend a resin with rubber to make a composition. Among them, in order to improve tire performance, methods have been proposed to improve wet grip by blending a highly compatible hydrogenated resin with rubber (see, for example, Patent Documents 1 to 4).

JP, 2008-174696, A JP, 2009-138025, A JP, 2011-88988, A JP, 2011-88998, A

  However, the methods proposed in Patent Documents 1 to 4 have problems in that the physical properties of the rubber composition are insufficient because the compatibility between the rubber component and the resin is still low, and the processability is deteriorated because the viscosity is high. It was a thing.

  Accordingly, as a result of intensive studies to solve the above problems, the present inventors have found that the compatibility of a rubber composition containing a specific cyclic organic compound and a diene rubber component is significantly improved. We came to complete the invention.

  That is, the present invention is a rubber composition comprising at least 5 to 100 parts by weight of a cyclic organic compound with respect to 100 parts by weight of a diene rubber, wherein the cyclic organic compound is represented by the following general formula (1) An alicyclic-aromatic compound containing an alicyclic unit and an aromatic unit represented by the following general formula (2), a fluorene compound, a tetralin compound, and an adamantane compound: at least one cyclic group selected from the group consisting of The present invention relates to a rubber composition characterized by being an organic compound.

(Here, each R ₁ independently represents an alkyl group having 1 to 6 carbon atoms.)

(Wherein, _{R 2} each independently represents the number 1-6 alkyl group carbon atoms.)
Hereinafter, the present invention will be described in detail.

  The rubber composition of the present invention is a rubber composition comprising at least 5 to 100 parts by weight of a cyclic organic compound with respect to 100 parts by weight of a diene rubber.

  The diene rubber constituting the rubber composition of the present invention is not particularly limited as long as it belongs to a diene rubber having a carbon / carbon double bond, and is, for example, a natural rubber (sometimes referred to as NR). And polyisoprene rubber (sometimes described as IR), polybutadiene rubber (sometimes described as BR), styrene-butadiene rubber (sometimes described as SBR), styrene-isoprene rubber, and the like. These may be used alone or in combination. Moreover, what was vulcanized may be used. In that case, it is preferable to use as a diene rubber containing 50% by weight or more of a styrene-butadiene rubber, since it is particularly suitable for tires. The method for producing the diene rubber is not particularly limited, and may be an anionic polymer or an emulsion polymer. The molecular weight and microstructure thereof are not particularly limited, and may be terminally modified with an amine, amide, silyl, alkoxysilyl, carboxyl, hydroxyl group or the like, or may be epoxidized. Among them, SBR is particularly preferable because it can easily provide a rubber composition excellent in compatibility with cyclic organic compounds and excellent in performance.

  The rubber composition of the present invention may contain other rubbers, resins and the like as long as the object is achieved. For example, fluorine-based rubber, acrylic rubber, butyl rubber, ethylene-propylene copolymer, urethane-based rubber Etc.

  The cyclic organic compound constituting the rubber composition of the present invention is an alicyclic-aromatic compound containing an alicyclic unit represented by the above general formula (1) and an aromatic unit represented by the above general formula (2) And at least one cyclic organic compound selected from the group consisting of fluorene compounds, tetralin compounds and adamantane compounds. Here, when the compound is other than the alicyclic-aromatic compound, the fluorene compound, the tetralin compound, and the adamantane compound, the compatibility with the rubber composition is poor, and the vibration absorption and the tackiness And effects such as adhesion and processability can not be achieved.

  The alicyclic-aromatic compound is a compound comprising an alicyclic unit represented by the general formula (1) and an aromatic unit represented by the general formula (2), and the alicyclic unit Examples thereof include a cyclohexyl unit, a methylcyclohexyl unit, a dimethylcyclohexyl unit, an ethylcyclohexyl unit, a butylcyclohexyl unit and the like, and examples of the aromatic unit include a phenyl unit, a methylphenyl unit, a dimethylphenyl unit, an ethylphenyl A unit, a butylphenyl unit etc. can be mentioned, It is preferable that the ratio of this alicyclic unit is 50-99 mol% as the compounding ratio. And, as a specific example, 1,4-dicyclohexylbenzene, di (methylcyclohexyl) benzene, di (butylcyclohexyl) benzene and the like can be mentioned.

  Examples of fluorene compounds include fluorene, perhydrofluorene and alkyl-substituted products thereof.

  Examples of tetralin compounds include tetralin, decalin and alkyl-substituted products thereof.

  Examples of the adamantane compound include adamantane and alkyl-substituted products thereof.

  The compounding amount of the cyclic organic compound is 5 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the diene rubber. When the compounding amount of the cyclic organic compound is less than 5 parts by weight, the compounding effect of the cyclic organic compound is not expressed, and the vibration absorptivity, the adhesiveness, the adhesiveness, and the processability improving effect can not be obtained. On the other hand, when the compounding amount of the cyclic organic compound exceeds 100 parts by weight, the rubber composition becomes less compatible, causing poor dispersion and deterioration of processability.

  There is no restriction | limiting in particular as a manufacturing method of the rubber composition of this invention, For example, it can manufacture by general blending methods, such as solution mixing, melt mixing, solid-phase mixing, etc.

  The rubber composition of the present invention may further contain an additive which is usually blended into a resin composition and a rubber composition. For example, resins such as petroleum resins, crosslinking agents including sulfur, vulcanization accelerators, vulcanization accelerators, stearic acid, zinc white, plasticizers, oils, antioxidants, fillers such as silica and carbon black, etc. The following ingredients may be added. A commercial item can be used suitably as these compounding agents.

  Furthermore, the rubber composition of the present invention can be added to resin compositions and rubber compositions as long as the object of the present invention is not deviated, such as phenolic antioxidants, phosphorus antioxidants, sulfur compounds Antioxidants, lactone antioxidants, UV absorbers, pigments, calcium carbonate, glass beads and the like may be blended.

  The rubber composition of the present invention is excellent in compatibility. It is expected to be excellent in vibration absorbability, adhesiveness, adhesiveness, processability, and wet grip when made into a tire, and various types of tires, anti-vibration rubber, belts, hoses, footwear, adhesives, adhesive tapes, etc. It becomes usable in the application.

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited to these examples. In addition, the raw material, analysis, and test method which were used in the Example and the comparative example are as follows.

Raw material styrene-butadiene rubber (manufactured by JSR Co., Ltd., (trade name) SL 552) (hereinafter referred to as SBR)
Styrene-isoprene block copolymer rubber (manufactured by JSR Corporation, (trade name) HPR350R) (hereinafter referred to as SIS)
1,4-dicyclohexylbenzene (hereinafter referred to as DCHB); reagent manufactured by Wako Pure Chemical Industries, Ltd.
Adamantane (hereinafter referred to as ADM); reagent manufactured by Wako Pure Chemical Industries, Ltd.
Fluorene (hereinafter referred to as FL); reagent manufactured by Wako Pure Chemical Industries, Ltd.
Perhydrofluorene (hereinafter referred to as HFL); reagent manufactured by Aldrich.
Tetralin (hereinafter referred to as TL); reagent manufactured by Wako Pure Chemical Industries, Ltd.
Decalin (hereinafter referred to as DL); reagent manufactured by Wako Pure Chemical Industries, Ltd.
Aliphatic / aromatic copolymer based petroleum resin (Tosoh Corp. (trade name) Petrotac 130V) (hereinafter referred to as PR-1).
Aromatic petroleum resin (manufactured by Tosoh Corporation, (trade name) Petocol LX) (hereinafter referred to as PR-2).

Vibration absorption and compatibility evaluation Using a visco-elasticity measuring device (manufactured by Rheometrics, Inc.), the temperature is -100 to 100 ° C., the temperature rising rate is 2 ° C./min, the frequency is 10 Hz, tan δ is measured in shear mode, and the peak of tan δ The value (height) was evaluated as an index of vibration absorbency. In addition, with regard to the compatibility, the measured value (tan δ) of Comparative Example 1 of SBR alone and Comparative Example 4 of SIS alone as a reference is set as a reference value (100) as a reference, and It was judged that the compatibility was better as the relative value to the reference value was larger.
Compatibility index = ((measured tan δ value) / (tan δ of comparative example 1 or 4)) × 100
Example 1
100 parts by weight of SBR and 20 parts by weight of DCHB were added to a vial (20 ml) and dissolved in 1000 parts by weight of toluene using a stirrer. The solution was cast on an aluminum cup, preliminarily dried under a nitrogen stream, and vacuum dried at 40 ° C. to obtain a rubber composition.

  The obtained rubber composition had a high tan δ value and was excellent in vibration absorption as well as in compatibility. The results are shown in Table 1.

Examples 2 and 3
A rubber composition was obtained in the same manner as in Example 1 except that FL and TL were used instead of DCHB.

  The obtained rubber composition had a high tan δ value and was excellent in vibration absorption as well as in compatibility. The results are shown in Table 1.

Comparative Example 1
Viscoelasticity was measured only with SBR. The results are shown in Table 1.

Comparative Examples 2 and 3
A composition was obtained in the same manner as in Example 1 except that PR-1 and PR-2 were used instead of DCHB. The results are shown in Table 1.

Example 4
A rubber composition was obtained in the same manner as in Example 1 except that SIS was used instead of SBR.

  The obtained rubber composition had a high tan δ value and was excellent in vibration absorption as well as in compatibility. The results are shown in Table 2.

Examples 5 to 8
A rubber composition was obtained by the same method as Example 5, except that ADM, FL, HFL, and DL were used instead of DCHB.

  The obtained rubber composition had a high tan δ value and was excellent in vibration absorption as well as in compatibility. The results are shown in Table 2.

Comparative example 4
Viscoelasticity was measured only by SIS. The results are shown in Table 2.

Comparative Examples 5 and 6
A composition was obtained in the same manner as in Example 4 except that PR-1 and PR-2 were used instead of DCHB. The results are shown in Table 2.

  The rubber composition of the present invention can be used as a tire, anti-vibration rubber, belt, hose, footwear, adhesive agent, adhesive tape and the like because it has excellent compatibility, and its industrial value is extremely high.

Claims (4)

A rubber composition comprising at least 5 to 100 parts by weight of a cyclic organic compound with respect to 100 parts by weight of a diene rubber, wherein the cyclic organic compound is an alicyclic unit represented by the following general formula (1) and An alicyclic-aromatic compound containing an aromatic unit represented by the general formula (2), a fluorene compound, a tetralin compound, and at least one cyclic organic compound selected from the group consisting of adamantane compounds; Rubber composition characterized by

(Here, each R ₁ independently represents an alkyl group having 1 to 6 carbon atoms.)

(Wherein, _{R 2} each independently represents the number 1-6 alkyl group carbon atoms.) The rubber composition according to claim 1, wherein the diene rubber is a diene rubber containing 50% by weight or more of styrene-butadiene rubber. The rubber composition according to claim 1, which is a vulcanized rubber. A tire, wherein the tread comprises the rubber composition according to claim 3.