JP2019089882A - Method of producing rubber composition for tire - Google Patents

Abstract

To provide a method of producing a rubber composition for a tire, capable of providing a tire (vulcanized rubber) having low heat build-up properties and capable of suppressing a reduction in scorch resistance.SOLUTION: The method of producing a rubber composition for a tire comprises blending a rubber with a surface-treated carbon black treated with a compound represented by formula (I). (Rand Reach independently represent H or a C1-20 alkyl, alkenyl or alkynyl group; and Mrepresents Na, Kor Li.)SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a rubber composition for a tire.

  Conventionally, it is known to use surface-treated carbon black having good dispersibility in a rubber composition for the purpose of improving properties such as low fuel consumption and low heat buildup of a pneumatic tire using a rubber composition as a raw material. (Patent documents 1 and 2). In Patent Document 1, an amphoteric compound having an acidic or basic functional group in one molecule is used as a compound for treating the surface of carbon black, and in Patent Document 2, a diamine compound is used.

  Also, it is known to use a specific compound having a nitrogen functional group at the end and a carbon-carbon double bond in the rubber composition for the purpose of improving the dispersibility of carbon black in the rubber composition. (Patent Document 3).

JP, 2013-241483, A JP 2012-241160 A JP, 2014-95013, A

  On the other hand, in the market, rubber compositions which are more excellent in scorchability (processability) and which have lower heat buildup are required in tires (vulcanized rubber) which are made of the rubber compositions as a raw material. Vulcanized rubber obtained from a rubber composition as in the above-mentioned patent documents has room for improvement in the properties.

  The present invention has been made in view of the above-described circumstances, and provides a method for producing a rubber composition for a tire capable of obtaining a tire with low heat buildup (vulcanized rubber) and suppressing a decrease in scorchability. The purpose is

（式（Ｉ）中、Ｒ^１およびＲ^２は、水素原子、または炭素数１〜２０のアルキル基、アルケニル基、もしくはアルキニル基を示し、Ｒ^１およびＲ^２は同一であっても異なっていてもよい。Ｍ^＋はナトリウムイオン、カリウムイオンまたはリチウムイオンを示す。）で表される化合物で処理して、表面処理カーボンブラックを得る工程（工程（ｉ））と、得られた表面処理カーボンブラックと、ゴムを混練する工程（工程（ｉｉ））を含むタイヤ用ゴム組成物の製造方法に関する。 The present invention is a method for producing a rubber composition for a tire, comprising
The surface of carbon black is represented by the general formula (I):

(In formula (I), R ¹ and R ^{2 each} represent a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, or an alkynyl group, and R ¹ and R ² are the same or different; M ⁺ represents a sodium ion, a potassium ion or a lithium ion)) to obtain a surface-treated carbon black (step (i)), and the obtained surface-treated carbon black The present invention relates to a method for producing a rubber composition for a tire including the step of kneading the rubber (step (ii)).

  Although the details of the mechanism of action of the effects in the surface-treated carbon black according to the present invention are unclear, they are presumed as follows. However, the present invention may not be interpreted as being limited to this mechanism of action.

  The method for producing a rubber composition for a tire according to the present invention comprises the steps of treating the surface of carbon black with the compound represented by the general formula (I) to obtain surface-treated carbon black (step (i)); The process (process (ii)) which knead | mixes the obtained surface-treated carbon black and rubber is included. By treating the surface of the carbon black with the compound represented by the general formula (I) in advance, the compound represented by the general formula (I) is the surface of the carbon black (the number of functional groups present in the surface is small It is presumed that they can be efficiently attached (bonded) to (for example, a carboxyl group). In particular, when an aqueous solution containing the compound represented by the general formula (I) is used, the contact efficiency of the carbon black and the compound represented by the general formula (I) is increased. It is presumed that the compound can be attached (bonded) more efficiently. Further, the surface-treated carbon black obtained by the above treatment can be used as it is as a raw material of a rubber composition for a tire, without providing a step of drying treatment in particular, so that the productivity of production of the rubber composition is improved. .

  By using such surface-treated carbon black as a raw material for a rubber composition for a tire, the carbon-carbon double bond part of the compound represented by the above general formula (I) present in the surface-treated carbon black is a rubber The vulcanized rubber obtained has excellent low heat build-up, since it is presumed that it can be combined with the rubber component (polymer) by the reaction with the radical of the component (polymer) or the reaction accompanied by sulfur crosslinking.

  By using the surface-treated carbon black as described above as a raw material of the rubber composition for a tire, it is presumed that the unreacted compound represented by the general formula (I) does not promote the vulcanization reaction. It is possible to suppress the deterioration (deterioration) of the scorch property of the composition.

<Method of producing rubber composition for tire>
The method for producing a rubber composition for a tire according to the present invention comprises the steps of treating the surface of carbon black with the compound represented by the general formula (I) to obtain surface-treated carbon black (step (i)); The process (process (ii)) which knead | mixes the obtained surface-treated carbon black and rubber is included.

（式（Ｉ）中、Ｒ^１およびＲ^２は、水素原子、または炭素数１〜２０のアルキル基、アルケニル基、もしくはアルキニル基を示し、Ｒ^１およびＲ^２は同一であっても異なっていてもよい。Ｍ^＋はナトリウムイオン、カリウムイオンまたはリチウムイオンを示す。）で表される化合物で処理されたものである。 <Step (i): Method for producing surface-treated carbon black>
In the step (i) of the present invention, the surface-treated carbon black has a surface of carbon black represented by the general formula (I):

(In formula (I), R ¹ and R ^{2 each} represent a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, or an alkynyl group, and R ¹ and R ² are the same or different; M ⁺ is one treated with a compound represented by sodium ion, potassium ion or lithium ion).

  As said carbon black, conductive carbon blacks, such as acetylene black and ketjen black, can be used besides carbon black used by usual rubber industry, such as SAF, ISAF, HAF, FEF, GPF, for example. . The carbon black may be granulated carbon black or non-granulated carbon black which is granulated in consideration of its handling property in ordinary rubber industry. Carbon black may be used alone or in combination of two or more.

The carbon black, from the viewpoint of improving the reinforcing property of the vulcanized rubber, DBP absorption amount (dibutyl phthalate absorption) ^is preferably at 80 cm 3/100 g or ^more, more preferably 110 cm 3/100 g or more ^and it is preferably 180cm 3/100 g or ^less, and more preferably less 140cm 3 / 100g.

The carbon black, from the viewpoint of improving the low heat generation property of the vulcanized rubber, the nitrogen adsorption specific surface area, is preferably ^{30 m} 2 / g or more, more preferably ^{50 m} 2 / g or more, ^{80 m} 2 / It is more preferably g or more, and preferably 250 m ² / g or less, more preferably 200 m ² / g or less, still more preferably 150 m ² / g or less, 120 m ² / g It is even more preferable that

を使用することが好ましい。 From the viewpoint of enhancing the affinity to carbon black, in the compound represented by the general formula (I), R ¹ and R ² in the general formula (I) are a hydrogen atom, and M ⁺ is a sodium ion Compounds described in general formula (I ′):

It is preferred to use

  The compound represented by the general formula (I) is preferably used in an aqueous solution containing the compound represented by the general formula (I) from the viewpoint of enhancing the contact efficiency to carbon black. The medium in the aqueous solution is a medium containing water as a main component, such as ion exchanged water, distilled water, industrial water, etc., but may be water containing an organic solvent, for example. The media may be used alone or in combination of two or more.

  The proportion of the compound represented by the general formula (I) in the aqueous solution containing the compound represented by the general formula (I) is 0.1% by weight from the viewpoint of improving the low heat buildup of the vulcanized rubber Or more, more preferably 0.3% by weight or more, still more preferably 0.5% by weight or more, and still more preferably 1.5% by weight or more. From the viewpoint of sufficiently dissolving the compound represented by the general formula (I) in the medium and from the viewpoint of suppressing (preventing) the decrease (deterioration) of the scorch property of the rubber composition, it is 80% by weight or less The content is preferably 75% by weight or less, more preferably 50% by weight or less, and still more preferably 30% by weight or less.

  In the surface-treated carbon black, the amount of the compound represented by the general formula (I) (surface treatment amount) is 100 parts by weight of the carbon black from the viewpoint of improving the low heat buildup of the crosslinked rubber. The content is preferably 0.1 to 30 parts by weight, more preferably 0.25 to 10 parts by weight, still more preferably 0.5 to 5.0 parts by weight, and further preferably 0.5 to 3.0. Even more preferably, it is in parts by weight.

  In the method of producing surface-treated carbon black of the present invention, the method of surface treatment is not particularly limited. For example, while stirring (flowing) carbon black in a mixer or blender, 1) the general A method of adding a compound represented by the formula (I) or an aqueous solution containing the compound and stirring the mixture, 2) an aqueous solution containing the compound represented by the general formula (I) using a spray machine such as a spray Examples of the method include a method of spray treatment, and a method of treatment by adding the compound represented by the general formula (I) to water used in the step of 3) carbon black granulation. From the viewpoint of uniform application, the method of surface treatment is preferably a method of spray treatment.

  In the surface treatment, the treatment temperature is preferably about 10 to 50 ° C., and more preferably about 20 to 30 ° C. Further, the treatment time depends on the amount of carbon black to be used and can not be generally stated, but it is usually about 3.0 to 5.0 minutes.

  The surface-treated carbon black obtained by the above surface treatment can be used without providing a drying step such as natural drying or forced drying from the viewpoint of shortening the mixing time, but after the above-mentioned surface treatment step Can also be provided with the above-mentioned drying step.

<Step (ii): Production of Rubber Composition>
Step (ii) of the present invention can produce a rubber composition by the step of kneading the surface-treated carbon black obtained above and a rubber. As a raw material of the rubber composition, besides the above-mentioned rubber, various compounding agents usually used in the rubber industry can be mentioned.

  Examples of the rubber include synthetic dienes such as natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR), chloroprene rubber (CR) and nitrile rubber (NBR). Rubber is mentioned. The rubber may be used alone or in combination of two or more. The rubber is preferably natural rubber (NR), butadiene rubber (BR), styrene butadiene rubber (SBR), or a blend of two or more thereof.

  The rubber is more preferably a blend rubber of natural rubber (NR) and butadiene rubber (BR). The ratio of NR / BR is preferably 30/70 to 80/20 by weight, and more preferably about 40/60 to 70/30.

  The compound represented by the general formula (I) in the surface-treated carbon black relative to 100 parts by weight of the rubber component in the rubber composition is 0.01 from the viewpoint of improving the low heat buildup of the vulcanized rubber. It is preferably 10 parts by weight, more preferably 0.1 to 5.0 parts by weight, and still more preferably 0.5 to 2.0 parts by weight.

  The surface-treated carbon black is preferably 30 to 100 parts by weight, preferably 35 to 80 parts by weight, with respect to 100 parts by weight of the rubber component in the rubber composition, from the viewpoint of improving the reinforcing property of the vulcanized rubber. Is more preferably 40 to 70 parts by weight.

  Examples of the various compounding agents include sulfur-based vulcanizing agents, vulcanization accelerators, antiaging agents, silica, silane coupling agents, zinc oxide, methylene acceptors and methylene donors, stearic acid, and vulcanization accelerators Vulcanization retarders, organic peroxides, softeners such as waxes and oils, processing aids and the like.

  The sulfur as the sulfur-based vulcanizing agent may be any conventional sulfur for rubber, and for example, powder sulfur, precipitated sulfur, insoluble sulfur, highly dispersible sulfur and the like can be used. The sulfur-based vulcanizing agent may be used alone or in combination of two or more.

  The content of sulfur is preferably 0.3 to 6.5 parts by weight with respect to 100 parts by weight of the rubber component in the rubber composition. If the content of sulfur is less than 0.3 parts by weight, the crosslink density of the vulcanized rubber will be insufficient to lower the rubber strength, etc. If it exceeds 6.5 parts by weight, both the heat resistance and the durability will be particularly good. Getting worse. In order to ensure the rubber strength of the vulcanized rubber favorably and to further improve the heat resistance and durability, the sulfur content is 1.0 to 5.5 with respect to 100 parts by weight of the rubber component in the rubber composition. It is more preferable that it is a weight part.

  As the vulcanization accelerator, any conventional vulcanization accelerator for rubber may be used, and a sulfenamide-based vulcanization accelerator, a thiuram-based vulcanization accelerator, a thiazole-based vulcanization accelerator, a thiourea-based vulcanization accelerator And guanidine-based vulcanization accelerators and dithiocarbamate-based vulcanization accelerators. The vulcanization accelerators may be used alone or in combination of two or more.

  The content of the vulcanization accelerator is preferably 1 to 5 parts by weight with respect to 100 parts by weight of the rubber component in the rubber composition.

  The anti-aging agent may be any conventional anti-aging agent for rubber, such as aromatic amine based anti-aging agent, amine-ketone based anti-aging agent, monophenol based anti-aging agent, bisphenol based anti-aging agent, polyphenol based Antiaging agents, dithiocarbamate antiaging agents, thiourea antiaging agents, etc. may be mentioned. The antioxidant may be used alone or in combination of two or more.

  The content of the anti-aging agent is preferably 1 to 5 parts by weight with respect to 100 parts by weight of the rubber component in the rubber composition.

The silica is not particularly limited as long as it can be used as a reinforcing filler, but wet silica (hydrous silicic acid) is preferable. Colloidal properties of the silica is also not particularly limited, preferably has a nitrogen adsorption specific surface area (BET) is 150 to 250 ² / g by BET method, and more preferred is a 180~230m ² / g . The BET of silica is measured in accordance with the BET method described in ISO 5794. The silica may be used alone or in combination of two or more.

  The content of the silica is more preferably 1 to 50 parts by weight, and still more preferably 10 to 30 parts by weight with respect to 100 parts by weight of the rubber component contained in the tire member.

  The silane coupling agent may be any one commonly used for rubber, and examples thereof include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, and bis (2-trithio) silane. Sulfidosilanes such as ethoxysilylethyl) tetrasulfide, bis (4-triethoxysilylbutyl) disulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) disulfide; 3-mercaptopropyltri Mercaptosilanes such as methoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethylmethoxysilane and mercaptoethyltriethoxysilane; 3-O Tanoiruchio -1-propyltriethoxysilane, and protection mercaptosilane such as 3-propionylthio trimethoxy silane. The silane coupling agents may be used alone or in combination of two or more.

  The content of the silane coupling agent is more preferably 2 to 20% by weight of the weight of the silica, and still more preferably 4 to 15% by weight.

  The method of blending (adding) the surface-treated carbon black, the rubber, and the various compounding agents is, for example, a method of kneading using a kneader used in a usual rubber industry such as a Banbury mixer, a kneader, or a roll. It can be mentioned.

  Although the method of kneading is not particularly limited, for example, a method of adding and kneading components other than a vulcanizing component such as a sulfur-based vulcanizing agent and a vulcanization accelerator in any order, and a method of simultaneously adding and kneading Also, a method of simultaneously adding and kneading all the components may be mentioned. The number of times of kneading may be one or more. The time for kneading varies depending on the size of the kneader used, etc., but may usually be about 2 to 5 minutes. Moreover, it is preferable to set it as 120-170 degreeC, and, as for the discharge temperature of a kneading machine, it is more preferable to set it as 120-150 degreeC. In addition, when the discharge temperature of a kneading machine contains the said vulcanization system component, it is preferable to set it as 80-110 degreeC, and it is more preferable to set it as 80-100 degreeC.

  According to the method for producing a rubber composition for a tire of the present invention, a tire (vulcanized rubber) having low heat buildup can be obtained, and a tire rubber composition capable of suppressing a decrease in scorch property can be produced.

  EXAMPLES The present invention will be described by way of examples, but the present invention is not limited by these examples.

(Raw material used)
a) Compound represented by the general formula (I '): (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoate sodium "Sumilink 200" (manufactured by Sumitomo Chemical Co., Ltd.)
b) carbon black (1): "SEAST 6 (ISAF)" (nitrogen adsorption specific surface area of 119m ² / g, DBP absorption amount of 114cm ³ / 100g) (manufactured by Tokai Carbon Co., Ltd.)
c) carbon black (2): "SEAST 3 (HAF)" (nitrogen adsorption specific surface area of ^79m 2 / g, DBP absorption amount of 101cm ³ / 100g) (manufactured by Tokai Carbon Co., Ltd.)
d) Natural rubber: "RSS # 3"
e) Polybutadiene: "BR150B" (manufactured by Ube Industries, Ltd.)
f) Silica: “Nip seal AQ” (BET = 205 m ² / g) (manufactured by Nippon Silica Kogyo Co., Ltd.)
g) Silane coupling agent: "Si 69" (manufactured by Evonik Degussa)
h) Zinc flower: "Zinc oxide type 2" (Mitsui Metal Mining Co., Ltd.)
i) Stearic acid: "beads stearic acid" (manufactured by NOF Corporation)
j) Sulfur: "5% oil-filled fine powder sulfur" (made by Tsurumi Chemical Industry Co., Ltd.)
k) Vulcanization accelerator (A): N-cyclohexyl-2-benzothiazolesulfenamide, "Sunseller CM-G" (manufactured by Sanshin Chemical Industry Co., Ltd.)
l) Vulcanization accelerator (B): N-tert-butyl-2-benzothiazolylsulfenamide, "Noxceler NS-P" (manufactured by Ouchi New Chemical Co., Ltd.)

Example 1
<Step (i): Production of Surface-Treated Carbon Black 1>
In a predetermined amount of carbon black (1), the weight ratio of the compound represented by the general formula (I ') (trade name "Sumilink 200"), the carbon black / the compound represented by the general formula (I') is It measured so that it might become the weight ratio described in Table 1. Distilled water was added such that the concentration of the compound represented by the general formula (I ′) was 0.5% by weight based on the total amount of the compounds represented by the general formula (I ′) measured. The total amount of the aqueous solution (0.5% by weight) containing the compound represented by the general formula (I ') thus obtained is mixed with a predetermined amount of carbon black (1) in a mixer (stock The surface-treated carbon black 1 was manufactured by spraying using a spray gun while stirring with "SMV-20" manufactured by Kawata Co., Ltd. In addition, the compounding ratio in Table 1 is shown by weight part (phr) when the whole quantity of the rubber component contained in the rubber composition of Table 2 is made into 100 weight part.

<Step (ii): Production of Rubber Composition and Unvulcanized Rubber Composition>
Dry mixing (using time: 3 minutes, discharge temperature: 150) of the surface-treated carbon black 1 obtained above and each raw material listed in Table 2 (components excluding sulfur and vulcanization accelerator) using a Banbury mixer The rubber composition was manufactured by carrying out (C). Next, the sulfur, vulcanization accelerator (A) and vulcanization accelerator (B) listed in Table 2 are added to the obtained rubber composition, and dry mixing (kneading time: 1 minute, discharge using a Banbury mixer) The unvulcanized rubber composition was manufactured by carrying out temperature: 90 degreeC. In addition, the compounding ratio in Table 2 is shown by the weight part (phr) when the whole quantity of the rubber component contained in a rubber composition is 100 weight part. Further, parts by weight of the surface-treated carbon black in Table 2 represent only the total weight of the carbon black and the compound represented by the general formula (I ′).

Examples 2 to 11
<Production of surface-treated carbon black>
The type of carbon black, the weight ratio of carbon black / the compound represented by the general formula (I ′), and the concentration of the aqueous solution containing the compound represented by the general formula (I ′) were changed as shown in Table 1. Surface-treated carbon blacks 2 to 9 were produced in the same manner as in Example 1 except for the above.

<Production of rubber composition and unvulcanized rubber composition>
A rubber composition and an unvulcanized rubber composition were produced in the same manner as in Example 1 except that the types of the respective raw materials and the blending amounts (content) thereof were changed as shown in Table 2.

<Comparative Examples 1 to 5>
A rubber composition was produced by dry mixing (kneading time: 3 minutes, discharge temperature: 150 ° C.) of each raw material (component excluding sulfur and vulcanization accelerator) described in Table 2 using a Banbury mixer. . Next, the sulfur, vulcanization accelerator (A) and vulcanization accelerator (B) listed in Table 2 are added to the obtained rubber composition, and dry mixing (kneading time: 1 minute, discharge using a Banbury mixer) Temperature: 90 ° C.) to produce an unvulcanized rubber composition.

  The following evaluation was performed about the unvulcanized rubber composition obtained by said Example and comparative example. The evaluation results are shown in Table 2.

<Evaluation of scorch resistance>
The scorch resistance is evaluated according to JIS K 6300 using a Rotares Mooney measuring machine manufactured by Toyo Seiki Seisakusho Co., Ltd., and after preheating the unvulcanized rubber composition at 125 ° C. for 1 minute, the minimum viscosity Vm 5 The time t5 required to increase the Mooney unit was measured, and in Examples 1 to 8 and Comparative Example 2 the index with the value of Comparative Example 1 being 100, Example 9 the index with the value of Comparative Example 3 being 100, Example 10 was expressed as an index with the value of Comparative Example 4 being 100, and Example 11 was expressed as an index with the value of Comparative Example 5 being 100. The larger the index, the longer the scorch time, and the better the scorch resistance.

  A vulcanized rubber was produced by vulcanizing the unvulcanized rubber compositions obtained in the above Examples and Comparative Examples under the conditions of 150 ° C. and 30 minutes. The following evaluation was performed about the obtained vulcanized rubber. The evaluation results are shown in Table 2.

<Evaluation of heat buildup>
For evaluation of heat buildup, using a visco-elastic tester manufactured by Toyo Seiki Seisaku-sho, the loss factor tan δ is measured under the conditions of static strain 10%, dynamic strain ± 2%, frequency 50 Hz and temperature 60 ° C. Examples 1 to 8 and Comparative Example 2 are indexes where the value of Comparative Example 1 is 100, Example 9 is an index where the value of Comparative Example 3 is 100, and Example 10 is an index where the value of Comparative Example 4 is 100. Example 11 was expressed as an index with the value of Comparative Example 5 being 100. The smaller the index is, the less the heat is generated and the lower the heat buildup is.

Claims (5)

A method for producing a rubber composition for a tire, comprising
The surface of carbon black is represented by the general formula (I):

(In formula (I), R ¹ and R ^{2 each} represent a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, or an alkynyl group, and R ¹ and R ² are the same or different; M ⁺ represents a sodium ion, a potassium ion or a lithium ion)) to obtain a surface-treated carbon black (step (i));
The manufacturing method of the rubber composition for tires characterized by including the process (process (ii)) which knead | mixes the obtained surface-treated carbon black and rubber | gum.   The rubber composition for a tire according to claim 1, wherein the step (i) is a step of treating with an aqueous solution containing the compound represented by the general formula (I) to obtain a surface-treated carbon black. Manufacturing method.   The method for producing a rubber composition for a tire according to claim 2, wherein the treatment in the aqueous solution containing the compound represented by the general formula (I) in the step (i) is a spray treatment.   The ratio of the compound represented by the general formula (I) in the aqueous solution containing the compound represented by the general formula (I) is 0.1 to 80% by weight. The manufacturing method of the rubber composition for tires of 3 statement.   The compound represented by the general formula (I) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the rubber component in the rubber composition. The manufacturing method of the rubber composition for tires as described.