阅读说明：本技术 橡胶用添加剂 (Additive for rubber ) 是由 川原央帆 龟上翔吾 于 2020-05-28 设计创作，主要内容包括：本发明为一种橡胶用添加剂,其含有下述化学式(1)所示的化合物。(式中,R～(1)和R～(2)分别为碳原子数1以上且33以下的脂肪族烃基,R～(1)和R～(2)的合计碳原子数为2以上且34以下,X为单键或碳原子数1以上且5以下的脂肪族烃基,A表示-O-CH-(2)-CH(OH)-CH-(2)OH、-O-CH(-CH-(2)-OH)-(2)或-N(R～(3))(R～(4)),R～(3)表示氢原子、甲基或碳原子数2以上且4以下的羟基烷基,R～(4)表示碳原子数2以上且4以下的羟基烷基。)(1)：(The present invention is an additive for rubber, which contains a compound represented by the following chemical formula (1). (in the formula, R 1 And R 2 Each is an aliphatic hydrocarbon group having 1 to 33 carbon atoms, R 1 And R 2 Has a total carbon number of 2 to 34 inclusive, X is a single bond or an aliphatic hydrocarbon group having 1 to 5 inclusive carbon atoms, A represents-O-CH 2 ‑CH(OH)‑CH 2 OH、‑O‑CH(‑CH 2 ‑OH) 2 or-N (R) 3 )(R 4 )，R 3 Represents a hydrogen atom, a methyl group or a hydroxyalkyl group having 2 to 4 carbon atoms, R 4 Represents a hydroxyalkyl group having 2 to 4 carbon atoms. )(1):)

1. An additive for rubber, which contains a compound represented by the following chemical formula (1),

chemical formula (1):

in the formula, R¹And R²Each is an aliphatic hydrocarbon group having 1 to 33 carbon atoms, R¹And R²Has 2 to 34 carbon atoms in total, and X isA single bond or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, wherein A represents-O-CH₂-CH(OH)-CH₂OH、-O-CH(-CH₂-OH)₂or-N (R)³)(R⁴)，R³Represents a hydrogen atom, a methyl group or a hydroxyalkyl group having 2 to 4 carbon atoms, R⁴Represents a hydroxyalkyl group having 2 to 4 carbon atoms.

2. The additive for rubber according to claim 1, wherein in the compound represented by the chemical formula (1), X is a single bond.

3. The additive for rubber according to claim 1 or 2, wherein the compound represented by the chemical formula (1) contains:

a in the chemical formula (1) is-O-CH₂-CH(OH)-CH₂Compounds of OH, hereinafter referred to as ether alcohol 1; and

a in the chemical formula (1) is-O-CH (-CH)₂-OH)₂The compound of (1), hereinafter referred to as ether alcohol 2,

the content of the ether alcohol 1 is 1 mass% or more and 99 mass% or less with respect to the total of the ether alcohol 1 and the ether alcohol 2.

4. A rubber composition comprising a rubber, a reinforcing filler and the additive for rubber according to any one of claims 1 to 3.

5. The rubber composition according to claim 4, wherein the content of the rubber additive is 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the rubber.

6. The rubber composition according to claim 4 or 5, wherein the reinforcing filler contains silica.

7. The rubber composition according to any one of claims 4 to 6, wherein the rubber is a conjugated diene rubber.

8. The rubber composition according to any one of claims 4 to 7, wherein a mass ratio of a content of the rubber additive to a content of the reinforcing filler, that is, a content of the rubber additive/a content of the reinforcing filler is 0.003 or more and 1 or less.

9. The rubber composition according to any one of claims 4 to 8, further comprising a coupling agent.

10. The rubber composition according to claim 9, wherein the content of the coupling agent is 1 part by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the inorganic reinforcing filler.

11. A method for producing a rubber composition, comprising a first kneading step and a second kneading step,

a first mixing step: a step of mixing a rubber, a reinforcing filler and the additive for rubber according to any one of claims 1 to 3 to obtain an unvulcanized rubber composition,

a second mixing step: and a step of mixing a vulcanizing agent and a vulcanization accelerator with the unvulcanized rubber composition to obtain a vulcanized rubber composition.

12. The method for producing a rubber composition according to claim 11, wherein the reinforcing filler contains silica.

13. A method for reducing the viscosity of an unvulcanized rubber composition, which comprises a step of mixing the additive for rubber, rubber and reinforcing filler according to any one of claims 1 to 3.

14. Use of the additive for rubber as defined in any one of claims 1 to 3 as an additive in a composition containing a rubber and a reinforcing filler.

15. Use of the additive for rubber as described in any one of claims 1 to 3 for reducing the viscosity of an unvulcanized rubber composition.

Technical Field

The present invention relates to an additive for rubber, a rubber composition, and a method for producing a rubber composition.

Background

The rubber is an amorphous and soft polymer substance, and particularly, an elastic rubber, which is a material having a high elastic limit and a low elastic modulus and mainly composed of an organic polymer such as natural rubber or synthetic rubber, is often used. By utilizing this property, rubber-containing compositions (rubber compositions) are used in various fields such as tires, sealing materials, vibration-isolating and vibration-damping materials, and the like.

For example, in a vehicle tire, rubber elasticity of rubber plays a role of absorbing a shock generated when a vehicle travels on a road surface having irregularities, improving ride comfort of the vehicle, and alleviating the shock to the vehicle itself. Further, since the rubber hardly allows water and air to pass therethrough, the air can be firmly held in the tire, and the tire can also withstand rain and snow. Further, since the friction force of the rubber is large, the friction force of the tire contacting the road surface is also large, and the power and the braking force are rapidly transmitted to the road surface, so that the tire is less likely to slip.

In order to effectively utilize the characteristics of such rubbers and to obtain more preferable performance, various additives are used in the rubbers. For example, silica is sometimes blended in a rubber composition for a tire as a filler for improving low heat build-up property, grip property on a wet road surface, and the like. However, silica tends to agglomerate with each other due to hydrogen bonding of silanol groups as surface functional groups, and it is necessary to extend the kneading time in order to achieve good dispersion of silica in rubber. Further, since the dispersion of silica in rubber is insufficient, the mooney viscosity of the rubber composition tends to be high, and the processability such as extrusion tends to be poor. Further, since the surface of the silica particles is acidic, an alkaline substance used as a vulcanization accelerator may be adsorbed, so that vulcanization of the rubber composition may not be sufficiently performed, and the storage modulus may not be improved to a desired degree. Therefore, improvement in processability and the like of a rubber composition containing silica has been conventionally required.

For example, international publication No. 2014/098155 discloses a rubber composition comprising at least one rubber component selected from natural rubber and/or diene synthetic rubber, silica, and a glycerin fatty acid ester composition, wherein the glycerin fatty acid ester composition is incorporated in an amount of 0.5 to 15 parts by mass per 100 parts by mass of the rubber component, the fatty acid has 8 to 28 carbon atoms, the glycerin fatty acid ester composition contains a glycerin fatty acid monoester and a glycerin fatty acid diester, and the glycerin fatty acid monoester content in the glycerin fatty acid ester composition is 85% by mass or less.

International publication No. 2012/070626 discloses a rubber composition obtained by blending at least one rubber component selected from natural rubber and/or diene synthetic rubber with at least one of a white filler and a predetermined monoalkanolamide.

Japanese patent application laid-open No. 2001-72801 discloses a rubber composition comprising a natural rubber and/or a diene synthetic rubber and carbon black and a predetermined tertiary amine, wherein the amount of the tertiary amine is 1 to 15 parts by weight based on 100 parts by weight of the rubber.

Disclosure of Invention

The invention provides an additive for rubber, which can reduce the viscosity of an unvulcanized rubber composition to improve the processability, a rubber composition with excellent processability and a preparation method thereof.

The present invention relates to an additive for rubber, which contains a compound represented by the following chemical formula (1).

[ chemical formula 1]

Chemical formula (1):

(in the formula, R¹And R²Each is an aliphatic hydrocarbon group having 1 to 33 carbon atoms, R¹And R²Has a total carbon number of 2 to 34 inclusive, X is a single bond or an aliphatic hydrocarbon group having 1 to 5 inclusive carbon atoms, A represents-O-CH₂-CH(OH)-CH₂OH、-O-CH(-CH₂-OH)₂or-N (R)³)(R⁴)，R³Represents a hydrogen atom, a methyl group or a hydroxyalkyl group having 2 to 4 carbon atoms, R⁴Represents a hydroxyalkyl group having 2 to 4 carbon atoms. )

The present invention also relates to a rubber composition containing a rubber, a reinforcing filler and the additive for rubber of the present invention.

The present invention also relates to a method for producing a rubber composition, which comprises the following first and second kneading steps.

A first mixing step: a step of mixing a rubber, a reinforcing filler and the additive for rubber of the present invention to obtain an unvulcanized rubber composition,

a second mixing step: and a step of mixing a vulcanizing agent and a vulcanization accelerator with the unvulcanized rubber composition to obtain a vulcanized rubber composition.

The present invention also relates to a method for reducing the viscosity of an unvulcanized rubber composition, which comprises a step of mixing the additive for rubber of the present invention, a rubber and a reinforcing filler.

The present invention also relates to the use of the additive for rubber of the present invention as an additive in a composition containing a rubber and a reinforcing filler.

The present invention also relates to the use of the additive for rubber of the present invention for reducing the viscosity of an unvulcanized rubber composition.

According to the present invention, an additive for rubber capable of improving processability by reducing the viscosity of an unvulcanized rubber composition, a rubber composition having excellent processability, and a method for producing the same are provided.

Detailed Description

[ additive for rubber ]

The additive for rubber of the present invention contains a compound [ hereinafter, also referred to as compound (1) ] represented by the following chemical formula (1).

In the present invention, it is presumed that the hydroxyl group or amino group as the polar functional group of the compound (1) is adsorbed on the surface of a filler such as silica which is usually compounded in the rubber composition, the aliphatic hydrocarbon group of the compound (1) exhibits high affinity with the rubber component, thereby improving the dispersibility of the filler in the rubber composition, and the filler imparts lubricity to the rubber component, thereby improving the processability (decrease in mooney viscosity) of the rubber composition.

[ chemical formula 2]

Chemical formula (1):

(in the formula, R¹And R²Each is an aliphatic hydrocarbon group having 1 to 33 carbon atoms, R¹And R²Has a total carbon number of 2 to 34 inclusive, X is a single bond or an aliphatic hydrocarbon group having 1 to 5 inclusive carbon atoms, A represents-O-CH₂-CH(OH)-CH₂OH、-O-CH(-CH₂-OH)₂or-N (R)³)(R⁴)，R³Represents a hydrogen atom, a methyl group or a hydroxyalkyl group having 2 to 4 carbon atoms, R⁴Represents a hydroxyalkyl group having 2 to 4 carbon atoms. )

The present invention includes an additive for rubber, which contains a compound (1) represented by the above chemical formula (1), wherein the compound (1) is represented by the formula (1) wherein A is-O-CH₂-CH(OH)-CH₂OH or-O-CH (-CH)₂-OH)₂The compound (hereinafter, also referred to as an ether alcohol of the present invention).

In addition, the invention comprises a rubber compositionAn additive comprising a compound (1) represented by the above chemical formula (1), wherein A in the compound (1) is-N (R)³)(R⁴)，R³Is a hydrogen atom, a methyl group or a hydroxyalkyl group having 2 to 4 carbon atoms, R⁴A hydroxyalkyl compound having 2 to 4 carbon atoms (hereinafter, also referred to as "aminoalcohol" in the present invention).

The rubber additive of the present invention may contain 1 or 2 or more compounds (1).

An additive for rubber comprising the ether alcohol of the present invention and the aminoalcohol of the present invention as the compound (1) is also included in the present invention.

R¹And R²Each of the aliphatic hydrocarbon groups having 1 to 33 carbon atoms is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. The aliphatic hydrocarbon group may have a substituent such as a hydroxyl group, a ketone group, a carboxyl group, an aryl group, and an alkoxy group as long as the effect of the present invention is not impaired. R¹And R²The aliphatic hydrocarbon groups may be the same or different. In addition, from the viewpoint of miscibility with rubber, R is¹And R²The number of substituents of (A) is R¹And R²The total of (a) and (b) is preferably 5 or less, more preferably 3 or less, still more preferably 1 or less, and still more preferably 0.

R¹And R²The total number of carbon atoms of (a) is 2 or more and 34 or less, and from the viewpoint of miscibility with rubber, is preferably 12 or more, more preferably 14 or more, and preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and further preferably 16 or less. In addition, in R¹And R²When the aliphatic hydrocarbon group (2) has a carbon-containing substituent, a carbon atom bonded through an atom other than carbon to X in the formula (1), for example, a carbon atom of a methyl group bonded through an oxygen atom of a "methoxy group", is not counted as R¹And R²The total number of carbon atoms.

In which A is-N (R)³)(R⁴) In the case of (1), R³Represents a hydrogen atom, a methyl group or a hydroxyl group having 2 to 4 carbon atomsAlkyl radical, R⁴Represents a hydroxyalkyl group having 2 to 4 carbon atoms. From the viewpoint of viscosity-reducing effect on an unvulcanized rubber composition, R³Preferably a hydrogen atom or a hydroxyalkyl group having 2 to 4 carbon atoms, more preferably a hydroxyalkyl group having 2 to 4 carbon atoms. From the viewpoint of miscibility with rubber, R³And R⁴The number of carbon atoms of each hydroxyalkyl group is preferably 2 or more and 3 or less, and more preferably 2.

X is a single bond or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and from the viewpoint of miscibility with the rubber, is preferably a single bond or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a single bond or an aliphatic hydrocarbon group having 1 to 2 carbon atoms, still more preferably a single bond or an aliphatic hydrocarbon group having 1 carbon atom, and yet still more preferably a single bond.

From the viewpoint of miscibility with rubber, the compound (1), for example, the ether alcohol or aminoalcohol of the present invention preferably contains R, and R are a single bond or an aliphatic hydrocarbon group having 1 to 3 carbon atoms¹And R²Has the same total carbon number and R¹And R²2 or more compounds each having a different carbon number.

From the viewpoint of miscibility with rubber, the compound (1) such as the ether alcohol or aminoalcohol of the present invention more preferably contains R, R being a single bond or an aliphatic hydrocarbon group having 1 to 2 carbon atoms¹And R²Has the same total carbon number and R¹And R²2 or more compounds each having a different carbon number.

From the viewpoint of miscibility with rubber, the compound (1) such as the ether alcohol or aminoalcohol of the present invention preferably further contains R and R, wherein X is a single bond or an aliphatic hydrocarbon group having 1 carbon atom¹And R²Has the same total carbon number and R¹And R²2 or more compounds each having a different carbon number.

From the viewpoint of miscibility with rubber, it is more preferable that the compound (1) such as the ether alcohol or aminoalcohol of the present invention further contains X as a single bond and R¹And R²Has the same total carbon number and R¹And R²2 or more compounds each having a different carbon number.

In the case where the compound (1) such as the ether alcohol or aminoalcohol of the invention contains X as a single bond and R is¹And R²In the case of 2 or more compounds having different total carbon atoms in (A), R is a carbon atom number of the rubber compound in the rubber composition from the viewpoint of miscibility with the rubber¹And R²The total content of the compounds having 14 or 16 carbon atoms in total in the compound (1) is preferably 75% by mass or more, more preferably 85% by mass or more, further preferably 95% by mass or more, and further preferably 100% by mass, for example, in the ether alcohol or amino alcohol of the present invention.

When X is an aliphatic hydrocarbon group, the alkyl group is preferably a linear or branched alkyl group, and more preferably a linear alkyl group, from the viewpoint of miscibility with rubber. Further, the aliphatic hydrocarbon group of X may include a divalent hydrocarbon group such as an alkylene (alkanediyl) group.

Containing R in the compound (1), e.g. the ether alcohol or amino alcohol of the invention¹And R²In the case of compounds having 2 or more different carbon atoms, R is a carbon atom in the rubber composition, from the viewpoint of miscibility with the rubber¹Has 5 or more carbon atoms and R²The content ratio of the compound having 5 or more carbon atoms in the compound (1), for example, in the ether alcohol or amino alcohol of the present invention, is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less. In the case of producing the compound (1) such as the ether alcohol or aminoalcohol of the present invention, R is a compound obtained by using an internal olefin as a starting material¹Has 5 or more carbon atoms and R²The content ratio of the compound having 5 or more carbon atoms in (b) can be estimated from the double bond distribution of the internal olefin in the raw material.

The melting point of the compound (1) such as the ether alcohol or aminoalcohol of the present invention is preferably 30 ℃ or lower, more preferably 20 ℃ or lower, and still more preferably 10 ℃ or lower, from the viewpoint of miscibility with rubber. Further, it may be at-200 ℃ or higher.

In the compound (1), the method for producing the ether alcohol of the present invention is not particularly limited, and for example, the ether alcohol can be produced by synthesizing an internal epoxide by oxidizing a double bond of an internal olefin compound with a peroxide such as hydrogen peroxide, performic acid, peracetic acid, or the like, and reacting the obtained internal epoxide with glycerin. The ether alcohol obtained by the above production method is R¹Or R²A mixture of a plurality of compounds having different carbon atoms. In addition, the product obtained by the above production method is usually such that A is-O-CH₂-CH(OH)-CH₂The ether alcohol of OH (hereinafter, also referred to as ether alcohol 1) and A are-O-CH (-CH)₂-OH)₂And (3) a mixture of ether alcohols (hereinafter, also referred to as ether alcohol 2).

In the compound (1), the method for producing the aminoalcohol of the present invention is not particularly limited, and for example, the aminoalcohol can be produced by synthesizing an internal epoxide by oxidizing a double bond of an internal olefin compound with a peroxide such as hydrogen peroxide, performic acid, peracetic acid, or the like, and reacting the obtained internal epoxide with a primary alkanolamine or a secondary alkanolamine. As the primary or secondary alkanolamine, an alkanolamine having a hydroxyalkyl group with a carbon number of 2 or more and 4 or less can be used. Examples of the alkanolamines include monoethanolamine, N-methylethanolamine, diethanolamine, propanolamine (3-amino-1-propanol), dipropanolamine, isopropanolamine (1-amino-2-propanol), diisopropanolamine, and 4-amino-1-butanol. The aminoalcohol obtained by the production method is preferably R¹Or R²A mixture of a plurality of compounds having different carbon atoms.

In addition, the process for producing an aminoalcohol of the present invention can be, for example, the process described in japanese patent laid-open No. 2013-543927.

The olefin used for producing the ether alcohol of the present invention or the aminoalcohol of the present invention may contain an α -olefin in addition to the internal olefin. In this case, the content of the α -olefin contained in the olefin is, for example, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, further preferably 1% by mass or less, further preferably 0.5% by mass or less.

The additive for rubber of the present invention contains at least 1 compound (1).

The additive for rubber of the present invention contains, for example, at least 1 ether alcohol of the present invention.

The additive for rubber of the present invention may contain at least 1 of the above ether alcohols 1 and at least 1 of the above ether alcohols 2.

The additives for rubbers according to the invention contain, for example, at least 1 amino alcohol according to the invention.

The additive for rubber of the present invention may contain a in the formula (1) wherein A is-N (R)³)(R⁴) And R is³At least 1 kind of compound which is hydrogen atom, and A in the formula (1) is-N (R)³)(R⁴) And R is³At least 1 kind of compound of hydroxyalkyl with more than 2 and less than 4 carbon atoms.

The total content of the compound (1) in the additive for rubber of the present invention is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, and further preferably 90% by mass or more, from the viewpoint of obtaining the effects of the present invention. The upper limit of the content of the compound (1) in the additive for rubber of the present invention is 100% by mass. That is, the compound (1) may be used as it is as an additive for rubber.

When the compound (1) is the ether alcohol of the present invention, the total content of the ether alcohol of the present invention in the additive for rubber of the present invention is not particularly limited, and is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, and further preferably 90% by mass or more, from the viewpoint of obtaining the effects of the present invention. The upper limit of the content of the ether alcohol of the present invention in the additive for rubber of the present invention is 100 mass%. That is, the ether alcohol of the present invention can be used as it is as an additive for rubber.

In the case where the additive for rubber of the present invention contains the ether alcohol 1 and the ether alcohol 2, the content of the ether alcohol 1 is preferably 1% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, further preferably 50% by mass or more, preferably 99% by mass or less, more preferably 90% by mass or less, and further preferably 80% by mass or less with respect to the total amount of the ether alcohol 1 and the ether alcohol 2, from the viewpoint of obtaining a high adsorption force to the reinforcing filler. From the same viewpoint, the amount is preferably 1 to 99% by mass, more preferably 30 to 99% by mass, even more preferably 40 to 90% by mass, and even more preferably 50 to 80% by mass.

When the compound (1) is the aminoalcohol of the present invention, the total content of the aminoalcohol of the present invention in the additive for rubber of the present invention is not particularly limited, and is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, and further preferably 90% by mass or more, from the viewpoint of obtaining the effects of the present invention. The upper limit of the content of the aminoalcohol of the present invention in the additive for rubber of the present invention is 100 mass%. That is, the aminoalcohol of the present invention may be used as it is as an additive for rubber.

The rubber additive of the present invention may contain, for example, a vulcanizing agent such as sulfur, a vulcanization accelerator such as zinc oxide, a softening agent, stearic acid, an antioxidant, a solvent, water, and the like, in addition to the compound (1) such as the ether alcohol of the present invention and the amino alcohol of the present invention, within a range not to impair the object of the present invention.

[ rubber composition ]

The rubber composition of the present invention contains a rubber, a reinforcing filler and the additive for rubber of the present invention. The rubber composition of the present invention may be a rubber composition containing a rubber, a reinforcing filler and the compound (1).

The present invention includes a rubber composition containing a rubber, a reinforcing filler and the additive for rubber of the present invention, wherein the compound (1) is the ether alcohol of the present invention.

The present invention also includes a rubber composition containing a rubber, a reinforcing filler and the above-described additive for rubber of the present invention, wherein the compound (1) is the aminoalcohol of the present invention.

The rubber composition of the present invention may contain 1 or 2 or more compounds (1).

Rubber compositions containing the ether alcohol of the present invention and the aminoalcohol of the present invention as the compound (1) are also encompassed in the present invention.

From the viewpoint of processability, the content of the rubber additive in the rubber composition of the present invention is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, further preferably 1 part by mass or more, and further preferably 2 parts by mass or more, per 100 parts by mass of the rubber. From the viewpoint of the fracture characteristics of the rubber composition, the content of the rubber additive in the rubber composition of the present invention is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, further preferably 10 parts by mass or less, further preferably 8 parts by mass or less, and further preferably 6 parts by mass or less, per 100 parts by mass of the rubber.

From the viewpoint of processability, the content of the compound (1) in the rubber composition of the present invention is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, further preferably 1 part by mass or more, and further preferably 2 parts by mass or more, per 100 parts by mass of the rubber. From the viewpoint of the fracture characteristics of the rubber composition, the content of the compound (1) in the rubber composition of the present invention is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, further preferably 10 parts by mass or less, further preferably 8 parts by mass or less, and further preferably 6 parts by mass or less, relative to 100 parts by mass of the rubber.

In addition, when the compound (1) is the ether alcohol of the present invention, the content of the ether alcohol of the present invention in the rubber composition of the present invention is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, further preferably 1 part by mass or more, and further preferably 2 parts by mass or more, relative to 100 parts by mass of the rubber, from the viewpoint of processability. From the viewpoint of the fracture characteristics of the rubber composition, the content of the ether alcohol of the present invention in the rubber composition of the present invention is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, further preferably 10 parts by mass or less, further preferably 8 parts by mass or less, and further preferably 6 parts by mass or less, relative to 100 parts by mass of the rubber.

When the compound (1) is the aminoalcohol of the present invention, the content of the aminoalcohol of the present invention in the rubber composition of the present invention is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, further preferably 1 part by mass or more, and further preferably 2 parts by mass or more, per 100 parts by mass of the rubber, from the viewpoint of processability. From the viewpoint of the fracture properties of the rubber composition, the content of the aminoalcohol of the present invention in the rubber composition of the present invention is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, further preferably 10 parts by mass or less, further preferably 8 parts by mass or less, and further preferably 6 parts by mass or less, relative to 100 parts by mass of the rubber.

< rubber >

The rubber used in the rubber composition of the present invention includes diene rubbers, and further includes conjugated diene rubbers.

Examples of the diene rubber include at least 1 selected from Natural Rubber (NR) and synthetic diene rubbers.

Specific examples of the synthetic diene rubber include polybutadiene rubber (BR), synthetic polyisoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), styrene-isoprene copolymer rubber (SIR), and the like.

The diene rubber preferably contains a styrene-butadiene copolymer rubber from the viewpoint of reducing tan δ of the rubber composition, for example, reducing rolling resistance when used in a tire. From the above viewpoint, the content of the styrene-butadiene copolymer rubber in the diene rubber is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and further preferably 90% by mass or more. The upper limit of the content is 100 mass%.

These diene rubbers may be used alone in 1 kind, or may be used in combination in 2 or more kinds. The diene rubber used may be modified or unmodified.

The content of the rubber in the rubber composition is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more, from the viewpoint of exhibiting physical properties derived from the rubber. Further, it is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less.

< Filler for reinforcing >

The rubber composition of the present invention further contains a reinforcing filler from the viewpoint of enhancing the mechanical properties of the rubber and obtaining a rubber composition exhibiting a desired storage modulus and tan δ.

Examples of the reinforcing filler used in the rubber composition of the present invention include an organic reinforcing filler and an inorganic reinforcing filler, which will be described later, in addition to carbon black. These reinforcing fillers may be used alone in 1 kind or in combination of 2 or more kinds.

Carbon black may be used as long as it has improved mechanical properties and the like, and I may be appropriately selected₂Amount of adsorption, CTAB specific surface area, N₂And a known carbon black having an adsorption amount, a DBP adsorption amount, and the like. The carbon black is not particularly limited, and examples thereof include GPF, FEF, HAF, ISAF and SAF grade carbon blacks. These carbon blacks may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Examples of the organic reinforcing filler include organic functional polyvinyl aromatic fillers described in WO2006/069792 and WO 2006/069793.

Examples of the inorganic reinforcing filler include at least 1 selected from the group consisting of silica, aluminum hydroxide, clay, talc, calcium carbonate and zeolite. From the viewpoint of obtaining a rubber composition exhibiting excellent storage modulus and tan δ, the inorganic reinforcing filler is preferably at least 1 selected from silica and aluminum hydroxide, and more preferably silica.

The silica is not particularly limited, and examples thereof include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, and the like, and among these, wet silica is preferable from the viewpoint of availability. These silicas may be used alone in 1 kind, or in combination of 2 or more kinds.

The rubber composition of the present invention preferably contains 1 or more kinds selected from carbon black and silica as a reinforcing filler, and more preferably contains silica. The content of silica in the reinforcing filler is preferably 60 mass% or more, more preferably 80 mass% or more, and still more preferably 85 mass% or more, and is preferably 100 mass% or less, and more preferably 950 mass% or less. In the reinforcing filler, the total content of carbon black and silica is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably substantially 100% by mass.

From the viewpoint of reinforcement, the content of the reinforcing filler in the rubber composition is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, further preferably 20 parts by mass or more, further preferably 30 parts by mass or more, and further preferably 40 parts by mass or more, per 100 parts by mass of the rubber. From the viewpoint of processability of the rubber composition, the content of the reinforcing filler in the rubber composition is preferably 120 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 80 parts by mass or less, relative to 100 parts by mass of the rubber.

In the rubber composition of the present invention, the mass ratio of the content of the rubber additive to the content of the reinforcing filler (the content of the rubber additive)/(the content of the reinforcing filler) is preferably 0.003 or more, more preferably 0.005 or more, and further preferably 0.01 or more, and is preferably 1 or less, more preferably 0.5 or less, and further preferably 0.1 or less.

In the rubber composition of the present invention, the mass ratio of the content of the compound (1) to the content of the reinforcing filler (the content of the compound (1))/(the content of the reinforcing filler) is preferably 0.003 or more, more preferably 0.005 or more, further preferably 0.01 or more, and is preferably 1 or less, more preferably 0.5 or less, further preferably 0.1 or less.

< coupling agent >

In order to enhance the effect of blending the inorganic reinforcing filler, the rubber composition of the present invention preferably further contains a coupling agent. The coupling agent is not particularly limited, but a silane coupling agent is preferable, and a silane coupling agent containing a sulfur atom is more preferable, from the viewpoint of reactivity with the inorganic reinforcing filler.

Examples of the sulfur atom-containing silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, n-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, etc. These coupling agents may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Among the above, bis (3-triethoxysilylpropyl) tetrasulfide is preferred.

From the viewpoint of reinforcement, the amount of the coupling agent to be blended in the rubber composition is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more, per 100 parts by mass of the inorganic reinforcing filler. From the viewpoint of reducing components that do not contribute to the coupling reaction, the amount is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 15 parts by mass or less.

< other ingredients, uses, etc. >

In the rubber composition of the present invention, compounding agents generally used for rubber compositions, for example, a vulcanizing agent such as sulfur, a vulcanization accelerator such as zinc oxide, a softening agent, stearic acid, an antioxidant, and the like can be appropriately selected and compounded within a range not to impair the object of the present invention, in addition to the above-mentioned rubber additive, rubber, reinforcing filler, and coupling agent. Commercially available products can be suitably used as these components.

The rubber composition of the present invention can exhibit its effect particularly by being used for a tire. That is, the rubber composition of the present invention can be used as a tire or a member of a tire. The tire member is suitably used for a tread and a base tread. According to the present invention, a tire using the rubber composition of the present invention can be provided.

The pneumatic tire is produced by a usual method using the rubber composition of the present invention. That is, the rubber composition of the present invention is extruded at an unvulcanized stage to form, for example, a tread member, and the tread member is attached and molded by a usual method on a tire molding machine to form a green tire. The green tire was heated and pressurized in a vulcanizer to obtain a tire.

The present inventors have found that the compound (1) can reduce the viscosity of unvulcanized rubber to improve the processability.

According to the present invention, there is provided a method for reducing the viscosity of an unvulcanized rubber composition, which comprises a step of mixing a compound (1), a rubber and a reinforcing filler.

According to the present invention, there is provided a method for reducing the viscosity of an unvulcanized rubber composition, which comprises a step of mixing the additive for rubber of the present invention, a rubber and a reinforcing filler.

Further, according to the present invention, there is provided a use of the compound (1) as an additive in a composition containing a rubber and a reinforcing filler.

Further, according to the present invention, there is provided a use of the additive for rubber of the present invention as an additive in a composition containing a rubber and a filler for reinforcement.

Further, according to the present invention, there is provided the use of the compound (1) for reducing the viscosity of an unvulcanized rubber composition.

Further, according to the present invention, there is provided a use of the additive for rubber of the present invention for reducing the viscosity of an unvulcanized rubber composition.

Further, according to the present invention, there is provided a use of the compound (1) as an additive for rubber.

Further, according to the present invention, there is provided a use of a composition containing a rubber, a reinforcing filler and the compound (1) as a rubber composition.

In these methods and methods, the additives for rubber and the matters described in the rubber composition of the present invention can be suitably used.

[ method for producing rubber composition ]

The method for producing the rubber composition of the present invention is not particularly limited. For example, the respective components contained in the rubber composition may be compounded and mixed by using a kneading machine such as a banbury mixer, a roll, or an intensive mixer.

From the viewpoint of suppressing the occurrence of vulcanization during the production of the rubber composition and improving the workability during the production, the rubber composition is preferably produced by the following method: the rubber composition is prepared by mixing and mixing components other than the vulcanizing agent and the vulcanization accelerator in advance (first mixing step), and then mixing and mixing the vulcanizing agent and the vulcanization accelerator (second mixing step). That is, according to the present invention, there is provided a method for producing a rubber composition, which comprises the following first kneading step and second kneading step. In the production method of the present invention, the additives for rubber and the matters described in the rubber composition of the present invention can be suitably applied. The content or blending amount of each component in the rubber composition of the present invention may be replaced with a blending amount (a blending amount with respect to the whole blending materials) and applied to the production method of the present invention.

A first mixing step: a step of mixing a rubber, a reinforcing filler and the additive for rubber of the present invention to obtain an unvulcanized rubber composition,

a second mixing step: and a step of mixing a vulcanizing agent and a vulcanization accelerator with the unvulcanized rubber composition to obtain a vulcanized rubber composition.

The present invention includes a method for producing a rubber composition having the above-described first kneading step and second kneading step, wherein the compound (1) of the additive for rubber of the present invention used in the first kneading step is the ether alcohol of the present invention.

The present invention also includes a method for producing a rubber composition, which comprises the above-described first and second mixing steps, wherein the compound (1) of the additive for rubber of the present invention used in the first mixing step is the aminoalcohol of the present invention.

In the method for producing the rubber composition of the present invention, 1 or 2 or more compounds (1) may be mixed.

The present invention also includes a method for producing a rubber composition having the first mixing step and the second mixing step, wherein the ether alcohol of the present invention and the amino alcohol of the present invention are mixed as the compound (1) of the additive for rubber of the present invention used in the first mixing step.

By this method, vulcanization does not occur even if the first kneading step is performed under high temperature conditions, and therefore the rubber composition of the present invention can be produced with good productivity. The first kneading step may be a step of mixing the rubber, the reinforcing filler and the compound (1) to obtain an unvulcanized rubber composition.

The mixing temperature in the first kneading step is preferably in the range of the maximum temperature of 250 ℃ or less, more preferably 200 ℃ or less, and still more preferably 180 ℃ or less, from the viewpoint of suppressing thermal decomposition of each component. From the viewpoint of productivity, the mixing temperature in the first kneading step is preferably 100 ℃ or higher, more preferably 120 ℃ or higher, and still more preferably 140 ℃ or higher.

The mixing temperature in the second mixing step is preferably 150 ℃ or lower, and more preferably 130 ℃ or lower, from the viewpoint of suppressing occurrence of vulcanization during mixing. From the viewpoint of productivity, the mixing temperature in the second kneading step is preferably 80 ℃ or higher, and more preferably 100 ℃ or higher.

Examples

[ example 1 and comparative example 1]

< method for measuring position of double bond of internal olefin >

The position of the double bond of the internal olefin produced as a starting compound of the epoxide-glycerol ring-opening product was measured by gas chromatography (hereinafter, abbreviated as GC). Specifically, after a disulfide derivative is produced by reacting dimethyldisulfide with an olefin, the respective components are separated by GC. And (5) solving the position of the double bond of the internal olefin according to each peak area. The apparatus and analysis conditions used for the measurement are as follows.

A GC device: trade name HP6890 (manufactured by HEWLETT PACKARD Co.)

Column: trade name of Ultra-Alloy-1HT capillary column 30 m.times.250. mu.m.times.0.15. mu.m (manufactured by Frontier Laboratories K.K.)

A detector: hydrogen Flame Ion Detector (FID)

Injection temperature: 300 deg.C

Detector temperature: 350 deg.C

Oven: 60 ℃ (0min.) → 2 ℃/min. → 225 ℃ → 20 ℃/min. → 350 ℃ → 350 ℃ (5.2min.)

< method for measuring content ratio of structural isomers >

0.05g of the epoxide-glycerol ring-opened product produced in example 1 and comparative example 1, 0.2g of trifluoroacetic anhydride, and 1g of deuterated chloroform were mixed, and the mixture was used¹H-NMR was measured. The measurement conditions were as follows.

Nuclear magnetic resonance apparatus: agilent 400-MR DD2, produced by Frontier Laboratories, Inc

The observation range is as follows: 6410.3Hz

Data points: 65536

Measurement mode: preset (Presat)

Pulse width: 45 degree

Pulse delay time: 10sec

And (4) accumulating times: 128 times

< determination of the melting Point of the reaction product (additive) of an internal epoxide with Glycerol >

Each additive was added to a 70. mu.L pan using a High-sensitivity differential scanning calorimeter (product name: DSC7000X, manufactured by Hitachi High-Tech Science Co., Ltd.), and the temperature was raised from-60 ℃ to 80 ℃ at 2 ℃/min, and the temperature at the maximum peak of the temperature difference detected by the differential thermode with respect to the temperature rise time was defined as the melting point.

< production of internal olefin >

Production example A1

(production of C16 internal olefin (C16 internal olefin))

Into a flask equipped with a stirrer, 7000g (28.9 mol) of 1-hexadecanol (product name: Kalcol6098, manufactured by Kao corporation) and 700g (10 wt% based on the starting alcohol) of gamma-alumina (STREM Chemicals, Inc.) as a solid acid catalyst were charged, and a reaction was carried out for 32 hours while introducing nitrogen (7000 mL/min) into the system at 280 ℃ under stirring. The conversion of alcohol after the reaction was completed was 100%, and the purity of C16 olefin was 99.6%. The obtained crude C16 internal olefin is transferred to a distiller and distilled at 136-160 ℃/4.0mmHg, thereby obtaining C16 internal olefin with the olefin purity of 100%. The double bond distribution of the C16 internal olefin was 0.2% at C1, 15.8% at C2, 14.5% at C3, 15.7% at C4, 17.3% at C5, 16.5% at C6, and the total of C7 and C8 was 20.0%.

Production example A2

(production of C18 internal olefin (C18 internal olefin))

800kg (3.0 kmol) of 1-octadecanol (Kalkol 8098, product name, Kao corporation) and 80kg (10 wt% relative to the starting alcohol) of activated alumina GP-20 (Kazuku Kogyo Co., Ltd.) as a solid acid catalyst were charged into a reactor equipped with a stirrer, and the reaction was carried out for 16 hours while introducing nitrogen (15L/min) into the system at 280 ℃ under stirring. The conversion of alcohol after the reaction was completed was 100%, and the purity of C18 olefin was 98.7%. The obtained crude C18 internal olefin is transferred to a distiller and distilled at 163-190 ℃/4.6mmHg to obtain C18 internal olefin with olefin purity of 100%. The double bond distribution of the obtained C18 internal olefin is 0.3% at C1, 13.3% at C2, 12.6% at C3, 13.9% at C4, 14.8% at C5, 13.7% at C6, 12.6% at C7, and the total of C8 and C9 is 18.8%.

< production of internal epoxide >

Production example B1

(production of C16 internal epoxy Compound (C16 internal epoxy Compound))

Into a flask equipped with a stirrer were charged C16 internal olefin (800g, 3.56 mol) obtained in production example A1, acetic acid (Fuji film and Wako pure chemical industries, Ltd.), 107g (1.78 mol), sulfuric acid (Fuji film and Wako pure chemical industries, Ltd.), 15.6g (0.15 mol), 35% hydrogen peroxide (Fuji film and Wako pure chemical industries, Ltd.) 415.7g (4.28 mol), and sodium sulfate (Fuji film and Wako pure chemical industries, Ltd.) 25.3g (0.18 mol), and the reaction was carried out at 50 ℃ for 4 hours. Then, the temperature was raised to 70 ℃ to further conduct the reaction for 2 hours. After the reaction, the layers were separated and the aqueous layer was removed, and the oil layer was washed with ion-exchanged water, a saturated aqueous sodium carbonate solution (Fuji film and Wako pure chemical industries, Ltd.), a saturated aqueous sodium sulfite solution (Fuji film and Wako pure chemical industries, Ltd.), and a 1% saline solution (Fuji film and Wako pure chemical industries, Ltd.) and concentrated by an evaporator to obtain 820g of C16 inner epoxide.

Production example B2

(production of C18 internal epoxy Compound (C18 internal epoxy Compound))

Into a flask equipped with a stirrer were charged C18 internal olefin (595g, 2.38 mol) obtained in production example A2, acetic acid (Fuji film and Wako pure chemical industries, Ltd.), 71.7g (1.20 mol), sulfuric acid (Fuji film and Wako pure chemical industries, Ltd.) 9.8g (0.10 mol), and 324g (4.00 mol) of 35% hydrogen peroxide (Fuji film and Wako pure chemical industries, Ltd.), and the mixture was reacted at 50 ℃ for 4 hours. Then, the temperature was raised to 80 ℃ to further conduct the reaction for 5 hours. After the reaction, the layers were separated and the aqueous layer was removed, and the oil layer was washed with ion-exchanged water, a saturated aqueous sodium carbonate solution (manufactured by Fuji film and Wako pure chemical industries, Ltd.), a saturated aqueous sodium sulfite solution (manufactured by Fuji film and Wako pure chemical industries, Ltd.), and ion-exchanged water and concentrated by an evaporator to obtain 629g of the C18 inner oxide.

< production of reaction product of internal epoxide with Glycerol >

Production example (I)

[ production of additive 1[ reaction product of C16 internal epoxide with Glycerol (Ring-opened product of C16 internal epoxide Glycerol) ] ]

Into a flask equipped with a stirrer, 2298g (25.0 mol) of glycerol (Fuji film and Wako pure chemical industries, Ltd.) and 0.122g (1.25 mmol) of 98% sulfuric acid (Fuji film and Wako pure chemical industries, Ltd.) were charged, and the temperature was raised to 130 ℃. Then, 300g (1.25 mol) of the C16 internal epoxide obtained in production example B1 was added dropwise over 1 hour, followed by reaction at 130 ℃ for 8 hours. Hexane was added to the liquid obtained by the reaction, and the mixture was washed with ion-exchanged water and then concentrated under reduced pressure using an evaporator to obtain 400g of a C16 internal epoxide glycerin ring-opened product (additive 1) having a melting point of-18 ℃. As the obtained additive 1, in the above chemical formula (1), R¹And R²Each of which contains an alkyl group having 1 to 13 carbon atoms, R¹And R²Has 14 carbon atoms in total, X is a single bond, and 73 mass% of A is-O-CH₂-CH(OH)-CH₂OH Ether alcohol 1 containing 27% by mass of A-O-CH (-CH)₂-OH)₂Ether alcohol 2 of (1). Further, from the double bond distribution of the internal olefin used in the raw material, R is estimated¹Has 5 or more carbon atoms and R²The content of the compound having 5 or more carbon atoms in (b) is 37% by mass.

Production example (II)

[ production of additive 2[ reaction product of epoxide and Glycerol in C18 (Ring-opened product of glycerol, epoxide having 18 carbon atoms) ] ]

The same production as in production example (I) was carried out except that 1.25 mol of the C18 internal oxide obtained in production example B2 was used in place of 1.25 mol of the C16 internal oxide obtained in production example B1The method provided glycerol ring-opening product (additive 2) of C18 internal epoxide with melting point of 1 deg.C. In the obtained additive 2, R in the above chemical formula (1)¹And R²Each of which contains an alkyl group having 1 to 15 carbon atoms, R¹And R²Has 16 carbon atoms in total, X is a single bond, and 72 mass% of A is-O-CH₂-CH(OH)-CH₂OH Ether alcohol 1 containing 28% by mass of A as-O-CH (-CH)₂-OH)₂Ether alcohol 2 of (1). Further, from the double bond distribution of the internal olefin used in the raw material, R is estimated¹Has 5 or more carbon atoms and R²The content ratio of the compound having 5 or more carbon atoms in (b) is 45% by mass.

Production example C

[ production of glycerin fatty acid ester 2]

In a 1L four-necked flask equipped with a stirrer, a dehydration tube-condenser, a thermometer, and a nitrogen introduction tube, 450g of glycerin and stearic acid [ produced by kaowski corporation, Lunac S-98]694g [ glycerin/fatty acid (molar ratio) ═ 2.0] were charged, and 10ppm of sodium hydroxide dissolved in a small amount of water was added, and while nitrogen was passed through the liquid upper space at 100 mL/min, the temperature was raised to 240 ℃ over about 1.5 hours under stirring at 400 r/min. After reaching 240 ℃, the acid component was dehydrated while being refluxed into the flask, and reacted at this temperature for 4 hours.

Subsequently, the reaction mixture was cooled to 170 ℃ and glycerol was distilled off under reduced pressure under a pressure of 2.7kPa or less, and further steam was supplied at 150 ℃ and 2kPa for 2 hours, followed by pressure-adsorption filtration using ZetaPlus 30S (manufactured by CUNO Corp.) to obtain a monoglyceride-containing composition.

< preparation and evaluation of rubber composition >

The rubber compositions were prepared by kneading the components according to the compounding recipe shown in table 1 by using a general banbury mixer in the order of the first kneading step and the second kneading step. The components other than zinc oxide, sulfur and vulcanization accelerators 1 and 2 in the components in table 1 were kneaded in the first kneading step, and zinc oxide, sulfur and vulcanization accelerators 1 and 2 were kneaded in the second kneading step. The maximum temperature of the rubber composition in the first kneading step was 150 ℃, and the maximum temperature of the rubber composition in the second kneading step was 110 ℃.

With respect to the obtained rubber composition, the rubber composition was measured in accordance with JIS K6300-1: 2001) mooney viscosity (unvulcanized rubber viscosity) was measured. A smaller value of the Mooney viscosity indicates better processability. In Table 1, the processability is represented by a relative value where the Mooney viscosity of comparative example 1-1 to which no additive was added is 100.

[ Table 1]

The details of each component shown in table 1 are as follows.

Rubber: styrene-butadiene copolymer rubber, manufactured by ZEON corporation of Japan, emulsion SBR, trade name "Nipol 1502"

Carbon black: manufactured by Tokai Carbon corporation, trade name "SEAST 3 (HAF)"

Silica: manufactured by Tosoh silicon corporation, trade name "Nipsil AQ"

Silane coupling agent: bis (triethoxysilylpropyl) tetrasulfide, product name "Si 69" from Evonik "

Stearic acid: "Lunac S70-V" trade name, manufactured by Kao corporation "

Anti-aging agents: n- (1, 3-dimethylbutyl) -N' phenyl-1, 4-phenylenediamine, manufactured by Tokyo chemical industries, Ltd

Oil: sunten 410 manufactured by JAPAN SUN OIL corporation

Additive for rubber 1: c16 internal epoxide Glycerol Ring-opened product produced in production example (I)

Additive 2 for rubber: c18 internal epoxide Glycerol Ring-opened product produced in production example (II)

Dimethyl stearyl amine: product name "FARMIN DM 8098" manufactured by Kao corporation "

Glycerin fatty acid ester 1: molecular distillation monoglyceride, product of Kao corporation, trade name "excel V95"

Glycerin fatty acid ester 2: monoglyceride-containing composition obtained in production example C

Alkyl alkanolamides: kao corporation, trade name "Aminon C-01", coconut oil fatty acid monoethanolamide

Zinc oxide: fuji film and Wako pure chemical industries, Ltd

Sulfur: fuji film and Wako pure chemical industries, Ltd

Vulcanization accelerator 1: fuji film and N-cyclohexyl-2-benzothiazolesulfenamide available from Wako pure chemical industries, Ltd

Vulcanization accelerator 2: fuji film and 1, 3-diphenylguanidine, manufactured by Wako pure chemical industries, Ltd

[ example 2 and comparative example 2]

< C18 internal olefin (C18 internal olefin) >)

The C18 internal olefin produced in production example a2 was used.

< C18 inner epoxide (C18 inner epoxide) >)

The C18 internal epoxide of manufacturing example B2, manufactured from the above-described C18 internal olefin, was used.

< method for measuring content ratio of structural isomers >

The content ratio of the structural isomers was measured in the same manner as in example 1 using 0.05g of the epoxide diethanolamine ring-opened product or the monoethanolamine ring-opened product produced in example 2 and comparative example 2.

< determination of the melting Point of the reaction product (additive) of an internal epoxide with diethanolamine or monoethanolamine >

The melting point of the additive was measured in the same manner as in example 1.

< production of reaction product of internal epoxide with diethanolamine (additive for rubber 3)

Production example (III)

A reaction product of the internal epoxy compound having 18 carbon atoms (C18 internal epoxy compound) produced in production example B2 and diethanolamine was produced (rubber additive 3).

With stirringInto a flask of a stirrer, 470g (4.47 mol) of C18 internal epoxide (400g, 1.49 mol) obtained in production example B2 and diethanolamine (Fuji film, Wako pure chemical industries, Ltd.) were charged, and the temperature was raised to 160 ℃ to conduct a reaction for 20 hours. Hexane was added to the liquid obtained by the reaction, and after washing with ion-exchanged water, the mixture was concentrated under reduced pressure using an evaporator to obtain 530g of an aminoalcohol (additive 3 for rubber) which is a ring-opened product of internal epoxy diethanol amine. The melting point of the obtained additive 3 for rubber was-4 ℃. In addition, with respect to the obtained rubber additive 3, in the above chemical formula (1), R is¹And R²Each of which contains an alkyl group having 1 to 15 carbon atoms, R¹And R²Has a total of 16 carbon atoms, X is a single bond, A is-N (R)³)(R⁴)，R³Is hydroxyethyl having 2 carbon atoms, R⁴Is a hydroxyethyl group having 2 carbon atoms. Further, from the double bond distribution of the internal olefin used in the raw material, R is estimated¹Has 5 or more carbon atoms and R²The content ratio of the compound having 5 or more carbon atoms in (b) is 45% by mass.

< production of reaction product of internal epoxide with monoethanolamine (additive for rubber 4) >

Production example (IV)

A reaction product of the internal epoxy oxide having 18 carbon atoms (C18 internal epoxy oxide) produced in production example B2 and monoethanolamine (additive 4 for rubber) was produced.

A flask equipped with a stirrer was charged with the C18 epoxide (500g, 1.86 mol) obtained in production example B2 and 341g (5.59 mol) of monoethanolamine (manufactured by Fuji film and Wako pure chemical industries, Ltd.), and the temperature was raised to 140 ℃ to carry out a reaction for 8 hours. Hexane was added to the liquid obtained by the reaction, and after washing with ion-exchanged water, the mixture was concentrated under reduced pressure using an evaporator to obtain 600g of aminoalcohol (additive 4 for rubber) as an internal monoethanol amine ring-opened product. The melting point of the obtained additive 4 for rubber was 15 ℃. In the above chemical formula (1), R is the additive 4 for rubber obtained¹And R²Each of which contains an alkyl group having 1 to 15 carbon atoms, R¹And R²Total number of carbon atoms ofIs 16, X is a single bond, A is-N (R)³)(R⁴)，R³Is a hydrogen atom, R⁴Is a hydroxyethyl group having 2 carbon atoms. Further, from the double bond distribution of the internal olefin used in the raw material, R is estimated¹Has 5 or more carbon atoms and R²The content ratio of the compound having 5 or more carbon atoms in (b) is 45% by mass.

< preparation and evaluation of rubber composition >

According to the compounding recipe shown in table 2, the rubber compositions were prepared by kneading in the order of the first kneading step and the second kneading step in the same manner as in example 1. The mooney viscosity (unvulcanized rubber viscosity) of the obtained rubber composition was measured in the same manner as in example 1. In Table 2, the processability is represented by a relative value where the Mooney viscosity of comparative example 2-1 to which no additive was added is defined as 100.

[ Table 2]

The ingredients shown in table 2 are the same as in table 1. The rubber additives 3 and 4 are as follows.

Additive for rubber 3: c18 internal epoxide diethanolamine Ring-opened product produced in production example (III)

Additive for rubber 4: c18 internal epoxide monoethanolamine Ring-opened product produced in production example (IV)