WO2021161838A1 - Diarylamine compound, surface-treated filler, and polymer composition - Google Patents

Abstract

Provided is a diarylamine compound represented by general formula (1) below.　(A1)m – A2 – (A3 – A4)n (In general formula (1): A1 is a group that is capable of bonding with a hydroxyl group; A2 is an optionally substituted C1–30 organic group having a valence of (m+n); A3 is a chemical single bond or a divalent group containing a group selected from ether groups, keto groups, ester groups, and amide groups; A4 is a monovalent group derived from a specific diarylamine compound; m is an integer from 1 to 5; and n is an integer from 1 to 5.)

Description

Diarylamine compounds, surface treatment fillers, and polymer compositions

INDUSTRIAL APPLICABILITY The present invention provides a novel diarylamine-based compound capable of providing a surface-treating filler exhibiting an excellent anti-aging effect on a polymer material, a surface-treating filler obtained by using such a diarylamine-based compound, and a surface-treating filler. The present invention relates to a polymer composition containing such a surface treatment filler.

With the development of petrochemistry, polymers composed of organic compounds have contributed to the development of humankind in various forms such as plastics, rubbers, fibers, and films. Since these are used in various environments depending on the application, improvements have been made so that they can be used for a long period of time by imparting durability under the assumed environment. For example, products have been developed that impart ultraviolet resistance to plastics used outdoors and cold resistance to rubber that functions even in extremely cold regions.

On the other hand, internal combustion engines such as engines, whose usage has increased with the development of industry, require lubricating oil and generate a large amount of heat. Resistance is required. In particular, polymers around automobile engines are required to have characteristics such that they can maintain flexibility for a long time even when exposed to oil or high temperature, and do not cause defects such as cracks. Various oil-resistant and heat-resistant rubbers have been developed to meet these demands. Among them, acrylic rubber is a polymer that has rubber elasticity and is excellent in oil resistance, heat resistance, and flexibility, and seals around automobile engines. , Gaskets, packings, hoses, etc. are widely used, and the cross-linked structure, anti-aging agent, and compounding agent are devised according to the required characteristics to further enhance oil resistance and heat resistance.

For example, Patent Document 1 discloses an antiaging agent that improves heat resistance. However, such an anti-aging agent alone cannot suppress the reduction in molecular weight of the polymer due to heat and the unintended cross-linking reaction, and therefore, it is insufficient to meet the heat resistance requirement in a higher temperature region such as 190 ° C. or higher. ..

Japanese Patent No. 5682575

The present invention has been made in view of the above circumstances, and is obtained by using a novel diarylamine-based compound, such a diarylamine-based compound, which can provide a surface-treating filler showing an excellent anti-aging effect on a polymer material. It is an object of the present invention to provide a surface treatment filler to be used, and a polymer composition containing such a surface treatment filler.

As a result of studies to achieve the above object, the present inventor has found that the above object can be achieved by a specific diarylamine compound having a group capable of binding to a hydroxyl group, and completes the present invention. It came to.

　（上記式（２）～（８）中、芳香環を形成する炭素原子と結合する水素原子は、置換基を有していてもよい炭素数１～３０の１価の有機基で置換されていてもよい。） That is, according to the present invention, a diarylamine-based compound represented by the following general formula (1) is provided.
(A ¹ ) _m- A ^2- (A ^3- A ⁴ ) _n (1)
(In the above general formula (1), A ¹ is a group capable of binding to a hydroxyl group, and A ² is a (m + n) -valent organic group having 1 to 30 carbon atoms which may have a substituent. Yes, A ³ is a chemical single bond or a divalent group containing a group selected from an ether group, a keto group, an ester group, and an amide group, and A ⁴ is the following formula (2). It is a monovalent group having a structure excluding one hydrogen atom forming a carbon-hydrogen bond in the compound selected from (8), where m is an integer of 1 to 5 and n is an integer of 1 to 5. Is.)

(In the above formulas (2) to (8), the hydrogen atom bonded to the carbon atom forming the aromatic ring is substituted with a monovalent organic group having 1 to 30 carbon atoms which may have a substituent. May be.)

　（上記式（９）中、「＊」は、Ａ^３で表される基との結合位置を示し、上記式（９）中、芳香環を形成する炭素原子と結合する水素原子は、炭素数１～３０の１価の有機基で置換されていていてもよい。）
　本発明のジアリールアミン系化合物において、Ａ^１が、少なくとも１つのアルコキシ基を有するシリル基であることが好ましい。
　本発明のジアリールアミン系化合物において、Ａ^３が、アミド基であることが好ましい。 In diarylamine compound of the present invention, A ⁴ is preferably a group represented by the following formula (9).

(In the above formula (9), "*" indicates the bonding position to the group represented by A ^3, hydrogen atoms bonded in the formula (9), with the carbon atoms forming the aromatic ring, the number of carbon atoms It may be substituted with 1 to 30 monovalent organic groups.)
In the diarylamine-based compound of the present invention, A ¹ is preferably a silyl group having at least one alkoxy group.
In diarylamine compound of the present invention, A ³ is preferably an amide group.

Further, according to the present invention, there is provided a surface treatment filler obtained by immobilizing the above diarylamine compound on the surface of the filler.
The surface treatment filler of the present invention is preferably obtained by immobilizing a diarylamine compound on the surface of silica.

Further, according to the present invention, there is provided a polymer composition containing a polymer and the above-mentioned surface treatment filler.
In the polymer composition of the present invention, the polymer is preferably rubber.
In the polymer composition of the present invention, the rubber is preferably acrylic rubber.

According to the present invention, a novel diarylamine-based compound capable of providing a surface-treating filler exhibiting an excellent anti-aging effect on a polymer material, a surface-treating filler obtained by using such a diarylamine-based compound, And, a polymer composition containing such a surface treatment filler can be provided.

　（上記式（２）～（８）中、芳香環を形成する炭素原子と結合する水素原子は、置換基を有していてもよい炭素数１～３０の１価の有機基で置換されていていてもよい。） <Diarylamine compound>
The diarylamine compound of the present invention is a compound represented by the following general formula (1). The diarylamine compound of the present invention is immobilized on the surface of the filler, and the compound represented by the following general formula (1) is used as a surface-treated filler immobilized on the surface, whereby excellent aging of the polymer material is achieved. The surface-treating filler obtained by using such a diarylamine-based compound of the present invention, which can exhibit an inhibitory action, is preferably used as an antiaging agent.
(A ¹ ) _m- A ^2- (A ^3- A ⁴ ) _n (1)
(In the above general formula (1), A ¹ is a group capable of binding to a hydroxyl group, and A ² is a (m + n) -valent organic group having 1 to 30 carbon atoms which may have a substituent. Yes, A ³ is a chemical single bond or a divalent group containing a group selected from an ether group, a keto group, an ester group, and an amide group, and A ⁴ is the following formula (2). It is a monovalent group having a structure excluding one hydrogen atom forming a carbon-hydrogen bond in the compound selected from (8), where m is an integer of 1 to 5 and n is an integer of 1 to 5. Is.)

(In the above formulas (2) to (8), the hydrogen atom bonded to the carbon atom forming the aromatic ring is substituted with a monovalent organic group having 1 to 30 carbon atoms which may have a substituent. May be.)

In the above general formula (1), A ¹ is a group capable of binding to a hydroxyl group, and is not particularly limited as long as it is a group capable of reacting with a hydroxyl group to form a chemical bond. Examples thereof include an isocyanato group, an isothiocyanate group, an epoxy group and a carboxyl group. A ¹ contributes to the immobilization of the diarylamine compound of the present invention on the filler surface by reacting with the hydroxyl group contained in the filler. Among these, the A ^1, an alkoxysilyl group, i.e., preferably a silyl group having at least one alkoxy group, more preferably an alkoxysilyl group represented by the following general formula (10).
-Si (R ¹ ) _x (OR ² ) _3-x (10)
In the above general formula (10), R ¹ is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and further preferably 2 carbon atoms. Alkyl group of. Further, R ² is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and further preferably an alkyl group having 2 carbon atoms. x is an integer of 0 to 2, preferably 0 or 1, and more preferably 0. When R ^1, R ² there are a plurality each of the plurality of R ^1, R ² are may be the same as or may be different.

Examples of the alkoxysilyl group constituting A ¹ include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, an ethyldimethoxysilyl group, a diethylmethoxysilyl group, and a methyl. Examples thereof include a diethoxysilyl group, a dimethylethoxysilyl group, an ethyldiethoxysilyl group and a diethylethoxysilyl group. Among these, a trimethoxysilyl group, a triethoxysilyl group, and a triisopropoxysilyl group are preferable, and a triethoxysilyl group is particularly preferable, from the viewpoint that the filler can be more preferably immobilized on the surface.

A ² is a (m + n) -valent organic group having 1 to 30 carbon atoms which may have a substituent. That is, A ² is an organic group having a valence corresponding to the number of m and n in the above general formula (1). For example, when m = 1 and n = 1, A ² is substituted. It is a divalent organic group having 1 to 30 carbon atoms which may have a group. Examples of the (m + n) -valent organic group having 1 to 30 carbon atoms which may have a substituent include an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent or an aliphatic hydrocarbon group having 1 to 30 carbon atoms. Examples thereof include an aromatic hydrocarbon ring group having 6 to 30 carbon atoms which may have a substituent. When the (m + n) -valent organic group having 1 to 30 carbon atoms has a substituent, the position of the substituent can be any position. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy group having 1 to 10 carbon atoms such as methoxy group, ethoxy group and isopropoxy group; nitro group; cyano group; methyl group and ethyl group. An alkyl group having 1 to 10 carbon atoms such as a t-butyl group; and the like can be mentioned.

Specific examples of the aliphatic hydrocarbon group constituting A ² include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a butylene group, a pentamethylene group, a hexamethylene group, an octamethylene group and a decamethylene group. Examples thereof include an alkylene group having 1 to 20 carbon atoms. Specific examples of the aromatic hydrocarbon ring group constituting A ² include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group and 1,5-naphthylene. Examples include a group, a 2,6-naphthylene group, a 4,4'-biphenylene group and the like. Among these, an alkylene group having 1 to 20 carbon atoms is preferable, and an alkylene group having 2 to 5 carbon atoms is more preferable.

In the general formula (1), A ³ is a chemical single bond, or an ether group, a keto group, an ester group, and a divalent group containing a group selected from an amide group. Specific examples of A ³ include chemical single bonds, -O-, -C (= O)-, -C (= O) -O-, -OC (= O)-, and -NR ^{3-. C (= O) -, -} C (= O) -NR 3 -, - O-C (= O) -O -, - NR 3 -C (= O) -O -, - O-C (= O ^{) -NR 3 -, - NR 3} -C (= O) -NR 4 - , and the like. In addition, R ³ and R ⁴ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ^{Among these, an amide group is preferable, -NR 3} -C (= O)-is more preferable, and -NH-C (= O)-is particularly preferable, from the viewpoint of being able to further enhance the anti-aging effect.

In the above general formula (1), m is an integer of 1 to 5, preferably 1 or 2, and more preferably 1. Further, n is an integer of 1 to 5, preferably 1 or 2, and more preferably 1.

　上記式（２）～（８）中、芳香環を形成する炭素原子と結合する水素原子は、置換基を有していてもよい炭素数１～３０の１価の有機基で置換されていてもよい。
　なお、上記において、「＊」は、上記一般式（１）中において、Ａ^３と結合する炭素原子位置を示している。すなわち、上記式（２）～（８）で表される化合物は、「＊」が付された炭素原子位置において、水素原子を１つ除いた構造を有する１価の置換基となり、「＊」が付された炭素原子位置（「＊」が複数付されている化合物については、「＊」が付されている複数の炭素原子位置のうち、いずれか一つの炭素原子位置）において、Ａ^３と化学結合を形成し得る。 In the general formula (1), A ⁴ is carbon in the compound is selected from the following formulas (2) to (8) - a monovalent radical having one except the structure of the hydrogen atoms to form hydrogen bonds be.

In the above formulas (2) to (8), the hydrogen atom bonded to the carbon atom forming the aromatic ring is substituted with a monovalent organic group having 1 to 30 carbon atoms which may have a substituent. May be good.
In the above, "*" in the above general formula (1), shows a carbon atom position which binds to A ^3. That is, the compounds represented by the above formulas (2) to (8) are monovalent substituents having a structure excluding one hydrogen atom at the carbon atom positions marked with "*", and are "*". (for "*" are assigned multiple compounds, "*" is out of the plurality of carbon atoms positions are assigned to any one of the carbon atoms located) carbon atom positions accompanied by a suffix in a a ³ Can form chemical bonds.

In the above formulas (2) to (8), the hydrogen atom bonded to the carbon atom forming the aromatic ring may be substituted with a monovalent organic group having 1 to 30 carbon atoms, and such a 1-valent carbon atom may be substituted. Examples of the organic groups of to 30 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group and n-hexyl group. Alkyl group having 1 to 30 carbon atoms such as n-heptyl group, n-octyl group, n-nonyl group and n-decyl group; carbon such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Cycloalkyl group number 3 to 30; aryl group having 6 to 30 carbon atoms such as phenyl group, biphenyl group, naphthyl group, anthranyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group , Isobutoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group and other alkoxy groups having 1 to 30 carbon atoms; and the like.

Further, the organic group having 1 to 30 carbon atoms may have a substituent, and the position of the substituent can be any position. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy group having 1 to 10 carbon atoms such as methoxy group, ethoxy group and isopropoxy group; nitro group; cyano group; methyl group and ethyl group. An alkyl group having 1 to 10 carbon atoms such as a t-butyl group; and the like can be mentioned.

　上記式（９）中、「＊」は、Ａ^３で表される基との結合位置を示し、上記式（９）中、芳香環を形成する炭素原子と結合する水素原子は、炭素数１～３０の１価の有機基で置換されていていてもよく、炭素数１～３０の１価の有機基としては、上述したものが挙げられる。 Among the compounds represented by the above formulas (2) to (8), the compound represented by the above formula (2) is represented by the above formula (3) from the viewpoint of being able to further enhance the anti-aging effect. The compound, the compound represented by the above formula (5) and the above formula (6) is preferable, and the compound represented by the above formula (2) is particularly preferable. That position, as the A ^4, among the compounds represented by groups represented by the following formula (9) (the formula (2), the carbon atom position which binds to A ³ are, represented by the following formula (9) Is a compound).

In the above formula (9), "*" indicates the bonding position to the group represented by A ^3, hydrogen atoms bonded in the formula (9), with the carbon atoms forming the aromatic ring, 1 to 4 carbon atoms It may be substituted with a monovalent organic group of about 30 to 30, and examples of the monovalent organic group having 1 to 30 carbon atoms include those described above.

　上記一般式（１１）中、Ｒ^５は、炭素数１～５のアルキル基、好ましくは炭素数１～３のアルキル基、より好ましくは炭素数１～２のアルキル基、さらに好ましくは炭素数２のアルキル基であり、Ｒ^６は、炭素数１～５のアルキル基、好ましくは炭素数１～３のアルキル基、より好ましくは炭素数１～２のアルキル基、さらに好ましくは炭素数２のアルキル基であり、ｐは１～３０の整数、好ましくは１～２０の整数、より好ましくは２～５の整数、さらに好ましくは３であり、ｑは、０～２の整数、好ましくは０または１、より好ましくは０である。 Specific examples of the diarylamine-based compound represented by the general formula (1) are not particularly limited, but the compound represented by the following general formula (11) is particularly preferable.

In the general formula (11), R ⁵ represents an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, more preferably 2 carbon atoms R ⁶ is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and further preferably an alkyl group having 2 carbon atoms. It is a group, p is an integer of 1 to 30, preferably an integer of 1 to 20, more preferably an integer of 2 to 5, still more preferably 3, and q is an integer of 0 to 2, preferably 0 or 1. , More preferably 0.

The method for producing the diarylamine compound represented by the general formula (1) is not particularly limited, but for example, the diarylamine compound represented by the general formula (1) is represented by the general formula (11). Examples of the represented compound include the following methods.

That is, first, as shown in the following reaction formula, trimellitic anhydride and 4-aminodiphenylamine are reacted in a solvent, and the compound represented by the following formula (12) and / or the following formula (13) is used. A reaction solution containing the represented compound is obtained.

Then, by heating the reaction solution containing the compound represented by the above formula (12) and / or the compound represented by the above formula (13) obtained by the above reaction, as shown in the following reaction formula, The imidization reaction is allowed to proceed to obtain a compound represented by the following formula (14).

The imidization reaction is usually carried out in the presence of an acid catalyst or a base catalyst. Examples of the acid used as the acid catalyst include, but are not limited to, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; and organic acids such as p-toluene sulfonic acid, 10-campar sulfonic acid and acetic acid. Bases used as base catalysts include tertiary amines such as triethylamine, diisopropylethylamine, N-methylmorpholine; pyridines such as pyridine, picoline, lutidine, 4- (dimethylamino) pyridine; sodium hydroxide, potassium hydroxide, carbonic acid. Examples include, but are not limited to, inorganic bases such as potassium. The reaction of trimellitic anhydride, 4-aminodiphenylamine, and the imidization reaction may proceed at the same time.

Then, as shown in the following reaction scheme, a compound shown by the above reaction by obtained above formula (14), in the amino group-containing silane compound represented by the following general formula (15) (the following general formula (15), R ⁵ , R ⁶ , p, q are the same as those in the general formula (11)), so that the compound represented by the general formula (11) can be obtained.

　上記一般式（１６）中、Ｒ^５、Ｒ^６、ｐ、ｑは、上記一般式（１１）と同様である。 Further, for example, when the diarylamine compound represented by the general formula (1) is a compound represented by the following general formula (16), the following method can be mentioned.

In the general formula (16), R ⁵ , R ⁶ , p, and q are the same as those in the general formula (11).

That is, as shown in the following reaction formula, the compound represented by the following formula (17) is formed by reacting trimellitic anhydride and 4,4'-diaminodiphenylamine in a solvent and advancing imidization by heating. To get. The reaction and imidization of trimellitic anhydride with 4,4'-diaminodiphenylamine in the following reaction formula can be the same as in the case of the compound represented by the above general formula (11).

Then, as shown in the following reaction formula, the compound represented by the above formula (17) obtained by the above reaction is reacted with phthalic anhydride in a solvent, and imidization is promoted by heating to carry out the following formula ( The compound shown in 18) is obtained. The reaction and imidization of phthalic anhydride with the compound represented by the above formula (17) in the following reaction formula can be the same as that of the compound represented by the above general formula (11).

Next, in addition to the compound represented by the above formula (18) obtained by the above reaction, the amino group-containing silane compound represented by the following general formula (15) (in the following general formula (15), R ⁵ , R ⁶ , p and q are added. , The same as the above general formula (16)), the compound represented by the above general formula (16) can be obtained.

In the above, the diarylamine compound represented by the general formula (1) is a compound represented by the general formula (11) and a compound represented by the general formula (16) (that is,). , a ⁴ is is a group derived from a compound represented by the formula (2), and the formula in case of a group derived from the compound represented by (3)), it is exemplified a method for manufacturing , ^{a 4} is, in the above formulas (4) - is a group derived from a compound represented by (8) or the like, for example, the method described in WO 2018/159459, WO 2011/058918 It can be produced by combining the method described in No. 1 and the method described in International Publication No. 2011/093443 with the above method and a known synthetic method.

<Surface treatment filler>
The surface treatment filler of the present invention is a diarylamine compound represented by the general formula (1) obtained by immobilizing the diarylamine compound represented by the general formula (1) on the surface of the filler. It is a surface-treated filler. The surface-treating filler of the present invention can be blended with a polymer material to exhibit an excellent anti-aging effect on the polymer material, and is suitable as an anti-aging agent.

The filler used in the present invention is not particularly limited, but silica is preferable from the viewpoint that the diarylamine compound represented by the above general formula (1) can be suitably fixed on the surface thereof.

Examples of silica include dry white carbon, wet white carbon, colloidal silica, and precipitated silica. Among these, wet white carbon containing hydrous silicic acid as a main component is preferable. Further, a carbon-silica dual phase filler in which silica is supported on the surface of carbon black may be used. These silicas can be used alone or in combination of two or more. The nitrogen adsorption specific surface area of silica (measured by the BET method according to ASTM D3037-81) is preferably 50 to 300 m ² / g, more preferably 80 to 220 m ² / g, and particularly preferably 100 to 170 m ² / g. Is. The pH of silica is preferably pH 5-10.

The diarylamine compound represented by the general formula (1), as a method for immobilizing on the filler surface is not particularly limited, the A ¹ diaryl amine compound represented by the general formula (1) A method capable of reacting the constituent groups capable of bonding with the hydroxyl group with the hydroxyl groups present on the surface of the filler may be adopted. For example, constituting A ¹ diaryl amine compound represented by the general formula (1), capable of binding groups and hydroxyl groups, in the case of alkoxysilyl group, in the presence of an acid catalyst, the Examples thereof include a method of mixing the diarylamine compound represented by the general formula (1) with the filler.

In the surface treatment filler of the present invention, the amount of the diarylamine compound represented by the above general formula (1) fixed to the filler is not particularly limited, but is preferably 0.1 to 10% by weight with respect to 100 parts by weight of the filler. Parts, more preferably 0.5 to 7 parts by weight, still more preferably 1 to 5 parts by weight, and particularly preferably 1.2 to 3 parts by weight. By setting the fixed amount of the diarylamine compound represented by the general formula (1) in the above range, the antiaging effect on the polymer material can be further enhanced. In the present invention, the above general state of being fixed to the filler with respect to 100 parts by weight of the filler (when the molecule is eliminated due to the immobilization reaction, the state after the molecule is eliminated). The amount of the diarylamine compound represented by the formula (1) is preferably in the above range.

<Polymer composition>
The polymer composition of the present invention is obtained by blending the above-mentioned surface treatment filler with the polymer. The surface treatment filler usually acts as an anti-aging agent for the polymer in the polymer composition of the present invention.

Examples of the polymer used in the present invention include synthetic resin and rubber. The synthetic resin can be used without particular limitation as long as it is a synthetic resin used for applications requiring heat resistance, and examples thereof include polyolefins, polystyrene-based resins, polyesters, polycarbonates, and polyamides. These synthetic resins may be used alone or in combination of two or more.

The rubber can be used without particular limitation as long as it is used for applications requiring heat resistance. For example, natural rubber, isoprene rubber, butadiene rubber, butyl rubber, chloroprene rubber, and styrene-butadiene copolymer are used. Rubber containing conjugated diene units such as rubber, acrylonitrile-butadiene copolymer rubber (nitrile rubber), styrene-butadiene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber; acrylic rubber; Hydrin rubber; ethylene propylene rubber; and the like can be mentioned. These rubbers may have a hydroxyl group, a carboxyl group, an alkoxysilyl group, an amino group, an epoxy group and the like. Further, these rubbers may be hydrogenated, and examples thereof include an acrylonitrile-butadiene copolymer rubber hydrogenated additive (hydrogenated nitrile rubber). These rubbers may be used alone, in combination of two or more, or in combination of the synthetic resins described above. Among these, acrylic rubber is particularly preferable because it has a high effect of improving the heat resistance when applied to acrylic rubber or hydrogenated nitrile rubber, which is required to have high heat resistance.

The method of blending the surface treatment filler into the polymer is not particularly limited, and in addition to the method of blending in the polymer latex or the polymer solution, any method after the polymer is precipitated by coagulating the polymer latex or the polymer solution. Examples thereof include a method of blending in the process of. For example, it may be blended at the stage of producing polymer pellets, at the stage of blending and kneading various compounding agents, or at the stage of molding using a molding machine. The compounding time that can be sufficiently uniformly dispersed in the polymer may be appropriately selected.

The blending amount of the surface treatment filler is preferably 20 to 90 parts by weight, more preferably 30 to 80 parts by weight, and further preferably 40 to 70 parts by weight with respect to 100 parts by weight of the polymer. By setting the blending amount within the above range, a sufficient anti-aging effect can be obtained while ensuring the reinforcing effect as a filler.

<Acrylic rubber>
Acrylic rubber as an example of the polymer constituting the polymer composition of the present invention comprises 50 to 100% by weight of a (meth) acrylic acid ester monomer unit, 10 to 0% by weight of a crosslinkable monomer unit, and if necessary. It is a rubber having a unit of 50 to 0% by weight of other monomers copolymerizable with the monomer forming these monomer units, and the ratio of each monomer unit constituting the acrylic rubber is adjusted. Thereby, the physical properties of the rubber can be adjusted. In the present invention, "(meth) acrylic" refers to acrylic and / or methacrylic.

Acrylic rubber is known as rubber that has excellent oil resistance, especially oil resistance at high temperatures, and also has good heat resistance, and is in demand as hoses for automobiles, oil seals, O-rings, conveyor belts built into devices and machines, etc. It is increasing.

The (meth) acrylic acid ester monomer forming the (meth) acrylic acid ester monomer unit which is the main component of the acrylic rubber is not particularly limited, but for example, a (meth) acrylic acid alkyl ester is preferable. Monomers, (meth) acrylic acid alkoxyalkyl ester monomers and the like can be mentioned.

The (meth) acrylic acid alkyl ester monomer is not particularly limited, but an ester of alkanol having 1 to 8 carbon atoms and (meth) acrylic acid is preferable, and specifically, methyl (meth) acrylic acid, ( Ethyl acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) Examples thereof include 2-ethylhexyl acrylate and cyclohexyl (meth) acrylate. Among these, ethyl (meth) acrylate and n-butyl (meth) acrylate are preferable, and ethyl acrylate and n-butyl acrylate are more preferable. These can be used alone or in combination of two or more.

The (meth) acrylic acid alkoxyalkyl ester monomer is not particularly limited, but an ester of an alkoxyalkyl alcohol having 2 to 8 carbon atoms and (meth) acrylic acid is preferable, and specifically, (meth) acrylic acid. Methoxymethyl, ethoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate , (Meta) acrylate 3-methoxypropyl, (meth) acrylate 4-methoxybutyl and the like. Among these, 2-ethoxyethyl (meth) acrylate and 2-methoxyethyl (meth) acrylate are preferable, and 2-ethoxyethyl acrylate and 2-methoxyethyl acrylate are particularly preferable. These can be used alone or in combination of two or more.

The content of the (meth) acrylic acid ester monomer unit in the acrylic rubber is 50 to 100% by weight, preferably 60 to 99.5% by weight, and more preferably 70 to 99.5% by weight. If the content of the (meth) acrylic acid ester monomer unit is too small, the weather resistance, heat resistance and oil resistance of the obtained rubber crosslinked product may decrease.

The breakdown of the (meth) acrylic acid ester monomer unit is 30 to 100% by weight of the (meth) acrylic acid alkyl ester monomer unit and 70 to 0% by weight of the (meth) acrylic acid alkoxyalkyl ester monomer unit. Is preferable.

The crosslinkable monomer forming the crosslinkable monomer unit is not particularly limited, but is an α, β-ethylene unsaturated carboxylic acid monomer; a monomer having a halogen atom or an epoxy group; a diene unit amount. Body; etc.

The α, β-ethylenic unsaturated carboxylic acid monomer is not particularly limited, and for example, α, β-ethylene unsaturated monocarboxylic acid having 3 to 12 carbon atoms and α, β- having 4 to 12 carbon atoms are used. Examples thereof include an ethylenically unsaturated dicarboxylic acid and a monoester of α, β-ethylene unsaturated dicarboxylic acid having 4 to 12 carbon atoms and an alkanol having 1 to 8 carbon atoms. Examples of the α, β-ethylenically unsaturated monocarboxylic acid having 3 to 12 carbon atoms include acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, and cinnamic acid. Examples of the α, β-ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms include butenedioic acid such as fumaric acid or maleic acid, itaconic acid, citraconic acid, and chloromaleic acid. Monoesters of α, β-ethylenic unsaturated dicarboxylic acid having 4 to 12 carbon atoms and alkanol having 1 to 8 carbon atoms include monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monomethyl maleate, and monoethyl maleate. , Itaconic acid monochain alkyl ester such as monobutyl maleate; monocyclopentyl fumarate, monocyclohexyl fumarate, monocyclohexenyl fumarate, monocyclopentyl maleate, monocyclohexyl maleate, monocyclohexenyl maleate and other alicyclic structures Butendionic acid monoesters; monomethyl itaconic acid, monoethyl itaconic acid, monobutyl itaconic acid, monocyclohexyl itaconic acid and the like; and the like. Among these, a monochain alkyl ester of butenioic acid or a monoester of butendioate having an alicyclic structure is preferable, and monobutyl fumarate, monobutyl maleate, monocyclohexyl fumarate and monocyclohexyl maleate are more preferable. These α, β-ethylenically unsaturated carboxylic acid monomers can be used alone or in combination of two or more. Of the above-mentioned monomers, the dicarboxylic acid may be copolymerized as an anhydride, and may be hydrolyzed to generate a carboxyl group at the time of crosslinking.

The monomer having a halogen atom is not particularly limited, and for example, an unsaturated alcohol ester of a halogen-containing saturated carboxylic acid, a (meth) acrylic acid haloalkyl ester, a (meth) acrylic acid haloacyloxyalkyl ester, or (meth) acrylic. Examples thereof include acid (haloacetylcarbamoyloxy) alkyl esters, halogen-containing unsaturated ethers, halogen-containing unsaturated ketones, halomethyl group-containing aromatic vinyl compounds, halogen-containing unsaturated amides, and haloacetyl group-containing unsaturated monomers. Examples of the unsaturated alcohol ester of the halogen-containing saturated carboxylic acid include vinyl chloroacetate, vinyl 2-chloropropionate, and allyl chloroacetate. Examples of the (meth) acrylic acid haloalkyl ester include (meth) acrylic acid chloromethyl, (meth) acrylic acid 1-chloroethyl, (meth) acrylic acid 2-chloroethyl, (meth) acrylic acid 1,2-dichloroethyl, and (meth) acrylic acid. ) 2-Chloropropyl acrylate, 3-chloropropyl (meth) acrylate, 2,3-dichloropropyl (meth) acrylate and the like. Examples of the (meth) acrylic acid haloacyloxyalkyl ester include (meth) acrylic acid 2- (chloroacetoxy) ethyl, (meth) acrylic acid 2- (chloroacetoxy) propyl, and (meth) acrylic acid 3- (chloroacetoxy) propyl. , (Meta) acrylate 3- (hydroxychloroacetoxy) propyl and the like. Examples of the (meth) acrylic acid (haloacetylcarbamoyloxy) alkyl ester include 2- (chloroacetylcarbamoyloxy) ethyl (meth) acrylic acid and 3- (chloroacetylcarbamoyloxy) propyl (meth) acrylic acid. Examples of the halogen-containing unsaturated ether include chloromethyl vinyl ether, 2-chloroethyl vinyl ether, 3-chloropropyl vinyl ether, 2-chloroethyl allyl ether, 3-chloropropyl allyl ether and the like. Examples of the halogen-containing unsaturated ketone include 2-chloroethyl vinyl ketone, 3-chloropropyl vinyl ketone, and 2-chloroethyl allyl ketone. Examples of the halomethyl group-containing aromatic vinyl compound include p-chloromethylstyrene and p-chloromethyl-α-methylstyrene. Examples of the halogen-containing unsaturated amide include N-chloromethyl (meth) acrylamide. Examples of the haloacetyl group-containing unsaturated monomer include 3- (hydroxychloroacetoxy) propyl allyl ether and p-vinylbenzyl chloroacetic acid ester.

The monomer having an epoxy group is not particularly limited, and examples thereof include an epoxy group-containing (meth) acrylic acid ester and an epoxy group-containing ether. Examples of the epoxy group-containing (meth) acrylic acid ester include glycidyl (meth) acrylate, and examples of the epoxy group-containing ether include allyl glycidyl ether.

Examples of the diene monomer include a conjugated diene monomer and a non-conjugated diene monomer. Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, and piperylene. Examples of the non-conjugated diene monomer include ethylidene norbornene, dicyclopentadiene, dicyclopentadienyl (meth) acrylate, and 2-dicyclopentadienyl ethyl (meth) acrylate.

These crosslinkable monomers can be used alone or in combination of two or more. The content of the crosslinkable monomer unit in the acrylic rubber is 0 to 10% by weight, preferably 0.5 to 7% by weight, and more preferably 0.5 to 5% by weight. If the content of the crosslinkable monomer unit is too large, the elongation of the obtained rubber crosslinked product may decrease or the compression set may increase.

The other monomer copolymerizable with each of the above-mentioned monomers is not particularly limited, and for example, an aromatic vinyl monomer, an α, β-ethylenically unsaturated nitrile monomer, and an acryloyloxy group are used. Examples thereof include monomers having more than one, olefin-based monomers, and vinyl ether compounds.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, and divinylbenzene. Examples of the α, β-ethylenically unsaturated nitrile monomer include acrylonitrile and methacrylonitrile. Examples of the polyfunctional (meth) acrylic monomer include ethylene glycol (meth) acrylic acid diester and propylene glycol (meth) acrylic acid diester. Examples of the olefin-based monomer include ethylene, propylene, 1-butene, 1-octene and the like. Examples of the vinyl ether compound include vinyl acetate, ethyl vinyl ether, butyl vinyl ether and the like. Among these, styrene, acrylonitrile and methacrylonitrile are preferable, and acrylonitrile and metaacrylonitrile are more preferable.

These other copolymerizable monomers can be used alone or in combination of two or more. The content of other monomer units in the acrylic rubber is 0 to 50% by weight, preferably 0 to 39.5% by weight, and more preferably 0 to 29.5% by weight.

The acrylic rubber used in the present invention can be obtained by polymerizing the above-mentioned monomer. As the form of the polymerization reaction, any of an emulsion polymerization method, a suspension polymerization method, a massive polymerization method and a solution polymerization method can be used, but a conventionally known method for producing acrylic rubber is considered from the viewpoint of ease of control of the polymerization reaction and the like. It is preferable to use the emulsification polymerization method under normal pressure, which is generally used as the above.

The emulsion polymerization may be a batch type, a semi-batch type, or a continuous type. The polymerization is usually carried out in a temperature range of 0 to 70 ° C, preferably 5 to 50 ° C.

The Mooney viscosity [ML1 + 4, 100 ° C.] (polymer Mooney) of the acrylic rubber produced in this manner used in the present invention is preferably 10 to 80, more preferably 20 to 70, and particularly preferably 25 to 60. ..

<Other anti-aging agents>
Further, the polymer composition of the present invention may contain other antioxidants other than the surface treatment filler in addition to the polymer and the surface treatment filler as an antioxidant.

　上記一般式（１９）中、Ｒ^ａおよびＲ^ｂはそれぞれ独立して、置換基を有していてもよい炭素数１～３０の有機基を表す。Ｚ^ａおよびＺ^ｂはそれぞれ独立して、化学的な単結合または－ＳＯ_２－を表す。ｒおよびｓはそれぞれ独立して、０または１であり、ｒおよびｓの少なくとも一方は１である。 The other anti-aging agent is not particularly limited, but a compound represented by the following general formula (19) is preferably used.

In the above general formula (19), ^Ra and R ^b each independently represent an organic group having 1 to 30 carbon atoms which may have a substituent. Z ^a and Z ^b independently represent a chemical single bond or -SO _2-. r and s are independently 0 or 1, and at least one of r and s is 1.

In the above general formula (19), ^Ra and R ^b each independently represent an organic group having 1 to 30 carbon atoms which may have a substituent.
^{The organic group having 1 to 30 carbon atoms constituting Ra} and R ^b is not particularly limited, but for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec- Alkyl group having 1 to 30 carbon atoms such as butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group; cyclopropyl Cycloalkyl group having 3 to 30 carbon atoms such as group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; aryl group having 6 to 30 carbon atoms such as phenyl group, biphenyl group, naphthyl group and anthranyl group; methoxy 1 to 30 carbon atoms such as group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group An alkoxy group; and the like.

Further, ^{the organic groups constituting Ra} and R ^b described above may have a substituent, and the position of the substituent may be any position.
As such a substituent, when the organic group is an alkyl group, a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; an alkoxy having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group or an isopropoxy group. Groups; nitro groups; cyano groups; phenyl groups that may have substituents such as phenyl groups, 4-methylphenyl groups, 2-chlorophenyl groups; and the like.
When the organic group is a cycloalkyl group or an aryl group, the substituents include halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom; and 1 to 1 to carbon atoms such as a methoxy group, an ethoxy group and an isopropoxy group. Examples thereof include 10 alkoxy groups; nitro groups; cyano groups; alkyl groups having 1 to 10 carbon atoms such as methyl groups, ethyl groups, and t-butyl groups; and the like.
Further, when the organic group is an alkoxy group, examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; nitro group; cyano group; and the like.
Further, in the above general formula (19), when ^{the organic groups constituting Ra} and R ^b have a substituent, the carbon number of the organic group does not include the carbon number of the substituent.

R ^a and R ^b are each independently an alkyl group having 2 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent. It preferably has a linear or branched alkyl group having 2 to 20 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, or a substituent. It is more preferably a naphthyl group which may have a substituent, and may be a linear or branched alkyl group having 2 to 8 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. More preferably, a linear or branched alkyl group having 2 to 8 carbon atoms, which may have a substituent, is particularly preferable. Examples of these substituents include an alkyl group having 1 to 30 carbon atoms in which the organic group may have a substituent and an aryl group having 6 to 30 carbon atoms which may have a substituent. The same ones as illustrated can be mentioned.

Preferred specific examples of the organic groups constituting R ^a and R ^b include α-methylbenzyl group, α, α-dimethylbenzyl group, t-butyl group, phenyl group, 4-methylphenyl group and the like. Among these, α, α-dimethylbenzyl group or 4-methylphenyl group is more preferable, and α, α-dimethylbenzyl group is further preferable. It should be noted that these can be independent of each other.

Further, in the above general formula (19), Z ^a and Z ^b are each independently a chemical single bond or −SO _2- , and it is preferable that they are chemically single bonds.

Further, in the above general formula (19), r and s are independently 0 or 1, and at least one of r and s is 1. It is preferable that r and s are both 1.

　上記一般式（２０）～（２２）中、Ｒ^ａ、Ｒ^ｂ、Ｚ^ａおよびＺ^ｂは、上記一般式（１９）と同様である。 In the present invention, the compound represented by the general formula (19) is preferably any of the compounds represented by the following general formulas (20) to (22).

In the general formula ^{(20) ~ (22),} R a, R b, Z a and ^{Z b} is as defined in the above general formula (19).

Among the compounds represented by the general formulas (20) to (22), the compounds represented by the general formulas (20) and (22) are preferable, and the compounds represented by the general formula (22) are more preferable.

Further, in the above general formulas (20) to (22), -Z ^a- R ^a and -Z ^b- R ^b are independent of each other, and are α-methylbenzyl group, α, α-dimethylbenzyl group, and t-butyl. It is preferably a group, a phenylsulfonyl group, or a 4-methylphenylsulfonyl group, more preferably an α, α-dimethylbenzyl group, or a 4-methylphenylsulfonyl group, and is an α, α-dimethylbenzyl group. Is even more preferable.

That is, in the present invention, in the above general formula (19), ^Ra and R ^b are linear or branched alkyls having 2 to 8 carbon atoms which may independently have substituents. The groups, as well as Z ^a and Z ^b, are chemical single bonds, preferably r and s of 1.

The compound represented by the above general formula (19) is obtained by applying a known method for producing a phenothiazine-based compound to obtain a precursor phenothiazine-based compound, and then oxidizing the obtained compound. Can be manufactured.

Specifically, the compound represented by the general formula (19) is prepared by the reaction method described in International Publication No. 2011/093443, using the compound represented by the following general formula (23) (phenothiazine) as a starting material. ^{, Introducing substituents (-Z a-} R ^a , -Z ^b- R ^b ) at the 1, 3, 6, and / or 8-positions of the phenothiazine ring in general formula (23), and phenothiazine. It can be obtained by oxidizing the S of the ring to -SO _2-.

In the above general formula (19), ^Ra and R ^b each independently represent an organic group having 1 to 30 carbon atoms which may have a substituent, and may have a substituent. 1-30 aromatic or cyclic aliphatic groups are preferred.
The aromatic group having 1 to 30 carbon atoms is not particularly limited, and for example, an aromatic hydrocarbon group such as a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, or an anthranyl group, a frill group, a pyrrolyl group, or a thienyl group. , Aromatic heterocyclic groups such as pyridyl group and thiazolyl group.
The cyclic aliphatic group having 1 to 30 carbon atoms is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Among them, as ^Ra and R ^b , a phenyl group and a 4-methylphenyl group are preferable independently of each other.
Further, ^{the organic groups constituting Ra} and R ^b described above may have a substituent, and the position of the substituent may be any position. Examples of such a substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group and an isopropoxy group; a nitro group; a cyano group; a methyl group. An alkyl group having 1 to 10 carbon atoms such as an ethyl group and a t-butyl group; and the like can be mentioned.

The blending amount of the compound represented by the general formula (19) in the polymer composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the polymer. It is 5 parts by weight, more preferably 0.5 to 3 parts by weight. By setting the blending amount within the above range, the anti-aging effect by blending the compound represented by the general formula (19) can be more appropriately enhanced.

Further, an antioxidant other than the compound represented by the above general formula (19) may be blended, and examples of such an antioxidant include 2,6-di-t-butyl-p-cresol, 2. 6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-sec butylphenol, 2- (1-methylcyclohexyl) ) -4,6-Dimethylphenol, 2,6-di-t-butyl-α-dimethylamino-p-cresol, 2,4-bis [(octylthio) methyl] -o-cresol, styrenated phenol, alkylated Monophenolic anti-aging agents such as phenol; 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4' -Methylenebis (2,6-di-t-butylphenol), 2,2'-methylenebis (6-α-methylbenzyl-p-cresol), methylene-crosslinked polyvalent alkylphenol, 4,4'-butylidenebis (6-t) -Butyl-m-cresol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 2,2'-ethylidenebis (4,6-di-t-butylphenol), 1,1-bis -(4-Hydroxyphenyl) cyclohexane, 2,2'-dihydroxy-3,3'-(α-methylcyclohexyl) -5,5'-dimethyldiphenylmethane, alkylated bisphenol, butylation of p-cresol and dicyclopentadiene Reaction products, bis, tris, or polyphenolic anti-aging agents such as 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone; 4,4'-thiobis (6-t-butyl) -M-cresol), 4,4'-thiobis (6-t-butyl-o-cresol), 4,4'-thiobis (3-methyl-6-t-butylphenol), bis (3,5-di- Phenolic anti-aging agents such as t-butyl-4-hydroxybenzyl) sulfide: Phenolic anti-aging agents such as: phenyl-α-naphthylamine, octylated diphenylamine, 4,4'-bis (α, α-) Dimethylbenzyl) diphenylamine, p- (p-toluenesulfonylamide) diphenylamine, p-isopropoxydiphenylamine, bis (phenylisopropyridene) -4,4-diphenylamine, N, N'-diphenylethylenedia Min, N, N'-diphenyl-propylenedidiamine, N, N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N, N'-di-2-naphthyl-p -Phenyldiamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N, N'-bis (1-Methylheptyl) -p-phenylenediamine, N, N-bis (1,4-dimethylpentyl) -p-phenylenediamine, 4- (α-phenylethyl) diphenylamine, 4,4'-bis (α) Aromatic secondary amine compounds such as -phenylethyl) diphenylamine, 4,4'-bis (4-methylphenyl) sulfonyl) diphenylamine; dialkyldithiocarbamic acid such as nickel dimethyldithiocarbamate, nickel diethyldithiocarbamate, nickel dibutyldithiocarbamate Nickel; etc. can be used.

<Other additives, methods for preparing polymer compositions, etc.>
Further, in addition to other antioxidants such as a polymer, a surface treatment filler, and a compound represented by the above general formula (19) used as necessary, the polymer composition of the present invention is further added. The agent may be contained.

Other additives include those commonly used in the field of using synthetic polymeric materials. For example, reinforcing fillers such as carbon black; non-reinforcing fillers such as calcium carbonate and clay; light stabilizers; anti-scorch agents; plasticizers; processing aids; lubricants; adhesives; lubricants; flame retardants; Molds; antistatic agents; colorants; silane coupling agents; cross-linking agents; cross-linking accelerators; cross-linking retarders; etc.
The blending amount of these additives is not particularly limited as long as it does not impair the purpose and effect of the present invention, and an amount suitable for the blending purpose can be appropriately blended.

The polymer composition of the present invention can be prepared, for example, by mixing and kneading each component with a Banbury mixer, a kneader, or the like, and then further kneading with a kneading roll. The blending order of each component is not particularly limited, but after sufficiently mixing the components that are difficult to react or decompose with heat, the cross-linking agent, which is a component that easily reacts or decomposes with heat, is short at a temperature at which reaction or decomposition does not occur. It is preferable to mix in time.

For example, when a rubber such as acrylic rubber is used as the polymer constituting the polymer composition and a cross-linking agent is contained, a rubber cross-linked product can be obtained by cross-linking the rubber. The rubber crosslinked product can be obtained by molding with a molding machine corresponding to a desired shape, for example, an extruder, an injection molding machine, a compressor, a roll, etc., and fixing the shape as a rubber crosslinked product by a cross-linking reaction. Can be done. In that case, cross-linking may be performed after molding in advance, or cross-linking may be performed at the same time as molding. The molding temperature is usually 10 to 200 ° C, preferably 25 to 120 ° C. The cross-linking temperature is usually 130 to 220 ° C., preferably 150 to 190 ° C., and the cross-linking time is usually 2 minutes to 10 hours, preferably 3 minutes to 6 hours. As the heating method, a method used for cross-linking rubber such as press heating, steam heating, oven heating, and hot air heating may be appropriately selected.

Further, depending on the shape and size of the rubber crosslinked product, even if the surface is crosslinked, it may not be sufficiently crosslinked to the inside, so that the secondary crosslinking may be performed by further heating. The secondary cross-linking time varies depending on the heating method, cross-linking temperature, shape, etc., but is preferably 1 to 48 hours. The heating method and heating temperature may be appropriately selected.

The rubber crosslinked product obtained in this way has excellent heat resistance. Therefore, the rubber cross-linked product obtained by using the above rubber composition makes use of its characteristics, O-ring, packing, diaphragm, oil seal, shaft seal, bearing seal, mechanical seal, well head seal, electrical / electronic equipment. Various seals such as seals for pneumatic equipment, cylinder head gaskets attached to the joints between the cylinder block and the cylinder head, rocker cover gaskets attached to the joints between the rocker cover and the cylinder head, oil pans and cylinders. Oil pan gasket installed at the connection with the block or transmission case, fuel cell separator gasket installed between a pair of housings that sandwich a unit cell with a positive electrode, electrolyte plate, and negative electrode, gasket for the top cover of a hard disk drive. Various gaskets such as; various belts; fuel hose, turbo air hose, oil hose, radiator hose, heater hose, water hose, vacuum brake hose, control hose, air conditioner hose, brake hose, power steering hose, air hose, marine hose, etc. Various hoses such as risers and flow lines; various boots such as CVJ boots, propeller shaft boots, constant velocity joint boots, rack and pinion boots; damping materials such as cushioning materials, dynamic dampers, rubber couplings, air springs, and anti-vibration materials. It is preferably used as a rubber component; and is particularly applicable to applications used under harsh high temperatures.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Unless otherwise specified, the "part" in each example is based on weight.
Various physical properties were evaluated according to the following methods.

[Breaking elongation before and after heating]
The rubber compositions obtained in each Example and Comparative Example were molded and crosslinked by a press at 170 ° C. for 20 minutes, and then further heated at 170 ° C. for 4 hours for secondary cross-linking to form a sheet. A rubber crosslinked product in the shape was obtained. Next, a dumbbell-shaped No. 3 test piece was prepared from the obtained crosslinked rubber, and the elongation at break before and after heating was measured for this test piece according to JIS K6251. The heating conditions were 190 ° C. for 1008 hours, and the rate of change in breaking elongation before and after heating was determined according to the following formula. It can be judged that the smaller the value of the rate of change of elongation at break is, the more the deterioration due to heating is suppressed.
Rate of change in elongation at break (%) = [(Elongation at break after heating (%))-(Elongation before heating (%))] / (Elongation at break before heating (%))] × 100

[Synthesis Example 1]
80 g of trimellitic anhydride and 76.7 g of 4-aminodiphenylamine were dissolved in 1 liter of acetic acid in a four-port reactor equipped with a condenser and a thermometer in a nitrogen stream. This solution was reacted in an oil bath under heating under reflux for 10 hours. After completion of the reaction, the reaction solution was poured into 2 liters of water to precipitate a solid. Then, the precipitated solid was suction-filtered. The filtrate was washed with water and methanol in this order and then dried in a vacuum dryer to obtain 138.5 g of an intermediate represented by the following formula (14) in a yield of 92%. The structure of the obtained intermediate _{was identified by 1 1} H-NMR. _{1 1} H-NMR (500 MHz, THF-d8, TMS, δ ppm): 6.97 (t, 1H, J = 7.0 Hz), 7.24-7.28 (m, 4H), 7.33-7. 36 (m, 2H), 7.40-7.42 (m, 2H), 7.68 (s, 1H), 8.11 (d, 1H, J = 8.5Hz), 8.56-8. 58 (m, 2H), 12.20 (bs, 1H).

[Synthesis Example 2]
In a four-mouth reactor equipped with a thermometer, 5.38 g of the intermediate represented by the above formula (14) and 6.64 g of 3-aminopropyltriethoxysilane obtained in Synthesis Example 1 were placed in tetrahydrofuran (in a nitrogen stream). THF) was dissolved in 400 mL. The solution is cooled to 0 ° C. in an ice bath and 2.88 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC) and 2.30 g of 1-hydroxybenzotriazole monohydrate are added. rice field. Then, the reaction was carried out at room temperature for 15 hours. After completion of the reaction, tetrahydrofuran was distilled off, 200 mL of ethyl acetate and 100 mL of water were added, and the organic layer was separated using a separating funnel. The solid obtained by concentrating and drying the organic layer was purified by alumina column chromatography (chloroform: methanol = 50: 1) to obtain 5.40 g of the compound represented by the following formula (24) in a yield of 64%. rice field. The structure of the obtained compound ^{was identified by 1 1} H-NMR. ^{1 1} H-NMR (500 MHz, CDCl3, TMS, δppm): 8.29 (m, 2H), 8.01 (d, 1H, J = 8.5Hz), 7.30 (m, 4H), 7.15 (M, 4H), 7.00 (t, 1H, J = 7.5Hz), 6.92 (t, 1H, J = 5.5Hz), 5.88 (s, 1H), 3.86 (q) , 6H, J = 7.0Hz), 3.52 (q, 2H, J = 6.5Hz), 1,82 (quin, 2H, J = 7.0Hz), 1.23 (t, 9H, J = 7.0Hz), 0.75 (t, 2H, J = 7.5Hz).

[Synthesis Example 3]
In an eggplant flask, 0.96 g of the compound represented by the above formula (24) obtained in Synthesis Example 2 was dissolved in 640 mL of methanol. To this solution was added 40 g of silica (trade name "Nipsil ER", manufactured by Toso Silica Co., Ltd., specific surface area 70 to 120 m ² / g) and 160 mL of a 0.2 wt% acetic acid aqueous solution, and the mixture was stirred at room temperature for 72 hours. Then, the solvent was distilled off, the mixture was opened in a bat, air-dried for 24 hours, heat-treated in an oven at 120 ° C. for 24 hours, and then allowed to cool for 24 hours. A surface-treated silica prepared by fixing the represented compound was prepared. The surface-treated silica is obtained by reacting 100 parts of silica with a compound represented by the above formula (24) at a ratio of 2.4 parts (considering the desorbed ethanol molecule, the above formula (24)). The compound represented by (reacted at a ratio of 1.8 parts).

[Synthesis Example 4]
50.0 g of phenothiazine was added to a three-port reactor equipped with a thermometer in a nitrogen stream, and the mixture was dissolved in 200 ml of toluene. Then, 59.31 g of α-methylstyrene and 1.19 g of p-toluenesulfonic acid monohydrate were added to this solution, and the mixture was reacted at 80 ° C. for 1 hour. Then, the reaction solution was returned to room temperature, 48 ml of acetic acid and 85.34 g of 30 wt% hydrogen peroxide solution were added, and the mixture was further reacted at 80 ° C. for 2 hours. After the reaction, the obtained reaction solution was returned to room temperature and then added to 630 ml of methanol to precipitate crystals. Then, the precipitated crystals were filtered and rinsed with 320 ml of methanol to obtain 85.7 g of the compound represented by the following formula (25) in a yield of 73%. The structure of the obtained compound ^{was identified by 1 1} H-NMR. ^{1 1} H-NMR (500 MHz, DMSO-d6, TMS, δppm): 1.67 (s, 12H), 7.15-7.32 (m, 12H), 7.43 (dd, 2H, J = 9. 0, 2.0 Hz), 7.68 (d, 2H, J = 1.5 Hz), 10.84 (s, 1H).

[Example 1]
100 parts of acrylic rubber (trade name "Hytemp AR212HR", manufactured by Nippon Zeon Co., Ltd.), surface-treated silica obtained in Synthesis Example 3 (surface treatment in which the compound represented by the above formula (24) is fixed on the silica surface). Silica) 50.9 parts, silane coupling agent (trade name "KBM-403", manufactured by Shinetsu Silicone Co., Ltd.), 1 part, stearic acid 2 parts, ester wax (trade name "Greg G8205", manufactured by Dainippon Ink Co., Ltd.) After kneading 1 part and 1 part of the compound represented by the above formula (25) obtained in Synthesis Example 4 at 50 ° C. using an open roll, hexamethylenediamine carbamate as a cross-linking agent (trade name “Diak No.” .1 ”, 0.5 part of DuPontow Elastomer Japan Co., Ltd., and 2 parts of di-o-tolylguanidine (trade name“ Noxeller DT ”, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) as a cross-linking accelerator. , The rubber composition was obtained by kneading with an open roll at 50 ° C. Then, using the obtained rubber composition, the elongation at break before and after heating was evaluated according to the above method. The results are shown in Table 1.

[Comparative Example 1]
Rubber in the same manner as in Example 1 except that 50 parts of silica (trade name "Nipsil ER", manufactured by Tosoh Silica Co., Ltd.) was used instead of 50.9 parts of the surface-treated silica obtained in Synthesis Example 2. The composition was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 2]
Instead of 50.9 parts of the surface-treated silica obtained in Synthesis Example 2, 50 parts of silica (trade name "Nipsil ER", manufactured by Tosoh Silica Co., Ltd.) was used, and the above formula (trade name) obtained in Synthesis Example 2 was used. A rubber composition was produced in the same manner as in Example 1 except that 1.2 parts of the compound represented by 24) was used as it was, and the evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.

As shown in Table 1, a rubber crosslinked product obtained by using acrylic rubber containing surface-treated silica in which a compound represented by the above formula (24) is fixed on a silica surface has a elongation at break after heating. It was high, and the rate of change in elongation at break before and after heating was small, and deterioration due to heating was effectively suppressed (Example 1).
On the other hand, in both cases where silica is blended instead of surface-treated silica and when surface-treated silica is blended together with silica, the obtained rubber crosslinked product has a small elongation at break after heating and is heated. The rate of change in breaking elongation before and after was also large, and the deterioration due to heating was large (Comparative Examples 1 and 2).

Claims (9)

A diarylamine compound represented by the following general formula (1).
(A ¹ ) _m- A ^2- (A ^3- A ⁴ ) _n (1)
(In the above general formula (1), A ¹ is a group capable of binding to a hydroxyl group, and A ² is a (m + n) -valent organic group having 1 to 30 carbon atoms which may have a substituent. Yes, A ³ is a chemical single bond or a divalent group containing a group selected from an ether group, a keto group, an ester group, and an amide group, and A ⁴ is the following formula (2). It is a monovalent group having a structure excluding one hydrogen atom forming a carbon-hydrogen bond in the compound selected from (8), where m is an integer of 1 to 5 and n is an integer of 1 to 5. Is.)

(In the above formulas (2) to (8), the hydrogen atom bonded to the carbon atom forming the aromatic ring is substituted with a monovalent organic group having 1 to 30 carbon atoms which may have a substituent. May be.) A ⁴ is diarylamine compound according to claim 1 is a group represented by the following formula (9).

(In the above formula (9), "*" indicates the bonding position to the group represented by A ^3, hydrogen atoms bonded in the formula (9), with the carbon atoms forming the aromatic ring, the number of carbon atoms It may be substituted with 1 to 30 monovalent organic groups.) The diarylamine compound according to claim 1 or 2, wherein A ^{1 is a silyl group having at least one alkoxy group.} A ³ is, diarylamine compound according to any one of claims 1 to 3, an amide group. A surface-treated filler obtained by immobilizing the diarylamine compound according to any one of claims 1 to 4 on the surface of the filler. A surface treatment filler obtained by immobilizing the diarylamine compound according to any one of claims 1 to 4 on the surface of silica. A polymer composition containing the polymer and the surface treatment filler according to claim 5 or 6. The polymer composition according to claim 7, wherein the polymer is rubber. The polymer composition according to claim 8, wherein the rubber is acrylic rubber.