JP5541196B2 - Acrylic rubber composition and rubber cross-linked product - Google Patents

Description

  The present invention relates to an acrylic rubber composition and a rubber cross-linked product, and more specifically, an acrylic rubber composition that gives a rubber cross-linked product with improved mechanical properties and excellent heat resistance, and the acrylic rubber composition obtained by cross-linking The rubber | gum crosslinked material which becomes.

  Acrylic rubber is excellent in heat resistance, oil resistance, and the like, and is therefore widely used in rubber members such as hoses, seals, and gaskets in fields related to automobiles.

  On the other hand, for such rubber members for automobiles, especially rubber members in the engine compartment, the performance of the turbocharger (turbocharger) accompanying the increase in engine output and the recent tightening of exhaust gas regulations, There is a demand for improvement in mechanical properties of rubber members and further improvement in heat resistance performance.

  As a method for improving the mechanical properties of a rubber member, generally, a method of increasing the amount of an inorganic filler such as carbon black in an acrylic rubber composition is known. However, when the amount of the inorganic filler is increased, there is a problem that the heat resistance of the obtained rubber cross-linked product is deteriorated.

  In addition, as a method for improving the heat resistance of a rubber member, it has been conventionally studied to add an antioxidant to acrylic rubber. As such an anti-aging agent, a diphenylamine-based anti-aging agent or the like is used, and among the diphenylamine-based anti-aging agents, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine has a heat resistance effect. Known for being expensive. However, the conventional rubber that is blended alone with 4,4′-bis (α, α-dimethylbenzyl) diphenylamine cannot meet the demand for heat resistance in recent years. Various proposals have been made to further improve the above.

  For example, Patent Document 1 discloses a crosslinkable acrylic rubber composition obtained by blending a carboxyl group-containing acrylic rubber with a polyvalent primary amine crosslinking agent and p-aminodiphenylamine as an antiaging agent. In the technique described in Patent Document 1, as compared with the case where 4,4′-bis (α, α-dimethylbenzyl) diphenylamine is used alone as an anti-aging agent, the rate of change in elongation in the heat resistance test is higher than in the prior art. However, further improvements have been desired in order to sufficiently satisfy the mechanical properties of acrylic rubber compositions in recent years, particularly the requirements for hardness.

  On the other hand, Patent Document 2 discloses an acrylic rubber composition containing a diazabicycloalkene compound and a polyamine compound in a carboxyl group-containing acrylic rubber. Patent Document 3 discloses an acrylic rubber composition containing a carboxyl group-containing acrylic rubber having a specific composition ratio and a diazabicycloalkene compound. However, with the techniques described in Patent Document 2 and Patent Document 3, although mechanical characteristics are improved, it has been insufficient to satisfy recent demands for heat resistance.

JP 2009-84514 A JP 2008-189733 A JP 2009-97018 A

  The present invention provides a crosslinked rubber having improved mechanical properties, particularly hardness, high heat resistance, and capable of suppressing deterioration of physical properties such as elongation even when exposed to high temperature conditions for a long time. An object of the present invention is to provide an acrylic rubber composition that can be used. Another object of the present invention is to provide a rubber cross-linked product obtained by cross-linking the above acrylic rubber composition, particularly an extruded product.

  As a result of intensive studies to achieve the above object, the present inventors have found that specific amounts of condensed heterocyclic compounds, diazabicycloalkene compounds, and cross-linking agents as anti-aging agents are added to the carboxyl group-containing acrylic rubber in specific amounts. It has been found that the above object can be achieved by blending, and the present invention has been completed.

（上記一般式（１）中、Ｙは化学的な単結合または−ＳＯ_２−を表す。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。ｎおよびｍはそれぞれ独立して、０または１であり、ｎおよびｍの少なくとも一方は１である。） That is, according to the present invention, 0.1 to 10 parts by weight of a compound represented by the following general formula (1) and 0.1 to 20 parts by weight of a diazabicycloalkene compound with respect to 100 parts by weight of a carboxyl group-containing acrylic rubber. And an acrylic rubber composition containing 0.05 to 20 parts by weight of a crosslinking agent.

(In the general formula (1), Y represents a chemical single bond or —SO ₂ —. R ^a and R ^b each independently have 1 to 30 carbon atoms which may have a substituent. Represents an organic group, Z ^a and Z ^b each independently represents ^a chemical single bond or —SO ₂ —, n and m each independently represents 0 or 1, and at least one of n and m Is 1.)

Preferably, Y in the compound represented by the general formula (1) is —SO ₂ —, R ^a and R ^b are each independently a linear or branched group optionally having a substituent. the alkyl group having 2 to 8 carbon atoms and ^{Z a} and ^{Z b,} a chemical single bond, n and m are 1.

  Preferably, the crosslinking agent is a polyvalent amine compound or a carbonate of a polyvalent amine compound.

  Furthermore, according to this invention, the rubber crosslinked material formed by bridge | crosslinking the acrylic rubber composition in any one of the said is provided.

  Moreover, the rubber cross-linked product of the present invention is preferably an extruded product.

  According to the present invention, a rubber cross-linked product having improved mechanical properties, particularly hardness, high heat resistance, and capable of suppressing deterioration of physical properties such as elongation even when exposed to high temperature conditions for a long time. An acrylic rubber composition that can be provided can be provided. Furthermore, according to the present invention, it is also possible to provide a rubber cross-linked product obtained by cross-linking the acrylic rubber composition, particularly an extruded product.

<Acrylic rubber composition>
The acrylic rubber composition of the present invention comprises 0.1 to 10 parts by weight of a compound represented by the following general formula (1), diazabicycloalkene compound as an anti-aging agent with respect to 100 parts by weight of a carboxyl group-containing acrylic rubber. This is an acrylic rubber composition containing 0.1 to 20 parts by weight and 0.05 to 20 parts by weight of a crosslinking agent.

<Carboxyl group-containing acrylic rubber>
The carboxyl group-containing acrylic rubber used in the present invention is an acrylic rubber having a carboxyl group at the cross-linking point, and means that the main component (in the present application, 50% by weight or more of all monomer units in the rubber) is included in the molecule. ) (Meth) acrylic acid ester monomer [meaning acrylic acid ester monomer and / or methacrylic acid ester monomer. The same applies to methyl (meth) acrylate. It is not particularly limited as long as it contains a unit. The carboxyl group-containing acrylic rubber used in the present invention is (a) an acrylic rubber having an α, β-ethylenically unsaturated carboxylic acid monomer unit as a crosslinkable monomer unit, and (b) radical initiation with respect to the acrylic rubber. An acrylic rubber obtained by addition reaction of a carbon-carbon unsaturated bond-containing compound having a carboxyl group in the presence of an agent, or (c) a carboxylic acid derivative group such as a carboxylic acid ester group or an acid amide group in the acrylic rubber molecule. Any acrylic rubber obtained by converting a part thereof into a carboxyl group by hydrolysis may be used. Among these, (i) an acrylic rubber having an α, β-ethylenically unsaturated carboxylic acid monomer unit as a crosslinkable monomer unit is preferable, for example, as a carboxyl group-containing acrylic rubber used in the present invention. Are 50 to 99.9% by weight of (meth) acrylic acid ester monomer unit as a main component in the molecule, and an α, β-ethylenically unsaturated carboxylic acid monomer as a crosslinkable monomer unit. Examples thereof include polymers containing 0.1 to 10% by weight of units.

  Although it does not specifically limit as a (meth) acrylic acid ester monomer which forms the (meth) acrylic acid ester monomer unit which is a main component of the carboxyl group-containing acrylic rubber used by this invention, For example, (meth) acrylic Examples include acid alkyl ester monomers and (meth) acrylic acid alkoxyalkyl ester monomers.

  Although it does not specifically limit as a (meth) acrylic-acid alkylester monomer, The ester of C1-C8 alkanol and (meth) acrylic acid is preferable, Specifically, (meth) acrylic acid methyl, ( (Meth) ethyl acrylate, (meth) acrylic acid n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid n-hexyl, (meth) Examples 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 particularly preferable. These can be used alone or in combination of two or more.

  Although it does not specifically limit as a (meth) acrylic-acid alkoxyalkylester monomer, The ester of a C2-C8 alkoxyalkyl alcohol and (meth) acrylic acid is preferable, Specifically, (meth) acrylic acid Methoxymethyl, ethoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate , (Meth) acrylic acid 3-methoxypropyl, (meth) acrylic acid 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 carboxyl group-containing acrylic rubber used in the present invention is usually 50 to 99.9% by weight, preferably 60 to 99.5% by weight, 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 resulting rubber cross-linked product may be lowered. There is a risk that the heat resistance of the object will decrease.

  In the present invention, (meth) acrylic acid ester monomer units are 30 to 100% by weight of (meth) acrylic acid alkyl ester monomer units and (meth) acrylic acid alkoxyalkyl ester monomer units 70 to 70%. It is preferable to consist of 0% by weight.

  The α, β-ethylenically unsaturated carboxylic acid monomer that forms the crosslinkable monomer unit is not particularly limited, but examples thereof include α, β-ethylenically unsaturated monocarboxylic acid having 3 to 12 carbon atoms, Examples include α, β-ethylenically unsaturated dicarboxylic acids having 4 to 12 carbon atoms and monoesters of α, β-ethylenically unsaturated dicarboxylic acids having 4 to 12 carbon atoms and alkanols having 1 to 8 carbon atoms. .

Specific 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.
Specific examples of the α, β-ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms include butenedionic acid such as fumaric acid and maleic acid; itaconic acid; citraconic acid; chloromaleic acid;
Specific examples of monoesters of α, β-ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms and alkanol having 1 to 8 carbon atoms include monomethyl fumarate, monoethyl fumarate, mono n-butyl fumarate, malein Butenedionic acid mono-chain alkyl esters such as monomethyl acid, monoethyl maleate, mono-n-butyl maleate; monocyclopentyl fumarate, monocyclohexyl fumarate, monocyclohexenyl fumarate, monocyclopentyl maleate, monocyclohexyl maleate, maleate Butenedionic acid monoesters having an alicyclic structure such as acid monocyclohexenyl; itaconic acid monoesters such as monomethyl itaconate, monoethyl itaconate, mono n-butyl itaconate, monocyclohexyl itaconate; and the like.
Among these, butenedionic acid mono-chain alkyl ester or butenedionic acid monoester having an alicyclic structure is preferable, and mono n-butyl fumarate, mono n-butyl maleate, monocyclohexyl fumarate, and monocyclohexyl maleate are preferable. More preferred is mono n-butyl fumarate. These α, β-ethylenically unsaturated carboxylic acid monomers can be used alone or in combination of two or more. Among the above monomers, dicarboxylic acids include those that exist as anhydrides.

  By using an α, β-ethylenically unsaturated carboxylic acid monomer as a crosslinkable monomer, the acrylic rubber can be converted into a carboxyl group-containing acrylic rubber having a carboxyl group as a crosslinking point. The heat aging resistance of the acrylic rubber used in the invention can be improved.

  The α, β-ethylenically unsaturated carboxylic acid monomer can be used alone or in combination of two or more. The content of the α, β-ethylenically unsaturated carboxylic acid monomer unit in the carboxyl group-containing acrylic rubber used in the present invention is preferably 0.1 to 10% by weight, more preferably 0.5 to 7% by weight. %, More preferably 0.5 to 5% by weight. If the content of the α, β-ethylenically unsaturated carboxylic acid monomer unit is too large, the elongation of the resulting rubber cross-linked product may decrease or the compression set may increase, If the amount is too small, crosslinking may be insufficient, resulting in insufficient mechanical properties of the resulting rubber cross-linked product or reduced heat resistance.

The carboxyl group content of the carboxyl group-containing acrylic rubber used in the present invention, that is, the mole number of carboxyl groups per 100 g of acrylic rubber (ephr) is preferably 4 × 10 ⁻⁴ to 4 × 10 ⁻¹ (ephr), More preferably, it is 1 * 10 < ^-3 > -2 * 10 < ^-1 > (ephr), More preferably, it is 5 * 10 < ^-3 > ^-1 * 10 < ^-1 > (ephr). If the content of the carboxyl group is too small, crosslinking may be insufficient, resulting in insufficient mechanical properties of the resulting rubber crosslinked product or reduced heat resistance. On the other hand, if the amount is too large, the elongation of the resulting rubber cross-linked product may decrease, or the compression set may increase.

  The carboxyl group-containing acrylic rubber used in the present invention may have other crosslinkable monomer units as needed in addition to the α, β-ethylenically unsaturated carboxylic acid monomer units. The crosslinkable monomer that forms other crosslinkable monomer units is not particularly limited, and examples thereof include a monomer having a halogen atom; a monomer having an epoxy group; a diene monomer; It is done.

  The crosslinkable monomer which forms another crosslinkable monomer unit can be used individually by 1 type or in combination of 2 or more types. The content of other crosslinkable monomer units in the carboxyl group-containing acrylic rubber used in the present invention is preferably 0 to 9.9% by weight, more preferably 0 to 6.5% by weight, and still more preferably 0. -4.5 wt%. (However, the total amount of all crosslinkable monomer units in the carboxyl group-containing acrylic rubber is preferably 0.1 to 10% by weight, more preferably 0.5 to 7% by weight, still more preferably 0. 0.5-5% by weight.) If the content of these crosslinkable monomer units is too large, the elongation of the resulting rubber cross-linked product may decrease or the compression set may increase. .

  Further, the carboxyl group-containing acrylic rubber used in the present invention is in addition to a (meth) acrylic acid ester monomer unit and a crosslinkable monomer unit containing an α, β-ethylenically unsaturated carboxylic acid monomer unit. If necessary, units of other monomers copolymerizable with (meth) acrylic acid ester monomers and crosslinkable monomer units including α, β-ethylenically unsaturated carboxylic acid monomers You may have.

  Other monomers that can be copolymerized are not particularly limited, and examples thereof include aromatic vinyl monomers, α, β-ethylenically unsaturated nitrile monomers, and monomers having two or more acryloyloxy groups. (Hereinafter, referred to as “polyfunctional acrylic monomer”), olefin monomers, vinyl ether compounds, and the like.

Specific examples of the aromatic vinyl monomer include styrene, α-methylstyrene, divinylbenzene, and the like.
Specific examples of the α, β-ethylenically unsaturated nitrile monomer include acrylonitrile and methacrylonitrile.
Specific examples of the polyfunctional acrylic monomer include ethylene glycol di (meth) acrylate and propylene glycol di (meth) acrylate.
Specific examples of the olefin monomer include ethylene, propylene, 1-butene, and 1-octene.
Specific examples of the vinyl ether compound include vinyl acetate, ethyl vinyl ether, and n-butyl vinyl ether.

  Among these, styrene, acrylonitrile, methacrylonitrile, ethylene and vinyl acetate are preferable, and acrylonitrile, methacrylonitrile and ethylene are more preferable.

  The other copolymerizable monomers can be used alone or in combination of two or more. The content of other monomer units in the carboxyl group-containing acrylic rubber used in the present invention is usually 0 to 49.9% by weight, preferably 0 to 39.5% by weight, more preferably 0 to 29. .5% by weight.

  The carboxyl group-containing acrylic rubber used in the present invention can be obtained by polymerizing the above monomers. As the form of the polymerization reaction, any of an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, and a solution polymerization method can be used. From the viewpoint of easy control of the polymerization reaction, a conventionally known acrylic rubber It is preferable to use an emulsion polymerization method under normal pressure, which is generally used as a production method of the above.

  The emulsion polymerization may be any of batch, semi-batch and continuous. The polymerization is usually performed in a temperature range of 0 to 70 ° C, preferably 5 to 50 ° C.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) (polymer Mooney) of the carboxyl group-containing acrylic rubber used in the present invention thus produced is preferably 10 to 80, more preferably 20 to 70, and even more preferably 25. ~ 60. As the carboxyl group-containing acrylic rubber used in the present invention, the carboxyl group-containing acrylic rubber produced as described above can be used alone or in combination of two or more.

（上記一般式（１）中、Ｙは化学的な単結合または−ＳＯ_２−を表す。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。ｎおよびｍはそれぞれ独立して、０または１であり、ｎおよびｍの少なくとも一方は１である。） <Anti-aging agent>
The anti-aging agent used in the present invention is a compound represented by the following general formula (1).

(In the general formula (1), Y represents a chemical single bond or —SO ₂ —. R ^a and R ^b each independently have 1 to 30 carbon atoms which may have a substituent. Represents an organic group, Z ^a and Z ^b each independently represents ^a chemical single bond or —SO ₂ —, n and m each independently represents 0 or 1, and at least one of n and m Is 1.)

In the general formula (1), Y is a chemical single bond or —SO ₂ —, and preferably —SO ₂ —.

In the general formula (1), R ^a and R ^b each independently represent an organic group having 1 to 30 carbon atoms which may have a substituent.
Although it does not specifically limit as a C1-C30 organic group which comprises R ^<a> and R < ^b >, For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- C1-C30 alkyl groups 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 A cycloalkyl group having 3 to 30 carbon atoms such as a group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; an aryl group having 6 to 30 carbon atoms such as a phenyl group, a biphenyl group, a naphthyl group and an anthranyl group; Group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, n Pentyloxy group, an alkoxy group having 1 to 30 carbon atoms such as n- hexyloxy group; and the like.

Moreover, the organic group which comprises ^Ra and ^Rb mentioned above may have a substituent, and can be made into arbitrary positions as a position of this substituent.
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 Nitro group; cyano group; phenyl group optionally having substituents such as phenyl group, 4-methylphenyl group, 2-chlorophenyl group; and the like.
When the organic group is a cycloalkyl group or an aryl group, examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom; carbon atoms of 1 to 3 such as a methoxy group, an ethoxy group, and an isopropoxy group 10 alkoxy groups; nitro groups; cyano groups; alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, and t-butyl groups;
Furthermore, 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;

In the present invention, when the organic group constituting R ^a and R ^b has a substituent, the carbon number of the organic group does not include the carbon number of the substituent. That is, the organic group constituting R ^a and R ^b may have a number of carbon atoms in the range of 1 to 30 excluding the carbon atoms contained in the substituent. For example, when the organic group constituting R ^a and R ^b is a methoxyethyl group, the organic group has 2 carbon atoms. That is, in this case, since the methoxy group is a substituent, the carbon number of the organic group is obtained by removing the carbon number of the methoxy group that is the substituent.

In the present invention, R ^a and R ^b are each independently an alkyl group having 2 to 20 carbon atoms which may have a substituent, or 6 to 30 carbon atoms which may have a substituent. The aryl group is preferably 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 linear or branched alkyl group having 2 to 8 carbon atoms which may have a substituent, or a substituent. It is more preferably a good phenyl group, and a linear or branched alkyl group having 2 to 8 carbon atoms which may have a substituent is particularly preferred.

Preferable specific examples of the organic group constituting R ^a and R ^b include an α-methylbenzyl group, an α, α-dimethylbenzyl group, a t-butyl group, a phenyl group, or a 4-methylphenyl group. Among these, an α, α-dimethylbenzyl group or a 4-methylphenyl group is more preferable, and an α, α-dimethylbenzyl group is more preferable. These can be independent of each other.

Further, in the above general formula (1), and each of Z ^a and Z ^b independently, chemical single bond or -SO 2 _-, preferably a chemical single bond.

  Further, in the general formula (1), n and m are each independently 0 or 1, and at least one of n and m is 1. In addition, it is preferable that both n and m are 1.

（上記一般式（２）〜（８）中、Ｒ^ａ、Ｒ^ｂ、Ｚ^ａおよびＺ^ｂは、上記一般式（１）と同様である。） In the present invention, the compound represented by the general formula (1) is preferably any one of the compounds represented by the following general formulas (2) to (8).

(In the general formulas (2) to (8), R ^a , R ^b , Z ^a and Z ^b are the same as those in the general formula (1).)

  Among the compounds represented by the general formulas (2) to (8), the compounds represented by the general formulas (2), (6), and (7) are preferable, and the compounds represented by the general formula (6) Is more preferable.

In the general formulas (2) to (8), -Z ^a -R ^a and -Z ^b -R ^b are each independently α-methylbenzyl group, α, α-dimethylbenzyl group, t-butyl. Group, phenylsulfonyl group, or 4-methylphenylsulfonyl group, more preferably α, α-dimethylbenzyl group, or 4-methylphenylsulfonyl group, and α, α-dimethylbenzyl group. More preferably.

That is, in the present invention, in the above general formula (1), Y is —SO ₂ —, R ^a and R ^b are each independently a linear or branched chain which may have a substituent. alkyl group having 2 to 8 carbon atoms and Z ^a and Z ^b, is a chemical single bond, it is preferred n and m are 1.

Subsequently, the manufacturing method of the compound represented by the said General formula (1) is demonstrated.
When the compound represented by the general formula (1) is a compound in which Y is —SO ₂ —, by applying a known method for producing a phenothiazine-based compound, in the general formula (1), It can be prepared by obtaining a compound in which Y is S and then oxidizing the resulting compound.

（上記一般式（９）中、Ｙ^１は、Ｓまたは化学的な単結合である。） Further, the compound represented by the general formula (1) is obtained by starting from a compound represented by the following general formula (9) [phenothiazine (Y ¹ = S) and carbazole (Y ¹ = chemical single bond)]. As a substituent (—Z ^a —R ^a , —Z ^b —R ^b ) on the 1-position, 3-position, 6-position and / or 8-position of the aromatic ring in the general formula (9) by a known reaction method. And when Y ¹ = S, it can be obtained by oxidizing Y ¹ to —SO ₂ —.

(In the general formula (9), Y ¹ is S or a chemical single bond.)

1 or 2 substituents (—Z ^a —R ^a , —Z ^b —R ^b ) are introduced into the 1-position, 3-position, 6-position and / or 8-position of the aromatic ring in the general formula (9). As the reaction method, for example, a reaction for generating a carbon-carbon bond at the 1-position, 3-position, 6-position and / or 8-position carbon atom of the aromatic ring in the general formula (9) (this reaction method is referred to as “ Reaction method α ”), a reaction for forming a carbon-SO ₂ bond at the carbon atom at the 1-position, 3-position, 6-position and / or 8-position of the aromatic ring in the general formula (9) (this reaction method) Is referred to as “reaction method β”), a reaction for generating a carbon-sulfur bond at the 1-position, 3-position, 6-position and / or 8-position carbon atom of the aromatic ring in the general formula (9) (this The reaction method is referred to as “reaction method γ”).

  Hereinafter, with respect to the method for producing the compound represented by the general formula (1), the compound represented by the general formula (9) is used as a starting material, and the reaction method α, the reaction method β, and the reaction method γ described above are used. The case where each method is used is illustrated and described in detail.

[A. Production Method (1) Using Reaction Method α]
The reaction formula of the production method (1) using the reaction method α is shown below. In the following reaction formula, among the compounds represented by the general formula (1), Y is a chemical single bond or —SO ₂ —, n or m is 0, and —Z ^a —R. ^a or —Z ^b —R ^b is represented by the formula: —C (CH ₃ ) (r) —Ar (wherein r represents a hydrogen atom or an alkyl group, Ar represents a phenyl group which may have a substituent); The case where it is group shown by this is illustrated.

According to the above reaction formula, among the compounds represented by the above general formula (1), the compound where Y is a chemical single bond is a compound represented by the above general formula (9) (Y ¹ = chemical Carbazole which is a single bond) is used as a starting material, and in the presence of an acid catalyst, the styrene compound represented by the general formula (10) is reacted to thereby react the general formula (11a) and / or (11b). It can be obtained as a compound shown in (1).

In addition, according to the above reaction formula, among the compounds represented by the general formula (1), the compound in which Y is —SO ₂ — is a compound represented by the general formula (9) (Y ¹ = S A certain phenothiazine) is used as a starting material, and the styrene compound represented by the above general formula (10) is reacted in the presence of an acid catalyst, and the compound obtained by the reaction (the above general formula (11a) and / or (11b) The compound represented by () can be obtained as a compound represented by the general formula (12a) and / or (12b) by oxidation.

  Specific examples of the compound represented by the general formula (10) used in the above reaction include styrene; 4-methylstyrene, α-methylstyrene, 4, α-dimethylstyrene, 2,4-dimethylstyrene, and ethylstyrene. And alkylated styrene such as pt-butylstyrene; halogenated styrene such as 2-chlorostyrene and 2,4-dichlorostyrene; and the like. Moreover, the usage-amount of the compound represented by the said General formula (10) is 0.5-1.5 mol per 1 mol of compounds represented by the said General formula (9).

  Specific examples of the acid catalyst used in the above reaction include sulfonic acids such as methanesulfonic acid, phenylsulfonic acid, and p-toluenesulfonic acid; inorganic acids such as hydrochloric acid and sulfuric acid; The acid catalyst is usually charged at the start of the reaction, but can be added during the reaction. The usage-amount of an acid catalyst is 0.005-0.5 mol normally with respect to 1 mol of compounds represented by the said General formula (9), Preferably it is 0.01-0.3 mol, More preferably Is 0.02 to 0.1 mol.

  The above reaction can be carried out in a suitable solvent. The solvent to be used is not particularly limited as long as it is inert to the reaction. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene; chain formulas such as n-pentane, n-hexane and n-octane. Saturated hydrocarbon solvents; saturated alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; halogenated hydrocarbon solvents such as 1,2-dichloroethane and monochlorobenzene; These solvents can be used alone or in combination of two or more. The amount of the solvent used is 1 ml to 100 ml per 1 g of the compound represented by the general formula (9), although it depends on the reaction scale.

Moreover, in the compound represented by the general formula (9), the oxidizing agent used for the oxidation in the case where Y ¹ = S is not particularly limited, and acetic acid-hydrogen peroxide, m-chloroperbenzoic acid, etc. Of organic peroxides. The usage-amount of an oxidizing agent is 2-5 mol per 1 mol of compounds represented by the said general formula (11a) or (11b).

  Such an oxidation reaction can be performed in a suitable solvent. The solvent to be used is not particularly limited as long as it is inert to the reaction. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene; chain formulas such as n-pentane, n-hexane and n-octane. Saturated hydrocarbon solvents; saturated alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; halogenated hydrocarbon solvents such as dichloromethane, chloroform, 1,2-dichloroethane, and monochlorobenzene; acetic acid; These solvents can be used alone or in combination of two or more. The amount of the solvent used is 1 ml to 100 ml per 1 g of the compound represented by the general formula (11a) or (11b), although it depends on the reaction scale.

  Further, such an oxidation reaction may be continuously performed by adding a predetermined amount of acetic acid and hydrogen peroxide to a reaction solution containing a compound represented by the general formula (11a) and / or (11b). it can.

[B. Production method using reaction method α (2)]
The reaction formula of the production method (2) using the reaction method α is shown below. In the following reaction formula, among the compounds represented by the general formula (1), Y is a chemical single bond or —SO ₂ —, n and m are 1, and —Z ^a —R. ^a and ^-Z b -R ^b has the _{formula: -C (CH 3) (r} ) -Ar ( wherein, r is a hydrogen atom or an alkyl group, Ar is a phenyl group which may have a substituent The case where it is group shown by this is illustrated.

According to the above reaction formula, among the compounds represented by the above general formula (1), the compound where Y is a chemical single bond is a compound represented by the above general formula (9) (Y ¹ = chemical Carbazole which is a typical single bond) as a starting material, and by reacting the styrene compound represented by the above general formula (10) in the presence of an acid catalyst, the above general formula (11c) and / or (11d It can be obtained as a compound shown in (1).

In addition, according to the above reaction formula, among the compounds represented by the general formula (1), the compound in which Y is —SO ₂ — is a compound represented by the general formula (9) (Y ¹ = S A certain phenothiazine) is used as a starting material, and the styrene compound represented by the above general formula (10) is reacted in the presence of an acid catalyst, and the compound obtained by the reaction (the above general formula (11c) and / or (11d) The compound represented by () can be obtained as a compound represented by the general formula (12c) and / or (12d) by oxidation.

  In the above reaction, as the compound represented by the general formula (10), the acid catalyst, the solvent, and the oxidizing agent, the same production method (1) using the reaction method α described above may be used. it can. Moreover, about these usage-amounts, the usage-amount of the compound represented by the said General formula (10) shall be 2-3 mol with respect to 1 mol of compounds represented by the said General formula (9), and an oxidizing agent is used. It can be the same as that of the manufacturing method (1) using the reaction method α described above except that the amount used is 2 to 10 mol with respect to 1 mol of the compound represented by the general formula (11c) or (11d). .

[C. Production method using reaction method β)
The reaction formula of the production method using reaction method β is shown below. In the following reaction formula, among the compounds represented by the general formula (1), Y is a chemical single bond or —SO ₂ —, n or m is 0, and —Z ^a —R. ^a or ^-Z b -R ^b has the _formula: -SO 2 -Ar (wherein, Ar represents a phenyl group which may have a substituent.) illustrates the case where the group represented by.

According to the above reaction formula, among the compounds represented by the above general formula (1), the compound where Y is a chemical single bond is a compound represented by the above general formula (9) (Y ¹ = chemical Carbazole which is a typical single bond) as a starting material, and in the presence of a Lewis acid such as ferric chloride and an acetate salt such as potassium acetate, a sulfinate (M is (Representing an alkali metal such as sodium) can be obtained as a compound represented by the above general formula (11e) and / or (11f).

In addition, according to the above reaction formula, among the compounds represented by the general formula (1), the compound in which Y is —SO ₂ — is a compound represented by the general formula (9) (Y ¹ = S A certain phenothiazine) is used as a starting material, and a sulfinate represented by the above general formula (13) is reacted in the presence of a Lewis acid such as ferric chloride and an acetate such as potassium acetate. The compound (the compound represented by the above general formula (11e) and / or (11f)) can be obtained as a compound represented by the above general formula (12e) and / or (12f) by oxidation.

  Examples of the sulfinate represented by the general formula (13) used in the above reaction include sodium phenylsulfinate, potassium phenylsulfinate, sodium p-toluenesulfinate, and potassium p-toluenesulfinate. Moreover, the usage-amount of the compound represented by the said General formula (13) is 0.5-1.5 mol per 1 mol of compounds represented by the said General formula (9).

  In the said reaction, the usage-amount of a Lewis acid is 5-10 mol normally with respect to 1 mol of compounds represented by the said General formula (9), and the usage-amount of acetate is represented by the said General formula (9). The amount is usually 1 to 3 moles per mole of the compound.

  The above reaction can be carried out in a suitable solvent. The solvent to be used is not particularly limited as long as it is inert to the reaction, and examples thereof include alcohol solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, and isopropyl alcohol. The solvent to be used can be used singly or in combination of two or more. The amount of the solvent used is 1 ml to 100 ml per 1 g of the compound represented by the general formula (9), although it depends on the reaction scale.

In the compound represented by the general formula (9), the oxidation reaction when Y ¹ = S can be performed in the same manner as in the production method (1) using the reaction method α described above.

[D. Production method using reaction method γ]
The reaction formula of the production method using the reaction method γ is shown below. In the following reaction formula, among the compounds represented by the general formula (1), Y is a chemical single bond, n and m are 1, and -Z ^a -R ^a or -Z ^b -R ^b has the formula: _-SO 2 -R (wherein, R represents an organic group having 1 to 30 carbon atoms.) illustrates the case where the group represented by.

  Then, according to the above reaction formula, using the compound represented by the above general formula (9a) (carbazole) as a starting material, by reacting iodine in the presence of periodate and a catalytic amount of sulfuric acid, After obtaining the diiodide represented by the above general formula (14), the resulting diiodide is represented by the formula: R-SH (wherein R is carbon in the presence of a base and a catalytic amount of a palladium (II) complex). The compound represented by the general formula (15) is obtained by reacting the mercaptan represented by the formula (1) to (30). It can be obtained as a compound represented by the general formula (16).

  Among the above reactions, specific examples of periodate used in the reaction for obtaining the diiodide represented by the general formula (14) include sodium periodate and potassium periodate. The usage-amount of periodate is 0.1 mol-1 mol per 1 mol of compounds represented by the said General formula (9a). Moreover, the usage-amount of iodine is 1 mol-3 mol per 1 mol of compounds represented by the said General formula (9a).

  The reaction for obtaining the diiodide can be performed in a suitable solvent. The solvent to be used is not particularly limited as long as it is inert to the reaction, and examples thereof include alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol. The solvent to be used can be used singly or in combination of two or more. The amount of the solvent used is 1 ml to 100 ml per 1 g of the compound represented by the general formula (9a), although it depends on the reaction scale.

  Moreover, as a specific example of the mercaptan used for reaction which obtains the compound represented by the said General formula (15) among the said reaction, thiophenol, p-toluenethiol, benzyl mercaptan, (alpha) -methylbenzyl mercaptan, (alpha), (alpha) -Dimethyl mercaptan, t-butyl mercaptan, etc. are mentioned. The amount of mercaptan used is 1 mol to 3 mol per 1 mol of the compound represented by the general formula (14).

  Examples of the base used in the reaction for obtaining the compound represented by the general formula (15) include metal alkoxides such as sodium t-butoxide and potassium t-butoxide; DBU (1,8-diazabicyclo [5.4.0] undeca- 7-ene) and organic bases such as DABCO (1,4-diazabicyclo [2.2.2] octane). The usage-amount of a base is 1 mol-10 mol normally with respect to 1 mol of compounds represented by the said General formula (14).

  Specific examples of the palladium (II) complex used in the reaction for obtaining the compound represented by the general formula (15) include [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct and the like. Is mentioned.

  The reaction for obtaining the compound represented by the general formula (15) can be carried out in a suitable solvent. The solvent to be used is not particularly limited as long as it is inert to the reaction. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene; chain formulas such as n-pentane, n-hexane and n-octane. Saturated hydrocarbon solvents; saturated alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; halogenated hydrocarbon solvents such as dichloromethane, chloroform, 1,2-dichloroethane, and monochlorobenzene. These solvents can be used alone or in combination of two or more. The amount of the solvent used is 1 ml to 100 ml per 1 g of the compound represented by the general formula (14), although it depends on the reaction scale and the like.

  It does not restrict | limit especially as an oxidizing agent used for the oxidation reaction for obtaining the compound represented by the said General formula (16), Organic peroxides, such as an acetic acid-hydrogen peroxide and m-chloro perbenzoic acid, are mentioned. . The usage-amount of an oxidizing agent is 2-10 mol per 1 mol of compounds represented by the said General formula (15).

  As a suitable solvent for performing such an oxidation reaction, the same solvent as that used in the oxidation reaction of the production method (1) using the reaction method α described above can be used.

  Further, such an oxidation reaction can be continuously performed by adding a predetermined amount of acetic acid and hydrogen peroxide to a reaction solution containing the compound represented by the general formula (15).

  All the reactions in the above reaction method α, reaction method β, and reaction method γ proceed smoothly in a temperature range from 0 ° C. to the boiling point of the solvent used. The reaction time is usually several minutes to several hours. In any reaction method, after completion of the reaction, the usual post-treatment operation in organic synthetic chemistry is performed, and, if desired, known separation / purification means such as column chromatography, recrystallization method, distillation method, etc. are applied. Thus, the target product can be isolated. The structure of the target product can be identified by measurement of NMR spectrum, IR spectrum, mass spectrum, etc., and elemental analysis.

  The content of the compound represented by the general formula (1) in the acrylic rubber composition of the present invention is usually 0.1 to 10 weights on a weight basis with respect to 100 parts by weight of the carboxyl group-containing acrylic rubber. Part, preferably 0.3 to 5 parts by weight, more preferably 0.5 to 2.5 parts by weight. When the content of the compound represented by the general formula (1) is within the above range, the obtained rubber cross-linked product can suppress deterioration of physical properties such as elongation even when exposed to high temperature conditions for a long time. Yes, excellent heat resistance. On the other hand, if the content of the compound represented by the general formula (1) is too small, the heat resistance of the resulting rubber cross-linked product may be reduced. If the content is too large, the content is represented by the general formula (1). The bleed out of the compound, the physical properties of the rubber cross-linked product may be deteriorated, and the molded product may be discolored. The compound represented by the general formula (1) can be used alone or in combination of two or more.

<Diazabicycloalkene compound>
The diazabicycloalkene compound used in the present invention is not particularly limited as long as it is an alkene compound having a diazabicyclo structure. For example, 1,5-diazabicyclo [4.2.0] oct-5-ene, 1,8- Diazabicyclo [5.4.0] undec-7-ene (also referred to as “DBU”), 1,8-diazabicyclo [7.2.0] undec-8-ene, 1,4-diazabicyclo [3.3.0 ] Oct-4-ene, 3-methyl-1,4-diazabicyclo [3.3.0] oct-4-ene, 3,6,7,7-tetramethyl-1,4-diazabicyclo [3.3. 0] oct-4-ene, 7,8,8-trimethyl-1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [7.3.0] dodec-8- En, 1,7-diazabi Chlo [4.3.0] non-6-ene, 8-phenyl-1,7-diazabicyclo [4.3.0] non-6-ene, 1,5-diazabicyclo [4.3.0] non- 5-ene, 1,5-diazabicyclo [4.3.0] dec-5-ene, 4-phenyl-1,5-diazabicyclo [4.4.0] dec-5-ene, 1,8-diazabicyclo [ 5.3.0] dec-7-ene, 1,8-diazabicyclo [7.4.0] tridec-8-ene, 6-methylbutylamino-1,8-diazabicyclo [5.4.0] undeca 7-ene, 6-methyloctylamino-1,8-diazabicyclo [5.4.0] undec-7-ene, 6-dibutylamino-1,8-diazabicyclo [5.4.0] undec-7-ene 6-butylbenzylamino-1,8-diazabicyclo 5.4.0] Undec-7-ene, 6-dihexylamino-1,8-diazabicyclo [5.4.0] undec-7-ene, 9-methyl-1,8-diazabicyclo [5.4.0] ] Undec-7-ene, 9-methyl-1,8-diazabicyclo [5.3.0] undec-7-ene, 1,6-diazabicyclo [5.5.0] dodec-6-ene, 1,7 -Diazabicyclo [6.5.0] tridec-7-ene, 1,8-diazabicyclo [7.5.0] tetradec-8-ene, 1,10-diazabicyclo [7.3.0] dodec-9-ene. 1,10-diazabicyclo [7.4.0] tridec-9-ene, 1,14-diazabicyclo [11.3.0] hexadeca-13-ene, 1,14-diazabicyclo [114.0] heptadeca -13-ene etc. It is. Among these, 1,8-diazabicyclo [5.4.0] undec-7-ene is preferable because the effect of mechanical properties of the obtained rubber cross-linked product becomes more remarkable. These diazabicycloalkene compounds may form a salt, and as the compound forming the salt, an organic carboxylic acid and an alkyl phosphoric acid (including zinc dialkyldiphosphate) are preferable.

  The content ratio of the diazabicycloalkene compound in the acrylic rubber composition of the present invention is usually 0.1 to 20 parts by weight, preferably 0.2 to 10 parts per 100 parts by weight of the carboxyl group-containing acrylic rubber. Part by weight, more preferably 0.3 to 5 parts by weight. When the content of the diazabicycloalkene compound is within the above range, crosslinking is sufficiently performed, and mechanical properties, particularly hardness, of the resulting rubber crosslinked product is excellent. If the content ratio of the diazabicycloalkene compound is too small, crosslinking may not proceed sufficiently, and the mechanical properties of the resulting rubber cross-linked product may be inferior. On the other hand, if it is too large, the scorch stability will deteriorate. There is a tendency. In addition, a diazabicycloalkene compound has a property which acts as a crosslinking accelerator by combining with a crosslinking agent. These diazabicycloalkene compounds can be used alone or in combination of two or more.

<Crosslinking agent>
Although it will not specifically limit as a crosslinking agent used by this invention if the carboxyl group-containing acrylic rubber mentioned above can be bridge | crosslinked, For example, the carbonate of a polyvalent amine compound and a polyvalent amine compound is preferable. These crosslinking agents can be used alone or in combination of two or more.

  Although it does not specifically limit as a polyvalent amine compound and the carbonate of a polyvalent amine compound, A C4-C30 polyvalent amine compound and its carbonate are more preferable. Examples of such polyvalent amine compounds and carbonates thereof include aliphatic polyvalent amine compounds, carbonates thereof, and aromatic polyvalent amine compounds. On the other hand, those having non-conjugated nitrogen-carbon double bonds such as guanidine compounds are not included. Among these, aromatic polyvalent amine compounds are particularly preferred because the effect of mechanical properties of the resulting rubber cross-linked product becomes even more remarkable.

  Although it does not specifically limit as an aliphatic polyvalent amine compound and its carbonate, For example, hexamethylene diamine, hexamethylene diamine carbamate, N, N'- dicinnamylidene-1,6-hexanediamine etc. are mentioned. Among these, hexamethylenediamine carbamate is preferable.

  Although it does not specifically limit as an aromatic polyvalent amine compound, For example, 4,4'-methylenedianiline, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether 4,4 ′-(m-phenylenediisopropylidene) dianiline, 4,4 ′-(p-phenylenediisopropylidene) dianiline, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, Examples include 4,4′-diaminobenzanilide, 4,4′-bis (4-aminophenoxy) biphenyl, m-xylylenediamine, p-xylylenediamine, and 1,3,5-benzenetriamine. Among these, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane is preferable.

  The content of the crosslinking agent in the acrylic rubber composition of the present invention is 0.05 to 20 parts by weight, preferably 0.1 to 15 parts by weight, and more preferably 0.1 to 100 parts by weight of the acrylic rubber. 3 to 12 parts by weight. When the content of the crosslinking agent is within the above range, the crosslinking is sufficiently performed, and the mechanical properties of the resulting rubber crosslinked product are excellent. On the other hand, if the content of the crosslinking agent is too small, crosslinking may be insufficient, and it may be difficult to maintain the shape of the resulting rubber crosslinked product. If too much, the resulting rubber crosslinked product may be too hard. There is.

<Other ingredients>
In addition to the carboxyl group-containing acrylic rubber, the compound represented by the general formula (1), the diazabicycloalkene compound, and the crosslinking agent, the acrylic rubber composition of the present invention includes a compounding agent that is usually used in the rubber processing field. Can be blended. Examples of such a compounding agent include reinforcing fillers such as carbon black and silica; non-reinforcing fillers such as calcium carbonate and clay; anti-aging agents (excluding the compound represented by the general formula (1) above) ); Cross-linking accelerator (excluding diazabicycloalkene compounds); Light stabilizer; Scorch inhibitor; Plasticizer; Processing aid; Lubricant; Adhesive; Lubricant; Agents; silane coupling agents; crosslinking retarders; and the like. The compounding amount of these compounding agents is not particularly limited as long as it does not impair the object and effect of the present invention, and an amount corresponding to the compounding purpose can be appropriately compounded.

  Furthermore, in the acrylic rubber composition of the present invention, rubbers, elastomers, resins and the like other than the carboxyl group-containing acrylic rubber used in the present invention may be further blended within a range not impairing the effects of the present invention. For example, acrylic rubber other than carboxyl group-containing acrylic rubber, natural rubber, polybutadiene rubber, polyisoprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, silicone rubber, fluorine rubber, and other rubber other than carboxyl group-containing acrylic rubber; Elastomers, styrene elastomers, vinyl chloride elastomers, polyester elastomers, polyamide elastomers, polyurethane elastomers, polysiloxane elastomers, polyolefin resins, polystyrene resins, polyacrylic resins, polyphenylene ether resins, Polyester resins, polycarbonate resins, polyamide resins, vinyl chloride resins, fluororesins, and the like can be blended. The total amount of rubber, elastomer, and resin other than carboxyl group-containing acrylic rubber is preferably 50 parts by weight or less, more preferably 10 parts by weight with respect to 100 parts by weight of carboxyl group-containing acrylic rubber used in the present invention. Hereinafter, it is further preferably 1 part by weight or less.

<Method for preparing acrylic rubber composition>
The acrylic rubber composition of the present invention includes a compound represented by the above general formula (1), a diazabicycloalkene compound, a crosslinking agent, and other compounding agents used as necessary in the carboxyl group-containing acrylic rubber. Are mixed and kneaded with a Banbury mixer or kneader, and then further kneaded using a kneading roll.

  The blending order of each component is not particularly limited, but after sufficiently mixing components that are difficult to react or decompose with heat, a crosslinking agent or a diazabicycloalkene compound that is easily reacted or decomposed with heat is reacted or reacted. It is preferable to mix in a short time at a temperature at which decomposition does not occur.

  Moreover, about the compound represented by the said General formula (1) among said each component, for example, it adds beforehand in a polymer latex or a polymer solution, and the compound represented by the said General formula (1) is added. The polymer latex or polymer solution obtained may be coagulated. Or you may mix | blend the compound represented by the said General formula (1) in the arbitrary steps to the process of manufacturing a final product. Specifically, it may be blended at any stage of the polymer pellet production stage, the kneading stage, or the stage of charging into the molding machine, so that it can be dispersed sufficiently uniformly in the polymer. A suitable blending time can be selected as appropriate.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) (compound Mooney) of the acrylic rubber composition of the present invention is preferably 10 to 100, more preferably 20 to 90, and further preferably 25 to 80.

<Rubber cross-linked product>
The rubber cross-linked product of the present invention is obtained by cross-linking the acrylic rubber composition of the present invention described above.
The rubber cross-linked product of the present invention uses the acrylic rubber composition of the present invention, is molded by a molding machine corresponding to a desired shape, such as an extruder, an injection molding machine, a compressor, and a roll, and heated. It can be produced by carrying out a cross-linking reaction and fixing the shape as a rubber cross-linked product. In this case, crosslinking may be performed after molding in advance, or crosslinking may be performed simultaneously with molding. The molding temperature is usually 10 to 200 ° C, preferably 25 to 120 ° C. The crosslinking temperature is usually 130 to 220 ° C, preferably 150 to 190 ° C, and the crosslinking time is usually 2 minutes to 10 hours, preferably 3 minutes to 5 hours. As a heating method, a method used for crosslinking of rubber, such as press heating, steam heating, oven heating, and hot air heating, may be appropriately selected.

  In addition, depending on the shape and size of the rubber cross-linked product, the rubber cross-linked product of the present invention may be further heated to perform secondary cross-linking. The secondary crosslinking varies depending on the heating method, crosslinking temperature, shape, etc., but is preferably performed for 1 to 48 hours. What is necessary is just to select a heating method and heating temperature suitably.

The rubber cross-linked product of the present invention thus obtained is obtained by using the above-described acrylic rubber composition of the present invention, so that the mechanical properties are improved, the heat resistance is excellent, and the high-temperature condition for a long time. Even if exposed underneath, it is possible to suppress a decrease in physical properties such as elongation.
Therefore, the rubber cross-linked product of the present invention makes use of its characteristics to provide O-rings, packings, diaphragms, oil seals, shaft seals, bearing seals, mechanical seals, well head seals, electrical / electronic equipment seals, pneumatic equipments. Various seals such as seals; cylinder head gaskets attached to the connecting part of the cylinder block and the cylinder head, rocker cover gaskets attached to the connecting part of the rocker cover and the cylinder head, oil pan and cylinder block or transmission case Oil pan gasket attached to the connecting part, fuel cell separator gasket attached between a pair of housings sandwiching a unit cell having a positive electrode, electrolyte plate and negative electrode, hard disk drive top cover gasket, etc. Gaskets; 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, riser, flow Various hoses such as lines; Various boots such as CVJ boots, propeller shaft boots, constant velocity joint boots, rack and pinion boots; Damping material rubber parts such as cushion materials, dynamic dampers, rubber couplings, air springs, vibration-proof materials; In particular, it is preferably used for extrusion products such as hoses used under severe high temperatures.

  Hereinafter, the present invention will be described more specifically with reference to compound production examples, carboxyl group-containing acrylic rubber production examples, examples, and comparative examples, but the present invention is not limited to these production examples and examples. It is not limited. In the examples, “parts” and “%” are based on weight unless otherwise specified.

(Production Example 1 of Compound) Synthesis of Compound 1 Compound 1 represented by the following formula (17) was synthesized according to the following method.

That is, first, 50.0 g (250.92 mmol) of phenothiazine was added to a three-necked reactor equipped with a thermometer in a nitrogen stream and dissolved in 200 ml of toluene. Next, to this solution, 59.31 g (501.83 mmol) of α-methylstyrene and 1.19 g (6.27 mmol) of p-toluenesulfonic acid monohydrate were added and reacted at 80 ° C. for 1 hour. . Thereafter, the reaction solution was returned to room temperature, 48 ml of acetic acid and 85.34 g (752.7 mmol) of 30% hydrogen peroxide were added, and further reacted at 80 ° C. for 2 hours. The reaction solution was returned to room temperature and then poured into 630 ml of methanol. Then, the precipitated crystals were filtered and rinsed with 320 ml of methanol to obtain 85.7 g of white crystalline compound 1 in a yield of 73%. The structure of the obtained compound 1 was identified by ¹ H-NMR. ¹ H-NMR (500 MHz, DMSO-d6, TMS, δ ppm): 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).

  The chemical structure and molecular weight of 4,4′-bis (α, α-dimethylbenzyl) diphenylamine conventionally used as an anti-aging agent used in Compound 1 synthesized in Compound Production Example 1 and Comparative Example are shown below. It is shown in Table 1.

(Production Example 1 of carboxyl group-containing acrylic rubber)
A polymerization reactor equipped with a thermometer and a stirrer was charged with 200 parts of water, 3 parts of sodium lauryl sulfate, 58 parts of ethyl acrylate, 40 parts of n-butyl acrylate, and 2 parts of mono n-butyl fumarate. Then, after depressurization and nitrogen substitution twice to sufficiently remove oxygen, 0.005 part of cumene hydroperoxide and 0.002 part of sodium formaldehydesulfoxylate were added and emulsified at a temperature of 30 ° C. under normal pressure. Polymerization was started and the reaction was continued until the polymerization conversion reached 95%. The obtained emulsion polymerization solution was coagulated with an aqueous calcium chloride solution, washed with water and dried to obtain a carboxyl group-containing acrylic rubber A. The resulting Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the carboxyl group-containing acrylic rubber A was 45. In addition, the composition of the obtained carboxyl group-containing acrylic rubber A is composed of 58% by weight of ethyl acrylate monomer unit, 40% by weight of n-butyl acrylate monomer unit, and mono n-butyl fumarate monomer. The unit was 2% by weight.

  Various physical property tests in Examples and Comparative Examples were performed according to the following methods.

(Normal physical property test)
The acrylic rubber composition was molded and crosslinked by pressing at 170 ° C. and 10 MPa for 20 minutes to produce a 15 cm × 15 cm × 2 mm sheet, which was heated at 170 ° C. for 4 hours for secondary crosslinking. A dumbbell-shaped No. 3 test piece was prepared from the sheet after the subsequent crosslinking. And the tensile strength (strength) and breaking elongation (elongation) were each measured according to the tensile test of JISK6251 as a mechanical characteristic in normal temperature using the obtained test piece. Further, the hardness was measured according to the hardness test of JIS K6253.

(Heat resistance test)
The heat resistance test was carried out by using a test piece that had been heat aged by heating a test piece prepared in the same manner as the test for the above-mentioned normal physical property under a condition of 190 ° C. for 500 hours. Specifically, first, the elongation before and after heating was measured according to JIS K6251, and the rate of change in elongation was measured by calculating the rate of change according to the following formula. It is judged that the heat resistance is higher as the elongation change rate is closer to zero, and a preferable result is obtained.
Elongation change rate (%) = 100 × [(Elongation after heating (%)) − (Elongation before heating (%))] / (Elongation before heating (%))

Example 1
100 parts by weight of the carboxyl group-containing acrylic rubber A obtained in Production Example 1 of the carboxyl group-containing acrylic rubber described above, 60 parts by weight of carbon black (manufactured by Tokai Carbon Co., Ltd., Seast SO), 2 parts by weight of stearic acid, and the above-described compounds After kneading 2.0 parts by weight of Compound 1 (anti-aging agent) obtained in Production Example 1 at 50 ° C. for 5 minutes using a 0.8 liter Banbury, 2,2-bis [4- (4-Aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., BAPP) 1 part by weight, and 1,8-diazabicyclo [5.4.0] undec-7-ene (manufactured by Rhein Chemie, Rhenogran XLA-60; DBU 60% (including DBU zinc dialkyl diphosphate salt), acrylic polymer With addition of dispersants 40%) 2 parts by weight were kneaded in an open roll of 50 ° C., to prepare an acrylic rubber composition. And using the obtained acrylic rubber composition, according to the said method, elongation change rate was measured as a test of a normal physical property, and a heat resistance test. The results are shown in Table 2.

(Comparative Example 1)
Instead of compound 1 (anti-aging agent), 4,4′-bis (α, α-dimethylbenzyl) diphenylamine (anti-aging agent, manufactured by Chemtura Corp., Nowguard 445) was used, and the amount added was 2.0 parts. Except that, an acrylic rubber composition was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 2.

(Comparative Example 2)
Instead of 1,8-diazabicyclo [5.4.0] undec-7-ene, dialkyl (C8-18) amine (Armin 2C manufactured by Lion Akzo) was used as a crosslinking accelerator, and the blending amount was 2 An acrylic rubber composition was obtained and evaluated in the same manner as in Comparative Example 1 except that the content was 0.0 parts. The results are shown in Table 2.

(Comparative Example 3)
An acrylic rubber composition was obtained and evaluated in the same manner as in Comparative Example 2 except that the blending amount of carbon black was changed to 65 parts. The results are shown in Table 2.

  As shown in Table 2, in Example 1 using the compound 1 according to the present invention as an anti-aging agent, even under severe conditions of 500 hours in an environment of 190 ° C., compared with Comparative Examples 1 to 3, The elongation change rate is close to 0 and the change in elongation is small. Moreover, Example 1 which uses a diazabicycloalkene compound as a crosslinking accelerator increases the hardness of the rubber crosslinked product as compared with Comparative Example 2 which uses a dialkyl (C8-18) amine as a crosslinking accelerator. Therefore, it was confirmed that the rubber cross-linked product using the acrylic rubber composition of the present invention has improved heat resistance in a heat resistance test while improving mechanical properties, particularly hardness. In Comparative Example 3, compared to Comparative Example 2, it is possible to increase the hardness of the rubber cross-linked product by increasing the amount of carbon black, but in that case, the residual elongation after the heat resistance test is reduced. The heat resistance was inferior.

Claims (8)

0.1 to 10 parts by weight of a compound represented by the following general formula (1), 0.1 to 20 parts by weight of a diazabicycloalkene compound, and 0.05 to An acrylic rubber composition containing 20 parts by weight.

(In the general formula (1), Y represents a chemical single bond or —SO ₂ —. R ^a and R ^b are each independently selected from an alkyl group, a cycloalkyl group, an aryl group, and an alkoxy group. Represents an organic group having 1 to 30 carbon atoms that, when the organic groups are alkyl, alkoxy, alkyl group or phenyl group which may have a chlorine atom as a substituent, a halogen atom, nitro group or When the organic group is a cycloalkyl group or an aryl group, the organic group may be substituted with an alkyl group, an alkoxy group, a halogen atom, a nitro group, or a cyano group. when the alkoxy group, a halogen atom, each good .Z ^a and Z ^b be substituted by nitro group or a cyano group independently, chemical Bond or -SO ₂ - .n and m represents a are each independently 0 or 1, at least one of n and m is 1). The acrylic rubber composition according to claim 1, wherein the organic group is an alkyl group having 2 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms. In the compounds represented by the general formula (1), Y -SO ₂ -, as described above, and said organic group is a linear or branched alkyl group or a phenyl group having 2 to 8 carbon atoms, Z ^a and The acrylic rubber composition according to claim 1 or 2 , wherein ^Zb is a chemical single bond, and n and m are 1. The acrylic rubber composition according to any one of claims 1 to 3, wherein the organic group is an α-methylbenzyl group, an α, α-dimethylbenzyl group, a t-butyl group, a phenyl group, or a 4-methylphenyl group. object. The acrylic rubber according to any one of claims 1 to 4, wherein the carboxyl group-containing acrylic rubber contains 0.1 to 10% by weight of an α, β-ethylenically unsaturated carboxylic acid monomer unit. Composition. The acrylic rubber composition according to any one of claims 1 to 5, wherein the crosslinking agent is a polyvalent amine compound or a carbonate of a polyvalent amine compound. A crosslinked rubber product obtained by crosslinking the acrylic rubber composition according to any one of claims 1 to 6 . The crosslinked rubber product according to claim 7 , which is an extruded product.