JP2019206602A - Polyamine-vulcanizable carboxyl group-containing hydrogenated nitrile rubber composition for sliding seal member - Google Patents

Abstract

SOLUTION: The polyamine-vulcanizable carboxyl group-containing hydrogenated nitrile rubber composition for a sliding seal member contains, based on 100 pts.wt. of a polyamine-vulcanizable carboxyl group-containing hydrogenated nitrile rubber, 0.1 to 5 pts.wt. of a polyamine compound as a vulcanizer, 35 to 75 pts.wt. of silica, 0.1 to 10 pts.wt. of an epoxy-based, glycidoxy-based, methacryloxy-based, amino-based, mercapto-based or isocyanate-based silane coupling agent, and an aliphatic carboxylic acid diester compound of polyalkylene glycol as a plasticizer as represented by the general formula: RCOO(CHO)COR(in which Rand Rare each independently a C-Calkyl group or alkenyl group; n is an integer of 2 to 4; and m is an integer of 2 to 30) in an amount of the plasticizer as represented by Y which is in the range of 6X-132≤Y≤31 (provided that X is an acrylonitrile content in the polyamine-vulcanizable carboxyl group-containing hydrogenated nitrile rubber and is defined as 0 in the case when 6X-132 is a minus value).SELECTED DRAWING: None

Description

  The present invention relates to a polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubber composition for sliding seal members. More specifically, a polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubber composition for sliding seal members with improved compression set resistance while having low temperature and wear resistance equivalent to conventional hydrogenated nitrile rubber materials Related to things.

  For example, hydrogenated nitrile rubber may be used in packing materials used for automobile clutch actuators from the viewpoints of heat resistance, wear resistance, oil resistance (for hydraulic operation), cost, and the like.

  Due to the influence of the common use of automotive parts in recent years, the operating temperature range required for packing materials has been widened, and there are cases where conventional hydrogenated nitrile rubber materials cannot satisfy customer requirements. In particular, there is a need for improved compression set resistance at high temperatures that affect sealability. Furthermore, the low temperature property equivalent to hydrogenated nitrile rubber material is also calculated | required.

  In addition, there are many cases where silica, which is white carbon, is blended as a filler from the viewpoint of the degree of freedom in coloring. Generally, white carbon blends into the packing material as it is because it deteriorates wear resistance. There are difficulties to do.

  Patent Document 1 contains a filler per 100 parts by weight of a carboxyl group-containing highly saturated nitrile rubber containing 5 to 60% by weight of an α, β-ethylenically unsaturated nitrile monomer unit and having an iodine value of 120 or less. A nitrile rubber composition containing 100 parts by weight or more and less than 200 parts by weight is described. This nitrile rubber composition is a rubber having excellent normal physical properties, compression set resistance and sour gasoline resistance, and small permanent elongation. It is described as giving a cross-linked product.

  Here, as the filler, it is preferable to use silica and a non-reinforcing white filler in combination, and in that case, the amount of silica is preferably less than the amount of non-reinforcing white filler, The mixing ratio of silica: non-reinforcing white filler is preferably 1:37 to 10: 9, more preferably 1:13 to 1: 4.

  In fact, in each of the examples, 20 parts by weight of silica and 80 parts by weight of clay are used with respect to 100 parts by weight of carboxyl group-containing nitrile rubber, and the compression set value is improved. There is no mention of wear resistance.

WO 2016/148055 A1 JP 2008-179671 A JP 2010-106113 A WO 2005/103143 A1 WO 2008/038465 A1

  An object of the present invention is to provide a polyamine vulcanizable carboxyl group-containing hydrogenated nitrile for sliding seal members that has improved compression set resistance while having low temperature and wear resistance equivalent to those of conventional hydrogenated nitrile rubber materials. The object is to provide a rubber composition.

The object of the present invention is to provide 0.1 to 5 parts by weight of a polyamine compound vulcanizing agent, 35 to 75 parts by weight of silica, 100 parts by weight of a polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubber, epoxy-based, glycidoxy-based, methacloxy-based Amino, mercapto or isocyanate silane coupling agent 0.1-10 parts by weight and general formula
R ¹ COO (C _n H _2n O) _m COR ²
Wherein R ¹ and R ² are each independently a C _{1 to} C ₁₄ alkyl group or alkenyl group, n is an integer of 2 to 4, and m is an integer of 2 to 30. Polyalkylene glycol aliphatic carboxylic acid diester compound plasticizer when the plasticizer amount is Y
6X-132 ≦ Y ≦ 31
(Where X is the content of acrylonitrile in the polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubber, and 0 when 6X-132 is negative). This is achieved by the sulfurized carboxyl group-containing hydrogenated nitrile rubber composition.

  The nitrile rubber obtained by vulcanizing the polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubber composition for sliding seal members according to the present invention has low temperature and wear resistance equivalent to those of conventional hydrogenated nitrile rubber materials. On the other hand, since the compression set resistance is improved, it can be effectively used as a sliding seal member for an actuator packing of an automobile clutch.

  α, β-ethylenically unsaturated nitrile monomer unit, diene monomer unit, α, β-ethylenically unsaturated dicarboxylic acid monoester monomer unit and other α, β-ethylene as optional components Having an unsaturated carboxylic acid ester monomer unit and an α, β-ethylenically unsaturated nitrile monomer unit content of 10 to 60% by weight, preferably 15 to 55% by weight, particularly preferably 20 to 50% by weight %, For example, 34% by weight, and polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubber having an iodine value of 120 or less is described in, for example, Patent Documents 2-3.

  The α, β-ethylenically unsaturated nitrile monomer unit is not particularly limited as long as it is an α, β-ethylenically unsaturated compound having a nitrile group. For example, acrylonitrile and its α-position is a chloro group or a bromo group. Specific α-halogenoacrylonitrile, methacrylonitrile whose α-position is an alkyl group, and the like can be mentioned, and acrylonitrile or methacrylonitrile is preferably used.

  In the present invention, the α, β-ethylenically unsaturated nitrile monomer unit is 20 to 30% by weight, preferably 20 to 25% by weight in the polyamine vulcanizable highly saturated nitrile rubber.

Diene monomer units are 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, C ₄ ~ such as 1,4-hexadiene It is derived from a C ₁₂ conjugated or non-conjugated diene monomer, preferably a conjugated diene monomer, more preferably 1,3-butadiene.

These diene monomer units include C _{2 to} C ₁₂ α-olefin units such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene as optional components. It can be used together with a monomer unit.

  The diene monomer unit or the α-olefin monomer unit is 20 to 78.8% by weight, preferably 30 to 78.7% by weight, more preferably 40 to 40% in the polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubber. 78.4% by weight. If diene monomer units and the like are used in a smaller proportion, the rubber elasticity of the rubber vulcanizate may be reduced. On the other hand, if it is too much, heat resistance and chemical stability may be impaired. is there.

As the α, β-ethylenically unsaturated dicarboxylic acid monoester monomer unit, C ₁ -C ₁₀ , preferably C ₂ -C ₆ monoalkyl ester such as maleic acid, fumaric acid, citraconic acid, itaconic acid, C ₅ -C _12, preferably mono-cycloalkyl ester of _{C 6 ~C 10, C 6 ~C} 12, preferably include mono (alkyl-substituted cycloalkyl) esters of C ₇ -C ₁₀ is, more preferably maleic Examples thereof include monopropyl ester or mono n-butyl ester of acid, fumaric acid or citraconic acid, and maleic acid mono n-butyl ester is particularly preferred.

  These α, β-ethylenically unsaturated dicarboxylic acid monoester monomer units are 0.1 to 20% by weight, more preferably 0.2 to 15% by weight, particularly preferably in the polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubber. 0.5 to 10% by weight. If α, β-ethylenically unsaturated dicarboxylic acid monoester monomer units are used in a smaller proportion than this, the carboxyl groups necessary for amine vulcanization will be insufficient, and the tensile stress of the vulcanizate will be reduced. On the other hand, if it is used in a proportion higher than this, it will cause deterioration of the scorch stability of the vulcanizable carboxyl group-containing hydrogenated nitrile rubber composition, decrease in fatigue resistance of the vulcanizate, etc. .

In the present invention, polyamine vulcanizability preferably having an α, β-ethylenically unsaturated dicarboxylic acid monoester monomer unit and another α, β-ethylenically unsaturated carboxylic acid ester monomer unit. carboxyl group-containing hydrogenated nitrile rubber is used, such as the monomer unit having an alkyl group of C ₁ -C ₈ (meth) alkoxyalkyl group of the alkyl acrylate monomer units and C ₂ -C ₈ Examples thereof include at least one of (meth) acrylic acid alkoxyalkyl ester monomer units having and a diester monomer unit corresponding to the α, β-ethylenically unsaturated dicarboxylic acid monoester.

  These α, β-ethylenically unsaturated carboxylic acid ester monomer units are 30 wt% or less, preferably 20 wt% or less, particularly preferably 0.1 to 10 wt% in the polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubber. % Is used.

  As the polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubber comprising these monomer units, those having an iodine value of 120 or less, preferably 80 or less, more preferably 25 or less, particularly preferably 15 or less are used. It is done. If an iodine value indicating a decrease in saturation due to hydrogenation is used, the ozone resistance of the vulcanizate is impaired.

  Each of the above monomer units, that is, α, β-ethylenically unsaturated nitrile monomer unit, diene monomer unit, α, β-ethylenically unsaturated dicarboxylic acid monoester monomer unit, and other Polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubber having an α, β-ethylenically unsaturated carboxylic acid ester monomer unit as an essential monomer unit and an iodine value of 120 or less, and other α, A commercially available product that does not copolymerize the β-ethylenically unsaturated carboxylic acid ester monomer unit can be used as it is. For example, as the polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubber made of the former quaternary copolymer, Nippon Zeon products such as Zetpol 3710, Zetpol 3610, etc., and the polyamine vulcanization made of the latter ternary copolymer are used. As the hydrogenated nitrile rubber containing sulfur carboxyl groups, the company's product Zetpol 2510 is used as it is.

  These polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubbers are vulcanized with a polyamine compound vulcanizing agent as described in Patent Document 4. Examples of the polyvalent amine compound include hexamethylene diamine, its carbamate, benzoate or cinnamaldehyde adduct, aliphatic diamine such as diamino-modified siloxane, 4,4'-methylenebiscyclohexylamine or its cinnamaldehyde adduct, bis (4- (Amino-3-methyldicyclohexyl) alicyclic diamine such as methane, 4,4'-methylenedianiline, p, p'-ethylenedianiline, m- or p-phenylenediamine, 3,4'-diaminodiphenyl ether, 4 , 4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4 '-(m- or p-phenylenediisopropylidene) dianiline, 2,2-bis [4- (4-aminophenoxy) phenyl] Propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, biphenyl [4- (3-aminophenoxy) phenyl] sulfone, 4,4′-bis (4-aminophenoxy) biphenol, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- ( 4-Aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene and the like, preferably aromatic diamines More preferably, p-substituted aromatic diamines are used. These polyvalent amine compound vulcanizing agents are used at a ratio of about 0.1 to 5 parts by weight, preferably about 0.2 to 4 parts by weight, based on 100 parts by weight of the quaternary or ternary polymer, and less than this. When used, vulcanization becomes insufficient, and sufficient compression set resistance characteristics cannot be obtained.

  In order to improve the compression set resistance of quaternary or ternary polymers, 1,8-diazabicyclo [5.4.0] undecene-7 (salt) or 1,5-diazabicyclo [4.3 .0] A method of using a nonene (salt) vulcanization accelerator in combination, a method of using a mercaptobenzimidazole in addition to this vulcanization system, and an aromatic diamine compound vulcanizing agent and a guanidine compound vulcanizing aid in combination. Further, a method of using a benzothiazolylsulfenamide-based compound vulcanization accelerator in combination with this vulcanization system may be employed as appropriate.

The quaternary or ternary polymer has a general formula as a plasticizer from the viewpoint of cold resistance.
R ¹ COO (C _n H _2n O) _m COR ²
R ¹ and R ² : each independently a C _{1 to} C ₁₄ alkyl group or alkenyl group
n: Integer from 2 to 4
m: An aliphatic carboxylic acid diester compound of polyalkylene glycol represented by an integer of 2 to 30 is added.

Such aliphatic carboxylic acid diester compounds of polyalkylene glycol are described in Patent Document 5, and the following compounds are exemplified. After the compound name, the corresponding commercial product name is written in parentheses. Polyethylene glycol is abbreviated as PEG, polypropylene glycol is abbreviated as PPG, and polytetramethylene glycol is abbreviated as PTMG.
PEG (MW200) diheptanoate
PEG (MW300) di-2-ethylhexanoate (Adeka product RS700)
PEG (MW600) di-2-ethylhexanoate (manufactured by RS735)
PEG (MW1000) Didecanoate
PEG (MW300) Didecanoate
PEG (MW600) heptanoate / dodecanoate (equal mixture)
PPG (MW400) Diheptanoate
PTMG (MW600) di-2-ethylhexanoate
PEG / PPG equivalent mixture (MW600) diheptanoate

  Patent Document 5 describes that an aliphatic carboxylic acid diester compound of polyalkylene glycol is blended with a polyester resin as a crystallization accelerator together with a metal salt of a sulfonic acid amide compound.

  The aliphatic carboxylic acid diester compound of polyalkylene glycol is used in a proportion of 0 to 31 parts by weight, preferably 0 to 20 parts by weight, more preferably 5 to 15 parts by weight per 100 parts by weight of the quaternary or ternary polymer. It is done. If the ratio is more than this, the low temperature characteristics are improved, but the wear resistance (and compression set resistance characteristics) are deteriorated.

Here, when the AN content of the polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubber is X, the plasticizer amount Y is 0 to 31 parts by weight and from the data of each Example and Comparative Example described later,
6X-132 ≦ Y ≦ 31 (however, when 6X-132 is negative, it is 0)
It is set in the range. When the amount of plasticizer is used in a range larger than this, the amount of wear or the value of compression set is increased.

Silica can be produced by a thermal decomposition method of halogenated silicon or organosilicon compounds, a dry method produced by heat reduction of silica sand and air oxidation of evaporated SiO, etc., a thermal decomposition method of white carbon, sodium silicate It is possible to use amorphous silica such as a wet method white carbon produced by the above method, preferably having a particle diameter of 0.01 to 0.1 μm. If the particle size of the silica is larger than this, the wear resistance is deteriorated. On the other hand, if the particle size of the silica is smaller, the particles are aggregated and become larger when the silica is dispersed in the rubber, and the wear resistance is also deteriorated. To come. Further, a specific surface area of about 20 to 300 m ² / g, preferably of about 50 to 250 m ² / g are generally used. White carbon is inferior in wear resistance compared to commonly used carbon black due to its price, handleability and good wear resistance. Prevents rubber flow at surface pressure. As such silica, commercially available products such as Tosoh silica product Nipsil ER can be used as they are.

  Silica is used in a proportion of 35 to 75 parts by weight, preferably 40 to 65 parts by weight, per 100 parts by weight of the hydrogenated nitrile rubber. If silica is used at a lower ratio, the rubber layer will be peeled off at the time of friction and wear. On the other hand, if it is used at a higher ratio, rubber hardness will be higher and rubber elasticity will be lost. Become.

  Here, silica tends to agglomerate particles due to hydrogen bonding of silanol groups, which are surface functional groups. Therefore, in order to improve the dispersion of silica particles in rubber, it is necessary to increase the kneading time. It is. In addition, the silica surface is hydrophilic due to its silanol group characteristics, while rubber is oleophilic, so the rubber compounds that repel each other and have been left for a long time have reduced solubility in solvents and silica. Causes aggregation. As a result, wear resistance may be reduced.

Therefore, in order to prevent such agglomeration of silica, a specific silane coupling agent is preferably blended during silica kneading. The silica surface is treated with a silane coupling agent to prevent its aggregation. In general, the silane coupling agent XSi (OR) ₃ used in the rubber industry is composed of alkoxy groups that react with inorganic materials such as silica and functional groups that react with organic materials such as rubber. By dehydration condensation reaction with silanol group generated by hydrolysis of alkoxy group of silane coupling agent, that is, coupling reaction of silica and silane coupling agent, silanol group on silica particle surface is reduced and dispersion in rubber is reduced. In addition to the improvement, the silane coupling agent and the rubber molecule are chemically bonded to form a reinforcing structure by a gelation reaction between the other functional group of the silane coupling agent and the rubber molecule.

  Examples of silane coupling agents include epoxy-based, glycidoxy-based, methacryloxy-based, amino-based, mercapto-based, and isocyanate-based agents such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethyl. Methoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane , Γ-methacryloxypropylmethyldiethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-amino Propyltrimethoxysilane, γ-mercapto B pills trimethoxysilane, .gamma.-aminopropyltriethoxysilane, .gamma. isocyanatepropyltriethoxysilane and the like. Vinyl-based silane coupling agents are inferior in compression set value and are not suitable for sliding seal members.

  These silane coupling agents are used in a proportion of 0.1 to 10.0 parts by weight, preferably 1.0 to 3.0 parts by weight, per 100 parts by weight of hydrogenated nitrile rubber. If the silane coupling agent is used in a smaller proportion, there is agglomeration of silica and the wear resistance may be impaired. On the other hand, if the silane coupling agent is used in a larger proportion, the crosslinking density of the rubber is increased, and the sealing property is increased. Cracking occurs due to deterioration and bending after heat aging, and wear resistance after heat deterioration deteriorates. Also, a decrease in mechanical strength is observed.

  In addition to the above components, the polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubber composition for sliding seal members is prepared in addition to other compounding agents commonly employed in the case of hydrogenated nitrile rubber polymers, such as carbon black. A reinforcing agent or filler other than silica, such as, a lubricant, a processing aid, etc. is appropriately added, and kneading is performed using a closed kneader, a roll, etc. According to the vulcanization conditions of the vulcanizable carboxyl group-containing hydrogenated nitrile rubber composition, about 100 to 200 ° C, preferably about 130 to 200 ° C, more preferably about 150 to 200 ° C, about 30 seconds to 5 hours, preferably Is performed by press vulcanization for about 3 to 10 minutes and oven vulcanization (secondary vulcanization) for about 0.5 to 24 hours at about 150 to 200 ° C., which is performed as necessary.

  Next, the present invention will be described with reference to examples.

Example 1
Carboxyl group-containing hydrogenated nitrile rubber 100 parts by weight
(Nippon Zeon product Zetpol 3710; AN content 23.6% by weight)
Silica (Tosoh silica product E74P) 50 〃
γ-Aminopropyltriethoxysilane 1 〃
(Shin-Etsu Chemical Product KBE-903)
Polyether ester plasticizer (Adeka product RS700) 15 〃
Polyamine vulcanizing agent (Dupont product Diak No.1, 2.7 〃
(Hexamethylenediamine carbamate)
Vulcanization accelerator (Lanxess product XLA-60, active ingredient 4 〃
1,8-diazabicyclo [5.4.0] -7-undecene)
Processing aid (Toho Chemical Product Phosphanol RL210) 1 〃
The above components were kneaded with a kneader and an open roll, and the kneaded product was subjected to primary vulcanization at 170 ° C. for 20 minutes, and then oven vulcanized (secondary vulcanization) at 174 ° C. for 4 hours.

About the obtained vulcanizate, the following each item was measured and evaluated.
Abrasion resistance: JIS K6264 compliant, Taber abrasion test
Test temperature Room temperature
Whetstone H-18
Load 9.8N
Rotation speed 60rpm
Number of tests 1000 rotations (preliminary shear 1000 rotations)
(Evaluation) ◎: less than 150mm ³
○: 150 mm ³ or more, less than 200 mm ³
×: 200 mm ³ or more Compression set: Compliant with JIS K6262, compression set test
Specimen JIS large specimen (29mm diameter x 12.5mm)
Compression rate 25%
Test temperature 150 ℃
Test time 1000 hours
(Evaluation) A: Less than 35%
○: 35% or more, less than 45%
×: 45% or more Low temperature: JIS K6261 compliant, TR test
(Evaluation) ◎: TR-10 value less than -35 ℃
○: TR-10 value -35 ℃ or more, less than -30 ℃
× ： TR-10 value -30 ℃ or more

Example 2
In Example 1, the amount of the polyether ester plasticizer was changed to 30 parts by weight.

Example 3
In Example 1, the amount of silica was changed to 65 parts by weight.

Example 4
In Example 1, as a carboxyl group-containing hydrogenated nitrile rubber, the same amount (100 parts by weight) of Zetpol 3610 (AN content 20.5% by weight) of Nippon Zeon was used instead of Zetpol 3710, and the amount of polyether ester plasticizer was Changed to 10 parts by weight.

Example 5
In Example 4, the polyether ester plasticizer was not used.

Example 6
In Example 5, the amount of silica was changed to 40 parts by weight.

Example 7
In Example 1, in place of γ-aminopropyltriethoxysilane, the same amount (15 parts by weight) of γ-isocyanatopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd. KBE-9007) was used.

Example 8
In Example 1, the same amount (15 parts by weight) of γ-glycidoxypropyltriethoxysilane (Shin-Etsu Chemical Product KBE-403) was used instead of γ-aminopropyltriethoxysilane.

Example 9
In Example 1, the same amount (15 parts by weight) of γ-methacryloxypropyltriethoxysilane (Shin-Etsu Chemical Product KBE-503) was used instead of γ-aminopropyltriethoxysilane.

Example 10
In Example 1, instead of γ-aminopropyltriethoxysilane, the same amount (15 parts by weight) of γ-mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-803) was used.

Example 11
In Example 4, the amount of the polyether ester plasticizer was changed to 30 parts by weight, and the amount of silica was changed to 70 parts by weight.

Example 12
In Example 1, as the carboxyl group-containing hydrogenated nitrile rubber, a blend of Zetpol 3710 80 parts by weight and Nippon Zeon product Zetpol 2510 (AN content 35.2% by weight) 20 parts by weight (AN content 25.92% by weight) was used. The amount of ether ester plasticizer was changed to 25 parts by weight.

Comparative Example 1
In Example 1, in place of the carboxyl group-containing hydrogenated nitrile rubber, the same amount (100 parts by weight) of a carboxyl group-free hydrogenated nitrile rubber (Nippon Zeon product Zetpol 3300, AN content 23.6% by weight) was used. Instead of the vulcanization system, a peroxide cross-linking system (4 parts by weight of Japanese oil and fat product Perbutyl P, 2 parts by weight of Mitsubishi Rayon product acrylic ester TMP) was used, and no polyether ester plasticizer was used.

Comparative Example 2
In Comparative Example 1, the amount of silica was changed to 35 parts by weight.

Comparative Example 3
In Comparative Example 1, 35 parts by weight of a polyether ester plasticizer was further used.

Comparative Example 4
In Example 1, the amount of the polyether ester plasticizer was changed to 35 parts by weight, and the amount of silica was changed to 70 parts by weight.

Comparative Example 5
In Example 4, the amount of polyether ester plasticizer was changed to 35 parts by weight, and the amount of silica was changed to 70 parts by weight.

Comparative Example 6
In Example 1, the amount of the polyether ester plasticizer was changed to 5 parts by weight.

Comparative Example 7
In Example 12, the amount of the polyetherester plasticizer was changed to 15 parts by weight, and the amount of silica was changed to 40 parts by weight.

Comparative Example 8
In Example 1, instead of γ-aminopropyltriethoxysilane, the same amount (15 parts by weight) of vinyltriethoxysilane (Shin-Etsu Chemical Co., Ltd. KBE-1003) was used.

Comparative Example 9
In Example 1, no silane coupling agent was used.

The results obtained in the above examples and comparative examples are shown in the following table.

table
Abrasion resistance Compression set Low temperature resistance
Example Wear (mm ³ ) Evaluation CS (%) Evaluation TR-10 (° C) Evaluation Example 1 133 ◎ 31 ◎ -32 ○
〃 2 198 ○ 41 ○ -36 ◎
３ 3 191 ○ 42 ○ -36 ◎
４ 4 116 ◎ 28 ◎ -36 ◎
５ 5 82 ◎ 22 ◎ -32 ○
〃 6 88 ◎ 22 ◎ -32 ○
〃 7 137 ◎ 31 ◎ -32 ○
８ 8 140 ◎ 32 ◎ -32 ○
〃 9 165 ○ 33 ◎ -33 ○
〃 10 190 ○ 33 ◎ -33 ○
〃 11 198 ○ 41 ○ -41 ◎
〃 12 180 ○ 39 ○ -31 ○
Comparative Example 1 86 ◎ 24 ◎ -27 ×
〃 2 88 ◎ 23 ◎ -27 ×
〃 3 238 × 45 × -37 ◎
４ 4 231 × 46 × -37 ◎
５ 5 217 × 44 ○ -42 ◎
６ 6 103 ◎ 26 ◎ -28 ×
〃 7 142 ◎ 32 ◎ -28 ×
８ 8 185 ○ 49 × -37 ◎
９ 9 223 × 46 × -33 ○

From this result, the following can be said.
(1) When silica is used in the range of 35 to 75 parts by weight, it ensures wear resistance, compression set, and low temperature properties while ensuring appropriate mechanical strength, kneading processability and molding processability (each Example).
(2) When a peroxide crosslinking system is used instead of the polyamine vulcanizing system, the low temperature property is impaired (Comparative Examples 1 to 3).
(3) The ester plasticizer is used in the range of 0 to 31 parts by weight, and if it is used in a proportion higher than this, the amount of wear (and compression set) increases, and the hydrogenated nitrile rubber for sliding seal members Not suitable for the composition (Comparative Examples 4 to 5).
(4) When the plasticizer amount Y is used in a range that does not satisfy the value of 6X-132 with respect to the acrylonitrile content X in the hydrogenated nitrile rubber, the low temperature property becomes inferior (Comparative Examples 6 to 7).
(5) Silane coupling agents are limited to epoxy-based, glycidoxy-based, methacryloxy-based, amino-based, mercapto-based, and isocyanate-based ones. Vinyl-based ones are inferior in compression set value and are used for sliding seal members. Is unsuitable (Comparative Example 8).

Claims (3)

Polyamine compound vulcanizing agent, 0.1 to 5 parts by weight, 35 to 75 parts by weight of silica, epoxy, glycidoxy, metacloxy, amino, mercapto or isocyanate per 100 parts by weight of polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubber -Based silane coupling agent 0.1-10 parts by weight and general formula
R ¹ COO (C _n H _2n O) _m COR ²
Wherein R ¹ and R ² are each independently a C _{1 to} C ₁₄ alkyl group or alkenyl group, n is an integer of 2 to 4, and m is an integer of 2 to 30. Polyalkylene glycol aliphatic carboxylic acid diester compound plasticizer when the plasticizer amount is Y
6X-132 ≦ Y ≦ 31
(Where X is the content of acrylonitrile in the polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubber, and 0 if 6X-132 is negative). A sulfurized carboxyl group-containing hydrogenated nitrile rubber composition.   The polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubber composition for a sliding seal member according to claim 1, which is used as a vulcanization molding material for a packing material used in an actuator of an automobile clutch.   A packing material used for an actuator of an automobile clutch obtained by vulcanizing and molding the polyamine vulcanizable carboxyl group-containing hydrogenated nitrile rubber composition for a sliding seal member according to claim 2.