(19)
(11)EP 3 272 807 A1

(12)EUROPEAN PATENT APPLICATION
published in accordance with Art. 153(4) EPC

(43)Date of publication:
24.01.2018 Bulletin 2018/04

(21)Application number: 16768519.7

(22)Date of filing:  14.03.2016
(51)International Patent Classification (IPC): 
C08L 33/08(2006.01)
F16F 15/08(2006.01)
C08L 25/04(2006.01)
(86)International application number:
PCT/JP2016/057938
(87)International publication number:
WO 2016/152616 (29.09.2016 Gazette  2016/39)
(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
Designated Extension States:
BA ME
Designated Validation States:
MA MD

(30)Priority: 20.03.2015 JP 2015057622

(71)Applicant: NOK Corporation
Minato-ku Tokyo 105-8585 (JP)

(72)Inventor:
  • NEGAMI Tetsuro
    Saihaku-gun Tottori 683-0362 (JP)

(74)Representative: Adam, Holger 
Kraus & Weisert Patentanwälte PartGmbB Thomas-Wimmer-Ring 15
80539 München
80539 München (DE)

  


(54)ACRYLIC RUBBER COMPOSITION


(57) An acrylic rubber composition comprising 5 to 80 parts by weight, preferably 10 to 60 parts by weight, more preferably 20 to 40 parts by weight, of a styrene-based resin, based on 100 parts by weight of acrylic rubber. A vibration insulation member having an excellent tan δ value at a high temperature and improved vibration insulation properties can be molded by adding a specific ratio of a styrene-based resin to acrylic rubber. This acrylic rubber composition can be effectively used as a molding material for a mount, a grommet, or the like in the vicinity of an automobile engine used in a high temperature environment.


Description

TECHNICAL FIELD



[0001] The present invention relates to an acrylic rubber composition. More particularly, the present invention relates to an acrylic rubber composition that can form a member having excellent vibration insulation properties at a high temperature.

BACKGROUND ART



[0002] Conventional rubber materials have a tendency that tan δ is likely to decrease at a high temperature and vibration insulation effects are impaired. Acrylic rubber is used as a molding material of a vibration insulation member for a mount, a grommet, or the like in the vicinity of an automobile engine used in a high temperature environment; however, the same tendency is also observed in this case. There is a demand for improving this tendency.

PRIOR ART DOCUMENT


PATENT DOCUMENT



[0003] Patent Document 1 : JP-A-11-158343

OUTLINE OF THE INVENTION


PROBLEM TO BE SOLVED BY THE INVENTION



[0004] An object of the present invention is to provide an acrylic rubber composition that is effectively used, for example, as a molding material of a vibration insulation member having a high tan δ value at a high temperature and excellent vibration insulation properties.

MEANS FOR SOLVING THE PROBLEM



[0005] The above object of the present invention can be achieved by an acrylic rubber composition comprising 5 to 80 parts by weight, preferably 10 to 60 parts by weight, more preferably 20 to 40 parts by weight, of a styrene-based resin, based on 100 parts by weight of acrylic rubber.

EFFECT OF THE INVENTION



[0006] A vibration insulation member having an excellent tan δ value at a high temperature and improved vibration insulation properties can be molded by adding a specific ratio of a styrene-based resin to acrylic rubber. This acrylic rubber composition can be effectively used as a vibration insulation molding material for a mount, a grommet, or the like in the vicinity of an automobile engine used in a high temperature environment.

EMBODIMENTS FOR CARRYING OUT THE INVENTION



[0007] Acrylic rubber is obtained by emulsion polymerization or suspension polymerization of at least one of an acrylic acid ester and a methacrylic acid ester with a crosslinkable group-containing vinyl monomer (see Patent Document 1).

[0008] As the ester of acrylic acid or methacrylic acid, an alkyl ester having 1 to 8 carbon atoms or an alkoxy alkyl ester having 2 to 8 carbon atoms is generally used. For example, at least one of methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, and their corresponding methacrylates is used; preferably at least one of ethyl acrylate, n-butyl acrylate, and 2-methoxyethyl acrylate is used. In particular, when at least one of ethyl acrylate and n-butyl acrylate is used at a ratio of about 30 wt.% or more, preferably about 50 to 99 wt.%, in the copolymerization reaction, not only mechanical properties but also heat resistance will be increased. Therefore, it is desirable to properly use these esters, also in consideration of low temperature characteristics.

[0009] Examples of the crosslinkable group-containing vinyl monomer to be copolymerized with such a (meth)acrylic acid ester are listed below. A reactive halogen-containing vinyl monomer or an epoxy group-containing monomer is preferably used. Crosslinking using such a crosslinkable group is performed using a crosslinking agent described below; however, vulcanization of an acrylic rubber composition prepared by adding a styrene-based resin to such crosslinkable group-containing acrylic rubber is preferably performed using sulfur or a sulfur-containing vulcanization accelerator, as described later.

[0010] Reactive halogen group-containing vinyl monomer:

2-chloroethyl vinyl ether, vinyl chloroacetate, vinyl α-chloropropionate, allyl chloroacetate, chloroethyl acrylate, chloromethyl styrene, etc.



[0011] A copolymer of such a monomer is crosslinked by a crosslinking agent, such as polyamine (e.g., diethylenetriamine), polycarbamate, or the like.

[0012] Epoxy group-containing vinyl monomer:

vinyl glycidyl ether, allyl glycidyl ether, glycidyl (meth)acrylate, etc.



[0013] A copolymer of such a monomer is crosslinked by a crosslinking agent, such as polyamine (e.g., diethylenetriamine or m-phenylenediamine), polycarboxylic acid (e.g., adipic acid), acid anhydride (e.g., phthalic anhydride or maleic anhydride), polyamide, sulfonamide, or the like.

[0014] Hydroxyl group-containing vinyl monomer:

hydroxyalkyl (meth)acrylate, hydroxyalkoxy acrylate, N-methylolacrylamide, etc.



[0015] A copolymer of such a monomer is crosslinked by a crosslinking agent, such as polyisocyanate (e.g., hexamethylene diisocyanate or a blocked isocyanate thereof), polycarboxylic acid (e.g., adipic acid), alkoxymethyl melamine (e.g., methoxymethyl melamine), or the like.

[0016] Amide group-containing vinyl monomer:

acrylamide, methacrylamide, etc.



[0017] A copolymer of such a monomer is crosslinked by a crosslinking agent, such as aminoformaldehyde, polyisocyanate (e.g., hexamethylene diisocyanate or a blocked isocyanate thereof), or the like.

[0018] Each of these monomers is used in the copolymerization reaction such that at least one of (meth)acrylic acid esters is used at a ratio of about 60 to 99 wt.%, preferably about 70 to 99 wt.%, in the total monomers, and such that the crosslinkable group-containing vinyl monomer is used at a ratio of about 0.1 to 10 wt.%, preferably about 0.2 to 5 wt.%. In this case, other vinyl monomer or olefin monomer, such as (meth)acrylonitrile, vinyl acetate, ethylene, or propylene, may be further copolymerized within a range that does not impair the characteristics of the resulting copolymer, generally within a range of about 40 wt.% or less, preferably about 0.5 to 30 wt.%.

[0019] The copolymerization reaction is performed by an emulsion polymerization method or a suspension polymerization method in the presence of a generally used radical polymerization initiator. The radical polymerization initiator may be a redox initiator. The polymerization reaction is performed in the presence of an anionic surfactant, such as sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium dialkyl sulfosuccinate, or polyoxyethylene alkylphenyl ether sulfate ammonium salt; or a nonionic surfactant, such as polyoxyethylene nonylphenyl ether, polyethylene glycol monostearate, or sorbitan monostearate, by any method, such as a batch method, a continuous method, or an intermittent addition method, at a temperature of about -10 to 100°C, preferably about 2 to 80°C, to a polymerization conversion of about 90% or more, preferably about 95 to 99.8%. Therefore, ratio of each monomer supplied almost corresponds to the composition ratio of the copolymer.

[0020] Examples of the styrene-based resin to be added to the above acrylic rubber include homopolymers of styrene, α-methylstyrene, or p-methylstyrene; their mutual copolymers; copolymers of these monomers with vinyl or olefin monomers copolymerizable with these monomers, such as ethylene; syndiotactic polystyrene; and the like.

[0021] The styrene-based resin is used at a ratio of 5 to 80 parts by weight, preferably 10 to 60 parts by weight, more preferably 20 to 40 parts by weight, based on 100 parts by weight of acrylic rubber. If the ratio of the styrene-based resin used is less than this range, kneading properties and processability, as well as tan δ (23°C) and tan δ (70°C) are excellent; however, the tan δ (100°C) value decreases. Thus, the object of the present invention, that is, improvement of vibration insulation properties at a high temperature, cannot be achieved. In contrast, if the ratio of the styrene-based resin used is greater than this range, kneading properties and roll processability are deteriorated, which is not preferable.

[0022] When a plasticizer, preferably a polyether ester-based plasticizer is added to the acrylic rubber composition in an amount of 2 to 40 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of acrylic rubber, this is effective to improve moldability and tan δ values.

[0023] Any of kneader kneading properties, roll processability, and vulcanization molding properties of the acrylic rubber composition in which acrylic rubber and a styrene-based resin are used at the above ratio are excellent. Practically, for example, the components are kneaded by a pressurizing kneader, and then subjected to roll processing using an open roll. The resultant is vulcanized at about 180 to 200°C for about 5 to 20 minutes, optionally followed by oven vulcanization (secondary vulcanization) at about 150 to 200°C for about 1 to 15 hours.

[0024] Vulcanization is preferably performed using sulfur or a sulfur-containing vulcanization accelerator, such as 4,4'-dithiodimorpholine, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabuthylthiuram disulfide, 2-mercaptoimidazoline, tetramethylthiuram monosulfide, N-cyclohexyl-2-benzothiazole sulfenamide, dibenzothiazyl disulfide, or high molecular weight polysulfide, in an amount of about 0.1 to 5 parts by weight based on 100 parts by weight of acrylic rubber.

EXAMPLES



[0025] The following describes the present invention with reference to Examples.

Example 1



[0026] 
Active chlorine group-containing acrylic rubber 100 parts by weight
(Noxtite PA401-L, produced by Unimatec Co., Ltd.) Styrene resin A 20 parts by weight
(YS resin SX100, produced by Yasuhara Chemical Co., Sulfur Ltd.) 0.2 parts by weight
The above components were kneaded by a pressurizing kneader, and then subjected to roll processing using an open roll. The resultant was vulcanized at 190°C for 8 minutes, followed by oven vulcanization (secondary vulcanization) at 175°C for 5 hours, thereby forming a sheet-like material (thickness: 2 mm).

[0027] Kneading properties, roll processability, and vulcanization molding properties were evaluated. In addition, dynamic properties (tan δ) were measured.

[0028] Kneading properties:
  1. (1) No bridge (rubber block) in the gap between a rotor and a weight during kneading by a pressurizing kneader, and stable progress of the kneading process
  2. (2) No contamination in the kneader after the discharge of a compound


[0029] When both (1) and (2) were satisfied, the result was evaluated as ○; and when at least one of (1) and (2) was not satisfied, the result was evaluated as ×

[0030] Roll processability:
  1. (1) Low tackiness on the surface of the rubber compound
  2. (2) No cessation due to tackiness in the cutback operation for improving dispersibility; and the sheeting operation for sheet feeding, and excellent roll processability


[0031] When both (1) and (2) were satisfied, the result was evaluated as ○; and when at least one of (1) and (2) was not satisfied, the result was evaluated as ×

[0032] Vulcanization molding properties:
  1. (1) No compound burning, poor compound flow, foaming, etc., under the above vulcanization conditions, and stable vulcanization molding properties
  2. (2) No bleeding etc. on the surface of the vulcanized sheet, and low surface tackiness


[0033] When both (1) and (2) were satisfied, the result was evaluated as ○; and when at least one of (1) and (2) was not satisfied, the result was evaluated as ×

[0034] Dynamic properties (tan δ):

The test was carried out referring to JIS K6394 corresponding to ISO 4664-1



[0035] The tensile method and the form and size of test pieces were as follows: strip-like materials (width: 6 mm and thickness: 2 mm), holder interval: 20 mm, average strain: 10%, strain amplitude: ±0.1%, frequency: 100 Hz, and test temperature: 23°C, 70°C, or 100°C

[0036] In each temperature range, a tan δ of 0.2 or more was evaluated as excellent, and a tan δ of 0.3 or more was evaluated as more preferable

Example 2



[0037] In Example 1, the same amount of styrene resin B (ARUFON UH-1150, produced by Toagosei Co., Ltd.) was used in place of the styrene resin A.

Example 3



[0038] In Example 1, the amount of the styrene resin A was changed to 40 parts by weight.

Comparative Example 1



[0039] In Example 1, no styrene resin A was used.

Comparative Example 2



[0040] In Example 1, the same amount of carboxyl group-containing acrylic resin (ARUFON UC-3000, produced by Toagosei Co., Ltd.) was used in place of the styrene resin A.

Comparative Example 3



[0041] In Example 1, the same amount of carboxyl group-containing styrene acrylic resin (ARUFON UF-5041, produced by Toagosei Co., Ltd.; containing long chain alkyl group) was used in place of the styrene resin A.

Comparative Example 4



[0042] In Example 1, the same amount of aromatic modified terpene resin (YS RESIN TO105, produced by Yasuhara Chemical Co., Ltd.) was used in place of the styrene resin A.

Comparative Example 5



[0043] In Example 1, the same amount of aromatic modified, hydrogenated terpene resin (CLEARON K4100, produced by Yasuhara Chemical Co., Ltd.) was used in place of the styrene resin A.

[0044] Results of measurement or evaluation obtained in the foregoing Examples and Comparative Examples are shown in the following Table.
Table
 ExampleComparative Example
Measurement· evaluation item12312345
[Kneading·Processing properties]
kneader kneading properties × × x
roll processability × × x
vulcanization molding properties × ×
[Dynamic properties]
tan δ (23°C) 1.4 0.99 1.1 1.0 - - 0.90 0.88
tan δ (70°C) 0.30 0.22 0.27 0.24 - - 0.20 0.20
tan δ(100°C) 0.21 0.23 0.42 0.14 - - 0.17 0.26



Claims

1. An acrylic rubber composition comprising 5 to 80 parts by weight of a styrene-based resin, based on 100 parts by weight of acrylic rubber.
 
2. A vibration insulation member obtained by vulcanizing molding of the acrylic rubber composition according to claim 1.
 
3. The vibration insulation member according to claim 2, which is used as a mount or a grommet in the vicinity of an automobile engine.
 





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Cited references

REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description