KR101186168B1 - Bladder rubber composition excellent thermal conductivity - Google Patents
Bladder rubber composition excellent thermal conductivity Download PDFInfo
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- KR101186168B1 KR101186168B1 KR1020100126142A KR20100126142A KR101186168B1 KR 101186168 B1 KR101186168 B1 KR 101186168B1 KR 1020100126142 A KR1020100126142 A KR 1020100126142A KR 20100126142 A KR20100126142 A KR 20100126142A KR 101186168 B1 KR101186168 B1 KR 101186168B1
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Abstract
The present invention relates to a rubber composition for tire bladder having excellent thermal conductivity, and more particularly, in a rubber composition for tire bladder, 50 to 90 parts by weight of polyethylene acrylic rubber and 10 to acetylene black based on 100 parts by weight of halogenated butyl rubber as a raw material rubber. It relates to a tire bladder comprising a rubber composition for a tire bladder having excellent thermal conductivity, comprising 50 parts by weight, 0.1 to 5 parts by weight of amine, and 0.1 to 5 parts by weight of amine crosslinking accelerator. .
Tire vulcanization bladder made of the rubber composition of the present invention can reduce the green tire vulcanization time and improve tire productivity through improved thermal conductivity and reduced bladder manufacturing cost, and also reduce the consumable cost in the tire manufacturing process according to the bladder manufacturing cost It can be used industrially.
Description
The present invention relates to a rubber composition for tire bladder having excellent thermal conductivity, and more particularly, in a rubber composition for tire bladder, 50 to 90 parts by weight of polyethylene acrylic rubber and 10 to acetylene black based on 100 parts by weight of halogenated butyl rubber as a raw material rubber. It relates to a tire bladder comprising a rubber composition for a tire bladder having excellent thermal conductivity, comprising 50 parts by weight, 0.1 to 5 parts by weight of amine, and 0.1 to 5 parts by weight of amine crosslinking accelerator. .
The present invention relates to a rubber composition for tire bladder used in a tire vulcanization process, and more particularly, in addition to butyl rubber, which is a conventional generalized raw material rubber, for improving the thermal conductivity of the bladder for improving the vulcanization reaction rate. The present invention relates to a rubber composition for a bladder that can be mixed with butyl rubber so as to substitute an acrylic rubber to suppress an increase in selling price.
The bladder used in the tire manufacturing process is mounted inside the mold in the vulcanization process as shown in FIG. 1, and used as a heat transfer medium between the internal heat source and the unvulcanized
Therefore, the rubber composition should be designed to have a certain level of expansion rate (elongation) and fast crosslinking reaction, that is, high thermal conductivity for productivity improvement, so that the unvulcanized
In general, the temperature of the vulcanization mold 1 is 170 ° C to 180 ° C during the tire crosslinking reaction for manufacturing a tire, but the temperature of the internal heat source (usually using steam) supplied to the bladder 3 is Since a high temperature of 200 ° C. or higher is used, it is important to use a bladder having excellent thermal conductivity so as to quickly transfer an internal heat source to the unvulcanized
As such, improving the thermal conductivity of the bladder is a very important task of the tire industry and researching various rubbers and additional materials to improve the thermal conductivity of the bladder.
In general, in order to manufacture bladder rubber, general butyl rubber having excellent high temperature and thermal aging stability is used as a raw material rubber, and acetylene black is used together with carbon black as one of additives for rubber composition having high thermal conductivity.
However, only the content of acetylene black and carbon black on the basis of the general butyl rubber has a limit in improving the thermal conductivity.
Therefore, in order to overcome the limitation of improving the thermal conductivity of the bladder, it is a trend to evaluate the possibility of substitution with various kinds of raw rubbers in addition to the general butyl rubber, which is a conventional raw rubber, and one of them is the conversion to acrylic rubber. However, the use of acrylic rubber can improve the thermal conductivity, but the cost of rubber raw material is about 4 ~ 5 times higher than that of general butyl rubber. Few.
In general, improving the thermal conductivity of the bladder rubber reduces tire crosslinking time, thereby improving tire productivity.In the case of improving the thermal conductivity of the bladder rubber by 40%, it is possible to improve the tire productivity by reducing the tire crosslinking time by 5%. Since there is a desire to increase the content of acetylene black in order to improve the thermal conductivity of bladder rubber, there is a limit in improving the thermal conductivity because the content of acetylene cannot be increased indefinitely.
An object of the present invention is to provide a rubber composition for a tire bladder excellent in thermal conductivity.
Another object of the present invention is to provide a tire bladder comprising a rubber made of a rubber composition for a tire bladder excellent in the thermal conductivity mentioned above.
In the rubber composition for tire bladder, 50 to 90 parts by weight of polyethylene acrylic rubber, 10 to 50 parts by weight of acetylene black, 0.1 to 5 parts by weight of amine, and 0.1 to 5 parts by weight of amine crosslinking accelerator based on 100 parts by weight of halogenated butyl rubber as a raw material rubber. It is to provide a rubber composition for a tire bladder having excellent thermal conductivity, comprising a 5 parts by weight, a tire bladder comprising a rubber made of the rubber composition.
Tire vulcanization bladder made of the rubber composition of the present invention can reduce the green tire vulcanization time and improve tire productivity through improved thermal conductivity and reduced bladder manufacturing cost, and also reduce the consumable cost in the tire manufacturing process according to the bladder manufacturing cost can do.
1 is a schematic diagram showing a tire vulcanization device and a vulcanizing bladder.
The present invention shows a rubber composition for tire bladder excellent in thermal conductivity.
In the rubber composition for tire bladder, 10 to 50 parts by weight of acetylene black and 0.1 to 5 parts by weight of amine based on 100 parts by weight of the raw material rubber consisting of 10 to 50 parts by weight of halogenated butyl rubber and 50 to 90 parts by weight of polyethylene acrylic rubber. And 0.1 to 5 parts by weight of an amine crosslinking accelerator, thereby exhibiting a rubber composition for tire bladder having excellent thermal conductivity.
In the present invention, the raw material rubber may be a mixed rubber mixed with a halogenated butyl rubber and polyethylene acrylic rubber.
The halogenated butyl rubber may be any one or more selected from chloro butyl rubber and bromo butyl rubber.
As one component of the raw material rubber, polyethylene acrylic rubber may be a polyethylene methyl acrylate terpolymer of the following structural formula (1).
(CH 2 CH 2 ) x- (CHCOOCH 3 CH 2 ) y- (RCOOH) z ...
In the formula (1), R is an alkyl group having 1 to 20 carbon atoms, and x, y and z are each a natural number of 1 to 10.
The polyethylene acrylic rubber is a copolymer of ethylene and acrylate, and the butyl group is attached to a carboxyl group as a cure site for crosslinking with amine. The reaction does not occur and may be cured by an amine.
When using 100 parts by weight of the raw material rubber in the present invention, it is preferable to use 10 to 50 parts by weight of halogenated butyl rubber and 50 to 90 parts by weight of polyethylene acrylic rubber in view of improving thermal conductivity and cost.
In the present invention, acetylene black is used to improve the thermal conductivity of the rubber composition.
In the above acetylene black can be used 10 to 50 parts by weight based on 100 parts by weight of the raw material rubber, if less than 10 parts by weight based on 100 parts by weight of raw material rubber does not mean using acetylene black, more than 50 parts by weight If it is used, there is no significant effect of improving thermal conductivity and there is a possibility that the physical properties of rubber are reduced. Therefore, in the present invention, acetylene black is preferably used in an amount of 10 to 50 parts by weight based on 100 parts by weight of the raw material rubber.
In the above acetylene black can be used that has a thermal conductivity of 0.35 ~ 0.75w / mK.
In the rubber composition for tire bladder of the present invention, the amine and the amine crosslinking accelerator may be used to form an amine crosslinking to improve the high temperature property by using the bladder at 180 ° C or higher and approximately 180 ° C to 220 ° C. .
In the amine, 4,4-bis (α, α-dimethylbenzyl) diphenylamine (4,4-bis (α, α-dimethylbenzyl) diphenylamine) may be used.
The amine may be used octadecylamine (Octadecylamine).
In the above amine, 4,4-bis (α, α-dimethylbenzyl) diphenylamine (4,4-bis (α, α-dimethylbenzyl) diphenylamine) and octadecylamine (Octadecylamine) are mixed with amine in the same weight ratio. Can be used.
The amine crosslinking accelerator may be used hexamethylenediamine carbamate (Hexamethylenediamine carbamate).
In the amine crosslinking accelerator may be used ethylenediamine (Ethylenediamine, EDA).
In the amine crosslinking accelerator, hexamethylenediamine (Hexamethylenediamine, HMDA) may be used.
In the amine cross-linking accelerator may be used triethylenetetramine (Triethylenetetramine, TETA).
The amine crosslinking accelerator may be used two or more selected from hexamethylenediamine carbamate, ethylenediamine (Ethylenediamine, EDA), hexamethylenediamine (Hexamethylenediamine, HMDA), and triethylenetetramine (TETA). have.
In the amine crosslinking accelerator, at least two selected from hexamethylenediamine carbamate, ethylenediamine (Ethylenediamine, EDA), hexamethylenediamine (Hexamethylenediamine, HMDA) and triethylenetetramine (TETA) are the same. Mixed amine crosslinking accelerators mixed in weight ratio can be used.
In the above, the amino and amine crosslinking accelerators may be used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the raw material rubber, respectively. When used, since there is no meaning of using an amine and an amine crosslinking accelerator, in the present invention, it is preferable to use 0.1 to 5 parts by weight based on 100 parts by weight of the raw material rubber.
The rubber composition for tire bladder of the present invention may further include an additive to improve physical properties of the rubber.
The rubber composition for tire bladder of the present invention may further include 5 to 30 parts by weight of an additive based on 100 parts by weight of the raw material rubber to improve physical properties of the rubber composition.
The additive may further comprise wood powder.
The wood flour may be used wood flour milled to 10 ~ 200 mesh (mesh).
The additive may further include a glass fiber (class fiber).
Said glass fiber can use a diameter of 1-10 micrometers, and a length of 10-1000 micrometers.
The additive may further include carbon fiber.
Said carbon fiber can use what is 1-10 micrometers in diameter, and 10-1000 micrometers in length.
The additive may further include carbon fiber.
The additive may further comprise any two or more selected from wood powder, glass fiber, carbon fiber.
In the rubber composition for tire bladder of the present invention, the rubber composition for tire bladder is applied under conditions of various components, contents, etc., in order to achieve the object of the present invention, the rubber composition for tire bladder under the conditions mentioned above is preferable. I could see.
The rubber composition for tire bladder of the present invention has various additives such as activators, anti-aging agents, process oils, vulcanizing agents, and vulcanization accelerators, which are used in rubber compositions for tire bladder, in addition to the above-mentioned raw rubbers, acetylene black, amines, and amine crosslinking agents. It can be used in a predetermined amount by selecting the enemy as needed. However, these are general components used in a rubber composition for a tire bladder, and thus are not essential components of the present invention.
The present invention includes a bladder containing a rubber made of the above-mentioned rubber composition for tire bladder.
Hereinafter, the content of the present invention will be described by the following examples, comparative examples and test examples. However, these are not limited to the scope of the present invention by these as an embodiment of the present invention.
≪ Example 1 >
1.5 parts by weight of stearic acid and 2 parts by weight of wax (sunprax-652) based on 100 parts by weight of the raw material rubber consisting of 20 parts by weight of bromo butyl rubber and 80 parts by weight of polyethylene methyl acrylate terpolymer rubber. , 2 parts by weight of amine (4,4-bis (α, α-dimethylbenzyl) diphenylamine [4,4-bis (α, α-dimethylbenzyl) diphenylamine]), 30 parts by weight of carbon black (N330 [HAF]) And 30 parts by weight of acetylene black and 5 parts by weight of paraffin oil were mixed in a Banbury mixer to obtain a rubber compound.
5 parts by weight of zinc oxide (ZnO) and 1.0 parts by weight of an amine crosslinking accelerator (Hexamethylenediamine carbamate) were added to the rubber mixture, and the rubber mixture was vulcanized in a Banbury mixer at 160 ° C. for 15 minutes to prepare rubber. It was.
In the above polyethylene methyl acrylate terpolymer (polyethylene methyl acrylate terpolymer) was used as represented by the following structural formula (1).
(CH 2 CH 2 ) x- (CHCOOCH 3 CH 2 ) y- (RCOOH) z ...
In the above formula (1), R is an alkyl group having 2 carbon atoms [ethyl group], and x, y and z are each a natural number of 2.
Acetylene black in the above was used that the thermal conductivity is 0.65w / m-K.
Table 1 summarizes the composition of the rubber component.
<Example 2>
A rubber was manufactured in the same manner as in Example 1, except that 100 parts by weight of raw material rubber consisting of 30 parts by weight of bromo butyl rubber and 70 parts by weight of polyethylene methyl acrylate terpolymer rubber was used.
<Example 3>
A rubber was manufactured in the same manner as in Example 1, except that 100 parts by weight of raw material rubber consisting of 50 parts by weight of bromo butyl rubber and 50 parts by weight of polyethylene methyl acrylate terpolymer rubber was used.
≪ Comparative Example 1 &
100 parts by weight of raw material bromo butyl rubber, 1.5 parts by weight of stearic acid, 2 parts by weight of wax (sunprax-652), 60 parts by weight of carbon black (N330 [HAF]), and 5 parts by weight of paraffin oil in a Banbury mixer. Mixing gave a rubber compound.
5 parts by weight of zinc oxide (ZnO), 2.0 parts by weight of sulfur as a vulcanizing agent and N-tert-butyl-2-benzothiazylsulfenamide (Nt-butyl-2-benzothiazole sulfenamide, NS) as a vulcanization accelerator to the rubber compound. ) 1.5 parts by weight was added and the rubber compound was vulcanized in a Banbury mixer at 160 ° C. for 15 minutes to prepare rubber.
Comparative Example 2
A rubber was manufactured in the same manner as in Example 1, except that 100 parts by weight of polyethylene methyl acrylate terpolymer was used as the raw rubber.
* PMAT: Polyethylene methyl acrylate terpolymer rubber of the following structural formula (1)
(CH 2 CH 2 ) x- (CHCOOCH 3 CH 2 ) y- (RCOOH) z ... Structural formula (1) [wherein R is an alkyl group having 2 carbon atoms [ethyl group] and x, y and z Are each a natural number of 2.]
Amine: 4,4-bis (α, α-dimethylbenzyl) diphenylamine [4,4-bis (α, α-dimethylbenzyl) diphenylamine]
* Amine crosslinking accelerator: Hexamethylenediamine carbamate
≪ Test Example 1 >
Cost analysis of the rubber prepared in Examples 1 to 3 and the rubber prepared in Comparative Example 1 and Comparative Example 2 was carried out and the results are shown in Table 2 below.
≪ Test Example 2 &
Tensile properties (at 23 ° C), tensile properties (at 190 ° C), and thermal conductivity of the rubbers prepared in Examples 1 to 3 and the rubbers prepared in Comparative Examples 1 and 2 were determined by ASTM-related regulations. The results are shown in Table 3 below.
(at 23 degrees Celsius)
(at 190 ℃)
As shown in Table 2 and Table 3, the rubber prepared in Examples 1 to 3 of the present invention had excellent tensile properties when compared with the rubbers prepared in Comparative Examples 1 and 2.
In particular, the thermal conductivity was superior to the rubber prepared in Comparative Example 1, compared with the rubber prepared in Comparative Example 2 in terms of rubber manufacturing cost, the rubber prepared by the rubber composition of the present invention in consideration of thermal conductivity and cost Was found to be superior to the rubber prepared in Comparative Examples 1,2.
<Example 4>
1.5 parts by weight of stearic acid and 2 parts by weight of wax (sunprax-652) based on 100 parts by weight of raw material rubber consisting of 30 parts by weight of bromo butyl rubber and 70 parts by weight of polyethylene methyl acrylate terpolymer rubber. , 2 parts by weight of amine (4,4-bis (α, α-dimethylbenzyl) diphenylamine [4,4-bis (α, α-dimethylbenzyl) diphenylamine]), 30 parts by weight of carbon black (N330 [HAF]) , 30 parts by weight of acetylene black, 5 parts by weight of paraffin oil, and 10 parts by weight of 100 mesh (mesh) wood powder were mixed in a Banbury mixer to obtain a rubber compound.
5 parts by weight of zinc oxide (ZnO) and 1.0 parts by weight of an amine crosslinking accelerator (Hexamethylenediamine carbamate) were added to the rubber mixture, and the rubber mixture was vulcanized in a Banbury mixer at 160 ° C. for 15 minutes to prepare rubber. It was.
In the above polyethylene methyl acrylate terpolymer (polyethylene methyl acrylate terpolymer) was used as represented by the following structural formula (1).
(CH 2 CH 2 ) x- (CHCOOCH 3 CH 2 ) y- (RCOOH) z ...
In the above formula (1), R is an alkyl group having 2 carbon atoms [ethyl group], and x, y and z are each a natural number of 2.
Acetylene black in the above was used that the thermal conductivity is 0.65w / mK.
<Example 5>
A rubber was manufactured in the same manner as in Example 4, except that 15 parts by weight of glass fiber (class fiber) having a diameter of 3 ± 0.5 μm and a length of 200 ± 5 μm was used instead of 10 parts by weight of wood powder.
<Example 6>
Rubber was manufactured in the same manner as in Example 4, except that 25 parts by weight of carbon fiber having a diameter of 2 ± 0.5 μm and a length of 100 ± 5 μm was used instead of 10 parts by weight of wood powder.
≪ Example 7 >
Rubber was prepared in the same manner as in Example 4, except that 10 parts by weight of wood powder was used instead of a mixture of glass fiber and carbon fiber. In this case, 10 parts by weight of glass fiber having a diameter of 3 ± 0.5 μm and a length of 200 ± 5 μm was used, and 10 parts by weight of carbon fiber having a diameter of 2 ± 0.5 μm and a length of 100 ± 5 μm. .
As described above, the present invention has been described with reference to preferred embodiments, comparative examples, and test examples, but those skilled in the art should be aware of the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. It will be understood that various modifications and variations can be made to the invention.
Tire vulcanization bladder made of the rubber composition of the present invention can reduce the green tire vulcanization time and improve tire productivity through improved thermal conductivity and reduced bladder manufacturing cost, and also reduce the consumable cost in the tire manufacturing process according to the bladder manufacturing cost It can be used industrially.
1: vulcanization mold
2: Uncured Green Tire
3: bladder
Claims (3)
10 to 50 parts by weight of any one or more halogenated butyl rubbers selected from chloro butyl rubber and bromo butyl rubber, and 50 to 90 parts by weight of polyethylene acrylic rubber, which is a polyethylene methyl acrylate terpolymer of formula (1) 10 to 50 parts by weight of acetylene black having a thermal conductivity of 0.35 to 0.75 w / mK based on 100 parts by weight of the raw material rubber; 0.1 to 5 parts by weight of at least one amine selected from 4,4-bis (α, α-dimethylbenzyl) diphenylamine (4,4-bis (α, α-dimethylbenzyl) diphenylamine) and octadecylamine; Hexamethylenediamine carbamate (Hexamethylenediamine carbamate), ethylenediamine (Ethylenediamine, EDA), hexamethylenediamine (Hexamethylenediamine, HMDA) and triethylenetetramine (Triethylenetetramine, TETA) containing 0.1 to 5 parts by weight of one or more amine cross-linking accelerator Rubber composition for tire bladder, characterized in that.
(CH 2 CH 2 ) x- (CHCOOCH 3 CH 2 ) y- (RCOOH) z ...
In the formula (1), R is an alkyl group having 1 to 20 carbon atoms, and x, y and z are each a natural number of 1 to 10.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100126142A KR101186168B1 (en) | 2010-12-10 | 2010-12-10 | Bladder rubber composition excellent thermal conductivity |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100126142A KR101186168B1 (en) | 2010-12-10 | 2010-12-10 | Bladder rubber composition excellent thermal conductivity |
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| Publication Number | Publication Date |
|---|---|
| KR20120064884A KR20120064884A (en) | 2012-06-20 |
| KR101186168B1 true KR101186168B1 (en) | 2012-10-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1020100126142A KR101186168B1 (en) | 2010-12-10 | 2010-12-10 | Bladder rubber composition excellent thermal conductivity |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000191837A (en) | 1998-12-25 | 2000-07-11 | Sumitomo Rubber Ind Ltd | Rubber composition |
| JP2007161869A (en) | 2005-12-14 | 2007-06-28 | Nok Corp | Sealant vulcanization molding ethylene-alkylacrylate copolymer rubber composition |
| JP2010090351A (en) | 2008-10-11 | 2010-04-22 | Nok Corp | Acrylic rubber composition and seal parts vulcanized and molded using same |
| JP2010254908A (en) * | 2009-04-28 | 2010-11-11 | Kaneka Corp | Rubber composition for pneumatic tire and pneumatic tire using the same |
-
2010
- 2010-12-10 KR KR1020100126142A patent/KR101186168B1/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000191837A (en) | 1998-12-25 | 2000-07-11 | Sumitomo Rubber Ind Ltd | Rubber composition |
| JP2007161869A (en) | 2005-12-14 | 2007-06-28 | Nok Corp | Sealant vulcanization molding ethylene-alkylacrylate copolymer rubber composition |
| JP2010090351A (en) | 2008-10-11 | 2010-04-22 | Nok Corp | Acrylic rubber composition and seal parts vulcanized and molded using same |
| JP2010254908A (en) * | 2009-04-28 | 2010-11-11 | Kaneka Corp | Rubber composition for pneumatic tire and pneumatic tire using the same |
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| Publication number | Publication date |
|---|---|
| KR20120064884A (en) | 2012-06-20 |
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