CA2172935A1 - Rubber composition - Google Patents
Rubber compositionInfo
- Publication number
- CA2172935A1 CA2172935A1 CA002172935A CA2172935A CA2172935A1 CA 2172935 A1 CA2172935 A1 CA 2172935A1 CA 002172935 A CA002172935 A CA 002172935A CA 2172935 A CA2172935 A CA 2172935A CA 2172935 A1 CA2172935 A1 CA 2172935A1
- Authority
- CA
- Canada
- Prior art keywords
- rubber
- component
- ethylene
- rubber composition
- processibility
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
- B60J10/00—Sealing arrangements
- B60J10/15—Sealing arrangements characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0607—Rubber or rubber derivatives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0617—Polyalkenes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0617—Polyalkenes
- C09K2200/062—Polyethylene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0642—Copolymers containing at least three different monomers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A rubber composition comprising the following component (A) and component (B):
component (A): an ethylene-propylene-non-conjugated diene copolymer rubber having a Mooney viscosity (ML1+4 100°C) of 40 or less and having a weight ratio of ethylene/(ethylene + propylene) of (75-95)/100, component (B): a liquid polyisoprene rubber in which 70 % or more of double bonds are hydrogenated, in a weight ratio (A)/(B) of 65/35 - 95/5.
component (A): an ethylene-propylene-non-conjugated diene copolymer rubber having a Mooney viscosity (ML1+4 100°C) of 40 or less and having a weight ratio of ethylene/(ethylene + propylene) of (75-95)/100, component (B): a liquid polyisoprene rubber in which 70 % or more of double bonds are hydrogenated, in a weight ratio (A)/(B) of 65/35 - 95/5.
Description
~ ~ 7~935 RUBBER COMPOSITION
BACKGROUND OF T~E lNV~llON
Field of the Invention The present invention relates to a rubber composition and a high hardness vulcanized rubber. More precisely, the present invention relates to a rubber composition which makes effective use of characteristics of ethylene-propylene-non-conjugated diene copolymer rubbers excellent in heat resistance, weathering resistance, ozone resistance, chemical resistance and the like and which allows to provide a high hardness vulcanized rubber excellent in processibility and having sufficiently high hardness, a high hardness vulcanized rubber obtained by sulfur vulcanization of said rubber composition, as well as a weather strip for automobile, a glass run channel for automobile and a gasket for architecture comprising said high hardness vulcanized rubber.
Background Information Since ethylene-propylene-non-conjugated diene copolymer rubbers are excellent in heat resistance, weathering 2 1 72~3~
resistance, ozone resistance, chemical resistance and the like, they are widely used in various parts for automobile, materials for architecture and the like. The high hardness rubber is used independently or in the form of an integrated material with a sponge rubber for the weather strip and the glass run channel among the parts for automobile. Also, the high hardness rubber is used independently or in the form of an integrated material with another rubber for a glazing gasket, an airtight gasket and a joint gasket among the gaskets for architecture. A sufficiently high hardness is required for the high hardness rubber used for such applications and simultaneously excellent processibility such as roll processibility, extruding processibility or the like is required for the rubber composition for providing such high hardness rubber.
As methods for improving processibility of rubber compositions, JP-B-3-73584 disclosed a method in which a liquid polyisoprene rubber is blended with ethylene-propylene-diene terpolymer (EPDM). In this case, however, the hardness (JIS-A) of the vulcanized rubber obt~;ne~ by this method is 80 or less and a vulcanized rubber having a sufficiently high hardness such as a hardness (JIS-A) of 90 or more is not obtained.
A method in which the blending amount of carbon black is increased has been known as a common method for improving the hardness of vulcanized rubbers. The increase in the amount of carbon black, however, causes to increase the Mooney viscosity of the unvulcanized compound and to significantly lower the processibility. Thus, it is generally difficult to improve simultaneously the hardness of vulcanized rubbers and processibility (to lower the Mooney viscosity).
As the result of extensive studies on a rubber composition which makes effective use of characteristics of ethylene-propylene-non-conjugated diene copolymer rubbers and which allows to provide a high hardness vulcanized rubber excellent in processibility and having sufficiently high hardness, the present inventors have successfully found that a rubber composition comprising an ethylene-propylene-non-conjugated diene copolymer rubber having an ethylene/propylene ratio within a specific range and a liquid polyisoprene rubber in which 70 % or more of double bonds are hydrogenated, and said ethylene-propylene-non-conjugated diene copolymer rubber and said liquid polyisoprene rubber being in a specific ratio allows to provide a high hardness vulcanized rubber excellent 2~ 12935 in processibility and having sufficiently high hardness, and thus have completed the present invention.
SUMMARY OF THE lNV~NllON
Accordingly, the present invention provides a rubber composition comprising the following component (A) and component (B):
component (A): an ethylene-propylene-non-conjugated diene copolymer rubber having a Mooney viscosity (ML1+4 lOOC) of 40 or less and having a weight ratio of ethylene/(ethylene + propylene) of (75-95)/100, component (B): a liquid polyisoprene rubber in which 70 % or more of double bonds are hydrogenated, in a weight ratio (A)/(B) of 65/35 - 95/5.
DETATT-~D DESCRIPTION OF THE lNV ~:N'l'lON
The present invention is described in more detail in the followings.
The component (A) in the present invention is an ethylene-propylene-non-conjugated diene copolymer rubber having a Mooney viscosity (MLl+4 100C) of 40 or less and having a weight ratio of ethylene/(ethylene + propylene) of ~ 1 7~Y35 (75-95)/100.
The non-conjugated diene in the component (A) includes, for example, 1,4-pentadiene, 1,4-hexadiene, divinylbenzene, dicyclopentadiene, methylenenorbornene, ethylidenenorbornene (ENB), vinylnorbornene and the li~e. These may be used independently or in combination thereof.
The amount of the non-conjugated diene in the component (A) is preferably an amount providing an iodine value of 2-35 and more preferably an iodine value of 10-25. If the amount of non-conjugated diene is too small, the tensile strength on the sulfur vulcanization may lower and when the amount is too much, the heat resistance and ozone resistance after the sulfur vulcanization may be poor.
The Mooney viscosity (MLl+4 100C) of the component (A) should be 40 or less and preferably is 35-5. If the Mooney viscosity is too high, the Mooney viscosity (MLl+4 100C) of the compound is also high resulting in poor processibility.
The weight ratio ethylene/(ethylene + propylene) of the component (A) should be (75-95)/100 and preferably (78-90)/100. If the content of ethylene is too high, the crystallinity of ethylene becomes higher and the hardness of the vulcanized rubber increases but the production of the ethylene-propylene-non-conjugated diene copolymer rubber becomes difficult and the processibility of unvulcanized rubber becomes poor. On the other hand, when the content of ethylene is too low, a sufficiently high hardness is not obtained.
The component (B) in the present invention is a liquid polyisoprene rubber in which 70 % or more, preferably 75 % or more of double bonds are hydrogenated. If the rate of hydrogenation is too low, a sufficiently high hardness is not obtained.
It is preferred that the liquid polyisoprene has a viscosity average molecular weight of 5,000-50,000. If the viscosity average molecular weight is lower than 5,000, a sufficiently high hardness may not be obtained and when the viscosity average molecular weight is higher than 50,000, the viscosity of unvulcanized compound becomes high resulting in poor processibility. On the other hand, if a solid polyisoprene is used, the processibility is poor.
The weight ratio (A)/(B) in the rubber composition of the present invention should be 65/35-95/5 and preferably 70/30-95/5. If the amount of the component (A) is too small, a sufficiently high hardness is not obtained and when the ~ 1 729~5 amount of the component (A) is too much, the processibility becomes poor.
The rubber composition of the present invention may contain a reinforcing agent such as carbon black, silica and the like and a lubricant such as a mineral oil such as paraffin processing oil. The amoun~ is, for example, 50 - 200 parts by weight of FEF carbon black and 100 part by weight or less of paraffin processing oil, per 100 parts by weight of the rubber component. If the amount of the reinforcing agent is too small, a sufficiently high hardness may not be obtained, and when the amount of the reinforcing agent is too much, the rubber properties such as elasticity may be poor.
Further, if the amount of the lubricant is too small, the processibility may be poor and when the amount of the lubricant is too much, a sufficiently high hardness may not be obtained.
The rubber composition of the present invention can be converted into a compound by kneading the above ingredients with a vulcanizing agent and, if necessary, an antioxidant, a processing aid, stearic acid, zinc oxide, a filler, a vulcanization accelerator and the like by means of a Banbury mixer, a open roll or the like and then into a high hardness vulcanized rubber by molding and vulcanizing the compound.
While sulfur, organic peroxides or the like may be used as a vulcanizing agent, sulfur is preferred because it allows vulcanization in the air. The amount of sulfur is preferably 0.5-4 parts by weight, per 100 parts by weight of the rubber component. If the amount is too small, a sufficiently high hardness may not be obtained and when the amount is too much, the product may have bad appearance due to a bloom generated on the surface of the product or may be poor in heat resistance and permanent compression set. Preferably, the kneading is conducted by a Banbury mixer at a temperature of 60C - 250C, more preferably 100C - 160C or is conducted by an open roll preferably at a temperature of 20C - 200C, more preferably 30C - 60C. The vulcanization is conducted preferably at a temperature of 120C or more, more preferably 150C - 220C. The vulcanization time is generally about 1 - 30 minutes.
The high hardness vulcanized rubber thus obtained has a hardness of JIS-A (DUROMETER-A) of 90 or more. Also the high hardness vulcanized rubber is excellent in roll processibility and extrusion processibility.
The rubber composition of the present invention can be used in various fields, including weather strips for automobile, glass run channels for automobile and gaskets for architecture as suitable uses, making use of its excellent characteristics. More particularly, rubber parts of said weather strips for automobile, glass run channels for auto-mobile and gaskets for architecture may usually contain a high hardness rubber independently or in the form of an 8a ~ 72~3~
integrated material with a sponge rubber or another rubber and the high hardness rubber composition of the present invention can be suitably used in such rubber parts.
According to the present invention, it is possible to provide a rubber composition which makes effective use of characteristics of ethylene-propylene-non-conjugated diene copolymer rubbers excellent in heat resistance, weathering resistance, ozone resistance, chemical resistance and the like and which allows to provide a high hardness w lcanized rubber excellent in processibility and having sufficiently high hardness, a high hardness vulcanized rubber obtained by sulfur w lcanization of said rubber composition, as well as a weather strip for automobile, a glass run channel for automobile and a gasket for architecture comprising said high hardness w lcanized rubber.
EXAMPLES
The present invention will now be illustrated by means of Examples which should not be construed as a limitation upon the scope of the invention.
Examples 1 - S and Comparative Examples 1 - 6 Ingredients shown in Table 1 and, as a common combination, 100 parts by weight of FEF carbon black 2~1 ï2q3$
(manufactured by Asahi Carbon, "Asahi 60G" (trade-mark)), 5 parts by weight of Processing oil (manufactured by Idemitsu Rousan, "PW-90" (trade-mark))~ 5 parts by weight of zinc oxide, 1 part by weight of stearic acid, 2 parts by weight of polyethylene glycol (PEG 4000), 3 parts by weight of calcium oxide (manufactured by Inoue Sekkai, n Besuta BS" (trade-mark)), 2.5 parts by weight of Sox CZ (trade-mark of Sumitomo Chemical Co., Ltd., a vulcanization accelerator), 1.O
part by weight of Sox BZ (trade-mark of Sumitomo Chemical Co., Ltd., a vulcanization accelerator)~ 0.5 part by weight of Sox TT (trade-mark of Sumitomo Chemical Co., Ltd., a vulcanization accelerator) and 1.5 part by weight of sulfur were kneaded in a 1.7 liter BR-type Banbury mixer using open rolls to give a compound. The condition of kneading was visually observed and the processibility was evaluated by measuring the Mooney viscosity (MLl+4 100 ) of the produced compound. Then the compound was vulcanized to give a vulcanized rubber, which was evaluated by the tensile strength (TB), elongation (E9) and hardness (Hs; JIS-A) according to JIS
R6301.
The amounts of FEF carbon black are measured per 100 parts of components (A) and (B1 combined. The amounts of the lubricant and the vulcanizing agent are also measured per 100 parts of components(A) and (B) combined. The results are shown in Table 1.
lOa Table 1 ________ ______ __ _____ Examples 1 2 3 4 5 Composition Component (A)*1 MLlt4 (lOOC) 35 E/EP wt ratio*280/100 Component (B)*3 Hydrogenation %*4 90 1 ~ 75 95 Mv *5 25000 I 29000 (A)/(B) wt ratio*690/10 80/20 70/30 90/10 Results of Evaluation Compound MLl+4 (100C ) 73 62 51 70 72 processibility*7 0 O O O O
Extrusion processibility*8 0 0 0 0 0 Properties of Vulcanized Rubber TB kgf/cm2 153 129 115 135 149 EB % 170 170 170 200 180 Hs (JIS-A) 91 91 90 90 91 ______ __________ Table 2 __ ________ ___ Comparative examples 1 2 3 4 5 6 ____ _________ Composition Component (A)*l ML1+4 ( 100C ) 35 35 50 90 35 35 E/EP wt ratio*2 80/100 70/100 50/100 80/100 80/100 80/100 Component (B)*3 ~ydrogenation %*4 - 90 ~ 0 44 Mv *5 - 25000 f 47000 25000 A/B wt ratio*6 100/0 90/10 -Results of Evaluation Compound MLl+~ (100C) 95 75 120 147 64 68 Roll processibility*7 X O X X O O
Extrusion processibility*8 X O X X O O
Properties of Vulcanized Rubber TB kgf/cm2 160 157 147 234 108 130 EB % 170 230 290 220 300 240 Hs (JIS-A) 91 86 84 91 86 87 _________ _______________________ __________ .
~ 1 72935 *l Component (A): an ethylene-propylene-ethylidenenorbornene copolymer rubber *2 E/EP: a weight ratio of ethylene/(ethylene + propylene) *3 Component (B): a liquid polyisoprene rubber having a hydrogenation rate shown in the Table *4 Hydrogenation: hydrogenation r~te of double bonds in Component (B) *5 Mv: viscosity average molecular weight *6 A/B wt ratio: the weight ratio of Component(A)/Component(B) *7 Roll processibility: The state of winding the compound on to the rolls during the kneading was evaluated by using scoring criteria: O, good in winding on to the rolls and good in cutting; X, bad in winding on to the rolls and bad in cutting.
*8 Extrusion processibility: The extruding processibility of unvulcanized compound was evaluated by using scoring criteria:
0, extruding rate is fast and the surface of the extruded product is smooth; X, extruding rate is slow and the surface of the extruded product is rough.
9 ~ ~
It is noted that the results of Examples are satisfactory in all the evaluation items. On the other hand, in Comparative Example 1 lacking the component (B) of the present invention, the Mooney viscosity is too high and the processibility is poor. In Comparative Example 2 in which the content of ethylene in the component (A) is too small, the hardness is poor. In Comparative Example 3 in which the content of ethylene in the component (A) is too small and additionally the Mooney viscosity of the component ~A) is too high, the Mooney viscosity of the compound is too high, the processibility is poor and the hardness is also poor. In the Comp~rative Example 4 in which the Mooney viscosity of the component (A) is too high, the Mooney viscosity of the compound is too high and the processibility is poor. In Comparative Example 5 in which an unhydrogenated polyisoprene rubber is used as the component (B), the hardness is poor. In Comparative Example 6 in which an polyisoprene rubber having a hydrogenation rate of less than 70 % is used as the component (B), the hardness is poor.
BACKGROUND OF T~E lNV~llON
Field of the Invention The present invention relates to a rubber composition and a high hardness vulcanized rubber. More precisely, the present invention relates to a rubber composition which makes effective use of characteristics of ethylene-propylene-non-conjugated diene copolymer rubbers excellent in heat resistance, weathering resistance, ozone resistance, chemical resistance and the like and which allows to provide a high hardness vulcanized rubber excellent in processibility and having sufficiently high hardness, a high hardness vulcanized rubber obtained by sulfur vulcanization of said rubber composition, as well as a weather strip for automobile, a glass run channel for automobile and a gasket for architecture comprising said high hardness vulcanized rubber.
Background Information Since ethylene-propylene-non-conjugated diene copolymer rubbers are excellent in heat resistance, weathering 2 1 72~3~
resistance, ozone resistance, chemical resistance and the like, they are widely used in various parts for automobile, materials for architecture and the like. The high hardness rubber is used independently or in the form of an integrated material with a sponge rubber for the weather strip and the glass run channel among the parts for automobile. Also, the high hardness rubber is used independently or in the form of an integrated material with another rubber for a glazing gasket, an airtight gasket and a joint gasket among the gaskets for architecture. A sufficiently high hardness is required for the high hardness rubber used for such applications and simultaneously excellent processibility such as roll processibility, extruding processibility or the like is required for the rubber composition for providing such high hardness rubber.
As methods for improving processibility of rubber compositions, JP-B-3-73584 disclosed a method in which a liquid polyisoprene rubber is blended with ethylene-propylene-diene terpolymer (EPDM). In this case, however, the hardness (JIS-A) of the vulcanized rubber obt~;ne~ by this method is 80 or less and a vulcanized rubber having a sufficiently high hardness such as a hardness (JIS-A) of 90 or more is not obtained.
A method in which the blending amount of carbon black is increased has been known as a common method for improving the hardness of vulcanized rubbers. The increase in the amount of carbon black, however, causes to increase the Mooney viscosity of the unvulcanized compound and to significantly lower the processibility. Thus, it is generally difficult to improve simultaneously the hardness of vulcanized rubbers and processibility (to lower the Mooney viscosity).
As the result of extensive studies on a rubber composition which makes effective use of characteristics of ethylene-propylene-non-conjugated diene copolymer rubbers and which allows to provide a high hardness vulcanized rubber excellent in processibility and having sufficiently high hardness, the present inventors have successfully found that a rubber composition comprising an ethylene-propylene-non-conjugated diene copolymer rubber having an ethylene/propylene ratio within a specific range and a liquid polyisoprene rubber in which 70 % or more of double bonds are hydrogenated, and said ethylene-propylene-non-conjugated diene copolymer rubber and said liquid polyisoprene rubber being in a specific ratio allows to provide a high hardness vulcanized rubber excellent 2~ 12935 in processibility and having sufficiently high hardness, and thus have completed the present invention.
SUMMARY OF THE lNV~NllON
Accordingly, the present invention provides a rubber composition comprising the following component (A) and component (B):
component (A): an ethylene-propylene-non-conjugated diene copolymer rubber having a Mooney viscosity (ML1+4 lOOC) of 40 or less and having a weight ratio of ethylene/(ethylene + propylene) of (75-95)/100, component (B): a liquid polyisoprene rubber in which 70 % or more of double bonds are hydrogenated, in a weight ratio (A)/(B) of 65/35 - 95/5.
DETATT-~D DESCRIPTION OF THE lNV ~:N'l'lON
The present invention is described in more detail in the followings.
The component (A) in the present invention is an ethylene-propylene-non-conjugated diene copolymer rubber having a Mooney viscosity (MLl+4 100C) of 40 or less and having a weight ratio of ethylene/(ethylene + propylene) of ~ 1 7~Y35 (75-95)/100.
The non-conjugated diene in the component (A) includes, for example, 1,4-pentadiene, 1,4-hexadiene, divinylbenzene, dicyclopentadiene, methylenenorbornene, ethylidenenorbornene (ENB), vinylnorbornene and the li~e. These may be used independently or in combination thereof.
The amount of the non-conjugated diene in the component (A) is preferably an amount providing an iodine value of 2-35 and more preferably an iodine value of 10-25. If the amount of non-conjugated diene is too small, the tensile strength on the sulfur vulcanization may lower and when the amount is too much, the heat resistance and ozone resistance after the sulfur vulcanization may be poor.
The Mooney viscosity (MLl+4 100C) of the component (A) should be 40 or less and preferably is 35-5. If the Mooney viscosity is too high, the Mooney viscosity (MLl+4 100C) of the compound is also high resulting in poor processibility.
The weight ratio ethylene/(ethylene + propylene) of the component (A) should be (75-95)/100 and preferably (78-90)/100. If the content of ethylene is too high, the crystallinity of ethylene becomes higher and the hardness of the vulcanized rubber increases but the production of the ethylene-propylene-non-conjugated diene copolymer rubber becomes difficult and the processibility of unvulcanized rubber becomes poor. On the other hand, when the content of ethylene is too low, a sufficiently high hardness is not obtained.
The component (B) in the present invention is a liquid polyisoprene rubber in which 70 % or more, preferably 75 % or more of double bonds are hydrogenated. If the rate of hydrogenation is too low, a sufficiently high hardness is not obtained.
It is preferred that the liquid polyisoprene has a viscosity average molecular weight of 5,000-50,000. If the viscosity average molecular weight is lower than 5,000, a sufficiently high hardness may not be obtained and when the viscosity average molecular weight is higher than 50,000, the viscosity of unvulcanized compound becomes high resulting in poor processibility. On the other hand, if a solid polyisoprene is used, the processibility is poor.
The weight ratio (A)/(B) in the rubber composition of the present invention should be 65/35-95/5 and preferably 70/30-95/5. If the amount of the component (A) is too small, a sufficiently high hardness is not obtained and when the ~ 1 729~5 amount of the component (A) is too much, the processibility becomes poor.
The rubber composition of the present invention may contain a reinforcing agent such as carbon black, silica and the like and a lubricant such as a mineral oil such as paraffin processing oil. The amoun~ is, for example, 50 - 200 parts by weight of FEF carbon black and 100 part by weight or less of paraffin processing oil, per 100 parts by weight of the rubber component. If the amount of the reinforcing agent is too small, a sufficiently high hardness may not be obtained, and when the amount of the reinforcing agent is too much, the rubber properties such as elasticity may be poor.
Further, if the amount of the lubricant is too small, the processibility may be poor and when the amount of the lubricant is too much, a sufficiently high hardness may not be obtained.
The rubber composition of the present invention can be converted into a compound by kneading the above ingredients with a vulcanizing agent and, if necessary, an antioxidant, a processing aid, stearic acid, zinc oxide, a filler, a vulcanization accelerator and the like by means of a Banbury mixer, a open roll or the like and then into a high hardness vulcanized rubber by molding and vulcanizing the compound.
While sulfur, organic peroxides or the like may be used as a vulcanizing agent, sulfur is preferred because it allows vulcanization in the air. The amount of sulfur is preferably 0.5-4 parts by weight, per 100 parts by weight of the rubber component. If the amount is too small, a sufficiently high hardness may not be obtained and when the amount is too much, the product may have bad appearance due to a bloom generated on the surface of the product or may be poor in heat resistance and permanent compression set. Preferably, the kneading is conducted by a Banbury mixer at a temperature of 60C - 250C, more preferably 100C - 160C or is conducted by an open roll preferably at a temperature of 20C - 200C, more preferably 30C - 60C. The vulcanization is conducted preferably at a temperature of 120C or more, more preferably 150C - 220C. The vulcanization time is generally about 1 - 30 minutes.
The high hardness vulcanized rubber thus obtained has a hardness of JIS-A (DUROMETER-A) of 90 or more. Also the high hardness vulcanized rubber is excellent in roll processibility and extrusion processibility.
The rubber composition of the present invention can be used in various fields, including weather strips for automobile, glass run channels for automobile and gaskets for architecture as suitable uses, making use of its excellent characteristics. More particularly, rubber parts of said weather strips for automobile, glass run channels for auto-mobile and gaskets for architecture may usually contain a high hardness rubber independently or in the form of an 8a ~ 72~3~
integrated material with a sponge rubber or another rubber and the high hardness rubber composition of the present invention can be suitably used in such rubber parts.
According to the present invention, it is possible to provide a rubber composition which makes effective use of characteristics of ethylene-propylene-non-conjugated diene copolymer rubbers excellent in heat resistance, weathering resistance, ozone resistance, chemical resistance and the like and which allows to provide a high hardness w lcanized rubber excellent in processibility and having sufficiently high hardness, a high hardness vulcanized rubber obtained by sulfur w lcanization of said rubber composition, as well as a weather strip for automobile, a glass run channel for automobile and a gasket for architecture comprising said high hardness w lcanized rubber.
EXAMPLES
The present invention will now be illustrated by means of Examples which should not be construed as a limitation upon the scope of the invention.
Examples 1 - S and Comparative Examples 1 - 6 Ingredients shown in Table 1 and, as a common combination, 100 parts by weight of FEF carbon black 2~1 ï2q3$
(manufactured by Asahi Carbon, "Asahi 60G" (trade-mark)), 5 parts by weight of Processing oil (manufactured by Idemitsu Rousan, "PW-90" (trade-mark))~ 5 parts by weight of zinc oxide, 1 part by weight of stearic acid, 2 parts by weight of polyethylene glycol (PEG 4000), 3 parts by weight of calcium oxide (manufactured by Inoue Sekkai, n Besuta BS" (trade-mark)), 2.5 parts by weight of Sox CZ (trade-mark of Sumitomo Chemical Co., Ltd., a vulcanization accelerator), 1.O
part by weight of Sox BZ (trade-mark of Sumitomo Chemical Co., Ltd., a vulcanization accelerator)~ 0.5 part by weight of Sox TT (trade-mark of Sumitomo Chemical Co., Ltd., a vulcanization accelerator) and 1.5 part by weight of sulfur were kneaded in a 1.7 liter BR-type Banbury mixer using open rolls to give a compound. The condition of kneading was visually observed and the processibility was evaluated by measuring the Mooney viscosity (MLl+4 100 ) of the produced compound. Then the compound was vulcanized to give a vulcanized rubber, which was evaluated by the tensile strength (TB), elongation (E9) and hardness (Hs; JIS-A) according to JIS
R6301.
The amounts of FEF carbon black are measured per 100 parts of components (A) and (B1 combined. The amounts of the lubricant and the vulcanizing agent are also measured per 100 parts of components(A) and (B) combined. The results are shown in Table 1.
lOa Table 1 ________ ______ __ _____ Examples 1 2 3 4 5 Composition Component (A)*1 MLlt4 (lOOC) 35 E/EP wt ratio*280/100 Component (B)*3 Hydrogenation %*4 90 1 ~ 75 95 Mv *5 25000 I 29000 (A)/(B) wt ratio*690/10 80/20 70/30 90/10 Results of Evaluation Compound MLl+4 (100C ) 73 62 51 70 72 processibility*7 0 O O O O
Extrusion processibility*8 0 0 0 0 0 Properties of Vulcanized Rubber TB kgf/cm2 153 129 115 135 149 EB % 170 170 170 200 180 Hs (JIS-A) 91 91 90 90 91 ______ __________ Table 2 __ ________ ___ Comparative examples 1 2 3 4 5 6 ____ _________ Composition Component (A)*l ML1+4 ( 100C ) 35 35 50 90 35 35 E/EP wt ratio*2 80/100 70/100 50/100 80/100 80/100 80/100 Component (B)*3 ~ydrogenation %*4 - 90 ~ 0 44 Mv *5 - 25000 f 47000 25000 A/B wt ratio*6 100/0 90/10 -Results of Evaluation Compound MLl+~ (100C) 95 75 120 147 64 68 Roll processibility*7 X O X X O O
Extrusion processibility*8 X O X X O O
Properties of Vulcanized Rubber TB kgf/cm2 160 157 147 234 108 130 EB % 170 230 290 220 300 240 Hs (JIS-A) 91 86 84 91 86 87 _________ _______________________ __________ .
~ 1 72935 *l Component (A): an ethylene-propylene-ethylidenenorbornene copolymer rubber *2 E/EP: a weight ratio of ethylene/(ethylene + propylene) *3 Component (B): a liquid polyisoprene rubber having a hydrogenation rate shown in the Table *4 Hydrogenation: hydrogenation r~te of double bonds in Component (B) *5 Mv: viscosity average molecular weight *6 A/B wt ratio: the weight ratio of Component(A)/Component(B) *7 Roll processibility: The state of winding the compound on to the rolls during the kneading was evaluated by using scoring criteria: O, good in winding on to the rolls and good in cutting; X, bad in winding on to the rolls and bad in cutting.
*8 Extrusion processibility: The extruding processibility of unvulcanized compound was evaluated by using scoring criteria:
0, extruding rate is fast and the surface of the extruded product is smooth; X, extruding rate is slow and the surface of the extruded product is rough.
9 ~ ~
It is noted that the results of Examples are satisfactory in all the evaluation items. On the other hand, in Comparative Example 1 lacking the component (B) of the present invention, the Mooney viscosity is too high and the processibility is poor. In Comparative Example 2 in which the content of ethylene in the component (A) is too small, the hardness is poor. In Comparative Example 3 in which the content of ethylene in the component (A) is too small and additionally the Mooney viscosity of the component ~A) is too high, the Mooney viscosity of the compound is too high, the processibility is poor and the hardness is also poor. In the Comp~rative Example 4 in which the Mooney viscosity of the component (A) is too high, the Mooney viscosity of the compound is too high and the processibility is poor. In Comparative Example 5 in which an unhydrogenated polyisoprene rubber is used as the component (B), the hardness is poor. In Comparative Example 6 in which an polyisoprene rubber having a hydrogenation rate of less than 70 % is used as the component (B), the hardness is poor.
Claims (6)
1. A rubber composition comprising the following component (A) and component (B):
component (A): an ethylene-propylene-non-conjugated diene copolymer rubber having a Mooney viscosity (ML1+4 100°C) of 40 or less and having a weight ratio of ethylene/(ethylene + propylene) of (75-95)/100, component (B): a liquid polyisoprene rubber in which 70 % or more of double bonds are hydrogenated, in a weight ratio (A) / (B) of 65/35 - 95/5.
component (A): an ethylene-propylene-non-conjugated diene copolymer rubber having a Mooney viscosity (ML1+4 100°C) of 40 or less and having a weight ratio of ethylene/(ethylene + propylene) of (75-95)/100, component (B): a liquid polyisoprene rubber in which 70 % or more of double bonds are hydrogenated, in a weight ratio (A) / (B) of 65/35 - 95/5.
2. The rubber composition according to Claim 1, in which the viscosity average molecular weight of the component (B) is 5,000 - 50,000.
3. A high hardness vulcanized rubber having a hardness (JIS-A) of 90 or more obtained by sulfur vulcanization of the rubber composition according to Claim 1.
4. A weatherstrip for automobile comprising the rubber composition according to Claim 1.
5. A glass run channel for automobile comprising the rubber composition according to Claim 1.
6. A gasket for architecture comprising the rubber composition according to Claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7562395 | 1995-03-31 | ||
| JP07-75623 | 1995-03-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2172935A1 true CA2172935A1 (en) | 1996-10-01 |
Family
ID=13581538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002172935A Abandoned CA2172935A1 (en) | 1995-03-31 | 1996-03-28 | Rubber composition |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA2172935A1 (en) |
| DE (1) | DE19612735A1 (en) |
-
1996
- 1996-03-28 CA CA002172935A patent/CA2172935A1/en not_active Abandoned
- 1996-03-29 DE DE19612735A patent/DE19612735A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| DE19612735A1 (en) | 1996-10-02 |
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