Patent Application
20150183969
The present patent application claims priority based on Japanese Patent Application No. 2012-105923 filed in Japan on May 7, 2012, and the details thereof are incorporated herein.
The present invention relates to an additive for rubber and a rubber composition. More specifically, the present invention relates to an additive for rubber that has little impact on the environment and the human body and that can provide excellent heat resistance and spring properties and to a rubber composition prepared by blending the additive for rubber.
Rubber process oil is one of the additives for rubber used in rubber manufacture. The rubber process oil is an oil used to improve the plasticity of a rubber or lower the hardness of a vulcanized rubber to improve the processibility. It is used properly according to the raw materials of the rubber and the product applications. Ordinarily, aroma-based, naphthene-based, or paraffin-based rubber process oils are used. Since the rubber process oil is required to have compatibility with rubber related to the rubber properties, aroma-based rubber process oils have been usually used for natural rubbers or diene-based synthetic rubbers.
However, since aroma-based rubber process oils usually contain polycyclic aromatics (PCA), the carcinogenic impact on the human body becomes a problem. Handling of mineral oils containing 3 mass % or more of PCA is limited in Europe.
From this background, technologies regarding non-carcinogenic rubber process oil with reduced PCA and good compatibility with rubber have been studied. Technologies relating to naphthene-based rubber process oil (for example, patent documents 1 and 2) and paraffin-based rubber process oil (for example, patent document 3) are disclosed.
However, although the naphthene-based and paraffin-based rubber process oils can reduce the impact on the human body and the environment, they more easily evaporate from the rubber compositions compared to the aroma-based rubber process oil. As a result, the rubber hardness varies as the temperature changes, and heat resistance becomes a problem.
Patent Document 2: Japanese Unexamined Patent Application Publication No. H11-80434
In light of the above, an object of the present invention is to provide an additive for rubber that is capable of providing rubber that is not subject to environmental regulations and has excellent heat resistance and spring properties, and to provide a rubber composition obtained by blending the additive for rubber.
In order to realize the aforementioned objective, the present inventors conducted extensive research. As a result of this research, it was found that an additive for rubber including (A) a hydrocarbon-based oil instead of a conventional rubber process oil and (B) a styrene-diene block copolymer could satisfy the aforementioned objective, and the present invention was thereby achieved. That is, the present invention provides an additive for rubber that includes (A) a hydrocarbon-based oil and (B) a styrene-diene block copolymer, and the rubber composition is obtained by blending the additive for rubber into (C) a rubber.
The additive for rubber preferably includes component (A) in an amount of 60 to 99 mass % and component (B) in an amount of 1 to 40 mass % with respect to the total mass of the additive for rubber.
The component (A) is preferably an olefin oil, and more preferably a poly-α-oelfin oil.
The component (A) may use the poly-α-olefin oil alone or in combination with an olefin copolymer.
The component (B) is preferably a styrene-hydrogenated diene block copolymer, and more preferably a styrene-hydrogenated polyisoprene.
The component (B) may use styrene-hydrogenated polyisoprene alone or in combination with styrene-hydrogenated poly(isoprene/butadiene).
Preferably, all or part of the component (B) has a diblock structure.
Preferably, the component (C) is a natural rubber or a diene-based synthetic rubber or a combination of both.
Preferably, the additive for rubber is blended in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (C).
Preferably, the rubber composition further includes (D) a reinforcing agent, and the component (D) is preferably carbon black.
The rubber composition may be used for vibration damping, and a rubber part for vibration damping may be manufactured by crosslinking and molding the rubber composition.
The additive for rubber of the present invention is prepared by blending a hydrocarbon-based oil and a styrene-diene block copolymer. It can provide a rubber composition that has little impact on the environment and the human body and that has excellent heat resistance and spring properties. Also, the rubber composition of the present invention is prepared by blending the additive for rubber, and it has excellent heat resistance and spring properties. Further, this rubber composition may be used appropriately for vibration damping. More specifically, this rubber composition may be used appropriately as a vibration damping material for an engine mount, a stabilizer bushing, a suspension bushing, and the like used in automobiles or other vehicles.
In the following, an embodiment of the present invention will be described in detail.
First, the additive for rubber of the present invention will be described.
The additive for rubber of the present invention includes (A) a hydrocarbon-based oil and (B) a styrene-diene block copolymer. The content of component (A) is in a range of 60 to 99 wt %, and the content of component (B) is in the range of 1 to 40 wt % with respect to the total mass of the additive for rubber. More preferably, the content of component (A) is in the range of 80 to 99 wt %, and the content of component (B) is in the range of 1 to 20 mass %. When components (A) and (B) are in the aforementioned ranges, the evaporation loss of the additive for rubber can be reduced, and the rubber hardness will not change because of the temperature, and thus, excellent heat resistance can be realized.
It is possible to use mineral oil or synthetic oil as component (A) as long as it is a hydrocarbon-based oil, and these oils may be used either alone or as a mixture of two or more kinds. It is preferred to use an olefin oil as component (A), and it is more preferred to use a poly-α-olefin oil. Use of the poly-α-olefin oil alone or in combination with an olefin copolymer is preferred.
The dynamic viscosity of component (A) is preferably in a range of 0.1 to 10,000 mm2/s, more preferably in a range of 5 to 2,000 mm2/s, and most preferably in a range of 5 to 500 mm2/s at 40° C.
Preferred examples of poly-α-olefin oil include hydrogenated homopolymers and copolymers using one or more monomers selected from the group of 1-hexene, 1-octene, 1-decene, 1-dodecene, and 1-tetradecene as raw materials. Among these examples, it is preferred to use 1-decene hydrogenated homopolymer and 1-dodecene/1-decene hydrogenated copolymer. Preferred examples of the olefin copolymer include ethylene-α olefin copolymer and propylene-α olefin copolymer. When poly-α-olefin oil and olefin copolymer are used together, the mass ratio between them can be any mass ratio, but it is usually preferred to be in a range of 50:50 to 99:1.
The styrene-diene block copolymer of component (B) is suitably a block copolymer including a hard block A including styrene-based monomer units and a soft block B including conjugated diene-based monomer units, and/or the product obtained by hydrogenating this copolymer. Also, the soft block B is suitably a soft block mainly including butadiene units and/or isoprene units and/or a soft block obtained by hydrogenating the soft block. The bonding form of each block may be straight-chain form, branched form, radiation form, or a combination of two or more the forms. However, the straight-chain form is preferred. Examples include diblock copolymers of A-B, triblock copolymers of A-B-A, tetrablock copolymers of A-B-A-B, and pentablock copolymers of A-B-A-B-A. Among these examples, diblock copolymers of A-B or triblock copolymers of A-B-A are preferred in consideration of manufacturing ease. In particular, it is more preferred that all or part of the component (B) have a diblock structure. Needless to say, there is no limitation on the bonding form, block number, monomer type, and the like.
The content of the hard block A is in a range of 5 to 60 mass %, and is preferably in a range of 20 to 50 mass % with respect to the total mass of the styrene-diene block copolymer. The content of the soft block B is in a range of 40 to 95 mass %, and is preferably in a range of 50 to 80 mass % with respect to the total mass of the styrene-diene block copolymer.
From the point of view of heat resistance, the hard block A mainly including styrene-based monomer units is a block including a homopolymer or a copolymer including, preferably 50 wt % or more, and more preferably 70 mass % or more of styrene-based monomer units with respect to the total mass of the hard block A, and any other components (for example, conjugated diene-based monomer units). From the point of view of rubber elasticity, the soft block B mainly including conjugated diene-based monomer units is a block including preferably 50 mass % or more, and more preferably, 70 mass % or more of conjugated diene-based monomer units with respect to the total mass of the soft block B, and any other components (for example, styrene-based monomer units).
The entire styrene-diene block copolymer contains preferably 5 to 60 mass %, and more preferably 20 to 50 mass % of styrene-based monomer units and contains preferably 40 to 95 mass % and more preferably 50 to 80 mass % of conjugated diene-based monomer units with respect to the total mass of the styrene-diene block copolymer.
Also, for the hard block A mainly including styrene-based monomer units and the soft block B mainly including conjugated diene-based monomer units, the distribution of the conjugated diene-based monomers or styrene-based monomers in the molecular chain may be random, tapered (the monomer components increase or decrease along the molecular chain), partial block-shaped, or any combination thereof. If each of the hard block A mainly including styrene-based monomer units and the soft block B mainly including conjugated diene-based monomer units has two or more blocks, each block may have the same or different structures.
Examples of the styrene-based monomer used as a raw material for manufacturing the styrene-diene block copolymer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, monofluorostyrene, monochlorostyrene, and dichlorostyrene. One or several types of these monomers are selected and used, and of these, use of styrene is preferred.
Examples of the conjugated diene-based monomer used as another raw material for manufacturing the styrene-diene block copolymer include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene, and the like. One or two or more types of these monomers are selected and used, and of these, use of 1,3-butadiene, isoprene, and combinations thereof is preferred. For the soft block B mainly including conjugated diene-based monomer units, the micro structure thereof may be appropriately selected. For example, when the soft block B includes 1,3-butadiene and isoprene, in the butadiene block, a 1,2-micro structure (representing a structural unit generated as a result of additional polymerization between positions 1 and 2) is preferred to be in a range of 20 to 50 mol %, and particularly in a range of 25 to 45 mol %. For the isoprene block, it is preferred that 70 to 100 mol % of the isoprene have a 1,4-micro structure (representing a structural unit generated as a result of additional polymerization between 1st position and 4th position).
For the styrene-diene block copolymer, it is preferred that all or part of the carbon-carbon double bonds based on the conjugated diene-based monomer be hydrogenated in consideration of the heat resistance and weatherability of the obtained elastomer. Preferably 85 mol % or more, and more preferably 90 mol % or more of the carbon-carbon double bonds are hydrogenated.
The number average molecular weight of the styrene-diene block copolymer is not particularly limited, but is preferably 100000 or higher, and more preferably 150000 or higher. The number average molecular weight mentioned in the present invention is the molecular weight of polystyrene equivalent derived through gel permeation chromatography (GPC) measurements. If the number average molecular weight is less than 100000, the heat resistance represented by the permanent compression strain with processing at 70° C. of the molding product of the obtained thermoplastic elastomer composition (simply referred to as molding product hereinafter) becomes insufficient. On the other hand, if the number average molecular weight exceeds 500000, the moldability of the obtained thermoplastic elastomer composition becomes poor, and the surface gloss of the molding product thereof becomes excessively low, which is not preferable. Note that the number average molecular weight is preferably in a range of 150000 to 370000.
Many styrene-diene block copolymer manufacturing methods have been proposed. According to a typical method described in Japanese Examined Patent Application Publication No. S40-23798, a lithium catalyst or Ziegler catalyst is used to block polymerize a monomer used as the manufacturing raw material in an inactive medium. The hydrogenation method is also well known. The hydrogenated block copolymer is also commercially available.
The additive for rubber of the present invention can be manufactured by homogeneously blending components (A) and (B) using a conventional method. If the component (B) is a solid at 25° C., it is possible to blend components (A) and (B) under heating at a temperature in a range of 50 to 200° C.
If necessary, it is also possible to add various kinds of additives for lubricants within the aforementioned combination ratio range. Examples of the additives for lubricants include antioxidants, surfactants, corrosion inhibitors, dispersants, optical stabilizers, viscosity index improving agents, flow point decrease agents, corrosion inhibitors, metal deactivators, oily agents, extreme-pressure agents, and abrasion preventing agents. Examples of the preferred antioxidants include phosphite-based antioxidants, phenol-based antioxidants, and amine-based antioxidants.
In the following, the rubber composition of the present invention will be described. The rubber composition of the present invention mainly includes (C) a rubber and is obtained by blending an additive for rubber prepared by mixing (A) and (B). The additive for rubber prepared by mixing (A) and (B) is added and blended in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the component (C).
Examples of the component (C) include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), and ethylene-propylene-diene-based rubber (EPDM). Of these, it is preferred to use natural rubber, butadiene rubber, or styrene-butadiene rubber in consideration of strength and low dynamic magnification. These rubbers may be used either alone or as a mixture of two or more kinds.
Since a reinforcing agent (D) is usually blended into the rubber composition, the rubber composition may also contain one or several types of components (D) within the aforementioned combination ratio range. It is preferred to use calcium carbonate, silica, or carbon black as the component (D), and of these, carbon black is particularly preferred.
In addition to the aforementioned components, it is also possible to add vulcanizing agents, antioxidants, processing assistants, vulcanization promoters, vulcanization assistants, white fillers, reactive monomers, foaming agents, and the like as needed in appropriate amounts into the rubber composition of the present invention.
The rubber composition of the present invention can be prepared by kneading the components (A) to (C) as the essential materials as well as the component (D) and other components listed above used as needed with a kneader, banbury mixer, open roll, twin screw stirrer, or other kneading machine. This rubber composition is crosslinked by being heated and is used for vibration damping.
The rubber composition of the present invention can be used suitably as a vibration damping rubber composition. More specifically, this rubber composition may be used appropriately as a vibration damping material for an engine mount, a stabilizer bushing, a suspension bushing, and the like used in automobiles or other vehicles.
In the following, examples of the additive for rubber and the rubber composition according to the present invention will be described, but the present invention is not limited to these examples. In the examples, the term “parts” means part by mass.
First, the materials listed below were prepared prior to the examples and comparative examples.
Diana Process NM280 (3.978 cSt at 98.9° C., produced by Idemitsu Kosan Co., Ltd.)
Diana Process PW380 (30.10 cSt at 40° C., produced by Idemitsu Kosan Co., Ltd.)
Fukkol AROMAX #3 (24.46 cSt at 40° C., produced by Fuji Kosan Co., Ltd.)
DURASYN 164 (16.8 cSt at 40° C., produced by INEOS Corp.)
Lucant HC-600 (9850 cSt at 40° C., produced by Mitsui Chemicals, Inc.)
SEPTON 1020 (diblock, polystyrene-hydrogenated polyisoprene block copolymer, produced by Kuraray Co., Ltd.)
HYBRAR KL7350 (diblock, polystyrene-hydrogenated poly(isoprene/butadiene) block copolymer, produced by Kuraray Co., Ltd.)
SEPTON KL-J3341 (triblock, polystyrene-hydrogenated poly(isoprene/butadiene) block copolymer, produced by Kuraray Co., Ltd.)
SEPTON 2104 (triblock, polystyrene-hydrogenated polyisoprene block copolymer, produced by Kuraray Co., Ltd.)
SEPTON 4033 (triblock, polystyrene-hydrogenated poly(isoprene/butadiene) block copolymer, produced by Kuraray Co., Ltd.)
Natural rubber RSS #3
Two types of zinc oxide (produced by Sakai Chemical Industry Co., Ltd.)
Lunac S30 (produced by Kao Corporation)
Ozonon 6C (produced by Seiko Chemical K.K.)
Antigen RD-G (produced by Sumitomo Chemical Co., Ltd.)
Sanokku (produced by Ouchi Shinko Chemical Co., Ltd.)
Seast TA (produced by Tokai Carbon Co., Ltd.)
Nocceler CZ (produced by Ouchi Shinko Chemical Co., Ltd.)
Sanceler TT (produced by Sanshin Chemical Industry Co., Ltd.)
The poly-α-olefin oil and the olefin copolymer used as component (A) and polymers (1) to (6) used as component (B) were blended in the proportions shown in the following Tables 1 and 2 at room temperature in a tank using a double planetary mixer until component (B) was dispersed homogeneously in component (A). While stifling was continued, the temperature in the tank was raised to 120° C. Stirring was carried out at a high speed at 120 to 150° C. for 2 hours or longer. After that, while the system was cooled off to room temperature, defoaming stirring was performed at a low speed to thereby obtain an additive for rubber. The obtained additive for rubber was in a grease form with a consistency of 400 or less (Examples 1 to 4 and Examples 7 to 11) or in a liquid form with dynamic viscosity at 40° C. of 10,000 mm2/s or lower (Examples 5, 6 and 12).
As shown in Table 2, a poly-α-olefin oil that is a commercially available lubricant, and a naphthene-based oil, a paraffin-based oil, and an aroma-based oil, which are general rubber process oils, were directly used and evaluated as additives for rubbers.
As shown in Table 3, 100 parts of NR, 5 parts of zinc oxide, 1 part of stearic acid, 1.5 parts of an ozone antioxidant, 1 part of an amine antioxidant, 2 parts of wax, 30 parts of carbon black, and 5 parts of the additive for rubber described in Example 1 were kneaded at 140° C. for 5 minutes using a banbury mixer. Next, 1 part of a vulcanizing agent, 2 parts of a vulcanization accelerator (1), and 1 part of a vulcanization accelerator (2) were added therein, followed by 5 minutes of kneading performed at 60° C. using an open roll. As a result, a rubber composition was prepared.
As shown in Tables 3 and 4, rubber compositions were prepared according to Example 13 with the exception that the additives for rubber described in Examples 2 to 12 were used instead of the additive for rubber described in Example 1.
As shown in Table 4, rubber compositions were prepared according to Example 15 with the exception that the amount of the additive for rubber described in Example 3 was changed.
As shown in Table 5, rubber compositions were prepared according to Example 13 with the exception that the additive for rubbers described in Comparative Examples 1 to 4 were used instead of the additive for rubber described in Example 1.
The properties of the additives for rubber obtained in Examples 1 to 12, Comparative Examples 1 to 4 and the rubber compositions obtained in Examples 13 to 28 and Comparative Examples 5 to 9 were evaluated based on the following criteria.
An amount of 10 g of each additive for rubber was added into a petri dish, which was then set in a 120° C. atmosphere for 100 hours. Then, the evaporation loss (%) was determined and is shown in Tables 1 and 2. In this test, the evaporation amount required in the present invention is less than 3.0%. The samples meeting that requirement are indicated by a symbol “0” in the corresponding evaluation sections in Tables 1 and 2, while those failing to meet that requirement are indicated by a symbol “X”.
Each rubber composition was press molded (vulcanized) at 160° C. for 20 minutes to form a rubber sheet with a thickness of 2 mm. Then, the rubber sheet was used to measure the hardness (HS) according to JIS K 6251. This measurement was performed for the initial rubber sheet (prior to heat aging) and for a rubber sheet that had been thermally aged in a 100° C. atmosphere for 1000 hours. Next, the increase amount AHS of the hardness (difference from the initial hardness) caused by heat aging was determined, and the values thereof are shown in Tables 3 to 5. In this test, the increase amount of hardness required in the present invention is less than 10 points. The samples meeting that requirement are indicated by a symbol “O” in the corresponding evaluation sections in Tables 3 to 5, while those failing to meet that requirement are indicated by a symbol “X”.
Each rubber composition was press molded (vulcanized) at 160° C. for 20 minutes to form a test piece. The test piece was used to measure the dynamic spring constant and static spring constant according to JIS K 6251. The dynamic magnification was calculated based on these values, and the values thereof are shown in Tables 3 to 5. In this test, the hardness increase degree required in the present invention is 1.30 or less. The samples meeting that requirement are indicated by a symbol “0” in the corresponding evaluation sections in Tables 3 to 5, while those failing to meet that requirement are indicated by a symbol “X”.
As can be seen from the results shown in Tables 1 and 2, the additive for rubbers obtained in Examples 1 to 12 are not subject to environmental regulation (low PCA) and have low evaporation loss. Also, as can be seen from the results shown in Tables 3 and 4, the rubber compositions obtained in Examples 13 to 28 by blending the additives for rubber obtained in Examples 1 to 12 exhibit excellent heat resistance and spring properties.
On the other hand, although the additives for rubber obtained in Comparative Examples 1 to 4 are not subject to environmental regulation (low PCA), the evaporation loss is relatively high compared to the additives for rubber obtained in Examples 1 to 12 and does not meet the requirement of the present invention. Although the additive for rubber obtained in Comparative Example 4 has much lower evaporation loss, it is subject to environmental regulation since it contains a high content of PCA. Also, as can be seen from the results shown in Table 5, the rubber composition obtained in Comparative Example 5 prepared by blending the additive for rubber obtained in Comparative Example 1, and the rubber composition obtained in Comparative Example 8 prepared by blending the additive for rubber obtained in Comparative Example 4 cannot meet the requirement for the spring property of the present invention. The rubber composition obtained in Comparative Example 6 prepared by blending the additive for rubber obtained in Comparative Example 2 cannot meet the requirements for heat resistance and the spring property of the present invention. The rubber composition obtained in Comparative Example 7 prepared by blending the additive for rubber obtained in Comparative Example 3 cannot meet the requirement for heat resistance of the present invention. The rubber composition obtained in Comparative Example 9 prepared by blending components (A) and (B) separately cannot meet the requirement for the spring property of the present invention.
The additive for rubber of the present invention is not subject to environmental regulation and can provide a rubber composition with excellent heat resistance and spring property.
Moreover, the rubber composition of the present invention is prepared by blending the aforementioned additive for rubber and has excellent heat resistance and spring property. The rubber composition can be suitably used as a rubber composition for vibration isolation. Specifically, it can be suitably used as a vibration damping material for an engine mount, a stabilizer bushing, and a suspension bushing in automobiles or other vehicles, in addition, the rubber composition may also be used for a control damper of a computer hard disk, a vibration damper for a washing machine or other household appliance, an architectural anti-seismic wall in the construction and housing field, a vibration control (vibration suppression) damper or other vibration control (vibration suppression) apparatus and seismic isolation apparatuses, as well as for automobile tires, footwear, hoses, belts, air springs, anti-slip sheets, and other general and industrial products.
| Number | Date | Country | Kind |
|---|---|---|---|
| JP 2012105923 | May 2012 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2013/062602 | 4/30/2013 | WO | 00 |
