WO2015136792A1 - Rubber composition and vulcanized product thereof - Google Patents
Rubber composition and vulcanized product thereof Download PDFInfo
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- WO2015136792A1 WO2015136792A1 PCT/JP2014/081842 JP2014081842W WO2015136792A1 WO 2015136792 A1 WO2015136792 A1 WO 2015136792A1 JP 2014081842 W JP2014081842 W JP 2014081842W WO 2015136792 A1 WO2015136792 A1 WO 2015136792A1
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L11/00—Compositions of homopolymers or copolymers of chloroprene
Definitions
- the present invention relates to a rubber composition and a vulcanized product thereof. More specifically, the present invention relates to a rubber composition containing polychloroprene and a vulcanized product thereof.
- Polychloroprene has excellent mechanical properties, weather resistance and flame retardancy, and is widely used as a material for industrial rubber parts.
- the performance required for industrial rubber parts has been remarkably increased, and rubber with improved mechanical properties such as tensile stress, tensile strength and elongation at break of polychloroprene vulcanizate, as well as improved ozone resistance Compositions have been sought.
- a chloroprene elastomer composition (see Patent Document 1) in which polychloroprene sol and polychloroprene gel are mixed at a specific ratio, xanthogen-modified polychloroprene and / or A rubber composition (see Patent Document 2) is known in which sulfur-modified polychloroprene is mixed with mercaptan-modified polychloroprene at a specific ratio, and specific carbon black is further added.
- a rubber composition containing a specific amount of ethylene-propylene-diene copolymer rubber blended with chloroprene rubber and further containing a specific amount of a thiazole compound, a thiuram compound and a thiourea compound (Patent Document 3) See).
- Patent Documents 1 and 2 described above are improved in mechanical properties, the ozone resistance is not sufficiently improved.
- the rubber composition described in Patent Document 3 is resistant to Although the improvement in ozone is high, the mechanical strength is not sufficiently improved.
- the present invention provides a rubber composition and a vulcanized product thereof that can provide a vulcanized product with improved mechanical properties such as tensile stress, tensile strength, and elongation at break, and significantly improved ozone resistance.
- the main purpose is to provide a rubber composition and a vulcanized product thereof that can provide a vulcanized product with improved mechanical properties such as tensile stress, tensile strength, and elongation at break, and significantly improved ozone resistance.
- the rubber composition according to the present invention comprises 100 parts by mass of polychloroprene, 3 to 50 parts by mass of an ethylene / ⁇ -olefin / non-conjugated polyene copolymer, 10 to 100 parts by mass of carbon black, and the ethylene / ⁇ -olefin.
- non-conjugated polyene copolymer has the chemical formula I (in the chemical formula I, R is an alkyl group having 1 to 20 carbon atoms, n and n 'are the same or different integers of 1 to 8, and p is 1 to 20 parts by mass of a poly (alkylphenol) polysulfide having a structure represented by the formula:
- R is an alkyl group having 1 to 20 carbon atoms
- p is 1 to 20 parts by mass of a poly (alkylphenol) polysulfide having a structure represented by the formula:
- the ethylene / ⁇ -olefin / non-conjugated polyene copolymer those containing 1 to 10% by mass of non-conjugated polyene units in 100% by mass of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer can be used. .
- Non-conjugated polyene units of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer include 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 7-methyl-1,6-octadiene and At least one selected from 5-methyl-1,4-hexadiene can be used.
- the alkylphenol structure of the poly (alkylphenol) polysulfide is p-cresol, i-propylphenol, pt-butylphenol, amylphenol, pt-octylphenol, nonylphenol, dodecylphenol, allylphenol, cyclohexylphenol, 4,6- At least one selected from dioctyl resorcin can be used.
- the carbon black is a furnace carbon black such as SAF (Super Abrasion Furnace Black), ISAF (Intermediate Super Abrasion Furnace Black), IISA (Intermediate ISAF), HAF (High Abrasion Furnace Black), MAF (Medium Abrasion Furnace Black), FEF ( Fast Extruding Furnace Black), SRF (Semi-Reinforcing Furnace Black), GPF (General Purpose Furnace Black), FF (Fine Furnace Black) and CF (Conductive Furnace Black), FT (Fine Thermal Black) and MT (thermal carbon black) Medium thermal black), channel carbon black, at least one selected from EPC (Easy Processing Channel Black), MPC (Medium Processing Channel Black), and acetylene black can be used.
- the vulcanized product according to the present invention is obtained by vulcanizing the rubber composition described above.
- a rubber composition from which a vulcanizate having improved mechanical properties such as tensile stress, tensile strength and elongation at break and further improved ozone resistance can be obtained, and a vulcanizate thereof. it can.
- the rubber composition of the present embodiment comprises (1) polychloroprene, (2) ethylene / ⁇ -olefin / non-conjugated polyene copolymer, (3) carbon black, and (4) poly (alkylphenol) having a specific structure. It contains polysulfide.
- Polychloroprene is obtained by polymerizing chloroprene and then washing and drying as necessary.
- emulsifiers, dispersants, catalysts, catalyst activators, chain transfer agents and polymerizations added during the polymerization May contain banners.
- Monomers copolymerizable with chloroprene include acrylic acid esters such as methyl acrylate, butyl acrylate and 2-ethylhexyl acrylate, and methacrylic acid esters such as methyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate.
- Hydroxy (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxymethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and 2,3-dichloro-1,3-butadiene, There are 1-chloro-1,3-butadiene, butadiene, isoprene, ethylene, styrene and acrylonitrile.
- the monomer copolymerized with chloroprene is not limited to one type, and a copolymer obtained by copolymerizing three or more types of monomers including chloroprene can also be used. Further, the polymer structure of the obtained polychloroprene is not particularly limited.
- Polychloroprene is classified into sulfur-modified polychloroprene, mercaptan-modified polychloroprene, and xanthogen-modified polychloroprene.
- the sulfur-modified polychloroprene is obtained by copolymerizing a raw material monomer containing chloroprene as a main component and sulfur, and plasticizing the obtained copolymer with thiuram disulfide to adjust to a predetermined Mooney viscosity.
- Mercaptan-modified polychloroprene is obtained by using alkyl mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan and octyl mercaptan as molecular weight modifiers.
- Xanthogen-modified polychloroprene is obtained by using an alkyl xanthogen compound as a molecular weight modifier.
- the polychloroprene blended in the rubber composition may be any of the above-mentioned various polychloroprenes, and in particular, when improving heat resistance, use non-sulfur-modified polychloroprene such as mercaptan-modified polychloroprene or xanthogen-modified polychloroprene. Is preferred.
- Ethylene / ⁇ -olefin / non-conjugated polyene copolymer is a tensile stress, tensile strength, vulcanized product obtained by vulcanizing a rubber composition, Blended to improve mechanical properties such as elongation at break and ozone resistance.
- Ethylene / ⁇ -olefin / non-conjugated polyene copolymer is produced by copolymerizing ethylene with ⁇ -olefin and non-conjugated polyene by a conventionally known method such as a gas phase polymerization method, a solution polymerization method or a slurry polymerization method. can do.
- the ⁇ -olefin constituting the ethylene / ⁇ -olefin / non-conjugated polyene copolymer is not particularly limited, but from the viewpoint of processability, it has 3 to 20 carbon atoms. ⁇ -olefins are preferred. Examples of the ⁇ -olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene.
- ⁇ -olefins propylene, 1-butene, 1-hexene and 1-octene are preferable, and propylene is particularly preferable from the viewpoint of a balance between processability and heat-resistant physical properties.
- the ⁇ -olefin constituting the ethylene / ⁇ -olefin copolymer and the ethylene / ⁇ -olefin / non-conjugated polyene copolymer is not limited to one type, but two or more types of ⁇ -olefin are copolymerized. It may be.
- Non-conjugated polyene examples include 5-ethylidene-2-norbornene, dicyclopentadiene, 5-propylidene-2-norbornene, 5 -Cyclic polyenes such as vinyl-2-norbornene, 2,5-norbornadiene, 1,4-cyclohexadiene, 1,4-cyclooctadiene and 1,5-cyclooctadiene, 1,4-hexadiene, 4-methyl- 1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 6-methyl-1,6-octadiene, 7-methyl- 1,6-octadiene, 5,7-dimethyl-1,6-octa
- non-conjugated polyenes from the viewpoint of crosslinking efficiency, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 7-methyl-1,6-octadiene and 5-methyl-1, 4-hexadiene is preferred, and 5-ethylidene-2-norbornene is particularly preferred.
- the non-conjugated polyene constituting the ethylene / ⁇ -olefin / non-conjugated polyene copolymer is not limited to one type, and two or more types of non-conjugated polyenes may be copolymerized.
- the amount of non-conjugated polyene constituting the ethylene / ⁇ -olefin / non-conjugated polyene copolymer is 1 to 10% by mass of non-conjugated polyene units in 100% by mass of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer. It can be. By adjusting the bonding amount of the non-conjugated polyene unit within this range, the mechanical properties of the obtained vulcanizate are further improved.
- the blending amount of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer is 3 to 50 parts by mass per 100 parts by mass of polychloroprene. If the blending amount of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer is less than 3 parts by mass, the resulting vulcanizate may not exhibit sufficient ozone resistance. Further, when the blending amount of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer exceeds 50 parts by mass, the mechanical strength of the obtained vulcanizate is lowered.
- the blending amount of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer is preferably 5 to 40 parts by mass, more preferably 10 to 30 parts by mass.
- Carbon black is blended in order to improve mechanical properties such as tensile stress, tensile strength, and elongation at break of a vulcanized product obtained by vulcanizing a rubber composition.
- carbon black any of furnace black by incomplete combustion method, thermal black by thermal decomposition method, channel black, and acetylene black can be used.
- SAF Super Abrasion Furnace Black
- ISAF Intermediate Super Abrasion Furnace Black
- IISA Intermediate ISAF
- HAF High Abrasion Furnace Black
- MAF Medium Abrasion Furnace Black
- FEF Flud Extruding Furnace Black
- SRF Semi-Reinforcing Furnace Black
- GPF General Purpose Furnace Black
- FF Fluorine Furnace Black
- CF Conductive Furnace Black
- Thermal blacks include FT (Fine Thermal Black) and MT (Medium Thermal Black).
- Channel black includes EPC (Easy Processing Channel Black), MPC (Medium Processing Channel Black), and acetylene black.
- acetylene black is preferably used from the viewpoint of improving the heat resistance of the resulting vulcanizate.
- the blending amount of carbon black is 10 to 100 parts by mass per 100 parts by mass of polychloroprene. If the blending amount of the carbon black is less than 10 parts by mass, the reinforcing property when the rubber composition is vulcanized may be reduced, and the vulcanized product may be impractical. If the amount of carbon black exceeds 100 parts by mass, the heat resistance of the rubber composition may be drastically reduced.
- the amount of carbon black is preferably 15 to 80 parts by mass, more preferably 20 to 60 parts by mass.
- Poly (alkylphenol) polysulfide improves the mechanical properties of rubber compositions by vulcanizing polychloroprene and ethylene / ⁇ -olefin / non-conjugated polyene copolymers in the rubber composition.
- the type of poly (alkylphenol) polysulfide compounded in the rubber composition is not particularly limited, but from the viewpoint of improving mechanical properties, the alkylphenol skeleton is p-cresol, i-propylphenol, pt-butylphenol. , Amylphenol, pt-octylphenol, nonylphenol, dodecylphenol, allylphenol, cyclohexylphenol, and 4,6-dioctylresorcinol.
- the compounding amount of poly (alkylphenol) polysulfide is 1 to 20 parts by mass per 100 parts by mass of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer in the rubber composition. If the blending amount of the poly (alkylphenol) polysulfide is less than this range, the mechanical strength of the resulting vulcanizate may not be sufficiently developed. Moreover, when the compounding quantity of poly (alkylphenol) polysulfide exceeds this range, the heat resistance of the obtained vulcanizate will fall.
- the blending amount of poly (alkylphenol) polysulfide is preferably 2 to 15 parts by mass, more preferably 3 to 10 parts by mass.
- the rubber composition can be obtained by kneading each of the above-described compounds using an open roll, a Banbury mixer, an extruder, or the like at a vulcanization temperature or lower. At this time, after kneading (2) ethylene / ⁇ -olefin / non-conjugated polyene copolymer and (4) poly (alkylphenol) polysulfide, (1) adding polychloroprene and (3) carbon black and kneading, This is desirable because the mechanical properties of the resulting vulcanizate are further improved.
- the rubber composition contains a vulcanizing agent, a vulcanization accelerator, a scorch inhibitor, a processing aid, etc. that are usually used in the rubber industry as long as the effects of the present invention are not impaired. be able to.
- the rubber composition of the present embodiment contains a specific amount of polychloroprene, a specific amount of ethylene / ⁇ -olefin / non-conjugated polyene copolymer, carbon black, and poly (alkylphenol) polysulfide. Therefore, a rubber composition having not only excellent mechanical properties such as tensile stress, tensile strength and elongation at break of the vulcanizate but also extremely excellent ozone resistance can be obtained.
- Vulcanized material The vulcanized material of the present embodiment is obtained by molding and vulcanizing the rubber composition described above into a shape suitable for the purpose.
- the vulcanization method of the rubber composition is not particularly limited, and during or after molding, press vulcanization, injection vulcanization, direct kettle vulcanization, indirect kettle vulcanization, direct steam continuous vulcanization, Vulcanization may be performed by a vulcanization method such as normal pressure continuous vulcanization or continuous vulcanization press.
- vulcanization conditions such as vulcanization temperature and vulcanization time are not particularly limited, and can be set as appropriate.
- the vulcanization temperature is preferably 130 to 200 ° C, more preferably 140 to 190 ° C.
- machining safety is a machining characteristic evaluated by the scorch time, and greatly affects the defect occurrence rate. Specifically, when the scorch time is short, the frequency of occurrence of defective molding is increased because the unvulcanized rubber component is vulcanized during molding at a high temperature.
- the vulcanized product of the present embodiment uses the rubber composition described above, the vulcanized product has a tensile stress, tensile strength, elongation at break, and ozone resistance as compared with a vulcanized product using conventional polychloroprene. Improve gender comprehensively. For this reason, the vulcanizate of this embodiment has high ozone resistance such as a transmission belt, a conveyor belt, an air spring, an automobile hose, an automobile boot, an anti-vibration rubber as well as a seismic isolation rubber and sponge. It can also be suitably used for required molded articles.
- Tables 1 to 3 The components shown in Tables 1 to 3 are as follows. (Polychloroprene) ⁇ Mercaptan-modified polychloroprene (S-40V, manufactured by Denki Kagaku Kogyo Co., Ltd.) ⁇ Xanthogen-modified polychloroprene (DCR-66, manufactured by Denki Kagaku Kogyo Co., Ltd.) ⁇ Sulfur modified polychloroprene (DCR-107, manufactured by Denki Kagaku Kogyo Co., Ltd.)
- Carbon black Carbon black
- HAF Alignment Agent
- GPF Carbon black GPF
- SRF Alignment Reduction Function
- Poly (alkylphenol) polysulfide) ⁇ Poly (t-butylphenol) polysulfide (Altema VultacTB7) ⁇ Poly (t-amylphenol) disulfide (Sunshine AP manufactured by Sanshin Chemical Industry Co., Ltd.)
- Example 1 The rubber composition of Example 1 is composed of 100 parts by mass of mercaptan-modified polychloroprene, 30 parts by mass of an ethylene / ⁇ -olefin / non-conjugated polyene copolymer containing 8% by mass of 5-ethylidene-2-norbornene, and 40 parts by mass of carbon black HAF.
- thiourea vulcanization accelerator as a vulcanization accelerator (Kawaguchi Chemical Industry stock Company Axel 22S: Ethylenethiourea) 0.8 parts by mass, zinc oxide (2 types of zinc oxide manufactured by Sakai Chemical Industry Co., Ltd.) 5 parts by mass, and then kneaded using an 8-inch roll It is.
- the amount of poly (t-butylphenol) polysulfide added corresponds to 10 parts by mass with respect to 100 parts by mass of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer.
- the obtained rubber composition was vulcanized at 160 ° C. for 20 minutes with a hydraulic press, and formed into a sheet having a thickness of 2 mm to prepare a test piece. And using this test piece, "tensile stress”"tensilestrength””breakingelongation”,”durometer hardness (HS)", and "ozone resistance” were evaluated.
- Elastic modulus (durometer hardness (HS)) Based on JIS K6253, it measured using the type D durometer.
- Ozone resistance According to JIS K6258, evaluated under the conditions of 0 to 20% dynamic elongation, 40 ° C. ⁇ 50 pphm, 144 hours. It was.
- the vulcanizate using the rubber composition of Example 1 had improved ozone resistance as well as mechanical properties such as tensile stress, tensile strength, and elongation at break.
- Examples 2 to 18 and Comparative Examples 1 to 5 The formulation of the compound added when preparing the rubber composition was changed as shown in Tables 1 to 3, and the rubber composition was prepared and vulcanized in the same manner as in Example 1. did. The obtained vulcanized samples were evaluated in the same manner as in Example 1 for “tensile stress”, “tensile strength”, “breaking elongation”, “durometer hardness (HS)”, and “ozone resistance”. The evaluation results are shown in Tables 1 to 3.
- a rubber composition capable of obtaining a vulcanizate having improved ozone resistance as well as mechanical properties such as tensile stress, tensile strength and elongation at break was obtained.
- the vulcanizate obtained by vulcanizing this rubber composition has improved properties as described above, and can be suitably used as a material for industrial products.
Abstract
Provided are: a rubber composition capable of obtaining a vulcanized product having excellent mechanical properties such as vulcanized product tensile strength, break elongation, tear strength, and elastic force; and a vulcanized product thereof. The rubber composition contains 100 parts by mass polychloroprene , 3-50 parts by mass ethylene-α-olefin-unconjugated polyene copolymer, 10-100 parts by mass carbon black, and 1-20 parts by mass, relative to 100 parts by mass ethylene-α-olefin-unconjugated polyene copolymer, poly (alkyl phenol) polysulfide having a structure indicated by chemical formula I (in chemical formula I, R indicates a C1-20 alkyl group, n and n' indicate the same or different integers from 1 to 8, and p indicates an integer from 0 to 50.
Description
本発明は、ゴム組成物及びその加硫物に関する。より詳しくは、ポリクロロプレンを含有するゴム組成物及びその加硫物に関する。
The present invention relates to a rubber composition and a vulcanized product thereof. More specifically, the present invention relates to a rubber composition containing polychloroprene and a vulcanized product thereof.
ポリクロロプレンは、機械特性、耐候性及び難燃性に優れており、工業用ゴム部品の材料として広く使用されている。近年、工業用ゴム部品に要求される性能が著しく高まっており、ポリクロロプレンの加硫物の引張応力、引張強さ、破断伸びといった機械的特性を向上させるとともに、耐オゾン性を向上させたゴム組成物が求められるようになってきた。
Polychloroprene has excellent mechanical properties, weather resistance and flame retardancy, and is widely used as a material for industrial rubber parts. In recent years, the performance required for industrial rubber parts has been remarkably increased, and rubber with improved mechanical properties such as tensile stress, tensile strength and elongation at break of polychloroprene vulcanizate, as well as improved ozone resistance Compositions have been sought.
ポリクロロプレンの加硫物の機械的特性を向上させる手段として、ポリクロロプレンゾルとポリクロロプレンゲルを特定の割合で混合したクロロプレン系エラストマー組成物（特許文献１参照）や、キサントゲン変性ポリクロロプレン及び／またはメルカプタン変性ポリクロロプレンに硫黄変性ポリクロロプレンを特定の割合で混合し、さらに特定のカーボンブラックを添加したゴム組成物（特許文献２参照）が知られている。
また、耐オゾン性を向上させる手段として、クロロプレンゴムにエチレン－プロピレン－ジエン共重合ゴムを特定量ブレンドし、さらにチアゾール化合物と、チウラム化合物、チオウレア化合物を特定量含有させるゴム組成物（特許文献３参照）が知られている。 As means for improving the mechanical properties of the vulcanized product of polychloroprene, a chloroprene elastomer composition (see Patent Document 1) in which polychloroprene sol and polychloroprene gel are mixed at a specific ratio, xanthogen-modified polychloroprene and / or A rubber composition (see Patent Document 2) is known in which sulfur-modified polychloroprene is mixed with mercaptan-modified polychloroprene at a specific ratio, and specific carbon black is further added.
Further, as means for improving ozone resistance, a rubber composition containing a specific amount of ethylene-propylene-diene copolymer rubber blended with chloroprene rubber and further containing a specific amount of a thiazole compound, a thiuram compound and a thiourea compound (Patent Document 3) See).
また、耐オゾン性を向上させる手段として、クロロプレンゴムにエチレン－プロピレン－ジエン共重合ゴムを特定量ブレンドし、さらにチアゾール化合物と、チウラム化合物、チオウレア化合物を特定量含有させるゴム組成物（特許文献３参照）が知られている。 As means for improving the mechanical properties of the vulcanized product of polychloroprene, a chloroprene elastomer composition (see Patent Document 1) in which polychloroprene sol and polychloroprene gel are mixed at a specific ratio, xanthogen-modified polychloroprene and / or A rubber composition (see Patent Document 2) is known in which sulfur-modified polychloroprene is mixed with mercaptan-modified polychloroprene at a specific ratio, and specific carbon black is further added.
Further, as means for improving ozone resistance, a rubber composition containing a specific amount of ethylene-propylene-diene copolymer rubber blended with chloroprene rubber and further containing a specific amount of a thiazole compound, a thiuram compound and a thiourea compound (Patent Document 3) See).
前述した特許文献１や２に記載されているゴム組成物は、機械的特性の向上が認められるものの耐オゾン性の向上が十分ではなく、特許文献３に記載されているゴム組成物は、耐オゾン性の向上が高いものの機械的強度の向上が十分ではない。
Although the rubber compositions described in Patent Documents 1 and 2 described above are improved in mechanical properties, the ozone resistance is not sufficiently improved. The rubber composition described in Patent Document 3 is resistant to Although the improvement in ozone is high, the mechanical strength is not sufficiently improved.
そこで、本発明は、引張応力、引張強さ、破断伸びといった機械的特性を向上させるとともに、耐オゾン性を著しく向上させた加硫物が得られるゴム組成物及びその加硫物を提供することを主目的とする。
Accordingly, the present invention provides a rubber composition and a vulcanized product thereof that can provide a vulcanized product with improved mechanical properties such as tensile stress, tensile strength, and elongation at break, and significantly improved ozone resistance. The main purpose.
本発明に係るゴム組成物は、ポリクロロプレン１００質量部と、エチレン・α－オレフィン・非共役ポリエン共重合体３～５０質量部と、カーボンブラック１０～１００質量部と、前記エチレン・α－オレフィン・非共役ポリエン共重合体１００質量部に対して化学式Ｉ（化学式Ｉ中、Ｒは１～２０個の炭素原子を有するアルキル基、ｎおよびｎ’は同一または異なる１～８の整数、ｐは０～５０の整数を表す。）で表される構造のポリ（アルキルフェノール）ポリスルフィド１～２０質量部と、を含有するものである。
前記エチレン・α－オレフィン・非共役ポリエン共重合体は、エチレン・α－オレフィン・非共役ポリエン共重合体１００質量％中、非共役ポリエン単位を１～１０質量％含有するものを用いることができる。
前記エチレン・α－オレフィン・非共役ポリエン共重合体の非共役ポリエン単位は、５－エチリデン－２－ノルボルネン、ジシクロペンタジエン、５－ビニル－２－ノルボルネン、７－メチル－１，６－オクタジエン及び５－メチル－１，４－ヘキサジエンから選ばれる少なくとも一種を用いることができる。 The rubber composition according to the present invention comprises 100 parts by mass of polychloroprene, 3 to 50 parts by mass of an ethylene / α-olefin / non-conjugated polyene copolymer, 10 to 100 parts by mass of carbon black, and the ethylene / α-olefin. -100 parts by mass of the non-conjugated polyene copolymer has the chemical formula I (in the chemical formula I, R is an alkyl group having 1 to 20 carbon atoms, n and n 'are the same or different integers of 1 to 8, and p is 1 to 20 parts by mass of a poly (alkylphenol) polysulfide having a structure represented by the formula:
As the ethylene / α-olefin / non-conjugated polyene copolymer, those containing 1 to 10% by mass of non-conjugated polyene units in 100% by mass of the ethylene / α-olefin / non-conjugated polyene copolymer can be used. .
Non-conjugated polyene units of the ethylene / α-olefin / non-conjugated polyene copolymer include 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 7-methyl-1,6-octadiene and At least one selected from 5-methyl-1,4-hexadiene can be used.
前記エチレン・α－オレフィン・非共役ポリエン共重合体は、エチレン・α－オレフィン・非共役ポリエン共重合体１００質量％中、非共役ポリエン単位を１～１０質量％含有するものを用いることができる。
前記エチレン・α－オレフィン・非共役ポリエン共重合体の非共役ポリエン単位は、５－エチリデン－２－ノルボルネン、ジシクロペンタジエン、５－ビニル－２－ノルボルネン、７－メチル－１，６－オクタジエン及び５－メチル－１，４－ヘキサジエンから選ばれる少なくとも一種を用いることができる。 The rubber composition according to the present invention comprises 100 parts by mass of polychloroprene, 3 to 50 parts by mass of an ethylene / α-olefin / non-conjugated polyene copolymer, 10 to 100 parts by mass of carbon black, and the ethylene / α-olefin. -100 parts by mass of the non-conjugated polyene copolymer has the chemical formula I (in the chemical formula I, R is an alkyl group having 1 to 20 carbon atoms, n and n 'are the same or different integers of 1 to 8, and p is 1 to 20 parts by mass of a poly (alkylphenol) polysulfide having a structure represented by the formula:
As the ethylene / α-olefin / non-conjugated polyene copolymer, those containing 1 to 10% by mass of non-conjugated polyene units in 100% by mass of the ethylene / α-olefin / non-conjugated polyene copolymer can be used. .
Non-conjugated polyene units of the ethylene / α-olefin / non-conjugated polyene copolymer include 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 7-methyl-1,6-octadiene and At least one selected from 5-methyl-1,4-hexadiene can be used.
前記ポリ（アルキルフェノール）ポリスルフィドのアルキルフェノール構造は、ｐ－クレゾール、ｉ－プロピルフェノール、ｐ－ｔ－ブチルフェノール、アミルフェノール、ｐ－ｔ－オクチルフェノール、ノニルフェノール、ドデシルフェノール、アリルフェノール、シクロヘキシルフェノール、４，６－ジオクチルレゾルシンから選ばれる少なくとも一種を用いることができる。
前記カーボンブラックは、ファーネスカーボンブラックとしてＳＡＦ(Super Abrasion Furnace Black)やＩＳＡＦ(Intermediate Super Abrasion Furnace Black)、ＩＩＳＡＦ(Intermediate ISAF)、ＨＡＦ(High Abrasion Furnace Black)、ＭＡＦ(Medium Abrasion Furnace Black)、ＦＥＦ(Fast Extruding Furnace Black)、ＳＲＦ(Semi-Reinforcing Furnace Black)、ＧＰＦ(General Purpose Furnace Black)、ＦＦ(Fine Furnace Black)及びＣＦ(Conductive Furnace Black) 、サーマルカーボンブラックとしてＦＴ（Fine Thermal Black）やＭＴ（Medium Thermal Black）、チャンネルカーボンブラックとしてＥＰＣ（Easy Processing Channel Black）やＭＰＣ（Medium Processing Channel Black）、並びにアセチレンブラックから選ばれる少なくとも一種を用いることができる。
本発明に係る加硫物は、前述したゴム組成物を加硫して得られるものである。 The alkylphenol structure of the poly (alkylphenol) polysulfide is p-cresol, i-propylphenol, pt-butylphenol, amylphenol, pt-octylphenol, nonylphenol, dodecylphenol, allylphenol, cyclohexylphenol, 4,6- At least one selected from dioctyl resorcin can be used.
The carbon black is a furnace carbon black such as SAF (Super Abrasion Furnace Black), ISAF (Intermediate Super Abrasion Furnace Black), IISA (Intermediate ISAF), HAF (High Abrasion Furnace Black), MAF (Medium Abrasion Furnace Black), FEF ( Fast Extruding Furnace Black), SRF (Semi-Reinforcing Furnace Black), GPF (General Purpose Furnace Black), FF (Fine Furnace Black) and CF (Conductive Furnace Black), FT (Fine Thermal Black) and MT (thermal carbon black) Medium thermal black), channel carbon black, at least one selected from EPC (Easy Processing Channel Black), MPC (Medium Processing Channel Black), and acetylene black can be used.
The vulcanized product according to the present invention is obtained by vulcanizing the rubber composition described above.
前記カーボンブラックは、ファーネスカーボンブラックとしてＳＡＦ(Super Abrasion Furnace Black)やＩＳＡＦ(Intermediate Super Abrasion Furnace Black)、ＩＩＳＡＦ(Intermediate ISAF)、ＨＡＦ(High Abrasion Furnace Black)、ＭＡＦ(Medium Abrasion Furnace Black)、ＦＥＦ(Fast Extruding Furnace Black)、ＳＲＦ(Semi-Reinforcing Furnace Black)、ＧＰＦ(General Purpose Furnace Black)、ＦＦ(Fine Furnace Black)及びＣＦ(Conductive Furnace Black) 、サーマルカーボンブラックとしてＦＴ（Fine Thermal Black）やＭＴ（Medium Thermal Black）、チャンネルカーボンブラックとしてＥＰＣ（Easy Processing Channel Black）やＭＰＣ（Medium Processing Channel Black）、並びにアセチレンブラックから選ばれる少なくとも一種を用いることができる。
本発明に係る加硫物は、前述したゴム組成物を加硫して得られるものである。 The alkylphenol structure of the poly (alkylphenol) polysulfide is p-cresol, i-propylphenol, pt-butylphenol, amylphenol, pt-octylphenol, nonylphenol, dodecylphenol, allylphenol, cyclohexylphenol, 4,6- At least one selected from dioctyl resorcin can be used.
The carbon black is a furnace carbon black such as SAF (Super Abrasion Furnace Black), ISAF (Intermediate Super Abrasion Furnace Black), IISA (Intermediate ISAF), HAF (High Abrasion Furnace Black), MAF (Medium Abrasion Furnace Black), FEF ( Fast Extruding Furnace Black), SRF (Semi-Reinforcing Furnace Black), GPF (General Purpose Furnace Black), FF (Fine Furnace Black) and CF (Conductive Furnace Black), FT (Fine Thermal Black) and MT (thermal carbon black) Medium thermal black), channel carbon black, at least one selected from EPC (Easy Processing Channel Black), MPC (Medium Processing Channel Black), and acetylene black can be used.
The vulcanized product according to the present invention is obtained by vulcanizing the rubber composition described above.
本発明によれば、引張応力、引張強さ、破断伸びといった機械的特性を向上させ、更に耐オゾン性を著しく向上させた加硫物が得られるゴム組成物及びその加硫物を得ることができる。
According to the present invention, it is possible to obtain a rubber composition from which a vulcanizate having improved mechanical properties such as tensile stress, tensile strength and elongation at break and further improved ozone resistance can be obtained, and a vulcanizate thereof. it can.
本実施形態のゴム組成物は、（１）ポリクロロプレンと、（２）エチレン・α－オレフィン・非共役ポリエン共重合体と、（３）カーボンブラックと、（４）特定構造のポリ（アルキルフェノール）ポリスルフィドを含有するものである。
The rubber composition of the present embodiment comprises (1) polychloroprene, (2) ethylene / α-olefin / non-conjugated polyene copolymer, (3) carbon black, and (4) poly (alkylphenol) having a specific structure. It contains polysulfide.
（１）ポリクロロプレン
ポリクロロプレンは、クロロプレンを重合した後、必要に応じて洗浄や乾燥を行うことにより得られるものである。重合反応の生成物であるクロロプレン単独重合体又はクロロプレンと他の単量体との共重合体の他に、重合時に添加された乳化剤、分散剤、触媒、触媒活性化剤、連鎖移動剤及び重合禁止剤などが含まれている場合がある。 (1) Polychloroprene Polychloroprene is obtained by polymerizing chloroprene and then washing and drying as necessary. In addition to the chloroprene homopolymer or the copolymer of chloroprene and other monomers that are the products of the polymerization reaction, emulsifiers, dispersants, catalysts, catalyst activators, chain transfer agents and polymerizations added during the polymerization May contain banners.
ポリクロロプレンは、クロロプレンを重合した後、必要に応じて洗浄や乾燥を行うことにより得られるものである。重合反応の生成物であるクロロプレン単独重合体又はクロロプレンと他の単量体との共重合体の他に、重合時に添加された乳化剤、分散剤、触媒、触媒活性化剤、連鎖移動剤及び重合禁止剤などが含まれている場合がある。 (1) Polychloroprene Polychloroprene is obtained by polymerizing chloroprene and then washing and drying as necessary. In addition to the chloroprene homopolymer or the copolymer of chloroprene and other monomers that are the products of the polymerization reaction, emulsifiers, dispersants, catalysts, catalyst activators, chain transfer agents and polymerizations added during the polymerization May contain banners.
クロロプレンと共重合可能な単量体としては、アクリル酸メチル、アクリル酸ブチル及びアクリル酸２－エチルヘキシルなどのアクリル酸エステル類、メタクリル酸メチル、メタクリル酸ブチル及びメタクリル酸２－エチルヘキシルなどのメタクリル酸エステル類、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシメチル（メタ）アクリレート及び２－ヒドロキシプロピル（メタ）アクリレートなどのヒドロキシ（メタ）アクリレート類、並びに２，３－ジクロロ－１，３－ブタジエン、１－クロロ－１，３－ブタジエン、ブタジエン、イソプレン、エチレン、スチレン及びアクリロニトリルがある。
Monomers copolymerizable with chloroprene include acrylic acid esters such as methyl acrylate, butyl acrylate and 2-ethylhexyl acrylate, and methacrylic acid esters such as methyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate. , Hydroxy (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxymethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and 2,3-dichloro-1,3-butadiene, There are 1-chloro-1,3-butadiene, butadiene, isoprene, ethylene, styrene and acrylonitrile.
クロロプレンと共重合する単量体は、１種類に限定されるものではなく、クロロプレンを含む３種以上の単量体を共重合したものを使用することもできる。また、得られるポリクロロプレンのポリマー構造も、特に限定されるものではない。
The monomer copolymerized with chloroprene is not limited to one type, and a copolymer obtained by copolymerizing three or more types of monomers including chloroprene can also be used. Further, the polymer structure of the obtained polychloroprene is not particularly limited.
ポリクロロプレンは、硫黄変性ポリクロロプレン、メルカプタン変性ポリクロロプレン及びキサントゲン変性ポリクロロプレンに分類される。硫黄変性ポリクロロプレンは、クロロプレンを主成分とする原料単量体と硫黄を共重合し、得られた共重合体をチウラムジスルフィドで可塑化して、所定のムーニー粘度に調整したものである。
Polychloroprene is classified into sulfur-modified polychloroprene, mercaptan-modified polychloroprene, and xanthogen-modified polychloroprene. The sulfur-modified polychloroprene is obtained by copolymerizing a raw material monomer containing chloroprene as a main component and sulfur, and plasticizing the obtained copolymer with thiuram disulfide to adjust to a predetermined Mooney viscosity.
メルカプタン変性ポリクロロプレンは、分子量調整剤としてｎ－ドデシルメルカプタン、ｔｅｒｔ－ドデシルメルカプタン及びオクチルメルカプタンなどのアルキルメルカプタン類を使用することにより得られたものである。キサントゲン変性ポリクロロプレンは、分子量調整剤にアルキルキサントゲン化合物を使用することにより得られたものである。ゴム組成物に配合されるポリクロロプレンは、前述した各種ポリクロロプレンのいずれでもよく、特に耐熱性を向上させたい場合は、メルカプタン変性ポリクロロプレンやキサントゲン変性ポリクロロプレン等の非硫黄変性ポリクロロプレンを用いることが好適である。
Mercaptan-modified polychloroprene is obtained by using alkyl mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan and octyl mercaptan as molecular weight modifiers. Xanthogen-modified polychloroprene is obtained by using an alkyl xanthogen compound as a molecular weight modifier. The polychloroprene blended in the rubber composition may be any of the above-mentioned various polychloroprenes, and in particular, when improving heat resistance, use non-sulfur-modified polychloroprene such as mercaptan-modified polychloroprene or xanthogen-modified polychloroprene. Is preferred.
（２）エチレン・α－オレフィン・非共役ポリエン共重合体
エチレン・α－オレフィン・非共役ポリエン共重合体は、ゴム組成物を加硫して得られる加硫物の引張応力、引張強さ、破断伸びといった機械的特性と、耐オゾン性を向上させるために配合する。 (2) Ethylene / α-olefin / non-conjugated polyene copolymer The ethylene / α-olefin / non-conjugated polyene copolymer is a tensile stress, tensile strength, vulcanized product obtained by vulcanizing a rubber composition, Blended to improve mechanical properties such as elongation at break and ozone resistance.
エチレン・α－オレフィン・非共役ポリエン共重合体は、ゴム組成物を加硫して得られる加硫物の引張応力、引張強さ、破断伸びといった機械的特性と、耐オゾン性を向上させるために配合する。 (2) Ethylene / α-olefin / non-conjugated polyene copolymer The ethylene / α-olefin / non-conjugated polyene copolymer is a tensile stress, tensile strength, vulcanized product obtained by vulcanizing a rubber composition, Blended to improve mechanical properties such as elongation at break and ozone resistance.
エチレン・α－オレフィン・非共役ポリエン共重合体は、気相重合法、溶液重合法及びスラリー重合法などの従来公知の方法により、エチレンとα－オレフィン及び非共役ポリエンを共重合させることで製造することができる。
Ethylene / α-olefin / non-conjugated polyene copolymer is produced by copolymerizing ethylene with α-olefin and non-conjugated polyene by a conventionally known method such as a gas phase polymerization method, a solution polymerization method or a slurry polymerization method. can do.
（２－１）α―オレフィン
エチレン・α－オレフィン・非共役ポリエン共重合体を構成するα－オレフィンは、特に限定されるものではないが、加工性の観点から、炭素数が３～２０のα－オレフィンが好ましい。炭素数が３～２０のα－オレフィンとしては、プロピレン、１－ブテン、１－ペンテン、１－ヘキセン、１－ヘプテン、１－オクテン及び１－デセンなどがある。 (2-1) α-Olefin The α-olefin constituting the ethylene / α-olefin / non-conjugated polyene copolymer is not particularly limited, but from the viewpoint of processability, it has 3 to 20 carbon atoms. α-olefins are preferred. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene.
エチレン・α－オレフィン・非共役ポリエン共重合体を構成するα－オレフィンは、特に限定されるものではないが、加工性の観点から、炭素数が３～２０のα－オレフィンが好ましい。炭素数が３～２０のα－オレフィンとしては、プロピレン、１－ブテン、１－ペンテン、１－ヘキセン、１－ヘプテン、１－オクテン及び１－デセンなどがある。 (2-1) α-Olefin The α-olefin constituting the ethylene / α-olefin / non-conjugated polyene copolymer is not particularly limited, but from the viewpoint of processability, it has 3 to 20 carbon atoms. α-olefins are preferred. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene.
これらのα－オレフィンの中でも、加工性と耐熱性の物性のバランスの観点から、プロピレン、１－ブテン、１－ヘキセン及び１－オクテンが好ましく、特にプロピレンが好ましい。なお、エチレン・α－オレフィン共重合体及びエチレン・α－オレフィン・非共役ポリエン共重合体を構成するα－オレフィンは、１種には限定されず、２種以上のα－オレフィンが共重合されていてもよい。
Among these α-olefins, propylene, 1-butene, 1-hexene and 1-octene are preferable, and propylene is particularly preferable from the viewpoint of a balance between processability and heat-resistant physical properties. The α-olefin constituting the ethylene / α-olefin copolymer and the ethylene / α-olefin / non-conjugated polyene copolymer is not limited to one type, but two or more types of α-olefin are copolymerized. It may be.
（２－２）非共役ポリエン
エチレン・α－オレフィン・非共役ポリエン共重合体を構成する非共役ポリエンとしては、５－エチリデン－２－ノルボルネン、ジシクロペンタジエン、５－プロピリデン－２－ノルボルネン、５－ビニル－２－ノルボルネン、２，５－ノルボルナジエン、１，４－シクロヘキサジエン、１，４－シクロオクタジエン及び１，５－シクロオクタジエンなどの環状ポリエン、１，４－ヘキサジエン、４－メチル－１，４－ヘキサジエン、５－メチル－１，４－ヘキサジエン、５－メチル－１，５－ヘプタジエン、６－メチル－１，５－ヘプタジエン、６－メチル－１，６－オクタジエン、７－メチル－１，６－オクタジエン、５，７－ジメチル－１，６－オクタジエン、７－メチル－１，７－ノナジエン、８－メチル－１，７－ノナジエン、８－メチル－１，８－デカジエン、９－メチル－１，８－デカジエン、４－エチリデン－１，６－オクタジエン、７－メチル－４－エチリデン－１，６－オクタジエン、７－メチル－４－エチリデン－１，６－ノナジエン、７－エチル－４－エチリデン－１，６－ノナジエン、６，７－ジメチル－４－エチリデン－１，６－オクタジエン及び６，７－ジメチル－４－エチリデン－１，６－ノナジエンなどの炭素数が６～１５の内部不飽和結合を有する鎖状ポリエン、並びに１，５－ヘキサジエン、１，６－ヘプタジエン、１，７－オクタジエン、１，８－ノナジエン、１，９－デカジエン、１，１０－ウンデカジエン、１，１１－ドデカジエン、１，１２－トリデカジエン及び１，１３－テトラデカジエンなどのα，ω－ジエンがある。 (2-2) Non-conjugated polyene Examples of the non-conjugated polyene constituting the ethylene / α-olefin / non-conjugated polyene copolymer include 5-ethylidene-2-norbornene, dicyclopentadiene, 5-propylidene-2-norbornene, 5 -Cyclic polyenes such as vinyl-2-norbornene, 2,5-norbornadiene, 1,4-cyclohexadiene, 1,4-cyclooctadiene and 1,5-cyclooctadiene, 1,4-hexadiene, 4-methyl- 1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 6-methyl-1,6-octadiene, 7-methyl- 1,6-octadiene, 5,7-dimethyl-1,6-octadiene, 7-methyl-1,7-nonadiene, 8-methyl 1,7-nonadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 4-ethylidene-1,6-octadiene, 7-methyl-4-ethylidene-1,6-octadiene, 7-methyl-4-ethylidene-1,6-nonadiene, 7-ethyl-4-ethylidene-1,6-nonadiene, 6,7-dimethyl-4-ethylidene-1,6-octadiene and 6,7-dimethyl- A chain polyene having an internal unsaturated bond having 6 to 15 carbon atoms, such as 4-ethylidene-1,6-nonadiene, and 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8 Α, ω such as nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene and 1,13-tetradecadiene There is a diene.
エチレン・α－オレフィン・非共役ポリエン共重合体を構成する非共役ポリエンとしては、５－エチリデン－２－ノルボルネン、ジシクロペンタジエン、５－プロピリデン－２－ノルボルネン、５－ビニル－２－ノルボルネン、２，５－ノルボルナジエン、１，４－シクロヘキサジエン、１，４－シクロオクタジエン及び１，５－シクロオクタジエンなどの環状ポリエン、１，４－ヘキサジエン、４－メチル－１，４－ヘキサジエン、５－メチル－１，４－ヘキサジエン、５－メチル－１，５－ヘプタジエン、６－メチル－１，５－ヘプタジエン、６－メチル－１，６－オクタジエン、７－メチル－１，６－オクタジエン、５，７－ジメチル－１，６－オクタジエン、７－メチル－１，７－ノナジエン、８－メチル－１，７－ノナジエン、８－メチル－１，８－デカジエン、９－メチル－１，８－デカジエン、４－エチリデン－１，６－オクタジエン、７－メチル－４－エチリデン－１，６－オクタジエン、７－メチル－４－エチリデン－１，６－ノナジエン、７－エチル－４－エチリデン－１，６－ノナジエン、６，７－ジメチル－４－エチリデン－１，６－オクタジエン及び６，７－ジメチル－４－エチリデン－１，６－ノナジエンなどの炭素数が６～１５の内部不飽和結合を有する鎖状ポリエン、並びに１，５－ヘキサジエン、１，６－ヘプタジエン、１，７－オクタジエン、１，８－ノナジエン、１，９－デカジエン、１，１０－ウンデカジエン、１，１１－ドデカジエン、１，１２－トリデカジエン及び１，１３－テトラデカジエンなどのα，ω－ジエンがある。 (2-2) Non-conjugated polyene Examples of the non-conjugated polyene constituting the ethylene / α-olefin / non-conjugated polyene copolymer include 5-ethylidene-2-norbornene, dicyclopentadiene, 5-propylidene-2-norbornene, 5 -Cyclic polyenes such as vinyl-2-norbornene, 2,5-norbornadiene, 1,4-cyclohexadiene, 1,4-cyclooctadiene and 1,5-cyclooctadiene, 1,4-hexadiene, 4-methyl- 1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 6-methyl-1,6-octadiene, 7-methyl- 1,6-octadiene, 5,7-dimethyl-1,6-octadiene, 7-methyl-1,7-nonadiene, 8-methyl 1,7-nonadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 4-ethylidene-1,6-octadiene, 7-methyl-4-ethylidene-1,6-octadiene, 7-methyl-4-ethylidene-1,6-nonadiene, 7-ethyl-4-ethylidene-1,6-nonadiene, 6,7-dimethyl-4-ethylidene-1,6-octadiene and 6,7-dimethyl- A chain polyene having an internal unsaturated bond having 6 to 15 carbon atoms, such as 4-ethylidene-1,6-nonadiene, and 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8 Α, ω such as nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene and 1,13-tetradecadiene There is a diene.
これらの非共役ポリエンの中でも、架橋効率の観点から、５－エチリデン－２－ノルボルネン、ジシクロペンタジエン、５－ビニル－２－ノルボルネン、７－メチル－１，６－オクタジエン及び５－メチル－１，４－ヘキサジエンが好ましく、５－エチリデン－２－ノルボルネンが特に好ましい。エチレン・α－オレフィン・非共役ポリエン共重合体を構成する非共役ポリエンは、１種には限定されず、２種以上の非共役ポリエンが共重合されていてもよい。
Among these non-conjugated polyenes, from the viewpoint of crosslinking efficiency, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 7-methyl-1,6-octadiene and 5-methyl-1, 4-hexadiene is preferred, and 5-ethylidene-2-norbornene is particularly preferred. The non-conjugated polyene constituting the ethylene / α-olefin / non-conjugated polyene copolymer is not limited to one type, and two or more types of non-conjugated polyenes may be copolymerized.
エチレン・α－オレフィン・非共役ポリエン共重合体を構成する非共役ポリエンの結合量は、エチレン・α－オレフィン・非共役ポリエン共重合体１００質量％中、非共役ポリエン単位を１～１０質量％とすることができる。非共役ポリエン単位の結合量をこの範囲に調整することによって、得られる加硫物の機械的特性がより向上する。
The amount of non-conjugated polyene constituting the ethylene / α-olefin / non-conjugated polyene copolymer is 1 to 10% by mass of non-conjugated polyene units in 100% by mass of the ethylene / α-olefin / non-conjugated polyene copolymer. It can be. By adjusting the bonding amount of the non-conjugated polyene unit within this range, the mechanical properties of the obtained vulcanizate are further improved.
エチレン・α－オレフィン・非共役ポリエン共重合体の配合量は、ポリクロロプレン１００質量部あたり３～５０質量部である。エチレン・α－オレフィン・非共役ポリエン共重合体の配合量が３質量部に満たないと、得られる加硫物の耐オゾン性が十分に発現しないことがある。また、エチレン・α－オレフィン・非共役ポリエン共重合体の配合量が５０質量部を超えてしまうと、得られる加硫物の機械的強度が低下してしまう。エチレン・α－オレフィン・非共役ポリエン共重合体の配合量は好ましくは５～４０質量部、更に好ましくは１０～３０質量部である。
The blending amount of the ethylene / α-olefin / non-conjugated polyene copolymer is 3 to 50 parts by mass per 100 parts by mass of polychloroprene. If the blending amount of the ethylene / α-olefin / non-conjugated polyene copolymer is less than 3 parts by mass, the resulting vulcanizate may not exhibit sufficient ozone resistance. Further, when the blending amount of the ethylene / α-olefin / non-conjugated polyene copolymer exceeds 50 parts by mass, the mechanical strength of the obtained vulcanizate is lowered. The blending amount of the ethylene / α-olefin / non-conjugated polyene copolymer is preferably 5 to 40 parts by mass, more preferably 10 to 30 parts by mass.
（３）カーボンブラック
カーボンブラックは、ゴム組成物を加硫して得られる加硫物の引張応力、引張強さ、破断伸びといった機械的特性を向上させるために配合する。カーボンブラックとしては、不完全燃焼法によるファーネスブラック、熱分解法によるサーマルブラック、チャンネルブラック、アセチレンブラックのいずれも使用可能である。ファーネスブラックとしては、ＳＡＦ(Super Abrasion Furnace Black)、ＩＳＡＦ(Intermediate Super Abrasion Furnace Black), ＩＩＳＡＦ(Intermediate ISAF)、ＨＡＦ(High Abrasion Furnace Black)、ＭＡＦ(Medium Abrasion Furnace Black)、ＦＥＦ(Fast Extruding Furnace Black)、ＳＲＦ(Semi-Reinforcing Furnace Black)、ＧＰＦ(General Purpose Furnace Black)、ＦＦ(Fine Furnace Black)、ＣＦ(Conductive Furnace Black) がある。サーマルブラックとしては、ＦＴ（Fine Thermal Black）、ＭＴ（Medium Thermal Black）がある。チャンネルブラックとしては、ＥＰＣ（Easy Processing Channel Black）、ＭＰＣ（Medium Processing Channel Black）、並びにアセチレンブラックがある。これらカーボンブラックの中でも、得られる加硫物の耐熱性を向上させるという観点からは、アセチレンブラックを用いることが好ましい。 (3) Carbon black Carbon black is blended in order to improve mechanical properties such as tensile stress, tensile strength, and elongation at break of a vulcanized product obtained by vulcanizing a rubber composition. As carbon black, any of furnace black by incomplete combustion method, thermal black by thermal decomposition method, channel black, and acetylene black can be used. As furnace black, SAF (Super Abrasion Furnace Black), ISAF (Intermediate Super Abrasion Furnace Black), IISA (Intermediate ISAF), HAF (High Abrasion Furnace Black), MAF (Medium Abrasion Furnace Black), FEF (Fast Extruding Furnace Black) ), SRF (Semi-Reinforcing Furnace Black), GPF (General Purpose Furnace Black), FF (Fine Furnace Black), and CF (Conductive Furnace Black). Thermal blacks include FT (Fine Thermal Black) and MT (Medium Thermal Black). Channel black includes EPC (Easy Processing Channel Black), MPC (Medium Processing Channel Black), and acetylene black. Among these carbon blacks, acetylene black is preferably used from the viewpoint of improving the heat resistance of the resulting vulcanizate.
カーボンブラックは、ゴム組成物を加硫して得られる加硫物の引張応力、引張強さ、破断伸びといった機械的特性を向上させるために配合する。カーボンブラックとしては、不完全燃焼法によるファーネスブラック、熱分解法によるサーマルブラック、チャンネルブラック、アセチレンブラックのいずれも使用可能である。ファーネスブラックとしては、ＳＡＦ(Super Abrasion Furnace Black)、ＩＳＡＦ(Intermediate Super Abrasion Furnace Black), ＩＩＳＡＦ(Intermediate ISAF)、ＨＡＦ(High Abrasion Furnace Black)、ＭＡＦ(Medium Abrasion Furnace Black)、ＦＥＦ(Fast Extruding Furnace Black)、ＳＲＦ(Semi-Reinforcing Furnace Black)、ＧＰＦ(General Purpose Furnace Black)、ＦＦ(Fine Furnace Black)、ＣＦ(Conductive Furnace Black) がある。サーマルブラックとしては、ＦＴ（Fine Thermal Black）、ＭＴ（Medium Thermal Black）がある。チャンネルブラックとしては、ＥＰＣ（Easy Processing Channel Black）、ＭＰＣ（Medium Processing Channel Black）、並びにアセチレンブラックがある。これらカーボンブラックの中でも、得られる加硫物の耐熱性を向上させるという観点からは、アセチレンブラックを用いることが好ましい。 (3) Carbon black Carbon black is blended in order to improve mechanical properties such as tensile stress, tensile strength, and elongation at break of a vulcanized product obtained by vulcanizing a rubber composition. As carbon black, any of furnace black by incomplete combustion method, thermal black by thermal decomposition method, channel black, and acetylene black can be used. As furnace black, SAF (Super Abrasion Furnace Black), ISAF (Intermediate Super Abrasion Furnace Black), IISA (Intermediate ISAF), HAF (High Abrasion Furnace Black), MAF (Medium Abrasion Furnace Black), FEF (Fast Extruding Furnace Black) ), SRF (Semi-Reinforcing Furnace Black), GPF (General Purpose Furnace Black), FF (Fine Furnace Black), and CF (Conductive Furnace Black). Thermal blacks include FT (Fine Thermal Black) and MT (Medium Thermal Black). Channel black includes EPC (Easy Processing Channel Black), MPC (Medium Processing Channel Black), and acetylene black. Among these carbon blacks, acetylene black is preferably used from the viewpoint of improving the heat resistance of the resulting vulcanizate.
カーボンブラック配合量は、ポリクロロプレン１００質量部あたり１０～１００質量部である。カーボンブラックの配合量が１０質量部に満たないと、ゴム組成物を加硫した際の補強性が低下し、加硫物が実用性に乏しくなる場合がある。カーボンブラック配合量が１００質量部を超えてしまうと、ゴム組成物の耐熱性が急激に低下する場合がある。カーボンブラックの配合量は好ましくは１５～８０質量部、更に好ましくは２０～６０質量部である。
The blending amount of carbon black is 10 to 100 parts by mass per 100 parts by mass of polychloroprene. If the blending amount of the carbon black is less than 10 parts by mass, the reinforcing property when the rubber composition is vulcanized may be reduced, and the vulcanized product may be impractical. If the amount of carbon black exceeds 100 parts by mass, the heat resistance of the rubber composition may be drastically reduced. The amount of carbon black is preferably 15 to 80 parts by mass, more preferably 20 to 60 parts by mass.
（４）ポリ（アルキルフェノール）ポリスルフィド
ポリ（アルキルフェノール）ポリスルフィドは、ゴム組成物中のポリクロロプレンやエチレン・α－オレフィン・非共役ポリエン共重合体を加硫してゴム組成物の機械的特性を向上させるために配合する。ゴム組成物に配合するポリ（アルキルフェノール）ポリスルフィドの種類は、特に限定されるものではないが、機械的特性向上の観点から、アルキルフェノール骨格が、ｐ－クレゾール、ｉ－プロピルフェノール、ｐ－ｔ－ブチルフェノール、アミルフェノール、ｐ－ｔ－オクチルフェノール、ノニルフェノール、ドデシルフェノール、アリルフェノール、シクロヘキシルフェノール、４，６－ジオクチルレゾルシンのいずれかの構造をとることが望ましい。 (4) Poly (alkylphenol) polysulfide Poly (alkylphenol) polysulfide improves the mechanical properties of rubber compositions by vulcanizing polychloroprene and ethylene / α-olefin / non-conjugated polyene copolymers in the rubber composition. For blending. The type of poly (alkylphenol) polysulfide compounded in the rubber composition is not particularly limited, but from the viewpoint of improving mechanical properties, the alkylphenol skeleton is p-cresol, i-propylphenol, pt-butylphenol. , Amylphenol, pt-octylphenol, nonylphenol, dodecylphenol, allylphenol, cyclohexylphenol, and 4,6-dioctylresorcinol.
ポリ（アルキルフェノール）ポリスルフィドは、ゴム組成物中のポリクロロプレンやエチレン・α－オレフィン・非共役ポリエン共重合体を加硫してゴム組成物の機械的特性を向上させるために配合する。ゴム組成物に配合するポリ（アルキルフェノール）ポリスルフィドの種類は、特に限定されるものではないが、機械的特性向上の観点から、アルキルフェノール骨格が、ｐ－クレゾール、ｉ－プロピルフェノール、ｐ－ｔ－ブチルフェノール、アミルフェノール、ｐ－ｔ－オクチルフェノール、ノニルフェノール、ドデシルフェノール、アリルフェノール、シクロヘキシルフェノール、４，６－ジオクチルレゾルシンのいずれかの構造をとることが望ましい。 (4) Poly (alkylphenol) polysulfide Poly (alkylphenol) polysulfide improves the mechanical properties of rubber compositions by vulcanizing polychloroprene and ethylene / α-olefin / non-conjugated polyene copolymers in the rubber composition. For blending. The type of poly (alkylphenol) polysulfide compounded in the rubber composition is not particularly limited, but from the viewpoint of improving mechanical properties, the alkylphenol skeleton is p-cresol, i-propylphenol, pt-butylphenol. , Amylphenol, pt-octylphenol, nonylphenol, dodecylphenol, allylphenol, cyclohexylphenol, and 4,6-dioctylresorcinol.
ポリ（アルキルフェノール）ポリスルフィドの配合量は、ゴム組成物中のエチレン・α－オレフィン・非共役ポリエン共重合体１００質量部あたり１～２０質量部である。ポリ（アルキルフェノール）ポリスルフィドの配合量がこの範囲に満たないと、得られる加硫物の機械的強度が十分に発現しない可能性がある。また、ポリ（アルキルフェノール）ポリスルフィドの配合量がこの範囲を超えてしまうと、得られる加硫物の耐熱性が低下しまう。ポリ（アルキルフェノール）ポリスルフィドの配合量は好ましくは２～１５質量部、更に好ましくは３～１０質量部である。
The compounding amount of poly (alkylphenol) polysulfide is 1 to 20 parts by mass per 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer in the rubber composition. If the blending amount of the poly (alkylphenol) polysulfide is less than this range, the mechanical strength of the resulting vulcanizate may not be sufficiently developed. Moreover, when the compounding quantity of poly (alkylphenol) polysulfide exceeds this range, the heat resistance of the obtained vulcanizate will fall. The blending amount of poly (alkylphenol) polysulfide is preferably 2 to 15 parts by mass, more preferably 3 to 10 parts by mass.
（５）ゴム組成物
ゴム組成物は、上述の各化合物を加硫温度以下でオープンロールやバンバリーミキサー、押出機などを用いて混練することで得られる。
この際に、（２）エチレン・α－オレフィン・非共役ポリエン共重合体と（４）ポリ（アルキルフェノール）ポリスルフィドを混練した後、（１）ポリクロロプレン及び（３）カーボンブラックを加えて混練すると、得られる加硫物の機械的特性が更に向上するため望ましい。 (5) Rubber composition The rubber composition can be obtained by kneading each of the above-described compounds using an open roll, a Banbury mixer, an extruder, or the like at a vulcanization temperature or lower.
At this time, after kneading (2) ethylene / α-olefin / non-conjugated polyene copolymer and (4) poly (alkylphenol) polysulfide, (1) adding polychloroprene and (3) carbon black and kneading, This is desirable because the mechanical properties of the resulting vulcanizate are further improved.
ゴム組成物は、上述の各化合物を加硫温度以下でオープンロールやバンバリーミキサー、押出機などを用いて混練することで得られる。
この際に、（２）エチレン・α－オレフィン・非共役ポリエン共重合体と（４）ポリ（アルキルフェノール）ポリスルフィドを混練した後、（１）ポリクロロプレン及び（３）カーボンブラックを加えて混練すると、得られる加硫物の機械的特性が更に向上するため望ましい。 (5) Rubber composition The rubber composition can be obtained by kneading each of the above-described compounds using an open roll, a Banbury mixer, an extruder, or the like at a vulcanization temperature or lower.
At this time, after kneading (2) ethylene / α-olefin / non-conjugated polyene copolymer and (4) poly (alkylphenol) polysulfide, (1) adding polychloroprene and (3) carbon black and kneading, This is desirable because the mechanical properties of the resulting vulcanizate are further improved.
ゴム組成物は、上述の各化合物のほか、本発明の効果が損なわれない範囲で、通常ゴム工業界で用いられる加硫剤、加硫促進剤、スコーチ防止剤、加工助剤などを配合することができる。
In addition to the above-mentioned compounds, the rubber composition contains a vulcanizing agent, a vulcanization accelerator, a scorch inhibitor, a processing aid, etc. that are usually used in the rubber industry as long as the effects of the present invention are not impaired. be able to.
以上詳述したように、本実施形態のゴム組成物は、ポリクロロプレンと特定量のエチレン・α－オレフィン・非共役ポリエン共重合体、カーボンブラック及びポリ（アルキルフェノール）ポリスルフィドを特定量配合しているため、加硫物の引張応力、引張強さ、破断伸びといった機械的特性が優れるだけでなく、耐オゾン性が著しく優れたゴム組成物が得られる。
As described above in detail, the rubber composition of the present embodiment contains a specific amount of polychloroprene, a specific amount of ethylene / α-olefin / non-conjugated polyene copolymer, carbon black, and poly (alkylphenol) polysulfide. Therefore, a rubber composition having not only excellent mechanical properties such as tensile stress, tensile strength and elongation at break of the vulcanizate but also extremely excellent ozone resistance can be obtained.
（６）加硫物
本実施形態の加硫物は、前述したゴム組成物を、目的に応じた形状に成形加工して加硫したものである。その際、ゴム組成物の加硫方法は、特に限定されるものではなく、成形中又は成形後に、プレス加硫、インジェクション加硫、直接釜加硫、間接釜加硫、直接蒸気連続加硫、常圧連続加硫又は連続加硫プレスなどの加硫方法により、加硫すればよい。 (6) Vulcanized material The vulcanized material of the present embodiment is obtained by molding and vulcanizing the rubber composition described above into a shape suitable for the purpose. At that time, the vulcanization method of the rubber composition is not particularly limited, and during or after molding, press vulcanization, injection vulcanization, direct kettle vulcanization, indirect kettle vulcanization, direct steam continuous vulcanization, Vulcanization may be performed by a vulcanization method such as normal pressure continuous vulcanization or continuous vulcanization press.
本実施形態の加硫物は、前述したゴム組成物を、目的に応じた形状に成形加工して加硫したものである。その際、ゴム組成物の加硫方法は、特に限定されるものではなく、成形中又は成形後に、プレス加硫、インジェクション加硫、直接釜加硫、間接釜加硫、直接蒸気連続加硫、常圧連続加硫又は連続加硫プレスなどの加硫方法により、加硫すればよい。 (6) Vulcanized material The vulcanized material of the present embodiment is obtained by molding and vulcanizing the rubber composition described above into a shape suitable for the purpose. At that time, the vulcanization method of the rubber composition is not particularly limited, and during or after molding, press vulcanization, injection vulcanization, direct kettle vulcanization, indirect kettle vulcanization, direct steam continuous vulcanization, Vulcanization may be performed by a vulcanization method such as normal pressure continuous vulcanization or continuous vulcanization press.
また、加硫温度及び加硫時間などの加硫条件も、特に限定されるものではなく、適宜設定することができる。生産性及び加工安全性の観点から、加硫温度は１３０～２００℃とすることが好ましく、１４０～１９０℃とすることがより好ましい。ここで、「加工安全性」とは、スコーチタイムにより評価される加工特性であり、不良発生率に大きく影響する。具体的には、スコーチタイムが短いと、高温での成形中に未加硫ゴム成分が加硫されて成形不良が発生する頻度が高くなる。
Also, vulcanization conditions such as vulcanization temperature and vulcanization time are not particularly limited, and can be set as appropriate. From the viewpoint of productivity and processing safety, the vulcanization temperature is preferably 130 to 200 ° C, more preferably 140 to 190 ° C. Here, “machining safety” is a machining characteristic evaluated by the scorch time, and greatly affects the defect occurrence rate. Specifically, when the scorch time is short, the frequency of occurrence of defective molding is increased because the unvulcanized rubber component is vulcanized during molding at a high temperature.
本実施形態の加硫物は、前述したゴム組成物を用いているため、従来のポリクロロプレンを用いた加硫物に比べて、加硫物の引張応力、引張強さ、破断伸び、耐オゾン性を包括的に向上させる。このため、本実施形態の加硫物は、免震ゴムやスポンジだけなく、伝動ベルト、コンベアベルト、空気バネ、自動車用ホース、自動車用ブーツ、防振ゴムなどのように、高い耐オゾン性が要求される成形品にも、好適に用いることができる。
Since the vulcanized product of the present embodiment uses the rubber composition described above, the vulcanized product has a tensile stress, tensile strength, elongation at break, and ozone resistance as compared with a vulcanized product using conventional polychloroprene. Improve gender comprehensively. For this reason, the vulcanizate of this embodiment has high ozone resistance such as a transmission belt, a conveyor belt, an air spring, an automobile hose, an automobile boot, an anti-vibration rubber as well as a seismic isolation rubber and sponge. It can also be suitably used for required molded articles.
表１～表３に示す各配合成分は、以下の通りである。
（ポリクロロプレン）
・メルカプタン変性ポリクロロプレン（電気化学工業株式会社製 Ｓ－４０Ｖ）
・キサントゲン変性ポリクロロプレン（電気化学工業株式会社製 ＤＣＲ－６６）
・硫黄変性ポリクロロプレン（電気化学工業株式会社製 ＤＣＲ－１０７） The components shown in Tables 1 to 3 are as follows.
(Polychloroprene)
・ Mercaptan-modified polychloroprene (S-40V, manufactured by Denki Kagaku Kogyo Co., Ltd.)
・ Xanthogen-modified polychloroprene (DCR-66, manufactured by Denki Kagaku Kogyo Co., Ltd.)
・ Sulfur modified polychloroprene (DCR-107, manufactured by Denki Kagaku Kogyo Co., Ltd.)
（ポリクロロプレン）
・メルカプタン変性ポリクロロプレン（電気化学工業株式会社製 Ｓ－４０Ｖ）
・キサントゲン変性ポリクロロプレン（電気化学工業株式会社製 ＤＣＲ－６６）
・硫黄変性ポリクロロプレン（電気化学工業株式会社製 ＤＣＲ－１０７） The components shown in Tables 1 to 3 are as follows.
(Polychloroprene)
・ Mercaptan-modified polychloroprene (S-40V, manufactured by Denki Kagaku Kogyo Co., Ltd.)
・ Xanthogen-modified polychloroprene (DCR-66, manufactured by Denki Kagaku Kogyo Co., Ltd.)
・ Sulfur modified polychloroprene (DCR-107, manufactured by Denki Kagaku Kogyo Co., Ltd.)
（非共役ポリエン単位の種類）
・Ａ：５－エチリデン－２－ノルボルネン
・Ｂ：ジシクロペンタジエン
・Ｃ：５－メチル－１，４－ヘキサジエン (Types of non-conjugated polyene units)
A: 5-ethylidene-2-norbornene B: dicyclopentadiene C: 5-methyl-1,4-hexadiene
・Ａ：５－エチリデン－２－ノルボルネン
・Ｂ：ジシクロペンタジエン
・Ｃ：５－メチル－１，４－ヘキサジエン (Types of non-conjugated polyene units)
A: 5-ethylidene-2-norbornene B: dicyclopentadiene C: 5-methyl-1,4-hexadiene
（カーボンブラック）
・カーボンブラックＨＡＦ（旭カーボン株式会社製 旭＃７０）
・カーボンブラックＧＰＦ（旭カーボン株式会社製 旭＃５５）
・カーボンブラックＳＲＦ（旭カーボン株式会社製 旭＃３５）
・アセチレンブラック（電気化学工業株式会社製 デンカブラック粒状品） (Carbon black)
・ Carbon black HAF (Asahi # 70, Asahi Carbon Co., Ltd.)
・ Carbon black GPF (Asahi # 55, Asahi Carbon Co., Ltd.)
・ Carbon black SRF (Asahi Carbon 35 Asahi # 35)
-Acetylene black (Denka Black granular product manufactured by Denki Kagaku Kogyo Co., Ltd.)
・カーボンブラックＨＡＦ（旭カーボン株式会社製 旭＃７０）
・カーボンブラックＧＰＦ（旭カーボン株式会社製 旭＃５５）
・カーボンブラックＳＲＦ（旭カーボン株式会社製 旭＃３５）
・アセチレンブラック（電気化学工業株式会社製 デンカブラック粒状品） (Carbon black)
・ Carbon black HAF (Asahi # 70, Asahi Carbon Co., Ltd.)
・ Carbon black GPF (Asahi # 55, Asahi Carbon Co., Ltd.)
・ Carbon black SRF (Asahi Carbon 35 Asahi # 35)
-Acetylene black (Denka Black granular product manufactured by Denki Kagaku Kogyo Co., Ltd.)
（ポリ（アルキルフェノール）ポリスルフィド）
・ポリ（ｔ－ブチルフェノール）ポリスルフィド（アルケマ製 ＶｕｌｔａｃＴＢ７）
・ポリ（ｔ－アミルフェノール）ジスルフィド（三新化学工業株式会社製 サンセラーＡＰ） (Poly (alkylphenol) polysulfide)
・ Poly (t-butylphenol) polysulfide (Altema VultacTB7)
・ Poly (t-amylphenol) disulfide (Sunshine AP manufactured by Sanshin Chemical Industry Co., Ltd.)
・ポリ（ｔ－ブチルフェノール）ポリスルフィド（アルケマ製 ＶｕｌｔａｃＴＢ７）
・ポリ（ｔ－アミルフェノール）ジスルフィド（三新化学工業株式会社製 サンセラーＡＰ） (Poly (alkylphenol) polysulfide)
・ Poly (t-butylphenol) polysulfide (Altema VultacTB7)
・ Poly (t-amylphenol) disulfide (Sunshine AP manufactured by Sanshin Chemical Industry Co., Ltd.)
実施例１
実施例１のゴム組成物は、メルカプタン変性ポリクロロプレン１００質量部、５－エチリデン－２－ノルボルネンを８質量％含有するエチレン・α－オレフィン・非共役ポリエン共重合体３０質量部、カーボンブラックＨＡＦ４０質量部、ポリ（t－ブチルフェノール）ポリスルフィド３質量部、その他の添加剤として、可塑剤として菜種油（当栄ケミカル株式会社製 ＃８１１５－Ｒ）５質量部、滑剤・加工助剤としてステアリン酸（新日本理化株式会社製 ステアリン酸５０Ｓ）１質量部、老化防止剤としてアミン系老化防止剤（大内新興化学工業株式会社製 ノクラックＣＤ：４，４－ビス（α，α－ジメチルベンジル）ジフェニルアミン）２質量部、イミダゾール系老化防止剤（大内新興化学工業株式会社製 ノクラックＭＢ：２－メルカプトベンズイミダゾール）１質量部、酸化マグネシウムとしてキョーワマグ１５０（協和化学工業株式会社製（ＢＥＴ比表面積＝１４８ｍ２／ｇ））４質量部、加硫促進剤としてチオウレア系加硫促進剤（川口化学工業株式会社製 アクセル２２Ｓ：エチレンチオ尿素）０．８質量部、酸化亜鉛として（堺化学工業株式会社製 酸化亜鉛２種）５質量部を配合した後、８インチロールを用いて混練して得られたものである。なお、ポリ（t－ブチルフェノール）ポリスルフィドの添加量はエチレン・α－オレフィン・非共役ポリエン共重合体１００質量部に対して１０質量部に相当する。
得られたゴム組成物を、油圧プレスにて１６０℃、２０分間加硫し、厚さ２ｍｍのシート状に成形して試験片を作製した。そして、この試験片を用いて、「引張応力」「引張強さ」「破断伸び」、「デュロメータ硬さ（ＨＳ）」及び「耐オゾン性」について評価した。 Example 1
The rubber composition of Example 1 is composed of 100 parts by mass of mercaptan-modified polychloroprene, 30 parts by mass of an ethylene / α-olefin / non-conjugated polyene copolymer containing 8% by mass of 5-ethylidene-2-norbornene, and 40 parts by mass of carbon black HAF. Parts, 3 parts by weight of poly (t-butylphenol) polysulfide, 5 parts by weight of rapeseed oil (# 8115-R made by Toei Chemical Co., Ltd.) as a plasticizer, and stearic acid as a lubricant and processing aid (Shin Nihon) 1 part by weight of Rika Co., Ltd., stearic acid 50S), 2 parts by weight of amine-based anti-aging agent (no-crack CD: 4,4-bis (α, α-dimethylbenzyl) diphenylamine, manufactured by Ouchi Shinsei Chemical Co., Ltd.) Part, Imidazole-based anti-aging agent (Nocrack MB: 2-mercap manufactured by Ouchi Shinsei Chemical Co., Ltd.) Benzimidazole) 1 part by weight, Mag 150 (manufactured by Kyowa Chemical Industry Co., Ltd. (BET specific surface area = 148m 2 / g) as a magnesium oxide) 4 parts by weight, thiourea vulcanization accelerator as a vulcanization accelerator (Kawaguchi Chemical Industry stock Company Axel 22S: Ethylenethiourea) 0.8 parts by mass, zinc oxide (2 types of zinc oxide manufactured by Sakai Chemical Industry Co., Ltd.) 5 parts by mass, and then kneaded using an 8-inch roll It is. The amount of poly (t-butylphenol) polysulfide added corresponds to 10 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer.
The obtained rubber composition was vulcanized at 160 ° C. for 20 minutes with a hydraulic press, and formed into a sheet having a thickness of 2 mm to prepare a test piece. And using this test piece, "tensile stress""tensilestrength""breakingelongation","durometer hardness (HS)", and "ozone resistance" were evaluated.
実施例１のゴム組成物は、メルカプタン変性ポリクロロプレン１００質量部、５－エチリデン－２－ノルボルネンを８質量％含有するエチレン・α－オレフィン・非共役ポリエン共重合体３０質量部、カーボンブラックＨＡＦ４０質量部、ポリ（t－ブチルフェノール）ポリスルフィド３質量部、その他の添加剤として、可塑剤として菜種油（当栄ケミカル株式会社製 ＃８１１５－Ｒ）５質量部、滑剤・加工助剤としてステアリン酸（新日本理化株式会社製 ステアリン酸５０Ｓ）１質量部、老化防止剤としてアミン系老化防止剤（大内新興化学工業株式会社製 ノクラックＣＤ：４，４－ビス（α，α－ジメチルベンジル）ジフェニルアミン）２質量部、イミダゾール系老化防止剤（大内新興化学工業株式会社製 ノクラックＭＢ：２－メルカプトベンズイミダゾール）１質量部、酸化マグネシウムとしてキョーワマグ１５０（協和化学工業株式会社製（ＢＥＴ比表面積＝１４８ｍ２／ｇ））４質量部、加硫促進剤としてチオウレア系加硫促進剤（川口化学工業株式会社製 アクセル２２Ｓ：エチレンチオ尿素）０．８質量部、酸化亜鉛として（堺化学工業株式会社製 酸化亜鉛２種）５質量部を配合した後、８インチロールを用いて混練して得られたものである。なお、ポリ（t－ブチルフェノール）ポリスルフィドの添加量はエチレン・α－オレフィン・非共役ポリエン共重合体１００質量部に対して１０質量部に相当する。
得られたゴム組成物を、油圧プレスにて１６０℃、２０分間加硫し、厚さ２ｍｍのシート状に成形して試験片を作製した。そして、この試験片を用いて、「引張応力」「引張強さ」「破断伸び」、「デュロメータ硬さ（ＨＳ）」及び「耐オゾン性」について評価した。 Example 1
The rubber composition of Example 1 is composed of 100 parts by mass of mercaptan-modified polychloroprene, 30 parts by mass of an ethylene / α-olefin / non-conjugated polyene copolymer containing 8% by mass of 5-ethylidene-2-norbornene, and 40 parts by mass of carbon black HAF. Parts, 3 parts by weight of poly (t-butylphenol) polysulfide, 5 parts by weight of rapeseed oil (# 8115-R made by Toei Chemical Co., Ltd.) as a plasticizer, and stearic acid as a lubricant and processing aid (Shin Nihon) 1 part by weight of Rika Co., Ltd., stearic acid 50S), 2 parts by weight of amine-based anti-aging agent (no-crack CD: 4,4-bis (α, α-dimethylbenzyl) diphenylamine, manufactured by Ouchi Shinsei Chemical Co., Ltd.) Part, Imidazole-based anti-aging agent (Nocrack MB: 2-mercap manufactured by Ouchi Shinsei Chemical Co., Ltd.) Benzimidazole) 1 part by weight, Mag 150 (manufactured by Kyowa Chemical Industry Co., Ltd. (BET specific surface area = 148m 2 / g) as a magnesium oxide) 4 parts by weight, thiourea vulcanization accelerator as a vulcanization accelerator (Kawaguchi Chemical Industry stock Company Axel 22S: Ethylenethiourea) 0.8 parts by mass, zinc oxide (2 types of zinc oxide manufactured by Sakai Chemical Industry Co., Ltd.) 5 parts by mass, and then kneaded using an 8-inch roll It is. The amount of poly (t-butylphenol) polysulfide added corresponds to 10 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer.
The obtained rubber composition was vulcanized at 160 ° C. for 20 minutes with a hydraulic press, and formed into a sheet having a thickness of 2 mm to prepare a test piece. And using this test piece, "tensile stress""tensilestrength""breakingelongation","durometer hardness (HS)", and "ozone resistance" were evaluated.
＜評価＞
引張応力、引張強さ、破断伸び
ＪＩＳ－Ｋ６２５１に準拠して引張試験機（株式会社上島製作所製Ｑｕｉｃｋ Ｒｅａｄｅｒ ｍｘ）を用いて伸長し、１００％伸長時の引張応力、破断に至った際の引張強さ、破断伸びを測定した。１００％伸長時の引張応力は、３ＭＰａ以上、破断時の引張強さは、１３ＭＰａ以上、破断伸びは３００％以上の値を示したものを合格とした。 <Evaluation>
Tensile stress, Tensile strength, Elongation at break Tensile stress at the time of 100% elongation and elongation at breakage using a tensile tester (Quick Reader mx manufactured by Ueshima Seisakusho Co., Ltd.) according to JIS-K6251 Strength and elongation at break were measured. The tensile stress at 100% elongation was 3 MPa or more, the tensile strength at break was 13 MPa or more, and the elongation at break was 300% or more.
引張応力、引張強さ、破断伸び
ＪＩＳ－Ｋ６２５１に準拠して引張試験機（株式会社上島製作所製Ｑｕｉｃｋ Ｒｅａｄｅｒ ｍｘ）を用いて伸長し、１００％伸長時の引張応力、破断に至った際の引張強さ、破断伸びを測定した。１００％伸長時の引張応力は、３ＭＰａ以上、破断時の引張強さは、１３ＭＰａ以上、破断伸びは３００％以上の値を示したものを合格とした。 <Evaluation>
Tensile stress, Tensile strength, Elongation at break Tensile stress at the time of 100% elongation and elongation at breakage using a tensile tester (Quick Reader mx manufactured by Ueshima Seisakusho Co., Ltd.) according to JIS-K6251 Strength and elongation at break were measured. The tensile stress at 100% elongation was 3 MPa or more, the tensile strength at break was 13 MPa or more, and the elongation at break was 300% or more.
弾性率（デュロメータ硬さ（ＨＳ））
ＪＩＳ Ｋ６２５３に準拠し、タイプＤデュロメータを用いて測定した。 Elastic modulus (durometer hardness (HS))
Based on JIS K6253, it measured using the type D durometer.
ＪＩＳ Ｋ６２５３に準拠し、タイプＤデュロメータを用いて測定した。 Elastic modulus (durometer hardness (HS))
Based on JIS K6253, it measured using the type D durometer.
耐オゾン性
ＪＩＳ Ｋ６２５８に準拠し、０～２０％動的伸長、４０℃×５０ｐｐｈｍ、１４４時間の条件で評価し、試験片に全くクラック発生しなかったものを○、クラックが入ったものを×とした。 Ozone resistance According to JIS K6258, evaluated under the conditions of 0 to 20% dynamic elongation, 40 ° C. × 50 pphm, 144 hours. It was.
ＪＩＳ Ｋ６２５８に準拠し、０～２０％動的伸長、４０℃×５０ｐｐｈｍ、１４４時間の条件で評価し、試験片に全くクラック発生しなかったものを○、クラックが入ったものを×とした。 Ozone resistance According to JIS K6258, evaluated under the conditions of 0 to 20% dynamic elongation, 40 ° C. × 50 pphm, 144 hours. It was.
実施例１のゴム組成物を用いた加硫物は、引張応力、引張強さ、破断伸びといった機械的特性とともに耐オゾン性が向上されたものであった。
The vulcanizate using the rubber composition of Example 1 had improved ozone resistance as well as mechanical properties such as tensile stress, tensile strength, and elongation at break.
実施例２～１８、比較例１～５
ゴム組成物を作製する際に添加する化合物の処方を、表１～表３に示した通り変更して実施例１と同様にゴム組成物を作製して加硫し、加硫物のサンプルとした。得られた加硫物のサンプルについて、実施例１と同様に「引張応力」「引張強さ」「破断伸び」、「デュロメータ硬さ（ＨＳ）」及び「耐オゾン性」について評価した。評価結果を表１～表３に示す。 Examples 2 to 18 and Comparative Examples 1 to 5
The formulation of the compound added when preparing the rubber composition was changed as shown in Tables 1 to 3, and the rubber composition was prepared and vulcanized in the same manner as in Example 1. did. The obtained vulcanized samples were evaluated in the same manner as in Example 1 for “tensile stress”, “tensile strength”, “breaking elongation”, “durometer hardness (HS)”, and “ozone resistance”. The evaluation results are shown in Tables 1 to 3.
ゴム組成物を作製する際に添加する化合物の処方を、表１～表３に示した通り変更して実施例１と同様にゴム組成物を作製して加硫し、加硫物のサンプルとした。得られた加硫物のサンプルについて、実施例１と同様に「引張応力」「引張強さ」「破断伸び」、「デュロメータ硬さ（ＨＳ）」及び「耐オゾン性」について評価した。評価結果を表１～表３に示す。 Examples 2 to 18 and Comparative Examples 1 to 5
The formulation of the compound added when preparing the rubber composition was changed as shown in Tables 1 to 3, and the rubber composition was prepared and vulcanized in the same manner as in Example 1. did. The obtained vulcanized samples were evaluated in the same manner as in Example 1 for “tensile stress”, “tensile strength”, “breaking elongation”, “durometer hardness (HS)”, and “ozone resistance”. The evaluation results are shown in Tables 1 to 3.
以上の試験結果より、本発明によれば、引張応力、引張強さ、破断伸びといった機械的特性とともに耐オゾン性を向上させた加硫物が得られるゴム組成物が得られることが確認された。このゴム組成物を加硫して得られる加硫物は上述の特性が向上されたものであり、工業製品の材料として好適に用いることができるものであった。
From the above test results, according to the present invention, it was confirmed that a rubber composition capable of obtaining a vulcanizate having improved ozone resistance as well as mechanical properties such as tensile stress, tensile strength and elongation at break was obtained. . The vulcanizate obtained by vulcanizing this rubber composition has improved properties as described above, and can be suitably used as a material for industrial products.
Claims (6)
- ポリクロロプレン１００質量部と、エチレン・α－オレフィン・非共役ポリエン共重合体３～５０質量部と、カーボンブラック１０～１００質量部と、前記エチレン・α－オレフィン・非共役ポリエン共重合体１００質量部に対して、化学式Ｉ（化学式Ｉ中、Ｒは１～２０個の炭素原子を有するアルキル基、ｎおよびｎ’は同一または異なる１～８の整数、ｐは０～５０の整数を表す。）で表される構造のポリ（アルキルフェノール）ポリスルフィド１～２０質量部と、を含有するゴム組成物。
- エチレン・α－オレフィン・非共役ポリエン共重合体が、エチレン・α－オレフィン・非共役ポリエン共重合体１００質量％中、非共役ポリエン単位を１～１０質量％含有するものである請求項１記載のゴム組成物。 2. The ethylene / α-olefin / non-conjugated polyene copolymer contains 1 to 10% by mass of non-conjugated polyene units in 100% by mass of the ethylene / α-olefin / non-conjugated polyene copolymer. Rubber composition.
- エチレン・α－オレフィン・非共役ポリエン共重合体の非共役ポリエン単位が、５－エチリデン－２－ノルボルネン、ジシクロペンタジエン、５－ビニル－２－ノルボルネン、７－メチル－１，６－オクタジエン及び５－メチル－１，４－ヘキサジエンから選ばれる少なくとも一種である請求項１又は２記載のゴム組成物。 The non-conjugated polyene unit of the ethylene / α-olefin / non-conjugated polyene copolymer contains 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 7-methyl-1,6-octadiene and 5 The rubber composition according to claim 1 or 2, which is at least one selected from -methyl-1,4-hexadiene.
- ポリ（アルキルフェノール）ポリスルフィドのアルキルフェノール構造が、ｐ－クレゾール、ｉ－プロピルフェノール、ｐ－ｔ－ブチルフェノール、アミルフェノール、ｐ－ｔ－オクチルフェノール、ノニルフェノール、ドデシルフェノール、アリルフェノール、シクロヘキシルフェノール、４，６－ジオクチルレゾルシンから選ばれる少なくとも一種である請求項１～３いずれか一項記載のゴム組成物。 The alkylphenol structure of poly (alkylphenol) polysulfide is p-cresol, i-propylphenol, pt-butylphenol, amylphenol, pt-octylphenol, nonylphenol, dodecylphenol, allylphenol, cyclohexylphenol, 4,6-dioctyl. The rubber composition according to any one of claims 1 to 3, which is at least one selected from resorcin.
- カーボンブラックが、ＳＡＦ(Super Abrasion Furnace Black)、ＩＳＡＦ(Intermediate Super Abrasion Furnace Black), ＩＩＳＡＦ(Intermediate ISAF)、ＨＡＦ(High Abrasion Furnace Black)、ＭＡＦ(Medium Abrasion Furnace Black)、ＦＥＦ(Fast Extruding Furnace Black)、ＳＲＦ(Semi-Reinforcing Furnace Black)、ＧＰＦ(General Purpose Furnace Black)、ＦＦ(Fine Furnace Black)、ＣＦ(Conductive Furnace Black)、ＦＴ（Fine Thermal Black）、ＭＴ（Medium Thermal Black）、ＥＰＣ（Easy Processing Channel Black）、ＭＰＣ（Medium Processing Channel Black）、アセチレンブラックから選ばれる少なくとも一種である請求項１～４いずれか一項記載のゴム組成物。 Carbon Black is SAF (Super Abrasion Furnace Black), ISAF (Intermediate Abrasion Furnace Black), IISAF (Intermediate ISAF), HAF (High Abrasion Furnace Black), MAF (Medium Abrasion Furnace Black), FEF , SRF (Semi-Reinforcing Furnace Black), GPF (General Purpose Furnace Black), FF (Fine Furnace Black), CF (Conductive Furnace Black), FT (Fine Thermal Black), MT (Medium Thermal Black), EPC (Easy) The rubber composition according to any one of claims 1 to 4, wherein the rubber composition is at least one selected from Channel Black, MPC (Medium Processing Channel Black), and acetylene black.
- 請求項１～５いずれか一項記載のゴム組成物を加硫して得られる加硫物。 A vulcanized product obtained by vulcanizing the rubber composition according to any one of claims 1 to 5.
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| JP2016507270A JPWO2015136792A1 (en) | 2014-03-12 | 2014-12-02 | Rubber composition and vulcanized product thereof |
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| JP2014048396 | 2014-03-12 | ||
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Cited By (5)
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| WO2017086282A1 (en) * | 2015-11-16 | 2017-05-26 | デンカ株式会社 | Rubber-based composition improving agent, vulcanizate of rubber composition to which improving agent is added, and molded article |
| RU2692316C1 (en) * | 2018-06-20 | 2019-06-24 | федеральное государственное унитарное предприятие "Федеральный научно-производственный центр "Прогресс" (ФГУП "ФНПЦ "Прогресс") | Fire-resistant rubber mixture with improved antifriction properties |
| WO2020045454A1 (en) * | 2018-08-30 | 2020-03-05 | 住友化学株式会社 | Rubber composition, metal-rubber composite molded body and method for producing metal-rubber composite molded body |
| KR20200024865A (en) * | 2017-06-29 | 2020-03-09 | 알케마 인코포레이티드 | Polymer composition stabilized with organopolysulfide |
| CN116144123A (en) * | 2023-02-22 | 2023-05-23 | 湖北辰诺医药包装科技有限公司 | Chlorinated butyl rubber plug for in-vitro diagnostic reagent and preparation method thereof |
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| JPWO2021141012A1 (en) * | 2020-01-06 | 2021-07-15 |
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- 2014-12-02 JP JP2016507270A patent/JPWO2015136792A1/en active Pending
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| WO2017086282A1 (en) * | 2015-11-16 | 2017-05-26 | デンカ株式会社 | Rubber-based composition improving agent, vulcanizate of rubber composition to which improving agent is added, and molded article |
| CN108350230A (en) * | 2015-11-16 | 2018-07-31 | 电化株式会社 | The sulfide and formed products of composition modified dose of rubber series and the rubber composition added with the modifying agent |
| CN108350230B (en) * | 2015-11-16 | 2020-10-20 | 电化株式会社 | Rubber composition modifier, and vulcanizate and molded article of rubber composition to which modifier is added |
| US10882985B2 (en) | 2015-11-16 | 2021-01-05 | Denka Company Limited | Rubber-based composition modifier, and vulcanizate and molded product of rubber composition containing the rubber-based composition modifier |
| KR20200024865A (en) * | 2017-06-29 | 2020-03-09 | 알케마 인코포레이티드 | Polymer composition stabilized with organopolysulfide |
| JP2020526606A (en) * | 2017-06-29 | 2020-08-31 | アーケマ・インコーポレイテッド | Polymer composition stabilized by organopolysulfide |
| JP7181234B2 (en) | 2017-06-29 | 2022-11-30 | アーケマ・インコーポレイテッド | Polymer compositions stabilized by organopolysulfides |
| KR102584689B1 (en) | 2017-06-29 | 2023-10-10 | 알케마 인코포레이티드 | Polymer composition stabilized with organopolysulfide |
| RU2692316C1 (en) * | 2018-06-20 | 2019-06-24 | федеральное государственное унитарное предприятие "Федеральный научно-производственный центр "Прогресс" (ФГУП "ФНПЦ "Прогресс") | Fire-resistant rubber mixture with improved antifriction properties |
| WO2020045454A1 (en) * | 2018-08-30 | 2020-03-05 | 住友化学株式会社 | Rubber composition, metal-rubber composite molded body and method for producing metal-rubber composite molded body |
| CN116144123A (en) * | 2023-02-22 | 2023-05-23 | 湖北辰诺医药包装科技有限公司 | Chlorinated butyl rubber plug for in-vitro diagnostic reagent and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| JPWO2015136792A1 (en) | 2017-04-06 |
| TW201534646A (en) | 2015-09-16 |
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