JP2022073207A - Method for producing rubber composition, rubber composition, method for producing re-crosslinked rubber, re-crosslinked rubber, tire and rubber industrial product - Google Patents
Method for producing rubber composition, rubber composition, method for producing re-crosslinked rubber, re-crosslinked rubber, tire and rubber industrial product Download PDFInfo
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- 239000005060 rubber Substances 0.000 title claims abstract description 292
- 239000000203 mixture Substances 0.000 title claims abstract description 109
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 43
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 41
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- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 27
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 16
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 239000004636 vulcanized rubber Substances 0.000 claims description 26
- RUVINXPYWBROJD-ONEGZZNKSA-N trans-anethole Chemical compound COC1=CC=C(\C=C\C)C=C1 RUVINXPYWBROJD-ONEGZZNKSA-N 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229940011037 anethole Drugs 0.000 claims description 8
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 8
- RUVINXPYWBROJD-UHFFFAOYSA-N para-methoxyphenyl Natural products COC1=CC=C(C=CC)C=C1 RUVINXPYWBROJD-UHFFFAOYSA-N 0.000 claims description 8
- ZFMSMUAANRJZFM-UHFFFAOYSA-N Estragole Chemical compound COC1=CC=C(CC=C)C=C1 ZFMSMUAANRJZFM-UHFFFAOYSA-N 0.000 claims description 6
- 229920003244 diene elastomer Polymers 0.000 claims description 6
- -1 pinene Chemical compound 0.000 claims description 6
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 claims description 4
- 229940087305 limonene Drugs 0.000 claims description 4
- 235000001510 limonene Nutrition 0.000 claims description 4
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 claims description 2
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 claims description 2
- 229930006739 camphene Natural products 0.000 claims description 2
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 15
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 description 42
- 239000003431 cross linking reagent Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
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- 244000043261 Hevea brasiliensis Species 0.000 description 11
- 239000000945 filler Substances 0.000 description 11
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- 239000003795 chemical substances by application Substances 0.000 description 10
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- 238000004132 cross linking Methods 0.000 description 9
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
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- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 229920001195 polyisoprene Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- CLNYHERYALISIR-UHFFFAOYSA-N nona-1,3-diene Chemical compound CCCCCC=CC=C CLNYHERYALISIR-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
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- 239000008117 stearic acid Substances 0.000 description 2
- 239000010920 waste tyre Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000005063 High cis polybutadiene Substances 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical group C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
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- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
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Landscapes
- Tires In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、ゴム組成物の製造方法、ゴム組成物、再架橋ゴムの製造方法、再架橋ゴム、タイヤ及びゴム工業用品に関する。 The present invention relates to a method for producing a rubber composition, a rubber composition, a method for producing a recrosslinked rubber, a recrosslinked rubber, a tire and a rubber industrial product.
環境及び省資源化の視点から、架橋ゴムを再生し、新たな架橋ゴムとして再利用することが検討されている。
例えば、特許文献１には、架橋ゴムを、炭素数２以上の第一級アルコールを含む反応溶媒下において３００℃以下で加熱して液状炭化水素を含むゴム組成物を得る方法が開示されている。
From the viewpoint of environment and resource saving, it is considered to recycle the crosslinked rubber and reuse it as a new crosslinked rubber.
For example, Patent Document 1 discloses a method for obtaining a rubber composition containing a liquid hydrocarbon by heating a crosslinked rubber at 300 ° C. or lower in a reaction solvent containing a primary alcohol having 2 or more carbon atoms. ..
しかし、特許文献１に記載の方法では、温和な条件下であっても、液状炭化水素を高い収率で回収できるが、高い分子量の液状炭化水素を得るには更なる検討が必要である。 However, although the method described in Patent Document 1 can recover liquid hydrocarbons in high yield even under mild conditions, further studies are required to obtain liquid hydrocarbons having a high molecular weight.
本発明は、穏和な条件下においても、より分子量の高い液状炭化水素を高分解率で製造することができるゴム組成物の製造方法、並びに、該製造方法により製造されたゴム組成物、該ゴム組成物を用いる再架橋ゴムの製造方法、該ゴム組成物から得られる再架橋ゴム、タイヤ及びゴム工業用品を提供することを目的とし、該目的を解決することを課題とする。 The present invention comprises a method for producing a rubber composition capable of producing a liquid hydrocarbon having a higher molecular weight at a high decomposition rate even under mild conditions, a rubber composition produced by the production method, and the rubber. An object of the present invention is to provide a method for producing a re-crosslinked rubber using a composition, a re-crosslinked rubber obtained from the rubber composition, a tire, and a rubber industrial product, and it is an object to solve the object.
＜１＞ 架橋ゴムを、脂肪族炭素間二重結合を少なくとも１つ含み、ヒドロキシ基及びアルデヒド基の数がそれぞれ０である化合物を含む反応溶媒下において、１５０℃以上３００℃以下で加熱して液状炭化水素を含むゴム組成物を得るゴム組成物の製造方法。 <1> The crosslinked rubber is heated at 150 ° C. or higher and 300 ° C. or lower in a reaction solvent containing a compound containing at least one aliphatic carbon-carbon double bond and having 0 hydroxy groups and 0 aldehyde groups, respectively. A method for producing a rubber composition for obtaining a rubber composition containing a liquid hydrocarbon.
＜２＞ 前記化合物の炭素数が、４～１８である＜１＞に記載のゴム組成物の製造方法。
＜３＞ 前記化合物が、アネトール、ピネン、エストラゴール、リモネン、カレン、及びカンフェン、及びこれらの誘導体からなる群より選択される少なくとも１種を含む＜１＞又は＜２＞に記載のゴム組成物の製造方法。
＜４＞ 前記化合物が、アネトール、ピネン、及びこれらの誘導体からなる群より選択される少なくとも１種を含む＜１＞～＜３＞のいずれか１つに記載のゴム組成物の製造方法。
＜５＞ 前記反応溶媒が、アネトール及びその誘導体からなる群より選択される少なくとも１種を含む＜１＞～＜４＞のいずれか１つに記載のゴム組成物の製造方法。
<2> The method for producing a rubber composition according to <1>, wherein the compound has 4 to 18 carbon atoms.
<3> The rubber composition according to <1> or <2>, wherein the compound comprises at least one selected from the group consisting of anethole, pinene, estragole, limonene, curene, and camphene, and derivatives thereof. Manufacturing method.
<4> The method for producing a rubber composition according to any one of <1> to <3>, wherein the compound contains at least one selected from the group consisting of anethole, pinene, and derivatives thereof.
<5> The method for producing a rubber composition according to any one of <1> to <4>, wherein the reaction solvent contains at least one selected from the group consisting of anethole and its derivatives.
＜６＞ 前記架橋ゴムが、ジエン系ゴムを５０～１００質量％含むゴム成分の架橋物である＜１＞～＜５＞のいずれか１つに記載のゴム組成物の製造方法。
＜７＞ 前記架橋ゴムが、加硫ゴムを含む＜１＞～＜６＞のいずれか１つに記載のゴム組成物の製造方法。
<6> The method for producing a rubber composition according to any one of <1> to <5>, wherein the crosslinked rubber is a crosslinked product of a rubber component containing 50 to 100% by mass of a diene rubber.
<7> The method for producing a rubber composition according to any one of <1> to <6>, wherein the crosslinked rubber contains vulcanized rubber.
＜８＞ ＜１＞～＜７＞のいずれか１つに記載のゴム組成物の製造方法で製造されたゴム組成物。 <8> A rubber composition produced by the method for producing a rubber composition according to any one of <1> to <7>.
＜９＞ ＜８＞に記載のゴム組成物を１～１００質量％含むゴム成分を再架橋する再架橋ゴムの製造方法。
＜１０＞ ＜８＞に記載のゴム組成物を１～１００質量％含むゴム成分を再架橋してなる再架橋ゴム。
<9> A method for producing a recrosslinked rubber, which recrosslinks a rubber component containing 1 to 100% by mass of the rubber composition according to <8>.
<10> A recrosslinked rubber obtained by recrosslinking a rubber component containing 1 to 100% by mass of the rubber composition according to <8>.
＜１１＞ ＜１０＞に記載の再架橋ゴムからなるタイヤ。
＜１２＞ ＜１０＞に記載の再架橋ゴムからなるゴム工業用品。
<11> The tire made of the recrosslinked rubber according to <10>.
<12> A rubber industrial product made of the recrosslinked rubber according to <10>.
本発明によれば、穏和な条件下においても、より分子量の高い液状炭化水素を高分解率で製造することができるゴム組成物の製造方法、並びに、該製造方法により製造されたゴム組成物、該ゴム組成物を用いる再架橋ゴムの製造方法、該ゴム組成物から得られる再架橋ゴム、タイヤ及びゴム工業用品を提供することができる。 According to the present invention, a method for producing a rubber composition capable of producing a liquid hydrocarbon having a higher molecular weight at a high decomposition rate even under mild conditions, and a rubber composition produced by the production method. It is possible to provide a method for producing a recrosslinked rubber using the rubber composition, a recrosslinked rubber obtained from the rubber composition, a tire, and a rubber industrial product.
＜ゴム組成物の製造方法＞
本発明のゴム組成物の製造方法は、架橋ゴムを、脂肪族炭素間二重結合を少なくとも１つ含み、ヒドロキシ基及びアルデヒド基の数がそれぞれ０である化合物を含む反応溶媒下において、１５０℃以上３００℃以下で加熱して液状炭化水素を含むゴム組成物を得る工程（以下、「分解工程」と称することがある）を有する。
本発明のゴム組成物の製造方法は、分解工程に加え、分解工程で得られた反応物を乾燥する乾燥工程を有していてもよい。
また、本発明の製造方法により製造されるゴム組成物に含まれる液状炭化水素は、架橋ゴムを構成するゴム分子であり、架橋ゴムの構成により異なるが、廃タイヤ由来の架橋ゴムを用いた場合、通常、天然ゴム、スチレン－ブタジエン共重合体ゴム等を含む。なお、液状とは、室温（２５℃）かつ大気圧（０．１ＭＰａ）の下で液体状態あるいは石油成分（アルコール、ジエチルエーテル、テトラヒドロフラン等）に容易に可溶化し液体状態になることをいう。
<Manufacturing method of rubber composition>
The method for producing a rubber composition of the present invention comprises a crosslinked rubber at 150 ° C. in a reaction solvent containing a compound containing at least one aliphatic carbon-carbon double bond and each having 0 hydroxy groups and 0 aldehyde groups. It has a step of obtaining a rubber composition containing a liquid hydrocarbon by heating at 300 ° C. or lower (hereinafter, may be referred to as a “decomposition step”).
The method for producing a rubber composition of the present invention may include, in addition to the decomposition step, a drying step of drying the reaction product obtained in the decomposition step.
Further, the liquid hydrocarbon contained in the rubber composition produced by the production method of the present invention is a rubber molecule constituting the crosslinked rubber, and varies depending on the composition of the crosslinked rubber, but when the crosslinked rubber derived from waste tire is used. , Usually includes natural rubber, styrene-butadiene copolymer rubber and the like. The term "liquid" means that it is easily solubilized in a liquid state or petroleum components (alcohol, diethyl ether, tetrahydrofuran, etc.) at room temperature (25 ° C.) and atmospheric pressure (0.1 MPa) to become a liquid state.
反応溶媒として脂肪族炭素間二重結合を少なくとも１つ含み、ヒドロキシ基及びアルデヒド基の数がそれぞれ０である化合物を含む反応溶媒を用いることで、架橋ゴムの架橋点は分解されるが、ゴム分子の主鎖の切断が抑えられ、回収した液状炭化水素の分子量を高く維持することができ、かつ液状炭化水素を高い収率で得ることができる。これは、脂肪族炭素間二重結合により、化合物のラジカル反応性が高いことが理由として考えられる。
以下、本発明のゴム組成物の製造方法の詳細について説明する。
By using a reaction solvent containing at least one aliphatic carbon-carbon double bond and a compound having 0 hydroxy groups and 0 aldehyde groups as the reaction solvent, the cross-linking points of the cross-linked rubber are decomposed, but the rubber Cleavage of the main chain of the molecule is suppressed, the molecular weight of the recovered liquid hydrocarbon can be maintained high, and the liquid hydrocarbon can be obtained in a high yield. This is considered to be because the radical reactivity of the compound is high due to the aliphatic carbon-carbon double bond.
Hereinafter, the details of the method for producing the rubber composition of the present invention will be described.
〔架橋ゴム〕
架橋ゴムは、ゴム成分の架橋物である。
架橋ゴムの原料であるゴム成分としては、ジエン系ゴム、非ジエン系ゴムのいずれでもよい。
ジエン系ゴムとしては、天然ゴム（ＮＲ）及び合成ジエン系ゴムからなる群より選ばれる少なくとも１種が挙げられる。
合成ジエン系ゴムは、例えば、ポリイソプレンゴム（ＩＲ）、スチレン－ブタジエン共重合体ゴム（ＳＢＲ）、ポリブタジエンゴム（ＢＲ）、エチレン－プロピレン－ジエンゴム（ＥＰＤＭ）、クロロプレンゴム（ＣＲ）、ハロゲン化ブチルゴム、アクリロニリトル－ブタジエンゴム（ＮＢＲ）等が挙げられる。
非ジエン系ゴムは、例えば、ブチルゴム、エチレンプロピレンゴム、ウレタンゴム、シリコーンゴム、アクリルゴム等が挙げられる。
これらゴム成分は、１種単独で用いてもよく、２種以上組み合わせて用いてもよい。
[Cross-linked rubber]
The crosslinked rubber is a crosslinked product of a rubber component.
The rubber component that is the raw material of the crosslinked rubber may be either a diene-based rubber or a non-diene-based rubber.
Examples of the diene-based rubber include at least one selected from the group consisting of natural rubber (NR) and synthetic diene-based rubber.
Examples of the synthetic diene rubber include polyisoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), ethylene-propylene-diene rubber (EPDM), chloroprene rubber (CR), and butyl halide rubber. , Acryloni Little-butadiene rubber (NBR) and the like.
Examples of the non-diene rubber include butyl rubber, ethylene propylene rubber, urethane rubber, silicone rubber, acrylic rubber and the like.
These rubber components may be used alone or in combination of two or more.
以上の中でも、タイヤ等のゴム製品は、一般に、ジエン系ゴムが用いられていることから、ゴム成分は、ジエン系ゴムを５０質量％以上含むことが好ましい。すなわち、架橋ゴムは、ジエン系ゴムを５０～１００質量％含むゴム成分の架橋物であることが好ましい。ゴム成分は、ジエン系ゴムを７０質量％以上含むことがより好ましく、ジエン系ゴムを９０質量％以上含むことが更に好ましい。また、ジエン系ゴムは、天然ゴム、ポリイソプレンゴム及びスチレン－ブタジエン共重合体ゴムからなる群より選択される少なくとも１つであることが好ましい。 Among the above, since diene-based rubber is generally used for rubber products such as tires, it is preferable that the rubber component contains 50% by mass or more of diene-based rubber. That is, the crosslinked rubber is preferably a crosslinked product having a rubber component containing 50 to 100% by mass of diene rubber. The rubber component more preferably contains 70% by mass or more of diene-based rubber, and further preferably contains 90% by mass or more of diene-based rubber. Further, the diene-based rubber is preferably at least one selected from the group consisting of natural rubber, polyisoprene rubber and styrene-butadiene copolymer rubber.
ゴム成分の架橋剤は、特に制限されず、例えば、硫黄系架橋剤、有機過酸化物系架橋剤、酸架橋剤、ポリアミン架橋剤、樹脂架橋剤、硫黄化合物系架橋剤、オキシム－ニトロソアミン系架橋剤等が挙げられる。
タイヤ等のゴム成分は、通常、硫黄系架橋剤（加硫剤）が用いられることから、架橋ゴムは、加硫剤で加硫された加硫物、すなわち、加硫ゴムを含むことが好ましい。
加硫ゴムを、脂肪族炭素間二重結合を少なくとも１つ含み、ヒドロキシ基及びアルデヒド基の数がそれぞれ０である化合物を含む反応溶媒下において、１５０℃以上３００℃以下で加熱することで、架橋ゴムの架橋点を分解しつつ、ゴム分子の主鎖の切断を抑える。
架橋ゴム中の加硫ゴムの含有量は、５０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、９０質量％以上であることが更に好ましく、架橋ゴムが加硫ゴムである（含有量が１００質量％である）ことが特に好ましい。
The cross-linking agent for the rubber component is not particularly limited, and is, for example, a sulfur-based cross-linking agent, an organic peroxide-based cross-linking agent, an acid cross-linking agent, a polyamine cross-linking agent, a resin cross-linking agent, a sulfur compound-based cross-linking agent, and an oxime-nitrosoamine-based cross-linking agent. Agents and the like can be mentioned.
Since a sulfur-based cross-linking agent (vulcanizing agent) is usually used as the rubber component of tires and the like, the cross-linked rubber preferably contains a vulcanized product vulcanized with a vulcanizing agent, that is, vulcanized rubber. ..
The crosslinked rubber is heated at 150 ° C. or higher and 300 ° C. or lower in a reaction solvent containing a compound containing at least one aliphatic carbon-carbon double bond and having 0 hydroxy groups and 0 aldehyde groups, respectively. While decomposing the cross-linking points of the cross-linked rubber, the breakage of the main chain of the rubber molecule is suppressed.
The content of the sulfide rubber in the crosslinked rubber is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and the crosslinked rubber is the vulture rubber. (The content is 100% by mass) is particularly preferable.
（充填剤）
架橋ゴムは、充填剤を含んでいてもよい。
タイヤは、一般に、タイヤの耐久性、耐摩耗性等の諸機能を上げるために、カーボンブラック、シリカ等の補強性充填剤を含む。
充填剤は、シリカ及びカーボンブラックのいずれか一方を単独で用いてもよいし、シリカ及びカーボンブラックの両方を用いてもよい。
(filler)
The crosslinked rubber may contain a filler.
Tires generally contain a reinforcing filler such as carbon black or silica in order to improve various functions such as tire durability and wear resistance.
As the filler, either silica or carbon black may be used alone, or both silica and carbon black may be used.
シリカは特に限定されず、一般グレードのシリカ、シランカップリング剤などで表面処理を施した特殊シリカなど、用途に応じて使用することができる。シリカは、例えば、湿式シリカを用いることが好ましい。
カーボンブラックは、特に限定されず、目的に応じて適宜選択することができる。カーボンブラックは、例えば、ＦＥＦ、ＳＲＦ、ＨＡＦ、ＩＳＡＦ、ＳＡＦグレードのものが好ましい。
架橋ゴム中の充填剤の含有量は、ゴム成分１００質量部に対して、２０～１００質量部であることが好ましく、３０～９０質量部であることがより好ましい。
The silica is not particularly limited, and can be used depending on the application, such as general grade silica and special silica surface-treated with a silane coupling agent or the like. As the silica, for example, wet silica is preferably used.
The carbon black is not particularly limited and may be appropriately selected depending on the intended purpose. The carbon black is preferably, for example, FEF, SRF, HAF, ISAF, SAF grade.
The content of the filler in the crosslinked rubber is preferably 20 to 100 parts by mass, more preferably 30 to 90 parts by mass with respect to 100 parts by mass of the rubber component.
架橋ゴムは、ゴム成分及び上記充填剤のほか、必要に応じて、ゴム工業界で通常使用される配合剤、例えば、軟化剤、ステアリン酸、老化防止剤、酸化亜鉛、加硫促進剤等を含むゴム組成物を架橋した架橋物であってもよい。タイヤは、一般に、これらの配合剤を含むゴム組成物を加硫した加硫ゴムを含む。 In addition to the rubber component and the above-mentioned filler, the crosslinked rubber contains, if necessary, a compounding agent usually used in the rubber industry, such as a softener, stearic acid, an antioxidant, zinc oxide, and a vulcanization accelerator. It may be a crosslinked product obtained by cross-linking the rubber composition contained therein. Tires generally include vulcanized rubber obtained by vulcanizing a rubber composition containing these formulations.
〔反応溶媒〕
反応溶媒は、脂肪族炭素間二重結合を少なくとも１つ含み、ヒドロキシ基及びアルデヒド基の数がそれぞれ０である化合物を含む。
以下、脂肪族炭素間二重結合を少なくとも１つ含み、ヒドロキシ基及びアルデヒド基の数がそれぞれ０である化合を、本発明における化合物と称することがある。
反応溶媒として本発明における化合物を選択することで、架橋ゴムの架橋点は分解されるが、ゴム分子の主鎖の切断が抑えられ、回収される液状炭化水素の分子量を高く維持することができる。
本発明における化合物は、分子鎖に脂肪族炭素間二重結合を少なくとも１つ含む。脂肪族炭素間二重結合とは、炭素間二重結合（－Ｃ＝Ｃ－）が芳香環を形成する二重結合ではなく、脂肪族炭化水素鎖中の二重結合であること、換言すると、不飽和炭化水素鎖としての二重結合であることを意味する。なお、本発明における化合物は、脂肪族炭素間二重結合を少なくとも１つ含む構造であれば、更に、芳香環を有していてもよい。換言すると、本発明における化合物は、脂肪族炭素間二重結合を少なくとも１つ含む芳香族化合物であってもよい。
また、本発明における化合物は、ヒドロキシ基及びアルデヒド基の数がそれぞれ０である。これは、本発明における化合物がヒドロキシ基及びアルデヒド基を共に有しないことを意味する。
反応溶媒が、脂肪族炭素間二重結合を有しないと、分子量の高い液状炭化水素を高分解率で製造することができない。
[Reaction solvent]
The reaction solvent contains a compound containing at least one aliphatic carbon-carbon double bond and having 0 hydroxy groups and 0 aldehyde groups, respectively.
Hereinafter, a compound containing at least one aliphatic carbon-carbon double bond and having 0 hydroxy groups and 0 aldehyde groups may be referred to as a compound in the present invention.
By selecting the compound in the present invention as the reaction solvent, the cross-linking point of the cross-linked rubber is decomposed, but the breakage of the main chain of the rubber molecule is suppressed, and the molecular weight of the recovered liquid hydrocarbon can be maintained high. ..
The compound in the present invention contains at least one aliphatic carbon-carbon double bond in the molecular chain. The aliphatic carbon-carbon double bond is not a double bond forming an aromatic ring but a double bond in an aliphatic hydrocarbon chain, in other words, the carbon-carbon double bond (-C = C-). , Means that it is a double bond as an unsaturated hydrocarbon chain. The compound in the present invention may further have an aromatic ring as long as it has a structure containing at least one aliphatic carbon-carbon double bond. In other words, the compound in the present invention may be an aromatic compound containing at least one aliphatic carbon-carbon double bond.
Further, the compound in the present invention has 0 hydroxy groups and 0 aldehyde groups, respectively. This means that the compounds in the present invention do not have both hydroxy and aldehyde groups.
If the reaction solvent does not have an aliphatic carbon-carbon double bond, a liquid hydrocarbon having a high molecular weight cannot be produced at a high decomposition rate.
本発明における化合物は、回収される液状炭化水素の分子量をより高く維持し、液状炭化水素を高分解率で製造する観点から、炭素数が４～１８であることが好ましく、４～１６であることがより好ましく、５～１４であることが更に好ましく、５～１２であることがより更に好ましく、５～１０であることがより更に好ましい。
本発明における化合物は、具体的には、アネトール（炭素数１０）、ピネン（炭素数１０）、エストラゴール（炭素数１０）、リモネン（炭素数１０）、カレン（炭素数１０）、カンフェン（炭素数１０）及びこれらの誘導体等が挙げられる。異性体がある場合は、異性体を含む。
The compound in the present invention preferably has 4 to 18 carbon atoms and 4 to 16 carbon atoms from the viewpoint of maintaining the molecular weight of the recovered liquid hydrocarbon higher and producing the liquid hydrocarbon at a high decomposition rate. It is more preferably 5 to 14, further preferably 5 to 12, and even more preferably 5 to 10.
Specifically, the compounds in the present invention include anethole (10 carbon atoms), pinene (10 carbon atoms), estragole (10 carbon atoms), limonene (10 carbon atoms), kalen (10 carbon atoms), and kanphen (carbon carbon atoms). Number 10) and derivatives thereof and the like can be mentioned. If there are isomers, they are included.
誘導体としては、本発明における化合物の水素原子の１つ以上がアルキル基等の置換基により置換された構造が挙げられる。アルキル基としては、メチル基、アミル基（プロピル基）、ブチル基、ヘキシル基等が挙げられる。
これらの化合物のうち１種を単独で用いてもよいし、２種以上を混合して用いてもよい。
Examples of the derivative include a structure in which one or more hydrogen atoms of the compound in the present invention are substituted with a substituent such as an alkyl group. Examples of the alkyl group include a methyl group, an amyl group (propyl group), a butyl group, a hexyl group and the like.
One of these compounds may be used alone, or two or more thereof may be mixed and used.
本発明における化合物は、回収される液状炭化水素の分子量をより高く維持し、液状炭化水素を高分解率で製造する観点から、アネトール、ピネン、エストラゴール、リモネン、カレン、カンフェン、及びこれらの誘導体からなる群より選択される少なくとも１種を含むことが好ましく、アネトール、ピネン、及びこれらの誘導体からなる群より選択される少なくとも１種を含むことがより好ましく、アネトール及びその誘導体からなる群より選択される少なくとも１種を含むことが更に好ましい。 The compound in the present invention maintains the molecular weight of the recovered liquid hydrocarbon higher, and from the viewpoint of producing the liquid hydrocarbon at a high decomposition rate, anetol, pinene, estragor, limonene, kalen, kanphen, and derivatives thereof. It is preferable to contain at least one selected from the group consisting of anator, pinene, and at least one selected from the group consisting of derivatives thereof, and more preferably to contain at least one selected from the group consisting of anator and its derivatives. It is more preferable to contain at least one of the above.
本発明における化合物は、東京化成工業社製、富士フイルム和光純薬社製等の各社試薬メーカーの溶媒を用いてもよい。 As the compound in the present invention, a solvent of each company's reagent manufacturer such as Tokyo Chemical Industry Co., Ltd. and Fujifilm Wako Pure Chemical Industries, Ltd. may be used.
反応溶媒は、本発明における化合物からなってもよいし、該アルデヒドに加え、他の溶媒を含んでいてもよいが、液状炭化水素の分解率を高める観点から、本発明における化合物が反応溶媒の主成分であることが好ましい。
ここで、主成分とは、反応溶媒中の本発明における化合物の含有量が５０体積％を越えることをいい、本発明における化合物の含有量は、７０体積％以上であることが好ましく、９０体積％以上であることがより好ましく、１００体積％であってもよい。
The reaction solvent may consist of the compound of the present invention, or may contain another solvent in addition to the aldehyde. However, from the viewpoint of increasing the decomposition rate of the liquid hydrocarbon, the compound of the present invention is the reaction solvent. It is preferably the main component.
Here, the main component means that the content of the compound in the present invention in the reaction solvent exceeds 50% by volume, and the content of the compound in the present invention is preferably 70% by volume or more, preferably 90% by volume. It is more preferably% or more, and may be 100% by volume.
分解工程では、反応溶媒を、反応溶媒の体積［ｍＬ］（Ｖｓ）と架橋ゴムの質量［ｍｇ］（Ｗｇ）との比（Ｖｓ／Ｗｇ）が、好ましくは０．００１／１～１／１、より好ましくは０．００５／１～０．１／１となる範囲で用いることが好ましい。
反応溶媒を上記範囲で用いることで、加溶媒分解反応がより促進されたり、架橋ゴムに十分な水素原子が供給され、熱分解で生成したラジカルの再結合を抑制し、架橋ゴムを効率よく分解することができる。
In the decomposition step, the ratio (Vs / Wg) of the reaction solvent to the volume [mL] (Vs) of the reaction solvent and the mass [mg] (Wg) of the crosslinked rubber is preferably 0.001 / 1/1 to 1/1. , More preferably, it is preferably used in the range of 0.005 / 1 to 0.1 / 1.
By using the reaction solvent in the above range, the solvolysis reaction is further promoted, sufficient hydrogen atoms are supplied to the crosslinked rubber, the recombination of radicals generated by thermal decomposition is suppressed, and the crosslinked rubber is efficiently decomposed. can do.
〔分解工程の反応条件〕
（温度）
分解工程において、架橋ゴムと反応溶媒は１５０℃以上３００℃以下で加熱される。
加熱温度が１５０℃未満では、架橋ゴムの架橋点を分解することができず、高分解率で液状炭化水素を製造することができない。また、加熱温度を３００℃以下とすることで、省エネルギー化に優れ、また、副反応等による分解率低下を抑制することができる。なお、分解工程における加熱温度を分解温度と称することもある。架橋ゴムをより低温で加熱することで、溶媒が関与する反応を優先させて架橋ゴムを分解することができる。
加熱温度は、１５０℃より高いことが好ましく、１５５℃以上がより好ましく、１６０℃以上が更に好ましく、１８０℃を超えることがより更に好ましく、また、２５０℃以下が好ましく、２４０℃以下がより好ましく、２３０℃以下が更に好ましく、２２０℃以下がより更に好ましく、２１０℃以下がより更に好ましい。
[Reaction conditions in the decomposition process]
(temperature)
In the decomposition step, the crosslinked rubber and the reaction solvent are heated at 150 ° C. or higher and 300 ° C. or lower.
If the heating temperature is less than 150 ° C., the cross-linking point of the cross-linked rubber cannot be decomposed, and a liquid hydrocarbon cannot be produced with a high decomposition rate. Further, by setting the heating temperature to 300 ° C. or lower, it is excellent in energy saving and it is possible to suppress a decrease in the decomposition rate due to a side reaction or the like. The heating temperature in the decomposition step may be referred to as the decomposition temperature. By heating the crosslinked rubber at a lower temperature, the reaction involving the solvent can be prioritized and the crosslinked rubber can be decomposed.
The heating temperature is preferably higher than 150 ° C, more preferably 155 ° C or higher, further preferably 160 ° C or higher, still more preferably 180 ° C or higher, still more preferably 250 ° C or lower, and even more preferably 240 ° C or lower. , 230 ° C. or lower is further preferable, 220 ° C. or lower is further preferable, and 210 ° C. or lower is even more preferable.
（分解時間）
分解工程において、架橋ゴムを加熱する時間（分解時間）は、架橋ゴムの分解反応を十分に進める観点から、３０分～２０時間であることが好ましく、６０分～１８時間であることがより好ましい。また、架橋ゴムが充填剤を含まない場合は、分解時間を２４０分以下、好ましくは１８０分以下とすることができる。
(Disassembly time)
In the decomposition step, the time for heating the crosslinked rubber (decomposition time) is preferably 30 minutes to 20 hours, more preferably 60 minutes to 18 hours from the viewpoint of sufficiently advancing the decomposition reaction of the crosslinked rubber. .. When the crosslinked rubber does not contain a filler, the decomposition time can be 240 minutes or less, preferably 180 minutes or less.
（圧力）
分解工程において、架橋ゴムと反応溶媒に与えられる圧力は特に制限されない。
架橋ゴムの分解反応の反応速度と、省資源及び省エネルギー化の観点から、０．１～２．０ＭＰａ（Ｇ）とすることが好ましく、０．１～１．５ＭＰａ（Ｇ）とすることがより好ましい。単位「ＭＰａ（Ｇ）」は圧力がゲージ圧であることを意味する。
圧力は、２．０ＭＰａ（Ｇ）以下であることで、液状炭化水素の分子量を低下させにくく、０．１ＭＰａ（Ｇ）以上であることで、架橋ゴムに反応溶媒が浸透し易く、反応速度を上げやすい。
(pressure)
In the decomposition step, the pressure applied to the crosslinked rubber and the reaction solvent is not particularly limited.
From the viewpoint of the reaction rate of the decomposition reaction of the crosslinked rubber and the viewpoint of resource saving and energy saving, it is preferably 0.1 to 2.0 MPa (G), more preferably 0.1 to 1.5 MPa (G). preferable. The unit "MPa (G)" means that the pressure is a gauge pressure.
When the pressure is 2.0 MPa (G) or less, it is difficult to reduce the molecular weight of the liquid hydrocarbon, and when it is 0.1 MPa (G) or more, the reaction solvent easily permeates the crosslinked rubber and the reaction rate is increased. Easy to raise.
（雰囲気）
１５０℃以上３００℃以下の分解工程における反応雰囲気は、特に制限されず、アルゴンガス、窒素ガス等の不活性ガスからなる気体の雰囲気（以下、単に不活性ガス雰囲気という）下で反応を進めてもよいし、空気からなる気体の雰囲気（以下、単に空気雰囲気という）下で反応を進めてもよいし、空気と不活性ガスとの混合ガス雰囲気下で反応を進めてもよい。不活性ガスを用いる場合、２種以上の不活性ガスを混合して用いてもよい。
架橋ゴムの分解をより軽微な設備で行い、また、低エネルギー化を進める観点から、架橋ゴムは、好気環境下、即ち、酸素含有雰囲気下で加熱することが好ましく、空気を含む気体の雰囲気下で加熱することがより好ましく、空気雰囲気下で加熱することが更に好ましい。
(atmosphere)
The reaction atmosphere in the decomposition step of 150 ° C. or higher and 300 ° C. or lower is not particularly limited, and the reaction proceeds in a gaseous atmosphere consisting of an inert gas such as argon gas or nitrogen gas (hereinafter, simply referred to as an inert gas atmosphere). Alternatively, the reaction may proceed in a gas atmosphere composed of air (hereinafter, simply referred to as an air atmosphere), or in a mixed gas atmosphere of air and an inert gas. When an inert gas is used, two or more kinds of inert gases may be mixed and used.
From the viewpoint of decomposing the crosslinked rubber with a lighter facility and promoting low energy, the crosslinked rubber is preferably heated in an aerobic environment, that is, in an oxygen-containing atmosphere, and has an atmosphere of a gas containing air. It is more preferable to heat underneath, and it is further preferable to heat under an air atmosphere.
〔乾燥工程〕
本発明のゴム組成物の製造方法は、分解工程で得られた反応物（液状炭化水素を含むゴム組成物）を乾燥する乾燥工程を有することが好ましい。
反応物は、例えば１００～１５０℃の温風を吹き付ければよい。温風は空気であってもよいし、窒素ガスのような不活性ガスであってもよい。
[Drying process]
The method for producing a rubber composition of the present invention preferably includes a drying step of drying the reaction product (rubber composition containing a liquid hydrocarbon) obtained in the decomposition step.
The reaction product may be blown with warm air at, for example, 100 to 150 ° C. The warm air may be air or an inert gas such as nitrogen gas.
以上のように、架橋ゴムを、本発明における化合物を含む反応溶媒下において、１５０℃以上３００℃以下で加熱することで、液状炭化水素を含むゴム組成物が得られる。このようにして得られるゴム組成物を「分解生成有機物」と称することがある。ゴム組成物（分解生成有機物）は、一般に、架橋ゴムの加熱分解により得られる液状炭化水素を含む液体生成物の他に、分解せずに残存する固形分を含む。更に、架橋ゴムとして、廃タイヤを用いた場合、タイヤには、通常、充填剤が含まれることから、固形分には、充填剤も含まれる。
加硫前の生ゴムは、イソプレンゴム（ＩＲ）の場合、一般に、重量平均分子量（Ｍｗ）が１２０万程度、数平均分子量（Ｍｎ）が４０万程度であり、また、スチレン－ブタジエン共重合体ゴム（ＳＢＲ）の場合、一般に、重量平均分子量（Ｍｗ）が４０万程度、数平均分子量（Ｍｎ）が１０万程度である。得られた液状炭化水素のＭｗ及びＭｎがこれらの値に近いほど、原料ゴムに近い分子鎖のゴムが得られたことを意味する。
液状炭化水素のＭｗ及びＭｎは、例えば、ゲル浸透クロマトグラフィー（ＧＰＣ）で測定することができる。
As described above, by heating the crosslinked rubber at 150 ° C. or higher and 300 ° C. or lower under the reaction solvent containing the compound of the present invention, a rubber composition containing a liquid hydrocarbon can be obtained. The rubber composition thus obtained may be referred to as a "decomposition-produced organic substance". The rubber composition (decomposition-produced organic substance) generally contains a liquid product containing a liquid hydrocarbon obtained by thermal decomposition of a crosslinked rubber, as well as a solid content remaining without decomposition. Further, when a waste tire is used as the crosslinked rubber, the tire usually contains a filler, so that the solid content also contains a filler.
In the case of isoprene rubber (IR), the raw rubber before vulcanization generally has a weight average molecular weight (Mw) of about 1.2 million, a number average molecular weight (Mn) of about 400,000, and a styrene-butadiene copolymer rubber. In the case of (SBR), the weight average molecular weight (Mw) is generally about 400,000 and the number average molecular weight (Mn) is about 100,000. The closer the Mw and Mn of the obtained liquid hydrocarbons are to these values, the closer the rubber having a molecular chain similar to that of the raw material rubber is obtained.
The liquid hydrocarbons Mw and Mn can be measured, for example, by gel permeation chromatography (GPC).
以上の方法によって製造された液状炭化水素は、架橋ゴムの再生に用いることができる。
また、架橋ゴムの再生には、液状炭化水素単独を原料とするのみならず、液状炭化水素と、分解工程で得られる固形分とを混合した状態で、すなわち、分解工程で得られるゴム組成物から液状炭化水素を分離することなく、ゴム組成物のまま再生ゴムの原料として用いてもよい。
このように、本発明のゴム組成物の製造方法により得られるゴム組成物は、架橋ゴム（再架橋ゴム）を再生可能なリサイクルゴムであり、本発明のゴム組成物の製造方法は、リサイクルゴムの製造方法である。
The liquid hydrocarbon produced by the above method can be used for regeneration of crosslinked rubber.
Further, for the regeneration of the crosslinked rubber, not only the liquid hydrocarbon alone is used as a raw material, but also the rubber composition obtained in a state where the liquid hydrocarbon and the solid content obtained in the decomposition step are mixed, that is, the rubber composition obtained in the decomposition step. The rubber composition may be used as a raw material for recycled rubber without separating the liquid hydrocarbon from the rubber composition.
As described above, the rubber composition obtained by the method for producing a rubber composition of the present invention is a recycled rubber that can recycle crosslinked rubber (recrosslinked rubber), and the method for producing a rubber composition of the present invention is a recycled rubber. It is a manufacturing method of.
＜ゴム組成物＞
本発明のゴム組成物は、本発明のゴム組成物の製造方法で製造されたゴム組成物である。
既述のように、本発明のゴム組成物は、架橋ゴムを本発明における化合物を含む反応溶媒で分解して得られるゴム組成物である。
<Rubber composition>
The rubber composition of the present invention is a rubber composition produced by the method for producing a rubber composition of the present invention.
As described above, the rubber composition of the present invention is a rubber composition obtained by decomposing a crosslinked rubber with a reaction solvent containing the compound of the present invention.
＜再架橋ゴム＞
本発明の再架橋ゴムは、本発明のゴム組成物を１～１００質量％含むゴム成分を再架橋してなる。
本発明の再架橋ゴムは、本発明のゴム組成物の製造方法で製造されたゴム組成物、すなわち、本発明のゴム組成物をゴム成分として用い、当該ゴム成分を再架橋してなる再架橋ゴムであって、ゴム成分中の本発明のゴム組成物の含有量が１～１００質量％である。
つまり、本発明の再架橋ゴムは、架橋ゴムの加熱分解により得られる液状炭化水素を含むゴム組成物の再架橋物であって、ゴム成分は本発明のゴム組成物を少なくとも１質量％含み、１００質量％であってもよい。ゴム成分中の本発明のゴム組成物の含有量は、５質量％以上であってもよいし、１０質量％以上であってもよいし、１５質量％以上であってもよいし、２０質量％以上であってもよい。また、ゴム成分中の本発明のゴム組成物の含有量は、７０質量％以下であってもよいし、６０質量％以下であってもよいし、５０質量％以下であってもよい。
<Re-crosslinked rubber>
The re-crosslinked rubber of the present invention is obtained by re-crosslinking a rubber component containing 1 to 100% by mass of the rubber composition of the present invention.
The re-crosslinked rubber of the present invention is a rubber composition produced by the method for producing a rubber composition of the present invention, that is, a re-crosslinked rubber composition of the present invention is used as a rubber component and the rubber component is re-crosslinked. It is a rubber, and the content of the rubber composition of the present invention in the rubber component is 1 to 100% by mass.
That is, the re-crosslinked rubber of the present invention is a re-crosslinked product of a rubber composition containing a liquid hydrocarbon obtained by thermal decomposition of the crosslinked rubber, and the rubber component contains at least 1% by mass of the rubber composition of the present invention. It may be 100% by mass. The content of the rubber composition of the present invention in the rubber component may be 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass. It may be% or more. Further, the content of the rubber composition of the present invention in the rubber component may be 70% by mass or less, 60% by mass or less, or 50% by mass or less.
ゴム成分中の本発明のゴム組成物の含有量が１００質量％未満の場合、本発明のゴム組成物と共に用いられる他のゴム成分は特に制限されない。なお、本発明のゴム組成物と共に用いられる他のゴム成分を純ゴム成分と称することがある。
純ゴム成分としては、架橋ゴムの原料であるゴム成分として挙げた既述のゴム成分である。中でも、天然ゴム（ＮＲ）及び合成ジエン系ゴムからなる群より選ばれる少なくとも１種が好ましく、天然ゴム、ポリイソプレンゴム、ポリブタジエンゴム及びスチレン－ブタジエン共重合体ゴムからなる群より選ばれる少なくとも１種がより好ましい。
When the content of the rubber composition of the present invention in the rubber component is less than 100% by mass, other rubber components used together with the rubber composition of the present invention are not particularly limited. In addition, other rubber components used together with the rubber composition of the present invention may be referred to as pure rubber components.
The pure rubber component is the above-mentioned rubber component mentioned as the rubber component which is the raw material of the crosslinked rubber. Among them, at least one selected from the group consisting of natural rubber (NR) and synthetic diene rubber is preferable, and at least one selected from the group consisting of natural rubber, polyisoprene rubber, polybutadiene rubber and styrene-butadiene copolymer rubber. Is more preferable.
本発明の再架橋ゴムの原料となる原料ゴム組成物は、本発明のゴム組成物を含むゴム成分の他に、充填剤、加硫剤、加硫促進剤、軟化剤、ステアリン酸、老化防止剤、亜鉛華等を含んでいてもよい。
既述のように、本発明のゴム組成物の製造方法で製造されたゴム組成物は、架橋ゴムの加熱分解により得られる液状炭化水素を含む液体生成物の他に、分解せずに残存する固形分を含み、固形分には、充填剤も含まれる場合もある。
再架橋ゴムの原料となる原料ゴム組成物が、そのような固形分を含む本発明のゴム組成物をゴム成分として含み、再架橋ゴムを製造することにより、環境負担をより低減することができる。
本発明のゴム組成物の製造方法で製造されたゴム組成物の再架橋の条件は特に制限されない。
本発明の再架橋ゴムは、本発明のゴム組成物を含むゴム成分が加硫剤によって加硫された再加硫ゴムであってもよい。
The raw rubber composition used as a raw material for the recrosslinked rubber of the present invention includes a filler, a vulcanizing agent, a vulcanization accelerator, a softening agent, stearic acid, and antiaging, in addition to the rubber component containing the rubber composition of the present invention. It may contain an agent, zinc oxide and the like.
As described above, the rubber composition produced by the method for producing a rubber composition of the present invention remains without decomposition in addition to the liquid product containing the liquid hydrocarbon obtained by the thermal decomposition of the crosslinked rubber. It contains solids, which may also include fillers.
The raw material rubber composition which is a raw material of the recrosslinked rubber contains the rubber composition of the present invention containing such a solid content as a rubber component, and by producing the recrosslinked rubber, the environmental burden can be further reduced. ..
The conditions for recrosslinking the rubber composition produced by the method for producing a rubber composition of the present invention are not particularly limited.
The re-crosslinked rubber of the present invention may be a re-vulcanized rubber in which the rubber component containing the rubber composition of the present invention is vulcanized with a vulcanizing agent.
＜再架橋ゴムの製造方法＞
本発明の再架橋ゴムの製造方法は、本発明のゴム組成物を１～１００質量％含むゴム成分を再架橋する工程を有する。
具体的には、本発明のゴム組成物の製造方法で製造されたゴム組成物を、ゴム成分として、該ゴム成分中１～１００質量％の範囲で用い、各種架橋剤でゴム成分を架橋する。
各種架橋剤としては、硫黄系架橋剤、有機過酸化物系架橋剤、酸架橋剤、ポリアミン架橋剤、樹脂架橋剤、硫黄化合物系架橋剤、オキシム－ニトロソアミン系架橋剤等が挙げられ、通常、硫黄系架橋剤、硫黄化合物系架橋剤等の加硫剤が用いられる。
ゴム成分中の本発明のゴム組成物の含有量が１００質量％未満の場合における、本発明のゴム組成物と共に用いられる他のゴム成分；再架橋ゴムの原料となる原料ゴム組成物が含み得るゴム成分以外の成分は、本発明の再架橋ゴムの項目において説明した成分が用いられる。
<Manufacturing method of re-crosslinked rubber>
The method for producing a recrosslinked rubber of the present invention includes a step of recrosslinking a rubber component containing 1 to 100% by mass of the rubber composition of the present invention.
Specifically, the rubber composition produced by the method for producing a rubber composition of the present invention is used as a rubber component in the range of 1 to 100% by mass in the rubber component, and the rubber component is crosslinked with various cross-linking agents. ..
Examples of various cross-linking agents include sulfur-based cross-linking agents, organic peroxide-based cross-linking agents, acid cross-linking agents, polyamine cross-linking agents, resin cross-linking agents, sulfur compound-based cross-linking agents, oxime-nitrosoamine-based cross-linking agents, and the like. Sulfur-based cross-linking agents, sulfur compound-based cross-linking agents and other sulphurizing agents are used.
Other rubber components used together with the rubber composition of the present invention when the content of the rubber composition of the present invention in the rubber component is less than 100% by mass; the raw material rubber composition which is a raw material of the recrosslinked rubber may be contained. As the component other than the rubber component, the component described in the item of the recrosslinked rubber of the present invention is used.
＜タイヤ＞
本発明のタイヤは、本発明の再架橋ゴムからなる。
タイヤを、架橋ゴムの加熱分解により得られる液状炭化水素を含むゴム組成物を再架橋して得られる再架橋ゴムを用いて構成することで、環境負荷の小さいタイヤとすることができる。
タイヤは、適用するタイヤの種類や部材に応じ、未架橋のゴム組成物を用いて成形後に架橋して得てもよく、または予備架橋工程等を経て、一旦未架橋のゴム組成物から半架橋ゴムを得た後、これを用いて成形後、さらに本架橋して得てもよい。タイヤに充填する気体としては、通常の或いは酸素分圧を調整した空気の他、窒素、アルゴン、ヘリウム等の不活性ガスを用いることができる。
<Tire>
The tire of the present invention is made of the recrosslinked rubber of the present invention.
By constructing the tire by using the re-crosslinked rubber obtained by re-crosslinking the rubber composition containing the liquid hydrocarbon obtained by the thermal decomposition of the cross-linked rubber, the tire can be made into a tire having a small environmental load.
The tire may be obtained by cross-linking after molding using an uncross-linked rubber composition depending on the type and member of the tire to be applied, or may be semi-cross-linked from the uncross-linked rubber composition once through a preliminary cross-linking step or the like. After obtaining the rubber, it may be used for molding, and then further cross-linked to obtain the rubber. As the gas to be filled in the tire, an inert gas such as nitrogen, argon or helium can be used in addition to normal air or air having an adjusted oxygen partial pressure.
＜ゴム工業用品＞
本発明のゴム工業用品は、本発明の再架橋ゴムからなる。
ゴム工業用品は、例えば、上記タイヤを除く自動車部品、ホースチューブ類、防振ゴム類、コンベアベルト、クローラー、ケーブル類、シール材等、船舶部品、建材等が挙げられる。ゴム工業用品を、本発明の再架橋ゴムを用いて構成することで、環境負荷の小さい工業用品とすることができる。
<Rubber industrial products>
The rubber industrial product of the present invention comprises the recrosslinked rubber of the present invention.
Examples of rubber industrial products include automobile parts excluding the above tires, hose tubes, anti-vibration rubbers, conveyor belts, crawlers, cables, sealing materials, ship parts, building materials and the like. By constructing the rubber industrial product by using the recrosslinked rubber of the present invention, it can be made into an industrial product having a small environmental load.
以下、実施例を挙げて本発明をさらに詳しく説明するが、これらの実施例は、本発明の例示を目的とするものであり、本発明を何ら限定するものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for the purpose of exemplifying the present invention and do not limit the present invention in any way.
＜加硫ゴムの用意＞
加硫ゴムとして、下記加硫ゴムを用意した。
加硫ゴム（ＩＲ）：ポリイソプレンゴムを加硫して得られた加硫ゴム
加硫ゴム（Ａ）：ゴム成分として、天然ゴム（ＮＲ）とポリブタジエンゴム（ＢＲ）；フィラー成分としてカーボンブラックを少なくとも含むゴム組成物の加硫ゴム
<Preparation of vulcanized rubber>
The following vulcanized rubber was prepared as the vulcanized rubber.
Vulcanized rubber (IR): Vulcanized rubber obtained by vulcanizing polyisoprene rubber Vulcanized rubber (A): Natural rubber (NR) and polybutadiene rubber (BR) as rubber components; carbon black as a filler component Vulcanized rubber in a rubber composition containing at least
＜液状炭化水素の製造Ａ＞
〔比較例１〕
（分解工程）
オートクレーブ（ＥＹＥＬＡ社製、耐圧容器、商品名「ＨＩＰ－３０Ｌ」）に、１ｍｍ程度の小片状にした加硫ゴム（ＩＲ）０．４ｇと、５ｍＬの１－ヘプタノールとを投入した。オートクレーブ内を密閉し、オートクレーブを加熱容器（ＥＹＥＬＡ社製、パーソナル有機合成装置ケミステーション、商品名「ＰＰＶ－ＣＴＲＬ１」）に入れ、投入物を空気雰囲気下において２００℃で２時間加熱した。加熱終了後、加熱容器を冷却水によって常温（２５℃）まで戻し、反応物を常温にした。
<Manufacturing of liquid hydrocarbon A>
[Comparative Example 1]
(Disassembly process)
0.4 g of vulcanized rubber (IR) in the form of small pieces of about 1 mm and 5 mL of 1-heptanol were put into an autoclave (pressure resistant container manufactured by EYELA, trade name "HIP-30L"). The inside of the autoclave was sealed, the autoclave was placed in a heating container (manufactured by EYELA, personal organic synthesizer Chemistation, trade name "PPV-CTRL1"), and the input was heated at 200 ° C. for 2 hours in an air atmosphere. After the heating was completed, the heating container was returned to room temperature (25 ° C.) with cooling water, and the reaction product was brought to room temperature.
（乾燥工程）
分解工程で得られた反応物を、吹付式試験管濃縮装置(ＥＹＥＬＡ社製、商品名「ＭＧＳ－３１００」)を用い、１３０℃における窒素フローの条件で乾燥し、比較例１の分解生成有機物を得た。
(Drying process)
The reaction product obtained in the decomposition step was dried using a spray-type test tube concentrator (manufactured by EYELA, trade name "MGS-3100") under the condition of nitrogen flow at 130 ° C., and the decomposition-produced organic substance of Comparative Example 1 was obtained. Got
〔比較例２～４、実施例１～５〕
反応溶媒を表１の「○」で示される溶媒に代え、分解温度（加熱温度）を表１の「○」で示される温度に代えた他は、比較例１と同様にして、分解工程と乾燥工程を進め、比較例２～４、及び実施例１～５の分解生成有機物を得た。例えば、実施例１は反応溶媒としてアネトールを用い、分解温度は１８０℃とした。
[Comparative Examples 2 to 4, Examples 1 to 5]
The decomposition step was carried out in the same manner as in Comparative Example 1, except that the reaction solvent was replaced with the solvent indicated by “◯” in Table 1 and the decomposition temperature (heating temperature) was replaced with the temperature indicated by “◯” in Table 1. The drying step was advanced to obtain decomposition-produced organic substances of Comparative Examples 2 to 4 and Examples 1 to 5. For example, in Example 1, anethole was used as a reaction solvent, and the decomposition temperature was 180 ° C.
＜分解生成有機物の分析＞
実施例及び比較例で得られた分解生成有機物を、テトラヒドロフランで溶解し、ゲル浸透クロマトグラフィー（ＧＰＣ）で分析した。分析結果から、分解生成有機物の可溶化率、重量平均分子量（Ｍｗ）を測定した。また、濃度の異なる純ゴム成分のテトラヒドロフラン溶液を用いて検量線を作成した。検量線を利用してテトラヒドロフラン中の液状炭化水素を定量し、分解率を算出し、有効数字３桁として表１に示した。
表１に示す分子量は、例えば、比較例１の場合、２９６×１０３、すなわち、２９６，０００であることを意味する。なお、比較例２、３及び４は、分解反応が進まずテトラヒドロフランに溶解する成分が得られなかったため、測定したが分子量に関する結果が得られなかった。
表１において、許容範囲は、重量平均分子量（Ｍｗ）が３００×１０３以上、かつ分解率が４０％以上である。
<Analysis of decomposition-generated organic matter>
The decomposition product organics obtained in Examples and Comparative Examples were dissolved in tetrahydrofuran and analyzed by gel permeation chromatography (GPC). From the analysis results, the solubilization rate and the weight average molecular weight (Mw) of the decomposition-produced organic matter were measured. In addition, a calibration curve was prepared using a solution of pure rubber components having different concentrations in tetrahydrofuran. The liquid hydrocarbon in tetrahydrofuran was quantified using a calibration curve, the decomposition rate was calculated, and it is shown in Table 1 as three significant figures.
The molecular weight shown in Table 1 means, for example, 296 × 10 3 in the case of Comparative Example 1, that is, 296,000. In Comparative Examples 2, 3 and 4, the decomposition reaction did not proceed and a component soluble in tetrahydrofuran was not obtained, so that the measurement was carried out, but the result regarding the molecular weight was not obtained.
In Table 1, the permissible range is that the weight average molecular weight (Mw) is 300 × 103 or more and the decomposition rate is 40% or more.
ＧＰＣ測定の条件は次のとおりである。
・カラム：東ソー（株）製造：ＴＳＫｇｅｌ ＧＭＨＸＬ
・溶離液：テトラヒドロフラン
・流速：１ｍＬ／ｍｉｎ
・温度：４０℃
・検出器：ＲＩ
The conditions for GPC measurement are as follows.
-Column: Tosoh Corporation Manufacturing: TSKgel GMHXL
・ Eluent: Tetrahydrofuran ・ Flow rate: 1 mL / min
・ Temperature: 40 ℃
・ Detector: RI
＜液状炭化水素の製造Ｂ＞
〔実施例６、実施例７、比較例６〕
実施例１の分解工程において、加硫ゴム（ＩＲ）を加硫ゴム（Ａ）に；１－ヘプタノールを表２に示す溶媒に；加硫ゴム及び溶媒の加熱時間（分解時間）を表２に示す時間に、それぞれ変更した他は同様にして、分解工程を行った。その後、溶媒除去のための精製を行い、乾燥工程を進め、実施例６、実施例７及び比較例６の分解生成有機物を得た。
<Manufacturing of liquid hydrocarbon B>
[Example 6, Example 7, Comparative Example 6]
In the decomposition step of Example 1, the vulcanized rubber (IR) was used as the vulcanized rubber (A); the 1-heptanol was used as the solvent shown in Table 2, and the heating time (decomposition time) of the vulcanized rubber and the solvent was shown in Table 2. The decomposition step was carried out at the indicated times in the same manner except that the respective changes were made. Then, purification for removing the solvent was carried out, and the drying step was advanced to obtain decomposition-produced organic substances of Example 6, Example 7, and Comparative Example 6.
＜分解生成有機物の分析＞
製造した分解生成有機物について、比較例１の分解生成有機物と同様の方法で分析して、重量平均分子量（Ｍｗ）及び分解率を測定し、有効数字３桁として表２に示した。
表２に示す分子量は、例えば、実施例５の場合、２１０×１０３、すなわち、２１０，０００であることを意味する。
表２において、許容範囲は、重量平均分子量（Ｍｗ）が２１０×１０３以上、かつ分解率が７０％以上である。
なお、表１は脱硫前の加硫ゴムが加硫ゴム（ＩＲ）であり、ゴム成分がポリイソプレンゴム（ＩＲ）であるため、許容範囲の分子量を３００×１０３以上と設定した。表２では脱硫前の加硫ゴムが加硫ゴム（Ａ）であり、ゴム成分としてポリブタジエンゴム（ＢＲ）が含まれているため、許容範囲の分子量を２１０×１０３と設定した。
<Analysis of decomposition-generated organic matter>
The produced decomposition-produced organic matter was analyzed by the same method as that of Comparative Example 1, and the weight average molecular weight (Mw) and the decomposition rate were measured and shown in Table 2 as three significant figures.
The molecular weight shown in Table 2 means, for example, 210 × 103 , that is, 210,000 in the case of Example 5.
In Table 2, the permissible range is that the weight average molecular weight (Mw) is 210 × 103 or more and the decomposition rate is 70% or more.
In Table 1, since the vulcanized rubber before vulcanization is vulcanized rubber (IR) and the rubber component is polyisoprene rubber (IR), the allowable molecular weight is set to 300 × 103 or more. In Table 2, the vulcanized rubber before vulcanization is the vulcanized rubber (A), and polybutadiene rubber (BR) is contained as a rubber component. Therefore, the allowable molecular weight is set to 210 × 103 .
＜再加硫ゴムの製造＞
〔実施例８～１３、比較例７～８〕
実施例６、実施例７、及び比較例６で製造した分解生成有機物を用い、又は用いずに、表３に示す組成で各成分を配合し、ゴム組成物を調製した。得られたゴム組成物をそれぞれ加硫して加硫ゴムを得た。
<Manufacturing of revulcanized rubber>
[Examples 8 to 13, Comparative Examples 7 to 8]
A rubber composition was prepared by blending each component with the composition shown in Table 3 with or without using the decomposition-produced organic substances produced in Example 6, Example 7, and Comparative Example 6. The obtained rubber compositions were vulcanized to obtain vulcanized rubber.
なお、表３に示す成分の詳細は下記のとおりである。
ＮＲ：天然ゴム
ＢＲ：ハイシスポリブタジエン、宇部興産社製、商品名「ＵＢＥＰＯＬ ＢＲ１５０Ｌ」
カーボンブラック：ＳＡＦグレード
老化防止剤：大内新興化学工業社製、商品名「ノクラック ６Ｃ」を含む老化防止剤
加硫パッケージ：硫黄を含む。
表３に示す以外に、その他薬品トータル７．９質量部を含む。
The details of the components shown in Table 3 are as follows.
NR: Natural rubber BR: High cis polybutadiene, manufactured by Ube Kosan Co., Ltd., trade name "UBEPOL BR150L"
Carbon black: SAF grade Anti-aging agent: Manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., anti-aging agent containing the trade name "Nocrack 6C" Vulcanization package: Contains sulfur.
In addition to those shown in Table 3, a total of 7.9 parts by mass of other chemicals is included.
＜加硫ゴムの特性評価＞
実施例８～１３及び比較例７～８の加硫ゴムを用いて、各加硫ゴムの引張強度を評価した。
<Characteristic evaluation of vulcanized rubber>
The tensile strength of each vulcanized rubber was evaluated using the vulcanized rubbers of Examples 8 to 13 and Comparative Examples 7 to 8.
１．引張強度
各加硫ゴムの引張強度は、破断強度（ＴＢ；Ｔｅｎｓｉｌｅ ｓｔｒｅｎｇｔｈ ａｔ Ｂｒｅａｋ）の観点から評価した。破断強度は、ＪＩＳ Ｋ ６２５１（２０１７年）に基づいて、加硫ゴムを室温（２３℃）で１００％伸長し、破断させるのに要した最大の引張り力として測定した。結果を表３に示す。
得られた破断強度の値は、比較例７の破断強度の値を１００として指数表示した。指数値が大きい程、加硫ゴムは、破断強度が大きいことを意味する。
1. 1. Tensile strength The tensile strength of each vulcanized rubber was evaluated from the viewpoint of breaking strength (TB; Tensile strength at Break). The breaking strength was measured as the maximum tensile force required to break the vulcanized rubber by 100% elongation at room temperature (23 ° C.) based on JIS K 6251 (2017). The results are shown in Table 3.
The obtained breaking strength value was expressed exponentially with the breaking strength value of Comparative Example 7 as 100. The larger the exponential value, the higher the breaking strength of the vulcanized rubber.
表１～２からわかるように、実施例では、比較例に比べ、より高い分子量の液状炭化水素を含むゴム組成物を、より高い分解率で製造することができる。
また、表３からわかるように、実施例の液状炭化水素を含むゴム組成物から製造された加硫ゴムは、比較例の液状炭化水素を含むゴム組成物から製造された加硫ゴムに比べ、引張強度が大きく、ゴム組成物中の含有量が増えても引っ張り強度が悪化しにくく、性能を維持していることがわかる。
As can be seen from Tables 1 and 2, in Examples, a rubber composition containing a liquid hydrocarbon having a higher molecular weight can be produced with a higher decomposition rate than in Comparative Examples.
Further, as can be seen from Table 3, the vulnerable rubber produced from the rubber composition containing the liquid hydrocarbon of the example is compared with the vulture rubber produced from the rubber composition containing the liquid hydrocarbon of the comparative example. It can be seen that the tensile strength is high, the tensile strength does not easily deteriorate even if the content in the rubber composition increases, and the performance is maintained.
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