WO2022202698A1 - Rubber composition for tire, and tire - Google Patents
Rubber composition for tire, and tire Download PDFInfo
- Publication number
- WO2022202698A1 WO2022202698A1 PCT/JP2022/012779 JP2022012779W WO2022202698A1 WO 2022202698 A1 WO2022202698 A1 WO 2022202698A1 JP 2022012779 W JP2022012779 W JP 2022012779W WO 2022202698 A1 WO2022202698 A1 WO 2022202698A1
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- WO
- WIPO (PCT)
- Prior art keywords
- carbon black
- mass
- recycled
- parts
- tire
- Prior art date
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 36
- 239000005060 rubber Substances 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 239000006229 carbon black Substances 0.000 claims abstract description 113
- 238000010521 absorption reaction Methods 0.000 claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 229920003244 diene elastomer Polymers 0.000 claims description 16
- 244000043261 Hevea brasiliensis Species 0.000 claims description 6
- 229920003052 natural elastomer Polymers 0.000 claims description 6
- 229920001194 natural rubber Polymers 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 abstract 2
- 230000009102 absorption Effects 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000010920 waste tyre Substances 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920003049 isoprene rubber Polymers 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
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002296 pyrolytic carbon Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- DLNKOYKMWOXYQA-CBAPKCEASA-N (-)-norephedrine Chemical compound C[C@H](N)[C@H](O)C1=CC=CC=C1 DLNKOYKMWOXYQA-CBAPKCEASA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C15/00—Tyre beads, e.g. ply turn-up or overlap
- B60C15/06—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
Definitions
- the present invention relates to a rubber composition for a tire and a tire, and more particularly, for a tire capable of maintaining breaking strength and achieving low heat build-up even when part of the total amount of carbon black is replaced with recycled carbon black.
- the present invention relates to rubber compositions and tires using the same.
- recycled carbon black (recycled CB. It is also sometimes called pyrolytic carbon black or recycled carbon black) obtained by pyrolyzing used rubber products such as waste tires is being studied (for example, the following patent Reference 1).
- recycled carbon black contains impurities derived from reinforcing materials, tire cords, etc., which are raw materials of tires, there is a problem that the strength and heat build-up properties of tires are greatly reduced.
- an object of the present invention is to provide a rubber composition for a tire and a tire using the same, which can achieve low heat build-up while maintaining breaking strength even when part of the total amount of carbon black is replaced with recycled carbon black. to do.
- the inventors of the present invention have found that in a rubber composition for tires containing at least a diene rubber, carbon black and recycled carbon black, the nitrogen adsorption specific surface area N 2 SA and DBP oil absorption of carbon black and recycled carbon black is set within a specific range and the content of the recycled carbon black is set within an appropriate range.
- the present invention provides a rubber composition for tires containing at least a diene rubber, carbon black and recycled carbon black
- the carbon black has a nitrogen adsorption specific surface area N 2 SA of 30 to 90 m 2 /g and a DBP oil absorption of 70 to 140 ml/100 g
- the regenerated carbon black has a nitrogen adsorption specific surface area N 2 SA of 65 to 95 m 2 /g and a DBP oil absorption of 75 to 105 ml/100 g
- the total carbon black amount of the carbon black and the recycled carbon black (excluding the ash contained in the recycled carbon black) is 30 to 130 parts by mass with respect to 100 parts by mass of the diene rubber
- a rubber composition for a tire is provided, wherein the ratio of the recycled carbon black (excluding ash contained in the recycled carbon black) in the total amount of carbon black is 3 to 30% by mass. be.
- the rubber composition for tires of the present invention is a rubber composition for tires containing at least a diene rubber, carbon black and recycled carbon black, wherein the nitrogen adsorption specific surface area N 2 SA and DBP oil absorption of carbon black and recycled carbon black are specified. and the blending amount of recycled carbon black is set within an appropriate range, so even if part of the total amount of carbon black is replaced with recycled carbon black, low heat build-up is achieved while maintaining breaking strength. It is possible to provide a rubber composition for tires that can be used and a tire using the same.
- the diene rubber used in the present invention is not particularly limited, but for example natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer polymer rubber (NBR), ethylene-propylene-diene terpolymer (EPDM), and the like. These may be used alone or in combination of two or more. Further, its molecular weight and microstructure are not particularly limited, and it may be terminally modified with an amine, amide, silyl, alkoxysilyl, carboxyl, hydroxyl group or the like, or epoxidized. From the viewpoint of improving the effects of the present invention, the amount of NR compounded is 30 parts by mass or more, preferably 30 to 50 parts by mass, when the entire diene rubber used in the present invention is 100 parts by mass. should be
- the carbon black (CB) used in the present invention has a nitrogen adsorption specific surface area N 2 SA of 30-90 m 2 /g and a DBP oil absorption of 70-140 ml/100 g.
- N 2 SA of the CB is less than 30 m 2 /g, the breaking strength is lowered, and when it exceeds 90 m 2 /g, low heat build-up cannot be obtained.
- DBP oil absorption of CB is less than 70 ml/100 g, the breaking strength is lowered, and when it exceeds 140 ml/100 g, the low heat build-up deteriorates.
- the N 2 SA of CB is preferably 30-70 m 2 /g, and the DBP oil absorption is preferably 80-120 ml/100 g.
- Recycled carbon black (recycled carbon black) used in the present invention can be, for example, recycled CB produced through thermal decomposition of waste tires.
- Recycled CB is sometimes called pyrolytic carbon black or recycled carbon black.
- Pyrolysis of waste tires can be carried out according to known methods. For example, a pyrolysis method at a temperature of 650° C. or higher can be mentioned.
- the regenerated CB used in the present invention has a nitrogen adsorption specific surface area N 2 SA of 65-95 m 2 /g and a DBP oil absorption of 75-105 ml/100 g. If the N 2 SA and DBP oil absorption of the recycled CB are outside the above ranges, the effect of the present invention cannot be obtained.
- regenerated CB can be used in the present invention.
- product name rCB660 ANHUI GREAT product name G685, Shandong Kaiyuan product name rCB, LDC product name GCB-774G, and the like.
- the PB365 is recycled CB produced through thermal decomposition of waste tires, and has an N 2 SA of 76 m 2 /g and a DBP oil absorption of 88 ml/100 g.
- the above various commercially available recycled CBs contain about 17% by mass of ash.
- a typical elemental composition contained in the ash of the PB365 is as follows. Generally, when the amounts of silica and calcium are compared in regenerated CB, silica is contained more than calcium.
- N 2 SA conforms to JIS K6217-2
- DBP oil absorption conforms to ASTM D2414
- ash content is measured by a known ICP method.
- the rubber composition of the present invention contains at least the diene rubber, the CB and the recycled CB, and the total carbon black amount of the CB and the recycled CB (excluding ash contained in the recycled CB) is 30 to 130 parts by mass (preferably 60 to 100 parts by mass) with respect to 100 parts by mass of diene rubber, and the ratio of the recycled CB to the total amount of carbon black (excluding ash contained in the recycled CB) is 3 to 30% by mass (preferably 5 to 15% by mass).
- the total amount of carbon black is less than 30 parts by mass with respect to 100 parts by mass of the diene rubber, the breaking strength is lowered.
- the proportion of the recycled CB in the total amount of carbon black is less than 3% by mass, low heat build-up deteriorates, and when it exceeds 30% by weight, the strength at break deteriorates.
- the rubber composition of the present invention includes vulcanizing or cross-linking agents; vulcanizing or cross-linking accelerators; various fillers such as silica, clay, talc and calcium carbonate; anti-aging agents; ; Resin; Various additives generally blended in rubber compositions such as curing agents can be blended. can be used for The blending amount of these additives can also be a conventional general blending amount as long as it does not contradict the object of the present invention.
- the rubber composition of the present invention can achieve low heat build-up while maintaining breaking strength even when part of the total amount of carbon black is replaced with recycled carbon black. tread, rim cushion, etc.).
- the tire of the present invention is preferably a pneumatic tire, and can be filled with air, an inert gas such as nitrogen, or other gases.
- Breaking strength (TB): Tested at room temperature according to JIS K 6251. The results were indexed with the value of Standard Example 1 or 2 as 100. A larger index indicates better breaking strength.
- tan ⁇ 60 ° C.: According to JIS K6394: 2007, using a viscoelastic spectrometer (manufactured by Toyo Seiki Seisakusho), under conditions of extension deformation strain rate 10 ⁇ 2%, frequency 20 Hz, temperature 60 ° C., tan ⁇ (60 °C) was measured. The results were indexed with the value of Standard Example 1 or 2 as 100. A smaller index indicates a lower heat build-up. Comparative Examples 1-4 and Examples 1-3 are compared with Standard Example 1, and Comparative Examples 5-8 and Examples 4-6 are compared with Standard Example 2.
- the rubber compositions of Examples 1 to 6 are tire rubber compositions containing at least a diene rubber, carbon black and recycled carbon black, and the nitrogen adsorption specific surface area of carbon black and recycled carbon black is N 2 Since the SA and DBP oil absorptions are set within specific ranges, and the blending amount of recycled carbon black is set within an appropriate range, compared to the rubber composition of Standard Example 1 or 2, part of the total amount of carbon black is recycled carbon It can be seen that even when replaced with black, low heat build-up can be achieved while maintaining breaking strength.
- Comparative Examples 3 and 7 the nitrogen adsorption specific surface area N 2 SA of the blended carbon black exceeded the upper limit specified in the present invention, so the heat build-up deteriorated. Comparative Examples 4 and 8 deteriorated in breaking strength because the nitrogen adsorption specific surface area N 2 SA of the blended carbon black was less than the lower limit specified in the present invention.
Abstract
This rubber composition for tires comprises a diene-based rubber, carbon black, and recycled carbon black, wherein the carbon black has a nitrogen-adsorption specific surface area N2SA of 30-90 m2/g and a DBP oil absorption of 70-140 ml/100 g, the recycled carbon black has a nitrogen-adsorption specific surface area N2SA of 65-95 m2/g and a DBP oil absorption of 75-105 ml/100 g, the total carbon black amount, which is the sum of the carbon black and the recycled carbon black, is 30-130 parts by mass per 100 parts by mass of the diene-based rubber, and the proportion of the recycled carbon black in the total carbon black amount is 3-30 mass%.
Description
本発明は、タイヤ用ゴム組成物およびタイヤに関するものであり、詳しくはカーボンブラック総量の一部を再生カーボンブラックに置換しても、破断強度を維持しつつ、低発熱性を達成し得るタイヤ用ゴム組成物およびそれを用いたタイヤに関するものである。
TECHNICAL FIELD The present invention relates to a rubber composition for a tire and a tire, and more particularly, for a tire capable of maintaining breaking strength and achieving low heat build-up even when part of the total amount of carbon black is replaced with recycled carbon black. The present invention relates to rubber compositions and tires using the same.
近年、資源の保全や環境保護が注目される中、タイヤにおいてもリサイクル率の向上が求められている。そこで廃タイヤなど使用済みのゴム製品を熱分解して得られる再生カーボンブラック（再生CB。また、熱分解カーボンブラック、リサイクルカーボンブラックと呼ばれる場合もある）の使用が検討されている（例えば下記特許文献１参照）。
しかし再生カーボンブラックにはタイヤの原材料である補強材、タイヤコード等由来の不純物が含まれているため、タイヤの強度や発熱性等が大幅に低下するという問題点がある。 In recent years, as conservation of resources and protection of the environment have attracted attention, improvement in the recycling rate of tires has also been demanded. Therefore, the use of recycled carbon black (recycled CB. It is also sometimes called pyrolytic carbon black or recycled carbon black) obtained by pyrolyzing used rubber products such as waste tires is being studied (for example, the following patent Reference 1).
However, since recycled carbon black contains impurities derived from reinforcing materials, tire cords, etc., which are raw materials of tires, there is a problem that the strength and heat build-up properties of tires are greatly reduced.
しかし再生カーボンブラックにはタイヤの原材料である補強材、タイヤコード等由来の不純物が含まれているため、タイヤの強度や発熱性等が大幅に低下するという問題点がある。 In recent years, as conservation of resources and protection of the environment have attracted attention, improvement in the recycling rate of tires has also been demanded. Therefore, the use of recycled carbon black (recycled CB. It is also sometimes called pyrolytic carbon black or recycled carbon black) obtained by pyrolyzing used rubber products such as waste tires is being studied (for example, the following patent Reference 1).
However, since recycled carbon black contains impurities derived from reinforcing materials, tire cords, etc., which are raw materials of tires, there is a problem that the strength and heat build-up properties of tires are greatly reduced.
したがって本発明の目的は、カーボンブラック総量の一部を再生カーボンブラックに置換しても、破断強度を維持しつつ、低発熱性を達成し得るタイヤ用ゴム組成物およびそれを用いたタイヤを提供することにある。
Accordingly, an object of the present invention is to provide a rubber composition for a tire and a tire using the same, which can achieve low heat build-up while maintaining breaking strength even when part of the total amount of carbon black is replaced with recycled carbon black. to do.
本発明者らは鋭意研究を重ねた結果、少なくともジエン系ゴム、カーボンブラックおよび再生カーボンブラックを含むタイヤ用ゴム組成物において、カーボンブラックおよび再生カーボンブラックの窒素吸着比表面積Ｎ２ＳＡおよびＤＢＰ吸油量を特定の範囲に定め、かつ再生カーボンブラックの配合量を適切な範囲に定めることにより、上記課題を解決できることを見出し、本発明を完成することができた。
As a result of extensive studies, the inventors of the present invention have found that in a rubber composition for tires containing at least a diene rubber, carbon black and recycled carbon black, the nitrogen adsorption specific surface area N 2 SA and DBP oil absorption of carbon black and recycled carbon black is set within a specific range and the content of the recycled carbon black is set within an appropriate range.
すなわち本発明は、少なくともジエン系ゴム、カーボンブラックおよび再生カーボンブラックを含むタイヤ用ゴム組成物であって、
前記カーボンブラックの窒素吸着比表面積Ｎ２ＳＡが３０～９０ｍ２／ｇであり、かつＤＢＰ吸油量が７０～１４０ｍｌ／１００ｇであり、
前記再生カーボンブラックの窒素吸着比表面積Ｎ２ＳＡが６５～９５ｍ２／ｇであり、かつＤＢＰ吸油量が７５～１０５ｍｌ／１００ｇであり、
前記カーボンブラックおよび前記再生カーボンブラックの合計のカーボンブラック総量（但し前記再生カーボンブラックに含まれる灰分を除く）が、前記ジエン系ゴム１００質量部に対して３０～１３０質量部であり、
前記カーボンブラック総量のうち、前記再生カーボンブラックの割合（但し前記再生カーボンブラックに含まれる灰分を除く）が、３～３０質量％である
ことを特徴とするタイヤ用ゴム組成物を提供するものである。 That is, the present invention provides a rubber composition for tires containing at least a diene rubber, carbon black and recycled carbon black,
The carbon black has a nitrogen adsorption specific surface area N 2 SA of 30 to 90 m 2 /g and a DBP oil absorption of 70 to 140 ml/100 g,
The regenerated carbon black has a nitrogen adsorption specific surface area N 2 SA of 65 to 95 m 2 /g and a DBP oil absorption of 75 to 105 ml/100 g,
The total carbon black amount of the carbon black and the recycled carbon black (excluding the ash contained in the recycled carbon black) is 30 to 130 parts by mass with respect to 100 parts by mass of the diene rubber,
A rubber composition for a tire is provided, wherein the ratio of the recycled carbon black (excluding ash contained in the recycled carbon black) in the total amount of carbon black is 3 to 30% by mass. be.
前記カーボンブラックの窒素吸着比表面積Ｎ２ＳＡが３０～９０ｍ２／ｇであり、かつＤＢＰ吸油量が７０～１４０ｍｌ／１００ｇであり、
前記再生カーボンブラックの窒素吸着比表面積Ｎ２ＳＡが６５～９５ｍ２／ｇであり、かつＤＢＰ吸油量が７５～１０５ｍｌ／１００ｇであり、
前記カーボンブラックおよび前記再生カーボンブラックの合計のカーボンブラック総量（但し前記再生カーボンブラックに含まれる灰分を除く）が、前記ジエン系ゴム１００質量部に対して３０～１３０質量部であり、
前記カーボンブラック総量のうち、前記再生カーボンブラックの割合（但し前記再生カーボンブラックに含まれる灰分を除く）が、３～３０質量％である
ことを特徴とするタイヤ用ゴム組成物を提供するものである。 That is, the present invention provides a rubber composition for tires containing at least a diene rubber, carbon black and recycled carbon black,
The carbon black has a nitrogen adsorption specific surface area N 2 SA of 30 to 90 m 2 /g and a DBP oil absorption of 70 to 140 ml/100 g,
The regenerated carbon black has a nitrogen adsorption specific surface area N 2 SA of 65 to 95 m 2 /g and a DBP oil absorption of 75 to 105 ml/100 g,
The total carbon black amount of the carbon black and the recycled carbon black (excluding the ash contained in the recycled carbon black) is 30 to 130 parts by mass with respect to 100 parts by mass of the diene rubber,
A rubber composition for a tire is provided, wherein the ratio of the recycled carbon black (excluding ash contained in the recycled carbon black) in the total amount of carbon black is 3 to 30% by mass. be.
本発明のタイヤ用ゴム組成物は、少なくともジエン系ゴム、カーボンブラックおよび再生カーボンブラックを含むタイヤ用ゴム組成物において、カーボンブラックおよび再生カーボンブラックの窒素吸着比表面積Ｎ２ＳＡおよびＤＢＰ吸油量を特定の範囲に定め、かつ再生カーボンブラックの配合量を適切な範囲に定めているので、カーボンブラック総量の一部を再生カーボンブラックに置換しても、破断強度を維持しつつ、低発熱性を達成し得るタイヤ用ゴム組成物およびそれを用いたタイヤを提供することができる。
The rubber composition for tires of the present invention is a rubber composition for tires containing at least a diene rubber, carbon black and recycled carbon black, wherein the nitrogen adsorption specific surface area N 2 SA and DBP oil absorption of carbon black and recycled carbon black are specified. and the blending amount of recycled carbon black is set within an appropriate range, so even if part of the total amount of carbon black is replaced with recycled carbon black, low heat build-up is achieved while maintaining breaking strength. It is possible to provide a rubber composition for tires that can be used and a tire using the same.
以下、本発明をさらに詳細に説明する。
The present invention will be described in further detail below.
（ジエン系ゴム）
本発明で使用されるジエン系ゴムは、とくに制限されないが、例えば天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレン－ブタジエン共重合体ゴム（ＳＢＲ）、アクリロニトリル－ブタジエン共重合体ゴム（ＮＢＲ）、エチレン－プロピレン－ジエンターポリマー（ＥＰＤＭ）等が挙げられる。これらは、単独で用いてもよく、２種以上を併用してもよい。また、その分子量やミクロ構造はとくに制限されず、アミン、アミド、シリル、アルコキシシリル、カルボキシル、ヒドロキシル基等で末端変性されていても、エポキシ化されていてもよい。
なお、本発明の前記効果が向上するという観点から、本発明で使用されるジエン系ゴム全体を１００質量部としたときに、ＮＲの配合量が３０質量部以上、好ましくは３０～５０質量部であるのがよい。 (Diene rubber)
The diene rubber used in the present invention is not particularly limited, but for example natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer polymer rubber (NBR), ethylene-propylene-diene terpolymer (EPDM), and the like. These may be used alone or in combination of two or more. Further, its molecular weight and microstructure are not particularly limited, and it may be terminally modified with an amine, amide, silyl, alkoxysilyl, carboxyl, hydroxyl group or the like, or epoxidized.
From the viewpoint of improving the effects of the present invention, the amount of NR compounded is 30 parts by mass or more, preferably 30 to 50 parts by mass, when the entire diene rubber used in the present invention is 100 parts by mass. should be
本発明で使用されるジエン系ゴムは、とくに制限されないが、例えば天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレン－ブタジエン共重合体ゴム（ＳＢＲ）、アクリロニトリル－ブタジエン共重合体ゴム（ＮＢＲ）、エチレン－プロピレン－ジエンターポリマー（ＥＰＤＭ）等が挙げられる。これらは、単独で用いてもよく、２種以上を併用してもよい。また、その分子量やミクロ構造はとくに制限されず、アミン、アミド、シリル、アルコキシシリル、カルボキシル、ヒドロキシル基等で末端変性されていても、エポキシ化されていてもよい。
なお、本発明の前記効果が向上するという観点から、本発明で使用されるジエン系ゴム全体を１００質量部としたときに、ＮＲの配合量が３０質量部以上、好ましくは３０～５０質量部であるのがよい。 (Diene rubber)
The diene rubber used in the present invention is not particularly limited, but for example natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer polymer rubber (NBR), ethylene-propylene-diene terpolymer (EPDM), and the like. These may be used alone or in combination of two or more. Further, its molecular weight and microstructure are not particularly limited, and it may be terminally modified with an amine, amide, silyl, alkoxysilyl, carboxyl, hydroxyl group or the like, or epoxidized.
From the viewpoint of improving the effects of the present invention, the amount of NR compounded is 30 parts by mass or more, preferably 30 to 50 parts by mass, when the entire diene rubber used in the present invention is 100 parts by mass. should be
（カーボンブラック）
本発明で使用するカーボンブラック（ＣＢ）は、窒素吸着比表面積Ｎ２ＳＡが３０～９０ｍ２／ｇであり、かつＤＢＰ吸油量が７０～１４０ｍｌ／１００ｇである。
ＣＢのＮ２ＳＡが３０ｍ２／ｇ未満であると破断強度が低下し、９０ｍ２／ｇを超えると低発熱性が得られない。
ＣＢのＤＢＰ吸油量が７０ｍｌ／１００ｇ未満であると破断強度が低下し、１４０ｍｌ／１００ｇを超えると低発熱性が悪化する。
本発明において、ＣＢのＮ２ＳＡは３０～７０ｍ２／ｇが好ましく、ＤＢＰ吸油量は８０～１２０ｍｌ／１００ｇが好ましい。 (Carbon black)
The carbon black (CB) used in the present invention has a nitrogen adsorption specific surface area N 2 SA of 30-90 m 2 /g and a DBP oil absorption of 70-140 ml/100 g.
When the N 2 SA of the CB is less than 30 m 2 /g, the breaking strength is lowered, and when it exceeds 90 m 2 /g, low heat build-up cannot be obtained.
When the DBP oil absorption of CB is less than 70 ml/100 g, the breaking strength is lowered, and when it exceeds 140 ml/100 g, the low heat build-up deteriorates.
In the present invention, the N 2 SA of CB is preferably 30-70 m 2 /g, and the DBP oil absorption is preferably 80-120 ml/100 g.
本発明で使用するカーボンブラック（ＣＢ）は、窒素吸着比表面積Ｎ２ＳＡが３０～９０ｍ２／ｇであり、かつＤＢＰ吸油量が７０～１４０ｍｌ／１００ｇである。
ＣＢのＮ２ＳＡが３０ｍ２／ｇ未満であると破断強度が低下し、９０ｍ２／ｇを超えると低発熱性が得られない。
ＣＢのＤＢＰ吸油量が７０ｍｌ／１００ｇ未満であると破断強度が低下し、１４０ｍｌ／１００ｇを超えると低発熱性が悪化する。
本発明において、ＣＢのＮ２ＳＡは３０～７０ｍ２／ｇが好ましく、ＤＢＰ吸油量は８０～１２０ｍｌ／１００ｇが好ましい。 (Carbon black)
The carbon black (CB) used in the present invention has a nitrogen adsorption specific surface area N 2 SA of 30-90 m 2 /g and a DBP oil absorption of 70-140 ml/100 g.
When the N 2 SA of the CB is less than 30 m 2 /g, the breaking strength is lowered, and when it exceeds 90 m 2 /g, low heat build-up cannot be obtained.
When the DBP oil absorption of CB is less than 70 ml/100 g, the breaking strength is lowered, and when it exceeds 140 ml/100 g, the low heat build-up deteriorates.
In the present invention, the N 2 SA of CB is preferably 30-70 m 2 /g, and the DBP oil absorption is preferably 80-120 ml/100 g.
（再生カーボンブラック）
本発明で使用する再生カーボンブラック（再生ＣＢ）は、例えば廃タイヤの熱分解を経て生成される再生ＣＢであることができる。また、再生ＣＢは、熱分解カーボンブラック、リサイクルカーボンブラックと呼ばれる場合もある。廃タイヤの熱分解は公知の方法にしたがって行うことができる。例えば、６５０℃以上の温度の熱分解法が挙げられる。
本発明で使用する再生ＣＢは、窒素吸着比表面積Ｎ２ＳＡが６５～９５ｍ２／ｇであり、かつＤＢＰ吸油量が７５～１０５ｍｌ／１００ｇである。再生ＣＢのＮ２ＳＡおよびＤＢＰ吸油が前記範囲を外れると、本発明の効果を奏することができない。
なお、本発明における再生ＣＢは市販されているものを利用することができ、例えばＥｎｒｅｓｔｅｃ社製商品名ＰＢ３６５、Hi Green社製商品名SS-330、SH665、Eco Infinic 社製商品名ECB560、GRE社製商品名rCB660、ANHUI GREAT社製商品名G685、山東開元社製商品名rCB、LDC社製商品名GCB-774G等が挙げられる。前記ＰＢ３６５は、廃タイヤの熱分解を経て生成される再生ＣＢであり、Ｎ２ＳＡが７６ｍ２／ｇであり、ＤＢＰ吸油量が８８ｍｌ／１００ｇである。また、上記各種市販されている再生ＣＢは、灰分を１７質量％程度含んでいる。前記ＰＢ３６５の灰分に含まれる代表的な元素組成は、以下の通りである。また一般的に、再生ＣＢにおいてシリカとカルシウムの量を比較した場合、シリカの方がカルシウムよりも多く含まれている。 (recycled carbon black)
Recycled carbon black (recycled CB) used in the present invention can be, for example, recycled CB produced through thermal decomposition of waste tires. Recycled CB is sometimes called pyrolytic carbon black or recycled carbon black. Pyrolysis of waste tires can be carried out according to known methods. For example, a pyrolysis method at a temperature of 650° C. or higher can be mentioned.
The regenerated CB used in the present invention has a nitrogen adsorption specific surface area N 2 SA of 65-95 m 2 /g and a DBP oil absorption of 75-105 ml/100 g. If the N 2 SA and DBP oil absorption of the recycled CB are outside the above ranges, the effect of the present invention cannot be obtained.
Commercially available regenerated CB can be used in the present invention. product name rCB660, ANHUI GREAT product name G685, Shandong Kaiyuan product name rCB, LDC product name GCB-774G, and the like. The PB365 is recycled CB produced through thermal decomposition of waste tires, and has an N 2 SA of 76 m 2 /g and a DBP oil absorption of 88 ml/100 g. In addition, the above various commercially available recycled CBs contain about 17% by mass of ash. A typical elemental composition contained in the ash of the PB365 is as follows. Generally, when the amounts of silica and calcium are compared in regenerated CB, silica is contained more than calcium.
本発明で使用する再生カーボンブラック（再生ＣＢ）は、例えば廃タイヤの熱分解を経て生成される再生ＣＢであることができる。また、再生ＣＢは、熱分解カーボンブラック、リサイクルカーボンブラックと呼ばれる場合もある。廃タイヤの熱分解は公知の方法にしたがって行うことができる。例えば、６５０℃以上の温度の熱分解法が挙げられる。
本発明で使用する再生ＣＢは、窒素吸着比表面積Ｎ２ＳＡが６５～９５ｍ２／ｇであり、かつＤＢＰ吸油量が７５～１０５ｍｌ／１００ｇである。再生ＣＢのＮ２ＳＡおよびＤＢＰ吸油が前記範囲を外れると、本発明の効果を奏することができない。
なお、本発明における再生ＣＢは市販されているものを利用することができ、例えばＥｎｒｅｓｔｅｃ社製商品名ＰＢ３６５、Hi Green社製商品名SS-330、SH665、Eco Infinic 社製商品名ECB560、GRE社製商品名rCB660、ANHUI GREAT社製商品名G685、山東開元社製商品名rCB、LDC社製商品名GCB-774G等が挙げられる。前記ＰＢ３６５は、廃タイヤの熱分解を経て生成される再生ＣＢであり、Ｎ２ＳＡが７６ｍ２／ｇであり、ＤＢＰ吸油量が８８ｍｌ／１００ｇである。また、上記各種市販されている再生ＣＢは、灰分を１７質量％程度含んでいる。前記ＰＢ３６５の灰分に含まれる代表的な元素組成は、以下の通りである。また一般的に、再生ＣＢにおいてシリカとカルシウムの量を比較した場合、シリカの方がカルシウムよりも多く含まれている。 (recycled carbon black)
Recycled carbon black (recycled CB) used in the present invention can be, for example, recycled CB produced through thermal decomposition of waste tires. Recycled CB is sometimes called pyrolytic carbon black or recycled carbon black. Pyrolysis of waste tires can be carried out according to known methods. For example, a pyrolysis method at a temperature of 650° C. or higher can be mentioned.
The regenerated CB used in the present invention has a nitrogen adsorption specific surface area N 2 SA of 65-95 m 2 /g and a DBP oil absorption of 75-105 ml/100 g. If the N 2 SA and DBP oil absorption of the recycled CB are outside the above ranges, the effect of the present invention cannot be obtained.
Commercially available regenerated CB can be used in the present invention. product name rCB660, ANHUI GREAT product name G685, Shandong Kaiyuan product name rCB, LDC product name GCB-774G, and the like. The PB365 is recycled CB produced through thermal decomposition of waste tires, and has an N 2 SA of 76 m 2 /g and a DBP oil absorption of 88 ml/100 g. In addition, the above various commercially available recycled CBs contain about 17% by mass of ash. A typical elemental composition contained in the ash of the PB365 is as follows. Generally, when the amounts of silica and calcium are compared in regenerated CB, silica is contained more than calcium.
なお本発明において、Ｎ２ＳＡは、ＪＩＳ Ｋ６２１７－２に準拠し、ＤＢＰ吸油量はＡＳＴＭ Ｄ２４１４に準拠し、灰分は、公知のＩＣＰ法により測定される。
In the present invention, N 2 SA conforms to JIS K6217-2, DBP oil absorption conforms to ASTM D2414, and ash content is measured by a known ICP method.
（ゴム組成物の配合割合）
本発明のゴム組成物は、少なくとも前記ジエン系ゴム、前記ＣＢおよび前記再生ＣＢを含み、前記ＣＢおよび前記再生ＣＢの合計のカーボンブラック総量（但し前記再生ＣＢに含まれる灰分を除く）が、前記ジエン系ゴム１００質量部に対して３０～１３０質量部（好ましくは６０～１００質量部）であり、前記カーボンブラック総量のうち、前記再生ＣＢの割合（但し前記再生ＣＢに含まれる灰分を除く）が、３～３０質量％（好ましくは５～１５質量％）であることを特徴とする。
前記カーボンブラック総量が、前記ジエン系ゴム１００質量部に対し３０質量部未満であると、破断強度が低下し、逆に１３０質量部を超えると低発熱性が悪化する。
前記カーボンブラック総量のうち、前記再生ＣＢの割合が３質量％未満であると、低発熱性が悪化し、逆に３０質量％を超えると破断強度が悪化する。 (Mixing ratio of rubber composition)
The rubber composition of the present invention contains at least the diene rubber, the CB and the recycled CB, and the total carbon black amount of the CB and the recycled CB (excluding ash contained in the recycled CB) is 30 to 130 parts by mass (preferably 60 to 100 parts by mass) with respect to 100 parts by mass of diene rubber, and the ratio of the recycled CB to the total amount of carbon black (excluding ash contained in the recycled CB) is 3 to 30% by mass (preferably 5 to 15% by mass).
When the total amount of carbon black is less than 30 parts by mass with respect to 100 parts by mass of the diene rubber, the breaking strength is lowered.
When the proportion of the recycled CB in the total amount of carbon black is less than 3% by mass, low heat build-up deteriorates, and when it exceeds 30% by weight, the strength at break deteriorates.
本発明のゴム組成物は、少なくとも前記ジエン系ゴム、前記ＣＢおよび前記再生ＣＢを含み、前記ＣＢおよび前記再生ＣＢの合計のカーボンブラック総量（但し前記再生ＣＢに含まれる灰分を除く）が、前記ジエン系ゴム１００質量部に対して３０～１３０質量部（好ましくは６０～１００質量部）であり、前記カーボンブラック総量のうち、前記再生ＣＢの割合（但し前記再生ＣＢに含まれる灰分を除く）が、３～３０質量％（好ましくは５～１５質量％）であることを特徴とする。
前記カーボンブラック総量が、前記ジエン系ゴム１００質量部に対し３０質量部未満であると、破断強度が低下し、逆に１３０質量部を超えると低発熱性が悪化する。
前記カーボンブラック総量のうち、前記再生ＣＢの割合が３質量％未満であると、低発熱性が悪化し、逆に３０質量％を超えると破断強度が悪化する。 (Mixing ratio of rubber composition)
The rubber composition of the present invention contains at least the diene rubber, the CB and the recycled CB, and the total carbon black amount of the CB and the recycled CB (excluding ash contained in the recycled CB) is 30 to 130 parts by mass (preferably 60 to 100 parts by mass) with respect to 100 parts by mass of diene rubber, and the ratio of the recycled CB to the total amount of carbon black (excluding ash contained in the recycled CB) is 3 to 30% by mass (preferably 5 to 15% by mass).
When the total amount of carbon black is less than 30 parts by mass with respect to 100 parts by mass of the diene rubber, the breaking strength is lowered.
When the proportion of the recycled CB in the total amount of carbon black is less than 3% by mass, low heat build-up deteriorates, and when it exceeds 30% by weight, the strength at break deteriorates.
（その他成分）
本発明におけるゴム組成物には、前記した成分に加えて、加硫又は架橋剤；加硫又は架橋促進剤；シリカ、クレー、タルク、炭酸カルシウムのような各種充填剤；老化防止剤；可塑剤；樹脂；硬化剤などのゴム組成物に一般的に配合されている各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量も、本発明の目的に反しない限り、従来の一般的な配合量とすることができる。 (Other ingredients)
In addition to the above components, the rubber composition of the present invention includes vulcanizing or cross-linking agents; vulcanizing or cross-linking accelerators; various fillers such as silica, clay, talc and calcium carbonate; anti-aging agents; ; Resin; Various additives generally blended in rubber compositions such as curing agents can be blended. can be used for The blending amount of these additives can also be a conventional general blending amount as long as it does not contradict the object of the present invention.
本発明におけるゴム組成物には、前記した成分に加えて、加硫又は架橋剤；加硫又は架橋促進剤；シリカ、クレー、タルク、炭酸カルシウムのような各種充填剤；老化防止剤；可塑剤；樹脂；硬化剤などのゴム組成物に一般的に配合されている各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量も、本発明の目的に反しない限り、従来の一般的な配合量とすることができる。 (Other ingredients)
In addition to the above components, the rubber composition of the present invention includes vulcanizing or cross-linking agents; vulcanizing or cross-linking accelerators; various fillers such as silica, clay, talc and calcium carbonate; anti-aging agents; ; Resin; Various additives generally blended in rubber compositions such as curing agents can be blended. can be used for The blending amount of these additives can also be a conventional general blending amount as long as it does not contradict the object of the present invention.
本発明のゴム組成物は、カーボンブラック総量の一部を再生カーボンブラックに置換しても、破断強度を維持しつつ、低発熱性を達成し得ることから、タイヤのケーシング部材（アンダートレッド、サイドトレッド、リムクッション等）に好適に用いられ得る。また本発明のタイヤは、空気入りタイヤであることが好ましく、空気、窒素等の不活性ガス及びその他の気体を充填することができる。
The rubber composition of the present invention can achieve low heat build-up while maintaining breaking strength even when part of the total amount of carbon black is replaced with recycled carbon black. tread, rim cushion, etc.). Moreover, the tire of the present invention is preferably a pneumatic tire, and can be filled with air, an inert gas such as nitrogen, or other gases.
以下、本発明を実施例および比較例によりさらに説明するが、本発明は下記例に制限されるものではない。
The present invention will be further described below with examples and comparative examples, but the present invention is not limited to the following examples.
標準例１～２、実施例１～６および比較例１～８
サンプルの調製
表２に示す配合（質量部）において、加硫系（加硫促進剤、硫黄）を除く成分を１．７リットルの密閉式バンバリーミキサーで５分間混練した後、ミキサー外に放出させて室温冷却した。続いて、該組成物を同バンバリーミキサーに再度入れ、加硫系を加えて混練し、ゴム組成物を得た。次に得られたゴム組成物を所定の金型中で１５０℃で３０分間プレス加硫して加硫ゴム試験片を調製した。得られた加硫ゴム試験片について以下に示す試験法で物性を測定した。 Standard Examples 1-2, Examples 1-6 and Comparative Examples 1-8
Sample preparation In the formulation (parts by mass) shown in Table 2, the components except for the vulcanization system (vulcanization accelerator, sulfur) were kneaded in a 1.7-liter closed Banbury mixer for 5 minutes, and then discharged out of the mixer. and cooled to room temperature. Subsequently, the composition was placed in the same Banbury mixer again, and the vulcanizing system was added and kneaded to obtain a rubber composition. Next, the obtained rubber composition was press-vulcanized in a predetermined mold at 150° C. for 30 minutes to prepare a vulcanized rubber test piece. The physical properties of the obtained vulcanized rubber test pieces were measured by the following test methods.
サンプルの調製
表２に示す配合（質量部）において、加硫系（加硫促進剤、硫黄）を除く成分を１．７リットルの密閉式バンバリーミキサーで５分間混練した後、ミキサー外に放出させて室温冷却した。続いて、該組成物を同バンバリーミキサーに再度入れ、加硫系を加えて混練し、ゴム組成物を得た。次に得られたゴム組成物を所定の金型中で１５０℃で３０分間プレス加硫して加硫ゴム試験片を調製した。得られた加硫ゴム試験片について以下に示す試験法で物性を測定した。 Standard Examples 1-2, Examples 1-6 and Comparative Examples 1-8
Sample preparation In the formulation (parts by mass) shown in Table 2, the components except for the vulcanization system (vulcanization accelerator, sulfur) were kneaded in a 1.7-liter closed Banbury mixer for 5 minutes, and then discharged out of the mixer. and cooled to room temperature. Subsequently, the composition was placed in the same Banbury mixer again, and the vulcanizing system was added and kneaded to obtain a rubber composition. Next, the obtained rubber composition was press-vulcanized in a predetermined mold at 150° C. for 30 minutes to prepare a vulcanized rubber test piece. The physical properties of the obtained vulcanized rubber test pieces were measured by the following test methods.
破断強度（ＴＢ）：ＪＩＳ Ｋ ６２５１に従い、室温で試験した。結果は標準例１または２の値を１００として指数表示した。指数が大きいほど、破断強度に優れることを示す。
ｔａｎδ（６０℃）：ＪＩＳ Ｋ６３９４：２００７に準じて、粘弾性スペクトロメーター（東洋精機製作所製）を用い、伸張変形歪率１０±２％、振動数２０Ｈｚ、温度６０℃の条件で、ｔａｎδ（６０℃）を測定した。結果は、標準例１または２の値を１００として指数表示した。指数が小さいほど、低発熱性であることを示す。
なお、比較例１～４および実施例１～３は標準例１と比較され、比較例５～８および実施例４～６は標準例２と比較される。 Breaking strength (TB): Tested at room temperature according to JIS K 6251. The results were indexed with the value of Standard Example 1 or 2 as 100. A larger index indicates better breaking strength.
tan δ (60 ° C.): According to JIS K6394: 2007, using a viscoelastic spectrometer (manufactured by Toyo Seiki Seisakusho), under conditions of extension deformation strain rate 10 ± 2%, frequency 20 Hz, temperature 60 ° C., tan δ (60 °C) was measured. The results were indexed with the value of Standard Example 1 or 2 as 100. A smaller index indicates a lower heat build-up.
Comparative Examples 1-4 and Examples 1-3 are compared with Standard Example 1, and Comparative Examples 5-8 and Examples 4-6 are compared with Standard Example 2.
ｔａｎδ（６０℃）：ＪＩＳ Ｋ６３９４：２００７に準じて、粘弾性スペクトロメーター（東洋精機製作所製）を用い、伸張変形歪率１０±２％、振動数２０Ｈｚ、温度６０℃の条件で、ｔａｎδ（６０℃）を測定した。結果は、標準例１または２の値を１００として指数表示した。指数が小さいほど、低発熱性であることを示す。
なお、比較例１～４および実施例１～３は標準例１と比較され、比較例５～８および実施例４～６は標準例２と比較される。 Breaking strength (TB): Tested at room temperature according to JIS K 6251. The results were indexed with the value of Standard Example 1 or 2 as 100. A larger index indicates better breaking strength.
tan δ (60 ° C.): According to JIS K6394: 2007, using a viscoelastic spectrometer (manufactured by Toyo Seiki Seisakusho), under conditions of extension deformation strain rate 10 ± 2%, frequency 20 Hz, temperature 60 ° C., tan δ (60 °C) was measured. The results were indexed with the value of Standard Example 1 or 2 as 100. A smaller index indicates a lower heat build-up.
Comparative Examples 1-4 and Examples 1-3 are compared with Standard Example 1, and Comparative Examples 5-8 and Examples 4-6 are compared with Standard Example 2.
結果を表２に示す。
The results are shown in Table 2.
＊１：ＮＲ（PT.KIRANA SAPTA製SIR20）
＊２：ＳＢＲ（ＺＳエラストマー株式会社製 Nipol 1502）
＊３：ＢＲ（ＺＳエラストマー株式会社製 Nipol BR1220）
＊４：ＧＰＦカーボンブラック１（日鉄カーボン株式会社製ニテロン＃ＧＮ、窒素吸着比表面積（Ｎ２ＳＡ）＝３２ｍ２／ｇ、ＤＢＰ吸油量＝８２ｍｌ／１００ｇ）
＊５：ＦＥＦカーボンブラック２（日鉄カーボン株式会社製ニテロン＃１０Ｎ、窒素吸着比表面積（Ｎ２ＳＡ）＝４０ｍ２／ｇ、ＤＢＰ吸油量＝１２０ｍｌ／１００ｇ）
＊６：ＳＡＦカーボンブラック３（東海カーボン株式会社製シースト９Ｍ、窒素吸着比表面積（Ｎ２ＳＡ）＝１５０ｍ２／ｇ、ＤＢＰ吸油量＝１１３ｍｌ／１００ｇ）
＊７：ＳＲＦカーボンブラック４（東海カーボン株式会社製シーストＧ－ＦＹ、窒素吸着比表面積（Ｎ２ＳＡ）＝２７ｍ２／ｇ、ＤＢＰ吸油量＝６５ｍｌ／１００ｇ）
＊８：再生カーボンブラック（Ｅｎｒｅｓｔｅｃ社製商品名ＰＢ３６５、窒素吸着比表面積（Ｎ２ＳＡ）＝７６ｍ２／ｇ、ＤＢＰ吸油量＝８８ｍｌ／１００ｇ）
＊９：酸化亜鉛（正同化学工業株式会社製酸化亜鉛３種）
＊１０：ステアリン酸（日油株式会社製ビーズステアリン酸ＹＲ）
＊１１：老化防止剤（EASTMAN社製６ＰＰＤ）
＊１２：オイル（昭和シェル石油株式会社製エキストラクト４号Ｓ）
＊１３：硫黄（四国化成工業株式会社製ミュークロンＯＴ－２０）
＊１４：加硫促進剤ＴＢＢＳ（三新化学工業株式会社製サンセラーＮＳ－Ｇ） *1: NR (SIR20 made by PT.KIRANA SAPTA)
*2: SBR (Nipol 1502 manufactured by ZS Elastomer Co., Ltd.)
*3: BR (Nipol BR1220 manufactured by ZS Elastomer Co., Ltd.)
*4: GPF carbon black 1 (Niteron #GN manufactured by Nippon Steel Carbon Co., Ltd., nitrogen adsorption specific surface area (N 2 SA) = 32 m 2 /g, DBP oil absorption = 82 ml/100 g)
*5: FEF carbon black 2 (Niteron #10N manufactured by Nippon Steel Carbon Co., Ltd., nitrogen adsorption specific surface area (N 2 SA) = 40 m 2 /g, DBP oil absorption = 120 ml/100 g)
*6: SAF carbon black 3 (SEAST 9M manufactured by Tokai Carbon Co., Ltd., nitrogen adsorption specific surface area (N 2 SA) = 150 m 2 /g, DBP oil absorption = 113 ml/100 g)
*7: SRF carbon black 4 (SEAST G-FY manufactured by Tokai Carbon Co., Ltd., nitrogen adsorption specific surface area (N 2 SA) = 27 m 2 /g, DBP oil absorption = 65 ml/100 g)
*8: Recycled carbon black (manufactured by Enrestec, trade name PB365, nitrogen adsorption specific surface area (N 2 SA) = 76 m 2 /g, DBP oil absorption = 88 ml/100 g)
*9: Zinc oxide (Type 3 zinc oxide manufactured by Seido Chemical Industry Co., Ltd.)
* 10: Stearic acid (bead stearic acid YR manufactured by NOF Corporation)
* 11: Anti-aging agent (6PPD manufactured by EASTMAN)
*12: Oil (Extract No. 4S manufactured by Showa Shell Sekiyu K.K.)
*13: Sulfur (Mucron OT-20 manufactured by Shikoku Kasei Co., Ltd.)
*14: Vulcanization accelerator TBBS (Suncellar NS-G manufactured by Sanshin Chemical Industry Co., Ltd.)
＊２：ＳＢＲ（ＺＳエラストマー株式会社製 Nipol 1502）
＊３：ＢＲ（ＺＳエラストマー株式会社製 Nipol BR1220）
＊４：ＧＰＦカーボンブラック１（日鉄カーボン株式会社製ニテロン＃ＧＮ、窒素吸着比表面積（Ｎ２ＳＡ）＝３２ｍ２／ｇ、ＤＢＰ吸油量＝８２ｍｌ／１００ｇ）
＊５：ＦＥＦカーボンブラック２（日鉄カーボン株式会社製ニテロン＃１０Ｎ、窒素吸着比表面積（Ｎ２ＳＡ）＝４０ｍ２／ｇ、ＤＢＰ吸油量＝１２０ｍｌ／１００ｇ）
＊６：ＳＡＦカーボンブラック３（東海カーボン株式会社製シースト９Ｍ、窒素吸着比表面積（Ｎ２ＳＡ）＝１５０ｍ２／ｇ、ＤＢＰ吸油量＝１１３ｍｌ／１００ｇ）
＊７：ＳＲＦカーボンブラック４（東海カーボン株式会社製シーストＧ－ＦＹ、窒素吸着比表面積（Ｎ２ＳＡ）＝２７ｍ２／ｇ、ＤＢＰ吸油量＝６５ｍｌ／１００ｇ）
＊８：再生カーボンブラック（Ｅｎｒｅｓｔｅｃ社製商品名ＰＢ３６５、窒素吸着比表面積（Ｎ２ＳＡ）＝７６ｍ２／ｇ、ＤＢＰ吸油量＝８８ｍｌ／１００ｇ）
＊９：酸化亜鉛（正同化学工業株式会社製酸化亜鉛３種）
＊１０：ステアリン酸（日油株式会社製ビーズステアリン酸ＹＲ）
＊１１：老化防止剤（EASTMAN社製６ＰＰＤ）
＊１２：オイル（昭和シェル石油株式会社製エキストラクト４号Ｓ）
＊１３：硫黄（四国化成工業株式会社製ミュークロンＯＴ－２０）
＊１４：加硫促進剤ＴＢＢＳ（三新化学工業株式会社製サンセラーＮＳ－Ｇ） *1: NR (SIR20 made by PT.KIRANA SAPTA)
*2: SBR (Nipol 1502 manufactured by ZS Elastomer Co., Ltd.)
*3: BR (Nipol BR1220 manufactured by ZS Elastomer Co., Ltd.)
*4: GPF carbon black 1 (Niteron #GN manufactured by Nippon Steel Carbon Co., Ltd., nitrogen adsorption specific surface area (N 2 SA) = 32 m 2 /g, DBP oil absorption = 82 ml/100 g)
*5: FEF carbon black 2 (Niteron #10N manufactured by Nippon Steel Carbon Co., Ltd., nitrogen adsorption specific surface area (N 2 SA) = 40 m 2 /g, DBP oil absorption = 120 ml/100 g)
*6: SAF carbon black 3 (SEAST 9M manufactured by Tokai Carbon Co., Ltd., nitrogen adsorption specific surface area (N 2 SA) = 150 m 2 /g, DBP oil absorption = 113 ml/100 g)
*7: SRF carbon black 4 (SEAST G-FY manufactured by Tokai Carbon Co., Ltd., nitrogen adsorption specific surface area (N 2 SA) = 27 m 2 /g, DBP oil absorption = 65 ml/100 g)
*8: Recycled carbon black (manufactured by Enrestec, trade name PB365, nitrogen adsorption specific surface area (N 2 SA) = 76 m 2 /g, DBP oil absorption = 88 ml/100 g)
*9: Zinc oxide (Type 3 zinc oxide manufactured by Seido Chemical Industry Co., Ltd.)
* 10: Stearic acid (bead stearic acid YR manufactured by NOF Corporation)
* 11: Anti-aging agent (6PPD manufactured by EASTMAN)
*12: Oil (Extract No. 4S manufactured by Showa Shell Sekiyu K.K.)
*13: Sulfur (Mucron OT-20 manufactured by Shikoku Kasei Co., Ltd.)
*14: Vulcanization accelerator TBBS (Suncellar NS-G manufactured by Sanshin Chemical Industry Co., Ltd.)
表２の結果から、実施例１～６のゴム組成物は、少なくともジエン系ゴム、カーボンブラックおよび再生カーボンブラックを含むタイヤ用ゴム組成物において、カーボンブラックおよび再生カーボンブラックの窒素吸着比表面積Ｎ２ＳＡおよびＤＢＰ吸油量を特定の範囲に定め、かつ再生カーボンブラックの配合量を適切な範囲に定めているので、標準例１または２のゴム組成物に比べ、カーボンブラック総量の一部を再生カーボンブラックに置換しても、破断強度を維持しつつ、低発熱性を達成し得ることが分かる。
一方、比較例１、５は、カーボンブラック総量のうち、再生カーボンブラックの割合（但し前記再生カーボンブラックに含まれる灰分を除く）が約３７．２質量％であるので（ＰＢ３６５の配合量２５質量部のうち、灰分が１７質量％であるので、カーボンブラック総量は、ＣＢ３５質量部＋（再生ＣＢ２５質量部－再生ＣＢ灰分４．２５質量部）＝５５．７５質量部であり、再生ＣＢの割合は、２０．７５質量部／５５．７５質量部 × １００＝３７．２質量％となる）、破断強度が悪化した。
比較例２、６は、配合したカーボンブラックの全てが再生カーボンブラックであるので、破断強度が悪化した。
比較例３、７は、配合したカーボンブラックの窒素吸着比表面積Ｎ２ＳＡが本発明で規定する上限を超えているので、発熱性が悪化した。
比較例４、８は、配合したカーボンブラックの窒素吸着比表面積Ｎ２ＳＡが本発明で規定する下限未満であるので、破断強度が悪化した。 From the results in Table 2, the rubber compositions of Examples 1 to 6 are tire rubber compositions containing at least a diene rubber, carbon black and recycled carbon black, and the nitrogen adsorption specific surface area of carbon black and recycled carbon black is N 2 Since the SA and DBP oil absorptions are set within specific ranges, and the blending amount of recycled carbon black is set within an appropriate range, compared to the rubber composition of Standard Example 1 or 2, part of the total amount of carbon black is recycled carbon It can be seen that even when replaced with black, low heat build-up can be achieved while maintaining breaking strength.
On the other hand, in Comparative Examples 1 and 5, the proportion of recycled carbon black in the total amount of carbon black (excluding the ash contained in the recycled carbon black) was about 37.2% by mass (the amount of PB365 blended was 25 mass Of the parts, the ash content is 17% by mass, so the total amount of carbon black is 35 parts by mass of CB + (25 parts by mass of recycled CB - 4.25 parts by mass of recycled CB ash) = 55.75 parts by mass, and the ratio of recycled CB is 20.75 mass parts/55.75 mass parts x 100 = 37.2 mass%), and the breaking strength deteriorated.
In Comparative Examples 2 and 6, all of the carbon black blended was recycled carbon black, so the breaking strength was deteriorated.
In Comparative Examples 3 and 7, the nitrogen adsorption specific surface area N 2 SA of the blended carbon black exceeded the upper limit specified in the present invention, so the heat build-up deteriorated.
Comparative Examples 4 and 8 deteriorated in breaking strength because the nitrogen adsorption specific surface area N 2 SA of the blended carbon black was less than the lower limit specified in the present invention.
一方、比較例１、５は、カーボンブラック総量のうち、再生カーボンブラックの割合（但し前記再生カーボンブラックに含まれる灰分を除く）が約３７．２質量％であるので（ＰＢ３６５の配合量２５質量部のうち、灰分が１７質量％であるので、カーボンブラック総量は、ＣＢ３５質量部＋（再生ＣＢ２５質量部－再生ＣＢ灰分４．２５質量部）＝５５．７５質量部であり、再生ＣＢの割合は、２０．７５質量部／５５．７５質量部 × １００＝３７．２質量％となる）、破断強度が悪化した。
比較例２、６は、配合したカーボンブラックの全てが再生カーボンブラックであるので、破断強度が悪化した。
比較例３、７は、配合したカーボンブラックの窒素吸着比表面積Ｎ２ＳＡが本発明で規定する上限を超えているので、発熱性が悪化した。
比較例４、８は、配合したカーボンブラックの窒素吸着比表面積Ｎ２ＳＡが本発明で規定する下限未満であるので、破断強度が悪化した。 From the results in Table 2, the rubber compositions of Examples 1 to 6 are tire rubber compositions containing at least a diene rubber, carbon black and recycled carbon black, and the nitrogen adsorption specific surface area of carbon black and recycled carbon black is N 2 Since the SA and DBP oil absorptions are set within specific ranges, and the blending amount of recycled carbon black is set within an appropriate range, compared to the rubber composition of Standard Example 1 or 2, part of the total amount of carbon black is recycled carbon It can be seen that even when replaced with black, low heat build-up can be achieved while maintaining breaking strength.
On the other hand, in Comparative Examples 1 and 5, the proportion of recycled carbon black in the total amount of carbon black (excluding the ash contained in the recycled carbon black) was about 37.2% by mass (the amount of PB365 blended was 25 mass Of the parts, the ash content is 17% by mass, so the total amount of carbon black is 35 parts by mass of CB + (25 parts by mass of recycled CB - 4.25 parts by mass of recycled CB ash) = 55.75 parts by mass, and the ratio of recycled CB is 20.75 mass parts/55.75 mass parts x 100 = 37.2 mass%), and the breaking strength deteriorated.
In Comparative Examples 2 and 6, all of the carbon black blended was recycled carbon black, so the breaking strength was deteriorated.
In Comparative Examples 3 and 7, the nitrogen adsorption specific surface area N 2 SA of the blended carbon black exceeded the upper limit specified in the present invention, so the heat build-up deteriorated.
Comparative Examples 4 and 8 deteriorated in breaking strength because the nitrogen adsorption specific surface area N 2 SA of the blended carbon black was less than the lower limit specified in the present invention.
Claims (7)
- 少なくともジエン系ゴム、カーボンブラックおよび再生カーボンブラックを含むタイヤ用ゴム組成物であって、
前記カーボンブラックの窒素吸着比表面積Ｎ２ＳＡが３０～９０ｍ２／ｇであり、かつＤＢＰ吸油量が７０～１４０ｍｌ／１００ｇであり、
前記再生カーボンブラックの窒素吸着比表面積Ｎ２ＳＡが６５～９５ｍ２／ｇであり、かつＤＢＰ吸油量が７５～１０５ｍｌ／１００ｇであり、
前記カーボンブラックおよび前記再生カーボンブラックの合計のカーボンブラック総量（但し前記再生カーボンブラックに含まれる灰分を除く）が、前記ジエン系ゴム１００質量部に対して３０～１３０質量部であり、
前記カーボンブラック総量のうち、前記再生カーボンブラックの割合（但し前記再生カーボンブラックに含まれる灰分を除く）が、３～３０質量％である
ことを特徴とするタイヤ用ゴム組成物。 A tire rubber composition comprising at least a diene rubber, carbon black and recycled carbon black,
The carbon black has a nitrogen adsorption specific surface area N 2 SA of 30 to 90 m 2 /g and a DBP oil absorption of 70 to 140 ml/100 g,
The regenerated carbon black has a nitrogen adsorption specific surface area N 2 SA of 65 to 95 m 2 /g and a DBP oil absorption of 75 to 105 ml/100 g,
The total carbon black amount of the carbon black and the recycled carbon black (excluding the ash contained in the recycled carbon black) is 30 to 130 parts by mass with respect to 100 parts by mass of the diene rubber,
A rubber composition for a tire, wherein the ratio of the recycled carbon black (excluding ash contained in the recycled carbon black) to the total amount of the carbon black is 3 to 30% by mass. - 前記ジエン系ゴム１００質量部中、天然ゴムの割合が３０質量部以上であることを特徴とする請求項１に記載のタイヤ用ゴム組成物。 The rubber composition for a tire according to claim 1, wherein the proportion of natural rubber is 30 parts by mass or more in 100 parts by mass of the diene rubber.
- 前記ジエン系ゴム１００質量部中、天然ゴムの割合が３０～５０質量部であることを特徴とする請求項１に記載のタイヤ用ゴム組成物。 The rubber composition for a tire according to claim 1, wherein the ratio of natural rubber is 30 to 50 parts by mass in 100 parts by mass of the diene rubber.
- 前記カーボンブラックの窒素吸着比表面積Ｎ２ＳＡが３０～７０ｍ２／ｇであり、かつＤＢＰ吸油量が８０～１２０ｍｌ／１００ｇであることを特徴とする請求項１に記載のタイヤ用ゴム組成物。 2. The rubber composition for tires according to claim 1, wherein the carbon black has a nitrogen adsorption specific surface area N 2 SA of 30 to 70 m 2 /g and a DBP oil absorption of 80 to 120 ml/100 g.
- 前記カーボンブラックおよび前記再生カーボンブラックの合計のカーボンブラック総量（但し前記再生カーボンブラックに含まれる灰分を除く）が、前記ジエン系ゴム１００質量部に対して６０～１００質量部であり、
前記カーボンブラック総量のうち、前記再生カーボンブラックの割合（但し前記再生カーボンブラックに含まれる灰分を除く）が、５～１５質量％である
ことを特徴とする請求項１に記載のタイヤ用ゴム組成物。 The total carbon black amount of the carbon black and the recycled carbon black (excluding the ash contained in the recycled carbon black) is 60 to 100 parts by mass with respect to 100 parts by mass of the diene rubber,
2. The rubber composition for a tire according to claim 1, wherein the ratio of the recycled carbon black (excluding ash contained in the recycled carbon black) is 5 to 15% by mass in the total amount of the carbon black. thing. - 請求項１に記載のタイヤ用ゴム組成物を用いたタイヤ。 A tire using the rubber composition for tires according to claim 1.
- 請求項１に記載のタイヤ用ゴム組成物を、アンダートレッド、サイドトレッドまたはリムクッションに用いたタイヤ。 A tire using the rubber composition for tires according to claim 1 as an undertread, a side tread or a rim cushion.
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| JP2013151584A (en) * | 2012-01-24 | 2013-08-08 | Toyo Tire & Rubber Co Ltd | Rubber composition for rubber vibration isolator |
| JP2014031425A (en) * | 2012-08-02 | 2014-02-20 | Yokohama Rubber Co Ltd:The | Rubber composition for tire rim cushion or gum finishing and pneumatic tire using the same |
| CN104479722A (en) * | 2014-05-12 | 2015-04-01 | 中机国宏（北京）高分子裂解技术研究院 | Continuous segmented cracking equipment and technology used for waste and old tyres and capable of preventing generation of dioxin |
| EP3173251A1 (en) * | 2015-11-27 | 2017-05-31 | Bridgestone Corporation | Rubber compound for tyres comprising recycled carbon black |
| CN111455183A (en) * | 2020-05-14 | 2020-07-28 | 沈阳鑫迪环境技术有限公司 | Method for purifying and recovering lead and zinc by waste tire cracking carbon black |
| JP2020523456A (en) * | 2017-06-29 | 2020-08-06 | 株式会社ブリヂストン | Rubber compound for pneumatic tires containing recycled carbon black |
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2021
- 2021-03-22 JP JP2021047455A patent/JP2022146475A/en active Pending
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2022
- 2022-03-18 WO PCT/JP2022/012779 patent/WO2022202698A1/en active Application Filing
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| JPS55500113A (en) * | 1978-02-15 | 1980-02-28 | ||
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| JP2011046299A (en) * | 2009-08-27 | 2011-03-10 | Yokohama Rubber Co Ltd:The | Pneumatic tire |
| JP2012001682A (en) * | 2010-06-21 | 2012-01-05 | Bridgestone Corp | Rubber composition and tire using the same |
| JP2013151584A (en) * | 2012-01-24 | 2013-08-08 | Toyo Tire & Rubber Co Ltd | Rubber composition for rubber vibration isolator |
| CN102634075A (en) * | 2012-04-25 | 2012-08-15 | 杭州电子科技大学 | Rubber reinforcing method |
| JP2014031425A (en) * | 2012-08-02 | 2014-02-20 | Yokohama Rubber Co Ltd:The | Rubber composition for tire rim cushion or gum finishing and pneumatic tire using the same |
| CN104479722A (en) * | 2014-05-12 | 2015-04-01 | 中机国宏（北京）高分子裂解技术研究院 | Continuous segmented cracking equipment and technology used for waste and old tyres and capable of preventing generation of dioxin |
| EP3173251A1 (en) * | 2015-11-27 | 2017-05-31 | Bridgestone Corporation | Rubber compound for tyres comprising recycled carbon black |
| JP2020523456A (en) * | 2017-06-29 | 2020-08-06 | 株式会社ブリヂストン | Rubber compound for pneumatic tires containing recycled carbon black |
| CN111455183A (en) * | 2020-05-14 | 2020-07-28 | 沈阳鑫迪环境技术有限公司 | Method for purifying and recovering lead and zinc by waste tire cracking carbon black |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023249020A1 (en) * | 2022-06-23 | 2023-12-28 | 住友ゴム工業株式会社 | Tire |
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| Publication number | Publication date |
|---|---|
| JP2022146475A (en) | 2022-10-05 |
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