CN117511005A - Rubber composition and conveyor belt - Google Patents
Rubber composition and conveyor belt Download PDFInfo
- Publication number
- CN117511005A CN117511005A CN202310851024.7A CN202310851024A CN117511005A CN 117511005 A CN117511005 A CN 117511005A CN 202310851024 A CN202310851024 A CN 202310851024A CN 117511005 A CN117511005 A CN 117511005A
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- China
- Prior art keywords
- rubber
- flame retardant
- rubber composition
- mass
- present
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 127
- 239000005060 rubber Substances 0.000 title claims abstract description 127
- 239000000203 mixture Substances 0.000 title claims abstract description 90
- 239000003063 flame retardant Substances 0.000 claims abstract description 104
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 97
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 239000006229 carbon black Substances 0.000 claims abstract description 40
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 37
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 37
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 36
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 30
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 30
- 229920001194 natural rubber Polymers 0.000 claims abstract description 30
- 238000004073 vulcanization Methods 0.000 claims abstract description 29
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 16
- 239000011593 sulfur Substances 0.000 claims abstract description 16
- 238000010521 absorption reaction Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 16
- 239000004636 vulcanized rubber Substances 0.000 abstract description 37
- 235000019241 carbon black Nutrition 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000004744 fabric Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920000459 Nitrile rubber Polymers 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 239000002174 Styrene-butadiene Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 239000012792 core layer Substances 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 239000006237 Intermediate SAF Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- VTEKOFXDMRILGB-UHFFFAOYSA-N bis(2-ethylhexyl)carbamothioylsulfanyl n,n-bis(2-ethylhexyl)carbamodithioate Chemical compound CCCCC(CC)CN(CC(CC)CCCC)C(=S)SSC(=S)N(CC(CC)CCCC)CC(CC)CCCC VTEKOFXDMRILGB-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- -1 methylene, ethylene, trimethylene, propylene, butylene, pentylene, hexylene, heptylene Chemical group 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 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 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- UEZWYKZHXASYJN-UHFFFAOYSA-N cyclohexylthiophthalimide Chemical compound O=C1C2=CC=CC=C2C(=O)N1SC1CCCCC1 UEZWYKZHXASYJN-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65G—TRANSPORT OR STORAGE DEVICES, e.g. CONVEYORS FOR LOADING OR TIPPING, SHOP CONVEYOR SYSTEMS OR PNEUMATIC TUBE CONVEYORS
- B65G15/00—Conveyors having endless load-conveying surfaces, i.e. belts and like continuous members, to which tractive effort is transmitted by means other than endless driving elements of similar configuration
- B65G15/30—Belts or like endless load-carriers
- B65G15/32—Belts or like endless load-carriers made of rubber or plastics
- B65G15/34—Belts or like endless load-carriers made of rubber or plastics with reinforcing layers, e.g. of fabric
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a rubber composition which has excellent flame retardant properties and can be maintained without adding a flame retardant even if a flame retardant is added thereto when a vulcanized rubber is producedThe obtained vulcanized rubber has excellent electricity-saving performance, and a conveyer belt. The rubber composition comprises a diene rubber comprising a natural rubber and a butadiene rubber, and has a nitrogen adsorption specific surface area of 20 to 100m 2 The dibutyl phthalate oil absorption is 70-120 cm 3 100g of carbon black, a flame retardant comprising a compound represented by a specific formula and antimony trioxide, sulfur, and a vulcanization accelerator, wherein the mass ratio of the natural rubber to the butadiene rubber is 40/60 to 80/20, and the content of the carbon black is 20 to 50 parts by mass relative to 100 parts by mass of the diene rubber, and the total content of the compound represented by a specific formula and antimony trioxide is 15 to 50 parts by mass relative to 100 parts by mass of the diene rubber. The conveyor belt is formed using the rubber composition described above.
Description
Technical Field
The present invention relates to a rubber composition and a conveyor belt.
Background
Conventionally, it is known that a rubber composition containing natural rubber and butadiene rubber can be used for a conveyor belt (for example, patent document 1).
In addition, in recent years, it has been demanded to impart flame retardancy to a conveyor belt.
In general, flame retarding of rubber is carried out by adding a halogen flame retardant, a phosphorus flame retardant, a metal hydroxide, an antimony compound, or other flame retardant to a rubber composition.
However, it is known that the addition of the flame retardant as described above is a factor of deteriorating physical properties of rubber (for example, patent document 2), and is a factor of deteriorating low tan δ of vulcanized rubber (for example, patent document 3).
Patent document 2 discloses that when an antimony-based flame retardant such as antimony trioxide is blended, the rubber composition is preferably not blended with the antimony-based flame retardant because it may adversely affect the physical properties of the rubber (see paragraph [0021] of patent document 2, comparative example 1).
Patent document 3 discloses that by adding a flame retardant to a diene rubber, the tan δ (under 20 ℃) of a vulcanized rubber is increased as compared with the case where no flame retardant is added to a diene rubber (the comparison results of comparative example 3 and comparative examples 4 to 6 of patent document 3).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2021-181543
Patent document 2: japanese patent application laid-open No. 2021-24872
Patent document 3: japanese patent application laid-open No. 2012-180758
Disclosure of Invention
Problems to be solved by the invention
As described above, conventionally, even if flame retardant performance can be imparted to a vulcanized rubber obtained from the rubber composition by adding a flame retardant to a rubber composition containing a diene rubber, it has been difficult to maintain the same level of power saving performance (low tan δ) as that of a vulcanized rubber obtained from a rubber composition without adding a flame retardant to the vulcanized rubber.
In addition, when the power saving performance (low tan δ) of the vulcanized rubber obtained from the rubber composition to which the flame retardant is not added is excellent at a temperature condition of-20 ℃, 0 ℃ and +20 ℃, it is more difficult to maintain the same excellent power saving performance as described above with respect to the rubber composition to which the flame retardant is added to the rubber composition.
Accordingly, an object of the present invention is to provide a rubber composition which is excellent in flame retardant performance when produced into a vulcanized rubber and which can maintain excellent power saving performance of a vulcanized rubber obtained from a rubber composition to which no flame retardant is added even if a flame retardant is added.
Furthermore, the invention aims to provide a conveyor belt.
Means for solving the problems
As a result of intensive studies to solve the above problems, the present inventors have found that when a rubber composition is made into a vulcanized rubber, the flame retardant performance is excellent, and even if a flame retardant is added, the excellent power saving performance of the vulcanized rubber obtained from a rubber composition to which no flame retardant is added can be maintained, by containing a diene rubber comprising a natural rubber and a butadiene rubber in a specific mass ratio, a carbon black having a nitrogen adsorption specific surface area and a dibutyl phthalate oil absorption in specific ranges, a flame retardant comprising two specific compounds, sulfur, and a vulcanization accelerator, and the content of the carbon black and the total content of the two specific compounds as flame retardants in specific ranges, respectively, and have completed the present invention.
The present invention has been made based on the above-described findings, and specifically, the following configuration is adopted to solve the above-described problems.
[1] A rubber composition comprising
Diene rubber comprising natural rubber and butadiene rubber,
The specific surface area of nitrogen adsorption is 20-100 m 2 The dibutyl phthalate oil absorption is 70-120 cm 3 100g of carbon black,
A flame retardant comprising a compound represented by the following formula (1) and antimony trioxide,
Sulfur and sulfur
A vulcanization accelerator;
the mass ratio of the natural rubber to the butadiene rubber is 40/60 to 80/20,
the carbon black content is 20 to 50 parts by mass relative to 100 parts by mass of the diene rubber,
the total content of the compound represented by the formula (1) and the antimony trioxide is 15 to 50 parts by mass per 100 parts by mass of the diene rubber,
in the formula (1), R represents an aliphatic hydrocarbon group which may contain an unsaturated bond.
[2] The rubber composition according to [1], wherein the content of the compound represented by the above formula (1) is 1 to 10 times by mass the content of the antimony trioxide.
[3] A conveyor belt formed using the rubber composition described in [1] or [2 ].
[4] The conveyor belt according to [3], which has a coating rubber formed using the rubber composition.
Effects of the invention
According to the present invention, it is possible to provide a rubber composition which is excellent in flame retardant performance when producing a vulcanized rubber and which can maintain excellent power saving performance of a vulcanized rubber obtained from a rubber composition to which no flame retardant is added even if a flame retardant is added, and a conveyor belt formed using the rubber composition.
Brief description of the drawings
Fig. 1 is a cross-sectional view of one embodiment of a conveyor belt of the present invention.
Fig. 2 is a cross-sectional view of another embodiment of the conveyor belt of the present invention.
Detailed Description
The present invention will be described in detail below.
In the present specification, the numerical range indicated by the term "to" refers to a range including numerical values described before and after the term "to".
In this specification, the production method of each component is not particularly limited unless otherwise specified. For example, a conventionally known method is given.
In this specification, unless otherwise specified, 2 or more kinds of substances equivalent to the respective components may be used singly or in combination. In the case where the component contains two or more substances, the content of the component refers to the total content of the two or more substances.
[ rubber composition ]
The rubber composition of the present invention contains
Diene rubber comprising natural rubber and butadiene rubber,
The specific surface area of nitrogen adsorption is 20-100 m 2 The dibutyl phthalate oil absorption is 70-120 cm 3 100g of carbon black,
A flame retardant comprising a compound represented by the following formula (1) and antimony trioxide,
Sulfur and sulfur
A vulcanization accelerator;
the mass ratio of the natural rubber to the butadiene rubber is 40/60 to 80/20,
the carbon black content is 20 to 50 parts by mass relative to 100 parts by mass of the diene rubber,
the total content of the compound represented by the formula (1) and the antimony trioxide is 15 to 50 parts by mass per 100 parts by mass of the diene rubber,
in the formula (1), R represents an aliphatic hydrocarbon group which may contain an unsaturated bond.
The reason why the above desired effects can be obtained by the rubber composition of the present invention is not clear, but is estimated as follows. That is, it is considered that the rubber composition of the present invention has the above-described constitution, and in the vulcanized rubber obtained from the rubber composition of the present invention, the compound represented by the formula (1) and/or antimony trioxide as the flame retardant are kept in a dispersed state, and the above-described flame retardant can be prevented from bleeding out of the above-described vulcanized rubber, and therefore, according to the rubber composition of the present invention, excellent flame retardant performance is imparted to the vulcanized rubber, and at the same time, excellent power saving performance of the vulcanized rubber obtained from the rubber composition without the flame retardant can be maintained even if the flame retardant is added.
The components contained in the rubber composition of the present invention will be described in detail below.
[ diene rubber ]
The rubber composition of the present invention contains a diene rubber, which contains a natural rubber and a butadiene rubber.
[ Natural rubber ]
In the present invention, the Natural Rubber (NR) contained as the diene rubber is not particularly limited. For example, conventionally known products can be used.
[ butadiene rubber ]
In the present invention, the Butadiene Rubber (BR) contained as the diene rubber is not particularly limited. For example, conventionally known products can be used.
As one of preferable embodiments of BR, there is mentioned, for example, polybutadiene which is solid at 23 ℃. The BR may be an unmodified BR or a modified BR.
The weight average molecular weight of BR is preferably 20 ten thousand or more, more preferably 30 ten thousand to 100 ten thousand, from the viewpoint of more excellent power saving performance and excellent wear resistance.
In the present specification, the weight average molecular weight (Mw) of BR may be a standard polystyrene equivalent measured by Gel Permeation Chromatography (GPC) under the following conditions.
Solvent: tetrahydrofuran (THF)
Detector: RI detector
[ mass ratio of Natural rubber to butadiene rubber ]
In the present invention, the mass ratio (NR/BR) of the natural rubber to the butadiene rubber is 40/60 to 80/20.
The mass ratio (NR/BR) is preferably 50/50 to 80/20, more preferably 60/40 to 75/25, from the viewpoints of more excellent power saving performance and excellent rubber properties (for example, tensile strength: TB, elongation: EB).
[ total content of Natural rubber and butadiene rubber ]
The total content of the natural rubber and the butadiene rubber is preferably 80 to 100 mass%, more preferably 100 mass%, based on the total amount of the diene rubber, from the viewpoints of more excellent power saving performance and excellent rubber physical properties.
[ other diene rubber ]
The diene rubber may further contain a diene rubber other than natural rubber and butadiene rubber (other diene rubber). The other diene rubber is not particularly limited as long as it is a polymer formed of, for example, a monomer containing a conjugated diene monomer (except for natural rubber and butadiene rubber).
[ carbon black ]
The rubber composition of the present invention contains a nitrogen adsorption specific surface area of 20 to 100m 2 The dibutyl phthalate oil absorption is 70-120 cm 3 100g of carbon black.
In the present specification, the nitrogen adsorption specific surface area may be 20 to 100m 2 The dibutyl phthalate oil absorption is 70-120 cm 3 100g of carbon black is referred to as "specific carbon black" or "specific CB".
[ Nitrogen adsorption specific surface area ]
In the present invention, the nitrogen adsorption specific surface area (N 2 SA) of 20 to 100m 2 /g。
From the standpoint of more excellent power saving performance and excellent bending fatigue resistance, N of a specific CB 2 SA is preferably 30 to 70m 2 Preferably 30 to 50m 2 /g。
Specific nitrogen adsorption surface area (N) 2 SA) can be determined according to JIS K6217-2: 2017.
Dibutyl phthalate oil absorption
In the present invention, dibutyl phthalate oil absorption (DBP) of specific CB is 70 to 120cm 3 /100g。
The DBP of the specific CB is preferably 70 to 90cm from the viewpoints of more excellent power saving performance and excellent bending fatigue resistance 3 /100g。
Dibutyl phthalate oil absorption (DBP) of carbon black may be determined in accordance with JIS K6217-4: 2017.
[ content of specific carbon black ]
In the present invention, the content of the specific carbon black is 20 to 50 parts by mass based on 100 parts by mass of the diene rubber.
The content of the specific carbon black is preferably 20 to 35 parts by mass based on 100 parts by mass of the diene rubber, from the viewpoint of more excellent power saving performance and excellent rubber physical properties.
(silica)
The rubber composition of the present invention may further contain silica. When the rubber composition of the present invention further contains silica, the resulting vulcanized rubber is more excellent in power saving performance and rubber properties.
The silica which may be further contained in the rubber composition of the present invention is not particularly limited. For example, conventionally known silica is used. Specifically, examples thereof include wet silica, dry silica, and fumed silica.
The silica content is preferably 0 to 50 parts by mass, more preferably 5 to 30 parts by mass, based on 100 parts by mass of the diene rubber, from the viewpoints of more excellent power saving performance and excellent rubber physical properties.
[ flame retardant ]
The rubber composition of the present invention contains a flame retardant comprising a compound represented by the following formula (1) and antimony trioxide.
[ Compound represented by the formula (1) ]
In the present invention, the flame retardant comprises a compound represented by the following formula (1).
In the formula (1), R represents an aliphatic hydrocarbon group which may contain an unsaturated bond.
In the present specification, the compound represented by the formula (1) is also referred to as a "specific compound". In the present invention, a specific compound may function as a flame retardant.
In the formula (1), the aliphatic hydrocarbon group which may contain an unsaturated bond as R may be any one of a straight chain, a branched chain, a cyclic group, and a combination thereof, and a preferable mode is a straight chain.
The number of carbon atoms of the aliphatic hydrocarbon group is not particularly limited. For example, 1 to 10 can be set. The number of carbon atoms is preferably 2 to 8.
The aliphatic hydrocarbon group which may contain an unsaturated bond may be any of a saturated aliphatic hydrocarbon group which does not contain an unsaturated bond and an unsaturated aliphatic hydrocarbon group which contains an unsaturated bond, and as a preferable mode, a saturated aliphatic hydrocarbon group is exemplified.
Examples of the saturated aliphatic hydrocarbon group include methylene, ethylene, trimethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene.
Examples of the unsaturated bond that the aliphatic hydrocarbon group may have include vinyl, ethenylene, ethynyl, and ethynylene.
When the aliphatic hydrocarbon group optionally containing an unsaturated bond is an unsaturated aliphatic hydrocarbon group, examples of the unsaturated aliphatic hydrocarbon group include a combination of the saturated aliphatic hydrocarbon group and the unsaturated bond.
Examples of the specific compound include bis (pentabromophenyl) ethane.
The specific compound preferably contains bis (pentabromophenyl) ethane from the viewpoint of more excellent flame retardancy and power saving performance.
[ antimony trioxide ]
In the present invention, it is contained as a flame retardantAntimony trioxide (Sb) 2 O 3 ) There is no particular limitation.
Antimony trioxide can act as a flame retardant aid for the compound represented by the above formula (1). Thus, antimony trioxide is treated as a flame retardant in the present invention.
[ total content of Compound represented by the formula (1) and antimony trioxide ]
In the present invention, the total content of the compound represented by the formula (1) (specific compound) and antimony trioxide is 15 to 50 parts by mass based on 100 parts by mass of the diene rubber.
The total content is preferably 20 to 40 parts by mass, more preferably 25 to 35 parts by mass, per 100 parts by mass of the diene rubber, from the viewpoint of more excellent flame retardancy and power saving performance.
(content of Compound represented by the formula (1))
The content of the compound represented by the formula (1) (specific compound) is preferably 1 to 10 times, more preferably 2.0 to 4.0 times, the content of antimony trioxide on a mass basis, from the viewpoint of more excellent flame retardancy and power saving performance.
[ Total content of the Compound represented by the formula (1) and antimony trioxide in the total amount of the rubber composition ]
Further, from the viewpoint of more excellent flame retardant property and power saving property, the total content of the compound represented by the formula (1) and antimony trioxide is preferably 5 to 25 mass% in the total amount of the rubber composition.
[ Total content of the Compound represented by the formula (1) and antimony trioxide in the total amount of flame retardant ]
Further, from the viewpoint of more excellent flame retardant performance and power saving performance, the total content of the compound represented by the formula (1) (specific compound) and antimony trioxide is preferably 80 to 100 mass%, more preferably 100 mass%, of the total amount of the flame retardant.
(other flame retardant)
The flame retardant may further contain a flame retardant (other flame retardant) other than the compound represented by the formula (1) and antimony trioxide. The other flame retardant is not particularly limited as long as it is a compound capable of imparting flame retardant properties (except for the compound represented by formula (1) and antimony trioxide).
In a preferred embodiment, the rubber composition of the present invention preferably contains no chlorinated paraffin.
[ Sulfur ]
The rubber composition of the present invention contains sulfur.
The sulfur is not particularly limited as long as it is sulfur used in vulcanization of diene rubber. For example, conventionally known sulfur may be used.
The sulfur content is preferably 0.5 to 5.0 parts by mass per 100 parts by mass of the diene rubber, from the viewpoints of more excellent flame retardancy and/or power saving performance and excellent rubber physical properties.
[ vulcanization accelerator ]
The rubber composition of the present invention contains a vulcanization accelerator.
The vulcanization accelerator is not particularly limited as long as it is a vulcanization accelerator used for vulcanization of diene rubber. Examples of the vulcanization accelerator include sulfenamide vulcanization accelerators such as N-cyclohexyl-2-benzothiazolyl sulfenamide (CZ) and N-t-butyl-2-benzothiazolyl sulfenamide (NS); thiuram vulcanization accelerators such as tetra (2-ethylhexyl) thiuram disulfide (TOT-N); guanidine vulcanization accelerators such as Diphenylguanidine (DPG).
The vulcanization accelerator preferably contains a sulfenamide vulcanization accelerator in view of more excellent flame retardancy and/or power saving performance.
The content of the vulcanization accelerator is preferably 0.5 to 8.0 parts by mass based on 100 parts by mass of the diene rubber, from the viewpoint of more excellent flame retardancy and/or power saving performance.
(additive)
The rubber composition of the present invention may contain additives in addition to the above-mentioned components. Examples of the additives include a vulcanization aid such as zinc oxide and stearic acid, a vulcanization retarder, an anti-aging agent, an antioxidant, and a plasticizer.
In addition, as one of preferable embodiments, it is mentioned that the rubber composition of the present invention does not contain a metal molybdate compound as described in patent document 2.
[ method of production ]
The method for producing the rubber composition of the present invention is not particularly limited. For example, a method of mixing the essential components with additives which may be further used if necessary by a Banbury mixer or the like is mentioned.
(vulcanization)
The vulcanization of the rubber composition of the present invention can be carried out under conventional practice conditions. The vulcanization temperature may be, for example, 120 to 180 ℃. In vulcanization, pressurization may be performed.
(use)
The rubber composition of the present invention may be used, for example, as a conveyor belt.
[ conveyer belt ]
The conveyor belt of the present invention is a conveyor belt formed using the rubber composition of the present invention.
The rubber composition used in the conveyor belt of the present invention is not particularly limited as long as it is the rubber composition of the present invention.
The conveyor belt of the present invention is not particularly limited, except that it is formed using the rubber composition of the present invention.
The rubber composition of the present invention is not particularly limited as to the application of any of the constituent members constituting the conveyor belt of the present invention. All or a part of the rubber constituting the conveyor belt of the present invention may be formed of the rubber composition of the present invention.
Since the vulcanized rubber obtained from the rubber composition of the present invention is excellent in flame retardant property and can maintain excellent power saving property of the vulcanized rubber obtained from the rubber composition containing no flame retardant, one preferable embodiment is a conveyor belt having a coating rubber formed using the rubber composition of the present invention.
Embodiments of the conveyor belt according to the present invention will be described below with reference to the drawings. The present invention is not limited to the drawings.
Fig. 1 is a cross-sectional view of one embodiment of a conveyor belt of the present invention. An embodiment of the conveyor belt of the present invention shown in fig. 1 (hereinafter, also referred to as a first embodiment of the conveyor belt of the present invention) is a conveyor belt 4 in which a cloth layer 1 is covered with a coating rubber (adhesive rubber) 2 as a core layer and the outer periphery thereof is covered with a coating rubber 3. Preferably, the coating rubber 3 is formed from the rubber composition of the present invention.
In fig. 1, the conveyor belt 4 uses the cloth layer 1 as a core material, and the number of layers of the cloth layer 1, the thickness of the coating rubber 3, the width of the belt, and the like can be appropriately determined according to the purpose of use.
Examples of the cloth layer include canvas formed of woven cloth of synthetic fibers such as nylon, vinylon, and polyester.
Thickness T of coating rubber 3 1 、T 2 In general, the thickness may be about 1.5 to 20 mm.
The coating rubber 2 may be any known coating rubber used for conveyor belts. As the coating rubber, for example, a rubber composition containing Natural Rubber (NR), acrylonitrile-butadiene rubber (NBR), styrene-butadiene copolymer rubber (SBR), butadiene Rubber (BR), ethylene-propylene rubber (EPT), ethylene-propylene-diene rubber (EPDM), or the like as a rubber component can be used.
Next, a second embodiment of the conveyor belt of the present invention will be described with reference to fig. 2.
Fig. 2 is a cross-sectional view of another embodiment of the conveyor belt of the present invention.
As shown in fig. 2, in the second embodiment of the conveyor belt of the present invention, a steel cord 5 is covered with a cushion rubber (adhesive rubber) 6 as a core layer, and the outer periphery of the conveyor belt 8 is covered with a cover rubber 7. Preferably, the coating rubber 7 is formed from the rubber composition of the present invention.
The conveyor belt 8 may be constructed by arranging, for example, about 50 to 230 steel cords 5 as a core material, the steel cords 5 being formed by twisting a plurality of wires having diameters of about 0.2 to 0.4mm and having diameters of about 2.0 to 9.5 mm. In general, the total thickness T of the conveyor belt 8 may be about 10 to 50 mm.
The cushion rubber 6 may be, for example, an adhesive rubber that can be adhered to a galvanized steel cord used for a known steel conveyor belt. Specifically, as the cushion rubber, for example, a rubber composition containing Natural Rubber (NR), acrylonitrile-butadiene rubber (NBR), styrene-butadiene copolymer rubber (SBR), butadiene Rubber (BR), or the like as a rubber component can be used.
The conveyor belt of the present invention can be produced, for example, by sandwiching a cloth layer, a steel cord, a core layer or the like as a core material between unvulcanized rubber sheets molded from the rubber composition of the present invention according to a conventional method and performing heat press vulcanization. The vulcanization conditions may be, for example, about 10 to 90 minutes at about 120 to 180℃and about 0.1 to 4.9 MPa.
The conveyor belt of the present invention is formed using the rubber composition of the present invention described above, and therefore is excellent in flame retardant performance, and can maintain excellent power saving performance of vulcanized rubber (conveyor belt) obtained from the rubber composition containing no flame retardant.
[ example ]
The present invention is specifically illustrated by the following examples. However, the present invention is not limited thereto.
< production of rubber composition >
The components in table 1 below were used in the compositions (parts by mass) shown in the table, and the components were mixed with a banbury mixer to prepare rubber compositions (unvulcanized).
< evaluation >
(Electricity saving Property)
Production of vulcanized sheet
The rubber compositions (unvulcanized) produced as described above were vulcanized under a surface pressure of 3.0MPa for 30 minutes using a press molding machine at 148℃to produce vulcanized pieces having a length of 150mm, a width of 150mm and a thickness of 2mm, and the vulcanized pieces were punched out to a size of 40mm, a width of 5mm and a thickness of 2mm to produce test pieces.
Evaluation method
Using each of the vulcanized sheets produced as described above, dynamic viscoelasticity was measured under the conditions of measuring a chuck pitch of 10mm, a dynamic strain of 2% and a frequency of 20Hz by using a viscoelasticity spectrometer (manufactured by Toyo Seisakusho Co., ltd.), and loss tangents (tan. Delta.) at-20℃and 0℃and +20℃were measured. The results are shown in the column "tan δ" of table 1.
Further, tan δ at each temperature is represented by an index. Regarding tan δ at-20 ℃, tan δ "0.3950" at-20 ℃ is expressed as an index "100". Regarding tan δ at 0 ℃, tan δ "0.1835" at 0 ℃ is expressed as an index "100". For tan delta at +20 ℃, tan delta at +20 ℃ of "0.1660" is denoted as an index of "100". The case where tan δ (index) at each temperature is 100 or less is denoted as "good", and the case where tan δ (index) at each temperature exceeds 100 is denoted as "x". The results are shown in the column "tan δ (index)" of table 1.
Evaluation criteria
First, in the present invention, when tan δ (index) at-20 ℃, 0 ℃ and +20 ℃ is 100 or less in the vulcanized rubber obtained from the rubber composition without the flame retardant, it is considered that the vulcanized rubber obtained from the rubber composition without the flame retardant is excellent in power saving performance.
Next, when tan δ (index) at-20 ℃, 0 ℃ and +20 ℃ of a vulcanized rubber obtained from a rubber composition to which a flame retardant is not added and tan δ (index) at-20 ℃, 0 ℃ and +20 ℃ of a vulcanized rubber obtained from a rubber composition to which a flame retardant is added are 100 or less, the power saving performance of a vulcanized rubber obtained from a rubber composition to which a flame retardant is added was evaluated as being capable of maintaining excellent power saving performance of a vulcanized rubber obtained from a rubber composition to which a flame retardant is not added.
The smaller the index of tan δ at each temperature, the more excellent the power saving performance.
On the other hand, even if the tan δ (index) at-20 ℃, 0 ℃ and +20 ℃ of the vulcanized rubber obtained from the rubber composition to which the flame retardant is not added is 100 or less, when the tan δ (index) at-20 ℃, 0 ℃ and +20 ℃ of the vulcanized rubber obtained from the rubber composition to which the flame retardant is added exceeds 100, the power saving performance of the vulcanized rubber obtained from the rubber composition to which the flame retardant is added is evaluated as not being able to maintain the excellent power saving performance of the vulcanized rubber obtained from the rubber composition to which the flame retardant is not added.
When the tan δ (index) of the vulcanized rubber obtained from the rubber composition to which the flame retardant was not added exceeds 100 at any one of-20 ℃, 0 ℃ and +20 ℃, the power saving performance of the vulcanized rubber was evaluated as originally poor.
(flame retardant Property)
Test piece production
Each of the rubber compositions produced as described above was used in accordance with JIS K6324:2013 "flame retardant property conveyor belt-grade and test method" test pieces (3 each) were made of the cloth layer conveyor belt rubber of item 7.2.1.
Evaluation method
According to JIS K6324:2013 "flame retardant conveyor-grade and test method", the duration of flame (in seconds) was measured.
Evaluation criteria
When the flame retardant test standard [ flame duration of less than 60 seconds (flame duration is an average of 3 test pieces), no reburning ] of JIS3 class was satisfied, the flame retardant performance was evaluated as excellent, and it was expressed as "good".
On the other hand, when the flame retardant test standard of JIS3 was not satisfied, the flame retardant performance was evaluated as poor, and it was expressed as "x".
The results are shown in table 1.
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Details of the components shown in table 1 are as follows.
[ diene rubber ]
NR: natural rubber. RSS #3
BR: butadiene rubber. Trade name Nipol BR1220 (weight average molecular weight: 46 ten thousand, manufactured by zeon company)
SBR (comparative): styrene butadiene rubber. Trade name of Nipol 1502 manufactured by zeon corporation
(carbon black)
The Table shows N of each Carbon Black (CB) 2 SA (Unit m) 2 /g), DBP (in cm 3 /100g)。
SAF stage CB (comparison): trade name of fuzhu is a raku S118, a fuzhu company
ISAF stage CB (comparison): trade name of fuzhu, rakun 220, rakun corporation
The SAF stage CB and the ISAF stage CB are N 2 SA exceeds 100m 2 /g, and therefore do not belong to a specific carbon black.
HAF stage CB: trade name of the solvent, east asian company
FEF stage CB: teflon #10N, new Highatti Corp
GPF stage CB: teflon #GN, new Highway chemical Co., ltd
The HAF grade CB, FEF grade CB and GPF grade CB described above correspond to specific carbon blacks.
[ vulcanization accelerator ]
Vulcanization accelerator NS: n-tert-butyl-2-benzothiazolyl sulfenamide (trade name, cylins NS, manufactured by Dai Xin Chemicals Co., ltd.)
Vulcanization retarder PVI: n-cyclohexylthio-phthalimide. Trade name of the product is Davida CTP, manufactured by Toli Fine chemical Co Ltd
(Sulfur)
Insoluble sulfur: sibiradin OT-20 manufactured by Sibiradin chemical industry Co., ltd
(flame retardant)
Antimony trioxide: PATOX-M manufactured by Japanese concentrate Co., ltd
Compound 1 represented by formula (1): bis (pentabromophenyl) ethane. Trade name "SAYTEX8010" (manufactured by ALBEMARLE CORPORATION Co., ltd.)
Chlorinated paraffin (comparative): the case is a case 70S manufactured by the company (trade name) of chemical industry
Aluminum hydroxide (comparative): aluminum hydroxide BF013 manufactured by Japanese light metals company (trade name)
According to the results shown in Table 1, comparative example 1 containing no flame retardant was excellent in power saving performance but poor in flame retardant performance.
Comparative examples 2 and 3 containing only antimony trioxide or the compound represented by the formula (1) as a flame retardant were inferior in flame retardant performance and inferior in power saving performance to comparative example 1.
Comparative examples 4 and 5, which do not contain the compound represented by formula (1) as a flame retardant, but contain chlorinated paraffin or aluminum hydroxide, have inferior power saving performance to comparative example 1.
Containing N 2 Comparative example 19, in which SA was outside the specified range of carbon black and no flame retardant was contained, was inferior in power saving performance and flame retardant performance. In addition, comparative example 6, which is the same as comparative example 19 except that the compound represented by formula (1) and antimony trioxide were included as flame retardants, was further deteriorated in power saving performance as compared with comparative example 19.
Containing N 2 The comparative example 20 having SA deviated from the carbon black of the prescribed range and containing no flame retardant was inherently inferior in power saving performance and flame retardant performance. In addition, comparative example 7, which is the same as comparative example 20 except that the compound represented by formula (1) and antimony trioxide were included as flame retardants, was further deteriorated in power saving performance as compared with comparative example 20.
Comparative example 8, which does not contain BR but SBR and does not contain flame retardant, is inherently inferior in power saving performance and flame retardant performance. In addition, comparative example 9, which is the same as comparative example 8 except that the compound represented by formula (1) and antimony trioxide were included as flame retardants, was further deteriorated in power saving performance as compared with comparative example 8.
Comparative example 10 containing no NR but SBR and no flame retardant had originally poor power saving performance and flame retardant performance. In addition, comparative example 11, which is the same as comparative example 10 except that the compound represented by formula (1) and antimony trioxide were included as flame retardants, was further deteriorated in power saving performance as compared with comparative example 10.
The comparative examples 12 and 13, which have a mass ratio of natural rubber to butadiene rubber outside the prescribed range and do not contain a flame retardant, are inferior in power saving performance and flame retardant performance.
The comparative examples 14 and 15 having a specific carbon black content outside the specified range and containing no flame retardant were inferior in power saving performance and flame retarding performance.
On the other hand, examples 1 to 3 were excellent in flame retardant performance as compared with comparative example 1, and even when the compound represented by the formula (1) and antimony trioxide were contained as flame retardants, the same excellent power saving performance as in comparative example 1 could be maintained.
Example 4 when a vulcanized rubber was produced, flame retardant performance was superior to that of comparative example 16 (the same as in example 4 except that the flame retardant was not contained), and even if the compound represented by formula (1) and antimony trioxide were contained as flame retardants, the same excellent power saving performance as in comparative example 16 could be maintained.
The same results as described above were obtained also in the comparison of example 5 and comparative example 17 and the comparison of example 6 and comparative example 18.
Thus, the rubber composition of the present invention is excellent in flame retardant performance when it is used in the production of a vulcanized rubber, and even if a flame retardant is added, it is possible to maintain excellent power saving performance of the vulcanized rubber obtained from the rubber composition without the flame retardant.
As described above, the rubber composition of the present invention can achieve both flame retardant properties and power saving properties.
In addition, the rubber composition of the present invention is excellent in power saving performance at a temperature of-20℃and 0℃and +20℃.
Symbol description
1: cloth layer
2: coated rubber
3. 7: coated rubber
4. 8: conveying belt
5: steel cord
6: buffer rubber
Claims (4)
1. A rubber composition comprising
Diene rubber comprising natural rubber and butadiene rubber,
The specific surface area of nitrogen adsorption is 20-100 m 2 The dibutyl phthalate oil absorption is 70-120 cm 3 100g of carbon black,
A flame retardant comprising a compound represented by the following formula (1) and antimony trioxide,
Sulfur and sulfur
A vulcanization accelerator;
the mass ratio of the natural rubber to the butadiene rubber is 40/60-80/20,
the carbon black content is 20 to 50 parts by mass relative to 100 parts by mass of the diene rubber,
the total content of the compound represented by the formula (1) and the antimony trioxide is 15 to 50 parts by mass per 100 parts by mass of the diene rubber,
in the formula (1), R represents an aliphatic hydrocarbon group which may contain an unsaturated bond.
2. The rubber composition according to claim 1, wherein the content of the compound represented by the formula (1) is 1 to 10 times by mass the content of the antimony trioxide.
3. A conveyor belt formed using the rubber composition of claim 1 or 2.
4. A conveyor belt as in claim 3 having a coated rubber formed using the rubber composition.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022123958A JP2024021248A (en) | 2022-08-03 | 2022-08-03 | Rubber composition and conveyor belt |
| JP2022-123958 | 2022-08-03 |
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| Publication Number | Publication Date |
|---|---|
| CN117511005A true CN117511005A (en) | 2024-02-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310851024.7A Pending CN117511005A (en) | 2022-08-03 | 2023-07-12 | Rubber composition and conveyor belt |
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|---|---|
| JP (1) | JP2024021248A (en) |
| CN (1) | CN117511005A (en) |
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- 2022-08-03 JP JP2022123958A patent/JP2024021248A/en active Pending
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