JP5615811B2 - セルフシーリングエラストマー組成物 - Google Patents
セルフシーリングエラストマー組成物 Download PDFInfo
- Publication number
- JP5615811B2 JP5615811B2 JP2011513907A JP2011513907A JP5615811B2 JP 5615811 B2 JP5615811 B2 JP 5615811B2 JP 2011513907 A JP2011513907 A JP 2011513907A JP 2011513907 A JP2011513907 A JP 2011513907A JP 5615811 B2 JP5615811 B2 JP 5615811B2
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- elastomer
- phr
- self
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims description 96
- 229920001971 elastomer Polymers 0.000 title claims description 77
- 239000000806 elastomer Substances 0.000 title claims description 73
- 238000007789 sealing Methods 0.000 title claims description 63
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 67
- 239000003921 oil Substances 0.000 claims description 38
- 229920006395 saturated elastomer Polymers 0.000 claims description 23
- 239000004606 Fillers/Extenders Substances 0.000 claims description 20
- 229920001169 thermoplastic Polymers 0.000 claims description 18
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 17
- 239000004416 thermosoftening plastic Substances 0.000 claims description 16
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 12
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 11
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 8
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 8
- -1 ethylene-ethylene Chemical group 0.000 claims description 6
- 239000010690 paraffinic oil Substances 0.000 claims description 5
- 239000005060 rubber Substances 0.000 claims description 5
- 229920001400 block copolymer Polymers 0.000 claims description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000010692 aromatic oil Substances 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 229920001083 polybutene Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 229920005549 butyl rubber Polymers 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000011324 bead Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 229920002367 Polyisobutene Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229920002633 Kraton (polymer) Polymers 0.000 description 6
- 238000009472 formulation Methods 0.000 description 5
- 230000002787 reinforcement Effects 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000001542 size-exclusion chromatography Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- 239000013032 Hydrocarbon resin Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000011208 chromatographic data Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 239000012156 elution solvent Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229920005555 halobutyl Polymers 0.000 description 2
- 229920006270 hydrocarbon resin Polymers 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229920006132 styrene block copolymer Polymers 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920002368 Glissopal ® Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920005987 OPPANOL® Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000215175 Telura Species 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- JKPSVOHVUGMYGH-UHFFFAOYSA-M sodium;(4,6-dimethoxypyrimidin-2-yl)-[[3-methoxycarbonyl-6-(trifluoromethyl)pyridin-2-yl]sulfonylcarbamoyl]azanide Chemical compound [Na+].COC(=O)C1=CC=C(C(F)(F)F)N=C1S(=O)(=O)NC(=O)[N-]C1=NC(OC)=CC(OC)=N1 JKPSVOHVUGMYGH-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
- B29C73/16—Auto-repairing or self-sealing arrangements or agents
- B29C73/163—Sealing compositions or agents, e.g. combined with propellant agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
- B29C73/16—Auto-repairing or self-sealing arrangements or agents
- B29C73/18—Auto-repairing or self-sealing arrangements or agents the article material itself being self-sealing, e.g. by compression
- B29C73/20—Auto-repairing or self-sealing arrangements or agents the article material itself being self-sealing, e.g. by compression the article material only consisting in part of a deformable sealing material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/18—Layered products comprising a layer of natural or synthetic rubber comprising butyl or halobutyl rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
-
- 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
- B60C1/0008—Compositions of the inner liner
-
- 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
- B60C19/00—Tyre parts or constructions not otherwise provided for
- B60C19/12—Puncture preventing arrangements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- 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
- C08L9/06—Copolymers with styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2030/00—Pneumatic or solid tyres or parts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/107—Ceramic
- B32B2264/108—Carbon, e.g. graphite particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2274/00—Thermoplastic elastomer material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/542—Shear strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/58—Cuttability
- B32B2307/581—Resistant to cut
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/762—Self-repairing, self-healing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2581/00—Seals; Sealing equipment; Gaskets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T152/00—Resilient tires and wheels
- Y10T152/10—Tires, resilient
- Y10T152/10495—Pneumatic tire or inner tube
- Y10T152/10666—Automatic sealing of punctures [e.g., self-healing, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249994—Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Description
本発明は、より詳細には、運行中の穿孔による穴を閉鎖する、インフレータブル物品、特にインフレータブルタイヤにおけるこのような組成物の使用に関する。
このような目的を達成することができ、定義によれば、自動的に、即ち、何らの外的介入なしで、クギのような異物によるタイヤの穿孔の場合にタイヤを密封することができるセルフシーリング組成物は、開発が特に困難である。
使用することができるように、セルフシーリング層は、物理的及び化学的性質の多くの条件を満たさなければならない。これは、特に、極めて広い操作温度範囲にわたって、またタイヤの寿命全体にわたって効果的でなければならない。これは、穿孔物体がその場に残存している場合にその穴を閉鎖することができなければならず、穿孔物体が除かれた場合に、穴を充填することができ且つタイヤを密封することができなければならない。
多くの解決法が構想されてきたが、特に時間が経つにつれて安定性を欠き或いは極端な操作温度条件下で有効性を欠くために、車両用タイヤにおいて開発されることができていない。
文献US-A-4 426 468には、また、極めて高い分子量の架橋ブチルゴムをベースにした、タイヤ用のセルフシーリング組成物が提案されている。
更に、出願人は、ブチルゴムをベースにしたこれらの組成物が、タイヤの構造内で長時間その場に残存する穿孔物体の遅い排除又は除去後に有効性が不充分であり得ることを見出している。
文献EP-B1-1 090 069には、ブチルゴムを含まないセルフシーリング組成物が確かに提案されており、その特定の配合は、スチレン系熱可塑性エラストマー100質量部当り、80から140質量部までの液体可塑剤、110から190質量部までの粘着付与樹脂及び2から20質量部までの添加剤を含んでいる。
大量の粘着付与樹脂は、タイヤが引き起こすより高い工業コストの他に、それ自体でセルフシーリング組成物の過度の剛性化のリスクのためにタイヤの転がり抵抗も悪化することになる。
通常のセルフシーリング組成物と比較すると、特に、穿孔物体を除去した後、特に除去が遅れた後にも、穴の密封速度が改善される。
- 少なくとも30phrの飽和熱可塑性スチレン(“TPS”)エラストマー;
- 多くても70phrの不飽和TPSエラストマー; 及び
- 200phrを超える前記エラストマーのためのオイル増量剤
を含む、前記組成物に関する。
本説明において、特にことわらない限り、示されるパーセント(%)は全て質量%である。
更に、表現“aとbの間”によって示される値の間隔は、いずれも、aよりも大きくbよりも小さい範囲の値の領域を示し(即ち、限界値aとbを除く)、一方表現“aからbまで”によって示される値の間隔は、いずれも、aからbまでの範囲である値の領域を意味する(即ち、厳格な限定値a及びbを含む)。
本発明に従って用いられるセルフシーリング組成物又は材料は、少なくとも1つの飽和TPSエラストマーを少なくとも30phr(少なくとも30phr以上)の量で、不飽和TPSエラストマーを多くても70phr(即ち、70phr以下)の量で及び200phrを超える前記TPSエラストマーのためのオイル増量剤を含むエラストマー組成物である(phrはゴム100質量部当たりの質量部を意味する)。
熱可塑性スチレン(TPS)エラストマーは、スチレン系ブロックコポリマーの形の熱可塑性エラストマーである。
- 少なくとも30phr(即ち、30phrから100phr未満まで)、好ましくは少なくとも50phr(即ち、50phrから100phr未満まで)の飽和TPSエラストマー; 及び
- 多くても70phr(即ち、0phrより大きく70phrまで)、好ましくは多くても50phr(即ち、0phrより大きく50phrまで)の不飽和TPSエラストマー。
- 飽和TPSエラストマーは、エチレン系不飽和基を含まない(即ち、炭素-炭素二重結合がない)TPSエラストマーを意味すると理解され;
- 不飽和TPSエラストマーは、エチレン系不飽和基がある、即ち、(共役であっても共役でなくてもよい)炭素-炭素二重結合を含むTPSエラストマーを意味すると理解される。
セルフシーリング組成物の第2の必須成分は、200phrを超える - 全エラストマー(即ち、飽和及び不飽和TPSエラストマーと、適切な場合、1つ又は複数の追加のエラストマー)100質量部当たり200質量部を超える - 好ましくは250phrを超える極めて高い含量で用いられるオイル増量剤(又は可塑化用オイル)である。
他の各種添加剤、例えば、カーボンブラックのような補強用充填剤、非補強用又は不活性充填剤、ラメラ充填剤、UV安定剤、酸化防止剤又はオゾン劣化防止剤のような保護剤、他の各種安定剤、及びセルフシーリング組成物を着色するのに有利に使用し得る着色剤は、典型的には少量で(好ましくは20phr未満、より好ましくは10phr未満の含量で)添加され得る。
上記のセルフシーリング組成物又は材料は、弾性固体化合物の固体(23℃で)であり、その特定の配合のために、非常に高い可撓性及び変形能を特に特徴とする。
ルゴム”は、知られている通り、イソブチレン/イソプレンコポリマー(略号 IIR)、及びこのタイプのコポリマーのハロゲン化、好ましくは塩素化又は臭素化変形例を意味すると理解すべきである。好ましくは、ブチルゴムは、ハロゲン化ブチルゴム又はハロゲン化及び非ハロゲン化ブチルゴムのブレンドである。ブチルゴムは、それ自体で、或いは、1つ以上の他のエラストマー、特にジエンエラストマー、例えば、天然ゴム又は合成ポリイソプレンと組み合せて用いることができる。また、気密組成物には、当業者にとって既知の気密層において通常存在する各種添加剤、例えば、カーボンブラック、シーリングを改良するラメラ充填剤(例えば、カオリン、タルク、雲母、クレー又は変性クレー(“オルガノクレー”)のようなフィロケイ酸塩)、酸化防止剤又はオゾン劣化防止剤のような保護剤、架橋系(例えば、イオウ系または過酸化物系)及び各種加工助剤又は他の安定剤のような補強用充填剤が含まれる。
上記セルフシーリング組成物及び多層ラミネートは、有利には、すべての車両タイプのタイヤに、特に非常に高速で走行しやすい乗用車用のタイヤ又は特に高内部温度条件下で走行及び操作しやすい重量産業用車両のタイヤに用いることができる。
Claims (11)
- インフレータブル物品においてパンク防止層として使用し得るセルフシーリング熱可塑性エラストマー組成物であって、少なくとも以下の成分(phrはゴム100質量部当たりの質量部を意味する):
- 少なくとも30phrの飽和熱可塑性(TPS)エラストマー;
- 多くても70phrの不飽和TPSエラストマー; 及び
- 200phrを超える前記エラストマーのためのオイル増量剤
を含む、前記組成物。 - 飽和TPSエラストマーの量が少なくとも50phrであり、不飽和TPSエラストマーの量が多くても50phrである、請求項1に記載の組成物。
- 飽和TPSエラストマーが、スチレン/エチレン/ブチレン(SEB)、スチレン/エチレン/プロピレン(SEP)、スチレン/エチレン-エチレン/プロピレン(SEEP)、スチレン/エチレン-ブチレン/スチレン(SEBS)、スチレン/エチレン-プロピレン/スチレン(SEPS)、スチレン/エチレン-エチレン-プロピレン/スチレン(SEEPS)コポリマー及びこれらのコポリマーのブレンドによって形成される群より選ばれる、請求項1又は2に記載の組成物。
- 不飽和TPSエラストマーが、スチレン/ブタジエン(SB)、スチレン/イソプレン(SI)、スチレン/ブタジエン/ブチレン(SBB)、スチレン/ブタジエン/イソプレン(SBI)、スチレン/ブタジエン/スチレン(SBS)、スチレン/ブタジエン/ブチレン/スチレン(SBBS)、スチレン/イソプレン/スチレン(SIS)、スチレン/ブタジエン/イソプレン/スチレン(SBIS)ブロックコポリマー及びこれらのコポリマーのブレンドによって形成される群より選ばれる、請求項1〜3のいずれか1項に記載の組成物。
- 飽和TPSエラストマー及び不飽和TPSエラストマーの数平均分子量が、各々50 000と500 000g/モルの間にある、請求項1〜4のいずれか1項に記載の組成物。
- 増量剤オイルが、ポリオレフィンオイル、パラフィン系オイル、ナフテン系オイル、芳香族オイル、鉱油及びこれらのオイルの混合物によって形成される群より選ばれる、請求項1〜5のいずれか1項に記載の組成物。
- オイル増量剤が、ポリブテンオイル、パラフィン系オイル及びこれらのオイルの混合物によって形成される群より選ばれる、請求項6に記載の組成物。
- 増量剤オイルの含量が、200と900phrの間にある、請求項1〜7のいずれか1項に記載の組成物。
- 飽和TPSエラストマーの量が少なくとも60phrに等しく、不飽和TPSエラストマーの量が多くても40phrに等しい請求項1〜8のいずれか1項に記載の組成物。
- インフレータブル物品において使用し得るパンク防止気密多層ラミネートであって、少なくとも:
- 請求項1〜9のいずれか1項に記載のセルフシーリングエラストマー組成物を含む第1パンク防止層; 及び
- 第2気密層
を含む、前記ラミネート。 - 請求項1〜10のいずれか1項に記載のセルフシーリング組成物又はパンク防止気密ラミネートを含むインフレータブル物品。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0854154A FR2932810B1 (fr) | 2008-06-24 | 2008-06-24 | Composition elastomere auto-obturante. |
FR0854154 | 2008-06-24 | ||
PCT/EP2009/003949 WO2009156050A1 (fr) | 2008-06-24 | 2009-06-03 | Composition elastomere auto-obturante |
Publications (3)
Publication Number | Publication Date |
---|---|
JP2011525435A JP2011525435A (ja) | 2011-09-22 |
JP2011525435A5 JP2011525435A5 (ja) | 2012-07-26 |
JP5615811B2 true JP5615811B2 (ja) | 2014-10-29 |
Family
ID=40351831
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2011513907A Expired - Fee Related JP5615811B2 (ja) | 2008-06-24 | 2009-06-03 | セルフシーリングエラストマー組成物 |
Country Status (7)
Country | Link |
---|---|
US (1) | US8871852B2 (ja) |
EP (1) | EP2303563B1 (ja) |
JP (1) | JP5615811B2 (ja) |
KR (1) | KR101605924B1 (ja) |
CN (1) | CN102066096B (ja) |
FR (1) | FR2932810B1 (ja) |
WO (1) | WO2009156050A1 (ja) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2955581B1 (fr) * | 2010-01-28 | 2012-02-17 | Michelin Soc Tech | Procede de fabrication d'une composition d'elastomere a propriete auto-obturante |
FR2955583B1 (fr) | 2010-01-28 | 2012-01-27 | Michelin Soc Tech | Procede de fabrication d'une composition auto-obturante |
FR2955587B1 (fr) * | 2010-01-28 | 2012-02-17 | Michelin Soc Tech | Composition d'elastomere pour objet pneumatique, a propriete auto-obturante |
FR2975044B1 (fr) | 2011-05-12 | 2013-06-14 | Michelin Soc Tech | Pneumatique pourvu d'une bande de roulement comprenant un elastomere thermoplastique |
FR2978154B1 (fr) * | 2011-07-21 | 2013-08-02 | Michelin Soc Tech | Bandage pneumatique pourvu d'une bande de roulement a base d'un elastomere thermoplastique |
FR2978447B1 (fr) | 2011-07-29 | 2014-12-19 | Michelin Soc Tech | Composition d'elastomere pour objet pneumatique, a propriete auto-obturante |
ITMI20112360A1 (it) | 2011-12-22 | 2013-06-23 | Pirelli | Pneumatico auto-sigillante per ruote di veicoli |
FR2995559B1 (fr) | 2012-09-17 | 2014-09-05 | Michelin & Cie | Pneumatique pourvu d'une bande de roulement comprenant un elastomere thermoplastique et du noir de carbone |
FR3002490B1 (fr) * | 2013-02-25 | 2015-03-27 | Michelin & Cie | Pneumatique auto-obturant comportant une armature de flanc supplementaire |
FR3002491B1 (fr) * | 2013-02-25 | 2015-03-27 | Michelin & Cie | Pneumatique auto-obturant comportant une armature de flanc supplementaire |
US10086577B2 (en) | 2015-12-01 | 2018-10-02 | The Goodyear Tire & Rubber Company | Method of making a self-sealing tire, and a tire |
US20170165872A1 (en) | 2015-12-11 | 2017-06-15 | The Goodyear Tire & Rubber Company | Modified tire sealant mixing device |
WO2018156036A1 (en) | 2017-02-23 | 2018-08-30 | Aircom Automotive Sp. Z.O.O. Sp. K. | A sealing composition for tires |
FR3067357A1 (fr) * | 2017-06-13 | 2018-12-14 | Compagnie Generale Des Etablissements Michelin | Compositions auto-obturantes |
CN109130710B (zh) * | 2018-08-17 | 2021-01-01 | 安徽佳通乘用子午线轮胎有限公司 | 内附密封胶层具有防穿孔性能的充气轮胎及其制造方法 |
FR3086947B1 (fr) * | 2018-10-03 | 2020-09-25 | Michelin & Cie | Compositions auto-obturantes |
FR3103491B1 (fr) * | 2019-11-27 | 2021-10-22 | Michelin & Cie | Composition auto-obturante pour objet pneumatique |
CN112094473A (zh) * | 2020-08-26 | 2020-12-18 | 中广核高新核材集团(东莞)祈富新材料有限公司 | 一种高韧可充气tpe材料及其制备方法 |
KR20220131734A (ko) | 2021-03-22 | 2022-09-29 | 주식회사 크레펀 | 사용자의 소셜 콘텐츠를 활용한 거점 기반 미디어 디스플레이 장치용 콘텐츠 자동화 시스템 및 그 방법 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4228839A (en) | 1978-08-03 | 1980-10-21 | The Firestone Tire & Rubber Company | Self-sealing pneumatic tire |
US4913209A (en) * | 1985-01-22 | 1990-04-03 | The Uniroyal Goodrich Tire Company | Sealant product, laminate thereof, and pneumatic tire constructed therewith |
CA2133763C (en) * | 1992-05-13 | 2004-04-13 | Philip J. Hammond | Gels |
CA2180912A1 (en) * | 1996-04-12 | 1997-10-13 | Terry Russell Phillips | Tire with rubber sidewall |
KR100277523B1 (ko) | 1998-05-30 | 2001-01-15 | 김호균 | 타이어 펑크방지 조성물 및 그 도포방법 |
US20060229402A1 (en) * | 2001-02-13 | 2006-10-12 | Varma Rajesh K | Essentially gas-impermeable thermoplastic sealant |
JP2003080909A (ja) * | 2001-09-14 | 2003-03-19 | Yokohama Rubber Co Ltd:The | 空気入りタイヤ及びその製造方法 |
DE60229991D1 (de) * | 2001-09-14 | 2009-01-02 | Honda Motor Co Ltd | Luftreifen und Verfahren zu seiner Herstellung |
JP4409814B2 (ja) * | 2001-09-26 | 2010-02-03 | 横浜ゴム株式会社 | 粘着シーラント層を備えた空気入りタイヤおよびその製造方法 |
JP2006515820A (ja) * | 2003-01-23 | 2006-06-08 | ソシエテ ド テクノロジー ミシュラン | タイヤへの剛性要素の固定 |
JP2005126654A (ja) * | 2003-10-22 | 2005-05-19 | Masstech:Kk | タイヤチューブに注入可能なタイヤパンクレス化軟質樹脂材料 |
JP3720349B2 (ja) * | 2003-12-24 | 2005-11-24 | 株式会社 型善 | タイヤチューブ内に溶液状樹脂を注入する装置 |
JP2006341679A (ja) * | 2005-06-08 | 2006-12-21 | Katazen:Kk | タイヤ、及びその製造方法 |
-
2008
- 2008-06-24 FR FR0854154A patent/FR2932810B1/fr not_active Expired - Fee Related
-
2009
- 2009-06-03 KR KR1020117001662A patent/KR101605924B1/ko not_active IP Right Cessation
- 2009-06-03 EP EP20090768899 patent/EP2303563B1/fr active Active
- 2009-06-03 WO PCT/EP2009/003949 patent/WO2009156050A1/fr active Application Filing
- 2009-06-03 JP JP2011513907A patent/JP5615811B2/ja not_active Expired - Fee Related
- 2009-06-03 US US13/001,083 patent/US8871852B2/en active Active
- 2009-06-03 CN CN200980123640.9A patent/CN102066096B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
JP2011525435A (ja) | 2011-09-22 |
KR20110039279A (ko) | 2011-04-15 |
FR2932810A1 (fr) | 2009-12-25 |
US20110165408A1 (en) | 2011-07-07 |
WO2009156050A1 (fr) | 2009-12-30 |
FR2932810B1 (fr) | 2010-08-20 |
KR101605924B1 (ko) | 2016-03-23 |
EP2303563A1 (fr) | 2011-04-06 |
CN102066096B (zh) | 2016-06-08 |
US8871852B2 (en) | 2014-10-28 |
CN102066096A (zh) | 2011-05-18 |
EP2303563B1 (fr) | 2012-10-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5615811B2 (ja) | セルフシーリングエラストマー組成物 | |
JP5615810B2 (ja) | インフレータブル物品用のパンク防止空気不透過性ラミネート | |
JP5400054B2 (ja) | セルフシーリング組成物を備えた空気式物品 | |
JP5275249B2 (ja) | インフレータブル物品用のセルフシーリング組成物 | |
JP5452611B2 (ja) | 熱可塑性エラストマーと増量剤オイルとを含むセルフシーリング性で且つ気密性の層を備えた空気式物品 | |
JP5357867B2 (ja) | 多層型の気密性パンク防止ラミネート、および該ラミネートを含む空気式物品 | |
JP5525522B2 (ja) | インフレータブル物品用のセルフシーリング組成物 | |
US9662844B2 (en) | Self-sealing composition for an inflatable article | |
JP5248520B6 (ja) | 自己密封プライを備えたタイヤ | |
JP5248520B2 (ja) | 自己密封プライを備えたタイヤ |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120604 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120604 |
|
A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20120809 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20131002 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140204 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140811 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140910 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5615811 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |