EP0000920A1 - Compositions d'élastomères thermoplastiques, procedure de préparation d'articles moulés, et moulages - Google Patents
Compositions d'élastomères thermoplastiques, procedure de préparation d'articles moulés, et moulages Download PDFInfo
- Publication number
- EP0000920A1 EP0000920A1 EP78100674A EP78100674A EP0000920A1 EP 0000920 A1 EP0000920 A1 EP 0000920A1 EP 78100674 A EP78100674 A EP 78100674A EP 78100674 A EP78100674 A EP 78100674A EP 0000920 A1 EP0000920 A1 EP 0000920A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- butadiene
- compositions
- composition
- molding
- molding composition
- 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.)
- Granted
Links
Classifications
-
- 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
-
- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
-
- 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
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/0005—Pretreatment of tyres or parts thereof, e.g. preheating, irradiation, precuring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- 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
-
- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0855—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using microwave
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2009/00—Use of rubber derived from conjugated dienes, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2809/00—Use of rubber derived from conjugated dienes as mould material
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/901—Radial block
Definitions
- thermoplastic molding compositions In one of its more specific aspects this invention relates to thermoplastic molding compositions. More particularly, the invention relates to thermoplastic molding compositions containing polar compounds. In another aspect of the invention it relates to a method for molding thermoplastic molding compositions. More particularly, the invention specifically relates to the use of energy of microwave frequency in molding thermoplastic compositions. In yet another aspect the invention relates to objects molded of thermoplastic molding compositions.
- microwave energy has been used in vulcanizing techniques to raise the temperature of vulcanizable compositions containing polar compounds to a level at which vulcanization can be accelerated by conventional means. It has now been discovered that microwave energy can be used to increase the temperature of polymer/resin compositions containing polar compounds above the softening point to permit low pressure molding. A number of polar components and polymers that will work well to promote the start of vulcanization using microwave energy are not, however, useful in promoting softening of thermoplastic compositions.
- thermoplastic polar polymers such as halogenated rubbers, nitrile rubbers, and/or fillers such as carbon black.
- highly filled resins do not react well to microwave energy so that highly filled thermoplastic elastomer based stocks result in lower melt flow rates because of lesser percentages of polymer in the total composition.
- Limited compatibility with thermoplastic elastomers also contributes to lack of efficiency of some ingredients which proved useful in promoting vulcanization, but are not useful in promoting softening of thermoplastic compositions.
- polar compounds useful in thermoplastic compositions used in low pressure molding must be selectively chosen.
- thermoplastic molding compositions containing polar compounds that can be molded at low pressures. It is another object of this invention to provide a method for molding thermoplastic compositions containing polar compounds. More particularly, it is an object of this invention to provide a method for molding thermoplastic compositions using energy at microwave frequencies in the molding process. It is still another object of this invention to provide molded objects of thermoplastic molding compositions containing polar compounds.
- compositions comprising a major amount of thermoplastic elastomer and minor amounts of solid resinous polymers along with one or more specific polar compounds so that the resulting compositions can be readily preheated by exposure to energy at microwave frequency to a moldable consistency that can be molded at a pressure of 200 psig or less.
- a method for molding articles in which molding composition solids as described above are introduced into a mold and enclosed therein, with the application of microwave energy to the composition for a time sufficient to produce a moldable consistency in the composition. Thereafter, molding pressure, up to about 200 psig, is applied to the molding composition for a time sufficient to produce a molded article after which the mold is cooled and the cooled molded article is unmolded.
- molded articles are provided which are produced from a molding composition as described above and/or are produced by the method of molding described above.
- compositions comprising a major amount of a thermoplastic elastomer, e.g., radial block butadiene-styrene copolymer and minor amounts of solid resinous polymers, stabilizers, fillers, plasticizers, and one or more polar compounds form the basis of this invention.
- a thermoplastic elastomer e.g., radial block butadiene-styrene copolymer
- solid resinous polymers stabilizers, fillers, plasticizers, and one or more polar compounds
- thermoplastic elastomers useful in practicing this invention are normally solid linear and radial teleblock copolymers which characteristically exhibit high tensile strength and elongation in their natural condition, e.g., nonvulcanized state.
- the copolymers are described in more detail in U.S. Patents 3,823,109; 3,826,776 and 3,959,545.
- Particularly suitable copolymers are those derived from butadiene and styrene in which the butadiene to styrene ratio can vary from about 85/15 to about 45/55 parts by weight and the rubber will contain from about 10 to about 55 wt. % of the styrene incorporated as terminal polystyrene blocks.
- the amount of the thermoplastic elastomer employed in the compositions constitutes from about 30 to about 100 wt. % of the total polymers utilized in preparing the compositions.
- the other polymers employed in forming the compositions are generally solid resinous polymers of a vinyl-substituted aromatic compound, e.g., styrene, alpha-methyl styrene, etc., alone or copolymerized with a monomer such as acrylonitrile or a conjugated diene such as butadiene.
- a vinyl-substituted aromatic compound e.g., styrene, alpha-methyl styrene, etc.
- a monomer such as acrylonitrile or a conjugated diene such as butadiene.
- Such homopolymers and copolymers generally have densities in the range from about 1.04 to about 1.10 g/cc (ASTM D 792), a tensile strength in the range from about 5,000 to about 12,000 psi (34.5 - 82.7 MPa), ASTM D 638, and a Shore A Hardness ranging from about 35 to about 95 (ASTM D 2240) at about 23°C.
- polar compounds (polarizing agent) employed in the invention compositions are normally liquid or solid in nature and are selected from among simple and polymeric alkylene glycols and their mono and dialkyl ethers, ethanolamines and isopropanolamines and their hydrocarbyl-substituted derivatives and mixtures thereof.
- Exemplary compounds include ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, thiodiethylene glycol, etc., polyethylene glycols having average molecular weights ranging from about 200 to about 6,000; polypropylene glycols having average molecular weights averaging from about 400 to about 2,000; mixed poly(ethylene)-poly(propylene) glycols having average molecular weights ranging up to about 6,000 and containing from about 30 to about 90 wt.
- % ethylene oxide ethylene oxide
- the alkanolamines and substituted alkanolamines based on ethanol and isopropanol such as mono-, di- and triethanolamine, mono-, di- and triisopropylamine, methylethanolamine, dibutylethanolamine, phenyldiethanolamine, di(2-ethylhexyl) ethanolamine, dimethylisopropanolamine, dibutylisopropanolamine, and the like; and mixtures thereof.
- polar compounds such as liquid acrylonitrile polymer butadiene polymers, acrylonitrile-butadiene blends with homopolymers of polyvinylchloride and styrene acrylonitrile copolymers are effective.
- Presently preferred compounds include diethylene glycol and triethanolamine and mixtures thereof.
- Polarizing agents selected from among solid nitrile rubbers, polychloroprene polymers and carbon black are not suitable for use in the applications envisioned in the instant invention because compositions containing such agents do not flow readily under the low molding pressures utilized in the process of this invention.
- Sufficient polarizing agent is included in the compositions of the instant invention to insure that they will be heat softened quickly when placed in a microwave field.
- the amount of polarizing agent utilized ranges from about 0.5 to about 20 parts by weight per 100 parts by weight thermoplastic elastomer and more preferably from about 0.75 to about 10 parts by weight for reasons of economy coupled with adequate response to the microwaves.
- Heating times employed are selected to achieve rapid softening of the compositions to moldable consistency without deleterious effects caused by local overheating. Generally, the heating times used can range from about 4 seconds to about 4 minutes. From a commercial standpoint, however, heating times ranging from about 4 to about 55 seconds are employed to obtain favorable production rates and this is a preferred range.
- odorants e.g., silica, clay, silicates, e.g., Wollastonite, calcium carbonate, glass beads and fibers, and the like.
- Plasticizing agents compatible with the thermoplastic elastomer and other resinous polymers can be employed if desired. Examples of these include naphthenic petroleum oils, e.g., ASTM type 104A, esters of adipic acid, phthalic acid, etc.
- Processing aids include the metal stearates, e.g., calcium stearate, zinc stearate, silicones, natural and synthetic waxes, and the like.
- Antioxidants and UV stabilizers can be added as desired from suitable commercially available materials.
- thiodipropionic esters e,g., dilauryl- thiodipropionate
- hindered phenolic antioxidants e.g., 2,6-di-t-butyl-4-methylphenol, octadecyl[3-(3,5-di-t-butyl-4-hydroxypheny-1)]propionate, thiodiethylene bis(3,5-di-t-butyl-4-hydroxy) hydrocinnamate, etc.
- UV stabilizers such as 2(2'-hydroxy-5'-methylphenyl) benzotriazole, 2-hydroxy-4-n-octoxybenzophenone, [2,2'-thiobis(4-t-octyl-phenolato)]-n-butylamine-nickel(II), etc.
- thermoplastic elastomer Generally, the amounts of the various components in parts by weight per 100 parts by weight thermoplastic elastomer (php) will be as follows: filler, 10 to 150 php, plasticizing agent 20 to 50 php; antioxidant, 0.1 to 1 php, and UV stabilizer, 0.1 to 3 php.
- the molds employed in shaping the invention compositions are generally constructed from low cost, relatively low strength materials including silicone rubber,polysulfide rubber, polyurethane, plaster, cast aluminum, and the like. The nature of the mold is dependent upon the molding process used. If the invention composition is placed within the mold and the en-tire assembly is preheated by microwave energy, it is preferred that the mold used be made of a material such as silicone rubber that has a lower dielectric loss factor than the invention composition. It is within the scope of this invention to preheat the composition in a low dielectric loss container such as glass or ceramic and transfer it to a mold constructed from metals and the like for the actual shaping step.
- the composition is placed within a silicone rubber mold, the mold top is covered with a silicone sheet or a release paper, e.g., paper or the like covered with a release agent such as a silicone, and the assembly is placed between the plates of a high frequency electrical field which form a part of commercially available molding machines.
- the top plate is lowered to contact the release paper covering the mold and the composition is preheated by application of microwave energy for a desired length of time.
- sufficient pressure is employed to compression mold the composition, e.g., about 10 to about 200 psig (68.9 - 1380 kPa), for a period of time generally ranging from about 0.1 to about 10 times the preheating time.
- the pressure is released, the assembly is preferably placed in a separate zone for cooling the mold and contents, after which the molded article is removed.
- a rotary table or the like containing a plurality of molds can be employed to provide molded parts at commercially attractive rates. Separation of the beating and cooling zones speeds production and reduces consumption of power and water.
- compositions were prepared containing one or more polarizing agents by mixing the components in a Banbury mixer for 6 minutes at a temperature of about 280°F (138°C). Each composition was dumped from the mixer at about 250°F (121°C) and converted into pellets.
- the base formulations employed shown in Table lA are in parts by weight.
- Each pelleted composition was used to fill a 5/16 inch (7.9 mm) thick silicone rubber, 2-cavity shoe soling mold maintained at about 77°F (25°C). The average cavity depth was about 5/16 inch.
- the assembly was placed in a commercial molding machine employing microwave energy as the heating medium, the top molding plate was lowered to contact the release paper covering the mold at a pressure of about 40 psig (276 kPa gage) and the microwave unit was energized to preheat the composition for the designated time.
- the microwave field was turned off, the pressure against the mold was increased to about 120 psig (827 kPa gage) and held for 45 seconds at that pressure.
- the pressure was released, the mold assembly was transferred to a cooling press through which water at a temperature of about 50°F (10°C) was being circulated and the assembly was cooled for 2 minutes by contact with the platens of the press.
- the molded product was stripped from the mold at about 120°F (49°C).
- compositions were prepared in which a polyethylene glycol was used along or in combination with TEA as a polarizing agent with a thermoplastic elastomer composition containing the following components in parts by weight as shown in Table 2A.
- the components employed are the same as described in Example 1 except when indicated otherwise.
- compositions were mixed as before and molded generally in the manner outlined previously. Specimens about 6 x 6 inches (15 x 15 cm) and about 100 mils (0.25 cm) thick were molded in this series. Preheating time for each mold assembly was 12 seconds and each composition was molded under a pressure of 80 psig (551 kPa gage) and cooled 20 seconds as described before.
- thermoplastic elastomer A series of combinations was prepared as described before by admixing a thermoplastic elastomer with generally the same components used in the first 2 examples. However, a resinous polar polymer was also included in the formulations as well as varying amounts of TEA/DEG. Molded samples were prepared from each composition in the manner described in Example 2 except that a variable preheat time was employed. The compositions prepared and results obtained are presented in Tables 3A and 3B. Unless otherwise described, the components, in parts by weight, are the same as previously used.
- thermoplastic elastomer consisting of a radial teleblock butadiene/styrene (70/30) copolymer having a molecular weight of 300,000 and Shore A Hardness of 84 and not containing extender oil was employed in place of the thermoplastic elastomer used previously.
- the composition employed was identical to composition A, Table lA, except that the thermoplastic elastomer described above was used. A molding preheat time of 20 seconds was used.
- thermoplastic elastomers consisting of teleblock butadiene/styrene copolymers of varying block styrene contents by employing the components described in this invention.
- the compositions are heated by means of microwave energy for a period of time of less than 60 seconds, the compositions are softened sufficiently to be easily moldable under pressure of about 200 psig or less.
- low cost, low strength molds can be employed in molding the compositions and very rapid cycle times result in practicing this invention.
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- 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)
- Toxicology (AREA)
- Thermal Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Physics & Mathematics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US825175 | 1977-08-17 | ||
US05/825,175 US4288399A (en) | 1977-08-17 | 1977-08-17 | Process for low pressure molding thermoplastic elastomer compositions |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0000920A1 true EP0000920A1 (fr) | 1979-03-07 |
EP0000920B1 EP0000920B1 (fr) | 1982-11-10 |
Family
ID=25243296
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78100674A Expired EP0000920B1 (fr) | 1977-08-17 | 1978-08-16 | Compositions d'élastomères thermoplastiques, procedure de préparation d'articles moulés, et moulages |
Country Status (7)
Country | Link |
---|---|
US (1) | US4288399A (fr) |
EP (1) | EP0000920B1 (fr) |
CA (1) | CA1109979A (fr) |
DE (1) | DE2862084D1 (fr) |
DK (1) | DK362678A (fr) |
ES (1) | ES472566A1 (fr) |
IT (1) | IT1098055B (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0009208A1 (fr) * | 1978-09-19 | 1980-04-02 | Phillips Petroleum Company | Compositions de moulage et procédé pour la fabrication d'articles moulés |
USRE31696E (en) * | 1979-07-31 | 1984-10-02 | Phillips Petroleum Company | Composition for producing article simulating plantation crepe rubber |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU529872B2 (en) * | 1977-08-17 | 1983-06-23 | Phillips Petroleum Co. | Thermoplastic molding compositions |
US4370189A (en) * | 1980-12-16 | 1983-01-25 | Phillips Petroleum Company | Modifying thermoplastic materials and products thereof |
US4379884A (en) * | 1981-12-30 | 1983-04-12 | Phillips Petroleum Company | Copolymer blend of improved impact resistance |
US4721739A (en) * | 1982-07-01 | 1988-01-26 | Bic Corp. | Erasable ink compositions |
AU1778783A (en) * | 1982-07-01 | 1984-01-26 | Bic Corporation | Erasable ink composition and process for forming erasable script |
US4444952A (en) * | 1982-08-23 | 1984-04-24 | Atlantic Richfield Company | Thermoplastic molding composition |
US4840758A (en) * | 1988-09-09 | 1989-06-20 | Phillips Petroleum Company | Methods of preparing molded thermoplastic articles wherein radio frequency energy is utilized to heat the thermoplastic material |
US5194190A (en) * | 1989-03-31 | 1993-03-16 | General Electric Company | Process for impregantion of glass fiber reinforcement with thermoplastic resins |
US5049323A (en) * | 1990-03-26 | 1991-09-17 | General Electric Company | Method for thermostamping thermoplastic composites |
US5572804A (en) * | 1991-09-26 | 1996-11-12 | Retama Technology Corp. | Shoe sole component and shoe sole component construction method |
EP0605485B2 (fr) * | 1991-09-26 | 2005-03-30 | Skydex Technologies, Inc. | Element constitutif de semelle de chaussure |
US6029962A (en) * | 1997-10-24 | 2000-02-29 | Retama Technology Corporation | Shock absorbing component and construction method |
US8726424B2 (en) | 2010-06-03 | 2014-05-20 | Intellectual Property Holdings, Llc | Energy management structure |
DE202011101868U1 (de) | 2011-06-16 | 2011-10-24 | Veljo Strucl | Quad-V-Servo Profil mit mehrfach geknickter Gleitfläche |
USD679058S1 (en) | 2011-07-01 | 2013-03-26 | Intellectual Property Holdings, Llc | Helmet liner |
US9516910B2 (en) | 2011-07-01 | 2016-12-13 | Intellectual Property Holdings, Llc | Helmet impact liner system |
USD683079S1 (en) | 2011-10-10 | 2013-05-21 | Intellectual Property Holdings, Llc | Helmet liner |
US9320311B2 (en) | 2012-05-02 | 2016-04-26 | Intellectual Property Holdings, Llc | Helmet impact liner system |
US9894953B2 (en) | 2012-10-04 | 2018-02-20 | Intellectual Property Holdings, Llc | Helmet retention system |
USD733972S1 (en) | 2013-09-12 | 2015-07-07 | Intellectual Property Holdings, Llc | Helmet |
EP3062650B1 (fr) | 2013-10-28 | 2019-07-03 | Intellectual Property Holdings, LLC | Système de retenue de casque |
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DE1220599B (de) * | 1960-06-20 | 1966-07-07 | Phillips Petroleum Co | Verfahren zum Vulkanisieren von fuellstoffhaltigen Synthesekautschukmischungen |
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US3985702A (en) * | 1975-05-27 | 1976-10-12 | Shell Oil Company | Dry blending and molding process |
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US3936365A (en) * | 1974-05-28 | 1976-02-03 | The Dow Chemical Company | Radiation crosslinked block copolymer blends with improved impact resistance |
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US4097550A (en) * | 1976-06-08 | 1978-06-27 | General Electric Company | Composition of a radial teleblock copolymer and a copolymer of a vinyl aromatic compound and an α,β unsaturated cyclic anhydride |
-
1977
- 1977-08-17 US US05/825,175 patent/US4288399A/en not_active Expired - Lifetime
-
1978
- 1978-06-29 CA CA306,452A patent/CA1109979A/fr not_active Expired
- 1978-08-14 IT IT26775/78A patent/IT1098055B/it active
- 1978-08-16 DK DK362678A patent/DK362678A/da unknown
- 1978-08-16 DE DE7878100674T patent/DE2862084D1/de not_active Expired
- 1978-08-16 EP EP78100674A patent/EP0000920B1/fr not_active Expired
- 1978-08-16 ES ES472566A patent/ES472566A1/es not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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DE1220599B (de) * | 1960-06-20 | 1966-07-07 | Phillips Petroleum Co | Verfahren zum Vulkanisieren von fuellstoffhaltigen Synthesekautschukmischungen |
DE1795547A1 (de) * | 1960-06-20 | 1973-07-19 | Phillips Petroleum Co | Zusammensetzungen fuer bodenplatten und schuhsohlen |
US3497572A (en) * | 1967-08-24 | 1970-02-24 | Phillips Petroleum Co | High impact resin compositions |
US3803274A (en) * | 1969-05-15 | 1974-04-09 | K Nakashima | Process for manufacturing foamed elastomeric materials having an interior foamed cellular structure covered with a non-foamed skin layer |
US3985702A (en) * | 1975-05-27 | 1976-10-12 | Shell Oil Company | Dry blending and molding process |
Non-Patent Citations (1)
Title |
---|
REVUE GENERALE DES CAOUTCHOUCS ET DES PLASTIQUES, vol. 49, no. 4, 1972, Paris. PIERRE CHANET and M. MONCEL: "Rôle de l'humidité des mélanges dans le chauffage diélectrique par ultrahaute fréquence", Pages 309-314 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0009208A1 (fr) * | 1978-09-19 | 1980-04-02 | Phillips Petroleum Company | Compositions de moulage et procédé pour la fabrication d'articles moulés |
USRE31696E (en) * | 1979-07-31 | 1984-10-02 | Phillips Petroleum Company | Composition for producing article simulating plantation crepe rubber |
Also Published As
Publication number | Publication date |
---|---|
IT1098055B (it) | 1985-08-31 |
DK362678A (da) | 1979-02-18 |
ES472566A1 (es) | 1979-10-16 |
CA1109979A (fr) | 1981-09-29 |
EP0000920B1 (fr) | 1982-11-10 |
DE2862084D1 (en) | 1982-12-16 |
US4288399A (en) | 1981-09-08 |
IT7826775A0 (it) | 1978-08-14 |
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