EP0000920B1 - 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
- EP0000920B1 EP0000920B1 EP78100674A EP78100674A EP0000920B1 EP 0000920 B1 EP0000920 B1 EP 0000920B1 EP 78100674 A EP78100674 A EP 78100674A EP 78100674 A EP78100674 A EP 78100674A EP 0000920 B1 EP0000920 B1 EP 0000920B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- butadiene
- molding composition
- composition
- thermoplastic elastomer
- mold
- 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
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
- the invention relates to molding compositions on the basis of thermoplastic elastomers useful for low pressure processing utilizing microwave energy.
- 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 thermoplastic elastomers-containing molding compositions above the softening point to permit low pressure molding, e.g. below about 1.4 MPa (200 psig), by incorporating certain polar compounds into said compositions. Thermoplastic elastomers exhibit the stress-strain properties of vulcanized rubbers without having been chemically vulcanized.
- thermoplastic compositions A number of polar compounds and polymers that work well to promote the start of vulcanization using microwave energy are not, however, useful in promoting softening of thermoplastic compositions. Temperatures obtained within practical time cycles are not enough to overcome the flow deficiency caused by the addition of solid non-thermoplastic polar polymers such as halogenated rubbers, nitrile rubbers, and/or fillers such as carbon black. It should also be pointed out that 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.
- thermoplastic elastomers 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. Overall, it has been found that polar compounds useful in thermoplastic compositions used in low pressure molding must be selectively chosen.
- the invention relates to a molding composition
- a molding composition comprising a thermoplastic elastomer and, optionally, a solid resinous polymer which composition is characterized by containing, as polar compounds, one or more of simple and polymeric alkylene glycols, their mono and dialkyl ethers; ethanolamines, isopropanolamines, and their hydrocarbyl-substituted derivatives; liquid acrylonitrile/butadiene polymers; acrylonitrile/butadiene polymer blends with homopolymers of polyvinyl chloride and styrene/acrylonitrile copolymers.
- the invention relates to a molding composition wherein said thermoplastic elastomer is a normally solid linear or radial teleblock copolymer being present in an amount of 30 to 100 weight percent, and said resinous polymer is a polymer of a vinyl-substituted aromatic compound being present in an amount of 0 to 70 weight percent, each based on the total polymeric content of the composition.
- said thermoplastic elastomer is a normally solid linear or radial teleblock copolymer being present in an amount of 30 to 100 weight percent
- said resinous polymer is a polymer of a vinyl-substituted aromatic compound being present in an amount of 0 to 70 weight percent, each based on the total polymeric content of the composition.
- the invention relates to a molding composition wherein said thermoplastic elastomer is a radial teleblock butadiene/styrene (52/48) copolymer extended with 60 parts by weight of naphthenic oil, said resinous polymer comprises poly-a-methylstyrene and polystyrene, and said polar compound is chosen from triethanolamine, a mixture of triethanolamine and diethylene glycol, butadiene/acrylonitrile rubber, and a mixture of triethanolamine and polyethylene glycol, said polyethylene glycol having an average molecular weight of 4000 to 6000.
- said thermoplastic elastomer is a radial teleblock butadiene/styrene (52/48) copolymer extended with 60 parts by weight of naphthenic oil
- said resinous polymer comprises poly-a-methylstyrene and polystyrene
- said polar compound is chosen from triethanolamine, a mixture of triethanolamine and diethylene glycol, buta
- the invention relates to a molding composition wherein said thermoplastic elastomer is a radial teleblock butadiene/styrene (52/48) copolymer extended with 60 parts by weight of naphthenic oil, said resinous polymer is crystalline polystyrene, and said polar compound is chosen from a mixture of triethanolamine and diethylene glycol and a 50/50 blend of butadiene/acrylonitrile rubber and polyvinyl chloride.
- said thermoplastic elastomer is a radial teleblock butadiene/styrene (52/48) copolymer extended with 60 parts by weight of naphthenic oil
- said resinous polymer is crystalline polystyrene
- said polar compound is chosen from a mixture of triethanolamine and diethylene glycol and a 50/50 blend of butadiene/acrylonitrile rubber and polyvinyl chloride.
- composition of the invention comprise a major amount of thermoplastic elastomer and, optionally, minor amounts of solid resinous polymers. They contain one or more of the aforesaid 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 1.4 MPa 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 1.4 MPa 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.
- the invention relates to a method wherein said microwave energy is applied for a time range of 4 seconds to 4 minutes and said pressure is from 69 to 1380 kPa and is applied for a period of time ranging from 0.1 to 10 times the length of time that said microwave energy was applied.
- 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, i.e. nonvulcanized state.
- the copolymers are described in more detail in US 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 45/55 parts by weight and the rubber will contain from about 10 to 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 100 wt.% of the total polymers utilized in preparing the compositions.
- the solid resinous polymers employed in forming the compositions are generally polymers of vinyl-substituted aromatic monomers, e.g., styrene or alpha-methyl styrene, alone or copolymerized with 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 1.10 g/ml (ASTM D 792), a tensile strength in the range from about 34.5 to 82.7 MPa (5,000 to 12,000 psi), ASTM D 638, and a Shore A Hardness ranging from about 35 to 95 (ASTM D 2240) at 23°C.
- polar compounds also referred as polarizing compounds hereinafter, employed in the invention compositions are normally liquid or solid in nature.
- 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 and thiodiethylene glycol; polyethylene glycols having average molecular weights ranging from about 200 to 6,000; polypropylene glycols having average molecular weights averaging from about 400 to 2,000; mixed poly(ethylene)-poly(propylene) glycols having average molecular weights ranging up to about 6,000 and containing from about 30 to 90 wt.% ethylene oxide; the monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol and diethylene glycol; the monomethyl and monoethyl ethers of triethylene glycol; the dimethyl and diethyl
- polar compounds such as liquid acrylonitrile-butadiene polymers acrylonitrile-butadiene polymer blends with homopolymers of polyvinyl chloride and styrene/acrylonitrile copolymers are effective. Mixtures of the polar compounds can be used. Presently preferred compounds include diethylene glycol and triethanolamine and mixtures thereof.
- Polarizing compounds selected from solid nitrile rubbers and polychloroprene polymers, or carbon black, are not suitable for use in the applications envisioned in the instant invention because compositions containing such materials do not flow readily under the low molding pressures utilized in the process of this invention.
- Sufficient polarizing compound 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 compound utilized ranges from 0.5 to 20 parts by weight per 100 parts by weight thermoplastic elastomer and more preferably from 0.75 to 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 range from 4 seconds to 4 minutes. From a commercial standpoint, however, heating times ranging from 4 to 55 seconds are employed to obtain favorable production rates and this is a preferred range.
- plasticizers e.g., odorants, colorants and fillers
- silica or clay e.g., silica or clay
- silicates e.g., Wollastonite
- calcium carbonate e.g., glass beads and fibers.
- Plasticizing agents compatible with the thermoplastic elastomer and the solid resinous polymers can be employed if desired. Examples of these include naphthenic petroleum oils, e.g., ASTM type 104A and esters of adipic acid or phthalic acid.
- Processing aids include the metal stearates, e.g., calcium stearate and zinc stearate, silicones, natural and synthetic waxes.
- Antioxidants and UV stabilizers can be added as desired from suitable commercially available materials.
- thiodipropionic esters e.g., dilaurylthiodipropionate
- hindered phenolic antioxidants e.g., 2,6 - di - t - butyl - 4 - methylphenol
- UV stabilizers such as 2(2'-hydroxy - 5' - methylphenyl) benzotriazole, 2 - hydroxy - 4 - n - octoxy- benzophenone and [2,2' - thiobis(4 - t - octyl -
- 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 molding compositions can be molded into various useful articles, e.g. sheet stock, shoe soles, mats and watch bands.
- 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 and cast aluminum. The nature of the mold is dependent upon the molding process used. If the invention composition is placed within the mold and the entire 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 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 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 68.9-1380 kPa (10 to 200 psig), for a period of time generally ranging from 0.1 to 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 containing a plurality of molds can be employed to provide molded parts at commercially attractive rates. Separation of the heating and cooling zones speeds production and reduces consumption of power and water.
- compositions were prepared containing one or more polarizing compounds by mixing the components in a Banbury mixer for 6 minutes at a temperature of about 138°C (280°F). Each composition was dumped from the mixer at about 121°C (250°F) and converted into pellets.
- the base formulations employed shown in Table 1 A are in parts by weight.
- Each pelleted composition was used to fill a (7,9 mm) thick silicone rubber, 2-cavity shoe soling mold maintained at about 25°C. The average cavity depth was about 7,9 mm.
- 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 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 (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 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 49°C.
- compositions were prepared in which a polyethylene glycol was used alone or in combination with TEA as a polarizing compound 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 15x 15 cm and about 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 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 solid resinous 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 1A, 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 below about 1.4 MPa (200 psig).
- low cost, low strength molds can be employed in molding the compositions and very rapid cycle times result in practicing this invention.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Mechanical Engineering (AREA)
- Engineering & Computer Science (AREA)
- Toxicology (AREA)
- Thermal Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Physics & Mathematics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
Claims (7)
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 EP0000920A1 (fr) | 1979-03-07 |
EP0000920B1 true 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 (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE202011101868U1 (de) | 2011-06-16 | 2011-10-24 | Veljo Strucl | Quad-V-Servo Profil mit mehrfach geknickter Gleitfläche |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU529872B2 (en) * | 1977-08-17 | 1983-06-23 | Phillips Petroleum Co. | Thermoplastic molding compositions |
US4256850A (en) * | 1978-09-19 | 1981-03-17 | Phillips Petroleum Company | Article and process simulating plantation crepe rubber |
USRE31696E (en) * | 1979-07-31 | 1984-10-02 | Phillips Petroleum Company | Composition for producing article simulating plantation crepe rubber |
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 |
JPS59501366A (ja) * | 1982-07-01 | 1984-08-02 | ビツク コ−ポレ−シヨン | 可消性インク組成物および可消性書体形成方法 |
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 |
ATE181647T1 (de) * | 1991-09-26 | 1999-07-15 | U S A Retama Inc | Schuhsohleelement |
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 |
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 |
ES2746011T3 (es) | 2013-10-28 | 2020-03-04 | Intellectual Property Holdings Llc | Sistema de retención de casco |
Family Cites Families (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB849048A (en) * | 1958-06-27 | 1960-09-21 | Ici Ltd | Improvements in or relating to the polymerisation of unsaturated organic compounds |
US3102303A (en) * | 1958-12-18 | 1963-09-03 | Western Plastics Corp | Apparatus for irradiation of plastics |
US3113912A (en) * | 1959-07-16 | 1963-12-10 | Phillips Petroleum Co | Preparation of vulcanizates by irradiation of block copolymers |
GB953750A (en) * | 1960-06-20 | 1964-04-02 | Phillips Petroleum Co | Floor tile and shoe sole compositions |
GB1068933A (en) * | 1964-09-11 | 1967-05-17 | Grace W R & Co | Thermoplastic reproduction |
GB1123235A (en) * | 1964-12-09 | 1968-08-14 | Dunlop Co Ltd | The manufacture of sheet material |
US3497572A (en) * | 1967-08-24 | 1970-02-24 | Phillips Petroleum Co | High impact resin compositions |
GB1242510A (en) | 1968-01-25 | 1971-08-11 | Conrad Goldman | Thermoforming of thermoplastic polymers |
GB1242509A (en) | 1968-01-25 | 1971-08-11 | Conrad Goldman | Thermoforming of thermoplastic polymers |
US3624189A (en) * | 1968-01-31 | 1971-11-30 | Conrad Goldman | Process of heating acrylonitrile-butadiene-styrene polymers with electromagnetic field energy |
DE1915033B2 (de) * | 1969-03-25 | 1972-04-06 | Vereinigte Deutsche Metallwerke Ag, 6000 Frankfurt | Verfahren zur herstellung von vernetzten formkoerpern |
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 |
GB1313102A (en) * | 1969-07-04 | 1973-04-11 | Int Synthetic Rubber | Process for producing moulded foam |
US3846265A (en) * | 1969-12-24 | 1974-11-05 | Mitsubishi Petrochemical Co | Production of shaped structures |
US3701702A (en) * | 1970-08-25 | 1972-10-31 | Uniroyal Inc | Method of free curing rubber |
US3846521A (en) * | 1971-02-03 | 1974-11-05 | Union Carbide Corp | Low energy electron beam treatment of polymeric films, and apparatus therefore |
US3832111A (en) * | 1971-03-29 | 1974-08-27 | Compo Ind Inc | Apparatus for making component parts of shoes and the like comprised of thermoplastic sheeting |
US3826776A (en) * | 1971-06-28 | 1974-07-30 | Phillips Petroleum Co | Block copolymers and oxidized carbon black compositions |
US3823109A (en) * | 1972-11-03 | 1974-07-09 | Phillips Petroleum Co | Polymer compositions |
US3959545A (en) * | 1974-02-06 | 1976-05-25 | Phillips Petroleum Company | Unvulcanized expanded high green strength synthetic rubber product and method of manufacture |
US3936365A (en) * | 1974-05-28 | 1976-02-03 | The Dow Chemical Company | Radiation crosslinked block copolymer blends with improved impact resistance |
GB1505403A (en) * | 1974-07-22 | 1978-03-30 | Sumitomo Bakelite Co | Thermoplastic resin composition |
US4115509A (en) * | 1974-11-12 | 1978-09-19 | British Industrial Plastics Ltd. | Moulding of filled synthetic plastics moulding compositions |
US3985702A (en) * | 1975-05-27 | 1976-10-12 | Shell Oil Company | Dry blending and molding process |
US4035467A (en) * | 1975-11-21 | 1977-07-12 | General Motors Corporation | Method of injection molding a thermoset polyurethane article |
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 EP EP78100674A patent/EP0000920B1/fr not_active Expired
- 1978-08-16 DK DK362678A patent/DK362678A/da unknown
- 1978-08-16 ES ES472566A patent/ES472566A1/es not_active Expired
- 1978-08-16 DE DE7878100674T patent/DE2862084D1/de not_active Expired
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE202011101868U1 (de) | 2011-06-16 | 2011-10-24 | Veljo Strucl | Quad-V-Servo Profil mit mehrfach geknickter Gleitfläche |
Also Published As
Publication number | Publication date |
---|---|
US4288399A (en) | 1981-09-08 |
IT1098055B (it) | 1985-08-31 |
EP0000920A1 (fr) | 1979-03-07 |
ES472566A1 (es) | 1979-10-16 |
DK362678A (da) | 1979-02-18 |
DE2862084D1 (en) | 1982-12-16 |
IT7826775A0 (it) | 1978-08-14 |
CA1109979A (fr) | 1981-09-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0000920B1 (fr) | Compositions d'élastomères thermoplastiques, procedure de préparation d'articles moulés, et moulages | |
US4400483A (en) | Thermoplastic elastomer compositions for low pressure molding | |
US4360607A (en) | Microwave energy sensitizing concentrate | |
CA1243794A (fr) | Elastomere thermoplastique | |
US3701702A (en) | Method of free curing rubber | |
US4173556A (en) | Elastoplastic compositions of rubber and polyamide | |
CN104603190B (zh) | Eva回收方法 | |
US4629583A (en) | Phosphorescent polymer-containing compositions and articles made therefrom | |
US4640797A (en) | Phosphorescent polymer-containing compositions and articles made therefrom | |
US4197379A (en) | Elastoplastic compositions of rubber and polyamide | |
US4234636A (en) | Thermoplastic elastomeric composition, product and method of manufacture | |
IE55160B1 (en) | Moulding compositions based on polymers reinforced by mineral fillers,processes for their preparation and their use | |
JP4023927B2 (ja) | 熱可塑性エラストマー組成物 | |
US4370189A (en) | Modifying thermoplastic materials and products thereof | |
US4256850A (en) | Article and process simulating plantation crepe rubber | |
PL108002B1 (pl) | Elastomeric and thermoplastic composition of rubbeelastomeryczna i termoplastyczna kompozycja kauczuku i zywicy poliamidowej r andpolyamide resin | |
US5624994A (en) | Process for the preparation of composite material formed from a vulcanized elastomer in combination with a thermoplastic elastomer containing polyamide blocks, composite material thus formed and sports articles produced with the aid of said materials | |
Naderi et al. | Studies on dynamic vulcanization of PP NBR thermoplastic elastomer blends | |
US2938011A (en) | Low shrinkage silicone rubber composition containing a mixture of fillers | |
JPH05230228A (ja) | 電子ビーム照射によるポリマー組成物の製造方法 | |
KR830001164B1 (ko) | 고무 성형물 제조 방법 | |
CA1160386A (fr) | Elastomere thermoplastique, produit et methode de fabrication connexes | |
CA1053826A (fr) | Melanges nitrile-pvc | |
KR100645661B1 (ko) | 가교가능한 회전성형용 폴리에틸렌 수지 조성물 | |
JPS5915351B2 (ja) | 非加硫の加圧及び加熱成形性組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): BE DE FR GB NL SE |
|
17P | Request for examination filed | ||
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Designated state(s): BE DE FR GB NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19821110 Ref country code: BE Effective date: 19821110 |
|
REF | Corresponds to: |
Ref document number: 2862084 Country of ref document: DE Date of ref document: 19821216 |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19830817 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19840501 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19840502 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19881117 |
|
EUG | Se: european patent has lapsed |
Ref document number: 78100674.7 Effective date: 19850610 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |