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    • 4. 发明专利
    • Improvements in or relating to the manufacture of transparent alginate films
    • GB552770A
    • 1943-04-23
    • GB1353741
    • 1941-10-21
    • CEFOIL LTDROBERT CHARLES ROSE
    • 552,770. Alginic films. CEFOIL, Ltd., and ROSE, R. C. Oct. 21, 1941, No. 13537 Drawings to Specification. [Class 2 (ii)] A solution of a soluble alginate is formed into a film and solidified by treatment with a salt which forms an insoluble alginate, and the film is at least partially dried and then converted into a film of alginic acid. A solution of sodium alginate may be subjected to compressed air pressure and extruded through a slot in the bottom of a hopper into a solution of calcium chloride or other alkaline-earth salt. The sodium alginate solution may be of a strength of 5 per cent. or more and may give a viscosity of 10-200 centipoises at 15‹ C. when diluted to a strength of 1 per cent. The coagulated film may be passed from the first coagulating bath into a second bath containing calcium chloride solution. It is then passed through nip rollers and through a washing bath continuously supplied with fresh water. It is passed through nip rollers and then round heated drying cylinders by which alternate sides of the film are exposed to the hot surfaces and. to the atmosphere. Drying may be carried out until the solid content of the film is 30 per cent. or more of the total weight. The partially dried film is passed into an acid conversion bath which may contain hydrochloric acid of 2 per cent. strength. The alginic acid film passes through a washing bath and then through a bath containing a solution of glycerol. It is dried and then passed over conditioning rollers located in a chamber containing air at a relative humidity of 65 per cent. The treatment results in an alginic acid film which is strong enough in wet condition to permit of rapid speed of production and which in finished condition is of improved toughness. Specifications 492,264 and 530,889 are referred to.
    • 6. 发明专利
    • Improvements in or relating to the manufacture of cellular material of low density
    • GB574382A
    • 1946-01-03
    • GB429743
    • 1943-03-16
    • EDWARD VICTOR APPLETONROBERT CHARLES ROSEPETER HARIOLF PLESCHCEFOIL LTD
    • C08J9/30
    • In the manufacture of set-foam cellular material from foamed alginate solution, a chromium salt is employed as a setting agent. The solution of alginate, which may be an alkali metal, ammonium or magnesium alginate or an amine alginate such as triethanolamine alginate or a mixture of these, is converted into a foam by aeration and while in the foamed state is converted into an insoluble form by addition of the chromium salt and thereafter dried. The chromium salt may be basic chromium sulphate or acetate, chrome-alum or normal chromium sulphate. The basic sulphate should be added in the form of a freshly boiled solution. A frothing agent such as sodium isopropyl naphthalene sulphonate or saponin may be present in the alginate solution. Hard foams are obtained when sodium or ammonium alginate is employed and resilient foams when triethanolamine alginate is used; tough set foams are obtained when fibre such as wood pulp is incorporated in the alginate solution prior to foaming. A more rigid set foam is produced by using a mixture of basic or normal chromium sulphate and calcium sulphate or zinc sulphite as setting agent. Also, a foam of ammonium alginate can be mixed with calcium carbonate or sulphite and thereafter set with a mixture of a complex chromium salt, such as the normal sulphate and formaldehyde to give a hard set foam; the chromium salt in this case gives rigidity to the gelled foam during drying while the setting reaction between alginate, calcium compound and formaldehyde goes to completion. Another method of preparing hard foams comprises dissolving casein in alginate solution, foaming the solution, setting by addition of chromium salt and using sufficient formaldehyde or calcium compound or both to harden the casein; the proportion of casein may range up to 100 per cent of the weight of alginate. In examples: (1) a foamed solution of sodium alginate containing sodium isopropyl naphthalene as sulphonate as frothing agent was set by addition of a freshly boiled solution of basic chromium sulphate and a resilient material obtained upon drying; (2) a foamed solution containing ammonium and triethanolamine alginate, sodium isopropyl naphthalene sulphonate and kraft paper fibre was set by addition of freshly boiled basic chromium sulphate solution and after drying gave a tough slab resembling cork of density approximately 0.15; (3) as in example (2) above, but using triethanolamine alginate only; (4) to a stirred foamed solution of sodium alginate containing sodium isopropyl naphthalene sulphonate and sodium hexametaphosphate was added a quantity of anhydrite and the foam set by addition of chromium sulphate solution; a hard material was obtained on drying; (5) a foamed solution containing ammonium alginate, kraft paper pulp, calcium carbonate and saponin was set by the simultaneous addition of both a solution of formaldehyde and sodium hexametaphosphate and a solution of normal chromium sulphate; drying gave a hard slab of density 0.13; (6) a foamed solution containing ammonium alginate, kraft paper fibre, sodium isopropyl naphthalene sulphonate and calcium sulphite was set by the simultaneous addition of both a solution containing formaldehyde and paraformaldehyde, and a solution of normal chromium sulphate; (7) a foamed solution comprising ammonium alginate, kraft paper fibre, casein (dissolved in sodium carbonate solution), saponin and calcium sulphite was set by the simultaneous addition of both a solution of formaldehyde and sodium hexametaphosphate and a solution of normal chromium sulphate; a very hard product, density 0.25, was obtained on drying. Specification 560,317 is referred to.ALSO:In the manufacture of set-foam cellular material from foamed alginate solutions, a chromium salt is employed as a setting agent. The solution of alginate which may be an alkali metal, ammonium or magnesium alginate or an amine alginate such as triethanolamine alginate or a mixture of these, is converted into a foam by aeration and while in the foamed state is converted into an insoluble form by addition of the chromium salt and thereafter dried. The chromium salt may be basic chromium sulphate or acetate, chrome-alum, or normal chromium sulphate; the basic sulphate should be added in the form of a freshly boiled solution. A frothing agent such as sodium isopropyl naphthalene sulphonate or saponin may be present in the alginate solution. Hard foams are obtained when sodium or ammonium alginate is used; triethanolamine alginate forms resilient material: tough set-foams are obtained by incorporating fibre such as wood pulp in the alginate solution prior to foaming. A more rigid set-foam is produced by using a mixture of basic or normal chromium sulphate and calcium or zinc sulphite as setting agent. A hard set-foam is obtained by mixing calcium carbonate or sulphite with a foamed ammonium alginate solution and setting the foam by means of a mixture of a complex chromium salt such as the normal sulphate and formaldehyde. Another hard set-foamed alginate is prepared by dissolving casein in an alginate solution, foaming the solution, and setting by addition of a chromium salt and using sufficient formaldehyde or calcium compound or both to harden the casein; the proportion of casein may range up to 100 per cent of the weight of alginate. In examples: (1) a foamed solution of sodium alginate containing sodium isopropyl naphthalene sulphonate as frothing agent, was set by addition of a freshly boiled solution of basic chromium alginate and dried to give a resilient material; (2) a foamed solution of ammonium and triethanolamine alginates, sodium isopropyl naphthalene sulphonate and containing kraft paper fibre was set by addition of freshly boiled basic chromium sulphate and after drying, a tough slab resembling cork was obtained of density 0.15; (3) a set foam was prepared and set as in (2) above using however triethanolamine alginate only; (4) to a foamed sodium alginate solution containing sodium isopropyl naphthalene sulphonate and sodium hexametaphosphate, was added a quantity of anhydrite and the stirred foam, set by means of chromium sulphate solution, gave a hard material on drying; (5) a foamed solution containing ammonium alginate, kraft paper fibre, calcium carbonate and saponin was set by simultaneous addition of both a solution of formaldehyde and sodium hexametaphosphate and a solution of normal chromium sulphate; drying gave a hard slab of density 0.13; (6) a foamed alginate solution containing ammonium alginate, kraft paper fibre, calcium sulphite and sodium isopropyl naphthalene sulphonate was set by the simultaneous addition of both a solution of normal chromium sulphate and a solution of formaldehyde and para-formaldehyde; (7) a foamed solution of ammonium alginate, kraft paper fibre, casein (dissolved in sodium carbonate solution), calcium sulphite and saponin was set by simultaneous addition of a both normal chromium sulphate solution and a solution of formaldehyde and sodium hexametaphosphate; a very hard product, density 0.25, was obtained on drying. Specification 560,317 is referred to.
    • 7. 发明专利
    • Improvements in or relating to the manufacture of transparent papers and artificial fibres
    • GB548248A
    • 1942-10-02
    • GB276441
    • 1941-02-28
    • CEFOIL LTDROBERT CHARLES ROSE
    • D01F9/04
    • 548,248. Artificial filaments, films, &c. CEFOIL, Ltd., and ROSE, R. C. Feb. 28, 1941, No. 2764. Drawings to Specification. [Class 2 (ii)] A solution of a soluble alginate is formed into filaments or films and coagulated in a bath containing in addition to an acid a soluble salt which facilitates the coagulation of a strong film or fibre, but does not itself produce an insoluble alginate. The salt is used in a concentration adequate to cause substantial strengthening of the film. 'An alkali salt of the acid employed may be used, e.g. sodium sulphate with sulphuric acid. Sodium sulphate may be used in a concentration of more than 10 per cent anhydrous salt, and the sulphuric acid may be of 5 per cent strength. Concentrations of sodium sulphate up to saturation may be used. The temperature of the coagulation bath is preferably fairly low, e.g. 20‹C. In an example, a solution of alginate passes from a feed hopper with adjustable slot into a coagulating bath containing dilute sulphuric acid and sodium sulphate. The film thus formed, passes into another bath containing dilute sulphuric acid, and then into a washing bath of water. From the water bath the film passes into a bath containing an aqueous solution of glycerine. The film then passes round heated drying cylinders which reduce the free moisture content to not more than 30 per cent. The film passes to a conditioning chamber and thence to a wind-up roller. The film may be produced at a speed of 30 feet per minute. Specifications 21586/12, [Class 2 (iii)], and 530,889 are referred to.
    • 8. 发明专利
    • Improvements in or relating to the manufacture of transparent films
    • GB530889A
    • 1940-12-24
    • GB1840839
    • 1939-06-23
    • ROBERT CHARLES ROSECEFOIL LTD
    • C08L5/04
    • 530,889. Films. ROSE, R. C., and CEFOIL, Ltd. June 23, 1939, No. 18408. [Class 2 (ii)] Transparent alginic films are obtained by causing a solution of an alginic compound to flow through a slot to form a liquid film, coagulating the film and, at the same time or subsequently, subjecting the undried film to the action of an acid so as to induce substantial syneresis, i.e. expulsion of water from the film, and finally drying the film. The coagulating bath may be strongly acidic so as to effect coagulation and syneresis simultaneously, or syneresis may be effected in a subsequent bath containing sulphuric acid or a solution of calcium chloride acidified with hydrochloric acid or other acid. The process may be conducted so that the production of the film is completed under slightly acid conditions, the film thus containing free alginic acid. The film may be subjected to the syneresis treatment and dried under conditions which allow three-dimensional contraction. The alginate material used may be such that it has a viscosity of not less than 10 centipoises in a 1 per cent. solution in water at 15‹C. In an example, a solution of sodium alginate is extruded through a slot into a solution of calcium chloride and the film is subjected to syneresis and allowed to contract in a bath of calcium chloride containing 0.2 normal HCl. It is further converted to alginic acid by a solution of HCl, washed and dried. When sulphuric acid is used for the syneresis a strength of 0.1-0.5 N may be used. When sulphuric acid is used in the coagulating bath and simultaneous syneresis is desired, a strength of 0.5-2.0 N may be used. Instead of converting the film into alginic acid or calcium alginate it may be converted into another salt or an amine derivative of alginic acid. As shown in Fig. 1, sodium alginate solution passes from tank 11 to storage tank 12, and thence to hopper 13. It then issues from an adjustable slot as a liquid film 16. This is received on an endless band 17 running round rollers 18 in a coagulating bath 19. The film is stripped from the band and passed successively through a synerizing bath 21 containing calcium chloride and hydrochloric acid, a conversion bath 25 containing calcium acetate, or an acid such as sulphuric acid, or calcium chloride solution rendered alkaline with ammonia, a washing bath containing water, and a plasticizing bath containing e.g. glycerol. It then passes into a drying chamber where it passes over drying rollers rotating at progressively lower speeds so as to allow for shrinkage. Contraction in the syneresis bath 21 is permitted by rotating rollers 24 at a lower speed than roller 20. As shown in Fig. 2, the alginate solution is extruded from the hopper 13 and the film is received on and forwarded by a system of rollers 31 immersed in a bath 19 containing calcium chloride and strong mineral acid whereby coagulation and syneresis take place simultaneously. Specification 492,264 is referred to.