US3738924A - Process for the solvent casting of cellulose films using radiation,and products thereof - Google Patents
Process for the solvent casting of cellulose films using radiation,and products thereof Download PDFInfo
- Publication number
- US3738924A US3738924A US00160131A US3738924DA US3738924A US 3738924 A US3738924 A US 3738924A US 00160131 A US00160131 A US 00160131A US 3738924D A US3738924D A US 3738924DA US 3738924 A US3738924 A US 3738924A
- Authority
- US
- United States
- Prior art keywords
- film
- dope
- cellulose ester
- cast
- solvent
- 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 - Lifetime
Links
- 229920002678 cellulose Polymers 0.000 title abstract description 34
- 238000000034 method Methods 0.000 title abstract description 33
- 230000005855 radiation Effects 0.000 title abstract description 10
- 238000000807 solvent casting Methods 0.000 title abstract description 10
- 239000001913 cellulose Substances 0.000 title description 8
- 239000000178 monomer Substances 0.000 abstract description 30
- 239000000463 material Substances 0.000 abstract description 12
- 238000005266 casting Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 20
- 230000005865 ionizing radiation Effects 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- -1 fatty acid ester Chemical class 0.000 description 13
- 238000001035 drying Methods 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 235000010980 cellulose Nutrition 0.000 description 7
- 229920002301 cellulose acetate Polymers 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 2
- 229920001727 cellulose butyrate Polymers 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NGFWAKGWMSOVMP-UHFFFAOYSA-N 2-(2-methoxyethoxycarbonyl)benzoic acid Chemical compound COCCOC(=O)C1=CC=CC=C1C(O)=O NGFWAKGWMSOVMP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229940106135 cellulose Drugs 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000012857 radioactive material Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
Definitions
- the present invention relates to improved processes for manufacturing film materials containing, as a major component, at least one lower fatty acid ester of cellulose. More particularly, this invention relates to a method for significantly increasing the maximum rates at which film materials containing such cellulose esters can be manufactured via the so-called solvent casting method or procedure.
- the drying or curing zone must conventionally be fairly long because of the necessity to remove from the film a very large proportion (i.e., generally about percent or more) of the total amount of organic volatile solvents that had originally been present in the dope solution.
- solvent casting processes for manufacturing films composed mainly of cellulose lower fatty acid esters can be markedly shortened in an economical way by (a) incorporating into the solvent portion of the dope an effective amount of a compatible organic monomer (which not only can serve as a solvent or co-solvent for the cellulose ester film former in the dope, but also can be polymerized via a free radical procedure) and (b) subjecting the layer of cast dope, While it remains on the coating web and before it has developed sufiicient integral strength to be satisfactorily strippable, to a sufficient amount of ionizing radation to cause the free radical polymerization of the monomer(s) in the cast layer, said amount of ionizing radiation being less than that which causes the cellulose ester in the cast layer to degrade excessively.
- a compatible organic monomer which not only can serve as a solvent or co-solvent for the cellulose ester film former in the dope, but also can be polymerized via a free radical procedure
- This amoun of ionizing radiation will preferably be from about 0.3 to about 10 megarads. Still further preferred dosage, in the presence of sensitizers, for example, is from about 0.5 to about 3 megarads.
- An additional advantage that can result from practicing the present improved processes is that relatively smaller amounts of organic solvent-(s) need be recovered from the drying and curing steps, thereby resulting in less total demand upon solvent collection and purification equipment (which presently represent a large necessary investment in conjunction with the conventional film solvent casting equipment described above).
- the compatible monomers referred to above are those well-known organic compounds
- Typical non-limiting examples of such compatible monomers are the lower alkyl acrylics such as methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylonitrile, butylene dimethacrylates, ethylene glycol dimethacrylate, and the like, as well as other unsaturated monomers such as acrylic acid, acrylamide, diacetone acrylamide, diallyl phthalates, styrene, vinyl acetate, vinyl butyrate, and the like.
- lower alkyl acrylics such as methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylonitrile, butylene dimethacrylates, ethylene glycol dimethacrylate, and the like
- unsaturated monomers such as acrylic acid, acrylamide, diacetone acrylamide, diallyl phthalates, styrene, vinyl acetate, vinyl butyrate, and the like.
- the polymeric products that result from practicing the processes of this invention are apparently copolymeric in nature, (rather than a simple admixture of cellulose ester and polymerized monomers, as would be expected), involving the apparent multiple grafting of polymerized monomer to the cellulosic material.
- the products that result from practicing the present processes have unique and unexpected properties. For example, practically none of the polystyrene portion can be extracted from the film product from Example I, below even after prolonged treatment in boiling toluene.
- the compatible monomer(s) that are used in the formulation of the various cellulose ester dopes should generally be present in the solvent fraction of the dopes (i.e., that portion that can be evaporated from the dopes in a circulating air oven at a temperature of 105 C. and at atmospheric pressure) in an amount equal to at least about 5 weight percent and will preferably represent from about 15 to about 80 weight percent of said volatile solvent fraction.
- the compatible monomers should be used in amounts equal to at least about weight percent of the cellulose esters in these compositions, but should not be used in amounts higher than twice the amount of cellulose ester(s) in the present dope compositions.
- the ratio of total compatible monomers to total cellulose ester(s) in the dope should be at most about 1 to 1, respectively, by weight.
- the remainder of the solvent fraction can contain any desired volatile, non-polymerizable organic solvent or blend of volatile non-polymerizable organic solvents that have conventionally been employed in cellulose ester dopes heretofore. This includes, but is not limited to methanol, ethanol, isopropanol, n-propanol, butanol, methylene chloride, cyclohexane, ethylene dichloride, chloroform, and the like. As is well known in the art, sometimes blends of such solvents are more desirable in certain formulations to yield completely clear dopes.
- the dissolved (non-volatile at 105 C.) fraction of the initial dope compositions of the present invention should consist essentially of one or more of the film-forming lower fatty acid cellulose esters described heretofore, and can also contain a relatively smaller amount [up to about 25 weight percent, based on the combined weights of plasticizer(s) and cellulose ester(s) in the dope of one (or a blend) of those materials that are known to plasticize the cellulose ester film], as well as colorants such as dyes, anti-oxidants, and stabilizers.
- plasticizers for cellulose ester films are triphenylphosphate, methoxyethyl phthalate, diallyl phthalate (a polymerizable plasticizer), and the like. This dissolved fraction represents at least about 10 weight percent of the present dope compositions, but preferably should represent from about 15 to about 35 weight percent of the dope compositions.
- Typical examples of the types of ionizing radiation that can be used in the successful practice of this invention include high energy electrons (see Industrial Radiation Cured Coatings Speed Product Finishing by John A. Mock, Material Engineering, October 1970, pp. 56 through 59), beta particles, gamma rays, X-rays, positive ions such as alpha particles, and ionizing radiation from decomposing radioactive materials such as radioactive cobalt, for example.
- the particular physical manner whereby the ionizing radiation is applied to the dope layers in the practice of this invention is not critical.
- the radiation should be of sufficient intensty or strength to penetrate through the entre thickness of the cast dope layer. Thus, it is preferred that at least half of the ionizing radiation be strong enough to pass completely through the cast dope layer.
- the particular source of the ionizing radiation that causes the polymerization of a substantial proportion of the compatible monomer in the dope compositions of this invention is not critical, so long as the dosage level at the cast dope layer is at least about 0.3 megarads.
- the ionizing radiation must be directed onto the cast dope layer while the layer remains on the initial casting Web.
- a high enegy electron beam can be directed onto the dope layer shortly, or practically immediately, after the dope layer is cast, thereby causing an immediate, very large increase in the integral strength of the layer and enabling the partially cured layer to be stripped successfully from the wheel in a much shorter time than would otherwise be possible without undesirable pickoff.
- the ionizing radiation should be applied to the wet dope layer within about three minutes of the time the layer is cast into the Web.
- EXAMPLE 1 Ten parts of cellulose acetate (containing 43.5% acetyl and having an intrinsic viscosity of 2.40 at 25 C. in a :10 blend of methylene chloride and methanol, respectively) are dissolved in 50 parts of a 90:10 blend of methylene chloride and methanol. Twenty parts of a solution containing equal amounts of styrene monomer and the same solvent blend are then mixed with the solution of cellulose ester. The resulting dope contains equal amounts of cellulose acetate and styrene monomer. This dope is then coated at room temperature on a glass plate to a thickness of 7 mils.
- Example 1 Percent elongation 3.8 Modulus (10 p.s.i.) 5.3 Tear (grams) 13
- Example 1 is repeated using 1,3-butylene dimethacrylate as the monomer in place of the styrene monomer.
- the resulting dried/cured film has the following properties:
- step (c) thereafter stripping said partially dried film from said web and passing said partially dried film through a drying zone to thereby remove at least half of the organic solvent material remaining in said partially dried film; the improvement which comprises (i) incorporating into said solvent portion at least about 5 weight percent of a soluble, compatible unsaturated monomer, and (ii) subjecting said wet film to ionizing radiation in an amount equal to at least about 0.3 megarad prior to step (c); said compatible unsaturated monomer having a molecular weight of at most about 300 and being capable of free radical polymerization.
- cellulose lower fatty acid ester is selected from the group consisting of cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, and cellulose butyrate film formers having intrinsic viscosities of at least about 1.
- a clear film product containing at least about 50 weight percent of lower fatty acid ester of cellulose and at least about 10 weight percent of polymerized compatible monomer unsaturated copolymerized therewith; said film product having been manufactured according to the process of claim 1.
- a film product as in claim 11, wherein said polymerized compatible unsaturated monomer is polystyrene.
- a film product as in claim 11, wherei said polymerized compatible unsaturated monomer is poly(methylmethacrylate) 14.
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Polymerisation Methods In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Moulding By Coating Moulds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US16013171A | 1971-07-06 | 1971-07-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3738924A true US3738924A (en) | 1973-06-12 |
Family
ID=22575646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00160131A Expired - Lifetime US3738924A (en) | 1971-07-06 | 1971-07-06 | Process for the solvent casting of cellulose films using radiation,and products thereof |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3738924A (show.php) |
| JP (1) | JPS5510618B1 (show.php) |
| CA (1) | CA959188A (show.php) |
| DE (1) | DE2233027C3 (show.php) |
| FR (1) | FR2144818B1 (show.php) |
| GB (1) | GB1381762A (show.php) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3878139A (en) * | 1972-01-31 | 1975-04-15 | Nippon Paint Co Ltd | Acrylate and styrene graft copolymers of mercapto-group-containing cellulose derivatives and coating composition containing same |
| US4057657A (en) * | 1973-12-13 | 1977-11-08 | John Lyndon Garnett | Curable pre-polymer compositions, method of making and method of coating articles therewith |
| US5686036A (en) * | 1996-01-11 | 1997-11-11 | Eastman Kodak Company | Process for making a cellulose triacetate photographic film base |
| US20060130227A1 (en) * | 2002-01-30 | 2006-06-22 | Belford Gary P | Arm rest massage feature for whirlpool tubs |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI66624C (fi) * | 1983-11-02 | 1984-11-12 | Neste Oy | Foerfarande foer framstaellning av cellulosakarbamatfibrer eller -filmer |
-
1971
- 1971-07-06 US US00160131A patent/US3738924A/en not_active Expired - Lifetime
-
1972
- 1972-06-12 CA CA144,436A patent/CA959188A/en not_active Expired
- 1972-07-05 DE DE2233027A patent/DE2233027C3/de not_active Expired
- 1972-07-06 FR FR7224406A patent/FR2144818B1/fr not_active Expired
- 1972-07-06 GB GB3169872A patent/GB1381762A/en not_active Expired
- 1972-07-06 JP JP6713772A patent/JPS5510618B1/ja active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3878139A (en) * | 1972-01-31 | 1975-04-15 | Nippon Paint Co Ltd | Acrylate and styrene graft copolymers of mercapto-group-containing cellulose derivatives and coating composition containing same |
| US4057657A (en) * | 1973-12-13 | 1977-11-08 | John Lyndon Garnett | Curable pre-polymer compositions, method of making and method of coating articles therewith |
| US5686036A (en) * | 1996-01-11 | 1997-11-11 | Eastman Kodak Company | Process for making a cellulose triacetate photographic film base |
| US20060130227A1 (en) * | 2002-01-30 | 2006-06-22 | Belford Gary P | Arm rest massage feature for whirlpool tubs |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1381762A (en) | 1975-01-29 |
| FR2144818A1 (show.php) | 1973-02-16 |
| FR2144818B1 (show.php) | 1974-12-27 |
| DE2233027C3 (de) | 1974-10-03 |
| JPS5510618B1 (show.php) | 1980-03-18 |
| CA959188A (en) | 1974-12-10 |
| DE2233027A1 (de) | 1973-01-25 |
| DE2233027B2 (de) | 1974-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4348238A (en) | Manufacture of cellulose ester film | |
| US3738924A (en) | Process for the solvent casting of cellulose films using radiation,and products thereof | |
| US2923673A (en) | Preparation of photopolymerizable compounds | |
| US4140605A (en) | Crosslinkable composition | |
| US2137377A (en) | Laminated glass | |
| US3085901A (en) | Process for coating regenerated cellulose film with subcoat of cellulose nitrate and thermosetting resin and topcoat of vinylidene chloride copolymer | |
| US2316274A (en) | Coating and production of coated structures | |
| EP0032998B1 (de) | Thermoplastische Formmassen aus Celluloseester-Copfropfpolymerisaten oder deren Abmischungen mit Celluloseestern | |
| US3984584A (en) | Opaque coatings and films produced by the hardening of synthetic resins with light | |
| US4273856A (en) | Positive resist terpolymer composition and method of forming resist pattern | |
| US2238730A (en) | Manufacture of sheets or films of artificial material | |
| US2114233A (en) | Polymeric materials | |
| US2539376A (en) | Process for the production of strain-free masses from crossedlinked polymerized methylmethacrylate | |
| JPS5657807A (en) | Manufacture of acrylicc and methacrylic acid ester polymer and use thereof | |
| Dotson et al. | Process for the solvent casting of cellulose films using radiation, and products thereof | |
| US3857768A (en) | Process for radiation cross-linking polymethyl acrylate-methyl acrylate compositions | |
| US3793043A (en) | Cellulose ester dope solution containing inorganic chromium salts | |
| US2362094A (en) | Polymeric dihalo-ethylene compound | |
| CH633640A5 (en) | Process for producing a photosensitive photographic film | |
| US4118366A (en) | Compositions for the production of opaque coatings by radiation | |
| DE2103996C3 (de) | Verfahren zur Herstellung von Formkörpern aus einer Acrylpolymerisat-Monomer-Mischung | |
| US3384503A (en) | Process for the formation of thin opaque coatings | |
| US2305859A (en) | Method for preparing resinous articles | |
| DE2150373A1 (de) | Haertbare filmbildende Zubereitung | |
| US4129487A (en) | Process for improving the properties of an aqueous emulsion type coating composition |