US3053605A - Articles of polyvinyl alcohol having improved dyeability - Google Patents
Articles of polyvinyl alcohol having improved dyeability Download PDFInfo
- Publication number
- US3053605A US3053605A US814367A US81436759A US3053605A US 3053605 A US3053605 A US 3053605A US 814367 A US814367 A US 814367A US 81436759 A US81436759 A US 81436759A US 3053605 A US3053605 A US 3053605A
- Authority
- US
- United States
- Prior art keywords
- polyvinyl alcohol
- filament
- filaments
- dyeability
- amine
- 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
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims description 55
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims description 55
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 30
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- -1 HYDROXYL GROUPS Chemical group 0.000 claims description 18
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 150000003335 secondary amines Chemical class 0.000 claims description 10
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 150000003141 primary amines Chemical class 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 150000001412 amines Chemical class 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000004043 dyeing Methods 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 5
- 150000002825 nitriles Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000006359 acetalization reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 241001072332 Monia Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 108010077895 Sarcosine Proteins 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- CWVZGJORVTZXFW-UHFFFAOYSA-N [benzyl(dimethyl)silyl]methyl carbamate Chemical compound NC(=O)OC[Si](C)(C)CC1=CC=CC=C1 CWVZGJORVTZXFW-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical class C(C)(=O)* 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- QXIKMJLSPJFYOI-UHFFFAOYSA-L calcium;dichlorite Chemical class [Ca+2].[O-]Cl=O.[O-]Cl=O QXIKMJLSPJFYOI-UHFFFAOYSA-L 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940077239 chlorous acid Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000983 mordant dye Substances 0.000 description 1
- BUIMWOLDCCGZKZ-UHFFFAOYSA-N n-hydroxynitramide Chemical compound ON[N+]([O-])=O BUIMWOLDCCGZKZ-UHFFFAOYSA-N 0.000 description 1
- OMEMQVZNTDHENJ-UHFFFAOYSA-N n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCNC OMEMQVZNTDHENJ-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229940043230 sarcosine Drugs 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/22—Effecting variation of dye affinity on textile material by chemical means that react with the fibre
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
- D06P1/67333—Salts or hydroxides
- D06P1/6735—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341
- D06P1/67358—Halides or oxyhalides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
-
- 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
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/10—Polyvinyl halide esters or alcohol fiber modification
Definitions
- This invention relates to the production of shaped articles of polyvinyl alcohol having improved dyeability.
- the invention is especially concerned with the production of polyvinyl alcohol filaments having improved dyeing properties.
- Polyvinyl alcohol shaped articles such as filaments and films are produced by known methods. Usually such shaped articles show undesirable sensitivity to water, especially hot water. In order to improve the properties of shaped articles such as filaments, the articles are usually subjected to a heat treatment at temperatures in the range of 200250 C. followed by acetalization as with formaldehyde.
- Polyvinyl alcohol shaped articles treated as above have inferior dyeing characteristics. Both heat treatment and subsequent acetalization have a deleterious effect on dyeability of the shaped articles.
- polyvinyl alcohol shaped articles are oxidized to convert some of the hydroxyl groups to carbonyl groups. After oxidation, the oxidized article is reacted with ammonia or a primary or secondary amine and with hydrogen cyanide or an inorganic cyanide salt. Through this combination of treating steps, basic nitrogen groups are introduced into the polyvinyl alcohol shaped article, and the thusly treated shaped article has greatly improved dyeing properties.
- Polyvinyl alcohol shaped articles which are treated in accordance with this invention are prepared by known methods.
- shaped articles are meant filaments, films, An especially preferred method for preparing filaments which are to be treated in accordance with this invention is described in Tomonari et al. application Serial No. 336,166, filed February 10, 1953. Other methods can be employed.
- the polyvinyl alcohol shaped article is first treated in the process of this invention to oxidize some of the hy- 2. acid salts, and hydrogen peroxide together with pervanadic acid, and the like.
- the oxidation it is generally preferred to carry out the oxidation by immersing the polyvinyl alcohol shaped article in an aqueous solution of the oxidizing agent.
- the oxidation can be carried out in organic solvent solutions of oxidizing agent or using gaseous oxidizing agents.
- the oxidation can be carried out at normal or elevated temperatures, e.g. 0100 C., for times ranging from a few minutes to several hours.
- the shaped polyvinyl alcohol article is reacted with ammonia or a primary or secondary amine and with hydrogen cyanide or a cyanide salt.
- the reaction is believed to proceed as follows:
- examples of primary and secondary amines which can be used include methyl amine, ethyl amine, Z-ethyl hexylamine, laurylamine, cyclohexylamine, benzylamine, ethanol amine, glycine, alanine, glutamic acid, w-amino caproic acid, taurine, dimethyl amine, diethyl amine, lauryl methyl amine, piperidine, diethanol amine, morpohline, and sarcosine, as well as diamines and polyamines such as ethylene diamine, tetramethylene diamine, hexamethylene diamine, piperazine, triethylene tetramine, polyethylene polyamine, polyethylene imine, and the like. Salts of ammonia and the amines such as hydrochloric acid, sulfuric acid, phosphoric acid, hypophosphoric acid, acid sulfite, alkali car bonate, formic acid and ace
- Cyanides which are used include hydrogen cyanide and alkali or alkaline earth metal salts thereof such as sodium cyanide, potassium cyanide, calcium cyanide, and the like.
- the reaction of the oxidized polyvinyl alcohol shaped article with amine and cyanide is preferably carried out by immersing the shaped article in an aqueous solution or a water-alcohol solution containing 150% by Weight of a mixture of droxyl groups to carbonyl groups.
- the oxidation can be before or after other treating steps such as heat treatment or acetalization.
- Suitable oxidizing agents include hypochlorous acid, chlorous acid, alkali metal chlorites and hypochlorites, calcium chlorites and hypochlorites (ineluding bleaching powders), nitric acid, hyponitric acid,
- the oxidized shaped articles need not be reacted simultaneously with the amine and cyanide.
- the oxidized article can be separately reacted with amine and cyanide in either order.
- Vapor phase reactions of the oxidized polyvinyl alcohol article with the arnine and cyanide can be employed.
- the treated polyvinyl alcohol shaped articles can be subjected to known treating steps such as heat treatment and acetalization to further improve properties thereof. These treating steps can be carried out before or after the various process steps of this invention.
- the shaped polyvinyl alcohol articles produced by this invention have greatly improved dyeing characteristics. These articles are readily dyed to a deep color with both acid type dyes and direct dyestuffs.
- the basic nitrogen 3 groups introduced into the shaped article are highly stable against acid, alkali and hot water.
- Dyeability of filaments produced by this invention is greatly superior to that of cotton fibers with direct dyes. With acidic dyes and mordant dyes, the dyeability is comparable with that of wool fibers. Both the amino and cyano radicals introduced by the instant process are believed to contribute to the improved product dyeability.
- the polyvinyl alcohol articles treated by the present process are preferably composed substantially completely of polyvinyl alcohol.
- copolymers of vinyl alcohol with up to about 20% of other compounds such as ethylene, maleic anhydride, and the like can be used.
- EXAMPLE 1 Polyvinyl alcohol filaments were prepared by wet spinning. The filaments were heat treated for 3 seconds at 235 C.
- Portion 1 of the filaments was treated for 1 hour at 60 C. in an aqueous solution containing by weight 0.5% N-bromosuccinimide, 0.23% pyridine, and 15% sodium sulfate.
- Portion 2 of the filaments was treated for 1 hour at 60 C. in an aqueous solution containing by weight 2% hydrogen peroxide and 15% sodium sulfate.
- Portion 3 of the filaments was not oxidized.
- Portions l and 2 each were treated for 30 minutes at 60 C. in an aqueous solution containing by weight 2% ethylene diamine monohydrochloric acid salt and 1% sodium cyanide.
- Portions l, 2 and 3 were formalized for 1 hour at 70 C. in an aqueous solution containing by weight formaldehyde, 15% sulfuric acid, and 15% sodium sulfate.
- Table 1 Portion No 1 2 3 Weight percent nitrogen after treatment with amine 1 Dyed 1 hour at 70 C. in aqueous bath containing Nippon Fast Vioet BB in amount of 2% by weight of filament.
- EXAMPLE 2 Polyvinyl alcohol film was formed -by known tech niques. The film was treated for 1 hour at 50 C. in an aqueous solution containing by weight 20% persulfuric acid and 20% sodium sulfate under tension. Then the film was treated under tension for 2 hours at 50 C. in a solution containing by weight 5% ammonia, 0.5 cyanide and 20% sodium sulfate. Subsequently, the film under tension was heat treated 30 minutes at 160 C. in steam at 4 kg./cm. gauge pressure.
- EXAMPLE 3 Polyvinyl alcohol filaments were prepared by wet spinning. The filaments were hot stretched 100% at 235 C. in 2 seconds, and further heat treated for 2 seconds at 235 C. The filaments were divided into 2 portions, B and C.
- Portion B of the filaments was further treated for 1 hour at C. in an aqueous solution containing by weight 0.5% sodium hypochlorite, 0.5 sulfuric acid 4 and 15% sodium sulfate.
- the oxidized portion B filaments were then treated for 1 hour at 70 C. in an aqueous solution containing by weight 1% ethylenediamine, 0.83% sodium cyanide and 1.73% sodium acid sulfite.
- the thusly treated portion B filaments contained 0.65% by weight nitrogen.
- Both portions B and C of the filaments were treated for 1 hour at 70 C. in an aqueous solution containing by weight 5% formaldehyde, 15 sulfuric acid and 15 sodium sulfate.
- Portion B filaments had high water resistance (3.5% shrinkage after 30 minutes in 100 C. water), dry tenacity of 4.1 grams/ denier, and excellent dyeability for acid dyestufi. At C. the filaments absorbed all the dyestuff Acid Brilliant Scarlet 3R from an aqueous bath containing 2% of the dyestuff based on the filament weight.
- EXAMPLE 4 Polyvinyl alcohol filaments were prepared by wet spinning. These filaments were heat treated and formalized by reaction with formaldehyde.
- the acetalized filaments were treated for 2 hours at 70 C. in an aqueous chlorite salt solution containing 3 grams/liter efiective chlorine. The filaments were then treated for 1 hour at 50 C. in a solution containing 22 grams/ liter chloric acid.
- the resulting filaments were dyed for 1 hour at 80 C. using acid or direct dyestuffs as described in Examples 1 and 3. Dyed color was much deeper when compared to similarly prepared and dyed polyvinyl alcohol filaments not treated by the invention. Strength of filaments prepared by the invention was about 30% lower than such similarly prepared filaments.
- the method of improving the dyeability of a polyvinyl alcohol filament which comprises forming a polyvinyl alcohol filament, oxidizing said filament with an oxidizing agent until 01-20% of the hydroxyl groups of said polyvinyl alcohol filament are converted to carbonyl radicals, and reacting the partially oxidized filament at a temperature of from 0l00 C. with a mixture consisting of approximately equal molar equivalents of a compound selected from the group consisting of ammonia, a primary amine, a secondary amine and salts thereof, and of a compound selected from the group consisting of hydrogen cyanide, alkali metal cyanides, and alkaline earth metal cyanides thereby to produce a polyvinyl alcohol filament having improved dyeability.
- a polyvinyl alcohol shaped article prepared by the method of claim 1.
- a polyvinyl alcohol filament prepared by the method of claim 2.
- the method of improving the dyeability of shaped polyvinyl alcohol articles which comprises forming a polyvinyl alcohol shaped article, oxidizing said shaped article with an oxidizing agent until 0.1-20% of the hydroxyl groups of said polyvinyl alcohol shaped article are converted to carbonyl radicals, and reacting the partially oxidized shaped article at a temperature of from 0-l00 C.
- the method of improving the dyeability of a polyvinyl alcohol filament which comprises forming a polyvinyl alcohol filament, oxidizing said filament with an oxidizing agent until 0.l20% of the hydroxyl groups of said polyvinyl alcohol filament are converted to carbonyl radicals and reacting the partially oxidized filament at a temperature of from 0100 C.
- the method of improving the dyeability of shaped polyvinyl alcohol articles which comprises forming a polyvinyl alcohol shaped article, oxidizing said shaped article with an oxidizing agent until 0.140% of the hydroxyl groups of said polyvinyl alcohol shaped article are converted to carbonyl radicals, and reacting the partially oxidized shaped article at a temperature of from 0l00 C.
- the method of improving the dyeability of a polyvinyl alcohol filament which comprises forming a polyvinyl alcohol filament, oxidizing said filament with an oxidizing agent until (L l-20% of the hydroxyl groups of said polyvinyl alcohol filament are converted to carbonyl radicals and reacting the partially oxidized filament at a temperature of from 0- C.
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Description
f rods, and the like.
Unite States Patent fificc 3,053,605 Patented Sept. 11, 1962 3,053,605 ARTICLES F POLYVENYL ALCOHOL HAVING IMPROVED DYEABILITY Kenichi Tanabe, Kurashiki City, and Kanji Matsubayashi, Mizue, Kurashiki City, Japan, assignors of three-fourths to Kurashiki Rayon Co., Ltd., Okayoma, Japan, a corporation of Japan, and one-fourth to Air Reduction Company Incorporated, New York, N.Y., a corporation of New York No Drawing. Filed May 20, 1959, Ser. No. 814,367
Claims priority, application Japan May 26, 1958 8 Claims. (Cl. 8-1155) This invention relates to the production of shaped articles of polyvinyl alcohol having improved dyeability. The invention is especially concerned with the production of polyvinyl alcohol filaments having improved dyeing properties.
Polyvinyl alcohol shaped articles such as filaments and films are produced by known methods. Usually such shaped articles show undesirable sensitivity to water, especially hot water. In order to improve the properties of shaped articles such as filaments, the articles are usually subjected to a heat treatment at temperatures in the range of 200250 C. followed by acetalization as with formaldehyde.
Polyvinyl alcohol shaped articles treated as above have inferior dyeing characteristics. Both heat treatment and subsequent acetalization have a deleterious effect on dyeability of the shaped articles.
It is an object of this invention to provide a method for the production of shaped articles of polyvinyl alcohol characterized by improved dyeing properties.
It is a further object of the invention to produce polyvinyl alcohol filaments of improved dyeability.
Other objects will be apparent from the following description of the invention.
In carrying out the present invention, polyvinyl alcohol shaped articles are oxidized to convert some of the hydroxyl groups to carbonyl groups. After oxidation, the oxidized article is reacted with ammonia or a primary or secondary amine and with hydrogen cyanide or an inorganic cyanide salt. Through this combination of treating steps, basic nitrogen groups are introduced into the polyvinyl alcohol shaped article, and the thusly treated shaped article has greatly improved dyeing properties.
Polyvinyl alcohol shaped articles which are treated in accordance with this invention are prepared by known methods. By shaped articles are meant filaments, films, An especially preferred method for preparing filaments which are to be treated in accordance with this invention is described in Tomonari et al. application Serial No. 336,166, filed February 10, 1953. Other methods can be employed.
The polyvinyl alcohol shaped article is first treated in the process of this invention to oxidize some of the hy- 2. acid salts, and hydrogen peroxide together with pervanadic acid, and the like.
It is generally preferred to carry out the oxidation by immersing the polyvinyl alcohol shaped article in an aqueous solution of the oxidizing agent. However, the oxidation can be carried out in organic solvent solutions of oxidizing agent or using gaseous oxidizing agents. The oxidation can be carried out at normal or elevated temperatures, e.g. 0100 C., for times ranging from a few minutes to several hours.
It is necessary in accordance with the invention to oxidize sufiicient of the polyvinyl alcohol hydroxyl groups so that after subsequent amine and cyanide treatment the shaped article has good dyeing characteristics. Generally oxidation of about 0.1 to 20% of the hydroxyl groups and usually about 0.2 to 10% is preferred.
After oxidation, the shaped polyvinyl alcohol article is reacted with ammonia or a primary or secondary amine and with hydrogen cyanide or a cyanide salt. The reaction is believed to proceed as follows:
Besides ammonia, examples of primary and secondary amines which can be used include methyl amine, ethyl amine, Z-ethyl hexylamine, laurylamine, cyclohexylamine, benzylamine, ethanol amine, glycine, alanine, glutamic acid, w-amino caproic acid, taurine, dimethyl amine, diethyl amine, lauryl methyl amine, piperidine, diethanol amine, morpohline, and sarcosine, as well as diamines and polyamines such as ethylene diamine, tetramethylene diamine, hexamethylene diamine, piperazine, triethylene tetramine, polyethylene polyamine, polyethylene imine, and the like. Salts of ammonia and the amines such as hydrochloric acid, sulfuric acid, phosphoric acid, hypophosphoric acid, acid sulfite, alkali car bonate, formic acid and acetic acid salts can be used.
Cyanides which are used include hydrogen cyanide and alkali or alkaline earth metal salts thereof such as sodium cyanide, potassium cyanide, calcium cyanide, and the like.
The reaction of the oxidized polyvinyl alcohol shaped article with amine and cyanide is preferably carried out by immersing the shaped article in an aqueous solution or a water-alcohol solution containing 150% by Weight of a mixture of droxyl groups to carbonyl groups. The oxidation can be before or after other treating steps such as heat treatment or acetalization. Suitable oxidizing agents include hypochlorous acid, chlorous acid, alkali metal chlorites and hypochlorites, calcium chlorites and hypochlorites (ineluding bleaching powders), nitric acid, hyponitric acid,
(a) An amine or ammonia together with a molar equiv-, alent or less of hydrogen cyanide, or
(b) A salt of ammonia or an amine together with a molar equivalent amount of a cyanide salt, or
(c) A salt of ammonia or an amine together with a molar equivalent amount of a cyanide salt, and excess am monia or amine.
Reaction times of several minutes to many hours, usually about 5 minutes to 2 hours at temperature of 0100 0., usually 20-70" C., are employed. The oxidized shaped articles need not be reacted simultaneously with the amine and cyanide. Alternatively, the oxidized article can be separately reacted with amine and cyanide in either order. Vapor phase reactions of the oxidized polyvinyl alcohol article with the arnine and cyanide can be employed. Y
The treated polyvinyl alcohol shaped articles can be subjected to known treating steps such as heat treatment and acetalization to further improve properties thereof. These treating steps can be carried out before or after the various process steps of this invention.
The shaped polyvinyl alcohol articles produced by this invention have greatly improved dyeing characteristics. These articles are readily dyed to a deep color with both acid type dyes and direct dyestuffs. The basic nitrogen 3 groups introduced into the shaped article are highly stable against acid, alkali and hot water.
Dyeability of filaments produced by this invention is greatly superior to that of cotton fibers with direct dyes. With acidic dyes and mordant dyes, the dyeability is comparable with that of wool fibers. Both the amino and cyano radicals introduced by the instant process are believed to contribute to the improved product dyeability.
The polyvinyl alcohol articles treated by the present process are preferably composed substantially completely of polyvinyl alcohol. However, copolymers of vinyl alcohol with up to about 20% of other compounds such as ethylene, maleic anhydride, and the like can be used.
The following examples illustrate the invention:
EXAMPLE 1 Polyvinyl alcohol filaments were prepared by wet spinning. The filaments were heat treated for 3 seconds at 235 C.
Portion 1 of the filaments was treated for 1 hour at 60 C. in an aqueous solution containing by weight 0.5% N-bromosuccinimide, 0.23% pyridine, and 15% sodium sulfate.
Portion 2 of the filaments was treated for 1 hour at 60 C. in an aqueous solution containing by weight 2% hydrogen peroxide and 15% sodium sulfate.
Portion 3 of the filaments was not oxidized.
Portions l and 2 each were treated for 30 minutes at 60 C. in an aqueous solution containing by weight 2% ethylene diamine monohydrochloric acid salt and 1% sodium cyanide.
Portions l, 2 and 3 were formalized for 1 hour at 70 C. in an aqueous solution containing by weight formaldehyde, 15% sulfuric acid, and 15% sodium sulfate.
The following table shows the results obtained:
Table 1 Portion No 1 2 3 Weight percent nitrogen after treatment with amine 1 Dyed 1 hour at 70 C. in aqueous bath containing Nippon Fast Vioet BB in amount of 2% by weight of filament.
These results show the improvement in dyeing properties of filaments treated by the invention. Filament strength decreased only slightly through practice of the invention.
EXAMPLE 2 Polyvinyl alcohol film was formed -by known tech niques. The film was treated for 1 hour at 50 C. in an aqueous solution containing by weight 20% persulfuric acid and 20% sodium sulfate under tension. Then the film was treated under tension for 2 hours at 50 C. in a solution containing by weight 5% ammonia, 0.5 cyanide and 20% sodium sulfate. Subsequently, the film under tension was heat treated 30 minutes at 160 C. in steam at 4 kg./cm. gauge pressure.
When dyed at room temperature using 5% by weight of the film of tartarizine, or acid dyestutf, a brightly yellow-dyed film was obtained.
EXAMPLE 3 Polyvinyl alcohol filaments were prepared by wet spinning. The filaments were hot stretched 100% at 235 C. in 2 seconds, and further heat treated for 2 seconds at 235 C. The filaments were divided into 2 portions, B and C.
Portion B of the filaments was further treated for 1 hour at C. in an aqueous solution containing by weight 0.5% sodium hypochlorite, 0.5 sulfuric acid 4 and 15% sodium sulfate. The oxidized portion B filaments were then treated for 1 hour at 70 C. in an aqueous solution containing by weight 1% ethylenediamine, 0.83% sodium cyanide and 1.73% sodium acid sulfite. The thusly treated portion B filaments contained 0.65% by weight nitrogen.
Both portions B and C of the filaments were treated for 1 hour at 70 C. in an aqueous solution containing by weight 5% formaldehyde, 15 sulfuric acid and 15 sodium sulfate.
Portion B filaments had high water resistance (3.5% shrinkage after 30 minutes in 100 C. water), dry tenacity of 4.1 grams/ denier, and excellent dyeability for acid dyestufi. At C. the filaments absorbed all the dyestuff Acid Brilliant Scarlet 3R from an aqueous bath containing 2% of the dyestuff based on the filament weight.
Portion C of the filaments had a dry tenacity of 5.0 grams/denier and absorbed no dye under the above dyeing conditions.
EXAMPLE 4 Polyvinyl alcohol filaments were prepared by wet spinning. These filaments were heat treated and formalized by reaction with formaldehyde.
The acetalized filaments were treated for 2 hours at 70 C. in an aqueous chlorite salt solution containing 3 grams/liter efiective chlorine. The filaments were then treated for 1 hour at 50 C. in a solution containing 22 grams/ liter chloric acid.
The oxidized filaments were treated with amine and cyanide as described in Example 3.
The resulting filaments were dyed for 1 hour at 80 C. using acid or direct dyestuffs as described in Examples 1 and 3. Dyed color was much deeper when compared to similarly prepared and dyed polyvinyl alcohol filaments not treated by the invention. Strength of filaments prepared by the invention was about 30% lower than such similarly prepared filaments.
We claim:
1. The method of improving the dyeability of shaped polyvinyl alcohol articles which comprises forming a polyvinyl alcohol shaped article, oxidizing said shaped article with an oxidizing agent until 01-20% of the hydroxyl groups of said polyvinyl alcohol shaped article are converted to carbonyl radicals, and reacting the partially oxidized shaped article at a temperature of from 0-100 C. with a mixture consisting of approximately equal molar equivalents of a compound selected from the group consisting of ammonia, a primary amine, a secondary amine and salts thereof, and of a compound selected from the group consisting of hydrogen cyanide, alkali metal cyanides and alkaline earth metal cyanides thereby to produce a shaped polyvinyl alcohol article having improved dyeability.
2. The method of improving the dyeability of a polyvinyl alcohol filament which comprises forming a polyvinyl alcohol filament, oxidizing said filament with an oxidizing agent until 01-20% of the hydroxyl groups of said polyvinyl alcohol filament are converted to carbonyl radicals, and reacting the partially oxidized filament at a temperature of from 0l00 C. with a mixture consisting of approximately equal molar equivalents of a compound selected from the group consisting of ammonia, a primary amine, a secondary amine and salts thereof, and of a compound selected from the group consisting of hydrogen cyanide, alkali metal cyanides, and alkaline earth metal cyanides thereby to produce a polyvinyl alcohol filament having improved dyeability.
3. A polyvinyl alcohol shaped article prepared by the method of claim 1.
4. A polyvinyl alcohol filament prepared by the method of claim 2.
5. The method of improving the dyeability of shaped polyvinyl alcohol articles which comprises forming a polyvinyl alcohol shaped article, oxidizing said shaped article with an oxidizing agent until 0.1-20% of the hydroxyl groups of said polyvinyl alcohol shaped article are converted to carbonyl radicals, and reacting the partially oxidized shaped article at a temperature of from 0-l00 C. with a compound selected from the group consisting of ammonia, a primary amine, a secondary amine and salts thereof, and with a compound selected from the group consisting of hydrogen cyanide, alkali metal cyanides and alkaline earth metal cyanides thereby to produce a shaped polyvinyl alcohol article having improved dyeability, said compounds being present in amounts sufficient to give said article a nitrogen content of at least about 0.4% by weight.
6. The method of improving the dyeability of a polyvinyl alcohol filament Which comprises forming a polyvinyl alcohol filament, oxidizing said filament with an oxidizing agent until 0.l20% of the hydroxyl groups of said polyvinyl alcohol filament are converted to carbonyl radicals and reacting the partially oxidized filament at a temperature of from 0100 C. with a compound selected from the group consisting of ammonia, a primary amine, a secondary amine and salts thereof, and with a compound selected from the group consisting of hydrogen cyanide, alkali metal cyanides, and alkaline earth metal cyanides thereby to produce a polyvinyl alcohol filament having improved dyeability, said compounds being present in amounts sufiicient to give said filament a nitrogen content of at least about 0.4% by weight.
7. The method of improving the dyeability of shaped polyvinyl alcohol articles Which comprises forming a polyvinyl alcohol shaped article, oxidizing said shaped article with an oxidizing agent until 0.140% of the hydroxyl groups of said polyvinyl alcohol shaped article are converted to carbonyl radicals, and reacting the partially oxidized shaped article at a temperature of from 0l00 C. with a mixture consisting of a compound selected from the group consisting of ammonia, a primary amine, a secondary amine and salts thereof, and of a compound selected from the group consisting of hydrogen cyanide, alkali metal cyanides and alkaline earth metal cyanides thereby to produce a shaped polyvinyl alcohol article having improved dyeability, said mixture of compounds being present in solution in a concentration of l to by weight.
8. The method of improving the dyeability of a polyvinyl alcohol filament which comprises forming a polyvinyl alcohol filament, oxidizing said filament with an oxidizing agent until (L l-20% of the hydroxyl groups of said polyvinyl alcohol filament are converted to carbonyl radicals and reacting the partially oxidized filament at a temperature of from 0- C. with a mixture consisting of a compound selected from the group consisting of ammonia, a primary amine, a secondary amine and salts thereof, and of a compound selected from the group consisting of hydrogen cyanide, alkali metal cyanides, and alkaline earth metal cyanides thereby to produce a polyvinyl alcohol filament having improved dyeability, said mixture of compounds being present in solution in a concentration of 1 to 50% by weight.
References Cited in the file of this patent UNITED STATES PATENTS 2,143,482 Herrmann Jan. 10, 1939
Claims (1)
- 2. THE METHOD OF IMPROVING THE DYEABILITY OF A POLYVINYL ALCOHOL FILAMENT WHICH COMPRISES FORMING A POLYVINYL ALCOHOL FILAMENT, OXIDIZING SIAD FILAMENT WITH AN OXIDIZING AGENT UNTIL 0.1-20% OF THE HYDROXYL GROUPS OF SAID POLYVINYL ALCOHOL FILAMENT ARE CONVERTED TO CARBONYL RADICALS, AND REACTING THE PARTIALLY OXIDIZED FILAMENT AT A TEMPERATURE OF FROM 0-100* C. WITH A MIXTURE CONSISTING OF APPROXIMATELY EQUAL MOLAR EQUIVALENTS OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF AMMONIA, A PRIMARY AMINE, A SECONDARY AMINE AND SALTS THEREOF, AND OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF HYDROGEN CYANIDE, ALKALI METAL CYANIDES, AND ALKALINE EARTH METAL CYANIDES THEREBY TO PRODUCE A POLYVINYL ALCOHOL FILAMENT HAVING IMPROVED DYEABILITY.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3053605X | 1958-05-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3053605A true US3053605A (en) | 1962-09-11 |
Family
ID=17944176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US814367A Expired - Lifetime US3053605A (en) | 1958-05-26 | 1959-05-20 | Articles of polyvinyl alcohol having improved dyeability |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3053605A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3488151A (en) * | 1967-09-01 | 1970-01-06 | Union Carbide Corp | Preparation of carbon fibers from polyvinyl alcohol base fibers |
| US5219930A (en) * | 1990-09-21 | 1993-06-15 | Quantum Chemical Corporation | Process for converting vinyl alcohol polymers to poly(keto-esters) therefrom |
| US5530046A (en) * | 1993-04-15 | 1996-06-25 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Method for producing an oxidation-treated polymer solution and a method for producing a laminate using the solution |
| US5972039A (en) * | 1997-04-07 | 1999-10-26 | Isolsyer Company, Inc. | Increased absorbency and hand-feel fabrics |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2143482A (en) * | 1934-02-21 | 1939-01-10 | Chemische Forschungs Gmbh | Nonfogging laminated glass |
-
1959
- 1959-05-20 US US814367A patent/US3053605A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2143482A (en) * | 1934-02-21 | 1939-01-10 | Chemische Forschungs Gmbh | Nonfogging laminated glass |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3488151A (en) * | 1967-09-01 | 1970-01-06 | Union Carbide Corp | Preparation of carbon fibers from polyvinyl alcohol base fibers |
| US5219930A (en) * | 1990-09-21 | 1993-06-15 | Quantum Chemical Corporation | Process for converting vinyl alcohol polymers to poly(keto-esters) therefrom |
| US5530046A (en) * | 1993-04-15 | 1996-06-25 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Method for producing an oxidation-treated polymer solution and a method for producing a laminate using the solution |
| US5972039A (en) * | 1997-04-07 | 1999-10-26 | Isolsyer Company, Inc. | Increased absorbency and hand-feel fabrics |
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