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Publication numberUS3053605 A
Publication typeGrant
Publication dateSep 11, 1962
Filing dateMay 20, 1959
Priority dateMay 26, 1958
Publication numberUS 3053605 A, US 3053605A, US-A-3053605, US3053605 A, US3053605A
InventorsTanabe Kenichi, Matsubayashi Kanji
Original AssigneeKurashiki Rayon Co, Air Reduction
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Articles of polyvinyl alcohol having improved dyeability
US 3053605 A
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Description  (OCR text may contain errors)

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

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2143482 *May 13, 1936Jan 10, 1939Chemische Forschungs GmbhNonfogging laminated glass
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3488151 *Sep 1, 1967Jan 6, 1970Union Carbide CorpPreparation of carbon fibers from polyvinyl alcohol base fibers
US5219930 *Jan 21, 1993Jun 15, 1993Quantum Chemical CorporationReacting with organic peroxyacid oxidizing agent
US5530046 *Sep 24, 1993Jun 25, 1996Nippon Gohsei Kagaku Kogyo Kabushiki KaishaDissolving saponified ethylene-vinyl acetate copolymer in alcohol-water mixture and oxidizing it with hydrogen peroxide in presence of polyvalent metal salt, then adding an enzyme to decompose residual hydrogen peroxide
US5972039 *Apr 7, 1997Oct 26, 1999Isolsyer Company, Inc.Involves subjecting the article to corona treatment for a period of time
Classifications
U.S. Classification8/115.59, 8/115.69, 8/115.66, 8/115.65, 8/DIG.100, 8/115.68, 8/115.6, 525/61
International ClassificationD06P5/22, D06P3/58, D06P1/673
Cooperative ClassificationY10S8/10, D06P1/67358, D06P3/58, D06P5/22
European ClassificationD06P1/673K3H, D06P3/58, D06P5/22