DE1050020B - Process for the production of artificial structures from cellulose acetate - Google Patents

Description

It is from Swiss patent specification 199 409 known to use cellulose esters to improve the coloring properties with an acrylic polymerisation product move that contains at least one amine functional group, but no amide functional group. It is also known from French patent specification 1,061,915, cellulose materials, z, 13. Viscose, by means of in To improve water-dispersible acrylamide polymers. According to this process, the polymers are thermally converted into a water-insoluble state and then added to an aqueous alkaline solution of the cellulosic material. After regenerating the cellulose, the mixture is heated to convert the added synthetic resin.

Since cellulose esters have only a low affinity for most wool dyes, difficulties arise when, for example, cellulose acetate staple fibers are to be dyed with the usual wool dyes. Since cellulose acetate per se is an excellent aggregate material for wool, this disadvantage is particularly noticeable since the mixed fabrics cannot be dyed in a satisfactory manner, ie with uniform coloring of the components thereof. Furthermore, fabrics which contain cellulose acetate cannot easily be finished with the customary textile finishes, such as those used, for example, for treating cotton or viscose fabrics in order to improve the grip, crease resistance and visual resistance. If, for example, finishes containing formaldehyde are applied to cellulose acetate, these only remain on the surface of the acetate and thus give a stiff, rigid fabric that has a low crease resistance and abrasion resistance. Furthermore, mixed fabrics containing cellulose acetate cannot be "drummed. Since the wool fibers in mixed fabrics contract in this process, but the cellulose acetate fibers remain unaffected, the mixed fabrics have the disadvantage that the cellulose acetal fibers remain longer and in some cases hang out of the fabric The frequently encountered, unpleasant, ie not wool-like feel of blended fabrics made of wool and cellulose acetate is due to the fact that these same materials cannot be subjected to the specified fulling process Exposure to the bare skin and static electrical charges on the fibers are due to this.

The known processes indicated are not able to overcome these difficulties or not completely. However, not only in the production of fibers and threads, but also in other artificial structures, e.g. B. films, occur in the known processes for the production of
artificial structures made of cellulose acetate

Applicant:

Eastman Kodak Company,
Rochester, NY (V. St. A.)

Representative: Dr.-Ing. W. Wolff, patent attorney,
Stuttgart-N, Lange Str. 51

Claimed priority:
V. St. v. America August 31, 1955

Harry Wesley Coover Jr., Kingsport, Tenn, (V. St. A.
has been named as the inventor

Disadvantages because the cellulose acetate and the modifying polymerization products used are different Have solution characteristics.

According to the invention, the stated difficulties are now overcome in that the cellulose acetate and a homopolymerization product of N-alkyl acrylamides the formula

= CHCON:

where R 'is hydrogen or 1 to 4 carbon atoms containing alkyl group and R is 1 to 4 carbon atoms and / or a homopolymerization product of an N-A) kylmethacrvlamides the formula

= C-CON

CH _S

.R '

where R 'is a hydrogen atom and R is an alkyl group containing 2 to 4 carbon atoms or R and R' are each an alkyl group containing 1 to 4 carbon atoms, and / or polymerization product of N-alkyl acrylamides with at least one unsaturated compound containing the group C =C or a Copolymerization product of N-alkyl methacrylamides with at least one unsaturated compound containing the group C = C, where at least 65 ° / _{0 of} the

809 748/427

monomeric mixture from which the copolymerization product was produced, of at least one N-alkyl acrylamide, an N-alkyl methacrylamide, various N-Alkylacrylamides with different substitutions on nitrogen or various N-alkyl methacrylamides with different substituents on nitrogen, in acetone or methylene chloride or in one Mixture of methylene chloride and methyl alcohol, are dissolved and that from this solution artificial structures, like fibers, threads or films, spun or cast will.

According to the method of the invention, structures are made which have the difficulties noted above and disadvantages in processing, e.g. B. with natural fibers, no longer have.

If a copolymerization product is used as the modifying polymerization product, this can contain up to 35 ° / ₀ vinyl esters, vinyl halides, acrylic acid and methacrylic acid compounds, e.g. B. nitriles, amides and esters, maleic acid and fumaric acid derivatives, such as nitriles, amides, esters, mixed ester amides and maleic acid amides. The monomeric compounds should preferably contain fewer than 20 carbon atoms. At the remaining 65 ° / _c , the copolymerization product consists of the acrylamides and methacrylamides given above.

The cellulose acetate and the modifying polymerization product can be used together in the solvent, especially in acetone. If the solutions are made separately, they will be subsequently united. The solutions can then either by dry spinning or by wet spinning spun into fibers or otherwise cast according to the known process.

If the cellulose acetate contains over 42% acetyl, then under normal conditions it is no longer in acetone completely soluble. There are then solvents such as methylene chloride, dimethylformamide, dirnethylacctamide or a mixture of methylene chloride and methanol is used. If necessary, for the cellulose acetate and various solvents from the group specified for the modifying polymerization product used and then combined the solutions.

45

example Cellulose acetate plus Solution
middle 1* 15% poly-N-isopropyl acrylamide acetone 2 * 10 ° / ₀ poly-N-N'-dimethylacrylamide acetone 3 * 20% poly-N-tert-butyl acrylamide acetone 4 * 10 ° / ₀ poly-N-methylacrylamide acetone 5 * 20 percent by weight poly acetone N, N-dimethyl methacrylamide 6 * 15 weight percent mixed poly acetone merisat 80:20 N-ethyl methacrylamide- Methyl acrylate 7 * 10 percent by weight mixed poly acetone merisat 90:10 N-isopropylacrylamide-acrylonitrile 8th 15 weight percent mixed poly acetone merisat 85:15 Ν, Ν-dimethyl methacrylamide— Vinyl acetate 9 * 25 percent by weight poly-N-methyl acetone N-ethyl methacrylamide

55

60

example Cellulose acetate plus solution
middle 10 * 15 percent by weight mixed acetone polymer 80: 10: 10 N, N-dimethylacrylamide-vinylidene chloride-methyl methacrylate 11 15% poly-N-isopropyl acrylamide Me ethylene chloride 12th 20% poly-N, N-dimethylacrylamide Me ethylene chloride Meth anol 90:10 13th 15% copolymer 75:25 Di- N, N-dimethylacrylamide- methyl- N-isopropyl acrylamide shape- amide 14th 10% poly-N.N-dimethylacrylamide Mc- ethylene chloride 15 * 15% copolymer 75:25 acetone N, N -wire thylacrylamide- N-isopropyl acrylamide 16 * 10% copolymer 90:10 acetone N, N-dimethylacrylamide- N-methyl methacrylamide 17 * 20% copolymer 70: 20: 10 acetone N, N-dimethyl acrylamide— ■ N-tert-butyl acrylamide- N-isopropyl acrylamide 18 * 5% copolymer 99: 1 acetone Ν, Ν-diraethylacrylamide — acrylamide 19 * 30 percent by weight mixed poly acetone merisat 85:15 N-isopropylacrylamide- N-methyl methacrylamide 20 * 20% copolymer 70:20:10 acetone N, N-dimethylacrylamide- N-isopropylacrylamide- Maleic anhydride 21 * 20% copolymer 70:20:10 acetone N.N-dimethylacrylamide- N-isopropylacrylamide- Diethyl fumarate 22 * 20% copolymer 70: 20: 10 acetone Ν, Ν-dimethylacrylamide— N-isopropylacrylamide- Vinyl acetate 23 * 20 percent by weight mixed poly acetone merisat 65:35 Ν, Ν-dimethylacrylamide— Methyl acrylate 24 * 15 weight percent mixed poly acetone merisat 75:15: 5: 5 Ν, Ν-dimethylacrylamide— N-isopropylacrylamide- Vinylidene chloride-vinyl acetate 25th 13 weight percent mixed poly acetone merisat 90:10 Ν, Ν-dimethylacrylamide— Methacrylamide

example

Cellulose acetate plus

IO

26 * 20 ° / ₀ copolymer 75: 15:10 acetone

Ν, Ν-dimethyl acrylamide—

N-isopropylacrylamide-fumaronitrile
27 * 20 »/ ο mixed polymer 75:15:10 acetone

N, N-dimethylacrylamide-

N-isopropylacrylamide-

Ν, Ν, Ν ', Ν'-tetramethylfumaramide
28 * 20 ° / ₀ copolymer 75:15:10 acetone

N.N-Dirnethylacrylamid-

N-isopropylacrylamide-

N-methylamidomaleic acid ester

* The examples marked with an asterisk represent preferred embodiments.

solvent

Comment on the examples

ao

The solutions given in the examples were spun into fibers which showed excellent affinity for direct dyes, acetate dyes, wool dyes and vat dyes. On the fibers according to Example 1, acetate dyes, which otherwise have poor gas resistance, surprisingly showed excellent gas resistance. Some Rcstfeuchtigkeitsgehalt of 8 ° / _0-containing fibers according to examples 3 "game 2 provide fabrics which have excellent wool-like feel. Mixtures of the fibers according to Example 4 with wool produce excellent dyeings in mixed fabrics with wool dyes, such as Fast Red S, cone. (Color Index 176) "and Milling Orange G (Color Index 377). A mixture of the fibers produced according to the examples with viscose fibers in a ratio of 50:50 results in an excellent dyeing with the dye Dark Orange G (Color Index 478) in the mixed fabric. Acid wool dyes show excellent lightfastness on the fibers according to Example 12. Wool dyes, which usually have poor lightfastness, surprisingly show excellent lightfastness on the fibers produced according to Example 15. Fabrics made from these fibers readily absorbed the commercial textile finishing agents and provided materials which have excellent properties, especially excellent grip.

In general, at least 5, but preferably so wise at least 10 and at most 30 percent by weight of the modifying homo- or mixed polymerisation product, based on the amount of cellulose acetate used. The concentration of the modifying polymerization product is of course chosen so that the desired excellent affinity for the dyes results. It is particularly surprising that the wool dyes are based on the cellulose acetates modified according to the invention have excellent lightfastness. The dyes given in the examples are for the purpose only the explanation. Of course, other commercially available dyes are also suitable for wool or Cellulose acetate. The percentages given are in each case to be understood as percentages by weight.

Claims (3)

Patent claims: 1. A process for the production of artificial structures, such as threads, fibers or films, from cellulose acetate and a modifying nitrogen-containing polymerization product, characterized in that the cellulose acetate and. ei n ^ H ^ omopolvmerisations- product o f JN-alkylacrylic amides of. FoHQsL.,
, R ' = CHCON: where R 'is a hydrogen or an alkyl group containing 1 to 4 carbon atoms and R is a 1 to 4 alkyl group containing carbon atoms, and / or a homopolymerization product of a N-alkyl methacrylamides of the formula = C-CON: CH ₃ where R 'is a hydrogen atom and R is an alkyl group containing 2 to 4 carbon atoms or R and R' are each an alkyl group containing 1 to 4 carbon atoms, and / or a mixed polymerization product of N-alkyl acrylamides with at least one unsaturated compound containing the group C = C or a Mischpolymerisationsprodukt of N-alkyl methacrylamides with at least one group C = C containing unsaturated compound, at least 65 ° / ₀ of the monomeric mixture from which the copolymerization products were prepared from at least one N-alkylacrylamide, a N-alkyl methacrylamide, a mixture of N-alkyl acrylamides and N-alkyl methacrylamides, different N-alkyl acrylamides with different substituents on nitrogen or different N-alkyl methacrylamides with different substituents on nitrogen bestefit ^ in acetone or methylene chloride or in a mixture "of" TÜefEylenchlörid and methyl alcohol dissolved ^ and then available become T. 2. The method according to claim 1, characterized in that a copolymerization product as a modifying polymerization product N-alkyl acrylamide or an N-alkyl methacrylamide with a vinyl ester containing fewer than 20 carbon atoms in the monomeric form, vinyl halide, Acrylic acid, methacrylic acid, maleic acid or fumaric acid ester amide or nitrile, a mixed ester amide the fumaric acids or maleic acids or with maleic anhydride is used. 3. The method according to claim 1 and 2, characterized in that a modifying polymerization product is used, which consists of an acrylamide which is water-soluble in the monomeric state given genus. Considered publications:
French Patent No. 1053 672;
Swiss Patent No. 199 409;
Report of the French patent specification No. 1,061,915 in the Chemisches Zentralblatt, 1955, p. 6427. φ $ 09 740/427 1.59