MXPA97009022A - Amination of regenerated cellulose with highly replaced starches and use of modified fibers - Google Patents

Abstract

The present invention relates to an aminated cellulose fiber which is obtained by adding one or more starches etherified with C2-C5 alkylamines which may be further substituted in the alkyl portion by 1 or 2 additional hydroxyl and methoxy groups and whose primary amino or ammonium group, or secondary, tertiary or quaternary substituted with C1-C4 alkyl and having a degree of substitution of between 0.1 and 3 to a paste of viscose, an alklicellulose or a cellulose solution and spinning the fiber from the same

Description

CELLULOSE FILLING REGENERATION CQN HIGHLY REPLACED PIPELINES AND USE OF MODIFIED FIBRO DESCRIPTIVE MEMORY The viscose fiber has essentially the same coloring characteristics as the cotton fiber, which is usually used, the dyeing of the natural or regenerated cellulose material requires the presence of lcali donating agents and also elec-t rol t-t so that satisfactory results can be obtained from fixation with reactive agents. However, the necessary additions are precisely those that are ecologically unacceptable. The future is thus increasingly linked to the regenerated cellulose fiber which first converts, without further process steps, to modifications which have a high affinity for dyeing, that is to say modifications that are dyeable without salt and alkali. Fiber modified in this manner resembles animal fiber, such as wool or silk, in its chemical behavior and can be dyed in neutral conditions with ammonic dyes without further additions of salt or alkali. A special field of application in this regard are the mixing fabrics, for example the fabrics composed of mixtures between polyurethane and modified viscose, which can then be dyed in a single bath. Viscose modifications have already been described in the literature. DE-fi-1 948 487 describes a process for producing viscose fiber having novel dyeing properties. It produces the fiber using polyarms, which not only severely alter the original character of the fiber but also are responsible for the unsatisfactory level of irishness of the subsequent dyeing. Simiiarrnent or, DE-fl-1 469 06? it refers to "armnalized fiber". The additions are arninoe-tiL- and diet laminoetii-cellulose in high concentrations and the dyeing is done exclusively with acid dyes. The disadvantage of this procedure is that the additions must first be synthesized and isolated in a complicated manner and, what is more, they are expensive. It is an object of the present invention to produce a viscose fiber that has significantly more affinity with the reactive as well as direct dyes and which differs absolutely from the normal fiber also in desired performance characteristics. This object is surprisingly achieved by mixing it with a paste of viscose, cellulose or alcalicellulose solution, highly substituted starch derivatives, ammonia containing compounds and the subsequent spinning. The present invention provides as aforesaid animated regenerated cellulose fiber which is obtained by adding one or more etherified starches with C2-C5alkylolamines which can be further substituted in the alkyl portion by one or two more hydroxyl and oxoxy groups and whose amino group is it a primary or secondary ammonium, or secondary, tertiary or quat ornario group substituted with Ci -O4 alkyl or with -0- (Cl I2)? -SO2- ÍOH2) and -NR or -0- (CH2)? -S? 2- (CH2) and -NR3 + ñ ", e where x and y are each 2 <3, the radicals R are identical or different and each is hydrogen, methyl or ethyl, and ft is an anion , and having a degree of substitution of between 3.1 and 3, preferably from 0.11 to 2, on a par from 0.2 to 1, in a concentration of 1 to 20% by weight, calculated as dry weight and based on the content of pulp cellulose, a viscose raisin, an alkali cellulose to a cellulose soludon and spinning the fiber therefrom.Etherified starch derivatives have a degree of substitution of 3.1 and 3. A degree of substitution of 3 means that each of the 3 free OH groups is etherified in each glucose unit A degree of substitution of 0.1 means that on average, each tenth glucose unit has an etherified OH group. degree of substitution of approximately 0.05 (Houben-Ueyi, 1987, Vol. E 20, part 3, pages 2135-2151), but no starches having a degree of substitution of (1.1 or higher. The present invention therefore also provides derivatives of the above-described alkylamino-modified starches having a degree of substitution between (1.1 and 3)., preferably from ü. 2, with the exception of a starch with a phylohydroxypropyl group, preference is given for the purpose of the present invention to those starch ethers whose ether group has the formula 0- (CH2) x -NR2, -0-CH2 -OHOH-CH -NR2, -0- (0H2) M -S02 - (0H2) and * MR2, -0- (CH2) "- 02-Í0H2) and -MR + 3H-, -0- (CH2) x - + NR3- or -0-OH2 CHOH -CH2 -NR + 3I1", where x and y are each 2 or 3, the radicals R are identical or different and each denote hydrogen, methyl or ethyl, and 0 is an anion, preferably chloride or sulfate, Particular preference is given to those starch ethers whose ether group has the formula -O-CH2-CH2-MH2, -0 -CH2 -CHOH-CH2 -N + (CH3) 3 or -O-CH2CH2 ~ N + (CH3) 3 - The novel starch ethers having said high degree of substitution form fluid to highly viscous materials in water ranging in viscosity of 1 at 30 Pas (approximately 20% strength by weight of aqueous solution, which, in the production of The regenerated cellulose fiber can be added to the spinning pulp, cellulose or alkalellulose solution without further processing. The degree of polymerization of the starch ethers of this invention is advantageously between 100 and 1000, preferably between 100 and 400, anhydroglucose units. If the degree of polymerization was less than 100, the starch ether could be extracted by washing the fiber after spinning. The starch ethers of this invention are prepared by reacting any desired starch, for example potato starch, corn starch or wheat starch, with an allyl of C 5 having a subst 11 reactive towards the OH groups, for example, substitution with or-e-chloro-fi-hydrox, 1,2-epox ?, L- (sulfa oetj isulfone) or sulphite, at a pH of 14, I preferred Pló of 9.5 to 13. The reaction temperature is advantageously from 40 to 100 ° C. The alkyl amine of C2-O5 is reacted in a molar ratio of the alkyl: anhydroglucose unit from 0.1: 1 to advantageously 4: 1, Depending on the desired degree of substitution for the starch, some of the above-mentioned 11-year-old axes that are used to modify the starch are glycylthiol glyceryl chloride, sulfate or sulfate chloride and 1 lt pmethiarium. , sulfate or sulfate or 3-chloro-2-hydroxypyr-opium chloride, 11-nitric oxide and sulphone my op1-oμ11 sul fatoet 1 lo. The starch compounds which are used to produce the purified regenerated cellulose fihra, which is soluble in water, are easily dispersible in the spinning pulp, preferably in an optional aqueous medium with the aid of the softeners and They exhibit considerable compatibility with viscose. The fluid starch ether is added in an amount of 1 to 20%, preferably 1 to 12% by weight, calculated as a dry substance, based on the cellulose content of the spinning pulp, before coagulation and molding. The filterability of the viscose does not show any deterioration compared to addition-free samples, so that no oration is now observed in the spinning mechanism during the spinning process. ("1 viscose molding <• e leads to or by conventional and known methods, for example by means of spinning mechanisms, a subsequent coagulation bath and opeonal between complementary baths subsequent to the treatment. Another way to produce the regenerated fiber is by stirring or integrating the above-mentioned starch derivatives to the lime and lime, the precursor to the viscose. Again, immediately after the extrusion and extrusion in a coagulating acid bath, a viscose fiber is obtained. The fiber obtained by the methods described can be dyed, after conversion by special treatment to woven and knitted fabrics, by various methods, such as depletion, impregnation and modern stamping processes, such as ink jet processes, use of salt or lcali. The present invention also provides a process for producing a stamped and embossed textile material, composed of regenerated cellulose fiber, which comprises adding said starch ethers to a viscose pulp, cellulose or alcalicellulose solution and spinning the fiber, for example by the process of spinning the viscose or from the cellulose solution, converting the fiber by special treatment to a woven or knitted fabric and dyeing or printing said fabric with one or more reactive dyes in the absence of salt or alkali. dic 1. The textile-modified fiber material used in the dyeing process of the invention may be present in all process states, for example, yarn, cut fiber, coarse wick and goods. (tissues). The modified textile materials are stamped according to the present invention analogously to the known procedures for dyeing and printing fiber materials with water soluble text and by using known ranges of temperature and usual amounts of dyeing. , except that dyeing solutions, impregnation processes, printing pastes and ink-jet formulations do not require any addition of alkaline compounds, as usual to fix the reactive dyes to the fibers, and the usual additions of salts electrolyte The dyeing or printing therefore takes place at a pH of between 4.5 and 8.5 and, if reagent dyes are used commercially available, in the presence of an electrolytic salt content of 0.01 to 0.5% by weight, based on the dyeing solution. Without the novelty of the cellulose fiber, this electrolytic content would be too low for a factorial satin dye by a factor of 20 to 1000. Suitable dyeing procedures for the purposes of this invention include, for example, the various processes of dyeing. exhaustion, such as dyed on the boat or on the < -Buy with winder or dyeing from long or short bath dyed in dyeing machines- by jet, dyed by procedure, -Batch with reduced pad or by a steam fixation procedure with overcall pad ada. Suitable dyeing processes for the purposes of this invention include tarnishing techniques, for example, ink jet printing and decal printing. The dyes that are used to dye the modified cellulose are generally ammonia in nature. Of particular convenience are textile dyes reactive to the fibers that are capable of reacting with hydroxyl groups, for example, cellulose, or arnmo and thiol groups, for example wool and silk, of synthetic polymers, such as polyesters. licks, or modified polymers, especially the aminated celluloses, to form a covalent bond. Suitable reactive components to the fibers on the textile dyes U include in particular sulfatoethylsulfonyl, vmiisulfonyl, chlor-ot pazimlo, fluorotpazinyl, and combinations of the same. Acid or direct dyes suitable for dyeing or printing the modified cellulose fiber according to the invention include, for example, diarrhea dyes, RSirius Light Fast dyes, Rftifanol dyes, RCotonerol dyes, RDuasyn dyes, such as, for example, C.í. Acid Black 27 (C.l. No. 26 31U), C.l. Black Pegida J5 (C.T. No. 26 320), O. L. ftzul Reído 113 (C.l. No. 26 360), C.l. Orange Direct 49 (C.l. No. 29,050), C.l. Orange Direct 69 (C.l. No, 29 055), C.r. Flrnarillo Directo 34 (C.l. No. 29 060), C.l. Red Direct 79 (C.T. No. 29,065), C.L. Direct Amendment 67 (C.l. No. 29,080), C.l. Cafe Directo 126 (C.T. No. 29,085), C.l. Ro o Directo 84 (C.l. No. 35 760), C.l. Red Direct B0 (C.l. No. 35 780), C.l. Red Direct 194 (C.l. No. 35 785), C. r. Red Direct 01 (C.l. No. 28 160), C.l. Direct Red 32 (C.l. No. 35 700), 0.1. Rzuí Direct 162 (C.T. No. 35 770), C.l. ftzui Directo 159 (C.l. No. 35 775), C.l. Negro Directo 162: 1 and C.l. Violeta Directo 9 (C.l. Mo. 27 885). unless stated otherwise, the parts and percentages in the Examples that follow are by weight. The molar masses of the starches that are used are usually based on an anhydrous glucose unit.

EXAMPLE 1 a) Preparation of starch ether: 162 g (1 rnol) of technically dry potato starch is added in a kneader to 500 rnl of water in which 26.4 g (0.66 mmol) of sodium hydroxide have been dissolved in advance. . Then, 130 g (0.6 mole) of epoxypropylnitrile-aluminum chloride is added as a 70% strength solution in water. The mixture is kneaded at 60 ° C for 4 hours, cooled to room temperature and adjusted with sulfuric acid.; > r? co to a pH of 6. The viscosity is 5.6 Pas at 5U ° C and from 19.6 Pas at 20 ° C. To characterize still the starch derivative, 5 viscous mass pairs are dissolved in 100 parts of water and rid of unconverted oxide and neutralization salts by means of a membrane desalting technique. The purified starch derivative is evaporated to dryness under reduced pressure. The degree of substitution is determined by means of a nitrogen analysis of the modified starch. The nitrogen content was 3.5% in the present case. The degree of substitution is calculated according to the following formulas: 162 + 151/14 x L ~% N] - P.M. r% Nl / 14 x P.M. 100 = [degree of substitution] The modified starch has a degree of substitution of 0.67 according to the above. b) The starch derivative thus obtained is incorporated into a fiber type viscose customary in the factories having a cellulose content of 8.9%, an alkali content of 5% and a viscosity at 30 ° C of 38 seconds of balls in descent as follows: 50 parts of modified starch are mixed with 436 parts of viscose of the fiber type. By shaking this preliminary mixture is integrated to 2,522 parts of vi fiber type thing. After the Laloza dosvolati, the spinning pulp is spun by the usual spinning process in the factories forming a barium containing sulfuric acid, sodium sulfate and zinc sulfate to form the fiber, the which is anger in acidic baths, it is cut, washed, its spinning is finished and it is damaged. 10 pairs of this dry viscous fiber are then mixed in a drying unit with LOO parts of water. The temperature is raised to 60 ° C and a total of 0.1 is delivered from a dye powder containing resistance electrolyte (predominantly sodium chloride) to 50% of the formula, known from DE-A-1 943 904, in a period of 30 minutes. After an additional period of 5 minutes for the circulation of the bath, the remaining, almost colorless, bath is discarded and the washing material is extracted and dried. The result obtained is a deep deep red dyeing that has very good properties of use in the use.

EXAMPLE 2 pairs of the modified viscose fiber are transferred as described in Example L to a dyeing apparatus and treated at a bath ratio of 10: 1 with an aqueous bath which, based on the weight of the dry fiber , includes 0..1 part of the reactive dye of the formula, known by the jeinplo 1 UB of KP-A-0 45 r * 15, in solution. The fiber is dyed at 60 ° C for 30 minutes. The dyeing thus produced is then treated by rinsing and soaping in a conventional manner. The obtained result is a deep red tint that has inconvenient properties of firmness in the use. 1 ) EXAMPLE 3 A io fiber viscose is mixed as described in Example 1 with a starch synthesized according to the following description: 200 g (1.2 moles) of corn starch are added in a 2 liter flask, equipped with an agitator. Descending movement, to 500 ml of water and 24 g (0.6 mmol) of sodium hydroxide. 113 g (0.4 mol) of sulfatoethyltrimethalammonium sulfate, dissolved in 200 ml of water, are then added to the mixture. The resulting mixture is stirred at 85 ° C for 6 hours, if necessary it is kept stirring by adding more water, cooled to room temperature and adjusted with sulfuric acid to a pH of 6. The starch ether has a degree of substitution of 0.3. By shaking the product is integrated into the viscose as described in Example i. Following the detour Latí Lizacion spinning the spinning paste is integrated by * common procedures in the factories of spinning the viscose to a bath containing sulfuric acid, sodium sulfate and zinc sulfate to form the fiber, which is stretched in bathrooms acids, it is cut, washed, its yarn is finished and dried. The screening thus produces a viscose fabric that can be further processed directly in a pad dyeing process. For this the fabric has applied at 25 ° C, by means of a scarf with alrnohailla, an aqueous solution of paint which, for every 1000 a is in volume, includes in the solution 20 parts of the dyeing of the formula known from Example 1 of EP-A-0 158 233, and 3 parts from a commercial nonionic wetting agent, with a bath catchment of 80%, based on the weight of the fiber. The fabric impregnated with the dyeing solution was rolled onto a handling roll, wrapped in plastic film, left for 4 hours at 40 to 50 ° C and then rinsed with hot and cold water, which may contain an agent commercial surfactant and if necessary subsequently rinsed once more with cold water and dried. The result obtained is a strong uniform yellow dyeing that has suitable properties of firmness, especially suitable properties of firmness against friction and light.

EXAMPLE 4 A viscose spun from the fiber type described in Example 1 is spun by the steps customary to the viscous process of the ti or fiber to form a fiber, which is reacted in a process of Exhaustion without salt or lcali added. For this purpose, 30 parts of viscose fiber are wound onto a reel and the yarn is treated in a yarn apparatus containing 450 parts, based on the weight of the fiber, a bath containing 0.6 part, on the basis of the initial weight of the genera, of a tet containing electrolyte (predo inantemen and sodium cioride) of the formula known by Example 1 of DE-A -2 840 380, and it is heated to 60 ° C, pumping the bath alternately inside and outside inside. After 60 minutes of this temperature the bath is discarded, the dyeing obtained is rinsed and washed under the usual conditions. The result obtained is a uniform yellow fiber that has the generally convenient properties of firmness of the reactive red,.

ADDITIONAL PREPARATION EXAMPLES 5 - 7 FOR MODIFIED ETERE5 STARCH In each case 162 g of potato Lrnidon 500 ml of water and 26.4 g of sodium hydroxide sirn Larrnente are added to Example L. This mixture is mixed in each case with the following modifiers and continues to be treated and analyzed in terms of its degree of substitution as in Example 1: ) Aminopropyl sulfone Lsul atoeti The formula HOjSO (Srado of substitution: 0.26 6) Chloride of 3-chloro-2-hydroxyroprot and Larnomo. Degree of substitution: 0.35. 7) Arninoetiisulfupic acid Degree of substitution: 0.31 Examples of dyeing with direct dyes EXAMPLE 8 Example 1 is repeated to obtain, by weaving, a textile fabric of viscose which can be further processed directly in a pad dyeing process. For this, the genre has applied to 25"C, by means of a scarf with pad, a dyeing solution in which, for every 1000 par-tees in volume, it includes 20 pairs of acid dyeing. The formul SO3NH4 / CuPc \ (S02NH2) 3 (PC- ft aiociaruna) (C.l. AzuL Directo 199) and 3 parts of a non-commercial commercial fermenting agent, with a bath catchment of 80%, based on the weight of the fiber. The dyeing solution has been adjusted in advance to pH 5 with acetic acid. The fabric impregnated with the dyeing solution is then treated with steam for 2 minutes. The dyeing thus produced is then treated by rinsing and soaping in a conventional manner. The result obtained is a strong turquoise dyeing that has suitable properties very suitable for firmness.

L3 EXAMPLE 9 A viscose modified in Example 3 is made by means of a 1 or 2 roll to guide and lay the fabric under an ink jet head and is stamped with aqueous solutions of direct dyes. To obtain polychrome prints, < A 4-color print is carried out with the primary colors of the substratum of the colors (yellow, cyan, magenta and black). The dye that was used was C.l. fizul 199, the yellow dye that was used was C.l. Direct Yellow 34 (C.l. No. 29060), the magenta dye that was used was C.l. Direct Red 79 (C.l. No. 29065) and the black component that was used was C.l. Direct Black 162: 1. The press works according to the drop procedure as required and the small ink drop is thermally created (bubble jet process). The patterned fabric is subsequently treated with steam for 2 minutes and then rinsed and suitably soaped. The resulting pattern has suitable properties of firmness.

EXAMPLE 10 Example 6 is repeated, the viscose is treated and the fiber is woven. The viscose modified in this way is applied to a rotating roller. A continuous-flow printhead then produces a continuous stream of small drops of direct dye which, controlled by computer, reach the viscose or are deflected. To obtain polychrome prints, a 4-color print is carried out with the primary color of the mixed subtraction of the colors (yellow, cyan, magenta and black). The dye that is used is C.l. Blue 199, the yellow dye used is C.l. Amarillo Directo 34, the magenta dye used e <; - C.l. Red Direct 01 and the black component used is C.r. Black Acid 35. The stamped fabric is then treated with steam-for 2 minutes and then rinsed and soaped conventionally. The resulting pattern has suitable properties of firmness.

EXAMPLE 11 A viscose fiber produced in accordance with Example 1 is converted to a woven fabric following the additional treatment by the usual process steps for the viscose fiber and is pulled. For this, the fabric is guided by means of two rollers to guide and tension the fabric underneath the ink jet head and is stamped with aqueous solutions of direct dyes. The press works according to the drop procedure as required and the small ink droplet is generated by the piezoelectric principle. To obtain * polychrome prints, a 4-color print is carried out with the primary colors of the subtraction mixture and the colors (yellow, cyan, magenta and black). In the dye that is used is C.l. Blue 199, the yellow dye used is C.l. Direct Yellow 6 ?, The magenta dye used is C.r ,, Direct Red Bl and the black component used is C.T. Black Acid 27. The patterned fabric is subsequently treated with steam for 2 minutes and then rinsed and suitably soaped. The resulting embossing has suitable properties of firmness. ADDITIONAL EXAMPLES Example 1 is repeated with similar results using the dyes listed below: C.l. Violeta Directo 9 C.l. No. 27885 C.l. Direct Cafe 126 C.l. No. 29085 C.l. Anaranjade Directo 69 C.l. No. 29055 C.l. Direct Blue 113 C.l. No. 26360 C.l. Direct blue 40 C.l. No. 62125

Claims (7)

NOVELTY OF THE INVENTION CLAIMS

1. - Reagent regenerated cellulose, which is obtained by adding one or more etherified starches with C2-C5 alkylarynols that can be substituted additionally in the alkyl portion by 1 to 2 additional hydroxyl and rnetoxy groups and with the group arnino is a secondary amino, tertiary or substituted quaternary ammonium group of Ci -C "or -0- (CH2) x -SO2 - (OH2) and -NR2 or -0- (CH2)? -SO2 - (OH2) and -NR + 3fl ", where x and y are each 2 or 3, the radicals R are identical, and each is hydrogen, methyl or ethyl, and A- is an anion, and has an grade of substition between 0.1 and 3 in a concentration of 1 to 2U% by weight, calculated as dry weight and based on the cellulose content of the spinning pulp, to a viscose paste, an alkali cellulose or a fiber cellulose solution of the fiber from the same

2. The animated regenerated cellulose fiber according to claim 1, further characterized in that the ether groups of the etherified starch are -0- (CH2) ? - NR2, -O-CH2-CHOH-CH2-NR2, -0- (CH2)? - + NR3A- O ~ 0 -CH2 -CH0H-CH2-NR + 3A- 3.- Animated regenerated cellulose fiber according to claim 1 or 2, further characterized in that the ether groups of the etherified starch are -O-CH2-CH2- '"•' * NH2, -0-CH2-CH0H-CH2 N (CH3) 3+ -O-CH2CH2 - + (CH3) 3 - 4.- The regenerated cellulose fiber aminated by at least one Je rei indications 1 to 3, characterized. Also, because the product (s) has been or has been added in a concentration of 1 to 1% by weight, calculated as dry weight, based on the cellulose content of the product. paste of h 11 ar .. 5.- Or procedure to produce a dyed or stamped textile material composed of regenerated cellulose fiber, which comprises converting by special treatment the reinforced regenerated cellulose fiber of one or more of the claims 1 4 to a woven or knitted fabric and dyeing or stamping said fabric with one or more reactive dyes in the absence of additional salt or alkali electrolysis or with an acid or direct dye. 6. The process according to claim 5, further characterized in that the extil material is dyed or stamped at a pH between 4.5 and 8.5. 7. An etherified acid with one or more radicals alkylated or O2-C5 which can be substituted in addition in the alkyl portion by 2 additional hydroxyl and methoxy groups and whose arnmo group is a primary or secondary ammonium or ammonium group , tertiary or quaternary substituted with Ci-C alkyl "or with -0- (CH2)? -SO2 - (CH2) and -NR2 or -0- (CH2)? - SO2- (CH2) -NR + A-, where x and y are each 2 or 3, the radicals R are identical or different and each is hydrogen , ?or methyl or ethyl, and A- is an anion, preferably chloride or sulfate, and having a degree of subsumption of between 3 and 3, preferably 0.11 and 2, with the exception of an etherified starch with a group f -hi drox íropro larnonio. p.- The starch in accordance with claim 7, further characterized in that the ether groups are -0- (CH2)? -NR2, -O-CH2-CHOH-CH2-NR2 or -0-ÍCH2)? - + NR3A-. 9. The etherified starch according to claim 7 or 8, further characterized in that the ether groups "ion 0-CH 2 -CH 2 -NH 2 or -0-CH 2 -CH 2 * + N (CH 3 '3 -10. E" The etherified starch of at least one of claims 7 to 9, having a degree of polymerization of between 100 and 1000, preferably between 100 and 400, units of arnine glucose 11.- A process for preparing an etherified starch according to one or more of claims 7 to 10, which comprises reacting a starch at a pH of between 9 and 14, preferably between 9.5 and 13, with a C2-C5 alkylamino having substituents that are reagents to OH groups 12. The process according to claim 11, further characterized in that the C2-C5 alkylammer has substitution of a-chloro-β-hydroxyl, 1- (sul fatoet 1 lsul phon) or sulfatoethyl 1

3. The process according to claim 11 or 12, further characterized in that the It is reacted with glycidi ltp sulfate rnet 11 ammonium sulfate or sulphonate atomethymethylmethanolamine sulfate, alkylamine sulfate sulfate, arnmopropiis sulphonate, fatoetiol sulfate or 3-chloro-2-hydroxyl chloride sulfate. ilarnonio.