DE29520890U1 - Highly substituted starches and regenerated cellulose aminated with highly substituted starches - Google Patents

Description

HOECHST AKTIENGESELLSCHAFT HOE 95/F 123 G Dr.HU/sch

Description

Highly substituted starches and regenerated cellulose aminated with highly substituted starches

In terms of their dyeing behavior, viscose fibers are essentially the same as cotton fibers. With the current state of technology, alkali-donating agents and electrolytes are necessary for dyeing cellulosic natural or regenerated fibers in order to achieve satisfactory fixation results with reactive dyes. However, for ecologically improved dyeing processes, these necessary additives represent unacceptable environmental pollution. Regenerated fibers based on cellulose, which have previously been converted into modifications with a high affinity for dyes, i.e. dyeable without salt and alkali, without additional process steps, will therefore be of increasing importance in the future. Fibers modified in this way resemble animal fibers such as wool or silk in their chemical behavior and can be dyed within certain limits under neutral conditions with anionic dyes without further salt or alkali additives.

A special area of application in this context will be mixed fabrics, such as polyester/modified viscose, which can then be dyed in one bath.

Modifications of viscose have already been described in the literature. DE-A-1 948 487 describes a process for producing viscose fibers with new dyeing properties. During production, polyamine amides are used, which not only significantly disrupt the native character of the fiber, but also result in an insufficient level of fastness of the subsequent dyeing.

* * · · I ti

DE-A-1 469 062 also deals with "aminalized fibers". The additives are aminoethyl and diethylaminoethyl celluloses in high concentrations, and the coloring is done exclusively with acid dyes. The disadvantage of this process is that the additives first have to be synthesized and isolated, which is a laborious process, and are also very expensive.

The object of the present invention was to produce a viscose fiber that is significantly more affine to dyeing with both reactive and direct dyes and also differs positively from standard fibers in other desired usage properties.

This task is surprisingly solved by adding starch derivatives highly substituted with amino group-containing compounds to a viscose mass, cellulose solution or alkali cellulose and subsequent spinning.

The present invention relates to aminated regenerated cellulose fibers, produced by adding one or more starches etherified with C ₂ -C ₅ alkylamines, which may be substituted in the alkyl radical by 1 to 2 further hydroxy and methoxy groups and whose amino group is a primary or secondary, tertiary or quaternary amino or ammonium group substituted by C 1 -C 4 alkyl groups, with a degree of substitution between 0.1 and 3, preferably 0.11 to 2, in particular 0.2 to 1, to a viscose mass, alkali cellulose or cellulose solution and spinning fibers therefrom.

The etherified starch derivatives have a degree of substitution between 0.1 and 3. A degree of substitution of 3 means that each of the three free OH groups in each glucose unit is etherified. A degree of substitution of 0.1 means that statistically one OH group is etherified in every tenth glucose unit.

Starches with a degree of substitution of about 0.05 are known per se (Houben-Weyl, 1987, Vol. E 20, Part 3, pp. 2135-2151), but those with a degree of substitution of 0.1 and higher have not yet been described.

The present invention therefore also relates to starch derivatives etherified with alkylamino groups as described above with a degree of substitution between 0.1 and 3, preferably 0.11 to 2.

Preferred in the sense of the present invention are said starch ethers whose ether group has the formula -O-(CH ₂ ) _X -NR ₂ , -O-CH ₂ -CHOH-CH ₂ -NR ₂ ,

-O-(CH ₂ ) _x -SO ₂ -(CH ₂ ) _y -NR ₂ , -O-(CH ₂ ) _x -SO ₂ -(CH ₂ ) _y -NR ^e ₃ A ^e , -0-(CH ₂ J _x - ⁰ NR ₃ A ⁹ or -O-CH ₂ -CHOH-CH ₂ -NR® ₃ A ^e , where &khgr; and y is the number 2 or 3, R is the same or different and is hydrogen, methyl or ethyl and A is an anion, for example chloride or sulfate. Particularly preferred are those starch ethers whose ether group has the formula -O-CH ₂ CH ₂ -NH ₂ , -O-CH ₂ -CHOH, CH ₂ -N®(CH ₃ ) ₃ or -O-CH ₂ CH ₂ -N ^e (CH ₃ ) ₃ .

The starch ethers according to the invention with the said high degree of substitution are water-flowing to highly viscous masses of 1 to 30 Pas (about 20% by weight aqueous solution) which can be added to the spinning mass, cellulose solution or alkaline cellulose without further processing during the production of the regenerated cellulose fibers.

The degree of polymerization of the starch ethers according to the invention is advantageously between 100 and 1000, preferably 100 and 400, anhydroglucose units. With degrees of polymerization less than 100, there is a risk that the starch ethers will be washed out of the fiber after spinning.

The starch ethers according to the invention are prepared by reacting any starch, for example potato starch, corn starch or wheat starch, with a C ₂ -C ₅ alkylamine which has an OH-reactive

Substituents, for example a &sgr;-chloro-ß-hydroxy, a 1,2-epoxy, a 1-{sulfatoethylsulfone) or a sulfatoethyl substitution, at a pH of 9 to 14, preferably 9.5 to 13. The reaction temperature is advantageously 40 to 100 ⁰ C. The C ₂ -C ₅ alkylamine is reacted, depending on the desired degree of substitution of the starch, in a molar ratio of alkylamine:an anhydroglucose unit of 0.1:1 to advantageously 4:1.

Examples of the above-mentioned alkylamines used to modify starch are glycidyltrimethylammonium sulfate or chloride, sulfatoethyltrimethylammonium sulfate or chloride, aminoethyl sulfate, 3-chloro-2-hydroxypropyltrimethylammonium sulfate or chloride and aminopropylsulfatoethylsulfone.

The starch ethers used to produce the aminated cellulose regenerated fibers can be stirred directly into the spinning mass in a good distribution due to their water solubility, preferably in an aqueous medium and if necessary with the help of emulsifiers, and show good compatibility with the viscose. The flowable starch ether is added in an amount of 1 to 20%, preferably 1 to 12% by weight, calculated as dry matter, based on the cellulose content of the spinning mass, before precipitation and shaping. The filterability of the viscose shows no deterioration in comparison with samples without additives, so that no blockage of the spinneret is observed during the spinning process. The shaping of the viscose is carried out using conventional and known methods, such as with spinnerets, a subsequent precipitation bath, and if necessary further post-treatment baths.

Another way to produce aminated cellulose regenerated fibers is to stir the starch derivatives mentioned into the alkali cellulose, a precursor to viscose. After xanthogenation and pressing into an acidic precipitation bath, this process is also used

An aminated viscose fibre is obtained in this way.

The fibers obtained using the methods described can be dyed after processing into fabrics and knitted fabrics using various processes, such as exhaust, padding and modern printing processes such as ink-jet processes, without the use of salt or alkali. The textile modified fiber material can be in all processing states, such as yarn, flake, combed topping and piece goods (fabric).

The dyeing of the modified textile fiber materials is carried out analogously to known dyeing methods and printing processes for dyeing and printing fiber materials with water-soluble textile dyes and using the temperature ranges and usual dye quantities known to be used for this purpose, but with the exception that for the dye baths, padding processes, printing pastes and ink-jet formulations, the addition of alkaline compounds, as are usually used to fix fiber-reactive dyes, is not necessary and the usual addition of electrolyte salts can also be dispensed with. Therefore, dyeing or printing is carried out at a pH value between 4.5 and 8.5 and, when using commercially available reactive or direct dyes, in the presence of an electrolyte salt content of 0.01 to 0.5% by weight, based on the dye solution. Without the amination of the cellulose fibers according to the invention, this electrolyte content would be 20 to 1000 times too low for a successful dyeing process.

Examples of dyeing processes include the various exhaust processes, such as dyeing on the jigger and on the winch or dyeing from long and short liquor, dyeing in jet dyeing machines, dyeing using the pad cold pad process or using a pad hot steam fixing process. The dyeing processes also include printing techniques, including ink-jet printing and transfer printing.

The dyes used to dye the modified cellulose are generally anionic in nature. Particularly suitable are the fiber-reactive textile dyes that can react with hydroxyl groups, for example from cellulose, or amino and thiol groups, for example from wool and silk, from synthetic polymers such as polyamides, or modified polymers, namely aminated celluloses, and are able to form a covalent bond. The fiber-reactive components of the textile dyes are particularly sulfatoethylsulfonyl, vinylsulfonyl, chlorotriazinyl, fluorotriazinyl, and combinations of these "anchor systems".

Suitable acid or direct dyes for dyeing or printing cellulose fibers modified according to the invention are, for example, the diamine dyes, ®Sirius lightfast dyes, ®Alphanol dyes, ®Cotonerol dyes and ®Duasyn dyes, such as C.I. Acid Black 27 (C.I. No. 26 310), C.I. Acid Black 35 (Cl. Mo. 26 320), C.I. Acid Blue 113 (Cl. No. 26 360), C.I. Direct Orange 49 (Cl. No. 29 050), C.I. Direct Orange 69 (C.I. No. 29 055), Cl. Direct Yellow 34 (C.I. No. 29 060), C.I. Direct Red 79 (C.I. No. 29 065), C.I. Direct Yellow 67 (Cl. No. 29 080), C.I. Direct Brown 126 (Cl. No. 29 085), C.I. Direct Red 84 (C.I. No. 35 760), C.I. Direct Red 80 (C.I. No. 35 780), C.I. Direct Red 194 (C.I. No. 35 785), Cl. Direct Red 81 (C.I. No. 28 160), C.I. Direct Red 32 (Cl. No. 35 790), C.I. Direct Blue 162 (C.I. No. 35 770), Cl. Direct Blue 159 (C.I. No. 35 775), C.I. Direct Black 162:1 and Cl. Direct Violet 9 (C.I. No. 27 885).

Unless otherwise stated, the parts and percentages given in the examples below are by weight.

The molecular weights of the starches used are usually based on one anhydroglucose unit.
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example 1

a) Production of starch ether:

162 g (1 mol) of potato starch, technically dry, are added to a kneader in 500 ml of water in which 26.4 g (0.66 mol) of caustic soda have previously been dissolved. 130 g (0.6 mol) of 2,3-epoxypropyltrimethylammonium chloride are then added to this mixture as a 70% solution in water. The mixture is kneaded for 4 hours at 60 ⁰ C, cooled to room temperature and adjusted to pH 6 with sulfuric acid. The viscosity is 5.6 Pas at 50 ⁰ C and 19.6 Pas at 20 ⁰ C.

To further characterize the starch derivative, 5 parts of the viscous mass are dissolved in 100 parts of water and freed of unreacted epoxy and neutralization salts using a membrane desalination technique. The purified starch derivative is evaporated to dryness in a vacuum. The degree of substitution is determined by determining the nitrogen content of the modified starch. In the present case, the nitrogen content was 3.5%. The degree of substitution is calculated using the following formulas:

162 + 151/14 x [%N] = MW

[%N]/14 &khgr; MW : 100 = degree of substitution

The modified starch therefore has a degree of substitution of 0.67.

b) The starch derivative thus obtained is incorporated into a standard spinning viscose with a cellulose content of 8.9%, an alkali content of 5% and a viscosity at 30 ^° C of 38 falling ball seconds as follows: 50 parts of the modified starch are mixed with 436 parts of spinning viscose. This premix is stirred into 2522 parts of spinning viscose.

After degassing, the spinning mass is processed according to standard

Viscose spinning process: spun into fibers in a bath containing sulfuric acid, sodium and zinc sulfate, stretched in acid baths, cut, washed, prepared and dried.

10

c) 10 parts of these dry viscose fibres are then mixed with 100 parts of water in a dyeing apparatus. The mixture is heated to ^60° C and a total of 0.1 parts of a 50% electrolyte-containing (predominantly sodium chloride-containing) dye powder of the formula known from DE-A-1 943 904 is added.

_NaO3SO

_NaO3S

NaO ₅ S

SO ₃ Na

20

over a period of 30 minutes. After a follow-up time of 5 minutes, the almost colorless residual liquor is drained off and the material is washed out and dried using conventional methods. A strong deep red dye with very good fastness to use is obtained.

Example 2

30

Parts of the viscose fibers modified according to Example 1 are transferred to a dyeing machine and treated in a liquor ratio of 1:10 with an aqueous liquor containing - based on the weight of the dry goods - 0.1 part of a reactive dye of the formula, known from EP-A-0 457 715, Example 106,

The fibre is dyed for 30 minutes at 60 ⁰ C. The dyeing thus produced is then further treated by rinsing and soaping in the usual way. A deep red dyeing with very good fastness properties is obtained.

Example 3

A starch synthesized according to the following instructions is mixed into a spinning viscose as described in Example 1: 200 g (1.2 mol) of corn starch are added to 500 ml of water and 24 g (0.6 mol) of caustic soda in a 2 l flask with a downward-moving stirrer. 113 g (0.4 mol) of sulfatoethyl-trimethyl-ammonium sulfate, dissolved in 300 ml of water, are then added to this mixture. The mixture is stirred for 6 hours at 85 ^° C, kept stirrable by adding more water if necessary, cooled to room temperature and adjusted to pH 6 with sulfuric acid. The starch ether has a degree of substitution of 0.3.

The product is stirred into the viscose as described in Example 1. After degassing, the spinning mass is spun into fibers in a bath containing sulfuric acid, sodium and zinc sulfate using standard viscose spinning processes, stretched in acidic baths, cut, washed, prepared and dried.

After weaving, a textile viscose fabric is obtained that can be further processed directly in a dyeing process using the padding method. For this purpose, an aqueous dye solution containing 20 parts of the dye of the formula

_NaO3S

_OCH3

OSO ₃ Na

known from EP-AO 158 233, Example 1 and 3 parts of a commercially available non-ionic wetting agent dissolved, applied to the fabric using a padder with a liquor pick-up of 80%, based on the weight of the fabric, at 25 ^° C. The fabric padded with the dye solution is wound onto a pad, wrapped in plastic film and left to stand for 4 hours at 40 to 50 ^° C and then rinsed with cold and hot water, which may optionally contain a commercially available surfactant, and then optionally again with cold water and dried. A strong, evenly colored yellow dye is obtained which has good general fastness properties, in particular good rubbing and light fastness properties.

Example 4

A modified spinning viscose as described in Example 1 is spun into a fibre using the usual process steps for spinning viscose, which is then reactively dyed in an exhaust process without the addition of salt or alkali. To do this, 30 parts of the viscose fibre are wound onto a cross-wound bobbin and the yarn is treated in a yarn dyeing machine which contains 450 parts, based on the weight of the product, of a liquor which contains 0.6 parts, based on the initial weight of the product, of a

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electrolyte-containing dye (mainly sodium chloride-containing) of the general formula, known from DE-A-2 840 380, i3example 1

SO ₃ Na

_NaO3S

HN-F

SO ₃ Na^CONH ₂

and heated to 60 ⁰ C, whereby the liquor is pumped alternately from the inside to the outside and from the outside to the inside. After 60 minutes at this temperature, the liquor is drained off and the dyeing obtained is rinsed and washed under the usual conditions. A level yellow dyed fiber with the generally good fastness properties for reactive dyes is obtained.

Further preparation examples 5 - 7 for modified starch ethers:

Analogous to Example 1, 162 g of potato starch are added to 500 ml of water and 26.4 g of caustic soda. The following modifiers are added to this mixture and processed as in Example 1 and the degree of substitution is determined:

5) Aminopropylsulfatoethylsulfone of the formula

HO ₃ SO-

6)

Degree of substitution: 0.26.

3-Chloro-2-hydroxypropyltrimethylammonium chloride Degree of substitution: 0.35

7) Aminoethylsulphuric acid
Degree of substitution: 0.31

Examples of dyeing with direct dyes:
5

Example 8

The procedure is as described in Example 1 and after weaving, a textile viscose fabric is obtained which can be further processed directly in a dyeing process using the padding method. For this purpose, a dye solution containing 20 parts of the acid dye of the formula in 1000 parts by volume is used.

^SO ₅ NH ₄

Ä 2 3

(Pc = phthalocyanine)

(Cl. Direct Blue 199) and 3 parts of a commercially available non-ionic wetting agent dissolved in water, is applied to the fabric using a padder with a liquor absorption of 80%, based on the weight of the fabric, at 25 ^° C. The dye solution was previously adjusted to a pH value of 5 with acetic acid. The fabric padded with the dye solution is then steamed for 2 minutes. The dyeing thus produced is further treated by rinsing and soaping in the usual way. The result is a strong turquoise dyeing with very good general fastness properties.

Example 9

A viscose modified as in Example 3 is passed under an ink-jet printing unit using one or two rollers to guide and tension the fabric and is printed with aqueous solutions of direct dyes.

To obtain multi-colored prints, a four-color print is carried out with the basic colors for the subtractive color mixture (yellow, cyan, magenta and black). C.I. Direct Blue 199 was used as the cyan dye, C.I. Direct Yellow 34 (Cl. No. 29060) as the yellow dye, C.I. Direct Red 79 (CI. No. 29065) as the magenta dye and C.I. Direct Black 162:1 as the black component. The printer works according to the "drop on demand" process and the ink drop is generated thermally (bubble jet process). The printed fabric is then steamed for 2 minutes and then rinsed and soaped in the usual way. The resulting print has good general fastness properties.

Example 10

The process is carried out as in example 6, and the fabric is worked up and woven. A viscose modified in this way is applied to a rotating roller. A print head working on the basis of the "continuous flow" technique now continuously releases drops of direct dye, which reach the viscose or are deflected, depending on the control by a computer. In order to obtain multi-coloured prints, a four-colour print is carried out with the basic colours for the subtractive colour mixture (yellow, cyan, magenta and black). C.I. Blue 199 is used as the cyan dye, C.I. Direct Yellow 34 as the yellow dye, Cl. Direct Red 81 as the magenta dye and C.I. Acid Black 35 as the black component. The printed fabric is then steamed for 2 minutes and then rinsed and soaped in the usual way. The resulting print has good general fastness properties.

Example 11

A viscose fibre produced according to the instructions in Example 1 is, after further processing, converted into a fabric and dyed according to the usual process steps for viscose fibres.

For this purpose, the fabric is passed under an inkjet printing unit using two rollers to guide and tension the fabric and is printed with aqueous solutions of direct dyes. The printer works according to the "drop on demand" process and the ink drop is generated by a pressure surge in the nozzle (piezzo process). In order to obtain multi-colored prints, a four-color print is carried out with the basic colors for the subtractive color mixture (yellow, cyan, magenta and black). Cl. Direct Blue 199 is used as the cyan dye, Cl. Direct Yellow 67 as the yellow dye, Cl. Direct Red 81 as the magenta dye and Cl. Acid Black 27 as the black component. The printed fabric is then steamed for 2 minutes and then rinsed and soaped in the usual way. The resulting print has good general fastness properties.

Further examples
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Proceed as described in Example 1 and dye the modified viscose fiber using the dyes listed below and obtain similarly good results:

Cl. Direct Violet 9 C.I. Mo. 27885

Cl. Direct Brown 126 Cl. Mo. 29085

Cl. Direct Orange 69 C.I. Mo. 29055

Cl. Acid Blue 113 C.I. No. 26360

C.I. Acid Blue 40 C.I. No. 62125 25

Claims (1)

15 HOE 95/F 123 G Protection claims: 1) Aminated regenerated cellulose fibers, produced by adding to a viscose mass, alkali cellulose or cellulose solution one or more starch(s) etherified with C ₂ -C ₅ alkylamines, which may be substituted in the alkyl radical by 1 to 2 further hydroxy and methoxy groups and whose amino group is a primary or secondary, tertiary or quaternary amino or ammonium group substituted by C 1 -C 4 alkyl groups, with a degree of substitution between 0.1 and 3, and spinning fibers therefrom. 2) Aminated regenerated cellulose fibers according to claim 1, characterized in that the ether groups of the etherified starch are -O-(CH ₂ J _x -NR ₂ , -O-CH ₂ -CHOH-CH ₂ -NR ₂ , -O-(CH ₂ ) _x - ^e NR ₃ A ^e , -O-(CH ₂ ) _x -SO ₂ -(CH ₂ ) _y -NR ₂ ,-O-(CH ₂ ) _x -SO ₂ -(CH ₂ ) _y -NR® ₃ A ^e or -O-CH ₂ -CHOH-Ch ₂ -NR ⁰ SA ⁶ , where x and y are the number 2 or 3, R is the same or different and is hydrogen, methyl or ethyl and A is an anion. 3) Aminated regenerated cellulose fibers according to claim 1 or 2, characterized in that the ether groups of the etherified starch are -O-CH ₂ CH ₂ -NH ₂ , -O-CH ₂ -CHOH-CH ₂ -N(CH ₃ )3 ⁺ or -O-CH ₂ CH ₂ - ⁰ N(CH ₃ J ₃ ). 4) Aminated regenerated cellulose fibers according to at least one of claims 1 to 3, characterized in that the etherified starch(s) has/have been added in a concentration of 1 to 20% by weight, preferably 1 to 12% by weight, calculated as dry weight, based on the cellulose content of the spinning mass. 5) A compound containing one or more C ₂ -C ₅ alkylamino radicals which may be substituted in the alkyl radical by 1 to 2 further hydroxy groups or methoxy groups 16 HOE 95/F 123 G may be substituted and whose amino group is a primary or secondary, tertiary or quaternary amino or ammonium group substituted with Cj-C^-alkyl groups, with a degree of substitution between 0.1 and 3, preferably 0.11 and 2, etherified starch. 5 6) Etherified starch according to claim 5, characterized in that the ether groups are -O-(CH ₂ J _x -NR ₂ , -O-CH ₂ -CHOH-CH ₂ -NR ₂ , -O-(CH ₂ ) _x -SO ₂ -(CH ₂ ) _y -NR ₂ , -O-(CH ₂ ) _x -SO ₂ -(CH ₂ ) _y -NR ^e ₃ A ^e , -O-(CH ₂ ) _x -®NR ₃ A ^e or -O-CH ₂ -CHOH-CH ₂ -NR® ₃ A ^e , where x and y are the number 2 or 3, R is the same or different and is hydrogen, methyl or ethyl and A is an anion, preferably chloride or sulfate. 7) Etherified starch according to claim 5 or 6, characterized in that the ether groups are -O-CH ₂ CH ₂ -NH ₂ , -O-CH ₂ -CHOH-CH ₂ - ⁰ N(CH ₃ J ₃ or -O-CH ₂ CH ₂ - ⁰ N(CHg) ₃ . 9) Etherified starch according to at least one of claims 5 to 7, characterized in that the degree of polymerization is between 100 and 1000, preferably between 100 and 400, anhydroglucose units.