Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
  • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
  • D01F2/08—Composition of the spinning solution or the bath
  • D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either

Definitions

• a process for the manufacture of viscose fibres with improved dyeing properties. -In this process a polyamine-amide from (a) a higher unsaturated fatty acid or its dimer or polymer and (b) a polyalkylene-polyamine and a further reaction product of (c) a polyepoxide compound and (d) a stoichiometric excess of a polyalkylenepolyamine are incorporated into the viscose spinning solution in a finely divided form from which spinning solution the viscose being thereafter precipitated and shaped.
• the fibres obtained show a good receptivity for dyestuffs suitable for dyeing cellulose materials and also for acid wool dyestuffs and dispersion dyestuffs.
• the present invention relates to a process for the manufacture of viscose fibres having novel dyeing properties.
• a process for the manufacture of viscose fibres which comprises adding to the viscose spinning solution before precipitation of a polyamide-amide derived from (a) an unsaturated fatty acid with at least 12 carbon atoms or a dimer or polymer thereof and, (b) a polyalkylene-polyamine, and a further reaction product of (c) a polyepoxide compound and (d) a stoichiometric excess of a polyalkylene-polyamine, the additives being in finely divided form and added in an amount totalling 1 to 20%, preferably 1 to 12% by weight relative to the cellulose content in the spinning solution.
• the nitrogen-containing additives employed in the process of this invention are known compounds, which can be incorporated into the viscose spinning solution in an aqueous medium, appropriately, with the aid of emulsifiers; they have good compatibility with the viscose.
• aliphatic, unsaturated monocarboxylic acids with at least are also suitable.
• the unsaturated fatty acids can also be used mixed with their dimerized, or polymerized deriva tvies, or the dimers or polymers may be used instead of the monomers.
• the polymerization of the acids probably takes place by a Diels-Alder mechanism, in that conjugated and, therefore, reactive carbon-carbon double bonds are produced in the unsaturated fatty acids by a partial or complete isomerization, these double bonds then completing the reaction to give a mixture of dimeric and higher polymeric fatty acids.
• oleic acid for example, it can only react if another compound having at least two conjugated double bonds is present.
• Aliphatic polyamines with at least two primary or secondary amine groups such as ethylenediamine, diethylenetiamine and triethylenetetramine, serve as component
• ethylenediamine, diethylenetiamine and triethylenetetramine serve as component
• Suitable polyepoxides which may be used include the polyglycidyl ethers such as those accessible by etherification of a dihydric alcohol or diphenol with epichlorohydrin in the presence of alkali.
• the epoxides which are obtained by reaction of bis(p-hydroxyphenyl)-dimethylmethane Bisphenol A) with epichlorohydrin should be particularly mentioned. Reaction of these products with the polyamines (d) then yields the second additive.
• the polyamines (d) may be the same or similar to the amines which have been mentioned for component (b).
• the adduct of (c) and (d) contains no further free epoxide groups since a stoichiometric excess of amine is always used.
• the amounts of the components (a) to (d) which are reacted can vary within wide limits.
• the amides containing amine groups may, for example, contain 40 to 80% by weight of fatty acid or dimerized or polymerized fatty acid and '60 to 20% by weight of polyamine whilst the epoxide-amine compound is suitably derived from 25 to 40% by weight of an epoxide compound and 75 to 60% by weight of polyamine.
• the additives (a) are added 90 to 10% by weight being a polyamine-amide derived from (a) and (b) and 10 to 90% by weight being a reaction product of (c) and (d).
• reaction products may contain furthed additives, such as solvents and additional reagents such as epoxides and phenols.
• the product of (a) and (b), mixed with a. product of (c) and (d), are suitably introduced in an aqueous medium into the viscose spinning solution.
• an aqueous medium can be used which contains emulsifiers and/or organic solvents.
• the emulsifiers used can be anionic or cationic, but are preferably non-ionic. Suitable non-ionic emulsifiers include the addition products of 4 to 12 mols of ethylene oxide to long chain amines or alcohols with 12 to 24 carbon atoms or to alkylphenols with 10 to 18 carbon atoms.
• the emulsifiers are generally employed in amounts of between 1 and 20%, preferably between 1 and 5% by weight relative to the cellulose.
• the compounds and preparations intended for the manufacture of the viscose with novel dyeing properties can now be stirred directly in finely dividedform into the spinning solution.
• the filtratability of the viscose is generally not adversely affected by the presence of the additives, so that during the spinning process blocking of sieven mounted in front of the spinning nozzle arising from the presence of such additives, does not occur and a homogeneous filament material can be manufactured without fluctuations in gauge.
• the shaping of the viscose may be carried out in known maner, e.g. through spinnerets into a precipitation bath (e.g. a Muller bath) with optional post-treatment in further baths.
• the metal-containing dyestuffs such as 1:2-chromium or cobalt complex dyestuffs, the dyestulf molecule of which can contain free acid groups conferring solubility in water, or 1:1 metal complex dyestuffs.
• the dispersion'dyestuffs azo and anthraquinone dyestuffs should particularly be mentioned.
• the cellulose material manufactured according to this invention behaves particularly well in a mixture with, for example, untreated cellulosic fibres.
• a dyestuff mixture of a direct dyestuff and wool dyestuff applied from a single dyebath, dyeing effects and color patterns which are determined by the fibre distribution (for example strips of any desired width and any desired spacing) in the mixed fabric.
• the direct dyestuff dyes the entire fabric whilst the wool dyestutf only dyes the fibres in the fabric which has been manufactured according to the invention (differential dying).
• Tone-in-tone dyeings of fibre mixtures of the fibre material according to the invention and wool/polyamides or polyester fibre material can be obtained using wool or dispersion dyestutf.
• the dyeing of the material may be carried out in the usual manner for these dyestuffs, for example, according to the padding process or the exhaustion process at an elevated temperature.
• the essential advantage of the cellulose material manufactured according to this invention resides in the fact it remains cellulose like and, nevertheless, possesses the novel dyeing properties described. It thus differs from the so-called animalized cellulosic fibres which are obtained from viscose spinning composition into which large amounts of nitrogen-containing substances are incorporated. These animalized cellulosic fibres have partially lost the dyeing properties of cellulose and in this respect behave more like wool. a g
• EXAMPLE I 5 g. of the preparation A described below are emulsified with 5 g. of an addition product of 8 mols of ethylene oxide to 1 mol of p-tert.octylphenol, filtered and stirred into 983 g. of viscos g. of cellulose). The viscose is spun in the usual manner with the aid of a precipitation bath containing sulphuric acid to give long fibres. The fibres are subsequently washed in after-treatment baths (for example water desulphurized (for example with dilute aqueous solutions of sodium sulphide. and sodium hydroxide) washed and brightened.
• after-treatment baths for example water desulphurized (for example with dilute aqueous solutions of sodium sulphide. and sodium hydroxide) washed and brightened.
• Preparation A consists of 28.6 parts of a Component I and 71.4 parts of'a Component II.
• Component I is manufactured as follows: A reaction mixture of 48.2 parts of diethylenetriamine, 34.6 parts of bisphenol A and 17.2 parts of a bisphenol A-epichlorohydrin resin with 182 to 191 epoxide equivalents per kg. of resin is reacted for about 5 hours at 200 C., with the'volatile constituents being distilled ofi towards the end of the reaction by -applying a water pump vacuum.
• Component II is manufactured as follows: A mixture of 40 parts oftall oil fatty acid and 13.8 parts of dimerised fatty acids is heated to C. whilst stirring and is mixed with 34 parts of triethylenetetramine at this temperature. The temperature is then raised to 200 C. and is kept for 3 hours at this value, with a water pump vacuum being applied in the last hour.
• the resulting polyamine-amide is then further mixed with 17.2 parts of xylene.
• the cellulose material manufactured with this preparation can be well dyed with acid wool dyestutf and dispersion dyestuffs according to the methods known for dyeing .with these dyestuffs.
• Suitable dyestuffs are, amongst others:
• Preparation B is manufactured as follows:
• a mixed cellulosic fabric of viscose fibres and fibres manufactured according to the invention with Preparation B, the latter having been woven in as stripes, is dyed by 7 the exhaustion process, in a known manner, with the following dyestufls:
• a process for the manufacture of viscose fibers with novel dyeing properties which comprises adding to the viscose spinning solution before precipitation from 1 to 20% by weight, based on the weight of cellulose content in said spinning solution, of a mixture comprising:
• A from 90 to by weight of a polyamine-amide obtained by reacting (a) from 40 to 80% by weight of an unsaturated fatty acid with at least 12 carbon atoms or a dimer or polymer thereof and, (b) from to 60% by weight of a polyalkylene-polyamine;

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Artificial Filaments (AREA)
• Coloring (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=4402775

Family Applications (1)

Country Status (8)

Cited By (5)

Families Citing this family (2)

• 1968
  • 1968-10-01 CH CH1466068A patent/CH508060A/de not_active IP Right Cessation
• 1969
  • 1969-09-03 FR FR6930083A patent/FR2019535A1/fr not_active Withdrawn
  • 1969-09-16 GB GB1258483D patent/GB1258483A/en not_active Expired
  • 1969-09-25 DE DE19691948487 patent/DE1948487A1/de active Pending
  • 1969-09-30 BE BE739578D patent/BE739578A/xx unknown
  • 1969-09-30 AT AT923769A patent/AT297910B/de not_active IP Right Cessation
  • 1969-10-01 BR BR212890/69A patent/BR6912890D0/pt unknown
• 1972
  • 1972-01-31 US US00222319A patent/US3793419A/en not_active Expired - Lifetime

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