Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
  • D06M15/03—Polysaccharides or derivatives thereof
  • D06M15/11—Starch or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B33/00—Preparation of derivatives of amylose
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B33/00—Preparation of derivatives of amylose
  • C08B33/04—Ethers
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/165—Ethers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2964—Artificial fiber or filament
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2964—Artificial fiber or filament
  • Y10T428/2967—Synthetic resin or polymer
  • Y10T428/2969—Polyamide, polyimide or polyester

Definitions

• yarns is to be understood here in its widest sense and is considered to comprise all threads or yarns that occur in the textile industry. They may consist of continuous filaments or of fibers, may be of a natural, semi-synthetic or synthetic nature and may be twisted or untwisted.
• hydrophilic textile materials such as cotton, wool or viscose rayon especially sizing agents from groups 1 and 2 are used.
• Strongly hydrophobic yarns are preferably sized by means of products from group 3.
• Cellulose acetate yarns may be sized both with protein products and with synthetic agents. 4
• the invention is more particularly of importance for sizing with amylose ethers and it will be therefore mainly described with reference to the use of the ethers.
• droxyalkyl ethers and mixed alkyl and hydroxyalkyl ethers having 1-4 carbon atoms in the alkyl or hydroxyalkyl group are particularly suitable.
• the alkyl or hydroxyalkyl group should not be too large because otherwise the solutions of the amylose ethers in the concentration that is conventional for the sizing operation, e.g. 5-10%, show the tendency in the heat to form a skin at the surface.
• At least about 1 alkyl group or hydroxyalkyl group should be introduced per 7 an'hydroglucose units of the amylose molecule in order to obtain products which form stable solutions both in the cold and in the heat, which is desirable for sizing solutions.
• amylose ethers to be used for sizing hydrophobic yarns and to the amylose ethers for sizing hydrophilic yarns.
• hydroxyalkyl ethers are to be used for sizing hydrophobic yarns it is desirable to use a product of a higher degree of substitution, having e.g. l hydroxyalkyl group per 2 /2 anhydroglucose units.
• alkyl ethers or hydroxyalkyl ethers which at the same time contain an arcmatic group, e.g. ethylbenzyl ethers or hydroxyethylbenzyl ethers, are also suitable.
• Amylose ethers containing hydrophilic groups in the substituent are especially eligible for sizing hydrophilic yarns.
• examples of such ethers are the amylose ether carboxylic acids and amylose ether sulphonic acids, which can be used as such or in the form of'their salts, e.g. the alkali salts.
• amylose ether carboxylic acids and amylose ether sulphonic acids which can be used as such or in the form of'their salts, e.g. the alkali salts.
• aminoalkyl ethers and aminoalkyl ethers substituted in the amino group are suitable.
• the linear fraction obtained by separating starch into its components is preferably used as amylose raw material.
• the linear fraction may be used both in its pure and in its impure state and in many cases it offers advantages for the preparation of the amylose ethers to work up the linear fraction without an intermediate drying.
• amylose preparations obtained by separating starch into its components it is also'possible to use particular native starches having a high amylose content e.g. starches of specific corn varieties.
• amylose ethers to be used according to the invention may be prepared by reacting the amylose with the etherifying agent in an aqueous mediumin the presence of the required catalysts, more particularly alkaline substances, in the conventional manner. If desired, however, the etherificationmay also take place in an organic solvent. 7 v
• amylose ethers may be isolated fromthe reaction mixture, but
• amylose ethers in the form of dry products.
• Such dry products may be obtained by recovering the amylose ethers from the reaction mixture and purifying and subsequently drying them.
• dry products of very good properties may be obtained by dry ing the reaction mass in its entirety on heated rollers and grinding the film thus formed into flakes of the desired size.
• Suitable etherifying agents for the preparation of amylose alkyl ethers are i.e. the alkyl halides, dialkyl sulphates, alkyl tosylates and diazomethane.
• alkylene oxides or alkylene chlorohydrins may be used.
• amylose may be, treated simultaneously or successively with the required etherifying agents.
• the treatment of the yarns with aqueous solutions of amylose ethers according to the invention may be efiected by conventional methods for sizing yarns. It is possible, for example, to submerge the yarns in the form of skeins in a solution of the sizing agent, to pass the yarns continuously through a solution of the sizing agent or to apply a solution of the sizing agent to the yarn by spraying or by means of a roller.
• the yarns thus treated may be dried on heated drums or in heated drying chambers.
• the sizing bath is preferably kept at a temperature between 30 and 90 C.
• the concentration of the sizing solution may vary; very good results are obtained if said concentration is such that the yarn will absorb 2l0% of the dry sizing agent.
• the pH of the sizing solution may likewise vary within wide ranges; for sizing cellulose acetate yarns, the pH of the solution, however, should not exceed about 8.0.
• the sizing solutions to be used may contain in addition to the amylose ethers small amounts of the auxiliary agents conventionally used in sizing operations, for example softening agents, wetting agents or the like, but in general such auxiliary agents are unnecessary. In addition to the amylose ethers the solutions may also contain other sizing agents, if desired.
• the yarns sized according to the invention are very resistent against mechanical influences, because they are coated with a strong, supple, smooth film. Especially in the weaving industry excellent results are obtained with said yarns.
• a further advantage of the use of said amylose ethers is that the yarns sized will not substantially take up a static charge. Furthermore they have the advantage that after the weaving operation they may easily be washed out from the yarns.
• Suitable amylose acetals are those obtained by prepared reacting amylose with formaldehyde.
• amylose derivatives containing both ether groups and ester groups or amylose derivatives which in addition to ether or esters groups contain acetal groups and may be obtained e.g. by reacting amylose ethers or amylose esters with formaldehyde.
• An example is an amylose benzyl ether which after the benzylation has been treated with formaldehyde.
• the sizing value is a measure for the coherence of the elementary threads and as such it is very important.
• the first sizing value relates to the point at which the elementary threads become detached from each other, unstuck, the second value relates to the complete dislocation of the threads. A high value, therefore, is indicative of a good sizing. All of the values are the average of at least five observations.
• the smoothness is expressed in the number of seconds which a thread of a specific length requires for passing an apparatus for determining the smoothness in the first and in the tenth passage respectively. Low values, therefore, are indicative of a high degree of smoothness.
• the abrasion resistance is a measure for the resistance of the sized yarn against abrasion. A high value is indicative of a good abrasion resistance.
• Example 1 A warp of acetate silk of 75 denier is continuously passed at a temperature of 60 C. through an 8% solution of an amylose ethyl ether (degree of substitution 0.40), whereupon the yarn is squeezed. The same test is made with a solution of an ethyl ether of tapioca starch of a corresponding degree of substitution. For purposes of comparison the same yarn is sized with a synthetic copolymer on styrene maleic acid anhydride basis, said copolymer being especially recommended for sizing acetate silk. The yarn is dried on drums at a temperature of from -90 C.
• Example 2 A warp of acetate silk of denier is sized at a temperature of 55 C. with aqueous solutions of some amylose alkyl ethers.
• amylose ethyl ether produces about the same results as the polymethacrylic acid which is especially recommended for nylon, but is much more expensive than amylose ethyl ether.
• Example 4 A hydroxypropyl ether of amylose with a degree of substitution of 0.5 1, a mixed ethylhydroxypropyl ether of amylose having a degree of substitution of 0.18 for the ethyl groups and of 0.30 for the hydroxyethyl groups, which two amylose ethers are excellently soluble both in cold and in hot water, and gelatin are used for sizing 75 denier acetate silk warps at a temperature of 60 C. To the solution of gelatin (which is frequently used for sizing acetate silk yarns in actual practice) a small amount of glycerol has been added.
• Example 5 O0nc., Degree Abrasion Breaking Elonga- Sizing agent perof resiststrength, tion,
• the sized spinning cake readily admits of being reeled off and the yarn has an excellent sizing.
• Example 7 A skein of acetate silk of 100 denier is submerged for some minutes in a 9.2% solution of an amylose ethyl ether having a degree of substitution of 0.23 at a temperature of 60 C. After squeezing the skein and loosening the threads the skein is dried in a drying box at about 90 C. The sizing value of the yarn thus treated is found to be 16.8, the elongation is 25%.
• Example 8 Continuous triacetate yarn of 100 denier is sized at a temperature of 50 C. with an aqueous solution of a water soluble mixed ethylbenzyl ether of amylose, obtained by treating amylose in :an alkaline medium in the heat with 0.7 mole of diethyl sulphate and 0.05 mole of benzylchloride per glucose unit and by subsequently removing the reaction salts in known manner and bringing the mass in dry form.
• the sizing is also effected under the same conditions with a synthetic sizing agent on the basis of polyvinyl alcohol, in the presence of a slight amount of boric acid. After the treatment the yarn is dried on a drum at 95 C.
• Example 10 The mixed ethylbenzyl ether of amylose described in Example 8 is compared with the corresponding ether of corn starch for sizing 75 denier diacetate silk warps at a Example 10
• Cotton yarn is continuously passed in warp form through a 10% aqueous solution of the sodium salt of a carboxymethyl ether of amylose at a temperature of 80 C., squeezed out and dried on a drum at 110 C.
• the amylose ether is prepared by treating amylose in an alkaline medium in the heat with 1 mole of sodium monochloroacetate per glucose unit, whereupon the amylose thus treated is freed in known manner from the reaction salts, and is brought in dry form.
• the degree of substitution of the amylose ether is 0.56 carboxymethyl group per anhydroglucose unit.
• For purposes of comparison sizing tests are also run with a sodium salt of a carboxymethyl ether of cassava starch (degree of substitution 0.59), as well as with the sodium salt of a carboxymethyl cellulose of low viscosity (degree of substitution 0.6).
• the starch ether is obtained by etherifying cassava starch in known manner with one mole of sodium monochloroacetate per glucose unit and by subsequently removing the reaction salts.
• a warp of diacetate silk of denier is continuously passed through an 8% aqueous solution of amylose acetate at a temperature of 60 C., whereupon the yarn is squeezed out.
• the water soluble amylose acetate is obtained by hydrolyzing a solution of amylose triacetate in the presence of water and a small amount of a catalyst until the amylose acetate has become fully water soluble.
• Example 12 Cotton yarn is sized with a 10% aqueous solution of an amylose formaldehyde compound. The yarn thus sized is very suitable for weaving.
• Example 13 A dry amylose ether to be used according to the invention having good properties may be prepared as follows: In an autoclave provided with a stirring apparatus 1000 grams of finely ground amylose (obtained by fractionating potato starch) is agitated with a solution of 170 grams of sodium hydroxide in 2000 cc. of water at a temperature of 50-60 C., until a smooth dispersion is obtained. Subsequently 350 cc. of dimethyl sulphate are added in a period of 45 minutes, whereupon the mass is allowed to react for another hour at the same temperature. The reaction mixture is subsequently dried in a thin layer on a heated drum at a steam pressure of 6 at. The amylose methyl ether obtained has an excellent solubility both in cold and in hot water. The ether has a degree of substitution of 0.53 and accordingly contains 1 methyl group per 1.88 anhydroglucose units.
• said sizing agent is an alkyl ether of amylose, wherein each alkyl group has from 1 to 4 carbon atoms.
• said sizing agent is a hydroxyalkyl ether of amylose, wherein each hydroxyalkyl group has from 1 to 4 carbon atoms.
• said sizing agent is a mixed alkyl hydroxyalkyl ether of amylose wherein each alkyl group has from 1 to 4 carbon atoms, and each hydroxy alkyl group has from 1 to 4 carbon atoms.
• the sizing agent is a hydroxyalkyl ether of amylose containing at least one ether group per 2 /2 anhydroglucose units of the amylose.
• the sizing agent is an ethyl benzyl ether of amylose.
• the sizing agent is an ester of amylose and a fatty acid having from 2 to 4 carbon atoms.
• said sizing agent is a carboxyalkyl ether of amylose, wherein the alkyl group has from 1 to 4 carbon atoms.
• said sizing agent is a sulfoalkyl ether of amylose, wherein the alkyl group has from 1 to 4 carbon atoms.
• said sizing agent is an aminoalkyl ether of amylose, wherein the alkyl group has from 1 to 4 carbon atoms.
• said sizing agent is a substituted aminoalkyl ether of amylose, wherein the alkyl group has from 1 to 4 carbon atoms.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Biochemistry (AREA)
• Materials Engineering (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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