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
  • D06M15/05—Cellulose or derivatives thereof
  • D06M15/09—Cellulose 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
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/50—Modified hand or grip properties; Softening compositions

Definitions

• This invention relates to a method for modifying fibers and also to modified fibers.
• the method of modifying fibers by coverage with viscose-derived, regenerated fibers includes the steps of applying to fibers a solution, i.e., viscose, obtained by dissolving in a sodium hydroxide aqueous solution cellulose xanthate which is prepared by degenerating cellulose with highly toxic carbon disulfide, and subsequently coagulating and regenerating the cellulose.
• a solution i.e., viscose
• the method needs not only the dissolution of cellulose in a sodium hydroxide aqueous solution at low temperature, but also the use of cellulose of the type which has a reduced degree of crystal structure sufficient to increase solubility, e.g. cellulose that is obtained by acid hydrolyzing wood pulp and grinding it in a ball mill, or regenerated cellulose that is prepared from viscose, thus imposing restrictions thereon.
• cellulose of the type which has a reduced degree of crystal structure sufficient to increase solubility e.g. cellulose that is obtained by acid hydrolyzing wood pulp and grinding it in a ball mill, or regenerated cellulose that is prepared from viscose, thus imposing restrictions thereon.
• fiber modifying finish is enabled by a procedure which comprises adding a crosslinking agent and/or an aqueous resin emulsion to an aqueous solution of a cellulose ether having such a low degree of substitution that a molar degree of substitution with an alkyl group and/or a hydroxyalkyl group ranges from 0.05 to 1.3, applying the resulting solution onto fibers, coagulating the applied solution with an acid for coagulation, and thermally treating the resulting fibers.
• another procedure may also be used, which comprises adding a crosslinking agent and/or an aqueous resin emulsion to an alkali aqueous solution dissolving a cellulose ether having a low degree of substitution, applying the resulting solution onto fibers, subjecting the fibers to heating treatment and then neutralizing with an acid.
• the resulting modified fibers are improved in washing resistance, have no problem on carbon disulfide, are prevented from fluffing, and have high tensile strength and excellent wear resistance, static resistance and water absorption.
• a method for modifying fibers comprising steps of adding a crosslinking agent and/or an aqueous resin emulsion to an aqueous solution of an alkali dissolving therein a cellulose ether having such a low degree of substitution that a molar degree of substitution with an alkyl group and/or a hydroxyalkyl group ranges 0.05 to 1.3, applying the resulting solution to fibers, neutralizing the applied solution with an acid for coagulation, and thermally treating the fibers.
• a method for modifying fibers comprising steps of adding a crosslinking agent and/or an aqueous resin emulsion to an aqueous solution of an alkali dissolving therein a cellulose ether having such a low degree of substitution that a molar degree of substitution with an alkyl group and/or a hydroxyalkyl group ranges 0.05 to 1.3, applying the resulting solution to fibers, thermally treating the thus applied fibers, and applying an acid to the fibers to neutralize the alkali left on the fibers.
• the crosslinking agent used should preferably be an isocyanate crosslinking agent
• the aqueous resin emulsion should preferably be an aqueous urethane resin emulsion or an O/W emulsion of a reactive organopolysiloxane.
• the cellulose ether having a low degree of substitution should preferably be a low-substituted hydroxypropyl cellulose having a molar degree of substitution ranging from 0.1 to 0.7.
• the aqueous solution of an alkali is a sodium hydroxide aqueous solution.
• a modified fiber article which includes fibers individually covered with a cellulose ether having such a low degree of substitution that a molar degree of substitution with an alkyl group and/or a hydroxyalkyl group ranges from 0.05 to 1.3, and also with a crosslinked product and/or an aqueous emulsion-derived resin component.
• modified fibers without an appreciable problem on safety because of no use of a toxic solvent such as carbon disulfide and without involving a complicated step of dissolution.
• modified fibers can be appropriately prevented from fluffing or fuzzing, and have high tensile strength and excellent wear resistance, static resistance and water absorption.
• the modified fibers obtained according to the invention have improved air permeability, a smooth feeling, and a solid touch with good resilience.
• the fibers used in the invention are not critical in type.
• the fibers include synthetic fibers such as polyethylene fibers, polypropylene fibers, polyester fibers, nylon fibers, acrylic fibers, vinylon fibers, rayon fibers, polyvinyl chloride fibers, and polyvinylidene chloride fibers; natural fibers such as of cotton, cellulose, and hemp; and animal fibers such as of wool, silk, and cashmere.
• the term “fibers” used herein include thread-shaped fibers, woven fabrics or textiles of thread-shaped fibers, or non-woven fabrics or textiles of thread-shaped fibers.
• the cellulose ether having a low degree of substitution used in the invention means a cellulose ether wherein the hydrogen atoms of the hydroxyl groups of glucose rings of cellulose are partially substituted with an alkyl group and/or a hydroxyalkyl group provided that a molar degree of substitution ranges from 0.05 to 1.3, preferably from 0.1 to 0.7 and which should not be dissolved in water but dissolved in an alkali aqueous solution. If the molar degree of substitution is lower than 0.05, such a cellulose ether is unlikely to dissolve in an alkali aqueous solution. On the contrary, when the molar degree/exceeds 1.3, dissolution in water increases with a decrease in solubility in an alkali solution.
• the cellulose ether of a low degree of substitution is referred as a low-substituted cellulose ether hereinafter.
• Examples of the cellulose ether of a low degree of substitution include low-substituted alkyl celluloses such as low-substituted methyl cellulose, and low-substituted ethyl cellulose; low-substituted hydroxyalkyl celluloses such as low-substituted hydroxyethyl cellulose, and low-substituted hydroxypropyl cellulose; low-substituted hydroxyalkylalkyl celluloses such as low-substituted hydroxypropylmethyl cellulose, low-substituted hydroxyethylmethyl cellulose, and low-substituted hydroxyethylethyl cellulose. Of these, low-substituted hydroxypropyl cellulose is preferred.
• a first procedure comprises adding a crosslinking agent and/or an aqueous resin emulsion to an aqueous solution of an alkali dissolving therein a low-substituted cellulose ether as mentioned above, applying the solution to fibers by coating or dipping, if necessary, removing an excessive applied solution from the fibers by a suitable means such as a centrifugal dehydrator, a mangle, a knife coater or the like, coagulating the applied solution by neutralization with an acid, and thermally treating the resulting fibers after washing with water and drying, if necessary.
• a second procedure comprises adding a crosslinking agent and/or an aqueous resin emulsion to an aqueous solution of an alkali dissolving therein a low-substituted cellulose ether as mentioned above, applying the solution to fibers by coating or dipping, if necessary, removing an excessive applied solution from the fibers by a suitable means such as a centrifugal dehydrator, a mangle, a knife coater or the like, thermally treating the fibers, neutralizing an alkali left in the fibers with an acid, and drying the fibers.
• the crosslinking reaction and the cured film formation from the aqueous resin emulsion proceed in the course of the thermally treating step. Either of the crosslinking reaction or the cured film formation contributes to enhancing the adhesion between the fibers and the low-substituted cellulose ether, thus resulting in an improved washing resistance.
• the alkali aqueous solutions include a sodium hydroxide aqueous solution, and a potassium hydroxide aqueous solution.
• concentration of the caustic alkali depends on the type of substituent of a low-substituted cellulose ether used and the degree of substitution and may be appropriately determined. In general, the concentration ranges from 2 to 25% by weight, preferably from 3 to 15% by weight. If the concentration is smaller than 2% by weight the low-substituted cellulose ether may not be dissolved in some case. On the other hand, if the concentration exceeds 25% by weight, a solution of the low-substituted cellulose ether becomes gelled, with some possibility that a difficulty is involved in coating or dipping operation.
• low-substituted hydroxypropyl cellulose having a molar degree of substitution as low as 0.2 is dissolved in a sodium hydroxide aqueous solution having a concentration of 9 to 10% by weight.
• the concentration of the low-substituted cellulose ether in an alkali aqueous solution is in the range of from 1 to 20% by weight, preferably from 1 to 10% by weight. If the concentration is smaller than 1% by weight, little effect of improving the hand of fibers is expected. Over 20% by weight, the resulting solution becomes too high in viscosity, so that the solution may be unlikely to be attached to the fibers in a given amount throughout the fibers.
• the solution can be coated by use of coaters such as a blade coater, a transfer coater, an air doctor coater and the like.
• coaters such as a blade coater, a transfer coater, an air doctor coater and the like.
• dipping machines such as of one thread sizing type, a pre-wetting type, a floating type, a doctor bar type and the like.
• the amount of the low-substituted cellulose solution on fibers is appropriately determined, and a pickup, i.e., [amount of an applied low-substituted cellulose ether solution/weight of fiber substrate] ⁇ 100, is in the range of 10 to 500% by weight, preferably 20 to 300% by weight. If the pickup is smaller than 10% by weight, a coverage of fibers with a low-substituted cellulose ether becomes small, with the possibility that a satisfactory effect of modifying the fibers cannot be expected.
• the acids used include mineral acids such as hydrochloric acid, sulfuric acid and the like, and organic acids such as citric acid, malic acid, formic acid, acetic acid and the like.
• the concentration of the acid in the aqueous solution ranges from 1 to 50% by weight, preferably 2 to 15% by weight.
• a salting-out method may be used in combination wherein the attached solution is coagulated by dipping in an aqueous solution of a salt such as ammonium chloride, ammonium sulfate, sodium sulfate, sodium chloride, zinc sulfate, magnesium sulfate, sodium phosphate, ammonium phosphate, sodium thiosulfate, sodium carbonate, sodium bicarbonate, sodium salts of aliphatic acids, and sodium benzenesulfonate.
• a salt such as ammonium chloride, ammonium sulfate, sodium sulfate, sodium chloride, zinc sulfate, magnesium sulfate, sodium phosphate, ammonium phosphate, sodium thiosulfate, sodium carbonate, sodium bicarbonate, sodium salts of aliphatic acids, and sodium benzenesulfonate.
• a salt such as ammonium chloride, ammonium sulfate, sodium sul
• the crosslinking agents used in the invention may be ones which cause crosslinking reaction through reaction with hydroxyl groups left in the low-substituted cellulose ether.
• Such crosslinking agents include those agents to carry out reaction with hydroxyl group as described in “HANDBOOK OF CROSSLINKING AGENTS” (published by Kabushiki Kaisha Taiseisha., on Oct. 20, 1981).
• epoxy compounds such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, alkylphenol glycidyl ethers, polyethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycidyl ether, 1,6-hexanediol, diglycidyl ether, glycerine polyglycidyl ether, diglycerine polyglycidyl ether, cresyl glycidyl ether, aliphatic diglycidyl ethers having 3 to 15 carbon atoms, monoglycidyl ether,
• silanes of the general formula SiR1R 2 R 3 R 4 wherein R 1 represents an alkyl group, an alkoxy group or an acyloxy group each having 1 or 2 carbon atoms, and R 2 , R 3 and R 4 independently represent an alkoxy group or an acyloxy group having 1 or 2 carbon atoms.
• the concentration of these crosslinking agents in the alkali solution is not critical and is preferably within a range of from 1 to 30% by weight, especially 5 to 10% by weight. If the concentration is smaller than 1% by weight, washing resistance may not be improved satisfactorily. When the concentration exceeds 30% by weight, there is the possibility that a further improvement in washing resistance as being commensurate with too much an amount is not expected.
• a method wherein an alkali aqueous solution dissolving therein a low-substituted cellulose ether and a crosslinking agent is applied to fibers, and the thus applied fibers are treated with an acid aqueous solution to permit coagulation of the cellulose ether, followed by washing with water, drying and heating at 100 to 170° C. at which crosslinking reaction is allowed to proceed.
• the heating time is not critical and is preferably within a range of from 1 to 20 minutes.
• a method wherein an alkali aqueous solution dissolving therein a low-substituted cellulose ether and a crosslinking agent is applied to fibers, and the fibers are heated at 100 to 170° C. to cause crosslinking reaction to proceed, after which the fibers are treated with an acid aqueous solution, for example, by immersion to cause the alkali left in the fibers to be neutralized, followed by washing with water and drying, if necessary.
• the heating time is not critical and is preferably within a range of 1 to 20 minutes. It will be noted that re-heating treatment may be carried out after the drying, if necessary.
• the acids used for the neutralization in the second procedure may be ones as used in the first procedure, and this is true of the concentration of an acid in the aqueous solution.
• surface active agents including alkyl ether penetrants such as propylene glycol, ethylene glycol and the like, and penetrants of block copolymers of propylene glycol and ethylene glycol may be added in an amount of 0.5 to 1% by weight along with a crosslinking agent.
• the aqueous resin in the emulsion is fixed to fibers along with a low-substituted cellulose ether in the course of coagulation of the low-substituted cellulose ether and the aqueous resin is formed as a cured film in a subsequent heating step.
• the aqueous resin in the emulsion is fixed to fibers and formed as a cured film during the heating step to cover the fiber surfaces along with the low-substituted cellulose ether, thereby improving the physical properties of fibers such as a washing resistance.
• the aqueous resin emulsion used may be one which is converted to film by heating to enhance adhesion between the fibers and the low-degree substituted cellulose ether.
• those emulsions ordinarily used for resin finishing for fibers are used including aqueous urethane resin emulsions, aqueous acrylic resin emulsions, aqueous vinyl acetate resin emulsions, aqueous ethylene/vinyl acetate emulsions, aqueous epoxy resin emulsions, reactive organopolysiloxane O/W emulsions, SBR latices and the like.
• aqueous urethane resin emulsions and reactive oganopolysiloxane O/W emulsions are preferred.
• the aqueous urethane resin emulsions include various types of emulsions prepared by reaction between polyethers such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxybutylene glycol and diisocyanates such as tolylene diisocyanate, 3,3′-bistolylene-4,4′-diisocyanate, diphenylmethane diisocyanate, 3,3-dimetyldiphenylmethane diisocyanate, and 4,4′-diisocyanate.
• polyethers such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxybutylene glycol
• diisocyanates such as tolylene diisocyanate, 3,3′-bistolylene-4,4′-diisocyanate, diphenylmethane diisocyanate, 3,3-dimetyldiphenylmethane diisocyanate, and 4,4′-diisocyanate.
• the first procedure there is adopted a method wherein an aqueous resin emulsion is added to an alkali solution dissolving therein a low-substituted cellulose ether and is applied to fibers along with the low-substituted cellulose ether upon coating of the low-substituted cellulose ether to the fibers. Thereafter, the cellulose ether on the fibers is coagulated by means of an acid aqueous solution, followed by washing with water and heating for film formation.
• the heating temperature may be one at which the resin component in the aqueous emulsion is formed as a cured film.
• the heating conditions preferably include a temperature ranging from 80 to 150° C. and a time ranging from 1 to 20 minutes.
• the concentration of the aqueous resin in the alkali aqueous solution is preferably from 1 to 30% by weight, especially 5 to 10% by weight.
• concentration is smaller than 1% by weight, a satisfactory improvement in washing resistance may not be obtained in some case.
• concentration exceeds 30% by weight, a further improvement in washing resistance may not be attained as being commensurate with such a large amount.
• an aqueous resin emulsion is added to an alkali solution dissolving a low-substituted cellulose ether, and is attached to fibers along with the low-substituted cellulose ether upon coating of the low-substituted cellulose ether.
• the resulting fibers are heated to convert the aqueous resin to a cured film, followed by treating the fibers with an acid aqueous solution such as by immersion to neutralize a remaining alkali, washing with water, if necessary, and drying.
• an acid aqueous solution such as by immersion to neutralize a remaining alkali, washing with water, if necessary, and drying. It is to be noted that the cured film conversion conditions are similar to those as used in the first procedure.
• a catalyst of promoting the crosslinking reaction of these reactive organopolysiloxanes in the form of an O/W emulsion mention is made of salts of metals such as tin, lead, zinc, cobalt, manganese chromium, zirconium, titanium, and platinum. Especially, zirconium acetate as described in JP-B 34-4199 and chloroplatinic acid as described in JP-B 51-9440 are favorably used.
• the amount of the catalyst is not critical and an effective amount for promoting the crosslinking reaction is within a range of from 0.001 to 120 parts by weight, preferably from 0.005 to 110 parts by weight per 100 parts by weight of reactive organopolysiloxane in an emulsion used.
• the particle size in the O/W emulsion is not critical and is within a range of from 0.01 to 100 ⁇ m. From the standpoint of stability, the particle size is preferably within a range of 0.1 to 80 ⁇ m.
• film formation may be carried out under the same curing conditions as for the above-stated aqueous urethane resin emulsion.
• the clothes or fabrics obtained by use of the modified fibers of the invention is improved in air permeability and becomes smooth and flexible to the touch.
• it is possible to provide fibers or clothes having a photocatalytic function by addition of about 1 to 20% by weight of titanium oxide to an alkali solution of low-substituted cellulose ether.
• dyes or pigments may be added to an alkali solution of low-substituted cellulose ether for coloration.
• all types of inorganic materials, organic material, and natural materials may be added to an alkali solution of low-substituted cellulose ether within ranges of amounts not impeding the purposes of the invention, modified fibers may be obtained.
• the thread was immediately removed from the sizer and immersed in a 10 wt % formic acid aqueous solution to coagulate the low-substituted cellulose ether. Subsequently, the thread was washed well with water, dried and thermally treated at 145° C. for 5 minutes to obtain a sample fiber thread.
• an alkali solution of the low-substituted hydroxypropyl cellulose dissolving the crosslinking agent and the aqueous resin emulsion was prepared to provide each sample solution.
• “Knit Comber” cotton thread #30/1 made by Omikenshi Co., Ltd was immersed in the sample solution by use of KHS Universal Sizer made by Kabushiki Kaisha Kakinoki so that a pickup reached 200 to 300% by weight.
• the thread was immediately removed from the sizer and immersed in a 10 wt % formic acid aqueous solution to coagulate the low-substituted cellulose ether. Subsequently, the thread was washed well with water, dried and thermally treated at 145° C. for 5 minutes to obtain a sample fiber thread.
• a sample was made and evaluated in the same manner as in Examples 1 to 6 except that a sample solution used was comprised of 100 parts by weight of a viscose containing 8% by weight, calculated as cellulose, of powdery cellulose KC FLOCK W 100 made by Nippon Paper Industries Co., Ltd., 6% by weight of sodium hydroxide and 2.5% by weight of carbon disulfide.
• a sample solution used was comprised of 100 parts by weight of a viscose containing 8% by weight, calculated as cellulose, of powdery cellulose KC FLOCK W 100 made by Nippon Paper Industries Co., Ltd., 6% by weight of sodium hydroxide and 2.5% by weight of carbon disulfide.
• Table 1 The results are shown in Table 1.
• an alkali solution of the low-substituted hydroxypropyl cellulose dissolving the crosslinking agent and the aqueous resin emulsion therein was prepared to provide each sample solution.
• “Knit Comber” cotton thread #30/1 made by Omikenshi Co., Ltd was immersed in the sample solution by use of KHS Universal Sizer made by Kabushiki Kaisha Kakinoki so that a pickup reached 200 to 300% by weight, followed by thermally treating at 145° C. for 5 minutes.
• the thermally treated thread was immersed in a 10 wt % formic acid aqueous solution to neutralize sodium hydroxide left in the thread.
• the fiber thread was washed with water and dried to obtain a sample thread.
• Tensilon tensile strength measuring device made by A&D Co., Ltd., the tensile strength of 10 threads with a length of 100 mm was measured to determine a ratio to that of non-treated threads.
• Hiruta's wear resistance tester was used to determine a number of cycles before a sample thread was broken, from which a value obtained by dividing the number by a number of cycles before breakage of a non-treated thread is calculated.
• a half life was measured according to a method described in JIS L 1094-1980 to determine a static resistance as a ratio to that of a non-treated thread.
• a thread was washed according to a method described in JIS L 0844 and, after the washing, observed through a microscope to determine such that the degree of fluffing of a treated thread which was less than that of a non-treated thread was evaluated as ⁇ and the degree which was not less than that of the non-treated thread was evaluated as X.

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