WO2006100290A1 - Textile treatment - Google Patents

Textile treatment Download PDF

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Publication number
WO2006100290A1
WO2006100290A1 PCT/EP2006/060990 EP2006060990W WO2006100290A1 WO 2006100290 A1 WO2006100290 A1 WO 2006100290A1 EP 2006060990 W EP2006060990 W EP 2006060990W WO 2006100290 A1 WO2006100290 A1 WO 2006100290A1
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WO
WIPO (PCT)
Prior art keywords
starch
unmodified
amylose
range
weight
Prior art date
Application number
PCT/EP2006/060990
Other languages
French (fr)
Inventor
Milton Noboru Kawahara
Christoffer Kieburg
Arno Luiz Campestrini
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to BRPI0607709A priority Critical patent/BRPI0607709A2/en
Publication of WO2006100290A1 publication Critical patent/WO2006100290A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/18—Oxidised starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C08L3/10—Oxidised starch
    • 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
    • D06M13/17—Polyoxyalkyleneglycol 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
    • 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
    • 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
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • 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
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • 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
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
    • 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
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
    • 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
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

Definitions

  • the present invention relates to a process for treating linear textiles, which comprises treating said linear textiles with an aqueous formulation or liquor containing (a1) at least one first chemically modified starch with an amylose content of the respective unmodified starch in the range of 20 to 30 % by weight, referring to the sum of amylose and amylopectin of said unmodified starch, (a2) at least one further chemically modified starch with an amylose content of the respective unmodified further starch in the range of 10 to 20 % by weight, referring to the sum of amylose and amylopectin of said unmodified further starch, (b) at least one synthetic polymer.
  • the present invention further relates to liquors and aqueous formulations useful for carrying out the process of the present invention and process for making said aqueous formulations and liquors.
  • Linear textiles are treated with a solution, a dispersion or a melt of a macromolecular compound before they are processed.
  • the macromolecular compound applied to the fiber can be washed off or removed otherwise, such as destroyed after processing.
  • Sizing agents also known as sizes, are typically washed off re- moved otherwise, such as destroyed again to a very substantial degree after weaving, in an operation also known as desizing.
  • Commonly used sizing agents are typically selected from natural macromolecular compounds such as for example starch, from modified natural macromolecular compounds such as for example modified starch and from synthetic macromolecular compounds such as for example polyvinyl alcohol, polyesters and poly(meth)acrylates; see for example Ullmann's Encyclopedia of Industrial Chemistry, Vol. 36, 6 th edition, pages 18 to 26, Wiley-VCH Weinheim, 2003.
  • natural macromolecular compounds such as for example starch
  • modified natural macromolecular compounds such as for example modified starch
  • synthetic macromolecular compounds such as for example polyvinyl alcohol, polyesters and poly(meth)acrylates
  • Treatment processes are therefore desired for sizes (but also for other applications to textiles) whereby the textile is treated with synthetic macromolecular compounds in order that the treated textile may have very good mechanical properties.
  • the applied synthetic macromolecular compounds shall be readily removable with aqueous liquors.
  • Numerous synthetic macromolecular compounds have been suggested as sizing materials but they are usually expensive. When at a later stage desizing takes place, considerable investments in size recovery will be required.
  • the present invention accordingly provides the process defined at the beginning.
  • Linear textile in the context of the present invention refers to linear structures such as textile fibers, including staple fibers, twine, filaments, rovings, spun yarns, lines, strings, cordage, threads.
  • Textiles can be of natural origin, examples being silk, wool, flax, ramie, hemp or coir or especially cotton, or synthetic, examples being regenerated cellulose such as for example cuprammonium silk, viscose or cellulose acetates such as acetate and triacetate, also polyamide, polyacrylonitrile, polypropylene and polyester. Blends are also useful, examples being cotton-polyester blends.
  • a textile for the purposes of the present invention may be present as staple fiber, in the form of filaments or as staple fiber yarn.
  • Linear textile treated by the process of the present invention can be of any color, and it can have one color or more than one color. Linear textile treated by the process of the present invention is preferably uncolored.
  • Linear textile in a preferred embodiment of the present invention refers to warp yarns composed of cellulosic fiber, polyester-cellulosic blends, wool, polyester- wool blends, viscose filament or acetate filament and particularly preferable to warp yarns composed of cellulosic fiber or polyester-cellulosic blends.
  • linear textile is treated with an aqueous formulation or liquor containing
  • (a1 ) at least one first chemically modified starch, in the context of the present invention also being referred to as chemically modified starch (a1) or briefly as component (a1 ), with an amylose content of the respective unmodified starch in the range of 20 to 30 % by weight, preferably 23 to 29 % by weight, referring to the sum of amylose and amy- lopectin of respective unmodified starch,
  • (a2) at least one further chemically modified starch, in the context of the present invention also being referred to as chemically modified starch (a2) or briefly as component (a2), with an amylose content of the respective unmodified further starch in the range of 10 to 20 % by weight, preferably 15 to 18 % by weight, referring to the sum of amylose and amylopectin of said unmodified further starch, (b) at least one synthetic polymer.
  • Chemically modified starch can be carboxymethylated starch or preferably oxidized starch. Most preferably, both chemically modified starches, component (a1 ) and com- ponent (a2), are oxidized starch.
  • Component (a1 ) can be obtained from sorghum starch or preferably from corn starch, in particular to so-called normal corn starch in contrast to waxy corn starch and further in contrast to so-called high-amylose starch.
  • Component (a2) can be obtained from tapioca starch.
  • starch will be slurried or dissolved in water and be treated with an oxidant or a mixture of oxidants.
  • chemically modified starch can be used as components (a1 ) and (a2) which have been oxidized under alkaline conditions, e.g., at a pH value in the range from 10 to 13, preferably from 10 to 11.
  • chemically modified starch can be used as components (a1) and (a2) which has been oxidized with one or more oxidants such as chlorine bleach, preferably with peroxides in aqueous solution, preferably with hydrogen peroxide.
  • oxidants such as chlorine bleach, preferably with peroxides in aqueous solution, preferably with hydrogen peroxide.
  • chemically modified starch can be used as components (a1) and (a2) which has been esterified, preferably partially esterified with one or more carboxylic acids and in particular dicarboxylic acids such as succinic acid, glutaric acid and most preferably adipic acid.
  • chemically modified starch can be used as components (a1) and (a2) which has been oxidized with one or more oxidants such as chlorine bleach, preferably with peroxides in aqueous solution, preferably with hydrogen peroxide, and after oxidation has been esterified, preferably partially esterified with one or more carboxylic acids and in particular dicarboxylic acids such as succinic acid, glutaric acid and most preferably adipic acid.
  • oxidants such as chlorine bleach, preferably with peroxides in aqueous solution, preferably with hydrogen peroxide
  • the weight ratio of (a1) to (a2) is in a range from 99 : 1 to 1 : 99, preferably from 20 : 1 to 1 : 20.
  • the process of the present invention furthermore includes (b) at least one synthetic polymer in an aqueous formulation or liquor for treating said linear textile, in the context of the present invention also referred to as synthetic polymer (b).
  • Synthetic polymer (b) can be made by, e.g., radical polymerization of one or more ethylenically unsaturated (vinylic) monomers and can refer to homo- or copolymers.
  • said synthetic polymer (b) has an average molecular weight M w in the range from 20,000 to 20,000,000 g/mol, preferably to 10,000,000 g/mol.
  • synthetic polymers can be selected from vinyl acetate polymers (b1 ), preferably polyvinyl alcohols (b2) and more preferably poly(meth)acrylates (b3), and preferably polyacrylamides (b4).
  • Suitable vinyl acetate polymers (b1) can be made by, e.g., free radical polymerization of vinyl acetate and/or vinyl propionate, the homopolymerization of vinyl acetate being preferred.
  • Suitable vinyl acetate polymers can have an average molecular weight M w in the range from 20,000 to 250,000 g/mol.
  • Suitable polyvinyl alcohols (b2) can be made by, e.g., free radical polymerization of vinyl acetate followed by hydrolysis of the ester groups.
  • Suitable polyvinyl alcohols (b2) can have an average molecular weight M w in the range from 20,000 to 250,000 g/mol.
  • polyvinyl alcohols (b2) have a viscosity in the range from 1 to 20 mPa-s, preferably from 10 to 15 mPa-s, measured by, e.g., on 4% by weight (bone dry basis) aqueous solution at 2O 0 C by the Hoeppler falling ball method.
  • Suitable poly(meth)acrylates (b3) include (co)polymers of (meth)acrylic acid preferably with one or more ethylenically unsaturated (di)carboxylic acid(s) and optionally with (meth)acrylic acid Ci-Ci O -alkyl esters, wherein Ci-Ci O -alkyl can be branched or non- branched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-non
  • Copolymers of (meth)acrylic acid C r C 10 -alkyl esters include blockcopolymers, alternating copolymers, and random copolymers of two or more (meth)acrylic acid Ci-C,o-alkyl esters and blockcopolymers, alternating copolymers, and random copolymers of one or more (meth)acrylic acid Ci-C 10 -alkyl esters with (meth)acrylic acid.
  • Preferred poly(meth)acrylates (b3) include homopolymers of acrylic acid and methacrylic acid and blockcopolymers, alternating copolymers, and preferably random copolymers of of acrylic acid and methacrylic acid and blockcopolymers, alternating copolymers, and preferably random copolymers of (meth)acrylic acid with one or more (di)carboxylic acids such as crotonic acid and preferably fumaric acid, itaconic acid and more preferably maleic acid.
  • one or more (di)carboxylic acids such as crotonic acid and preferably fumaric acid, itaconic acid and more preferably maleic acid.
  • Preferred (co)polymers of (meth)acrylic acid such as poly(meth)acrylic acid and block- copolymers, alternating copolymers, and preferably random copolymers of one or more (meth)acrylic acid
  • Ci-Ci O -alkyl esters with (meth)acrylic acid can be partially or fully neutralized to form their respective alkali metal salts or ammonium salts, alkali metals being selected from lithium and preferably from sodium and potassium.
  • Preferred poly(meth)acrylates (b3) can have an average molecular weight M w in the range from 20,000 to 250,000 g/mol, preferably from 50,000 to 150,000 g/mol.
  • synthetic polymer (b) is selected from poly(meth)acrylates (b3) obtained by free-radical copolymerization of 60 to 80 % by weight (meth)acrylic acid, preferably 65 to 75 % by weight, 20 to 40 % by weight maleic acid, preferably 35 to 25 % by weight, and subsequent neutralization with sodium hydroxide.
  • Suitable poly(meth)acrylamides (b4) include homopolymers of (meth)acrylamide, pref- erably acrylamide, blockcopolymers, alternating copolymers, and preferably random copolymers of acrylamide and methacrylamide, and blockcopolymers, alternating copolymers, and preferably random copolymers (co)polymers of (meth)acrylamide one or more ethylenically unsaturated acids such as maleic acid, crotonic acid and in particular methacrylic acid and acrylic acid.
  • ethylenically unsaturated acids such as maleic acid, crotonic acid and in particular methacrylic acid and acrylic acid.
  • Preferred poly(meth)acrylamides (b4) can have an average molecular weight M w in the range from 1 ,000,000 to 20,000,000 g/mol, preferably 2,000,000 to 10,000,000 g/mol and more preferably 4,000,000 to 8,000,000 g/mol.
  • poly(meth)acrylamides (b4) that are blockcopolymers, alternating copolymers, or preferably random copolymers of (meth)acrylamide with one or more ethylenically unsaturated acids such as maleic acid, crotonic acid and in particular methacrylic acid and acrylic acid
  • said ethylenically unsaturated acid can be partially or fully neutralized to form its respective alkali metal salt or ammonium salt, alkali metals being selected from lithium and preferably from sodium and potassium.
  • synthetic polymer (b) is selected from poly(meth)acrylamides (b4) obtained by free-radical copolymerization of 20 to 80 % by weight (meth)acrylamide, preferably 50 to 70 % by weight, and 20 to 80 % by weight (meth)acrylic acid, preferably 30 to 50 % by weight, and subsequent neutralization with sodium hydroxide.
  • At least one poly(meth)acrylamide (b4) has a dynamic viscosity in the range from 30 to 2,000 mPa-s, preferably from 1 ,000 to 1 ,800 and more preferably from 1 ,200 to 1 ,300 mPa-s, measured as a 5% by weight aqueous solution in accordance with DIN EN ISO 3219 at 23 0 C.
  • the aqueous formulation or liquor for carrying out the inventive process further contains at least one poly(meth)acrylate (b3) and at least one poly(meth)acrylamide (b4), poly(meth)acrylates (b3) and poly(meth)acrylamides (b4) being defined above.
  • the weight ratio between poly(meth)acrylate (b3) and poly(meth)acrylamide (b4) is in the range from 10,000 to 1 to 50 : 1 , preferably from 600 : 1 to 100 : 1.
  • the weight ratio of synthetic polymer (b) to the sum of (a1 ) and (a2) is in the range from 0.1 to 10 %, preferably from 1 to 7 %.
  • the aqueous formulation or liquor for carrying out the inventive process further contains (c) at least one polyethylene glycol.
  • Polyethylene glycols in the context of the present invention are compounds of the general formula HO(CH 2 CH 2 O) n H, n being an integer from 20 to 500.
  • Preferred polyethylene glycols are waxy compounds with an average molecular weight M w in the range from 1 ,000 to 10,000 g/mol.
  • polyethylene glycol (c) can be applied in an amount of from 0.01 to 10% by weight, preferably 0.1 to 2 % by weight, referring to the sum of (a1 ) and (a2).
  • the aqueous formulation or liquor for carrying out the inventive process further contains (d) at least one polysiloxane.
  • Polysiloxanes (d) used according to the present invention can be linear, branched or cyclic polysiloxanes or mixtures thereof. Polysiloxanes (d) have O-Si-0 chains. The free valences on the silicon can be saturated for example by OH, C r C 10 -alkyl or by phenyl, in which case phenyl and especially methyl are preferred. Polysiloxanes used as component (d) according to the present invention are known as such.
  • At least one polysiloxane (d) has a dynamic viscosity in the range from 100 to 2,000 mPa-s, preferably up to 500 and more preferably up to 200 mPa-s, measured in accordance with DIN EN ISO 3219 at 23 0 C.
  • polyethersiloxanes are used as special type of polysiloxanes (d).
  • Particular polyethersiloxanes are ethoxylation products of HO-(CH 2 ) 3 -Si(CH 3 )[OSi(CH 3 ) 3 ] 2 and HO-(CH 2 ) 3 -Si(CH 3 )[OSi(CH 3 ) 3 ][OSi(CH 3 ) 2 - OSi(CH 3 ) 3 ], e.g.
  • polysiloxane (d) can be applied in an amount of from 0.01 to 10% by weight, preferably 0.1 to 2 % by weight, referring to the sum of (a1 ), (a2), and (b).
  • polysiloxane (d) will applied in a weight ratio of from 10 : 1 to 1 : 10 by, preferably from 5 : 1 to 1 : 5, referring to the amount of polyethylene glycol (c).
  • the process of the present invention is carried out using water, e.g., by using an aqueous formulation or an aqueous liquor, wherein said water can be but need not be demineralized.
  • demineralized water or of water having up to 2° German hardness is preferred.
  • Demineralized water is obtainable by methods known to one skilled in the art.
  • the inventive process can be performed continuously.
  • the inventive process can be per- formed by using one or more foulards, preferably by using one or two foulards with one or two inventive aqueous liquors, respectively.
  • One embodiment of the present invention comprises practicing the process of the present invention by pulling a linear textile over one or more rollers and through plural con- tainers or preferably one or two foulards containing one or more aqueous liquors comprising (a1 ), (a2), (b), water and optionally (c) and optionally (d).
  • the rollers of said foulard(s) will exert a contact pressure in the range from 0.1 to 10 bar, prefera- bly in the range from 0.5 to 3 bar and particularly preferably around 2 bar.
  • the solids content of said liquor can be, e.g., in the range from 1 to 15 % by weight, preferably in the range from 3 to 15 % by weight and more preferably in the range from 5 to 10 % by weight.
  • typical treatment times are in the range of one to a few seconds, preferably such as 3 to 10 seconds.
  • the process according to the present invention can be performed at a temperature in the range from 70 to 95°C, preferably in the range from 90 to 95°C.
  • the temperature may be constant during the process of the present invention.
  • a linear textile which has been treated according to the present invention can subsequently be dried, for example by pulling it through a drying unit.
  • Useful drying units include for example cylinder dryers. Drying is done for example at temperatures in the range from 90 to 130 0 C.
  • component (a1 ), component (a2), synthetic polymer (b), optionally polyethylene glycol (c) and optionally polysiloxane (d) is allocated to different aqueous liquors.
  • a particularly preferred embodiment comprises treating a textile according to the present invention by allocating component (a1), component (a2), synthetic polymer (b), optionally polyethylene glycol (c) and optionally polysiloxane (d) to each or even more preferably to the aqueous liquor.
  • the treatment time of linear textile with component (a1 ), component (a2), synthetic polymer (b), optionally polyethylene glycol (c) and optionally polysiloxane (d) is typically short and in the case of a continuous process depends on the speed with which the linear textile to be treated is pulled through the foulard or foulards containing one or more liquors comprising component (a1), component (a2), synthetic polymer (b), optionally polyethylene glycol (c) and optionally polysiloxane (d).
  • Typical machine speeds are in the range from 5 to 300 m/min.
  • Machines pulling just a linear textile, especially just a single yarn through one or more containers containing one or more liquors comprising component (a1 ), component (a2), synthetic polymer (b), optionally polyethylene glycol (c) and optionally polysiloxane (d) can be run at machine speeds of up to 500 m/min.
  • aqueous formulation containing component (a1 ), component (a2), synthetic polymer (b), optionally polyethylene glycol (c) and optionally polysiloxane (d)
  • said aqueous formulation can be diluted to form a liquor with the above liquor ratio.
  • the process of the present invention is preferably carried out using a ratio of about 2 to 15% by weight of liquor to linear textile.
  • size add-ons in the range from 2% to 15% by weight, preferably from 10 to 12%. Size add-on as used herein refers to the ratio of size to linear textile and in particular to warp yarn.
  • a linear textile may further be treated with sulfonated tallow or sulfonated oil.
  • a further aspect of the present invention are aqueous formulations and aqueous liquors, containing
  • At least one synthetic polymer (b) is chosen from vinyl acetate polymers (b1 ), preferably polyvinyl alcohols (b2), more preferably poly(meth)acrylats (b3) and poly(meth)acrylamides (b4).
  • an inventive aqueous formulation or liquor further can contain (c) at least one polyethylene glycol, said polyethylene glycol (c) being described in more detail above.
  • an inventive aqueous formulation or liquor can further contain (d) at least one polysiloxane, said polysiloxane (d) being described in more detail above.
  • inventive aqueous formulations can have a total solids content in the range from 1 to 95 % by weight, preferably 3 to 92 % by weight.
  • inventive liquors can have a total solids content in the range from 1 to 15 % by weight, preferably in the range from 3 to 15 % by weight and more preferably in the range from 5 to 10 % by weight.
  • a further aspect of the present invention are powders, comprising
  • (a1 ) at least one first chemically modified starch with an amylose content of the respective unmodified starch in the range of 20 to 30 % by weight, preferably 23 to 29 %, referring to the sum of amylose and amylopectin of respective unmodified starch
  • (a2) at least one further chemically modified starch with an amylose content of the re- spective unmodified further starch in the range of 10 to 20 % by weight, preferably 15 to 18 % by weight, referring to the sum of amylose and amylopectin of said unmodified further starch
  • inventive powders can be made, e.g., from inventive aqueous formulations by conventional means of drying, e.g. filtration, vacuum filtration and drying at elevated temperature, e.g. flash drying at temperatures in the range from 100 to 150 0 C.
  • drying e.g. filtration, vacuum filtration and drying at elevated temperature, e.g. flash drying at temperatures in the range from 100 to 150 0 C.
  • inventive powders have a moisture con- tent in the range from 1 to 15 % by weight, preferably 5 to 10 % by weight.
  • Inventive powders can advantageously be used for making inventive liquors for the inventive process for treating linear textiles.
  • a further aspect of the present invention is a process for making an inventive aqueous formulation or liquor, comprising mixing
  • Aqueous formulations and particularly inventive aqueous liquors according to the present invention are obtainable for example by mixing water and components component (a1), component (a2), synthetic polymer (b), optionally polyethylene glycol (c) and optionally polysiloxane (d).
  • component (a1), component (a2), synthetic polymer (b), optionally polyethylene glycol (c) and optionally polysiloxane (d) is not critical.
  • Mixing can be performed, e.g., in containers, such as stirred tanks and preferably rotation tanks.
  • Mixing can be performed at elevated temperature, such as 70 to 98°C, preferably 80 to 95°C.
  • Mixing can be performed over a period of time in the range from 15 minutes to 3 hours, preferably 30 minutes to 2 hours.
  • Aqueous formulations according to the present invention are notable, e.g., for good stability in storage.
  • a further aspect of the present invention is a process for making an inventive aqueous formulation or liquor, comprising mixing at least one first unmodified starch with an amylose content of the unmodified starch in the range of 20 to 30 % by weight, preferably 23 to 29 %, referring to the sum of amylose and amylopectin of respective unmodified starch, with at least one further unmodified starch with an amylose content of the unmodified further starch in the range of 10 to 20 % by weight, preferably 15 to 18 % by weight, referring to the sum of amylose and amylopectin of said unmodified further starch, performing at least one chemical modification step, and then adding (b) at least one synthetic polymer, (c) optionally at least one polyethylene glycol, and (d) optionally at least one polysiloxane.
  • the chemical modification step includes an esterification step, e.g., by reacting said chemically unmodified starches with an esteri- fication agent such as acetic acid anhydride, or preferably an oxidation step.
  • an esterification step e.g., by reacting said chemically unmodified starches with an esteri- fication agent such as acetic acid anhydride, or preferably an oxidation step.
  • a mixture of said chemically unmodified starches can be oxidized with peroxides in aqueous solution, preferably with hydrogen peroxide under alkaline conditions, e.g., at a pH value in a range from 10 to 13, preferably 10 to 11.
  • said oxidation of starches can be carried out at temperatures in a range from 20 to 40°C, preferably 30 to 35°C. In one embodiment of the present invention, said oxidation of starches can be carried out at normal pressure.
  • unmodified starches can be used as aqueous solutions or slurries obtained after work-up of, e.g., tapioca, corn or sorghum palm trees.
  • Said aqueous solutions or slurries can have solid contents of, e.g., 25 to 35% by weight in the case of unmodified tapioca starch or, e.g., 75 to 85% by weight of unmodified corn starch.
  • excess base can be neutralized with, e.g. organic or inorganic acids or combinations thereof, to a pH value in the range from 6 to 7.5.
  • oxidant such as chlorine bleach or peroxide such as hydrogen peroxide
  • excess oxidant can be destroyed (removed) by adding a reducing agent, e.g. NaHSO 3 or KHSO 3 .
  • chemically modified starch will be obtained as an aqueous solution that needs no further purification other than neutraliza- tion and optionally removal of excess oxidant.
  • (partial) esterification of oxidized starch is desired, said (partial) esterification will be preferably performed after oxidation.
  • Said (partial) esterification can be carried out at, e.g., pH values in the range from 6.0 to 7.5, preferably to 7.0.
  • Said (partial) esterifica- tion can be carried out at, e.g., a temperature in the range from 20 0 C to 40 0 C.
  • Unreacted carboxylic acid, in particular unreacted adipic acid can be removed from said chemically modified starch. It is preferred, though, to not remove unreacted carboxylic acid, in particular unreacted adipic acid from chemically modified starch.
  • Synthetic polymers (b) as defined above are obtainable by methods known per se, especially free-radical (co)polymerization, batchwise or continuously, for example bulk (co)polymerization, emulsion (c)polymerization, precipitation (co)polymerization and preferably solution (co)polymerization, for example in water as a solvent.
  • Linear textiles treated according to the inventive process feature particularly good mechanical properties. If used as warp yarns, the weaving efficiency is very good and break of warp only rarely occurs. Furthermore, linear textiles treated according to the inventive process can be cleaned easily, the waste water having only little organic resi- dues. Linear textiles treated according to the present invention furthermore exhibit a very homogeneous appearance.
  • Linear textiles treated according to the inventive process thus also constitute an aspect of the present invention.
  • inventive linear textiles have an add-on in the range from 2 to 10% by weight, preferably to 7% by weight. If used as warp yarns, the weaving efficiency is very good and break of warp only rarely occurs.
  • inventive linear textiles are derived from natural fibers, in particular from cotton.
  • inventive linear textiles are se- lected from warp yarns, in particular with a diameter of 1 to 40 NE, preferably 2 to 30 NE and more preferably 5 to 10 NE.
  • a further aspect of the present invention is a method of use of inventive treated linear textiles as warp.
  • a further aspect of the present invention is a method of use of inven- tive treated linear textiles as warp for weaving textiles. In the course of the inventive method of use, breakage of warp rarely occurs and cleaning after weaving is particularly easy.
  • Amounts given in g/l are each based on g/l of liquor. Percentages refer to % by weight unless noted otherwise. Viscosity determinations were each carried out with a Brookfield spindle 2 at 100 revolutions/minute at 23°C on the lines of DIN EN ISO 3219.
  • Polyacrylate (b3.1) was added according to table 1. Stirring was continued for 10 minutes, then the pH value was adjusted to 8.0 with aqueous acetic acid (50%). Stirring was continued for another 10 minutes, then polyacrylamide (b4.1), polysiloxane (d.1) and optionally polyethylene glykol (c.1 ) were added according to table 1. Stirring was continued for 30 minutes, then the pH was adjusted to 7.0 with solid adipic acid. Stirring was continued for another five hours, then the pH value was adjusted to 6.0 to 6.5 with aqueous HCI (10%). The H 2 O 2 content was checked with Kl paper, when Kl was blue the remaining unreacted H 2 O 2 was destroyed with a sufficient amount of solid Na- HSO 3 , the progress of the removal H 2 O 2 of being monitored with the Kl test.
  • the solution obtained was filtered with a vacuum filter and dried up to a moisture content of 40%. Then, the residue was dried in a flash dryer at 140°C for 20 seconds. Inventive powders P.1 or P.2 or comparative powder V-P.3, respectively, was obtained. The moisture contents were 8% in each case.
  • Inventive liquor L.1 was prepared by cooking 93 I water (2° German hardness) and 7 kg inventive powder P.1 for 20 minutes at a temperature of 92°C.
  • Inventive liquor L.2 was prepared by cooking 93 I water (2° German hardness) and 7 kg inventive powder P.2 for 20 minutes at a temperature of 92°C.
  • Comparative liquor V-L.3 was prepared by cooking 93 I water (2° German hardness) and 7 kg comparative powder V-P.3 for 20 minutes at a temperature of 92°C.
  • the so-treated linear cotton was then dried continuously, the temperature being risen from 90 to 140 0 C, to 8% humidity.
  • inventive liquor L.2 or comparative liquor V-L.3 were applied and inventive treated linear cotton CT.2 and comparative treated cotton V-CT.3 were obtained, respectively.
  • Non-linear textiles were woven using each inventive treated cotton CT.1 , inventive treated cotton CT.2 and comparative treated cotton V-CT.3 as warp. There were less breakages when using inventive each inventive treated cotton CT.1 or inventive treated cotton CT.2 as warp compared to using comparative treated cotton V-CT.3. Woven non-linear textiles could be desized easily when using inventive each inventive treated cotton CT.1 or inventive treated cotton CT.2.

Abstract

Process for treating linear textiles, which comprises treating said linear textiles with an aqueous formulation or liquor containing (a1 ) at least one first chemically modified starch with an amylose content of the respective unmodified starch in the range of 20 to 30 % by weight, referring to the sum of amylose and amylopectin of said unmodified starch, (a2) at least one further chemically modified starch with an amylose content of the respective unmodified further starch in the range of 10 to 20 % by weight, referring to the sum of amylose and amylopectin of said unmodified further starch, (b) at least one synthetic polymer.

Description

Textile treatment
Description
The present invention relates to a process for treating linear textiles, which comprises treating said linear textiles with an aqueous formulation or liquor containing (a1) at least one first chemically modified starch with an amylose content of the respective unmodified starch in the range of 20 to 30 % by weight, referring to the sum of amylose and amylopectin of said unmodified starch, (a2) at least one further chemically modified starch with an amylose content of the respective unmodified further starch in the range of 10 to 20 % by weight, referring to the sum of amylose and amylopectin of said unmodified further starch, (b) at least one synthetic polymer.
The present invention further relates to liquors and aqueous formulations useful for carrying out the process of the present invention and process for making said aqueous formulations and liquors.
Linear textiles, especially spun yarns, are treated with a solution, a dispersion or a melt of a macromolecular compound before they are processed. The macromolecular compound applied to the fiber can be washed off or removed otherwise, such as destroyed after processing. When such a treatment is carried out in order that higher smoothness, suppleness, strength and coherency may be achieved prior to weaving, this is referred to as sizing of yarns. Sizing agents, also known as sizes, are typically washed off re- moved otherwise, such as destroyed again to a very substantial degree after weaving, in an operation also known as desizing.
Commonly used sizing agents are typically selected from natural macromolecular compounds such as for example starch, from modified natural macromolecular compounds such as for example modified starch and from synthetic macromolecular compounds such as for example polyvinyl alcohol, polyesters and poly(meth)acrylates; see for example Ullmann's Encyclopedia of Industrial Chemistry, Vol. 36, 6th edition, pages 18 to 26, Wiley-VCH Weinheim, 2003. Various starch formulations, however, have poor running properties and need a massive add-on.
Treatment processes are therefore desired for sizes (but also for other applications to textiles) whereby the textile is treated with synthetic macromolecular compounds in order that the treated textile may have very good mechanical properties. In addition, the applied synthetic macromolecular compounds shall be readily removable with aqueous liquors. Numerous synthetic macromolecular compounds have been suggested as sizing materials but they are usually expensive. When at a later stage desizing takes place, considerable investments in size recovery will be required.
It was task of the present invention to provide a process a process to treat linear textiles that avoids the disadvantages of the prior art processes. Furthermore, it was task of the present invention to provide formulations of reagents that are suitable for treating linear textiles, and to provide a process for making said formulations
The present invention accordingly provides the process defined at the beginning.
Linear textile in the context of the present invention refers to linear structures such as textile fibers, including staple fibers, twine, filaments, rovings, spun yarns, lines, strings, cordage, threads. Textiles can be of natural origin, examples being silk, wool, flax, ramie, hemp or coir or especially cotton, or synthetic, examples being regenerated cellulose such as for example cuprammonium silk, viscose or cellulose acetates such as acetate and triacetate, also polyamide, polyacrylonitrile, polypropylene and polyester. Blends are also useful, examples being cotton-polyester blends. A textile for the purposes of the present invention may be present as staple fiber, in the form of filaments or as staple fiber yarn.
Linear textile treated by the process of the present invention can be of any color, and it can have one color or more than one color. Linear textile treated by the process of the present invention is preferably uncolored.
Linear textile in a preferred embodiment of the present invention refers to warp yarns composed of cellulosic fiber, polyester-cellulosic blends, wool, polyester- wool blends, viscose filament or acetate filament and particularly preferable to warp yarns composed of cellulosic fiber or polyester-cellulosic blends.
In the present invention, linear textile is treated with an aqueous formulation or liquor containing
(a1 ) at least one first chemically modified starch, in the context of the present invention also being referred to as chemically modified starch (a1) or briefly as component (a1 ), with an amylose content of the respective unmodified starch in the range of 20 to 30 % by weight, preferably 23 to 29 % by weight, referring to the sum of amylose and amy- lopectin of respective unmodified starch,
(a2) at least one further chemically modified starch, in the context of the present invention also being referred to as chemically modified starch (a2) or briefly as component (a2), with an amylose content of the respective unmodified further starch in the range of 10 to 20 % by weight, preferably 15 to 18 % by weight, referring to the sum of amylose and amylopectin of said unmodified further starch, (b) at least one synthetic polymer.
Chemically modified starch can be carboxymethylated starch or preferably oxidized starch. Most preferably, both chemically modified starches, component (a1 ) and com- ponent (a2), are oxidized starch.
Component (a1 ) can be obtained from sorghum starch or preferably from corn starch, in particular to so-called normal corn starch in contrast to waxy corn starch and further in contrast to so-called high-amylose starch.
Component (a2) can be obtained from tapioca starch.
Processes for oxidizing starch are known as such. In most instances, starch will be slurried or dissolved in water and be treated with an oxidant or a mixture of oxidants.
In one embodiment of the present invention, chemically modified starch can be used as components (a1 ) and (a2) which have been oxidized under alkaline conditions, e.g., at a pH value in the range from 10 to 13, preferably from 10 to 11.
In one embodiment of the present invention, chemically modified starch can be used as components (a1) and (a2) which has been oxidized with one or more oxidants such as chlorine bleach, preferably with peroxides in aqueous solution, preferably with hydrogen peroxide.
In one embodiment of the present reaction, chemically modified starch can be be used as components (a1) and (a2) which has been esterified, preferably partially esterified with one or more carboxylic acids and in particular dicarboxylic acids such as succinic acid, glutaric acid and most preferably adipic acid.
In one preferred embodiment of the present reaction, chemically modified starch can be used as components (a1) and (a2) which has been oxidized with one or more oxidants such as chlorine bleach, preferably with peroxides in aqueous solution, preferably with hydrogen peroxide, and after oxidation has been esterified, preferably partially esterified with one or more carboxylic acids and in particular dicarboxylic acids such as succinic acid, glutaric acid and most preferably adipic acid.
In one embodiment of the present invention, the weight ratio of (a1) to (a2) is in a range from 99 : 1 to 1 : 99, preferably from 20 : 1 to 1 : 20.
The process of the present invention furthermore includes (b) at least one synthetic polymer in an aqueous formulation or liquor for treating said linear textile, in the context of the present invention also referred to as synthetic polymer (b). Synthetic polymer (b) can be made by, e.g., radical polymerization of one or more ethylenically unsaturated (vinylic) monomers and can refer to homo- or copolymers.
In one embodiment of the present invention, said synthetic polymer (b) has an average molecular weight Mw in the range from 20,000 to 20,000,000 g/mol, preferably to 10,000,000 g/mol.
In one embodiment of the present invention, synthetic polymers can be selected from vinyl acetate polymers (b1 ), preferably polyvinyl alcohols (b2) and more preferably poly(meth)acrylates (b3), and preferably polyacrylamides (b4).
Suitable vinyl acetate polymers (b1) can be made by, e.g., free radical polymerization of vinyl acetate and/or vinyl propionate, the homopolymerization of vinyl acetate being preferred. Suitable vinyl acetate polymers can have an average molecular weight Mw in the range from 20,000 to 250,000 g/mol.
Suitable polyvinyl alcohols (b2) can be made by, e.g., free radical polymerization of vinyl acetate followed by hydrolysis of the ester groups. Suitable polyvinyl alcohols (b2) can have an average molecular weight Mw in the range from 20,000 to 250,000 g/mol.
In one embodiment of the present reaction, polyvinyl alcohols (b2) have a viscosity in the range from 1 to 20 mPa-s, preferably from 10 to 15 mPa-s, measured by, e.g., on 4% by weight (bone dry basis) aqueous solution at 2O0C by the Hoeppler falling ball method.
Suitable poly(meth)acrylates (b3) include (co)polymers of (meth)acrylic acid preferably with one or more ethylenically unsaturated (di)carboxylic acid(s) and optionally with (meth)acrylic acid Ci-CiO-alkyl esters, wherein Ci-CiO-alkyl can be branched or non- branched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, preferably methyl.
Copolymers of (meth)acrylic acid CrC10-alkyl esters include blockcopolymers, alternating copolymers, and random copolymers of two or more (meth)acrylic acid Ci-C,o-alkyl esters and blockcopolymers, alternating copolymers, and random copolymers of one or more (meth)acrylic acid Ci-C10-alkyl esters with (meth)acrylic acid.
Preferred poly(meth)acrylates (b3) include homopolymers of acrylic acid and methacrylic acid and blockcopolymers, alternating copolymers, and preferably random copolymers of of acrylic acid and methacrylic acid and blockcopolymers, alternating copolymers, and preferably random copolymers of (meth)acrylic acid with one or more (di)carboxylic acids such as crotonic acid and preferably fumaric acid, itaconic acid and more preferably maleic acid.
Preferred (co)polymers of (meth)acrylic acid such as poly(meth)acrylic acid and block- copolymers, alternating copolymers, and preferably random copolymers of one or more (meth)acrylic acid Ci-CiO-alkyl esters with (meth)acrylic acid can be partially or fully neutralized to form their respective alkali metal salts or ammonium salts, alkali metals being selected from lithium and preferably from sodium and potassium.
Preferred poly(meth)acrylates (b3) can have an average molecular weight Mw in the range from 20,000 to 250,000 g/mol, preferably from 50,000 to 150,000 g/mol.
In one embodiment of the present invention, synthetic polymer (b) is selected from poly(meth)acrylates (b3) obtained by free-radical copolymerization of 60 to 80 % by weight (meth)acrylic acid, preferably 65 to 75 % by weight, 20 to 40 % by weight maleic acid, preferably 35 to 25 % by weight, and subsequent neutralization with sodium hydroxide.
Suitable poly(meth)acrylamides (b4) include homopolymers of (meth)acrylamide, pref- erably acrylamide, blockcopolymers, alternating copolymers, and preferably random copolymers of acrylamide and methacrylamide, and blockcopolymers, alternating copolymers, and preferably random copolymers (co)polymers of (meth)acrylamide one or more ethylenically unsaturated acids such as maleic acid, crotonic acid and in particular methacrylic acid and acrylic acid.
Preferred poly(meth)acrylamides (b4) can have an average molecular weight Mw in the range from 1 ,000,000 to 20,000,000 g/mol, preferably 2,000,000 to 10,000,000 g/mol and more preferably 4,000,000 to 8,000,000 g/mol.
In poly(meth)acrylamides (b4) that are blockcopolymers, alternating copolymers, or preferably random copolymers of (meth)acrylamide with one or more ethylenically unsaturated acids such as maleic acid, crotonic acid and in particular methacrylic acid and acrylic acid, said ethylenically unsaturated acid can be partially or fully neutralized to form its respective alkali metal salt or ammonium salt, alkali metals being selected from lithium and preferably from sodium and potassium.
In one embodiment of the present invention, synthetic polymer (b) is selected from poly(meth)acrylamides (b4) obtained by free-radical copolymerization of 20 to 80 % by weight (meth)acrylamide, preferably 50 to 70 % by weight, and 20 to 80 % by weight (meth)acrylic acid, preferably 30 to 50 % by weight, and subsequent neutralization with sodium hydroxide. In one embodiment of the present invention, at least one poly(meth)acrylamide (b4) has a dynamic viscosity in the range from 30 to 2,000 mPa-s, preferably from 1 ,000 to 1 ,800 and more preferably from 1 ,200 to 1 ,300 mPa-s, measured as a 5% by weight aqueous solution in accordance with DIN EN ISO 3219 at 230C.
In one embodiment of the present invention, the aqueous formulation or liquor for carrying out the inventive process further contains at least one poly(meth)acrylate (b3) and at least one poly(meth)acrylamide (b4), poly(meth)acrylates (b3) and poly(meth)acrylamides (b4) being defined above.
In a preferred embodiment, the weight ratio between poly(meth)acrylate (b3) and poly(meth)acrylamide (b4) is in the range from 10,000 to 1 to 50 : 1 , preferably from 600 : 1 to 100 : 1.
In one embodiment of the present reaction, the weight ratio of synthetic polymer (b) to the sum of (a1 ) and (a2) is in the range from 0.1 to 10 %, preferably from 1 to 7 %.
In one embodiment of the present invention, the aqueous formulation or liquor for carrying out the inventive process further contains (c) at least one polyethylene glycol.
Polyethylene glycols in the context of the present invention are compounds of the general formula HO(CH2CH2O)nH, n being an integer from 20 to 500. Preferred polyethylene glycols are waxy compounds with an average molecular weight Mw in the range from 1 ,000 to 10,000 g/mol.
In one embodiment of the present invention, polyethylene glycol (c) can be applied in an amount of from 0.01 to 10% by weight, preferably 0.1 to 2 % by weight, referring to the sum of (a1 ) and (a2).
In one embodiment of the present invention, the aqueous formulation or liquor for carrying out the inventive process further contains (d) at least one polysiloxane.
Polysiloxanes (d) used according to the present invention can be linear, branched or cyclic polysiloxanes or mixtures thereof. Polysiloxanes (d) have O-Si-0 chains. The free valences on the silicon can be saturated for example by OH, CrC10-alkyl or by phenyl, in which case phenyl and especially methyl are preferred. Polysiloxanes used as component (d) according to the present invention are known as such. In one embodiment of the present invention, at least one polysiloxane (d) has a dynamic viscosity in the range from 100 to 2,000 mPa-s, preferably up to 500 and more preferably up to 200 mPa-s, measured in accordance with DIN EN ISO 3219 at 230C.
In one embodiment of the present invention, polyethersiloxanes are used as special type of polysiloxanes (d). Particular polyethersiloxanes are ethoxylation products of HO-(CH2)3-Si(CH3)[OSi(CH3)3]2 and HO-(CH2)3-Si(CH3)[OSi(CH3)3][OSi(CH3)2- OSi(CH3)3], e.g. H(OCH2CH2)a-O-(CH2)3-Si(CH3)[OSi(CH3)3]2 and H(OCH2CH2)a-O-(CH2)3-Si(CH3)[OSi(CH3)3][OSi(CH3)2-OSi(CH3)3], with a being an in- teger in the range from 1 to 100, preferably in the range from 2 to 10.
In one embodiment of the present invention, polysiloxane (d) can be applied in an amount of from 0.01 to 10% by weight, preferably 0.1 to 2 % by weight, referring to the sum of (a1 ), (a2), and (b).
In one embodiment of the present invention, polysiloxane (d) will applied in a weight ratio of from 10 : 1 to 1 : 10 by, preferably from 5 : 1 to 1 : 5, referring to the amount of polyethylene glycol (c).
The process of the present invention is carried out using water, e.g., by using an aqueous formulation or an aqueous liquor, wherein said water can be but need not be demineralized. The use of demineralized water or of water having up to 2° German hardness is preferred. Demineralized water is obtainable by methods known to one skilled in the art.
In a preferred embodiment of the present invention, the inventive process can be performed continuously.
In a preferred embodiment of the present reaction, the inventive process can be per- formed by using one or more foulards, preferably by using one or two foulards with one or two inventive aqueous liquors, respectively.
One embodiment of the present invention comprises practicing the process of the present invention by pulling a linear textile over one or more rollers and through plural con- tainers or preferably one or two foulards containing one or more aqueous liquors comprising (a1 ), (a2), (b), water and optionally (c) and optionally (d).
In case one or more foulards are applied to carry out the inventive process, the rollers of said foulard(s) will exert a contact pressure in the range from 0.1 to 10 bar, prefera- bly in the range from 0.5 to 3 bar and particularly preferably around 2 bar. In case a liquor containing component (a1), component (a2), synthetic polymer (b), optionally polyethylene glycol (c) and optionally polysiloxane (d) is applied, the solids content of said liquor can be, e.g., in the range from 1 to 15 % by weight, preferably in the range from 3 to 15 % by weight and more preferably in the range from 5 to 10 % by weight.
In one embodiment of the present invention, typical treatment times are in the range of one to a few seconds, preferably such as 3 to 10 seconds.
The process according to the present invention can be performed at a temperature in the range from 70 to 95°C, preferably in the range from 90 to 95°C. The temperature may be constant during the process of the present invention.
Excess aqueous moisture can subsequently be squeezed off. A linear textile which has been treated according to the present invention can subsequently be dried, for example by pulling it through a drying unit. Useful drying units include for example cylinder dryers. Drying is done for example at temperatures in the range from 90 to 1300C.
To treat a textile with plural aqueous liquors according to the present invention, one option is to allocate component (a1 ), component (a2), synthetic polymer (b), optionally polyethylene glycol (c) and optionally polysiloxane (d) to different aqueous liquors.
A particularly preferred embodiment comprises treating a textile according to the present invention by allocating component (a1), component (a2), synthetic polymer (b), optionally polyethylene glycol (c) and optionally polysiloxane (d) to each or even more preferably to the aqueous liquor.
The treatment time of linear textile with component (a1 ), component (a2), synthetic polymer (b), optionally polyethylene glycol (c) and optionally polysiloxane (d) is typically short and in the case of a continuous process depends on the speed with which the linear textile to be treated is pulled through the foulard or foulards containing one or more liquors comprising component (a1), component (a2), synthetic polymer (b), optionally polyethylene glycol (c) and optionally polysiloxane (d). Typical machine speeds are in the range from 5 to 300 m/min. Machines pulling just a linear textile, especially just a single yarn through one or more containers containing one or more liquors comprising component (a1 ), component (a2), synthetic polymer (b), optionally polyethylene glycol (c) and optionally polysiloxane (d) can be run at machine speeds of up to 500 m/min.
In case an aqueous formulation containing component (a1 ), component (a2), synthetic polymer (b), optionally polyethylene glycol (c) and optionally polysiloxane (d) is applied, said aqueous formulation can be diluted to form a liquor with the above liquor ratio. The process of the present invention is preferably carried out using a ratio of about 2 to 15% by weight of liquor to linear textile. When the process of the present invention is practiced as a process for sizing linear textile, it is preferable to employ size add-ons in the range from 2% to 15% by weight, preferably from 10 to 12%. Size add-on as used herein refers to the ratio of size to linear textile and in particular to warp yarn.
In addition to the above-described measures of the present invention, a linear textile may further be treated with sulfonated tallow or sulfonated oil.
A further aspect of the present invention are aqueous formulations and aqueous liquors, containing
(a1) at least one first chemically modified starch with an amylose content of the respective unmodified starch in the range of 20 to 30 % by weight, preferably 23 to 29 %, re- ferring to the sum of amylose and amylopectin of respective unmodified starch,
(a2) at least one further chemically modified starch with an amylose content of the respective unmodified further starch in the range of 10 to 20 % by weight, preferably 15 to 18 % by weight, referring to the sum of amylose and amylopectin of said unmodified further starch, (b) at least one synthetic polymer,
components (a1), (a2) and synthetic polymer (b) being defined as mentioned above.
In a special embodiment of the present invention, at least one synthetic polymer (b) is chosen from vinyl acetate polymers (b1 ), preferably polyvinyl alcohols (b2), more preferably poly(meth)acrylats (b3) and poly(meth)acrylamides (b4).
In a special embodiment of the present invention, an inventive aqueous formulation or liquor further can contain (c) at least one polyethylene glycol, said polyethylene glycol (c) being described in more detail above.
In a special embodiment of the present invention, an inventive aqueous formulation or liquor can further contain (d) at least one polysiloxane, said polysiloxane (d) being described in more detail above.
In one embodiment of the present invention, inventive aqueous formulations can have a total solids content in the range from 1 to 95 % by weight, preferably 3 to 92 % by weight. In one embodiment of the present invention, inventive liquors can have a total solids content in the range from 1 to 15 % by weight, preferably in the range from 3 to 15 % by weight and more preferably in the range from 5 to 10 % by weight.
A further aspect of the present invention are powders, comprising
(a1 ) at least one first chemically modified starch with an amylose content of the respective unmodified starch in the range of 20 to 30 % by weight, preferably 23 to 29 %, referring to the sum of amylose and amylopectin of respective unmodified starch, (a2) at least one further chemically modified starch with an amylose content of the re- spective unmodified further starch in the range of 10 to 20 % by weight, preferably 15 to 18 % by weight, referring to the sum of amylose and amylopectin of said unmodified further starch,
(b) at least one synthetic polymer,
(c) optionally at least one polyethylene glycol and (d) optionally at least one polysiloxane,
components (a1 ), (a2), synthetic polymer (b), polyethylene glycol (c) and polysiloxane
(d) being defined as mentioned above.
Inventive powders can be made, e.g., from inventive aqueous formulations by conventional means of drying, e.g. filtration, vacuum filtration and drying at elevated temperature, e.g. flash drying at temperatures in the range from 100 to 1500C.
In one embodiment of the present invention, inventive powders have a moisture con- tent in the range from 1 to 15 % by weight, preferably 5 to 10 % by weight.
Inventive powders can advantageously be used for making inventive liquors for the inventive process for treating linear textiles.
A further aspect of the present invention is a process for making an inventive aqueous formulation or liquor, comprising mixing
(a1 ) at least one first starch, which can be chemically modified, with an amylose content of the unmodified starch in the range of 20 to 30 % by weight, preferably 23 to 29 %, referring to the sum of amylose and amylopectin of respective unmodified starch, (a2) at least one further starch, which can be chemically modified, with an amylose content of the unmodified further starch in the range of 10 to 20 % by weight, preferably 15 to 18 % by weight, referring to the sum of amylose and amylopectin of said unmodified further starch, (b) at least one synthetic polymer, and (c) optionally at least one polyethylene glycol and (d) optionally at least one polysiloxane. Aqueous formulations and particularly inventive aqueous liquors according to the present invention are obtainable for example by mixing water and components component (a1), component (a2), synthetic polymer (b), optionally polyethylene glycol (c) and optionally polysiloxane (d). The order of the addition of component (a1), component (a2), synthetic polymer (b), optionally polyethylene glycol (c) and optionally polysiloxane (d) is not critical.
Mixing can be performed, e.g., in containers, such as stirred tanks and preferably rotation tanks.
Mixing can be performed at elevated temperature, such as 70 to 98°C, preferably 80 to 95°C.
Mixing can be performed over a period of time in the range from 15 minutes to 3 hours, preferably 30 minutes to 2 hours.
Aqueous formulations according to the present invention are notable, e.g., for good stability in storage.
A further aspect of the present invention is a process for making an inventive aqueous formulation or liquor, comprising mixing at least one first unmodified starch with an amylose content of the unmodified starch in the range of 20 to 30 % by weight, preferably 23 to 29 %, referring to the sum of amylose and amylopectin of respective unmodified starch, with at least one further unmodified starch with an amylose content of the unmodified further starch in the range of 10 to 20 % by weight, preferably 15 to 18 % by weight, referring to the sum of amylose and amylopectin of said unmodified further starch, performing at least one chemical modification step, and then adding (b) at least one synthetic polymer, (c) optionally at least one polyethylene glycol, and (d) optionally at least one polysiloxane.
In one embodiment of the present invention, the chemical modification step includes an esterification step, e.g., by reacting said chemically unmodified starches with an esteri- fication agent such as acetic acid anhydride, or preferably an oxidation step.
In a preferred embodiment, a mixture of said chemically unmodified starches can be oxidized with peroxides in aqueous solution, preferably with hydrogen peroxide under alkaline conditions, e.g., at a pH value in a range from 10 to 13, preferably 10 to 11.
In one embodiment of the present invention, said oxidation of starches can be carried out at temperatures in a range from 20 to 40°C, preferably 30 to 35°C. In one embodiment of the present invention, said oxidation of starches can be carried out at normal pressure.
In one embodiment of the present reaction, unmodified starches can be used as aqueous solutions or slurries obtained after work-up of, e.g., tapioca, corn or sorghum palm trees. Said aqueous solutions or slurries can have solid contents of, e.g., 25 to 35% by weight in the case of unmodified tapioca starch or, e.g., 75 to 85% by weight of unmodified corn starch.
After oxidation, excess base can be neutralized with, e.g. organic or inorganic acids or combinations thereof, to a pH value in the range from 6 to 7.5.
After oxidation and in case non-consumed oxidant such as chlorine bleach or peroxide such as hydrogen peroxide is present, excess oxidant can be destroyed (removed) by adding a reducing agent, e.g. NaHSO3 or KHSO3.
In one embodiment of the present invention, chemically modified starch will be obtained as an aqueous solution that needs no further purification other than neutraliza- tion and optionally removal of excess oxidant.
If (partial) esterification of oxidized starch is desired, said (partial) esterification will be preferably performed after oxidation. Said (partial) esterification can be carried out at, e.g., pH values in the range from 6.0 to 7.5, preferably to 7.0. Said (partial) esterifica- tion can be carried out at, e.g., a temperature in the range from 200C to 400C.
Unreacted carboxylic acid, in particular unreacted adipic acid can be removed from said chemically modified starch. It is preferred, though, to not remove unreacted carboxylic acid, in particular unreacted adipic acid from chemically modified starch.
Synthetic polymers (b) as defined above are obtainable by methods known per se, especially free-radical (co)polymerization, batchwise or continuously, for example bulk (co)polymerization, emulsion (c)polymerization, precipitation (co)polymerization and preferably solution (co)polymerization, for example in water as a solvent.
Linear textiles treated according to the inventive process feature particularly good mechanical properties. If used as warp yarns, the weaving efficiency is very good and break of warp only rarely occurs. Furthermore, linear textiles treated according to the inventive process can be cleaned easily, the waste water having only little organic resi- dues. Linear textiles treated according to the present invention furthermore exhibit a very homogeneous appearance.
Linear textiles treated according to the inventive process thus also constitute an aspect of the present invention.
In one embodiment of the present invention, inventive linear textiles have an add-on in the range from 2 to 10% by weight, preferably to 7% by weight. If used as warp yarns, the weaving efficiency is very good and break of warp only rarely occurs.
In a preferred embodiment of the present invention, inventive linear textiles are derived from natural fibers, in particular from cotton.
In a preferred embodiment of the present invention, inventive linear textiles are se- lected from warp yarns, in particular with a diameter of 1 to 40 NE, preferably 2 to 30 NE and more preferably 5 to 10 NE.
A further aspect of the present invention is a method of use of inventive treated linear textiles as warp. A further aspect of the present invention is a method of use of inven- tive treated linear textiles as warp for weaving textiles. In the course of the inventive method of use, breakage of warp rarely occurs and cleaning after weaving is particularly easy.
Working examples further illustrate the invention.
General remarks:
Amounts given in g/l are each based on g/l of liquor. Percentages refer to % by weight unless noted otherwise. Viscosity determinations were each carried out with a Brookfield spindle 2 at 100 revolutions/minute at 23°C on the lines of DIN EN ISO 3219.
1. Preparation of inventive powders P.1 , P.2 and comparative example V-P.3, general procedure
In a stirred tank, solutions/slurries of unmodified corn starch (80% solids) and unmodified tapioca starch (30% solids) were mixed at room temperature in quantities according to table 1. The pH value of the milky solution obtained was adjusted to 10.5 with 6% aqueous NaOH. Then, an amount of 0.6 % of hydrogen peroxide was added as 30% aqueous H2O2 solution, percentages being based on solids of the starch solution and pure H2O2. The reaction mixture was stirred at room temperature for three hours. The reaction was monitored with a Kl (potassium iodide) test.
After three hours, the Kl test was still positive indicating that unreacted H2O2 was still present.
Polyacrylate (b3.1) was added according to table 1. Stirring was continued for 10 minutes, then the pH value was adjusted to 8.0 with aqueous acetic acid (50%). Stirring was continued for another 10 minutes, then polyacrylamide (b4.1), polysiloxane (d.1) and optionally polyethylene glykol (c.1 ) were added according to table 1. Stirring was continued for 30 minutes, then the pH was adjusted to 7.0 with solid adipic acid. Stirring was continued for another five hours, then the pH value was adjusted to 6.0 to 6.5 with aqueous HCI (10%). The H2O2 content was checked with Kl paper, when Kl was blue the remaining unreacted H2O2 was destroyed with a sufficient amount of solid Na- HSO3, the progress of the removal H2O2 of being monitored with the Kl test.
The solution obtained was filtered with a vacuum filter and dried up to a moisture content of 40%. Then, the residue was dried in a flash dryer at 140°C for 20 seconds. Inventive powders P.1 or P.2 or comparative powder V-P.3, respectively, was obtained. The moisture contents were 8% in each case.
Table 1: Further experimental details
Figure imgf000015_0001
Polyacrylate (b3.1): 40% aqueous solution of random copolymer of acrylic acid (70%) and maleic acid (30%), fully neutralized with NaOH, pH value 7.9, Mw 70,000 g/mol. Polyacrylamide (b4.1): random copolymer of acrylamide (60%) and acrylic acid (40%), fully neutralized with NaOH, dynamic viscosity (5% aqueous solution) 1250 mPa-s. Polyethylene glykol (c.1 ): Mw 9,000 g/mol. Polysiloxane (d.1 ): H(OCH2CH2)8-O-(CH2)3-Si(CH3)[OSi(CH3)3][OSi(CH3)2-OSi(CH3)3]. 2. Treatment of a linear textile
2.1. Preparation of inventive aqueous liquors and of a comparative liquor for treating a linear textile
Inventive liquor L.1 was prepared by cooking 93 I water (2° German hardness) and 7 kg inventive powder P.1 for 20 minutes at a temperature of 92°C.
Inventive liquor L.2 was prepared by cooking 93 I water (2° German hardness) and 7 kg inventive powder P.2 for 20 minutes at a temperature of 92°C.
Comparative liquor V-L.3 was prepared by cooking 93 I water (2° German hardness) and 7 kg comparative powder V-P.3 for 20 minutes at a temperature of 92°C.
2.2 Treatment of linear textile
On a continuous sizing machine (foulard) cotton yarn English ct 30 NE was sized using inventive liquor L.1. The machine was adjusted to the following parameters:
5,000 to 6,000 yarns, add-on: 7%, residence time: 5 seconds. Contact pressure 18 kN.
The so-treated linear cotton was then dried continuously, the temperature being risen from 90 to 1400C, to 8% humidity.
Inventive treated linear cotton CT.1 was obtained.
The experiment described above was repeated, but inventive liquor L.2 or comparative liquor V-L.3 were applied and inventive treated linear cotton CT.2 and comparative treated cotton V-CT.3 were obtained, respectively.
2.3 Weaving
Non-linear textiles were woven using each inventive treated cotton CT.1 , inventive treated cotton CT.2 and comparative treated cotton V-CT.3 as warp. There were less breakages when using inventive each inventive treated cotton CT.1 or inventive treated cotton CT.2 as warp compared to using comparative treated cotton V-CT.3. Woven non-linear textiles could be desized easily when using inventive each inventive treated cotton CT.1 or inventive treated cotton CT.2.

Claims

Claims
1. Process for treating linear textiles, which comprises treating said linear textiles with an aqueous formulation or liquor containing
(a1 ) at least one first chemically modified starch with an amylose content of the respective unmodified starch in the range of 20 to 30 % by weight, referring to the sum of amylose and amylopectin of said unmodified starch,
(a2) at least one further chemically modified starch with an amylose content of the respective unmodified further starch in the range of 10 to 20 % by weight, referring to the sum of amylose and amylopectin of said unmodified further starch,
(b) at least one synthetic polymer.
2. Process according to claim 1 , wherein at least one synthetic polymer (b) is chosen from polyvinyl alcohol, vinyl acetate polymers, poly(meth)acrylates, and poly- acrylamides.
3. Process according to any of claims 1 or 2, wherein said formulation or liquor further contains
(c) at least one polyethylene glycol.
4. Process according to any of claims 1 to 3, wherein said formulation or liquor fur- ther contains
(d) at least one polysiloxane.
5. Process according to any of claims 1 to 4, wherein said synthetic polymer (b) has an average molecular weight Mw in the range from 20,000 to 20,000,000 g/mol.
6. Process according to any of claims 1 to 5, wherein chemical modified starches (a1 ) and (a2) can be obtained from natural starch by oxidation of the respective natural starch with hydrogen peroxide in aqueous solution.
7. Aqueous formulation or liquor containing
(a1) at least one first starch, which can chemically modified, with an amylose content of the unmodified starch in the range of 20 to 30 % by weight, referring to the sum of amylose and amylopectin of said unmodified starch, (a2) at least one further starch, which can chemically modified, with an amylose content of the unmodified further starch in the range of 10 to 20 % by weight, referring to the sum of amylose and amylopectin of said unmodified further starch, (b) at least one synthetic polymer.
8. Aqueous formulation or liquor according to claim 7, wherein at least one synthetic polymer (b) is chosen from polyvinyl alcohol, vinyl acetate polymers, poly(meth)acrylates, and polyacrylamides.
9. Aqueous formulation or liquor according to any of claims 7 or 8, wherein said formulation or liquor further contains
(c) at least one polyethylene glycol.
10. Aqueous formulation or liquor according to any of claims 7 to 9, wherein said formulation or liquor further contains
(d) at least one polysiloxane.
11. Process for making an aqueous formulation or liquor according to any of claims 7 to 10, comprising mixing
(a1 ) at least one first starch, which can chemically modified, with an amylose content of the unmodified starch in the range of 20 to 30 % by weight, referring to the sum of amylose and amylopectin of said unmodified starch,
(a2) at least one further starch, which can chemically modified, with an amylose content of the unmodified further starch in the range of 10 to 20 % by weight, referring to the sum of amylose and amylopectin of said unmodified further starch,
(b) at least one synthetic polymer.
12. Process for making an aqueous formulation or liquor according to any of claims 7 to 10, comprising mixing at least one first unmodified starch with an amylose con- tent of the unmodified starch in the range of 20 to 30 % by weight, referring to the sum of amylose and amylopectin of said unmodified starch, with at least one further unmodified starch with an amylose content of the unmodified further starch in the range of 10 to 20 % by weight, referring to the sum of amylose and amylopectin of said unmodified further starch, performing at least one chemical modification step, and then adding (b) at least one synthetic polymer.
13. Powders, comprising
(a1 ) at least one first chemically modified starch with an amylose content of the respective unmodified starch in the range of 20 to 30 % by weight, preferably 23 to 29 %, referring to the sum of amylose and amylopectin of respective unmodified starch,
(a2) at least one further chemically modified starch with an amylose content of the respective unmodified further starch in the range of 10 to 20 % by weight, preferably 15 to 18 % by weight, referring to the sum of amylose and amylopectin of said unmodified further starch,
(b) at least one synthetic polymer.
14. Treated linear textiles, obtainable by a process according to any of claims 1 to 6.
15. Treated linear textiles according to claim 14, said linear textiles being derived from natural fibers.
16. Treated linear textiles according to claim 14 or 15, said treated linear textiles having a diameter in the range from 1 to 40 NE.
17. Treated linear textiles according to any of claims 14 to 16, said treated linear tex- tiles having a diameter in the range from 5 to 20 NE.
18. Method of use of treated linear textiles according to any of claims 14 to 17 as warp.
19. Method of use of treated linear textiles according to any of claims 14 to 17 as warp for weaving textiles.
PCT/EP2006/060990 2005-03-24 2006-03-23 Textile treatment WO2006100290A1 (en)

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EP0822287A1 (en) * 1996-08-01 1998-02-04 Südzucker Aktiengesellschaft Mannheim/Ochsenfurt Fiber treatment composition
WO1998033968A1 (en) * 1997-01-30 1998-08-06 Coöperatieve Verkoop- En Productievereniging Van Aardappelmeel En Derivaten Avebe B.A. Amylopectin potato starch products as sizing agents for textile yarns
US20020051882A1 (en) * 2000-02-18 2002-05-02 Lawton Ernest L. Forming size compositions, glass fibers coated with the same and fabrics woven from such coated fibers

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US5393804A (en) * 1992-11-24 1995-02-28 Parke, Davis & Company Biodegradable compositions comprising starch and alkenol polymers
EP0822287A1 (en) * 1996-08-01 1998-02-04 Südzucker Aktiengesellschaft Mannheim/Ochsenfurt Fiber treatment composition
WO1998033968A1 (en) * 1997-01-30 1998-08-06 Coöperatieve Verkoop- En Productievereniging Van Aardappelmeel En Derivaten Avebe B.A. Amylopectin potato starch products as sizing agents for textile yarns
US20020051882A1 (en) * 2000-02-18 2002-05-02 Lawton Ernest L. Forming size compositions, glass fibers coated with the same and fabrics woven from such coated fibers

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