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WO2014047833A1 - Treating solution for fibrous cellulosic material - Google Patents

Treating solution for fibrous cellulosic material Download PDF

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Publication number
WO2014047833A1
WO2014047833A1 PCT/CN2012/082148 CN2012082148W WO2014047833A1 WO 2014047833 A1 WO2014047833 A1 WO 2014047833A1 CN 2012082148 W CN2012082148 W CN 2012082148W WO 2014047833 A1 WO2014047833 A1 WO 2014047833A1
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WO
WIPO (PCT)
Prior art keywords
group
acid
treating solution
carbon atoms
emulsifier
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/CN2012/082148
Other languages
French (fr)
Inventor
Fuming Huang
Junbao GUO
Gary Wayne MURRAY
Fernando VAZQUEZ-CARRILLO
Zhihua Liu
Sheng Ho WU
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Shanghai Holding Co Ltd
Dow Corning Taiwan Inc
Dow Silicones Corp
Original Assignee
Dow Corning China Holding Co Ltd
Dow Corning Taiwan Inc
Dow Corning Corp
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 Dow Corning China Holding Co Ltd, Dow Corning Taiwan Inc, Dow Corning Corp filed Critical Dow Corning China Holding Co Ltd
Priority to CN201280073886.1A priority Critical patent/CN104350199A/en
Priority to EP12885501.2A priority patent/EP2900862A1/en
Priority to JP2015528831A priority patent/JP2015526569A/en
Priority to PCT/CN2012/082148 priority patent/WO2014047833A1/en
Publication of WO2014047833A1 publication Critical patent/WO2014047833A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • D06M13/11—Compounds containing epoxy groups or precursors 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
    • 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
    • D06M13/144—Alcohols; Metal alcoholates
    • D06M13/148—Polyalcohols, e.g. glycerol or glucose
    • 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
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts 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
    • 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
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts 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
    • 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
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/203—Unsaturated carboxylic acids; Anhydrides, halides or salts 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
    • 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
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • 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
    • 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
    • D06M15/65—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing epoxy groups

Definitions

  • the present invention relates to a treating solution for fibrous cellulosic material.
  • US 4820307 and US 4975209 disclose a treating solution for cellulosic material, comprising a polycarboxylic acid, a curing catalyst, and a solvent.
  • US 6582476 suggests a formulation comprising a polycarboxylic acid, a curing catalyst, calboxy group functionalized polysiloxane, a surfactant, and water.
  • WO 2003/033807 discloses a finish comprising a cross-linked polymaleate, a curing agent, a polycarboxylic acid, a silicone softner (GE SM21 12), a surfactant, and water.
  • the present invention provides a novel treating solution for fibrous cellulosic material, which displays sufficient strength, thus solving the technical problem in the art.
  • the present invention provides a treating solution for fibrous cellulosic material, comprising:
  • the treating solution further comprises (H) a maleic anhydride copolymer or protected-isocyanate.
  • the treating solution further comprises (I) a polyol.
  • the organopolysiloxane of the components is a polyol.
  • (A) and (B) is polyorganosiloxane represented by the average unit formula as follows:
  • f represents a number from 0 to 50
  • g represents a number from 0 to 10
  • a + b + c + d + e + f + g represents a number from 30 to 2700
  • R each independently represents a monovalent hydrocarbon group, an alkoxy group having 1 to 5 carbon atoms, or a hydroxyl group
  • X represents a group selected from the group consisting of an amino group and an epoxy group.
  • the monovalent hydrocarbon group include an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and an aralkyi group having 7 to 30 carbon atoms.
  • the amino group is a group represented by the formula: -R 1 -(NR 2 CH 2 CH 2 )i-NR 3 R 4 , wherein R 1 represents a divalent hydrocarbon group having 1 to 30 carbon atoms; R 2 , R 3 , and R 4 each independently represents a hydrogen atom, a monovalent hydrocarbon group, an acyl group, or a group represented by the formula: -CH2CH(OH)R 5 wherein R 5 represents a hydrogen atom, a monovalent hydrocarbon group, or an acyl group; at least one of R 2 R 3 and R 4 is a hydrogen atom; and I is an integer of 0 to 5.
  • the epoxy group is selected from the group consisting of glycidoxyalkyl group, an epoxy cycloalkylalkyl group, and an oxiranylalkyl group.
  • the polycarboxylic acid is selected from the group consisting of: malic acid, oxy-di succinic acid, succinic acid, 1 ,2,3,4- butantetracarboxylic acid, maleic acid, tricarbalic acid, citric acid, 1 ,2,3,4,5,6- cyclohexanehexacarboxylic 1 acid, 1 ,2,3,4-cyclobutanetetracarboxylic acid, propene- 1 ,2,3-tricarboxylic acid, 1 ,2,3,4-cyclopentanetetracarboxylic acid, tetrahydrofuran- 2,3,4,5-tetracarboxylic acid, 1 ,2,4-Benzenetricarboxylic acid, 1 ,2,4,5- Benzenetetracarboxylic acid, and mellitic acid.
  • esterifi cation catalyst is selected from the group consisting of: carbodiimides, hydroxy acids, mineral acids, Lewis acids, and phosphorous oxyacids.
  • the organic zirconium compound is selected from the group consisting of: zirconium tetrapropylate and zirconium tetrabutylate.
  • the emulsifier is selected from the group consisting of: an anionic emulsifier, cationic emulsifier, amphoteric emulsifier and nonionic emulsifier.
  • the components (A) and (B) of the treating solution for fibrous cellulosic material are polyorganosiloxanes that have silicon-bonded amino groups or epoxy groups, preferably polyorganosiloxanes represented by the average unit formula as follows:
  • a represents a number from 0 to 50, and is preferably 1 to 10 and more preferably 1 to 2;
  • "b” represents a number from 0 to 50, and is preferably 0.01 to 10, more preferably 0.1 to 5, and still more preferably 0.5 to 2;
  • c represents a number from 30 to 2700, and is preferably 60 to 1300 and more preferably 130 to 700;
  • "d” represents a number from 0 to 50, and is preferably 0 to 5, more preferably 0 to 1 , and still more preferably 0;
  • e represents a number from 0 to 50, and is preferably 0 to 5, more preferably 0 to 1 , and still more preferably 0;
  • f represents a number from 0 to 50, and is preferably 0 to 5, more preferably 0 to 1 , and still more preferably 0;
  • g represents a number from 0 to 10, and is preferably 0 to 1 , and more preferably 0;
  • b + d + f represents a number from 0.01 to 100, and is preferably 0.1 to 10, and more preferably 0.5 to 2;
  • a + b + c + d + e + f + g represents a number from 30 to 2700, and is preferably 60 to 1300, and more preferably 130 to 700;
  • R each independently represents a monovalent hydrocarbon group, an alkoxy group having 1 to 5 carbon atoms, or a hydroxyl group; and X represents a group selected from the group consisting of an amino group and an epoxy group.
  • the monovalent hydrocarbon group examples include an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms.
  • Examples of an alkyl group, an aryl group, an alkenyl group, and an aralkyl group include a linear or branched alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group; a cyclic alkyl group having 3 to 30 carbon atoms such as a cyclopentyl group and a cyclohexyl group; an aryl group having 6 to 30 carbon atoms such as a phenyl group, a tolyl group, and a xylyl group; an alkenyl group having 2 to 30 carbon atoms such as a vinyl group, an allyl group, a butenyl group, a hexenyl group, and an octenyl group; an aral
  • an alkyl group, an aryl group, an alkenyl group, or an aralkyl group be an alkyl group, an aryl group, an alkenyl group, or an aralkyl group, unsubstituted and having 1 to 10 carbon atoms.
  • a methyl group, an ethyl group, a propyl group, or a phenyl group is particularly preferable.
  • alkoxy group a methoxy group, an ethoxy group, a propoxy group or the like can be used.
  • the amino group is preferably a group represented by the formula: -R 1 -
  • R 1 represents a divalent hydrocarbon group
  • R 2 , R 3 , and R 4 each independently represents a hydrogen atom, a monovalent hydrocarbon group, an acyl group, or a group represented by the formula: -CH 2 CH(OH)R 5
  • R 5 represents a hydrogen atom, a monovalent hydrocarbon group, or an acyl group
  • at least one of R 2 , R 3 , and R 4 is a hydrogen atom
  • I is an integer of 0 to 5 ⁇ .
  • the monovalent hydrocarbon group those described above can be used.
  • divalent hydrocarbon group examples include a linear or branched and substituted or unsubstituted divalent hydrocarbon group having 1 to 30 carbon atoms.
  • linear or branched and substituted or unsubstituted divalent hydrocarbon group having 1 to 30 carbon atoms examples include a linear or branched alkylene group having 1 to 30 carbon atoms such as a methylene group, a
  • the divalent hydrocarbon group is preferably a divalent, unsubstituted and saturated hydrocarbon group having 1 to 30 carbon atoms, and is preferably a linear or branched alkylene
  • an acyl group an acyl group having 2 to 30 carbon atoms is preferable.
  • An aliphatic acyl group is more preferable.
  • the epoxy group is preferably selected from the group consisting of glycidoxyalkyl group, an epoxy cycloalkylalkyl group, and an oxiranylalkyl group.
  • the method for producing the polyorganosiloxane that has silicon-bonded amino group or epoxy group as used in the present invention is not specifically limited, but any method known in the field may be used.
  • the polyorganosiloxane that has the silicon-bonded amino group or epoxy groups may be obtained by hydrosilylation of (i) a polyorganosiloxane having silicone-bonded hydrogen atoms, and
  • R' represents a single bond or a divalent hydrocarbon group
  • R" represents a hydrogen atom or a monovalent hydrocarbon group
  • a vinyl group and an allyl group are preferable.
  • the organic compound contains at least one amino group or epoxy group.
  • a catalyst is preferably used.
  • the catalyst that may be used include those well known in the field as a catalyst for hydrosilylation, for example a compound such as platinum, ruthenium, rhodium, palladium, osmium, and iridium.
  • a platinum compound is useful.
  • the platinum compound include chloroplatinic acid, platinum, solid platinum supported on a carrier such as alumina, silica, or carbon black, platinum - vinylsiloxane complex, platinum - phosphine complex, platinum - phosphite complex, and platinum alcoholate catalyst.
  • the platinum catalyst may be used in an amount of about 0.0001 % by weight to 0.1 % by weight in terms of platinum.
  • a solvent may be used, if necessary.
  • the solvent include ether; ketone such as acetal and
  • the hydrosilylation reaction may be carried out, if the catalyst is used, for about 0 mins to 8 hours at the temperature of about 20°C to 1 50°C, and preferably about 40°C to 120°C.
  • the polyorganosiloxane that has amino group or epoxy group may be also obtained by equilibrium polymerization of
  • cyclic polyorganosiloxane examples include
  • hexamethylcyclotrisiloxane octamethylcyclotetrasiloxane, 1 ,3,5-trimethyl-1 ,3,5- triphenylcyclotrisiloxane, 1 ,3,5,7-tetramethyl-1 ,3,5,7-tetraphenylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane, 1 ,3,5-trimethyl-1 ,3,5- trivinylcyclotrisiloxane, 1 ,3,5,7-tetramethyl-1 ,3,5,7-tetravinylcyclotetrasiloxane, hexavinylcyclotrisiloxane, and octavinylcyclotetrasiloxane.
  • a catalyst for equilibrium polymerization may be used.
  • the catalyst for equilibrium polymerization include alkali hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, tetramethyl ammonium hydroxide, and tetrabutyl phosphonium hydroxide; alkali silanolate such as lithium silanolate, sodium silanolate, potassium silanolate, cesium silanolate, tetramethyl ammonium silanolate, and tetrabutyl phosphonium silanolate; and an organometallic compound such as butyl lithium, methyl lithium, sodium naphthalenide, and potassium naphthalenide.
  • a solvent for promoting polymerization that is conventionally known in the field may be used.
  • the equilibrium polymerization easily progresses at relatively low temperature and the dissociation reaction of an amide group during the equilibrium polymerization can be controlled, and therefore desirable.
  • the solvent for promoting polymerization include a polar organic solvent such as tetrahydrofuran, dimethylformamide, dimethylsulfoxide, and acetonitrile.
  • the reaction is preferably carried out within the temperature range of 50 to 200°C.
  • the reaction is more preferably carried out within the temperature range of 50 to 150°C.
  • the reaction is particularly preferably carried out within the temperature range of 50 to 140°C.
  • the equilibrium polymerization may be carried out for 10 mins to 0 hours.
  • the polyorganosiloxane that has silicon-bonded amino group or epoxy group may be also obtained by condensation of a diorganopolysiloxane of which both ends of the molecular chain are blocked with hydroxyl groups, and alkoxysilane having silicon-bonded functional groups such as alkoxysilane containing an amino group or alkoxy silane containing an epoxy group.
  • a catalyst for condensation may be used. However, it is not particularly necessary to use a catalyst for condensation.
  • a polyorganosiloxane having silicon-bonded functional groups at an end of the molecular chain can be obtained.
  • a polyorganosiloxane that contains an amino group as a silicon-bonded functional group may be obtained by condensation of
  • an amino group-containing organoalkoxysilane represented by the general formula: R 7 n R 8 Si(OR 9 )3-n (wherein R 7 represents a monovalent hydrocarbon group; R 8 represents the formula: -R 10 -(NR 11 CH 2 CH 2 )m-NH-R 12 (wherein R 10 represents a divalent hydrocarbon group; R 11 and R 12 each independently
  • the condensation may be carried out in the temperature range of 50°C to
  • the polycarboxylic acid is a crosslinking agent of the treating solution of the present invention.
  • Acids or their salts may be exemplified, malic acid, oxy-disuccinic acid, succinic acid, 1 ,2,3,4-butantetracarboxylic acid, maleic acid, imino disuccinate, thiodisuccinate, tricarbalic acid, citric acid, 1 ,2,3,4,5,6-cyclohexanehexacarboxylic 1 acid, 1 ,2,3,4-cyclobutanetetracarboxylic acid, propene-1 ,2,3-tricarboxylic acid,
  • 1 ,2,3,4-cyclopentanetetracarboxylic acid tetrahydrofuran-2,3,4,5-tetracarboxylic acid, 1 ,2,4-Benzenetricarboxylic acid, 1 ,2,4, 5-Benzenetetracarboxylic acid, and mellitic acid.
  • Preferred acids that may provide a benefit are oxy-disuccinic acid, propene- 1 ,2,3-tricarboxylic acid, and ,2,3, 4-butanetetracarboxylic acid.
  • sulfate salts and sulfate adducts of maleic acid containing polymers may also be present in the product mixture.
  • the polycarboxylic acid is 1 ,2,3,4- butanetetracarboxylic acid (BTCA). These polycarboxylic acids are preferably added at levels of from about 0.5% to about 75% of the treating solution of the present invention.
  • the treating solution for fibrous cellulosic material further include an esterification catalyst to facilitate the cross-linking by the component (C) with reactive sites on the textile articles, for example cellulose in the fibers of cellulosic containing textile articles.
  • the esterification catalyst of the present invention may be selected from a wide variety of materials such as carbodiimides, hydroxy acids, mineral acids, Lewis acids, and phosphorous oxyacids.
  • Catalyst that may be employed include, by way of example, cyanamide, guanidine or a salt thereof, dicyandiamide, urea, dimethylurea or thiourea, alkali metal salts of hypophosphorus, phosphorus or phosphoric acid, mineral acids, organic acids and salts thereof; more preferably sodium hypophosphite, hypophosphorous acid, and sodium phosphate.
  • Preferred catalysts include cyanamide, dicyanamide, urea, dimethylurea, sodium hypophosphite, phosphorous acid, sodium phosphate, and mixtures thereof.
  • the fabric is typically treated with an amount of catalyst sufficient to catalyze cross- linking of the natural fibers to provide a durable press treatment and/or reduced shrinkage, for example reduced I shrinkage upon aqueous laundering.
  • the catalyst may be employed in an amount sufficient to provide a cross-linking agent: catalyst weight ratio of from about 0.05 to about 75, and preferably from about 1 to about 60.
  • the organic zirconium compound can be represented by an organic zirconium ester or an organic zirconium chelate compound.
  • Such organic zirconium esters are known in the art and can be represented by zirconium tetrapropylate, or zirconium tetrabutylate.
  • Such organic zirconium chelate compounds are known in the art and can be represented by the following specific examples: zirconium (IV) tetraacetyl acetonate, zirconium (IV) hexafluoracetyl acetonate, zirconium (IV) trifluoroacetyl acetonate, tetrakis (ethyltrifluoroacetyl acetonate) zirconium, tetrakis (2,2,6,6- tetramethyl-heptanethionate) zirconium, zirconium (IV) dibutoxy bis(ethylacetonate), diisopropoxy bis (2,2,6,6-tetramethyl-heptanethionate) zirconium, or similar zirconium complexes having ⁇ -diketones (including alkyl-substituted and fluoro- substituted forms thereof) which are used as ligands
  • zirconium complexes of acetoacetate including alkyl-substituted and fluoro-substituted forms.
  • the treating solution for fibrous cellulosic material of the present invention may be used by dissolving in an organic solvent.
  • a water-in-oil or oil-in-water emulsion form is preferable.
  • water and an emulsifier may be added to a mixture of the components (A) to (E) to emulsify these.
  • Water and an emulsifier may be added to each of the component (A) and (B) to form preliminary emulsions, and subsequently, they can be mixed to produce a treating solution for fibrous cellulosic material in the form of an emulsion.
  • the emulsification method used therein can be carried out by means of conventional means or equipment.
  • any emulsifier used in the preparation of a silicone emulsion can be used, and any emulsifier such as an anionic, cationic, amphoteric or nonionic emulsifier can be used.
  • the emulsifier may be used alone or in combination with two or more types thereof.
  • anionic surfactants mention may be made of, for example, saturated or unsaturated higher fatty acid salts such as sodium stearate and the like; long-chain-alkylsulfuric acid salts, alkylbenzenesulfonic acids such as
  • polyoxyethylene alkylsulfuric acid ester salts sulfosuccinic acid alkyl ester salts; polyoxyalkylene sulfosuccinic acid salts; long-chain-alkanesulfonic acid salts;
  • polyoxyalkylene alkyl ether acetic acid salts long-chain-alkyl phosphoric acid salts; polyoxyalkylene alkyl ether phosphoric acid salts; acylglutamic acid salts; alkyloyl alkyl taurine salts; N-acylamino acid salts; alkyl alkyl ether carboxylic acid salts; a- sulfofatty acid ester salts; alanine derivatives; glycine derivatives; arginine derivatives and the like.
  • alkali metal salts such as sodium salts and the like, alkanolamine salts such as triethanolamine salts and the like, and ammonium salts. Sodium salts are preferable.
  • cationic surfactants mention may be made of, for example, quaternary ammonium salts such as alkyltrimethylammonium salts,
  • amphoteric surfactants mention may be made of imidazoline type, aminobetaine type, alkylbetaine type, alkylamidobetaine type, alkylsulfobetaine type, amidosulfobetaine type, hydroxysulfobetaine type,
  • carbobetaine type phosphobetaine type, aminocarboxylic acid type, and
  • amidoamino acid type amphoteric surfactants are amidoamino acid type amphoteric surfactants.
  • nonionic surfactants mention may be made of, for example, polyoxyalkylene ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene fatty acid diesters, polyoxyalkylene resin acid esters, polyoxyalkylene alkylphenols, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene alkyl esters, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene glycerol fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, alkylglucosides, polyoxyalkylene fatty acid bisphenyl ethers, and the like.
  • any additives may be blended within a range which does not impair the purposes thereof.
  • the types and blending amounts of the additives can be appropriately adjusted in accordance with usages of the non-curable coating compositions of the present invention. Examples:
  • Formulations of Table 1 were prepared by: 1 ) adding the ingredients to about 50% of weight of water; 2) stirring until homogeneous; 3) emulsifying the mixture at room temperature; and 4) adding water to the final ratio while stirring.
  • Q2-8797 amino group functionalised silicone emulsion, product of Dow Corning Corp. content of silicone is about 30 weight %.
  • Q2-8708 epoxy group functionalised silicone emulsion, product of Dow Corning Corp. content of silicone is about 20 weight %.
  • Phobol XAN product of HUNTSMAN: emulsion of an oxim-protected polyisocyanate, content of oxim-protected polyisocyanate is 40 wt %.
  • a cotton fabric is passed through a treatment bath and saturated with the treatment bath solution composition.
  • the treatment bath contains an aqueous solution composition of Table 1 .
  • the saturated cotton fabric is passed through pressurized rollers, resulting in a wet pick up of 50% - 70% of treatment solution on the fabric.
  • the fabric is cured for 3 minutes at 160 degree C in a curing oven.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

TREATING SOLUTION FOR FIBROUS CELLULOSIC MATERIAL
Technical Field
The present invention relates to a treating solution for fibrous cellulosic material.
Background Art
US 4820307 and US 4975209 disclose a treating solution for cellulosic material, comprising a polycarboxylic acid, a curing catalyst, and a solvent. To improve the softness of treated cellulose fabric, US 6582476 suggests a formulation comprising a polycarboxylic acid, a curing catalyst, calboxy group functionalized polysiloxane, a surfactant, and water.
However, with such treating compositions, strength of resulting treated fabrics tends to weak.
WO 2003/033807 discloses a finish comprising a cross-linked polymaleate, a curing agent, a polycarboxylic acid, a silicone softner (GE SM21 12), a surfactant, and water.
However, strength of resulting treated fabrics is still not sufficient. Disclosure of Invention
The present invention provides a novel treating solution for fibrous cellulosic material, which displays sufficient strength, thus solving the technical problem in the art.
The present invention provides a treating solution for fibrous cellulosic material, comprising:
(A) an amino group functionalized organopolysiloxane,
(B) an epoxy group functionalized organopolysiloxane,
(C) a polycarboxylic acid,
(D) an esterification catalyst,
(E) an organic zirconium compound,
(F) an emulsifier, and
(G) water. In a preferred embodiment, the treating solution further comprises (H) a maleic anhydride copolymer or protected-isocyanate.
In another preferred embodiment, the treating solution further comprises (I) a polyol. In another preferred embodiment, the organopolysiloxane of the components
(A) and (B) is polyorganosiloxane represented by the average unit formula as follows:
(R3SiOi/2)a(XR2Si01/2)b(R2Si02/2)C(XRSi02/2)d(RSi03/2)e(XSi03/2WSi04/2)g wherein "a" represents a number from 0 to 50; "b" represents a number from 0 to 50;
"c" represents a number from 30 to 2700;
"d" represents a number from 0 to 50;
"e" represents a number from 0 to 50;
"f represents a number from 0 to 50; "g" represents a number from 0 to 10;
"b + d + Γ represents a number from 0.01 to 100,;
"a + b + c + d + e + f + g" represents a number from 30 to 2700;
R each independently represents a monovalent hydrocarbon group, an alkoxy group having 1 to 5 carbon atoms, or a hydroxyl group; and
X represents a group selected from the group consisting of an amino group and an epoxy group.
In another preferred embodiment, the monovalent hydrocarbon group include an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and an aralkyi group having 7 to 30 carbon atoms.
In another preferred embodiment, the amino group is a group represented by the formula: -R1-(NR2CH2CH2)i-NR3R4, wherein R1 represents a divalent hydrocarbon group having 1 to 30 carbon atoms; R2, R3, and R4 each independently represents a hydrogen atom, a monovalent hydrocarbon group, an acyl group, or a group represented by the formula: -CH2CH(OH)R5 wherein R5 represents a hydrogen atom, a monovalent hydrocarbon group, or an acyl group; at least one of R2 R3 and R4 is a hydrogen atom; and I is an integer of 0 to 5.
In another preferred embodiment, the epoxy group is selected from the group consisting of glycidoxyalkyl group, an epoxy cycloalkylalkyl group, and an oxiranylalkyl group.
In another preferred embodiment, the polycarboxylic acid is selected from the group consisting of: malic acid, oxy-di succinic acid, succinic acid, 1 ,2,3,4- butantetracarboxylic acid, maleic acid, tricarbalic acid, citric acid, 1 ,2,3,4,5,6- cyclohexanehexacarboxylic 1 acid, 1 ,2,3,4-cyclobutanetetracarboxylic acid, propene- 1 ,2,3-tricarboxylic acid, 1 ,2,3,4-cyclopentanetetracarboxylic acid, tetrahydrofuran- 2,3,4,5-tetracarboxylic acid, 1 ,2,4-Benzenetricarboxylic acid, 1 ,2,4,5- Benzenetetracarboxylic acid, and mellitic acid.
In another preferred embodiment, the esterifi cation catalyst is selected from the group consisting of: carbodiimides, hydroxy acids, mineral acids, Lewis acids, and phosphorous oxyacids.
In another preferred embodiment, the organic zirconium compound is selected from the group consisting of: zirconium tetrapropylate and zirconium tetrabutylate.
In another preferred embodiment, the emulsifier is selected from the group consisting of: an anionic emulsifier, cationic emulsifier, amphoteric emulsifier and nonionic emulsifier.
Best Mode for Carrying Out the Invention
The treating solution for fibrous cellulosic material of the present invention will be detailedly described in the following non-limiting part. (A) Amino group functionalized organopolysiloxane and (B) Epoxy group functionalized organopolysiloxane
In the present invention, the components (A) and (B) of the treating solution for fibrous cellulosic material are polyorganosiloxanes that have silicon-bonded amino groups or epoxy groups, preferably polyorganosiloxanes represented by the average unit formula as follows:
( 3SiOi/2)a(X 2Si01/2)b(R2SiO(/2)c(XRSi02/2)d(RSi03/2)e(XSi03/2MSi04/2)g
In the formula above, "a" represents a number from 0 to 50, and is preferably 1 to 10 and more preferably 1 to 2;
"b" represents a number from 0 to 50, and is preferably 0.01 to 10, more preferably 0.1 to 5, and still more preferably 0.5 to 2;
"c" represents a number from 30 to 2700, and is preferably 60 to 1300 and more preferably 130 to 700; "d" represents a number from 0 to 50, and is preferably 0 to 5, more preferably 0 to 1 , and still more preferably 0;
"e" represents a number from 0 to 50, and is preferably 0 to 5, more preferably 0 to 1 , and still more preferably 0;
"f represents a number from 0 to 50, and is preferably 0 to 5, more preferably 0 to 1 , and still more preferably 0;
"g" represents a number from 0 to 10, and is preferably 0 to 1 , and more preferably 0;
"b + d + f represents a number from 0.01 to 100, and is preferably 0.1 to 10, and more preferably 0.5 to 2; "a + b + c + d + e + f + g" represents a number from 30 to 2700, and is preferably 60 to 1300, and more preferably 130 to 700;
R each independently represents a monovalent hydrocarbon group, an alkoxy group having 1 to 5 carbon atoms, or a hydroxyl group; and X represents a group selected from the group consisting of an amino group and an epoxy group. As for the monovalent hydrocarbon group, examples of the monovalent hydrocarbon group include an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. Examples of an alkyl group, an aryl group, an alkenyl group, and an aralkyl group include a linear or branched alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group; a cyclic alkyl group having 3 to 30 carbon atoms such as a cyclopentyl group and a cyclohexyl group; an aryl group having 6 to 30 carbon atoms such as a phenyl group, a tolyl group, and a xylyl group; an alkenyl group having 2 to 30 carbon atoms such as a vinyl group, an allyl group, a butenyl group, a hexenyl group, and an octenyl group; an aralkyl group having 7 to 30 carbon atoms such as a benzyl group; and those hydrocarbon groups in which the hydrogen atom bonded to the carbon atom is at least partially substituted with a halogen atom such as a fluorine. It is preferable that an alkyl group, an aryl group, an alkenyl group, or an aralkyl group be an alkyl group, an aryl group, an alkenyl group, or an aralkyl group, unsubstituted and having 1 to 10 carbon atoms. An alkyl group or an aryl group which is
unsubstituted and having 1 to 6 carbon atoms is more preferable. A methyl group, an ethyl group, a propyl group, or a phenyl group is particularly preferable.
As an alkoxy group, a methoxy group, an ethoxy group, a propoxy group or the like can be used. The amino group is preferably a group represented by the formula: -R1-
(NR2CH2CH2)i-NR3R4 {wherein R1 represents a divalent hydrocarbon group; R2, R3, and R4 each independently represents a hydrogen atom, a monovalent hydrocarbon group, an acyl group, or a group represented by the formula: -CH2CH(OH)R5
(wherein R5 represents a hydrogen atom, a monovalent hydrocarbon group, or an acyl group); at least one of R2, R3, and R4 is a hydrogen atom; and I is an integer of 0 to 5}. As for the monovalent hydrocarbon group, those described above can be used.
Examples of the divalent hydrocarbon group include a linear or branched and substituted or unsubstituted divalent hydrocarbon group having 1 to 30 carbon atoms. Examples of the linear or branched and substituted or unsubstituted divalent hydrocarbon group having 1 to 30 carbon atoms include a linear or branched alkylene group having 1 to 30 carbon atoms such as a methylene group, a
dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and an octamethylene group; an alkenylene group having 2 to 30 carbon atoms such as a vinylene group, an allylene group, a butenylene group, a hexenylene group, and an octenylene group; an arylene group having 6 to 30 carbon atoms such as a phenylene group and a diphenylene group; an alkylenearylene group having 7 to 30 carbon atoms such as a dimethylenephenylene group; and those hydrocarbon groups in which the hydrogen atom bonded to the carbon atom is at least partially a halogen atom such as a fluorine. The divalent hydrocarbon group is preferably a divalent, unsubstituted and saturated hydrocarbon group having 1 to 30 carbon atoms, and is preferably a linear or branched alkylene group having 1 to 30 carbon atoms.
As an acyl group, an acyl group having 2 to 30 carbon atoms is preferable. An aliphatic acyl group is more preferable.
The epoxy group is preferably selected from the group consisting of glycidoxyalkyl group, an epoxy cycloalkylalkyl group, and an oxiranylalkyl group. The method for producing the polyorganosiloxane that has silicon-bonded amino group or epoxy group as used in the present invention is not specifically limited, but any method known in the field may be used.
For example, the polyorganosiloxane that has the silicon-bonded amino group or epoxy groups may be obtained by hydrosilylation of (i) a polyorganosiloxane having silicone-bonded hydrogen atoms, and
(ii) an organic compound having unsaturated aliphatic groups.
Examples of the unsaturated aliphatic group include an aliphatic group having end unsaturation represented by the formula: -R'-C(R")=CH2 (wherein R' represents a single bond or a divalent hydrocarbon group; and R" represents a hydrogen atom or a monovalent hydrocarbon group). In particular, a vinyl group and an allyl group are preferable.
The organic compound contains at least one amino group or epoxy group. To perform the hydrosilylation rapidly at relatively low temperature, a catalyst is preferably used. Examples of the catalyst that may be used include those well known in the field as a catalyst for hydrosilylation, for example a compound such as platinum, ruthenium, rhodium, palladium, osmium, and iridium. In particular, a platinum compound is useful. Examples of the platinum compound include chloroplatinic acid, platinum, solid platinum supported on a carrier such as alumina, silica, or carbon black, platinum - vinylsiloxane complex, platinum - phosphine complex, platinum - phosphite complex, and platinum alcoholate catalyst. For the hydrosilylation, the platinum catalyst may be used in an amount of about 0.0001 % by weight to 0.1 % by weight in terms of platinum.
For the hydrosilylation, a solvent may be used, if necessary. Examples of the solvent that may be used include ether; ketone such as acetal and
cyclohexanone; ester; phenol; hydrocarbon; halogenated hydrocarbon; and a dimethylpolysiloxane. The hydrosilylation reaction may be carried out, if the catalyst is used, for about 0 mins to 8 hours at the temperature of about 20°C to 1 50°C, and preferably about 40°C to 120°C.
The polyorganosiloxane that has amino group or epoxy group may be also obtained by equilibrium polymerization of
(iii) a cyclic polyorganosiloxane, and (iv) a polyorganosiloxane that has silicone-bonded amino group or epoxy group.
Examples of the cyclic polyorganosiloxane include
hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, 1 ,3,5-trimethyl-1 ,3,5- triphenylcyclotrisiloxane, 1 ,3,5,7-tetramethyl-1 ,3,5,7-tetraphenylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane, 1 ,3,5-trimethyl-1 ,3,5- trivinylcyclotrisiloxane, 1 ,3,5,7-tetramethyl-1 ,3,5,7-tetravinylcyclotetrasiloxane, hexavinylcyclotrisiloxane, and octavinylcyclotetrasiloxane.
For the equilibrium polymerization, a catalyst for equilibrium polymerization may be used. Examples of the catalyst for equilibrium polymerization include alkali hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, tetramethyl ammonium hydroxide, and tetrabutyl phosphonium hydroxide; alkali silanolate such as lithium silanolate, sodium silanolate, potassium silanolate, cesium silanolate, tetramethyl ammonium silanolate, and tetrabutyl phosphonium silanolate; and an organometallic compound such as butyl lithium, methyl lithium, sodium naphthalenide, and potassium naphthalenide.
For the purpose of promoting the equilibrium polymerization, a solvent for promoting polymerization that is conventionally known in the field may be used. When a solvent for promoting polymerization is used, the equilibrium polymerization easily progresses at relatively low temperature and the dissociation reaction of an amide group during the equilibrium polymerization can be controlled, and therefore desirable. Examples of the solvent for promoting polymerization include a polar organic solvent such as tetrahydrofuran, dimethylformamide, dimethylsulfoxide, and acetonitrile.
As for the temperature for equilibrium polymerization, the reaction is preferably carried out within the temperature range of 50 to 200°C. The reaction is more preferably carried out within the temperature range of 50 to 150°C. The reaction is particularly preferably carried out within the temperature range of 50 to 140°C. The equilibrium polymerization may be carried out for 10 mins to 0 hours.
The polyorganosiloxane that has silicon-bonded amino group or epoxy group may be also obtained by condensation of a diorganopolysiloxane of which both ends of the molecular chain are blocked with hydroxyl groups, and alkoxysilane having silicon-bonded functional groups such as alkoxysilane containing an amino group or alkoxy silane containing an epoxy group. For the condensation, a catalyst for condensation may be used. However, it is not particularly necessary to use a catalyst for condensation. By reacting the alkoxysilane having silicon-bonded functional groups in an amount of less than 2 moles, preferably 1 .5 moles or less, and more preferably 1 mole or less with 1 mole of the diorganopolysiloxane of which both ends of the molecular chain are blocked with hydroxyl groups, without using catalyst, a polyorganosiloxane having silicon-bonded functional groups at an end of the molecular chain can be obtained. For example, a polyorganosiloxane that contains an amino group as a silicon-bonded functional group may be obtained by condensation of
(v) a diorganopolysiloxane of which both ends of the molecular chain are blocked with hydroxyl groups, represented by the formula: HO-(SiR620)x-H (wherein R5 represents a monovalent hydrocarbon group; and x is a number of 5 to 2700), and
(vi) an amino group-containing organoalkoxysilane represented by the general formula: R7 nR8Si(OR9)3-n (wherein R7 represents a monovalent hydrocarbon group; R8 represents the formula: -R10-(NR11CH2CH2)m-NH-R12 (wherein R10 represents a divalent hydrocarbon group; R11 and R12 each independently
represents a hydrogen atom or a monovalent hydrocarbon group; and m is an integer of 0 to 5); R9 represents a monovalent hydrocarbon group; and n is 0 or 1 ). As for the monovalent hydrocarbon group and the divalent hydrocarbon group, those described above can be used. The condensation may be carried out in the temperature range of 50°C to
150°C under a nitrogen atmosphere while maintaining the same temperature and removing alcohols or the like that are produced as a byproduct of the reaction. The condensation may be carried out for about 10 mins to 8 hours. (C) Polycarboxylic acid
The polycarboxylic acid is a crosslinking agent of the treating solution of the present invention. Acids or their salts may be exemplified, malic acid, oxy-disuccinic acid, succinic acid, 1 ,2,3,4-butantetracarboxylic acid, maleic acid, imino disuccinate, thiodisuccinate, tricarbalic acid, citric acid, 1 ,2,3,4,5,6-cyclohexanehexacarboxylic 1 acid, 1 ,2,3,4-cyclobutanetetracarboxylic acid, propene-1 ,2,3-tricarboxylic acid,
1 ,2,3,4-cyclopentanetetracarboxylic acid, tetrahydrofuran-2,3,4,5-tetracarboxylic acid, 1 ,2,4-Benzenetricarboxylic acid, 1 ,2,4, 5-Benzenetetracarboxylic acid, and mellitic acid. Preferred acids that may provide a benefit are oxy-disuccinic acid, propene- 1 ,2,3-tricarboxylic acid, and ,2,3, 4-butanetetracarboxylic acid. Additionally, sulfate salts and sulfate adducts of maleic acid containing polymers may also be present in the product mixture. In a preferred embodiment, the polycarboxylic acid is 1 ,2,3,4- butanetetracarboxylic acid (BTCA). These polycarboxylic acids are preferably added at levels of from about 0.5% to about 75% of the treating solution of the present invention.
(D) Esterification catalyst
The treating solution for fibrous cellulosic material further include an esterification catalyst to facilitate the cross-linking by the component (C) with reactive sites on the textile articles, for example cellulose in the fibers of cellulosic containing textile articles. The esterification catalyst of the present invention may be selected from a wide variety of materials such as carbodiimides, hydroxy acids, mineral acids, Lewis acids, and phosphorous oxyacids. Catalyst that may be employed include, by way of example, cyanamide, guanidine or a salt thereof, dicyandiamide, urea, dimethylurea or thiourea, alkali metal salts of hypophosphorus, phosphorus or phosphoric acid, mineral acids, organic acids and salts thereof; more preferably sodium hypophosphite, hypophosphorous acid, and sodium phosphate.
Preferred catalysts include cyanamide, dicyanamide, urea, dimethylurea, sodium hypophosphite, phosphorous acid, sodium phosphate, and mixtures thereof. The fabric is typically treated with an amount of catalyst sufficient to catalyze cross- linking of the natural fibers to provide a durable press treatment and/or reduced shrinkage, for example reduced I shrinkage upon aqueous laundering. In one embodiment, the catalyst may be employed in an amount sufficient to provide a cross-linking agent: catalyst weight ratio of from about 0.05 to about 75, and preferably from about 1 to about 60.
(E) Organic zirconium compound
The organic zirconium compound can be represented by an organic zirconium ester or an organic zirconium chelate compound.
Such organic zirconium esters are known in the art and can be represented by zirconium tetrapropylate, or zirconium tetrabutylate.
Such organic zirconium chelate compounds are known in the art and can be represented by the following specific examples: zirconium (IV) tetraacetyl acetonate, zirconium (IV) hexafluoracetyl acetonate, zirconium (IV) trifluoroacetyl acetonate, tetrakis (ethyltrifluoroacetyl acetonate) zirconium, tetrakis (2,2,6,6- tetramethyl-heptanethionate) zirconium, zirconium (IV) dibutoxy bis(ethylacetonate), diisopropoxy bis (2,2,6,6-tetramethyl-heptanethionate) zirconium, or similar zirconium complexes having β-diketones (including alkyl-substituted and fluoro- substituted forms thereof) which are used as ligands
Most preferable of these compounds are zirconium complexes of acetoacetate (including alkyl-substituted and fluoro-substituted forms).
(G) Water (Emulsion)
The treating solution for fibrous cellulosic material of the present invention may be used by dissolving in an organic solvent. However, in order to reduce environmental burden, a water-in-oil or oil-in-water emulsion form is preferable. In this case, water and an emulsifier may be added to a mixture of the components (A) to (E) to emulsify these. Water and an emulsifier may be added to each of the component (A) and (B) to form preliminary emulsions, and subsequently, they can be mixed to produce a treating solution for fibrous cellulosic material in the form of an emulsion. The emulsification method used therein can be carried out by means of conventional means or equipment.
(F) Emulsifier
As an emulsifier for preparing the aforementioned emulsion, any emulsifier used in the preparation of a silicone emulsion can be used, and any emulsifier such as an anionic, cationic, amphoteric or nonionic emulsifier can be used. The emulsifier may be used alone or in combination with two or more types thereof.
As examples of anionic surfactants, mention may be made of, for example, saturated or unsaturated higher fatty acid salts such as sodium stearate and the like; long-chain-alkylsulfuric acid salts, alkylbenzenesulfonic acids such as
dodecylbenzenesulfonic acid and the like and salts thereof; polyoxyalkylene alkyl ether sulfuric acid salts; polyoxyalkylene alkenyl ether sulfuric acid salts;
polyoxyethylene alkylsulfuric acid ester salts: sulfosuccinic acid alkyl ester salts; polyoxyalkylene sulfosuccinic acid salts; long-chain-alkanesulfonic acid salts;
polyoxyalkylene alkyl ether acetic acid salts; long-chain-alkyl phosphoric acid salts; polyoxyalkylene alkyl ether phosphoric acid salts; acylglutamic acid salts; alkyloyl alkyl taurine salts; N-acylamino acid salts; alkyl alkyl ether carboxylic acid salts; a- sulfofatty acid ester salts; alanine derivatives; glycine derivatives; arginine derivatives and the like. As examples of the aforementioned salts, mention may be made of alkali metal salts such as sodium salts and the like, alkanolamine salts such as triethanolamine salts and the like, and ammonium salts. Sodium salts are preferable.
As examples of cationic surfactants, mention may be made of, for example, quaternary ammonium salts such as alkyltrimethylammonium salts,
dialkyldimethylammonium salts and the like.
As examples of amphoteric surfactants, mention may be made of imidazoline type, aminobetaine type, alkylbetaine type, alkylamidobetaine type, alkylsulfobetaine type, amidosulfobetaine type, hydroxysulfobetaine type,
carbobetaine type, phosphobetaine type, aminocarboxylic acid type, and
amidoamino acid type amphoteric surfactants.
As examples of nonionic surfactants, mention may be made of, for example, polyoxyalkylene ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene fatty acid diesters, polyoxyalkylene resin acid esters, polyoxyalkylene alkylphenols, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene alkyl esters, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene glycerol fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, alkylglucosides, polyoxyalkylene fatty acid bisphenyl ethers, and the like.
Other Ingredients
In the non-curable coating composition of the present invention, any additives may be blended within a range which does not impair the purposes thereof. As examples of the aforementioned additives, mention may be made of, for example, a viscosity modifier, a pH modifier, an antifoaming agent and the like. The types and blending amounts of the additives can be appropriately adjusted in accordance with usages of the non-curable coating compositions of the present invention. Examples:
Formulations of Table 1 were prepared by: 1 ) adding the ingredients to about 50% of weight of water; 2) stirring until homogeneous; 3) emulsifying the mixture at room temperature; and 4) adding water to the final ratio while stirring. Q2-8797: amino group functionalised silicone emulsion, product of Dow Corning Corp. content of silicone is about 30 weight %.
Q2-8708: epoxy group functionalised silicone emulsion, product of Dow Corning Corp. content of silicone is about 20 weight %.
BTCA: 1 ,2,3,4-butantetracarboxylic acid
SHP: sodium hypophosphite
Phobol XAN (PBN), product of HUNTSMAN: emulsion of an oxim-protected polyisocyanate, content of oxim-protected polyisocyanate is 40 wt %.
An emulsion of Zirconium Tetrakisacetylacetonate (CV-ZA EM): product of Dow Corning: content of Zirconium Tetrakisacetylacetonate is 15 wt%.
A cotton fabric is passed through a treatment bath and saturated with the treatment bath solution composition. The treatment bath contains an aqueous solution composition of Table 1 . The saturated cotton fabric is passed through pressurized rollers, resulting in a wet pick up of 50% - 70% of treatment solution on the fabric. The fabric is cured for 3 minutes at 160 degree C in a curing oven.
DP, durable press appearance rating, of the resulting fabric was measured in accordance with AATCC Method 124-2001. And tear strength of the resulting fabric was measured in accordance with ASTM Method D1424-63.
Table 1
Comp Comp Comp Comp
Ex1 Ex2 Ex3
Ex1 Ex2 Ex3 Ex4
Q2-8797 9 9 9 36
Q2-8708 27 27 27 36
BTCA 4 4 4 4 4 4
SHP 2 2 2 2 2 2
PBN 1 1 1 1 1 1
Glycerin 1 .6
PVA 1
CV-ZA EM 0.1 0.1 0.1 0.1 0.1 0.1
Water 56.9 55.3 55.9 100 92.9 56.9 56.9
DP 1wash 2.75 3.00 2.75 2.00 2.50 3.10 3.00
5wash 2.50 2.75 3.00 2.00 2.50 3.10 3.00
Tear Weft 14.80 13.80 13.80 18.80 10.60
13.20 1 1.60
Strength
(N) Warp 19.80 18.90 18.50 22.90 13.80
17.20 14.90
Tear Weft 79 73 73 100 56 70 62
Strength Warp 86 83 81 100 60 75 65
Retain (%)

Claims

What is claimed is:
1 . A treating solution for fibrous cellulosic material, comprising:
(A) an amino group functionalized organopolysiloxane,
(B) an epoxy group functionalized organopolysiloxane,
(C) a polycarboxylic acid,
(D) an esterification catalyst,
(E) an organic zirconium compound,
(F) an emulsifier, and
(G) water.
2. The treating solution of claim 1 , further comprising (H) a maleic anhydride copolymer or protected-isocyanate.
3. The treating solution of claim 1 or 2, further comprising (I) a polyol.
4. The treating solution of claim 1 , wherein the organopolysiloxane of the components (A) and (B) is polyorganosiloxane represented by the average unit formula as follows:
(R3SiOi 2)a(X 2SiOi 2)b(R2Si02/2)c(XRSi02/2)d( Si03/2)e(XSi03/2)f(Si04/2)g wherein "a" represents a number from 0 to 50;
"b" represents a number from 0 to 50; "c" represents a number from 30 to 2700;
"d" represents a number from 0 to 50;
"e" represents a number from 0 to 50;
"Γ represents a number from 0 to 50;
"g" represents a number from 0 to 10; "b + d + f represents a number from 0.01 to 100,;
"a + b + c + d + e + f + g" represents a number from 30 to 2700; R each independently represents a monovalent hydrocarbon group, an alkoxy group having 1 to 5 carbon atoms, or a hydroxyl group; and
X represents a group selected from the group consisting of an amino group and an epoxy group.
5. The treating solution of claim 4, wherein the monovalent hydrocarbon group include an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms.
6. The treating solution of claim 4, wherein the amino group is a group represented by the formula: -R1-(NR2CH2CH2)i-NR3R4, wherein R1 represents a divalent hydrocarbon group having 1 to 30 carbon atoms; R2, R3, and R4 each independently represents a hydrogen atom, a monovalent hydrocarbon group, an acyl group, or a group represented by the formula: -CH2CH(OH)R5 wherein R5 represents a hydrogen atom, a monovalent hydrocarbon group, or an acyl group; at least one of R2, R3, and R4 is a hydrogen atom; and I is an integer of 0 to 5.
7. The treating solution of claim 4, wherein the epoxy group is selected from the group consisting of glycidoxyalkyl group, an epoxy cycloalkylalkyl group, and an oxiranylalkyl group.
8. The treating solution of claim 1 , wherein the polycarboxylic acid is selected from the group consisting of: malic acid, oxy-disuccinic acid, succinic acid, 1 ,2,3,4- butantetracarboxylic acid, maleic acid, tricarbalic acid, citric acid, 1 ,2,3,4,5,6- cyclohexanehexacarboxylic 1 acid, 1 ,2,3,4-cyclobutanetetracarboxylic acid, propene- 1 ,2,3-tricarboxylic acid, 1 ,2,3,4-cyclopentanetetracarboxylic acid, tetrahydrofuran- 2,3,4,5-tetracarboxylic acid, 1 ,2,4-Benzenetricarboxylic acid, 1 ,2,4,5- Benzenetetracarbox lie acid, and mellitic acid.
9. The treating solution of claim 1 , wherein the esterification catalyst is selected from the group consisting of: carbodiimides, hydroxy acids, mineral acids, Lewis acids, and phosphorous oxyacids.
10. The treating solution of claim 1 , wherein the organic zirconium compound is selected from the group consisting of: zirconium tetrapropylate and zirconium tetrabutylate.
1 1. The treating solution of claim 1 , wherein the emulsifier is selected from the group consisting of: an anionic emulsifier, cationic emulsifier, amphoteric emulsifier and nonionic emulsifier.
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WO2023118811A1 (en) * 2021-12-22 2023-06-29 Uea Enterprises Limited A method of modifying cellulose fibres and/or cellulose fabric

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6454047B1 (en) * 2018-06-28 2019-01-16 竹本油脂株式会社 Viscose rayon nonwoven treatment agent and viscose rayon

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4359545A (en) * 1981-02-05 1982-11-16 Toray Silicone Co., Ltd. Fiber-treating compositions comprising two organo-functional polysiloxanes
US4399247A (en) * 1981-06-26 1983-08-16 Toray Silicone Company, Ltd. Organopolysiloxane-containing composition for treating substrates
EP1490544B1 (en) * 2002-04-03 2007-07-18 Unilever Plc Fabric care composition
CN101638847A (en) * 2009-07-24 2010-02-03 东莞市德能化工有限公司 Formaldehyde-free durable non-ironing finishing agent for cellulose fiber fabric

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62276090A (en) * 1986-05-22 1987-11-30 信越化学工業株式会社 Treatment agent for synthetic fiber

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4359545A (en) * 1981-02-05 1982-11-16 Toray Silicone Co., Ltd. Fiber-treating compositions comprising two organo-functional polysiloxanes
US4399247A (en) * 1981-06-26 1983-08-16 Toray Silicone Company, Ltd. Organopolysiloxane-containing composition for treating substrates
EP1490544B1 (en) * 2002-04-03 2007-07-18 Unilever Plc Fabric care composition
CN101638847A (en) * 2009-07-24 2010-02-03 东莞市德能化工有限公司 Formaldehyde-free durable non-ironing finishing agent for cellulose fiber fabric

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10982050B2 (en) * 2019-04-25 2021-04-20 Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. Sealing composite material, preparation method, and application thereof
WO2023118811A1 (en) * 2021-12-22 2023-06-29 Uea Enterprises Limited A method of modifying cellulose fibres and/or cellulose fabric

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