WO2010115496A1 - Fluorine-free aqueous dispersion for treating textile fabrics - Google Patents

Fluorine-free aqueous dispersion for treating textile fabrics Download PDF

Info

Publication number
WO2010115496A1
WO2010115496A1 PCT/EP2010/001415 EP2010001415W WO2010115496A1 WO 2010115496 A1 WO2010115496 A1 WO 2010115496A1 EP 2010001415 W EP2010001415 W EP 2010001415W WO 2010115496 A1 WO2010115496 A1 WO 2010115496A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
component
monomeric building
building block
acrylate
Prior art date
Application number
PCT/EP2010/001415
Other languages
French (fr)
Inventor
Andreas Fuchs
Wilhelm Artner
Barbara Oberlaender
Original Assignee
Huntsman Textile Effects (Germany) Gmbh
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 Huntsman Textile Effects (Germany) Gmbh filed Critical Huntsman Textile Effects (Germany) Gmbh
Priority to ES10727348T priority Critical patent/ES2396202T3/en
Priority to JP2012501158A priority patent/JP5538518B2/en
Priority to BRPI1007542-9A priority patent/BRPI1007542B1/en
Priority to US13/259,182 priority patent/US8969492B2/en
Priority to KR1020117025216A priority patent/KR101697075B1/en
Priority to MX2011008337A priority patent/MX2011008337A/en
Priority to EP20100727348 priority patent/EP2411575B1/en
Priority to CN2010800095707A priority patent/CN102333915B/en
Publication of WO2010115496A1 publication Critical patent/WO2010115496A1/en

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—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
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—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 a halogen
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/06—Vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—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 a halogen
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/08—Vinylidene chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
    • C08F220/68—Esters
    • 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
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/02—Moisture-responsive characteristics
    • D10B2401/021—Moisture-responsive characteristics hydrophobic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2164—Coating or impregnation specified as water repellent

Definitions

  • This invention relates to aqueous dispersions comprising paraffin wax, copolymers and dispersants.
  • the present invention further relates to a process for treating textile fabrics wherein such dispersions are applied to the textile fabrics.
  • the cited EP-B1 describes systems containing C 1-12 esters of acrylic or methacrylic acid. These esters must also contain vinyl esters of certain acids as a monomeric building block. It has emerged that the products of this EP specification or of the two JP abstracts do not provide an optimal water- repellent effect on textiles.
  • the invention described hereinbelow has for its object to provide compositions that have high stability even after prolonged storage, that do not contain any fluorine compounds and that provide excellent water-repellent properties on textile fabrics such as wovens, knits or nonwovens, and also a process for obtaining excellent water-repellent properties on textile fabrics.
  • an aqueous dispersion comprising no fluorine and no N-methylol compound and comprising at least the components A) to D), where component A) is a copolymer constructed exclusively of the following monomeric building blocks: a) an acrylate or methacrylate of an alcohol containing 10 to 24 carbon atoms, preferably 12 to 24 and more preferably 16 to 22 carbon atoms, or a mixture of such acrylates and methacrylates b) styrene or ⁇ -methylstyrene c) vinylidene chloride and/or vinyl chloride d) optionally 3-chloro-2-hydroxypropyl (meth)acrylate and/or glycidyl (meth)acrylate, component B) is a paraffin wax having a melting range of 58 0 C to 80 0 C 1 preferably of 65°C - 75°C component C) is a dispersant or a mixture of dispersants, preferably a cationic dispers
  • compositions of the present invention are aqueous dispersions. They do not contain any fluorine compounds, which has positive repercussions for environmental aspects and for the costs of the products. Nor do they contain any N-methylol compounds. N-CH 2 OH compounds have the disadvantage that they can release formaldehyde in undesirable quantities into the ambient atmosphere at elevated temperatures in particular.
  • the products of the present invention are aqueous dispersions.
  • Their component C) is a dispersant or a mixture of dispersants to ensure the stability of the dispersion.
  • Useful dispersants include known commercially available surface-active products such as nonionic ethoxylated products, for example ethoxylated alcohols or ethoxylated carboxylic acids.
  • Preference for use as component C) is given to commercially available cationic products such as quaternary ammonium salts or dispersant mixtures comprising such cationic products and nonionic products such as mono- or dipropylene glycol for example.
  • cationic dispersant is the Ethoquad HT/25 product from AKZO Nobel.
  • the proportion attributable to cationic dispersant is advantageously about 20% - 100% by weight, based on the total amount of dispersant mixture.
  • the dispersions of the present invention preferably contain 0.5% to 3% by weight of dispersant or dispersant mixture (component C)).
  • the aqueous dispersions of the present invention have very high stability due to their composition.
  • Component A) in the dispersions of the present invention is a copolymer.
  • This copolymer is exclusively constructed from the hereinbelow recited monomeric building blocks a) to c) and also, optionally, in addition d), since it was found that the incorporation of other monomeric building blocks worsens the effect level with regard to dispersion stability and/or water repellency: a) an acrylate or methacrylate of an alcohol containing 10 to 24 carbon atoms, preferably 12 to 24 and more preferably 16 to 22 carbon atoms, or a mixture of such acrylates and methacrylates b) styrene or ⁇ -methylstyrene c) vinylidene chloride and/or vinyl chloride d) optionally 3-chloro-2-hydroxypropyl (meth)acrylate and/or glycidyl (meth)acrylate.
  • the acrylates/methacrylates used for preparing component A) of the dispersions of the present invention contain more particularly no carbon-carbon multiple bonds in the alcohol component of these esters.
  • Monomeric building block a) is an ester of acrylic acid and/or methacrylic acid and an alcohol containing 12 to 24, preferably 16 to 22 carbon atoms, or a mixture of such esters. Monohydric alcohols are preferred. Behenyl acrylate or behenyl methacrylate is particularly useful as monomeric building block a).
  • the underlying alcohols may have a linear construction or optionally include a branched alkyl group.
  • Acrylates or methacrylates useful as monomeric building block a) are commercially available or can be prepared by following generally known methods. A mixture of an acrylate and a methyacrylate in a molar ratio of about 1 :1 is very useful as monomeric building block a).
  • Monomeric building block b) is styrene or ⁇ -methylstyrene and is likewise commercially available.
  • Monomeric building block d) is not absolutely necessary in the copolymers useful as component
  • Monomeric building block d) is 3-chloro-2-hydroxypropyl (meth)acrylate or glycidyl
  • Copolymers particularly useful as component A) preferably contain the monomeric building blocks a) to d) in the following amounts:
  • the copolymers useful as component A) can be prepared from the monomeric building blocks a) to c) and also, optionally, in addition monomeric building block d) by following generally known methods.
  • the copolymerization is typically carried out as a free-radical copolymerization by using a polymerization catalyst.
  • a polymerization catalyst Generally known commercially available products used as - A - free radical initiators can be used as catalysts for the free-radical polymerizations.
  • Useful catalysts for the purposes of the present invention include azo compounds, for example Vazo 56 or Wako V-50 (CAS no. 2997-92-4) from DuPont or WAKO Pure Chemical Industries, respectively.
  • the amount of polymerization catalyst used can be in the customary known range.
  • it is in the range from 2.5% to 5% by weight, based on the mixture of the monomeric building blocks.
  • monomeric building block d) can additionally be present; however, no monomeric building blocks other than those mentioned may be present, or a deterioration of the effects would occur.
  • Absent monomeric building block a the water-repellent effect is not very pronounced. Absent monomeric building block b), the water-repellent effect is likewise not optimal. Absent monomeric building block c), the water-repellent effect is unsatisfactory in both magnitude and durability.
  • Tests were conducted outside the scope of protection conferred by the claimed invention to examine the effect of incorporating further monomeric building blocks into the copolymers, for example the incorporation of hydroxyethyl (meth)acrylate.
  • Component B) of dispersions according to the present invention is a paraffin wax having a melting range of 58°C to 80 0 C, preferably of 65°C - 75 0 C. Paraffin waxes having a melting range outside these limits are not very suitable, if at all, for dispersions according to the present invention. Paraffin waxes having a lower melting range than stated above do not provide the desired effect level concerning water repellency of textiles treated with the aqueous dispersions. They also lead to reduced laundering durability on the part of treated textiles.
  • Paraffin waxes having a melting range higher than indicated above may lead to acceptable water repellency and laundering durability for the textiles, but cause these aqueous dispersions to have elevated viscosity, so that these dispersions are technically no longer adequately handleable and, what is more, the dispersions are then more costly and less convenient to manufacture.
  • Paraffin waxes are known products which are described in the chemical literature, for example in "R ⁇ mpp Chemie-Lexikon, 9th edition, Georg-Thieme-Verlag, Stuttgart - New York, under the head words "Paraffin” and "Wachse"".
  • Products useful for the dispersions of the present invention in that they have a melting range of 58°C to 80 0 C are commercially available, an example being a paraffin having the melting range 68°C to 74 0 C (CAS no. 8002-74-2).
  • Component D) of dispersions according to the present invention is water.
  • Aqueous dispersions according to the present invention can be prepared by the following generally customary methods. The following method is suitable for example: The paraffin wax (component B)) is melted in a vessel. A second vessel is initially charged with a dispersant or dispersant mixture (component C)) before the monomeric building blocks a) and b) (acrylate and styrene or methylstyrene) and optionally d) are added. The mixture obtained is dispersed in hot water at 85°C by stirring. This dispersion is added to the molten paraffin wax with intensive stirring (using a Turrax for example). On completion of the addition, stirring is continued for a few more minutes.
  • the copolymerization ends, leaving a very stable aqueous dispersion.
  • the resulting aqueous dispersion of the present invention may have added to it further components which are known to be useful as constituents of textile-treating compositions.
  • no fluorine compounds shall be added nor N-methylol compounds, since the latter may release formaldehyde.
  • Dispersions according to the present invention preferably contain the components A) to D) in the following amounts:
  • component A 3% to 20% by weight of component A), preferably 5 - 15% by weight, 8% to 40% by weight of component B), preferably 10 to 35% by weight, 0.5% to 3% by weight of component C), 55% to 80% by weight of water, where the weight ratio of component A) to component B) is preferably in the range from 25:70 to 45:70.
  • Dispersions according to the present invention are particularly useful for conferring water- repellent properties on textile fabrics.
  • the textiles are treated with aqueous liquors comprising dispersions according to the present invention. They may further comprise further products known from the field of textile finishing.
  • the textile fabrics thus treated, such as wovens for example, can be used inter alia for the following final articles: ladies' and gents' outerwear.
  • the treatment of textile fabrics can be carried out by the following generally customary methods, for example by padding, subsequent drying and, where appropriate, curing at temperatures ranging from 140° to 190 0 C for example.
  • the textile fabrics preferably consist of cotton, polyester or a cotton-polyester blend. They are normally wovens, knits or nonwovens.
  • This example describes the treatment of textile fabrics with a dispersion prepared as per example 1.
  • a woven 100% cotton fabric and a woven 100% polyester fabric were treated.
  • the cotton fabric was treated in a pad-mangle with liquor containing 1 g/l of 60% acetic acid, 20 g/l of cellulose crosslinker, 6 g/l of crosslinking catalyst and 60 g/l of the dispersion of example 1.
  • the polyester fabric was padded with liquor containing 1 g/l of 60% acetic acid and 60 g/l of the dispersion of example 1. After padding, the fabrics were dried at 110 0 C for 10 minutes and then cured at 150 0 C for 5 minutes.
  • Example 1 was repeated except that no paraffin wax was used. A product having an active content of about 13% by weight (instead of 26% as in example 1 ) was obtained. The product was used on cotton in the spray test and gave a value of 80/80/70 (triplicate determination) without washing and a value of 0 after 5 washes.
  • the spray test initial value obtained was 0, while the values 50/50/50 were obtained after 5 washes in a triplicate determination.
  • Example 1 was repeated except that no vinylidene chloride was used.
  • the product obtained had an active content of 24% by weight.
  • Treating cotton fabric with this product in the spray test resulted 3 times in a value of 100 (without wash) and 3 times in a value of 0 (after 5 washes).
  • the values 3; 1 ; 1 were obtained without washing, coupled with a 33% water absorption.
  • the spray test on PES fabric resulted 3 times in a value of 0 (without washing) and 3 times in a value of 50 after 5 washes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Abstract

Aqueous dispersions comprise a specific copolymer based on acrylate, a specific paraffin wax and one or more dispersants. The dispersions have high stability and are useful for treating textile fabrics, conferring outstanding water-repellent properties thereon.

Description

Fluorine-free aqueous dispersion for treating textile fabrics
This invention relates to aqueous dispersions comprising paraffin wax, copolymers and dispersants. The present invention further relates to a process for treating textile fabrics wherein such dispersions are applied to the textile fabrics.
It is known to treat textile fabrics such as wovens, knits or nonwovens with aqueous dispersions to endow the fabrics with desired properties. A water-repellent effect is an example of such a desired property. Water-repellent properties on textiles are achieved by using, inter alia, aqueous dispersions of fluorine-containing products. However, such products are costly and can entail environmentally harmful influences. Also known from the prior art are aqueous systems comprising n-paraffin and acrylic polymers. This is described for example in EP 1 424 433 B1 and in the abstract of JP 2006/83 276 A2 and also in the abstract of JP 2005/105 042 A2 and of JP 2000/248 140 A2. The cited EP-B1 describes systems containing C1-12 esters of acrylic or methacrylic acid. These esters must also contain vinyl esters of certain acids as a monomeric building block. It has emerged that the products of this EP specification or of the two JP abstracts do not provide an optimal water- repellent effect on textiles.
The invention described hereinbelow has for its object to provide compositions that have high stability even after prolonged storage, that do not contain any fluorine compounds and that provide excellent water-repellent properties on textile fabrics such as wovens, knits or nonwovens, and also a process for obtaining excellent water-repellent properties on textile fabrics.
We have found that this object is achieved by an aqueous dispersion comprising no fluorine and no N-methylol compound and comprising at least the components A) to D), where component A) is a copolymer constructed exclusively of the following monomeric building blocks: a) an acrylate or methacrylate of an alcohol containing 10 to 24 carbon atoms, preferably 12 to 24 and more preferably 16 to 22 carbon atoms, or a mixture of such acrylates and methacrylates b) styrene or α-methylstyrene c) vinylidene chloride and/or vinyl chloride d) optionally 3-chloro-2-hydroxypropyl (meth)acrylate and/or glycidyl (meth)acrylate, component B) is a paraffin wax having a melting range of 580C to 800C1 preferably of 65°C - 75°C component C) is a dispersant or a mixture of dispersants, preferably a cationic dispersant or a mixture of a cationic dispersant and a nonionic dispersant, and component D) is water, and by a process for treating textile fabrics by applying a dispersion of the kind described herein to the fabrics.
The compositions of the present invention are aqueous dispersions. They do not contain any fluorine compounds, which has positive repercussions for environmental aspects and for the costs of the products. Nor do they contain any N-methylol compounds. N-CH2OH compounds have the disadvantage that they can release formaldehyde in undesirable quantities into the ambient atmosphere at elevated temperatures in particular.
The products of the present invention are aqueous dispersions. Their component C) is a dispersant or a mixture of dispersants to ensure the stability of the dispersion. Useful dispersants include known commercially available surface-active products such as nonionic ethoxylated products, for example ethoxylated alcohols or ethoxylated carboxylic acids.
Preference for use as component C) is given to commercially available cationic products such as quaternary ammonium salts or dispersant mixtures comprising such cationic products and nonionic products such as mono- or dipropylene glycol for example. An example of a suitable cationic dispersant is the Ethoquad HT/25 product from AKZO Nobel. In dispersant mixtures, the proportion attributable to cationic dispersant is advantageously about 20% - 100% by weight, based on the total amount of dispersant mixture.
The dispersions of the present invention preferably contain 0.5% to 3% by weight of dispersant or dispersant mixture (component C)). The aqueous dispersions of the present invention have very high stability due to their composition.
Component A) in the dispersions of the present invention is a copolymer. This copolymer is exclusively constructed from the hereinbelow recited monomeric building blocks a) to c) and also, optionally, in addition d), since it was found that the incorporation of other monomeric building blocks worsens the effect level with regard to dispersion stability and/or water repellency: a) an acrylate or methacrylate of an alcohol containing 10 to 24 carbon atoms, preferably 12 to 24 and more preferably 16 to 22 carbon atoms, or a mixture of such acrylates and methacrylates b) styrene or α-methylstyrene c) vinylidene chloride and/or vinyl chloride d) optionally 3-chloro-2-hydroxypropyl (meth)acrylate and/or glycidyl (meth)acrylate.
The acrylates/methacrylates used for preparing component A) of the dispersions of the present invention contain more particularly no carbon-carbon multiple bonds in the alcohol component of these esters.
Monomeric building block a) is an ester of acrylic acid and/or methacrylic acid and an alcohol containing 12 to 24, preferably 16 to 22 carbon atoms, or a mixture of such esters. Monohydric alcohols are preferred. Behenyl acrylate or behenyl methacrylate is particularly useful as monomeric building block a). The underlying alcohols may have a linear construction or optionally include a branched alkyl group.
Acrylates or methacrylates useful as monomeric building block a) are commercially available or can be prepared by following generally known methods. A mixture of an acrylate and a methyacrylate in a molar ratio of about 1 :1 is very useful as monomeric building block a).
Monomeric building block b) is styrene or α-methylstyrene and is likewise commercially available.
Monomeric building block c) is vinyl chloride CH2=CHCI or vinylidene chloride CH2=CCI2. Again, these products are commercially available.
Monomeric building block d) is not absolutely necessary in the copolymers useful as component
A), but can be additionally incorporated, if desired, in order that specific effects may be achieved. Monomeric building block d) is 3-chloro-2-hydroxypropyl (meth)acrylate or glycidyl
(meth)acrylate or a mixture thereof.
Copolymers particularly useful as component A) preferably contain the monomeric building blocks a) to d) in the following amounts:
25% to 60% by weight, preferably 35% to 50% by weight of monomeric building block a) 8% to 40% by weight, preferably 15% to 30% by weight of monomeric building block b) 10% to 30% by weight, preferably 15% to 25% by weight of monomeric building block c) 0% to 10% by weight of monomeric building block d)
The copolymers useful as component A) can be prepared from the monomeric building blocks a) to c) and also, optionally, in addition monomeric building block d) by following generally known methods. The copolymerization is typically carried out as a free-radical copolymerization by using a polymerization catalyst. Generally known commercially available products used as - A - free radical initiators can be used as catalysts for the free-radical polymerizations. Useful catalysts for the purposes of the present invention include azo compounds, for example Vazo 56 or Wako V-50 (CAS no. 2997-92-4) from DuPont or WAKO Pure Chemical Industries, respectively.
The amount of polymerization catalyst used can be in the customary known range.
Advantageously, it is in the range from 2.5% to 5% by weight, based on the mixture of the monomeric building blocks.
To achieve the positive properties of dispersions of the present invention, it is essential that the three monomeric building blocks a) to c) are present in the copolymer. If desired, monomeric building block d) can additionally be present; however, no monomeric building blocks other than those mentioned may be present, or a deterioration of the effects would occur.
Absent monomeric building block a), the water-repellent effect is not very pronounced. Absent monomeric building block b), the water-repellent effect is likewise not optimal. Absent monomeric building block c), the water-repellent effect is unsatisfactory in both magnitude and durability.
Tests were conducted outside the scope of protection conferred by the claimed invention to examine the effect of incorporating further monomeric building blocks into the copolymers, for example the incorporation of hydroxyethyl (meth)acrylate.
Component B) of dispersions according to the present invention is a paraffin wax having a melting range of 58°C to 800C, preferably of 65°C - 750C. Paraffin waxes having a melting range outside these limits are not very suitable, if at all, for dispersions according to the present invention. Paraffin waxes having a lower melting range than stated above do not provide the desired effect level concerning water repellency of textiles treated with the aqueous dispersions. They also lead to reduced laundering durability on the part of treated textiles. Paraffin waxes having a melting range higher than indicated above may lead to acceptable water repellency and laundering durability for the textiles, but cause these aqueous dispersions to have elevated viscosity, so that these dispersions are technically no longer adequately handleable and, what is more, the dispersions are then more costly and less convenient to manufacture. Paraffin waxes are known products which are described in the chemical literature, for example in "Rόmpp Chemie-Lexikon, 9th edition, Georg-Thieme-Verlag, Stuttgart - New York, under the head words "Paraffin" and "Wachse"". Products useful for the dispersions of the present invention in that they have a melting range of 58°C to 800C are commercially available, an example being a paraffin having the melting range 68°C to 740C (CAS no. 8002-74-2).
Component D) of dispersions according to the present invention is water. Aqueous dispersions according to the present invention can be prepared by the following generally customary methods. The following method is suitable for example: The paraffin wax (component B)) is melted in a vessel. A second vessel is initially charged with a dispersant or dispersant mixture (component C)) before the monomeric building blocks a) and b) (acrylate and styrene or methylstyrene) and optionally d) are added. The mixture obtained is dispersed in hot water at 85°C by stirring. This dispersion is added to the molten paraffin wax with intensive stirring (using a Turrax for example). On completion of the addition, stirring is continued for a few more minutes. This is followed by high-pressure dispersing, for example at 250 bar and 80 to 85°C. Then, the dispersion is cooled down to room temperature and monomeric building block c) (vinylidene chloride or vinyl chloride) and polymerization catalyst, the latter dissolved in water, are added.
After several hours' reaction time at about 500C to 60°C, the copolymerization ends, leaving a very stable aqueous dispersion. If desired, the resulting aqueous dispersion of the present invention may have added to it further components which are known to be useful as constituents of textile-treating compositions. To retain the advantages of dispersions according to the present invention, namely excellent stability and achievement of outstanding water-repellent properties on textiles, however, no fluorine compounds shall be added nor N-methylol compounds, since the latter may release formaldehyde.
Dispersions according to the present invention preferably contain the components A) to D) in the following amounts:
3% to 20% by weight of component A), preferably 5 - 15% by weight, 8% to 40% by weight of component B), preferably 10 to 35% by weight, 0.5% to 3% by weight of component C), 55% to 80% by weight of water, where the weight ratio of component A) to component B) is preferably in the range from 25:70 to 45:70.
When these amount ranges are adhered to, the aforementioned advantages of the dispersions are particularly prominent.
Dispersions according to the present invention are particularly useful for conferring water- repellent properties on textile fabrics. To this end, the textiles are treated with aqueous liquors comprising dispersions according to the present invention. They may further comprise further products known from the field of textile finishing. The textile fabrics thus treated, such as wovens for example, can be used inter alia for the following final articles: ladies' and gents' outerwear. The treatment of textile fabrics can be carried out by the following generally customary methods, for example by padding, subsequent drying and, where appropriate, curing at temperatures ranging from 140° to 1900C for example. The textile fabrics preferably consist of cotton, polyester or a cotton-polyester blend. They are normally wovens, knits or nonwovens.
The examples which follow illustrate the invention.
Example 1 (inventive)
17.5 g of behenyl acrylate, 17.5 g of behenyl methacrylate and 10.0 g of styrene were added to a hot mixture of 12.0 g of Ethoquad HT/25 (ethoxylated quaternary ammonium salt) and 30 g of dipropylene glycol in 450 g of water at 85°C and dispersed by stirring. In a separate vessel, 105 g of paraffin wax (melting range 68 - 74°C) were melted. The above-described dispersion of monomers was added to the molten paraffin wax. This was followed by a further 3 minutes of dispersing and then by a high-pressure dispersing operation (250 bar, 85°C) until a stable dispersion was obtained. After cooling down to room temperature, 20.0 g of vinylidene chloride and catalyst solution (2.5 g of Wako V-50 in 15 g of water) were added and the mixture was treated for 8 hours at 55°C under N2 under a donned reflux condenser.
This gives 550 g of a product having an active content of about 26% by weight (determined after drying at 120°C/90 minutes).
Example 2 (inventive)
This example describes the treatment of textile fabrics with a dispersion prepared as per example 1.
A woven 100% cotton fabric and a woven 100% polyester fabric were treated. The cotton fabric was treated in a pad-mangle with liquor containing 1 g/l of 60% acetic acid, 20 g/l of cellulose crosslinker, 6 g/l of crosslinking catalyst and 60 g/l of the dispersion of example 1. The polyester fabric was padded with liquor containing 1 g/l of 60% acetic acid and 60 g/l of the dispersion of example 1. After padding, the fabrics were dried at 1100C for 10 minutes and then cured at 1500C for 5 minutes.
The finished fabrics obtained as per example 2 were subjected to the following tests:
a) spray test as per AATCC 22-2005, ISO 4920 (EN 24 920)
b) Bundesmann test as per DIN EN 29865, ISO 9865
Results for cotton fabric: a) spray test, initial value 100 (determined 3x) after 5 washes at 40°C: 3 x rated 100 b) Bundesmann, initial values 5; 3; 2 (15% water absorption) after 5 washes at 400C: 3; 2; 2 (22% water absorption)
Results for PES fabric: before wash only minimal water-repellent effect, after wash prominent effect a) spray test, initial values: 80; 80; 80; after 5 washes (at 4O0C): 90 - 100; 90 - 100; 90 - 100 b) Bundesmann: after 5 washes at 400C: 5; 4; 4 (1 % water absorption)
Example 3 (comparative, not according to invention)
Woven fabrics were treated with the products as per example 3 by raising the quantities used to account for the different active content than example 1.
Example 3a:
Example 1 was repeated except that no paraffin wax was used. A product having an active content of about 13% by weight (instead of 26% as in example 1 ) was obtained. The product was used on cotton in the spray test and gave a value of 80/80/70 (triplicate determination) without washing and a value of 0 after 5 washes.
On PES fabric, the spray test initial value obtained was 0, while the values 50/50/50 were obtained after 5 washes in a triplicate determination.
The results with the formulation as per example 3a were therefore distinctly worse than those of example 1.
Example 3b: (not according to invention)
Example 1 was repeated except that no vinylidene chloride was used. The product obtained had an active content of 24% by weight. Treating cotton fabric with this product in the spray test resulted 3 times in a value of 100 (without wash) and 3 times in a value of 0 (after 5 washes). In the Bundesmann test, the values 3; 1 ; 1 were obtained without washing, coupled with a 33% water absorption. The spray test on PES fabric resulted 3 times in a value of 0 (without washing) and 3 times in a value of 50 after 5 washes.
Therefore the product as per example 3b gave distinctly worse results than the product as per example 1.

Claims

What is claimed is:
1. An aqueous dispersion comprising no fluorine and no N-methylol compound and comprising at least the components A) to D), where component A) is a copolymer constructed exclusively of the following monomeric building blocks: a) an acrylate or methacrylate of an alcohol containing 10 to 24 carbon atoms, preferably 12 to 24 and more preferably 16 to 22 carbon atoms, or a mixture of such acrylates and methacrylates b) styrene or α-methylstyrene c) vinylidene chloride and/or vinyl chloride d) optionally 3-chloro-2-hydroxypropyl (meth)acrylate and/or glycidyl (meth)acrylate, component B) is a paraffin wax having a melting range of 58°C to 80°C, preferably of 65°C
- 75°C component C) is a dispersant or a mixture of dispersants, preferably a cationic dispersant or a mixture of a cationic dispersant and a nonionic dispersant, and component D) is water.
2. The aqueous dispersion according to claim 1 comprising components A) to D) in the following amounts:
3% to 20% by weight of component A), preferably 5 - 15% by weight, 8% to 40% by weight of component B), preferably 10 to 35% by weight,
0.5% to 3% by weight of component C), 55% to 80% by weight of water, where the weight ratio of component A) to component B) is preferably in the range from 25:70 to 45:70.
3. The aqueous dispersion according to claim 1 or 2 wherein component A) is constructed from the following amounts of the monomeric building blocks a) to d): 25% to 60% by weight, preferably 35% to 50% by weight of monomeric building block a) 8% to 40% by weight, preferably 15% to 30% by weight of monomeric building block b) 10% to 30% by weight, preferably 15% to 25% by weight of monomeric building block c) 0% to 10% by weight of monomeric building block d)
4. A process for treating a textile fabric, which comprises applying a dispersion according to any one of claims 1 to 3 to the fabric.
5. The process according to claim 4 wherein the textile fabric consists of cotton, polyester or a cotton-polyester blend.
PCT/EP2010/001415 2009-03-28 2010-03-06 Fluorine-free aqueous dispersion for treating textile fabrics WO2010115496A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
ES10727348T ES2396202T3 (en) 2009-03-28 2010-03-06 Fluorine-free aqueous dispersion to treat textile fabrics
JP2012501158A JP5538518B2 (en) 2009-03-28 2010-03-06 Fluorine-free aqueous dispersion for treating textile fabrics
BRPI1007542-9A BRPI1007542B1 (en) 2009-03-28 2010-03-06 FLUOROUS FREE WATER DISPERSION FOR TEXTILE TREATMENT
US13/259,182 US8969492B2 (en) 2009-03-28 2010-03-06 Flourine-free aqueous dispersion for treating textile fabrics
KR1020117025216A KR101697075B1 (en) 2009-03-28 2010-03-06 Fluorine-free aqueous dispersion for treating textile fabrics
MX2011008337A MX2011008337A (en) 2009-03-28 2010-03-06 Fluorine-free aqueous dispersion for treating textile fabrics.
EP20100727348 EP2411575B1 (en) 2009-03-28 2010-03-06 Fluorine-free aqueous dispersion for treating textile fabrics
CN2010800095707A CN102333915B (en) 2009-03-28 2010-03-06 Fluorine-free aqueous dispersion for treating textile fabrics

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP09004522.0 2009-03-28
EP20090004522 EP2233633A1 (en) 2009-03-28 2009-03-28 Fluorine-free aqueous dispersion for the treatment of textile area-measured material

Publications (1)

Publication Number Publication Date
WO2010115496A1 true WO2010115496A1 (en) 2010-10-14

Family

ID=40941610

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/001415 WO2010115496A1 (en) 2009-03-28 2010-03-06 Fluorine-free aqueous dispersion for treating textile fabrics

Country Status (9)

Country Link
US (1) US8969492B2 (en)
EP (2) EP2233633A1 (en)
JP (1) JP5538518B2 (en)
KR (1) KR101697075B1 (en)
CN (1) CN102333915B (en)
BR (1) BRPI1007542B1 (en)
ES (1) ES2396202T3 (en)
MX (1) MX2011008337A (en)
WO (1) WO2010115496A1 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016130352A1 (en) * 2015-02-13 2016-08-18 3M Innovative Properties Company Fluorine-free fibrous treating compositions including a polycarbodiimide and an optional paraffin wax, and treating methods
WO2018007549A1 (en) 2016-07-07 2018-01-11 Rudolf Gmbh Preparation as water repelling agents
CN107849187A (en) * 2015-07-23 2018-03-27 日华化学株式会社 Non-fluoropolymer, water-repelling agent composition, the manufacture method of hydrophobic fibre product and hydrophobic fibre product
WO2018054712A1 (en) 2016-09-23 2018-03-29 Huntsman Textile Effects (Germany) Gmbh Fluorine-free aqueous dispersions for the finishing of textile fabrics
US10294609B2 (en) 2015-02-13 2019-05-21 3M Innovative Properties Company Fluorine-free fibrous treating compositions including isocyanate-derived ethylenically unsaturated monomer-containing oligomers, and treating methods
WO2021066052A1 (en) 2019-09-30 2021-04-08 ダイキン工業株式会社 Organic fine particle
US11072885B2 (en) 2014-07-04 2021-07-27 Archroma Ip Gmbh Fluorine-free water-repellent composition
WO2022138853A1 (en) 2020-12-25 2022-06-30 ダイキン工業株式会社 Water-repellent organic fine particles having slip prevention effect
WO2024012662A1 (en) 2022-07-12 2024-01-18 Huntsman Textile Effects (Germany) Gmbh Extender compounds for durable water repellence

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013209170A1 (en) 2013-05-17 2013-09-12 Cht R. Beitlich Gmbh Composition useful e.g. for waterproofing of absorbent materials, comprises silicone polymer, wax and/or fatty acid esters, aminoplast, urea derivatives and/or melamine derivatives, solvent, crosslinking agent, and dispersing auxiliaries
JP5811257B2 (en) * 2013-11-22 2015-11-11 ダイキン工業株式会社 Water-based emulsion surface treatment agent
CN105765025B (en) * 2013-11-22 2017-11-24 大金工业株式会社 Water system surface conditioning agent
CN103628324A (en) * 2013-12-02 2014-03-12 广东德美精细化工股份有限公司 Fluorine-free water-proofing agent and preparation method thereof as well as textile
TWI491721B (en) * 2014-01-20 2015-07-11 Jinex Corp Ltd Fluorine-free water repellent, preparation thereof, and applications thereof
WO2015111668A1 (en) * 2014-01-24 2015-07-30 日華化学株式会社 Water repellent agent composition, water repellent fiber product and method for producing water repellent fiber product
CA2944196A1 (en) * 2014-04-09 2015-10-15 Invista Technologies S.A R.L. Water repellent, soil resistant, fluorine-free compositions
JP5922706B2 (en) * 2014-05-23 2016-05-24 明成化学工業株式会社 Water repellent composition not containing fluorine and water repellent processing method
WO2016029922A1 (en) 2014-08-27 2016-03-03 W.L. Gore & Associates Gmbh Waterproof and water vapor permeable laminate
DE102015204736A1 (en) 2015-03-16 2016-09-22 Cht R. Beitlich Gmbh Fluorine-free hydrophobing
JP6580893B2 (en) * 2015-07-23 2019-09-25 日華化学株式会社 Non-fluorinated polymer, water repellent composition, water repellent fiber product, and method for producing water repellent fiber product
CN105111349B (en) * 2015-08-19 2017-08-11 江苏科技大学 A kind of copolymer emulsion containing nonionic emulsifier and preparation method thereof
JP6741442B2 (en) * 2016-02-29 2020-08-19 日華化学株式会社 Water repellent aid, non-fluorine-based water repellent composition, and method for producing water repellent fiber product
JP6839336B2 (en) * 2016-02-29 2021-03-10 大原パラヂウム化学株式会社 Textile processing agents and processing formulations and textile fabrics and textile products treated with them.
JP6680017B2 (en) * 2016-03-16 2020-04-15 ダイキン工業株式会社 Surface treatment agent
JP6727865B2 (en) * 2016-03-16 2020-07-22 ダイキン工業株式会社 Copolymer and surface treatment agent
JP6829553B2 (en) * 2016-05-27 2021-02-10 日華化学株式会社 Manufacturing method of water-repellent textile products
JP6688171B2 (en) * 2016-06-17 2020-04-28 日華化学株式会社 Water repellent composition, water repellent fiber product and method for producing water repellent fiber product
JP6987847B2 (en) * 2016-08-12 2022-01-05 スリーエム イノベイティブ プロパティズ カンパニー Fluorine-free fiber treatment composition, treated substrate, and treatment method
JP6319419B1 (en) * 2016-12-28 2018-05-09 ダイキン工業株式会社 Surface treatment agent
KR101822957B1 (en) * 2017-01-24 2018-01-30 주식회사 기쁨앤드 Water Repellent Fabric and Water Repellent Down Product Comprising Same
DE102017202827A1 (en) 2017-02-22 2018-08-23 Cht R. Beitlich Gmbh Aqueous formulation for improving abrasion resistance
JP6840385B2 (en) * 2017-04-21 2021-03-10 明成化学工業株式会社 Fluorine-free water repellent and water repellent processing method, water repellent textile products
US11661683B2 (en) * 2018-03-29 2023-05-30 Milliken & Company Flame resistant textile
CN109503742B (en) * 2018-12-07 2021-05-04 怀化学院 Silicon hybrid polyacrylate dispersion and application thereof
TWI682084B (en) * 2019-01-04 2020-01-11 遠東新世紀股份有限公司 Method for manufacturing non-fluorine water repellent and fabric
CN114174585A (en) 2019-05-24 2022-03-11 南磨房公司 Flame resistant finished fabrics exhibiting water repellency and methods of making the same
CN110527014A (en) * 2019-08-22 2019-12-03 浙江工业职业技术学院 A kind of free-floride cationic polyacrylate waterproofing agent and preparation method thereof
JP7039661B2 (en) * 2020-07-27 2022-03-22 日華化学株式会社 Method for manufacturing non-fluorine-based water repellent composition and water-repellent fiber product
NL2027946B1 (en) * 2021-04-08 2022-10-20 Lamoral Holding B V Method for conferring durable water repellence to woven or non-woven fabric and water repellent composition

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000248140A (en) 1999-03-03 2000-09-12 Seiko Kagaku Kogyo Co Ltd Resin composition for moisture-proofing and moisture- proof paper made by using it
EP1127898A1 (en) * 2000-02-22 2001-08-29 Nicca Chemical Co., Ltd. Process for production of copolymer composition and water-repellent, oil-repellent agent
US20040102114A1 (en) * 2002-11-26 2004-05-27 Boylan John Richard Waterborne hydrophobic barrier coatings derived from copolymers of higher vinyl esters
JP2005105042A (en) 2003-09-29 2005-04-21 Dainippon Ink & Chem Inc Textile size composition and thread adhered therewith
JP2006083276A (en) 2004-09-15 2006-03-30 Saiden Chemical Industry Co Ltd Paraffin emulsion
EP1424433B1 (en) 2002-11-26 2008-08-13 Air Products Polymers, L.P. Waterborne hydrophobic barrier coatings derived from copolymers of higher vinyl esters
EP2009035A1 (en) * 2007-06-27 2008-12-31 Huntsman Textile Effects (Germany) GmbH Copolymers with perfluor alkyl groups and their aqueous dispersions

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57108114A (en) * 1980-12-25 1982-07-06 Dainippon Ink & Chem Inc Aqueous dispersion type resin composition for fiber coating
JP3549920B2 (en) * 1994-05-23 2004-08-04 株式会社日本触媒 Wax composition and method for producing the same
US6696519B2 (en) * 2000-10-17 2004-02-24 Rohm And Haas Company Redox process for preparing emulsion polymer having low residual monomer content
DE60200324T2 (en) * 2001-01-10 2005-03-17 Rohm And Haas Co. Watery wood stain composition
JPWO2002083809A1 (en) * 2001-04-13 2004-08-05 旭硝子株式会社 Water / oil repellent composition
US7332160B2 (en) 2002-07-12 2008-02-19 Boston Scientific Scimed, Inc. Medical device and method for tissue removal and repair
US7652112B2 (en) * 2005-07-06 2010-01-26 E.I. Du Pont De Nemours And Company Polymeric extenders for surface effects
ATE527326T1 (en) * 2006-02-03 2011-10-15 Basf Se METHOD FOR TREATING SUBSTRATES

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000248140A (en) 1999-03-03 2000-09-12 Seiko Kagaku Kogyo Co Ltd Resin composition for moisture-proofing and moisture- proof paper made by using it
EP1127898A1 (en) * 2000-02-22 2001-08-29 Nicca Chemical Co., Ltd. Process for production of copolymer composition and water-repellent, oil-repellent agent
US20040102114A1 (en) * 2002-11-26 2004-05-27 Boylan John Richard Waterborne hydrophobic barrier coatings derived from copolymers of higher vinyl esters
EP1424433B1 (en) 2002-11-26 2008-08-13 Air Products Polymers, L.P. Waterborne hydrophobic barrier coatings derived from copolymers of higher vinyl esters
JP2005105042A (en) 2003-09-29 2005-04-21 Dainippon Ink & Chem Inc Textile size composition and thread adhered therewith
JP2006083276A (en) 2004-09-15 2006-03-30 Saiden Chemical Industry Co Ltd Paraffin emulsion
EP2009035A1 (en) * 2007-06-27 2008-12-31 Huntsman Textile Effects (Germany) GmbH Copolymers with perfluor alkyl groups and their aqueous dispersions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Rompp Chemie-Lexikon", GEORG-THIEME-VERLAG

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11072885B2 (en) 2014-07-04 2021-07-27 Archroma Ip Gmbh Fluorine-free water-repellent composition
US11421378B2 (en) 2015-02-13 2022-08-23 3M Innovative Properties Company Fluorine-free fibrous treating compositions including a polycarbodiimide and an optional paraffin wax, and treating methods
US11124918B2 (en) 2015-02-13 2021-09-21 3M Innovative Properties Company Fluorine-free fibrous treating compositions including a polycarbodiimide and an optional paraffin wax, and treating methods
US10294609B2 (en) 2015-02-13 2019-05-21 3M Innovative Properties Company Fluorine-free fibrous treating compositions including isocyanate-derived ethylenically unsaturated monomer-containing oligomers, and treating methods
TWI702324B (en) * 2015-02-13 2020-08-21 美商3M新設資產公司 Fluorine-free fibrous treating compositions including a polycarbodiimide and an optional paraffin wax, and treating methods
WO2016130352A1 (en) * 2015-02-13 2016-08-18 3M Innovative Properties Company Fluorine-free fibrous treating compositions including a polycarbodiimide and an optional paraffin wax, and treating methods
CN107849187B (en) * 2015-07-23 2021-03-02 日华化学株式会社 Non-fluorine-containing polymer, hydrophobizing agent composition, hydrophobic fiber product, and method for producing hydrophobic fiber product
CN107849187A (en) * 2015-07-23 2018-03-27 日华化学株式会社 Non-fluoropolymer, water-repelling agent composition, the manufacture method of hydrophobic fibre product and hydrophobic fibre product
US10597474B2 (en) 2015-07-23 2020-03-24 Nicca Chemical Co., Ltd. Non-fluorinated polymer, water repellent agent composition, water-repellent fiber product, and method for producing water-repellent fiber product
US10822500B2 (en) 2016-07-07 2020-11-03 Rudolf Gmbh Preparations as hydrophobing agents
DE102016212443A1 (en) 2016-07-07 2018-01-11 Rudolf Gmbh Preparations as water repellents
WO2018007549A1 (en) 2016-07-07 2018-01-11 Rudolf Gmbh Preparation as water repelling agents
US10844151B2 (en) 2016-09-23 2020-11-24 Huntsman Textile Effects (Germany) Gmbh Fluorine-free aqueous dispersions for the finishing of textile fabrics
WO2018054712A1 (en) 2016-09-23 2018-03-29 Huntsman Textile Effects (Germany) Gmbh Fluorine-free aqueous dispersions for the finishing of textile fabrics
WO2021066052A1 (en) 2019-09-30 2021-04-08 ダイキン工業株式会社 Organic fine particle
WO2022138853A1 (en) 2020-12-25 2022-06-30 ダイキン工業株式会社 Water-repellent organic fine particles having slip prevention effect
WO2024012662A1 (en) 2022-07-12 2024-01-18 Huntsman Textile Effects (Germany) Gmbh Extender compounds for durable water repellence

Also Published As

Publication number Publication date
EP2233633A1 (en) 2010-09-29
JP2012522062A (en) 2012-09-20
US8969492B2 (en) 2015-03-03
ES2396202T3 (en) 2013-02-19
BRPI1007542A2 (en) 2016-02-16
KR20120002999A (en) 2012-01-09
JP5538518B2 (en) 2014-07-02
EP2411575A1 (en) 2012-02-01
US20120015575A1 (en) 2012-01-19
CN102333915B (en) 2013-07-24
BRPI1007542B1 (en) 2019-04-16
CN102333915A (en) 2012-01-25
MX2011008337A (en) 2011-09-01
EP2411575B1 (en) 2012-10-24
KR101697075B1 (en) 2017-01-17

Similar Documents

Publication Publication Date Title
EP2411575B1 (en) Fluorine-free aqueous dispersion for treating textile fabrics
KR102410074B1 (en) Fluorine-free aqueous dispersion for the finishing of textile fabrics
US7652112B2 (en) Polymeric extenders for surface effects
US8993067B2 (en) Composition for oil- and/or water-repellent finishing of fiber materials
JP2008512547A (en) Hydrocarbon extenders for surface effect compositions
EP2267048B1 (en) Fluoropolymer and water-repellent and oil-repellent agent
AU2006269600B2 (en) Polymeric extenders for surface effects

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080009570.7

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10727348

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 5609/DELNP/2011

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: MX/A/2011/008337

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 13259182

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2012501158

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2010727348

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20117025216

Country of ref document: KR

Kind code of ref document: A

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: PI1007542

Country of ref document: BR

ENP Entry into the national phase

Ref document number: PI1007542

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20110728