EP1379724B1 - Verwendung von hydrophil modifizierten polyisocyanaten und polyurethanen als antiknitteradditiv für den heimbereich - Google Patents
Verwendung von hydrophil modifizierten polyisocyanaten und polyurethanen als antiknitteradditiv für den heimbereich Download PDFInfo
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- EP1379724B1 EP1379724B1 EP01993721A EP01993721A EP1379724B1 EP 1379724 B1 EP1379724 B1 EP 1379724B1 EP 01993721 A EP01993721 A EP 01993721A EP 01993721 A EP01993721 A EP 01993721A EP 1379724 B1 EP1379724 B1 EP 1379724B1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3726—Polyurethanes
-
- 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
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- 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
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/568—Reaction products of isocyanates with polyethers
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- 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
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease
Definitions
- Cellulose-containing textiles are, for example, by treatment with condensation products made of urea, glyoxal and formaldehyde easy-care.
- the Equipment takes place during the production of textile materials. At the equipment One often uses other additives such as plasticizing compounds.
- the Textiles finished in this way are more resistant to the untreated cellulose textiles the washing process the advantage that they have less wrinkles and wrinkles, lighter to iron and are softer and smoother.
- WO 92/01773 discloses the use of microemulsified aminosiloxanes in fabric softeners to reduce wrinkling and wrinkling during the washing process (Crease arm equipment) known. At the same time should by the use of aminosiloxanes the ironing can be facilitated.
- formulations which have an anti-wrinkle effect in the effect treated textiles.
- the formulations consist of lubricants, Polymers that ensure the dimensional and dimensional stability of textiles, lithium salts and optional other ingredients such as plasticizers, ionic and nonionic Surfactants, odor-binding substances and bactericides.
- the application of the formulation on the fabric is preferably carried out by spraying.
- EP-A 0 978 556 describes a mixture of a plasticizer and a crosslinker component with cationic properties as a means of furnishing textiles with wrinkle and wrinkle protection, and a method of anti-wrinkle finishing of Textiles.
- the object of the invention is a further process for anti-cellulite finishing of cellulosic Textiles and other finishing equipment for anti-wrinkle finishing such To provide textiles.
- hydrophilic modified Polyisocyanates (A) and of polyurethanes (B) as Antiknitteradditiv in Textile treatment products for the home, in solid and liquid Detergent formulations and laundry detergents.
- hydrophilic modified polyisocyanates used in the invention serve conventional diisocyanates and / or conventional higher functional polyisocyanates with a mean NCO functionality of 2.0 to 4.5. These components can be alone or in a mixture.
- Examples of common diisocyanates are aliphatic diisocyanates such as Tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisoanatohexane), Octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, Tetradecamethylene diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1,4-, 1,3- or 1,2-diisocyanatocyclohexane, 4,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (Isophorone diisocyanate) or 2,4- or 2,6-diisocyanato-1-methylcyclohexane and aromatic diisocyanates
- Suitable conventional higher-functional polyisocyanates are, for example, triisocyanates such as 2,4,6-triisocyanatotoluene or 2,4,4'-triisocyanatodiphenyl ether or the mixtures from di-, tri- and higher polyisocyanates obtained by phosgenation of corresponding Aniline / formaldehyde condensates are obtained and have methylene bridges Represent polyphenyl polyisocyanates.
- the diisocyanates described and / or higher functionalized polyisocyanates for conversion into non-ionic hydrophilic modified polyisocyanates which are particularly suitable for the use according to the invention are reacted with NCO-reactive compounds, the hydrophilic-making Structural elements with non-ionic groups or with polar groups that are not in Ion groups can be transferred, included.
- C 1 -C 4 -alkanol-started ethylene oxide or propylene oxide polyethers having average molecular weights of from 250 to 7,000, in particular from 450 to 1,500.
- Polyethers or polyols e.g. Ethylene glycol, trimethylolpropane or butanediol, Prepare prepolymers and these prepolymers then or simultaneously with the polyethers I in deficit to the hydrophilic modified polyisocyanates with implement free NCO groups.
- nonionically hydrophilically modified polyisocyanates from diisocyanate or polyisocyanate and polyalkylene glycols of the formula HO- (DO) n -H, in which D and n have the abovementioned meanings. Both terminal OH groups of the polyalkylene glycol react with isocyanate.
- non-ionic hydrophilic modified polyisocyanates are in the DE-A 24 47 135, DE-A 26 10 552, DE-A 29 08 844, EP-A 0 13 112, EP-A 019 844, DE-A 40 36 927, DE-A 41 36 618, EP-B 206 059, EP-A 464 781 and EP-A 516 361 described in more detail.
- the described diisocyanates and / or higher functionalized polyisocyanates are for conversion into anionically hydrophilic modified polyisocyanates with NCO-reactive Compounds reacted, the hydrophilic anionic groups, in particular Acid groups such as carboxyl groups, sulfonic acid groups or phosphonic acid groups, contain.
- the diisocyanate or polyisocyanate is in the stoichiometric Excess, so that the resulting hydrophilic modified polyisocyanate still free Having NCO groups.
- NCO-reactive compounds with anionic groups are especially Hydroxycarboxylic acids such as 2-hydroxyacetic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid or hydroxylpivalic acid and 2,2-bis- and 2,2,2-tris (hydroxymethyl) alkanoic acids, e.g. 2,2-bis (hydroxymethyl) acetic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butyric acid or 2,2,2-tris (hydroxymethyl) acetic acid, into consideration.
- the carboxyl groups may be partially or completely neutralized by a base to be in a water-soluble or water-dispersible form.
- the base used here is preferably a tertiary one Amine, which is known to be inert to isocyanate.
- the diisocyanates described and / or higher functionalized polyisocyanates can also with a mixture of non-ionic hydrophilic modifying and anionic hydrophilically modifying compounds which are successively or simultaneously be implemented, for example, with a deficit from the Polyethers I and the hydroxycarboxylic acids described.
- anionically hydrophilic modified polyisocyanates are in the DE-A 40 01 783, DE-A 41 13 160 and DE-A 41 42 275 described in more detail.
- the described diisocyanates and / or higher functionalized polyisocyanates are for conversion into cationically hydrophilic modified polyisocyanates with NCO-reactive Compounds reacted, the chemically incorporated alkylatable or protonatable Includes functions to form a cationic center.
- functions tertiary nitrogen atoms, which are known to isocyanate are inert and can be easily quaternized or protonated.
- Diisocyanate or polyisocyanate with these NCO-reactive compounds are the former in excess, so that the resulting hydrophilic modified polyisocyanate still free Having NCO groups.
- Suitable amino alcohols II are, in particular, N-methyldiethanolamine, N-methyldi (iso) propanolamine, N-butyldiethanolamine, N-butyldi (iso) propanolamine, N-stearyldiethanolamine, N-stearyldi (iso) propanolamine, N, N-dimethylethanolamine, N, N-dimethyl (iso) propanolamine, N, N-diethylethanolamine, N, N-diethyl (iso) -propanolamine, N, N-dibutylethanolamine, N, N-dibutyl (iso) -propanolamine, triethanolamine, Tri (iso) propanolamine, N- (2-hydroxyethyl) morpholine, N- (2-hydroxypropyl) morpholine, N- (2-hydroxyethyl) piperidine, N- (2-hydroxypropyl) piperidine, N-methyl-
- NCO-reactive compounds with tertiary nitrogen atoms are preferably diamines of the general formula IIIa or IIIb in which R 9 to R 11 have the abovementioned meanings and R 12 denotes C 1 - to C 5 -alkyl or forms with R 9 a five- or six-membered ring, in particular a piperazine ring, into consideration.
- Particularly suitable diamines IIIa are N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dimethyl-1,3-diamino-2,2-dimethylpropane, N, N-diethyl-1,3-propylenediamine, N- (3-aminopropyl) morpholine, N- (2-aminopropyl) morpholine, N- (3-aminopropyl) piperidine, N- (2-aminopropyl) piperidine, 4-amino-1- (N, N-diethylamino) pentane, 2-amino-1- (N, N-dimethylamino) propane, 2-amino-1- (N, N-diethylamino) propane or 2-amino-1- (N, N-diethylamino) -2-methylpropane.
- Suitable diamines IIIb are in particular N, N, N'-trimethylethylenediamine, N, N, N'-triethylethylenediamine, N-methylpiperazine or N-ethylpiperazine.
- NCO-reactive compounds and polyether (poly) ole with incorporated tertiary nitrogen atoms by propoxylation and / or ethoxylation Amine-containing starter molecules are produced can be used.
- Such polyether (poly) ole are, for example, the propoxylation and Ethoxylation products of ammonia, ethanolamine, diethanolamine, ethylenediamine or N-methylaniline.
- NCO-reactive compounds are tertiary nitrogens having polyester and polyamide resins, tertiary nitrogen atoms urethane-containing polyols and tertiary nitrogen atoms Polyhydroxypolyacrylates.
- the diisocyanates described and / or higher functionalized polyisocyanates can also with a mixture of non-ionic hydrophilic modifying and cationic hydrophilically modifying compounds which are successively or simultaneously be implemented, for example, with a deficit from the Polyethers I and the aminoalcohols II or the diamines IIIa or IIIb. Also mixtures from non-ionic hydrophilic modifying and anionic hydrophilic modifying Connections are possible.
- hydrophilic modified polyisocyanates (A) usually in aqueous Media are used is sufficient dispersibility of the polyisocyanates to care.
- the described hydrophilic act modified polyisocyanates certain reaction products of di- or polyisocyanates and hydroxyl-terminated polyethers (polyether alcohols) such as the Compounds I as emulsifiers for this purpose.
- the polyurethanes used in the invention are polyisocyanates (hereinafter also called monomers I) and polyisocyanate-reactive compounds with at least one hydroxyl group and optionally compounds having at least systems constructed of a primary or secondary amino group.
- the polyurethanes generally have no more free isocyanate groups.
- polyisocyanates for the preparation of the polyurethanes (B) used according to the invention serve conventional diisocyanates and / or conventional higher functional polyisocyanates, such as they are described in the hydrophilic modified polyisocyanates (A).
- aliphatic diisocyanates and aliphatic higher functional polyisocyanates prefers.
- the other structural components of the polyurethane are first Polyols having a molecular weight of 400 to 6000 g / mol, preferably 600 to 4000 g / mol (monomers II).
- the polyester diols are, in particular, the reaction products known per se of dihydric alcohols with dibasic carboxylic acids.
- the free polycarboxylic acids may also contain the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof be used for the preparation of polyester polyols.
- the polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic or heterocyclic and, where appropriate, e.g. by halogen atoms, substituted and / or unsaturated.
- succinic acid adipic acid, suberic acid, azelaic acid, sebacic acid, Phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, Glutaric anhydride, maleic acid, maleic anhydride, Fumaric acid, dimeric fatty acids.
- polyhydric alcohols e.g.
- lactone-based polyesterdiols which are homopolymers or Copolymers of lactones, preferably terminal hydroxyl groups having addition products of lactones or lactone mixtures, e.g. ⁇ -caprolactone, ⁇ -propiolactone, ⁇ -butyrolactone and / or methyl- ⁇ -caprolactone to suitable difunctional starter molecules, e.g. the above as a structural component for the Polyesterpolyole called low molecular weight, dihydric alcohols.
- the corresponding polymers of ⁇ -caprolactone are particularly preferred. Lower ones, too Polyester diols or polyether diols can be used as starters for the preparation of the lactone polymers be used.
- the corresponding, chemically equivalent polycondensates corresponding to the lactones Hydroxycarboxylic acids are used.
- the polyether diols which can be used, if appropriate also in a mixture with polyester diols, are in particular by polymerization of starting materials of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF 3 or by addition of these compounds in admixture or successively with reactive hydrogen atoms, such as alcohols or amines, for example water, ethylene glycol, propylene glycol- (1,3) or - (1,2), 4,4'-dihydroxydiphenylpropane and aniline.
- reactive hydrogen atoms such as alcohols or amines
- the proportion of the above-described monomer II is generally 0.1 to 0.8 Gram equivalent, preferably 0.2 to 0.7 gram equivalent of the hydroxyl group of Monomers II based on 1 gram equivalent of isocyanate of the polyisocyanate.
- polyurethane are chain extenders or crosslinker having at least two isocyanate-reactive groups from hydroxyl groups, primary or secondary amino groups.
- polyols in particular diols and triols, with a molecular weight below 400 g / mol to 62 g / mol (monomers III).
- polyester polyols suitable diols and triols, and higher than trifunctional alcohols such as pentaerythritol or sorbitol.
- the proportion of the monomers III is generally 0 to 0.8, in particular 0 to 0.7 Gram equivalent based on 1 gram equivalent of isocyanate.
- the optionally used monomers IV are at least difunctional amine chain extenders or crosslinkers of the molecular weight range of 32 to 500 g / mol, preferably from 60 to 300 g / mol, which have at least two primary, two secondary or one primary and one secondary amino group.
- diamines such as diaminoethane, diaminopropane, diaminobutane, Diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (Isophoronediamine, IPDA), 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, Aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as Diethylenetriamine or 1,8-diamino-4-aminomethyloctane.
- diamines such as diaminoethane, diaminopropane, diaminobutane, Diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (Isophoronediamine,
- the amino group-containing Chain extenders may also be in blocked form, e.g. in the form of the corresponding Ketimines (see, e.g., CA-1 129 128), ketazines (see, for example, U.S. Patent 4,269,748) or U.S. Pat Amine salts (see US Pat. No. 4,292,226).
- oxazolidines like them
- US-A-4,192,937 represent capped polyamines, for the preparation of the polyurethanes of the invention for chain extension of Prepolymer can be used.
- capped Polyamines are generally used with the prepolymers in the absence of Mixed water and this mixture then with the dispersion water or a portion of the dispersion water, so that intermediately hydrolytically the corresponding polyamines are released.
- V are aminoalcohols having a hydroxyl and a primary or secondary amino group such as ethanolamine, isopropanolamine, methylethanolamine or Aminoethoxyethanol.
- the proportion of the monomers IV or V is in each case preferably 0 to 0.4, especially preferably 0 to 0.2 gram equivalent, based on 1 gram equivalent of isocyanate of Polyisocyanate.
- isocyanate-reactive groups ie Hydroxyl, primary or secondary amino groups
- the polyurethanes themselves are dispersible, i. when dispersing in Water in this case no dispersing aids such as protective colloids or Needed emulsifiers.
- the introduction of the cationic or anionic groups may be by co-use of (potential) cationic or (potential) anionic groups
- Compounds with isocyanate-reactive hydrogen atoms take place.
- groups of compounds include e.g. having tertiary nitrogen atoms
- Polyethers preferably having two terminal hydroxyl groups, e.g. by Alkoxylation of two attached to amine nitrogen hydrogen atoms
- Amines e.g. Methylamine, aniline, or N, N'-dimethylhydrazine, in a conventional manner are accessible.
- Such polyethers generally have between 500 and 6,000 g / mol lying molecular weight.
- the ionic groups by concomitant use of comparatively low molecular weight compounds with (potential) ionic groups and isocyanate-reactive groups. Examples of this are listed in US-A 3,479,310 and 4,056,564 and GB-1 455 554. Also Dihydroxyphosphonates, such as the sodium salt of 2,3-Dihydroxypropanphosphonklathylesters or the corresponding sodium salt of unesterified phosphonic acid, can be used as ionic synthesis component.
- Preferred (potential) ionic monomers VI are N-alkyl dialkanolamines, e.g. N-methyl diethanolamine, N-ethyldiethanolamine, diaminosulfonates, such as the Na salt of N- (2-aminoethyl) -2-aminoethanesulfonic acid, Dihydroxysulfonates, dihydroxycarboxylic acids such as dimethylolpropionic acid, diaminocarboxylic acids or carboxylates such as lysine or the Na salt of N- (2-aminoethyl) -2-aminoethanecarboxylic acid and diamines with at least an additional tertiary amine nitrogen atom, e.g. N-methyl-bis- (3-aminopropyl) -amine.
- N-alkyl dialkanolamines e.g. N-methyl diethanolamine, N-ethyldiethanolamine, diaminosulfonates,
- diamino- and dihydroxycarboxylic acids in particular the Adduct of ethylenediamine with sodium acrylate or dimethylolpropionic acid.
- the conversion of the optionally initially incorporated in the polyaddition product potential ionic groups occur at least partially in ionic groups in usually by neutralization of the potential anionic or cationic Groups or by quaternization of tertiary amine nitrogen atoms.
- ком ⁇ онент groups e.g. Carboxyl groups
- be inorganic and / or organic bases used such as alkali metal hydroxides, carbonates or - hydrogencarbonates, ammonia or primary, secondary and most preferably tertiary Amines such as triethylamine or dimethylaminopropanol.
- quaternizing agents e.g. Methyl chloride, methyl bromide, methyl iodide, dimethyl sulfate, benzyl chloride, Chloroacetic acid ester or bromoacetamide suitable.
- Other neutralization or Quaternizing agents are e.g. in US Pat. No. 3,479,310, column 6.
- This neutralization or quaternization of the potential ion groups may during, but preferably after the isocyanate polyaddition reaction.
- monohydric polyether alcohols of the molecular weight range 500 to 10,000 g / mol, preferably from 800 to 5,000 g / mol.
- Monohydric polyether alcohols are e.g. by Alkoxylation of monovalent starter molecules, e.g. Methanol, ethanol or n-butanol available, wherein as the alkoxylating agent ethylene oxide or mixtures of Ethylene oxide with other alkylene oxides, especially propylene oxide. in the However, when using alkylene oxide mixtures, they preferably contain these at least 40, more preferably at least 65 mole percent ethylene oxide.
- the compounds of the type mentioned are preferred, so you use them used in amounts such that from 0 to 10, preferably from 0 to 5 wt .-% polyethylene oxide units are introduced into the polyurethane.
- Suitable monomers VIII which contain ethylenically unsaturated groups in contrast to the above monomers are, for example, esters of acrylic or methacrylic acid with polyols, where at least one OH group of the polyol remains unesterified.
- Particularly suitable are the adducts of (meth) acrylic acid with bisglycidyl ethers of diol
- adducts of (meth) acrylic acid with epoxidized diolefins e.g. 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate.
- the polyurethane may be thermally or photochemically, optionally in the presence of an initiator, subsequently cured become.
- the proportion of ethylenically unsaturated groups is below 0.2 mol per 100 g of polyurethane.
- the proportion of the structural components is preferably chosen so that the Sum of the isocyanate-reactive hydroxyl groups and primary or secondary amino groups 0.9 to 1.2, particularly preferably 0.95 to 1.1, based on 1 Isocyanate group.
- an inert, water-miscible solvent such as acetone, Tetrahydrofuran, methyl ethyl ketone or N-methylpyrrolidone from the monomers I and II and optionally III, V, VI, VII and VIII, if VI contains no amino groups, the Polyurethane or, if further reaction with amino-functional monomers IV or VI is intended to be a polyurethane prepolymer with still terminal Isocyanate groups produced.
- the reaction temperature is generally between 20 and 160 ° C, preferably between 50 and 100 ° C.
- the conventional catalysts as dibutyltin dilaurate, stannous octoate or diazabicyclo (2,2,2) octane, concomitantly used become.
- the polyurethane prepolymer obtained may, optionally after (further) dilution with solvents of the abovementioned type, preferably with solvents Boiling points below 100 ° C, at a temperature between 20 and 80 ° C with amino-functional compounds of the monomers VI and optionally IV further be implemented.
- the organic solvent After dispersion, the organic solvent, if its boiling point below the water is distilled off. If necessary, also used solvents with a higher boiling point can remain in the dispersion.
- the content of the polyurethane in the dispersions may in particular be between 5 and 70 Percent by weight, preferably between 20 and 50% by weight, based on the dispersions, lie.
- the dispersions may contain conventional adjuvants, e.g. Thickener, thixotropic agent, oxidation and UV stabilizers or release agents.
- adjuvants e.g. Thickener, thixotropic agent, oxidation and UV stabilizers or release agents.
- Hydrophobic aids which may be difficult to homogenize in the finished Dispersion can also be distributed according to that described in US-A 4,306,998 Method added to the polyurethane or prepolymer before the dispersion become.
- the invention relates to the use of hydrophilic modified polyisocyanates (A) and of polyurethanes (B) in anti-wrinkle finish equipment of cellulose-containing textiles.
- Finishing agents are any liquid formulations, the hydrophilic modified polyisocyanates (A) and / or the polyurethanes (B) for application to the textile material in dissolved or dispersed form.
- finishing agents can be used as finishing agents in the strict sense the production of textiles in the form of an aqueous wash liquor or as a liquid Textile treatment agent are present.
- solvents e.g. Water, alcohols such as methanol, ethanol and propanol, THF or mixtures thereof.
- the textiles containing the finishing agent to treat are not yet or only inadequate with finishing agents can be treated, for example, in the home area before or after washing, for example ironing, with a textile treatment agent, which contains the hydrophilic modified polyisocyanates and / or the polyurethanes treated become.
- a textile treatment agent which contains the hydrophilic modified polyisocyanates and / or the polyurethanes treated become.
- the textiles in the main wash or after the main wash in the care or fabric conditioning cycle of the washing machine hydrophilic modified polyisocyanates (A) and / or to treat the polyurethanes (B).
- the present invention also relates to the use of the hydrophilic modified polyisocyanates (A) and / or polyurethanes (B) in the preparation of Textiles, in the treatment of textiles before and after washing, in the textile washing main wash, in the textile laundry rinse cycle and ironing. Needed for this one each different formulations.
- a textile treatment agent as Finishing agents are used, which except the hydrophilic modified Polyisocyanates (A) and / or polyurethanes (B) in dissolved or dispersed form containing surfactant.
- the cellulosic Textiles for example, with the hydrophilic modified polyisocyanates (A) and / or sprayed the polyurethanes (B), wherein the application amount is generally 0.01 to 10 Wt.%, Preferably 0.1 to 7, particularly preferably 0.3 to 4 wt.%, Based on the Weight of the dry textile, can amount.
- the finishing agent can as well be applied to the fabric by dipping the textiles in a bath, which is generally from 0.1 to 10% by weight, preferably from 0.3 to 5% by weight, based on the Weight of the dry textile product, the hydrophilically modified polyisocyanates (A) and / or the polyurethane (B) dissolved or dispersed.
- the textile will either only for a short time immersed in the bath or can it in it for a period of for example, linger for 1 to 30 minutes.
- the cellulosic textiles containing the finishing agent either by spraying or have been treated by dipping, optionally be pressed and dried. Drying can be done in air or in a dryer or by hot ironing the treated textile material. By drying the finishing agent is fixed on the fabric. The cheapest for each Conditions can easily be determined by means of experiments.
- the temperature during drying, including ironing, is generally 40 to 150 ° C, preferably 60 to 110 ° C. For ironing is particularly the Cotton program of iron.
- the textiles described after the above Process with the hydrophilically modified polyisocyanates (A) or polyurethanes (B) in dissolved or dispersed form have an excellent Crease and wrinkle protection, which persists over several washes. Ironing the Textiles are often no longer required.
- the treated textiles have additionally a fiber and color protection.
- Preferred silicones are amino-containing silicones, preferably in microemulsified Form, alkoxylated, especially ethoxylated silicones, polyalkylene oxide polysiloxanes, Polyalkylene oxide aminopolydimethylsiloxanes, silicones with quaternary ammonium groups (silicon quats) and silicone surfactants.
- Suitable plasticizers or lubricants are, for example, oxidized polyethylenes or paraffin-containing Waxes and oils.
- Suitable water-soluble, film-forming and adhesive polymers are for example, (co) polymers based on acrylamide, N-vinylpyrrolidone, vinylformamide, N-vinylimidazole, vinylamine, N, N'-dialkylaminoalkyl (meth) acrylates, N, N'-dialkylaminoalkyl (meth) acrylamides, (Meth) acrylic acid, (meth) acrylic acid alkyl ester and / or vinyl sulfonate.
- the above basic monomers can also be used in quaternized form.
- the formulation may additionally contain a spray aid.
- a spray aid such as ethanol, isopropanol, ethylene glycol or propylene glycol.
- further customary additives are fragrances and dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, corrosion protection additives, bactericides and preservatives in the amounts customary for this purpose.
- the textile treatment agent can also be applied during ironing of the textile product after washing, generally by spraying. The ironing is thus not only considerably easier, the textiles are also equipped with a long-lasting crease and wrinkle protection.
- the use of the hydrophilically modified polyisocyanates (A) and / or polyurethanes (B) can also take place during the washing of the textiles in the main wash cycle of the washing machine.
- the anionic surfactants mentioned are preferably added to the detergent in the form of Salt added.
- Suitable cations in these salts are alkali metal ions such as Sodium, potassium and lithium and ammonium ions such as hydroxyethylammonium, Di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium.
- nonionic and anionic surfactants builders and Cobuilder be used.
- the concentration of the hydrophilically modified polyisocyanates or polyurethanes in the wash liquor is for example 10 to 5000 ppm and is preferably in the range of 50 to 1000 ppm.
- the with the hydrophilic modified Poylisocyantaten or polyurethanes in the main wash of the washing machine treated textiles not only do not wrinkle significantly less than untreated textiles. They are also easier too iron, softer and smoother, dimensional and dimensionally stable and look after repeated Wash less "used” due to their fiber and color protection less lint and knots and less color damage or fading on.
- hydrophilic modified polyisocyanates or polyurethanes can in so-called soft or Vietnamese Pattersongang done after the main wash.
- the Concentration of the hydrophilically modified polyisocyanates or polyurethanes in the Wash liquor is for example 10 to 5000 ppm and is preferably in the range from 50 to 1000 ppm.
- typical ingredients may possibly be present in the rinsing liquor.
- Even those treated in this way Textiles have after drying on a leash or preferably in a tumble dryer a very good crease protection, with the positive effects already described above connected to the ironing.
- the crease protection can by a one-time Short ironing of the textiles after drying can be significantly enhanced.
- the Treatment in the soft or Vietnamese Hughes Congressgang additionally has a favorable effect on the dimensional stability of textiles. Furthermore, the formation of knots and lint is inhibited and color damage suppressed.
- Preferred cationic surfactants are selected from the group of the quaternary diester ammonium salts, the tetraalkyl quaternary ammonium salts, the diamido ammonium quaternary salts, the amidoamine esters and imidazolium salts.
- Examples are diester ammonium quaternary salts which have two C 11 - to C 22 -alk (en) ylcarbonyloxy (mono- to pentamethylene) radicals and two C 1 - to C 3 -alkyl or -hydroxyalkyl radicals on the quaternary nitrogen atom and as counterion
- chloride, bromide, methyl sulfate or sulfate wear for example, chloride, bromide, methyl sulfate or sulfate wear.
- Quaternary diester ammonium salts are furthermore especially those which carry a C 11 -C 22 -alk (y) ylcarbonyloxytrimethylene radical which carries a C 11 -C 22 -alk (en) ylcarbonyloxy radical at the middle C atom of the trimethylene grouping , and three C 1 - to C 3 alkyl or hydroxyalkyl radicals on the quaternary nitrogen atom and carry as counterion, for example, chloride, bromide, methyl sulfate or sulfate.
- Quaternary tetraalkylammonium salts are in particular those which have two C 1 - to C 6 -alkyl radicals and two C 8 - to C 24 -alk (en) yl radicals on the quaternary nitrogen atom and, as counterion, for example, chloride, bromide, methylsulfate or Wear sulfate.
- Quaternary diamidoammonium salts are in particular those which contain two C 8 - to C 24 -alk (en) ylcarbonylaminoethylene radicals, a substituent selected from hydrogen, methyl, ethyl and polyoxyethylene with up to 5 oxyethylene units and as fourth radical a methyl group on the quaternary N -Atom and carry as counterion, for example, chloride, bromide, methyl sulfate or sulfate.
- Amidoaminoester are in particular tertiary amines having as substituents on the nitrogen atom, a C 11 - to C 22 -alk (en) ylcarbonylamino (mono- to trimethylene) radical, a C 11 - to C 22 -alk (en) ylcarbonyloxy (mono - to trimethylene) radical and carry a methyl group.
- Imidazolinium salts are, in particular, those which, in the 2-position of the heterocycle, are a C 14 - to C 18 -alk (en) yl radical, at the neutral N-atom a C 14 - to C 18 -alk (en) ylcarbonyl (oxy or amino) ethylene radical and on the positive charge carrying N atom carry hydrogen, methyl or ethyl, counterions here are, for example, chloride, bromide, methyl sulfate or sulfate.
Description
- R8
- für C1- bis C20-Alkyl, insbesondere C1- bis C4-Alkyl, oder C2- bis C20-Alkenyl, Cyclopentyl, Cyclohexyl, Glycidyl, Oxethyl, Phenyl, Tolyl, Benzyl, Furfuryl oder Tetrahydrofurfuryl steht,
- E
- Schwefel oder insbesondere Sauerstoff bezeichnet,
- D
- Propylen oder vor allem Ethylen bedeutet, wobei auch insbesondere blockweise gemischt ethoxylierte und propoxylierte Verbindungen auftreten können, und
- n
- für eine Zahl von 5 bis 120, insbesondere 10 bis 25 steht,
- R9 und R10
- lineares oder verzweigtes C1- bis C20-Alkyl, insbesondere C1- bis C5-Alkyl, bedeuten oder zusammen mit dem N-Atom einen fünf- oder sechsgliedrigen Ring bilden, der noch ein O-Atom oder ein tertiäres N-Atom enthalten kann, insbesondere einen Piperidin-, Morpholin-, Piperazin-, Pyrrolidin-, Oxazolin- oder Dihydrooxazin-Ring, wobei die Reste R9 und R10 noch zusätzlich Hydroxylgruppen, insbesondere jeweils eine Hydroxylgruppe, tragen können, und
- R11
- eine C2- bis C10-Alkylengruppe, insbesondere eine C2- bis C6-Alkylengruppe, die linear oder verzweigt sein kann, bezeichnet,
Das Texilbehandlungsmittel kann auch beim Bügeln des Textilguts nach der Wäsche, im allgemeinen durch Sprühen, appliziert werden. Das Bügeln wird dadurch nicht nur erheblich erleichtert, die Textilien werden zusätzlich mit einem langanhaltenden Knitter- und Faltenschutz ausgestattet.
Der Einsatz der hydrophil modifizierten Polyisocyanate (A) und/oder Polyurethane (B) kann auch beim Waschen der Textilien im Hauptwaschgang der Waschmaschine erfolgen.
- (Fett)alkoholsulfate von (Fett)alkoholen mit 8 bis 22, vorzugsweise 10 bis 18 Kohlenstoffatomen, z.B. C9- bis C11-Alkoholsulfate, C12- bis C14-Alkoholsulfate, C12-C18-Alkoholsulfate, Laurylsulfat, Cetylsulfat, Myristylsulfat, Palmitylsulfat, Stearylsulfat und Talgfettalkoholsulfat;
- sulfatierte alkoxylierte C8- bis C22-Alkohole (Alkylethersulfate). Verbindungen dieser Art werden beispielsweise dadurch hergestellt, dass man zunächst einen C8- bis C22-, vorzugsweise einen C10- bis C18-Alkohol, z.B. einen Fettalkohol, alkoxyliert und das Alkoxylierungsprodukt anschließend sulfatiert. Für die Alkoxylierung verwendet man vorzugsweise Ethylenoxid;
- lineare C8- bis C20-Alkylbenzosulfonate (LAS), vorzugsweise lineare C9- bis C13-Alkylbenzolsulfonate und-Alkyltoluolsulfonate,
- Alkansulfonate wie C8- bis C24-, vorzugsweise C10- bis C18-Alkansulfonate
- Seifen wie beispielsweise die Na- und K-Salze von C8- bis C24-Carbonsäuren.
- alkoxylierte C8- bis C22-Alkohole wie Fettalkoholalkoxylate oder Oxoalkoholalkoxylate. Diese können mit Ethylenoxid, Propylenoxid und/oder Butylenoxid alkoxyliert sein. Als Tenside einsetzbar sind hierbei sämtliche alkoxylierten Alkohole, die mindestens zwei Moleküle eines der vorstehend genannten Alkylenoxide addiert enthalten. Hierbei kommen Blockpolymerisate von Ethylenoxid, Propylenoxid und/oder Butylenoxid in Betracht oder Anlagerungsprodukte, die die genannten Alkylenoxide in statistischer Verteilung enthalten. Die nichtionischen Tenside enthalten pro Mol Alkohol im allgemeinen 2 bis 50, vorzugsweise 3 bis 20 Mol mindestens eines Alkylenoxids. Vorzugsweise enthalten diese als Alkylenoxid Ethylenoxid. Die Alkohole haben vorzugsweise 10 bis 18 Kohlenstoffatome. Je nach Art des bei der Herstellung verwendeten Alkoxylierungskatalysators weisen die Alkoxylate eine breite oder enge Alkylenoxid-Homologenverteilung auf;
- Alkylphenolalkoxylate wie Alkylphenolethoxylate mit C6- bis C14-Alkylketten und 5 bis 30 Alkylenoxideinheiten;
- Alkylpolyglucoside mit 8 bis 22, vorzugsweise 10 bis 18 Kohlenstoffatomen in der Alkylkette und im allgemeinen 1 bis 20, vorzugsweise 1,1 bis 5 Glucosideinheiten;
- N-Alkylglucamide, Fettsäureamidalkoxylate, Fettsäurealkanolamidalkoxylate sowie Blockcopolymere aus Ethylenoxid, Propylenoxid und/oder Butylenoxid.
- kristalline oder amorphe Alumosilicate mit ionenaustauschenden Eigenschaften wie insbesondere Zeolithe. Als Zeolithen geeignet sind insbesondere Zeolithe A, X, B, P, MAP und HS in ihrer Na-Form oder in Formen, in denen Na teilweise gegen andere Kationen wie Li, K, Ca, Mg, oder Ammonium ausgetauscht ist;
- kristalline Silicate wie insbesondere Disilicate oder Schichtsilicate, z.B. δ-Na2Si2O5 oder β-Na2Si2O5. Die Silicate können in Form ihrer Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze eingesetzt werden, vorzugsweise als Na-, Li- und Mg-Silicate;
- amorphe Silicate wie beispielsweise Natriummetasilicat oder amorphes Disilicat;
- Carbonate und Hydrogencarbonate. Diese können in Form ihrer Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze eingesetzt werden. Bevorzugt sind Na-,Li- und Mg-Carbonate bzw. -Hydrogencarbonate, insbesondere Natriumcarbonat und/oder Natriumhydrogencarbonat;
- Polyphosphate wie z.B. Pentanatriumtriphosphat;
- Geeignete niedermolekulare Carbonsäuren sind beispielsweise Citronensäure, hydrophob modifizierte Citronensäure wie z. B. Agaricinsäure, Äpfelsäure, Weinsäure, Gluconsäure, Glutarsäure, Bernsteinsäure, Imidodibernsteinsäure, Oxydibernsteinsäure, Propantricarbonsäure, Butantetracarbonsäure, Cyclopentantetracarbonsäure, Alkyl- und Alkenylbemsteinsäuren und Aminopolycarbonsäuren wie z.B. Nitrilotriessigsäure, β-Alanindiessigsäure, Ethylendiamintetraessigsäure, Serindiessigsäure, Isoserindiessigsäure, N-(2-Hydroxyethyl)iminodiessigsäure, Ethylendiamindibernsteinsäure und Methyl- und Ethylglycindiessigsäure;
- Geeignete oligomere oder polymere Carbonsäuren sind beispielsweise Homopolymere der Acrylsäure, Oligomaleinsäuren, Copolymere der Maleinsäure mit Acrylsäure, Methacrylsäure, C2-C22-Olefine wie z.B. Isobuten oder langkettige α-Olefine, Vinylalkylether mit C1-C8-Alkylgruppen, Vinylacetat, Vinylpropionat, (Meth)acrylester von C1-C8-Alkoholen und Styrol. Bevorzugt verwendet man die Homopolymeren der Acrylsäure sowie Copolymere von Acrylsäure mit Maleinsäure. Weiterhin eignen sich Polyasparaginsäuren als organische Cobuilder. Die oligomeren und polymeren Carbonsäuren werden in Säureform oder als Natriumsalz eingesetzt.
Claims (5)
- Verwendung von hydrophil modifizierten Polyisocyanaten (A) und von Polyurethanen (B) als Antiknitteradditiv in Textilbehandlungsmutteln für den Heimbereich, in festen und flüssigen Waschmittelformulierungen und Wäschepflegespülmitteln.
- Verwendung nach Anspruch 1, dadurch gekennzeichnet, dass das Textilbehandlungsmittel enthält:a) 0,1 bis 40 Gew.-% mindestens eines hydrophil modifizierten Polyisocyanats (A) und/oder mindestens eines Polyurethans (B),b) 0 bis 30 Gew.-% Silicone,c) 0 bis 30 Gew.-% kationische und/oder nichtionische Tenside,d) 0 bis 60 Gew.-% weitere Inhaltsstoffe wie weitere Netzmittel, Weichmacher, Gleitmittel, wasserlösliche, filmbildende und adhesive Polymere, Duft- und Farbstoffe, Stabilisatoren, Faser- und Farbschutzadditive, Viskositätsmodifizieter, Soil-Release-Additive, Korrosionsschutzadditive, Bakterizide, Konservierungsmittel und Sprühhilfsmittel, unde) 0 bis 99,9 Gew.-% Wasser,
- Verwendung nach Anspruch 1, dadurch gekennzeichnet, dass die feste Waschmittelformulierung enthält:a) 0,05 bis 20 Gew.% mindestens eines hydrophil modifizierten Polyisocyanats (A) und/oder mindestens eines Polyurethans (B),b) 0,1 bis 40 Gew.% mindestens eines nichtionischen und/oder anionischen Tensids,c) 0 bis 50 Gew.% eines anorganischen Builders,d) 0 bis 10 Gew.% eines organischen Cobuilders,e) 0 bis 60 Gew.% anderer üblicher Inhaltsstoffe wie Stellmittel, Enzyme, Parfum, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, kationische Tenside, Farbübertragungsinhibitoren, Vergrauungsinhibitoren, Soil-Release-Polyester, Farbstoffe, Bakterizide, Auflösungsverbesserer und/oder Sprengmittel,
- Verwendung nach Anspruch 1, dadurch gekennzeichnet, dass die flüssige Waschmittelformulierung enthält:a) 0,05 bis 20 Gew.% mindestens eines hydrophil modifizierten Polyisocyanats (A) und/oder mindestens eines Polyurethans (B),b) 0,1 bis 40 Gew.% mindestens eines nichtionischen und/oder anionischen Tensids,c) 0 bis 20 Gew.% eines anorganischen Builders,d) 0 bis 10 Gew.% eines organischen Cobuilders,e) 0 bis 60 Gew.% anderer üblicher Inhaltsstoffe wie Soda, Enzyme, Parfum, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, kationische Tenside, Farbübertragungsinhibitoren, Vergrauungsinhibitoren, Soil-Release-Polyester, Farbstoffe, Bakterizide, nicht wässrige Lösemittel, Löslichkeitsvermittler, Hydrotrope, Verdicker und/oder Alkanolamine.f) 0 bis 99,85 Gew.% Wasser,
- Verwendung nach Anspruch 1, dadurch gekennzeichnet, dass das WäschepflegeSpülmittel enthält:a) 0,05 % bis 40 Gew.% mindestens eines hydrophil modifizierten Polyisocyanats (A) und/oder mindestens eines Polyurethans (B),b) 0,1 bis 50 Gew.% mindestens eines kationischen Tensids,c) 0 bis 25 Gew. % eines nichtionischen Tensids,d) 0 bis 30 Gew.-% andere übliche Inhaltsstoffe wie Silicone, andere Gleitmittel, Benetzungsmittel, filmbildende Polymere, Duft- und Farbstoffe, Stabilisatoren, Faser- und Farbschutzadditive, Viskositätsmodifizierer, Soil-Release-Additive, Korrosionsschutzadditive, Bakterizide und Konservierungsmittel, unde) 0 bis 99,85 Gew.-% Wasser,
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE10056163 | 2000-11-13 | ||
DE10056163A DE10056163A1 (de) | 2000-11-13 | 2000-11-13 | Hydrophil modifizierte Polyisocyanate und Polyurethane zur Antiknitterausrüstung von cellulosehaltigen Textilien |
PCT/EP2001/013033 WO2002038852A1 (de) | 2000-11-13 | 2001-11-09 | Hydrophil modifizierte polyisocyanate und polyurethane zur antiknitterausrüstung von cellulosehaltigen textilien |
Publications (2)
Publication Number | Publication Date |
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EP1379724A1 EP1379724A1 (de) | 2004-01-14 |
EP1379724B1 true EP1379724B1 (de) | 2005-06-22 |
Family
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EP01993721A Expired - Lifetime EP1379724B1 (de) | 2000-11-13 | 2001-11-09 | Verwendung von hydrophil modifizierten polyisocyanaten und polyurethanen als antiknitteradditiv für den heimbereich |
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Country | Link |
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US (1) | US20040010858A1 (de) |
EP (1) | EP1379724B1 (de) |
JP (1) | JP2004513261A (de) |
CN (1) | CN1474891A (de) |
AT (1) | ATE298379T1 (de) |
AU (1) | AU2002217018A1 (de) |
BR (1) | BR0115302A (de) |
CA (1) | CA2426058A1 (de) |
DE (2) | DE10056163A1 (de) |
ES (1) | ES2241899T3 (de) |
MX (1) | MXPA03003147A (de) |
WO (1) | WO2002038852A1 (de) |
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DE10226932A1 (de) * | 2002-06-17 | 2003-12-24 | Bayer Ag | Strahlenhärtende Beschichtungsmittel |
DE10246836A1 (de) * | 2002-10-08 | 2004-04-22 | Saxol Chemie Gmbh | Wasserfreie oder wasserhaltige Zusammensetzung zur Behandlung eines hydrophilen Papierprodukts |
US20060234903A1 (en) * | 2004-10-08 | 2006-10-19 | Short Dan C | Ionized performance fabric |
US10080481B2 (en) | 2005-02-10 | 2018-09-25 | G.I. View Ltd. | Advancement techniques for gastrointestinal tool with guiding element |
CN100402737C (zh) * | 2005-07-18 | 2008-07-16 | 江苏阳光集团有限公司 | 含羊毛的免烫定型易护理西裤的生产方法 |
EP2013325B1 (de) * | 2006-04-04 | 2012-06-13 | Basf Se | Mit polymeren schichtförmig umhüllte bleichsysteme |
MX2010010236A (es) | 2008-03-28 | 2010-10-20 | Ecolab Inc | Acidos sulfoperoxicarboxilicos, su preparacion y metodos de uso como agentes blanqueadores y antimicrobianos. |
US8871807B2 (en) | 2008-03-28 | 2014-10-28 | Ecolab Usa Inc. | Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids |
US8809392B2 (en) | 2008-03-28 | 2014-08-19 | Ecolab Usa Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
US9321664B2 (en) | 2011-12-20 | 2016-04-26 | Ecolab Usa Inc. | Stable percarboxylic acid compositions and uses thereof |
CN106396037B (zh) | 2012-03-30 | 2019-10-15 | 艺康美国股份有限公司 | 过乙酸/过氧化氢和过氧化物还原剂用于处理钻井液、压裂液、回流水和排放水的用途 |
US8822719B1 (en) | 2013-03-05 | 2014-09-02 | Ecolab Usa Inc. | Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring |
US10165774B2 (en) | 2013-03-05 | 2019-01-01 | Ecolab Usa Inc. | Defoamer useful in a peracid composition with anionic surfactants |
US20140256811A1 (en) | 2013-03-05 | 2014-09-11 | Ecolab Usa Inc. | Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids |
CN104452149A (zh) * | 2013-09-13 | 2015-03-25 | 上海鼎天纺织品有限公司 | 一种提花面料纤维的两步法整理工艺 |
WO2016048684A1 (en) * | 2014-09-26 | 2016-03-31 | The Chemours Company Fc, Llc | Method of imparting water repellency with non-fluorinated laundry treatment compositions |
CN104389161B (zh) * | 2014-11-04 | 2016-06-22 | 苏州经贸职业技术学院 | 一种抗皱真丝复合面料的制备方法 |
CN105296187B (zh) * | 2015-11-02 | 2018-01-19 | 浙江芬尼奇工贸有限公司 | 一种基于支链脂肪醇含硅聚氨酯磺酸型表面活性剂的洗衣液及其制备方法 |
AU2017385962B2 (en) * | 2016-12-30 | 2021-09-02 | Olipass Corporation | Exon skipping by peptide nucleic acid derivatives |
CN109750498A (zh) * | 2017-11-02 | 2019-05-14 | 丹阳八紫光能有限公司 | 一种带有芳香气味的沙发布料 |
KR20200142772A (ko) * | 2019-06-13 | 2020-12-23 | 폴프랜즈 주식회사 | 영유아용 신축성 양말의 제조방법 및 그 방법에 의해 제조된 양말 |
CN112391841B (zh) * | 2020-11-16 | 2023-05-09 | 宁波丹盈服饰有限公司 | 一种抗皱面料的制作方法 |
CN112500939B (zh) * | 2020-12-08 | 2022-01-04 | 福建植嘉生物科技有限公司 | 一种柔顺二合一洗衣液及其制备方法 |
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-
2000
- 2000-11-13 DE DE10056163A patent/DE10056163A1/de not_active Withdrawn
-
2001
- 2001-11-09 CA CA002426058A patent/CA2426058A1/en not_active Abandoned
- 2001-11-09 CN CNA018187218A patent/CN1474891A/zh active Pending
- 2001-11-09 US US10/416,336 patent/US20040010858A1/en not_active Abandoned
- 2001-11-09 EP EP01993721A patent/EP1379724B1/de not_active Expired - Lifetime
- 2001-11-09 BR BR0115302-1A patent/BR0115302A/pt not_active Application Discontinuation
- 2001-11-09 AU AU2002217018A patent/AU2002217018A1/en not_active Abandoned
- 2001-11-09 JP JP2002541162A patent/JP2004513261A/ja not_active Withdrawn
- 2001-11-09 AT AT01993721T patent/ATE298379T1/de not_active IP Right Cessation
- 2001-11-09 DE DE50106600T patent/DE50106600D1/de not_active Expired - Lifetime
- 2001-11-09 MX MXPA03003147A patent/MXPA03003147A/es active IP Right Grant
- 2001-11-09 ES ES01993721T patent/ES2241899T3/es not_active Expired - Lifetime
- 2001-11-09 WO PCT/EP2001/013033 patent/WO2002038852A1/de active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
BR0115302A (pt) | 2004-02-10 |
AU2002217018A1 (en) | 2002-05-21 |
WO2002038852A1 (de) | 2002-05-16 |
DE50106600D1 (de) | 2005-07-28 |
ES2241899T3 (es) | 2005-11-01 |
CA2426058A1 (en) | 2003-04-15 |
MXPA03003147A (es) | 2003-08-19 |
ATE298379T1 (de) | 2005-07-15 |
CN1474891A (zh) | 2004-02-11 |
US20040010858A1 (en) | 2004-01-22 |
EP1379724A1 (de) | 2004-01-14 |
DE10056163A1 (de) | 2002-05-23 |
JP2004513261A (ja) | 2004-04-30 |
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