EP3218542A1 - Making fabrics easier to iron - Google Patents
Making fabrics easier to ironInfo
- Publication number
- EP3218542A1 EP3218542A1 EP15790877.3A EP15790877A EP3218542A1 EP 3218542 A1 EP3218542 A1 EP 3218542A1 EP 15790877 A EP15790877 A EP 15790877A EP 3218542 A1 EP3218542 A1 EP 3218542A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- weight
- polymer
- carboxylic acid
- substituents
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 14
- 229910052742 iron Inorganic materials 0.000 title claims description 7
- 239000004744 fabric Substances 0.000 title description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 76
- 239000004753 textile Substances 0.000 claims abstract description 46
- 125000003277 amino group Chemical group 0.000 claims abstract description 24
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 52
- 125000001424 substituent group Chemical group 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 22
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 238000010409 ironing Methods 0.000 claims description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000037303 wrinkles Effects 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 abstract description 15
- -1 1,2-propylene groups Chemical group 0.000 description 69
- 239000003795 chemical substances by application Substances 0.000 description 39
- 125000004432 carbon atom Chemical group C* 0.000 description 35
- 239000002253 acid Substances 0.000 description 27
- 150000007513 acids Chemical class 0.000 description 17
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- 239000000178 monomer Substances 0.000 description 17
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- 125000000217 alkyl group Chemical group 0.000 description 14
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- 229920001577 copolymer Polymers 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000000344 soap Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 9
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- 150000001298 alcohols Chemical class 0.000 description 8
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- 238000006243 chemical reaction Methods 0.000 description 8
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- 239000004367 Lipase Substances 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
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- 229940088598 enzyme Drugs 0.000 description 7
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 6
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- 239000004416 thermosoftening plastic Substances 0.000 description 6
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 5
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 5
- 239000013543 active substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
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- 229920000728 polyester Polymers 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 229920003043 Cellulose fiber Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 150000002338 glycosides Chemical class 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
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- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 3
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
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- 108010010803 Gelatin Proteins 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
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- DPUOLQHDNGRHBS-MDZDMXLPSA-N trans-Brassidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-MDZDMXLPSA-N 0.000 description 1
- AQWHMKSIVLSRNY-UHFFFAOYSA-N trans-Octadec-5-ensaeure Natural products CCCCCCCCCCCCC=CCCCC(O)=O AQWHMKSIVLSRNY-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- MXODCLTZTIFYDV-JHZYRPMRSA-L zinc;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Zn+2].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O.C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O MXODCLTZTIFYDV-JHZYRPMRSA-L 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
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
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
-
- 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
- C11D3/3723—Polyamines or polyalkyleneimines
-
- 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
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
- C11D3/3742—Nitrogen containing silicones
-
- 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
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
-
- 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
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
-
- 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
- D06M15/61—Polyamines polyimines
-
- 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
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/06—Processes in which the treating agent is dispersed in a gas, e.g. aerosols
-
- 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
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
-
- C11D2111/12—
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- 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
-
- 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
- D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
- D10B2201/01—Natural vegetable fibres
- D10B2201/02—Cotton
Definitions
- the present invention relates to the use of amino group-containing polymers having substituents carrying carboxylic acid groups for reducing crease tendency and facilitating the ironing of textiles made of cellulosic material, as well as a household practicable process for ironing and / or wrinkle reducing finishing of textiles made of cellulose-containing material.
- Textiles made of cellulose such as cotton or cellulose regenerated fibers (for example Modal or Lyocel) have from the consumer's point of view positive properties in terms of wearing comfort.
- cellulose regenerated fibers for example Modal or Lyocel
- a major disadvantage of these textiles is the slight creasing during wear, after washing and drying. This tendency to wrinkle is due to the swelling of the cellulose fibers and their low elastic restoring forces ("bounce") after deformation.
- Formaldehyde-free crosslinking processes for cellulose are also known, for example from US 2004/0043915 A1 a crosslinking process which is carried out with the aid of hydroxyl-bearing polymer and polycarboxylic acids, in particular butanetetracarboxylic acid (BTCA). From the article by CMWelch in Textile Research Journal, 1988, 480-486 the use of tetracarboxylic acids for crosslinking cellulose fibers is known. These formaldehyde-free approaches of cellulose crosslinking with the aid of polycarboxylic acids could be suitable from a toxicological point of view for a home application in principle.
- BTCA butanetetracarboxylic acid
- ion pair bonds are exploited for the crosslinking of the cellulose.
- Cotton usually has a content of carboxyl groups of about 10 ⁇ 6 mol / g.
- the cellulose can be treated with chloro or bromoacetic acid to increase the number of its carboxyl groups.
- Interaction of the carboxylated cellulose with polycations, such as cationized chitosan, can result in ionic crosslinks that reduce the tendency to crease. Without the carboxylation, the effect is too small and carboxylation of cotton fabrics with haloacetic acids is not considered for home use.
- the invention therefore relates to the use of an amino group-containing polymer having substituents carrying carboxylic acid groups for reducing the tendency of creases of textiles made of cellulose-containing material.
- Another object of the invention is the use of an amino-containing polymer having carboxylic acid group-bearing substituents to facilitate Bügeins of textiles made of cellulosic material.
- Further objects of the invention are methods which can be carried out in the household for ironing-facilitating and / or wrinkle-reducing finishing of textiles made of cellulosic material by contacting the textile with an amino group-containing polymer having substituents carrying carboxylic acid groups.
- the cellulosic materials from which the textiles to be treated are made include cotton, regenerated cellulosic fibers such as Modal or Lyocel, and blended fabrics of cotton or cellulose regenerated fibers with other apparel-based materials such as polyester and polyamide.
- the textile is ironed following treatment with said polymer with a standard household iron.
- the measures of the invention significantly reduce the creasing tendency of textiles made of cellulosic material compared to the untreated starting textiles or exclusive treatment with a noncarboxylic acid-substituted amino-containing polymer.
- a noncarboxylic acid-substituted amino-containing polymer it is conceivable that the reaction of carboxyl groups of the polymer with hydroxyl groups of the cotton leads to covalent bonds (ester bonds).
- the amino groups of the polymer may possibly interact electrostatically with carboxyl groups of the cotton (ionic crosslinking). Both covalent and ionic crosslinks could lead to an increased bounce of the textile and thus to crease reduction.
- KEW crease recovery angle
- the polymer used in the context of the invention has, in addition to the multiple amino groups and the carboxyl groups, no further nucleophilic units, such as, for example, hydroxyl groups.
- Polymers preferred according to the invention are selected from aminopolysiloxanes, polyvinylamines and polyalkyleneimines, such as polyethyleneimines, and mixtures thereof, which carry substituents with carboxyl groups on the nitrogen atom of the amino function.
- the polymers which can be used according to the invention are obtainable by reacting aminopolysilxanes, polyvinylamines or polyalkyleneimines with haloalkanoic acids, for example bromoacetic acid.
- haloalkanoic acids for example bromoacetic acid.
- preferably only molar amounts of haloalkanoic acid based on amino group-containing polymer are used so that substituents carrying carboxyl groups are not introduced into all the nitrogen atoms of the amino groups of the polymer.
- Polyvinylamines are prepared by polymer-analogous reactions, such as by hydrolysis of poly-N-vinylamides, such as poly-N-vinylformamide or poly-N-vinylacetamide, or poly-N-vinylimides, such as poly-N-vinylsuccinimide, produced by the polymerization the corresponding monomers are readily available, or prepared by Hofmann degradation of polyacrylamide.
- poly-N-vinylamides such as poly-N-vinylformamide or poly-N-vinylacetamide
- poly-N-vinylimides such as poly-N-vinylsuccinimide
- Polyalkyleneimines are polymers having an N-atom-containing backbone connected by alkylene groups, which may carry alkyl groups on the non-N atoms.
- the polyalkyleneimine preferably has primary amino functions at the ends and preferably both secondary and tertiary amino functions in the interior; if appropriate, it may also have only secondary amino functions on the inside, so that the result is not a branched-chain but a linear polymer.
- the ratio of primary to secondary amino groups in the polyalkyleneimine is preferably in the range from 1: 0.5 to 1: 1.5, in particular in the range from 1: 0.7 to 1: 1.
- the ratio of primary to tertiary amino groups in the polyalkyleneimine is preferably in the range from 1: 0.2 to 1: 1, in particular in the range from 1: 0.5 to 1: 0.8.
- the polyalkyleneimine preferably has an average molar mass in the range from 500 g / mol to 50,000 g / mol, in particular from 550 g / mol to 5000 g / mol.
- the average molecular weights given here and optionally for other polymeric ingredients are weight-average molar masses M w , which can in principle be determined by means of gel permeation chromatography with the aid of a RI detector, the measurement being expediently carried out against an external standard.
- the N atoms in the polyalkyleneimine are preferably separated from one another by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, where not all alkylene groups must have the same C atom number. Particular preference is given to ethylene groups, 1,2-propylene groups, 1,3-propylene groups, and mixtures thereof. If desired, some of the amino functions in the polyalkyleneimine may carry 1 or 2 alkyl groups, the alkyl groups preferably being propyl and / or ethyl groups.
- Aminopolysiloxanes preferred in the context of the present invention have the general formula
- R is straight-chain or branched or cyclic C 1 -C 6 -hydrocarbon radicals
- R 2 is R or one of the groups -R 3 -NHR 4 or -R 3 -NR 4 -R 3 -NHR 4 in which
- R 3 is a straight-chain or branched or cyclic divalent O to Cis hydrocarbon radical and
- R 4 is a hydrogen atom, an O to Cio-alkyl radical
- n is from 10 to 2000, wherein not all radicals R, not all radicals R 2 , not all radicals R 3 and not all radicals R 4 in the compound must be the same, with the proviso that at least 2 of the radicals R 2 are not R and in at least 1, preferably in at least 2 of the non R radicals R 2, the radical R 4 is a group -R 5 -COOX in which R 5 is a divalent hydrocarbon radical having 1 to 30 carbon atoms, in particular 2 to 20 carbon atoms, and X is hydrogen, an alkali metal or a Is ammonium group.
- C 1 -C 8 -hydrocarbon radicals R are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, tert-pentyl, n-hexyl , n-heptyl, n-octyl, trimethylpentyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, cycloalkyl, especially cyclopentyl or cyclohexyl, methylcyclohexyl, aryl, especially phenyl or naphthyl, alkaryl , in particular o-, m- or p-toluyl, xylyl or ethylphenyl; Aralkyl radicals, in particular benzyl, benz
- alkenyl radicals such as vinyl, allyl, 5-hexenyl, E-4-hexenyl, Z-4-hexen-1-yl, 2- (3-cyclohexenyl) -ethyl and cyclododeca-4,8-dienyl.
- Preferred radicals having aliphatic double bond are vinyl, allyl, and the 5-hexenyl radical.
- O to Oo-alkyl radicals R 4 are the examples listed above for R for linear and cyclic alkyl radicals having at most 10 C atoms.
- divalent Ci to Ci8 hydrocarbon radicals R 3 are saturated straight or branched chain or cyclic alkylene radicals such as the methylene and ethylene radical and propylene, butylene, pentylene, hexylene, 2-methylpropylene, cyclohexylene and Octadecylenreste or unsaturated alkylene or arylene radicals such as the hexenylene radical and phenylene radical, the n-propylene radical and the 2-methylpropylene radical being particularly preferred.
- Preferred examples of the divalent hydrocarbon radicals R 5 are the examples listed above at R, wherein the ethylene group is particularly preferred.
- the textile is made of cellulosic material at temperatures in the range of 10 ° C to 100 ° C, in particular from 20 ° C to 60 ° C, brought into contact with said amino group-containing polymer having substituents carrying carboxylic acid groups.
- the textile of cellulose-containing material is preferably brought into contact with the amino group-containing polymer having substituents carrying carboxylic acid groups over a period of from 10 minutes to 180 minutes, in particular from 30 minutes to 60 minutes.
- the observance of at least one of these conditions presumably leads - without wishing to be bound by this theory - to a chemical reaction of the cellulose with the amino group-containing polymer having substituents carrying carboxylic acid groups to such an extent that a particularly high reduction of the crease tendency is observed.
- the implementation of the invention can be carried out, for example, by bringing textiles made of cellulosic material into contact with an aqueous preparation containing said polymer. This can be used as part of a conventional washing process, which can be carried out by means of a household washing machine or by hand.
- the amino group-containing polymer is preferably used in the rinsing step, that is to say after the actual washing step. However, it is also possible to jointly use amino-containing polymer and detergent in the washing step.
- the polymer essential to the invention may be a constituent of agents used in such washing processes, or it may be added separately to such agents or aqueous formulations containing them.
- a further subject of the present invention is therefore a laundry or laundry care composition containing an amino group-containing polymer having substituents carrying carboxylic acid groups.
- the active ingredient can also be in the use of the user by facilitating confectioning form, for example in admixture or granulated with vehicles, binders, wrapping materials, extrusion aids, flowability improvers, stabilizers, solvents, Rheologiemo dificators and / or emulsifiers.
- This embodiment of the invention makes it possible for the consumer in a simple manner, the advantages of the invention by using said polymer in addition to conventional washing and / or laundry aftertreatment only to bear, if they are desirable.
- Said polymer may be present in a liquid or solid agent, whereby the single dosage (pouch packaging, Pouch) of the agent is possible.
- the said polymer can also be present in a liquid spray product which, after dilution with water or, in particular, undiluted, can be sprayed onto a textile.
- said polymer in particular by spraying in the form of a liquid spray product, after washing and drying of the textile applied to this.
- the subject of the present invention is therefore likewise a process in which a cotton or textile containing or containing other cellulosic material is brought into contact with an amino group-containing polymer having substituents carrying carboxylic acid groups and subsequently fixed in the desired shape with a household iron.
- Ironing temperatures preferably occur in the range from 50 ° C. to 220 ° C., in particular from 100 ° C. to 160 ° C.
- a cumulative effect of the system according to the invention results in some, for example 1 to 5, times repeated applications.
- the textile does not need to be ironed after each application of the polymer according to the invention. Crease recovery angle improves from application to application.
- This cumulative effect allows the use of lower concentrations of the active ingredient according to the invention. Furthermore, it reduces the danger of damaging a textile by ironing in an undesired shape (for example a fold); Ironing errors can be corrected at the next application. For this reason, a dosage of the active substances essential to the invention which brings about a cumulative effect is preferred.
- the concentration of amino-containing polymer having substituents carrying carboxylic acid groups in an aqueous treatment liquor is in particular in the range from 0.1 g / l to 10 g / l, more preferably from 0.2 g / l to 2 g / l.
- Detergents or laundry detergents which contain the active ingredient to be used according to the invention or are used together or used in the process according to the invention may contain all customary other constituents of such agents which do not undesirably interact with the active ingredient essential to the invention.
- Such agent preferably contains synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 20% by weight, in particular from 0.1 to 18% by weight, in each case based on the total agent.
- Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation. Preference is given to the derivatives of fatty alcohols containing in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols.
- the alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
- a conventional sulfating reagent in particular sulfur trioxide or chlorosulfonic acid
- alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases include the abovementioned sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates.
- Such ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule.
- the suitable anionic surfactants of the sulfonate Type include the obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization ⁇ -sulfoester, in particular those of fatty acids having 8 to 22 C-atoms, preferably 12 to 18 C-atoms, and linear alcohols having 1 to 6 C-atoms , preferably 1 to 4 carbon atoms, derivative sulfonation products, as well as the resulting by formal saponification of these sulfo fatty acids.
- the anionic surfactants which can be used also include the salts of sulfosuccinic acid esters, which are also referred to as alkylsulfosuccinates or dialkylsulfosuccinates, and which are monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain Cs to Cis fatty alcohol residues or mixtures of these.
- Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol radical, which in itself is a nonionic surfactant.
- Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
- Another synthetic anionic surfactant is alkylbenzenesulfonate in question.
- compositions comprises the presence of nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof, in particular in an amount in the range of 2 wt .-% to 25 wt .-%.
- nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid
- Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
- the degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
- Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates.
- alkoxylates in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof.
- suitable alkoxylation products of alkylamines, vicinal diols and carboxylic acid amides, which correspond to the said alcohols with respect to the alkyl part usable.
- the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters and Fettklarepolyhydroxyamide into consideration.
- alkylpolyglycosides which are suitable for incorporation into the compositions according to the invention are compounds of the general formula (G) n -OR 2 , in which R 2 is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean.
- the glycoside component (G) n are oligomers or polymers of naturally occurring aldose or ketose monomers, including especially glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, xylose and lyxose.
- the oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomermaschinesgrad.
- the degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1, 5, in particular between 1, 2 and 1, 4.
- Preferred monomer building block is glucose because of its good availability.
- the alkyl or alkenyl moiety R 2 of the glycosides preferably also originates from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxoalcohols, can be used to prepare useful glycosides.
- the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable.
- Nonionic surfactant is in agents which contain an active ingredient according to the invention or used in the context of the use according to the invention or the method according to the invention, preferably in amounts of 1 wt .-% to 30 wt .-%, in particular from 1 wt .-% to 25 Wt .-%, with amounts in the upper part of this range are more likely to be found in liquid agents and particulate preferably contain lower amounts of up to 5 wt .-%.
- soaps suitable being saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids.
- those soap mixtures are preferred which are composed of 50% by weight to 100% by weight of saturated C 12-18 fatty acid soaps and up to 50% by weight of oleic acid soap.
- soap is included in amounts of 0.1 to 5% by weight.
- higher amounts of soap can be contained, usually up to 20 wt .-%.
- compositions may also contain betaines and / or cationic surfactants, which, if present, are preferably used in amounts of from 0.5% by weight to 7% by weight.
- esterquats are particularly preferred.
- the compositions may contain peroxygen bleaching agents, in particular in amounts ranging from 5% by weight to 70% by weight, and optionally bleach activator, in particular Amounts in the range of 2 wt .-% to 10 wt .-%, contained.
- the bleaches in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanedioic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which may be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts, in particular as sodium salts.
- Such bleaching agents are in detergents containing an active ingredient used in the invention, preferably in amounts of up to 25 wt .-%, in particular up to 15% by weight and particularly preferably from 5 wt .-% to 15 wt .-%, respectively on total agent, present, in particular percarbonate is used.
- the optionally present component of the bleach activators comprises the conventionally used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and Cyanurates, in addition to carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phe- nolsulfonat, and acylated sugar derivatives, in particular pentaacetylglucose, and cationic nitro rilderivate such as trimethylammoniumacetonitrile salts.
- N- or O-acyl compounds for example polyacylated alkylenediamines, in particular te
- the bleach activators may have been coated and / or granulated in a known manner with coating substances, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated by means of carboxymethylcellulose 1, 5-diacetyl-2,4-dioxohexahydro-1, 3,5-triazine, and / or formulated in particulate Trialkylammoniumacetonitnl is particularly preferred.
- Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.
- the composition contains water-soluble and / or water-insoluble builder, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5 wt .-% to 60 wt .-%.
- water-soluble and / or water-insoluble builder in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5 wt .-% to 60 wt .-%.
- the agent preferably contains from 20% to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders.
- the water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and also the polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and Mixed polymers of these, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality.
- the molecular weight of homopolymers of unsaturated carboxylic acids is generally intermediate 5000 g / mol and 200000 g / mol, those of the copolymer between 2000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, based on the free acid.
- a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 g / mol to
- Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight.
- vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene
- the acid content is at least 50% by weight.
- Terpolymers which contain two carboxylic acids and / or salts thereof as monomers and also vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer may also be used as water-soluble organic builder substances.
- the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) acrylic acid.
- the second acidic monomer or its salt may be a derivative of a C4-Cs dicarboxylic acid, with maleic acid being particularly preferred.
- the third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. Particularly preferred are vinyl alcohol derivatives which are an ester of short chain carboxylic acids, for example, C1-C4 carboxylic acids, with vinyl alcohol.
- Preferred terpolymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, and maleic acid and / or maleate and also 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, of vinyl alcohol and / or vinyl acetate.
- the weight ratio of (meth) acrylic acid and / or (meth) acrylate to maleic acid and / or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1, and in particular 2: 1 and 2.5: 1. Both the amounts and the weight ratios are based on the acids.
- the second acidic monomer or its salt may also be a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives is.
- Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, 10% by weight.
- % to 30 wt .-% preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid and / or methallylsulfonate and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate.
- This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred.
- the use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer.
- terpolymers generally have a molecular weight between 1000 g / mol and 200000 g / mol, preferably between 2000 g / mol and 50,000 g / mol and in particular between 3000 g / mol and 10,000 g / mol. They may, in particular for the production of liquid agents, in the form of aqueous Lö- solutions, preferably in the form of 30 to 50 weight percent aqueous solutions. All the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
- Such organic builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.
- Crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials.
- the detergent-grade crystalline aluminosilicates especially zeolite NaA and optionally NaX, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents.
- suitable aluminosilicates have no particles with a particle size greater than 30 ⁇ m, and preferably consist of at least 80% by weight of particles having a size of less than 10 ⁇ m.
- Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali metal silicates which may be present alone or in a mixture with amorphous silicates.
- the alkali metal silicates useful as builders in the compositions preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1, 1 to 1: 12, and may be present in amorphous or crystalline form.
- Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of from 1: 2 to 1: 2.8.
- Such amorphous alkali silicates are commercially available, for example, under the name Portil®. Those with a molar ratio of Na 2 O: SiO 2 of 1: 1, 9 to 1: 2.8 are preferably added in the course of the production as a solid and not in the form of a solution.
- Crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na.sub.2SixO.sub.2 O.sub.x + VH.sub.2O, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4.
- Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
- both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5-yH 2 O
- compositions which contain an active ingredient to be used according to the invention can be used in compositions which contain an active ingredient to be used according to the invention.
- a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda.
- Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further preferred embodiment of detergents which contain an active ingredient used in the invention.
- alkali metal silicates are preferably 1 wt .-% to 50 wt .-% and in particular 5 wt .-% to 35 wt .-%, based on anhydrous active substance. If alkali metal silicate, in particular zeolite, is present as an additional builder substance, the content of alkali metal silicate is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance.
- the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances is then preferably 4: 1 to 10: 1.
- the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2 : 1 and especially 1: 1 to 2: 1.
- water-soluble or water-insoluble inorganic substances may be contained in the agents containing an active ingredient to be used according to the present invention, used together with it or used in methods of the invention. Suitable in this context are the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight.
- the agents may contain other ingredients customary in detergents or cleaners.
- These optional constituents include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, foam inhibitors, for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives.
- agents which contain an active substance used according to the invention up to 1% by weight, in particular 0.01% by weight to 0.5% by weight, of optical brighteners, in particular compounds from the class of the substituted 4,4 ' Bis (2,4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5% by weight, in particular 0, 1% by weight to 2% by weight
- optical brighteners in particular compounds from the class of the substituted 4,4 ' Bis (2,4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids
- up to 5% by weight in particular 0, 1% by weight to 2% by weight
- Complexing agents for heavy metals, in particular aminoalkylenephosphonic acids and their salts and up to 2% by weight, in particular from 0.1% by weight to 1% by weight, of foam inhibitors, the weight proportions in each case referring to the total agent.
- Solvents that can be used in particular for liquid agents are, in addition to water, preferably those nonaqueous solvents which are water-miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether.
- the active compounds used in the invention are usually dissolved or in suspended form.
- Optionally present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase, pectinase and mixtures thereof.
- proteases derived from microorganisms such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms.
- Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®.
- the lipase which can be used can be obtained, for example, from Humicola lanuginosa, from Bacillus species, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus species.
- Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Lipex®, Amano®-Lipase, Toyo-Jozo®-Lipase, Meito®-Lipase and Diosynth®-Lipase.
- Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm.
- the usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5.
- Such cellulases are commercially available under the names Celluzyme®, Carezyme® and Ecostone®.
- Suitable pectinases are, for example, under the names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the name Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L ®, Rohapect 10L®, Rohapect B1 L® from AB Enzymes and available under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.
- enzyme stabilizers include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid, alkali metal borates, boric acid-carboxylic acid combinations, boric acid esters, boronic acid derivatives, calcium salts, for example Ca-formic acid combination, magnesium salts, and / or sulfur-containing reducing agents.
- Suitable foam inhibitors include long-chain soaps, in particular behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica.
- foam inhibitors are preferably bound to granular, water-soluble carrier substances.
- polyester-active soil release polymers include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol.
- Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR-) aOH, which may also be present as a polymeric diol H- (O- (CHRn-) a ) b OH.
- Ph is an o-, m- or p-phenylene radical which may carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
- R is hydrogen
- a is a number from 2 to 6
- b is a number from 1 to 300.
- the molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10.
- the degree of polymerization b is preferably in the range from 4 to 200, in particular from 12 to 140.
- the molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil release polymers is in the range from 250 g / mol to 100,000 g / mol, in particular from 500 g / mol to 50,000 g / mol.
- the acid underlying the radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, metilitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable.
- acids having at least two carboxyl groups may be included in the soil release-capable polyester.
- these include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
- Preferred diols HO- (CHR-) a OH include those in which R is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R is hydrogen and the alkyl radicals have from 1 to 10 , in particular 1 to 3 C-atoms is selected.
- R is hydrogen and a is a number from 2 to 6
- a is 2 and R is hydrogen and the alkyl radicals have from 1 to 10 , in particular 1 to 3 C-atoms is selected.
- those of the formula HO-CH 2 -CHR -OH in which R has the abovementioned meaning are particularly preferred.
- diol components are ethyleneglycol, 1,2-propyleneglycol, 1,3-propyleneglycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
- Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range from 1000 g / mol to 6000 g / mol.
- the polyesters may also be end-capped, alkyl groups having from 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups.
- the ester groups bonded via end groups can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms.
- valeric acid caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, Myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroseloic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoic acid, cerotic acid, melissic acid, benzoic acid, which can carry 1 to 5 substituents with a total of up to 25 C atoms, in particular 1 to 12 C atoms, for example tert-buty
- the end groups may also be based on hydroxymonocarboxylic acids having from 5 to 22 carbon atoms, including, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, the hydrogenation product of which include hydroxystearic acid and also o-, m- and p-hydroxybenzoic acid.
- the hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group.
- the number of hydroxymonocarboxylic acid units per end group is preferably in the range from 1 to 50, in particular from 1 to 10.
- polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units Molar weights of 750 g / mol to 5000 g / mol and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 50:50 to 90:10 used in combination with an essential ingredient of the invention.
- the soil release polymers are preferably water-soluble, the term "water-soluble” being understood to mean a solubility of at least 0.01 g, preferably at least 0.1 g, of the polymer per liter of water at room temperature and pH 8.
- Polymers used are preferably polymers However, these conditions have a solubility of at least 1 g per liter, in particular at least 10 g per liter.
- the laundry care agents used as aftertreatment agents may contain additional plasticizer components, preferably cationic surfactants, with the amino group-containing polymer having substituents carrying carboxylic acid groups.
- additional plasticizer components preferably cationic surfactants
- fabric softening components are quaternary ammonium compounds, cationic polymers and emulsifiers, such as those used in hair care products and also in textile saliva.
- Suitable examples are quaternary ammonium compounds of the formulas (II) and (III),
- R - X " (
- X " represents either a halide, methosulfate, methophosphate or phosphate ion and mixtures of these Examples of cationic compounds of the formula (II) are didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.
- Ester quats are so-called ester quats. Esterquats are characterized by their good biodegradability and are preferred in the context of the present invention.
- R 4 is an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds
- R 5 is H, OH or 0 (CO) R 7
- R 6 is independently of R 5 is H, OH or 0 (CO) R 8
- R 7 and R 8 are each independently an aliphatic alkyl radical having 12 to 22 carbon atoms having 0, 1, 2 or 3 double bonds
- m, n and p may each independently have the value 1, 2 or 3 have.
- X " can be either a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof
- Preferred compounds are those for R 5, the group 0 (CO) R 7 and for R 4 and R 7 are alkyl radicals having 16 to 18 carbon atoms Particular preference is given to compounds in which R 6 additionally represents OH.
- Examples of compounds of the formula (III) are methyl N- (2-hydroxyethyl) -N, N-di (tallowacyl-oxyethyl) ammonium methosulfate , Bis (palmitoyl) -ethyl-hydroxyethyl-methyl-ammonium methosulfate or methyl N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate.
- the agents contain the additional plasticizer components in amounts of up to 35% by weight, preferably from 0.1 to 25% by weight, more preferably from 0.5 to 15% by weight and especially from 1 to 10 Wt .-%, each based on the total agent.
- the agents may contain pearlescing agents.
- Pearlescing agents give the textiles an extra shine and are therefore preferably used in mild detergents.
- suitable pearlescing agents are: alkylene glycol esters; fatty acid; partial glycerides; Esters of polybasic, optionally hydroxysubstituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms; Ring opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms, fatty acids and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.
- liquid agents may additionally contain thickeners.
- thickening agents have proven particularly useful in gel-type liquid detergents.
- Naturally derived polymers which are used as thickeners. agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein, cellulose derivatives such as carboxymethylcellulose, hydroxyethyl and -propylcellulose, and polymeric polysaccharide.
- the textile care agents according to the invention contain thickeners, preferably in amounts of up to 10% by weight, more preferably up to 5% by weight, in particular from 0.1 to 1% by weight, in each case based on the total composition ,
- the agents may additionally contain odor absorbers and / or color transfer inhibitors.
- the agents optionally contain from 0.1% to 2%, preferably from 0.2% to 1%, by weight of color transfer inhibitor which in a preferred embodiment of the invention comprises a vinylpyrrolidone polymer, Vinylimidazole, vinylpyridine-N-oxide, or a copolymer of these.
- polyvinylpyrrolidones having molecular weights of from 15,000 to 50,000 and polyvinylpyrrolidones having molecular weights of more than 1,000,000, in particular from 1,500,000 to 4,000,000, N-vinylimidazole / N-vinylpyrrolidone copolymers, polyvinyloxazolidones, copolymers based on vinyl monomers and Carbonchureami-, pyrrolidonement law attire polyesters and polyamides, grafted polyamidoamines, polyamine N-oxide polymers, polyvinyl alcohols and copolymers based on Acrylamidoalkenylsulfonkla.
- enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which gives off hydrogen peroxide in water.
- a mediator compound for the peroxidase for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, wherein also above-mentioned polymeric Farbschreibtragungsinhibitorwirkstoffe can be used.
- Polyvinylpyrrolidone preferably has an average molecular weight in the range from 10 000 to 60 000, in particular in the range from 25 000 to 50 000, for use in compositions according to the invention.
- the copolymers those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 having an average molecular weight in the range of 5,000 to 50,000, especially 10,000 to 20,000 are preferred.
- Preferred deodorizing substances are metal salts of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 16 carbon atoms and / or a rosin acid with the exception of the alkali metal salts and any desired mixtures thereof.
- a particularly preferred unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 16 carbon atoms is ricinoleic acid.
- a particularly preferred rosin acid is abietic acid.
- Preferred metals are the transition metals and the lanthanides, in particular the transition metals of the groups Villa, Ib and IIb of the Periodic Table and lanthanum, cerium and neodymium, particularly preferably cobalt, nickel, copper and zinc, most preferably zinc.
- the cobalt, nickel and copper salts and the zinc salts are similarly effective, but for toxicological reasons, the zinc salts are to be preferred. It is advantageous and therefore particularly preferred to use as deodorizing substances one or more metal salts of ricinoleic acid and / or abietic acid, preferably zinc ricinoleate and / or zinc abietate, in particular zinc ricinoleate.
- Cyclodextrins as well as mixtures of the abovementioned metal salts with cyclodextrin, preferably in a weight ratio of from 1:10 to 10: 1, particularly preferably from 1: 5 to 5: 1 and in particular from 1, also prove to be suitable further deodorizing substances in the sense of the invention.
- the term "cyclodextrin” includes all known cyclodextrins, ie both unsubstituted cyclodextrins having 6 to 12 glucose units, in particular alpha-, beta- and gamma-cyclodextrins and also their mixtures and / or their derivatives and / or their mixtures.
- compositions according to the invention presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, wherein, for example, enzymes and possibly other thermally sensitive ingredients such as bleaching agents are optionally added separately later.
- a process comprising an extrusion step is preferred.
- compositions in tablet form which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers
- the procedure is preferably such that all components - optionally one layer at a time - in a mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric presses or rotary presses, with pressing forces in the range of about 50 to 100 kN, preferably compressed at 60 to 70 kN.
- a tablet produced in this way has a weight of 10 g to 50 g, in particular 15 g up to 40 g.
- the spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm.
- the size of rectangular or cuboid-shaped tablets, which are predominantly introduced via the metering device, for example the washing machine is dependent on the geometry and the volume of this metering device.
- Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or 24x38 mm.
- Liquid or pasty compositions in the form of common solvents, in particular water, containing solutions are usually prepared by simply mixing the ingredients that can be given in bulk or as a solution in an automatic mixer.
- the agents are present, preferably in liquid form, as a portion in a completely or partially water-soluble coating. Portioning makes it easier for the consumer to dose.
- the funds can be packed, for example, in foil bags.
- Pouches made of water-soluble film make it unnecessary for the consumer to tear open the packaging. In this way, a convenient dosing of a single, sized for a wash portion by inserting the bag directly into the washing machine or by throwing the bag into a certain amount of water, for example in a bucket, a bowl or hand basin, possible.
- the film bag surrounding the washing portion dissolves without residue when it reaches a certain temperature.
- water-soluble detergent portions There are numerous processes in the prior art for producing water-soluble detergent portions, which are basically also useful in the context of the present invention.
- the best known methods are the tubular film processes with horizontal and vertical sealing seams.
- Further suitable for the production of film bags or dimensionally stable detergent portions is the Thermoformverrfahren (thermoforming process).
- the water-soluble envelopes need not necessarily consist of a film material, but can also represent dimensionally stable containers that can be obtained for example by means of an injection molding process.
- the filling material is injected into the forming capsule, wherein the injection pressure of the filling liquid presses the polymer bands in the Kugelschalenkavticianen.
- a process for the preparation of water-soluble capsules, in which initially the filling and then the sealing takes place, is based on the so-called Bottle-Pack ® method.
- a tubular preform is guided into a two-part cavity. The cavity is closed, the lower tube portion is sealed, then the tube is inflated to form the capsule shape in the cavity, filled and finally sealed.
- the shell material used for the preparation of the water-soluble portion is preferably a water-soluble polymeric thermoplastic, more preferably selected from the group (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof , Blends and composites, inorganic salts and mixtures of the materials mentioned, preferably hydroxypropylmethylcellulose and / or polyvinyl alcohol blends.
- Polyvinyl alcohols are commercially available, for example under the trade name Mowiol ® (Clariant).
- polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88, Mowiol ® 8-88 and Clariant L648.
- the water-soluble thermoplastic used to prepare the portion may additionally optionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and / or mixtures of the above polymers.
- the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%. It is further preferred that the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range of 10,000 to 100,000 gmol -1, preferably from 1 1 .000 to 90,000 gmol -1 , more preferably from 12,000 to 80,000 gmol -1 and especially from 13,000 to 70,000 gmol -1 is located.
- thermoplastics are used in amounts of at least 50% by weight, preferably of at least 70% by weight, more preferably of at least 80% by weight and in particular of at least 90% by weight, based in each case on the weight of the water-soluble polymeric thermoplastic.
- Example 2 The aminopropylmethylsiloxane-dimethylsiloxane copolymer without carboxylic acid groups (V2) used as starting material in Example 1 was applied in otherwise the same way, however from 2 weight percent formulation, tested and compared with amino group-containing polymer also having 2 weight percent formulation with carboxylic acid group carrying substituent E1.
- the crease recovery angles listed in Table 2 (mean values of 5-fold determinations) were observed.
Abstract
Description
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Applications Claiming Priority (2)
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DE102014222924.3A DE102014222924A1 (en) | 2014-11-11 | 2014-11-11 | Ironing relief of textiles |
PCT/EP2015/075075 WO2016074934A1 (en) | 2014-11-11 | 2015-10-29 | Making fabrics easier to iron |
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EP3218542A1 true EP3218542A1 (en) | 2017-09-20 |
EP3218542B1 EP3218542B1 (en) | 2019-04-10 |
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US (1) | US10697113B2 (en) |
EP (1) | EP3218542B1 (en) |
DE (1) | DE102014222924A1 (en) |
WO (1) | WO2016074934A1 (en) |
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AT330930B (en) | 1973-04-13 | 1976-07-26 | Henkel & Cie Gmbh | PROCESS FOR THE PRODUCTION OF SOLID, SPILLABLE DETERGENTS OR CLEANING AGENTS WITH A CONTENT OF CALCIUM BINDING SUBSTANCES |
JPS6036513B2 (en) * | 1981-02-05 | 1985-08-21 | ト−レ・シリコ−ン株式会社 | Textile treatment agent |
EP0095676A3 (en) * | 1982-05-21 | 1984-03-28 | SWS Silicones Corporation | Carboxylic acid-functional polysiloxane polymers, process for preparing the same and use thereof |
US6277445B1 (en) * | 1998-10-12 | 2001-08-21 | Shin-Etsu Chemical Co., Ltd. | Organopolysiloxane compound and composition containing the same |
DE19959949A1 (en) * | 1999-12-13 | 2001-06-21 | Bayer Ag | Hydrophobization with carboxyl-containing polysiloxanes |
DE10124387A1 (en) * | 2001-05-18 | 2002-11-28 | Basf Ag | Hydrophobically modified polyethyleneimine and polyvinylamine as anticrease agents for treatment of cellulose containing textiles, useful as textile finishing agents in both solid and liquid formulations |
GB0219281D0 (en) | 2002-08-19 | 2002-09-25 | Unilever Plc | Fabric care composition |
CN1793483A (en) | 2005-12-29 | 2006-06-28 | 苏州大学 | Process for preparing anti-wrinkle cotton fibre |
MX349047B (en) * | 2010-01-29 | 2017-07-06 | The Procter & Gamble Company * | Novel linear polydimethylsiloxane-polyether copolymers with amino and/or quaternary ammonium groups and use thereof. |
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EP3218542B1 (en) | 2019-04-10 |
DE102014222924A1 (en) | 2016-05-12 |
US10697113B2 (en) | 2020-06-30 |
US20170241073A1 (en) | 2017-08-24 |
WO2016074934A1 (en) | 2016-05-19 |
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