EP0279134A1 - Antiredeposition latex for washing textiles - Google Patents
Antiredeposition latex for washing textiles Download PDFInfo
- Publication number
- EP0279134A1 EP0279134A1 EP87402917A EP87402917A EP0279134A1 EP 0279134 A1 EP0279134 A1 EP 0279134A1 EP 87402917 A EP87402917 A EP 87402917A EP 87402917 A EP87402917 A EP 87402917A EP 0279134 A1 EP0279134 A1 EP 0279134A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- latex according
- meth
- acrylic
- latex
- acid
- 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
- 238000005406 washing Methods 0.000 title claims abstract description 33
- 239000004816 latex Substances 0.000 title claims abstract description 31
- 229920000126 latex Polymers 0.000 title claims abstract description 31
- 239000004753 textile Substances 0.000 title claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920000728 polyester Polymers 0.000 claims abstract description 19
- 230000003373 anti-fouling effect Effects 0.000 claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 23
- 239000003599 detergent Substances 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 5
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 150000002689 maleic acids Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001557 phthalyl group Chemical group C(=O)(O)C1=C(C(=O)*)C=CC=C1 0.000 claims description 2
- 125000002730 succinyl group Chemical group C(CCC(=O)*)(=O)* 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims 2
- 229920006243 acrylic copolymer Polymers 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- ZFACJPAPCXRZMQ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O.OC(=O)C1=CC=CC=C1C(O)=O ZFACJPAPCXRZMQ-UHFFFAOYSA-N 0.000 claims 1
- 239000001384 succinic acid Substances 0.000 claims 1
- 229920006163 vinyl copolymer Polymers 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 11
- 239000000654 additive Substances 0.000 description 33
- 230000000996 additive effect Effects 0.000 description 30
- 239000004744 fabric Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 20
- 239000002002 slurry Substances 0.000 description 13
- 238000005259 measurement Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 235000019832 sodium triphosphate Nutrition 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 7
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 239000008233 hard water Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YGUMVDWOQQJBGA-VAWYXSNFSA-N 5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S(O)(=O)=O)C(S(=O)(=O)O)=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 YGUMVDWOQQJBGA-VAWYXSNFSA-N 0.000 description 4
- 239000002519 antifouling agent Substances 0.000 description 4
- 238000004453 electron probe microanalysis Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920001567 vinyl ester resin Polymers 0.000 description 4
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 235000011180 diphosphates Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 108010003855 mesentericopeptidase Proteins 0.000 description 3
- KJPHTXTWFHVJIG-UHFFFAOYSA-N n-ethyl-2-[(6-methoxypyridin-3-yl)-(2-methylphenyl)sulfonylamino]-n-(pyridin-3-ylmethyl)acetamide Chemical compound C=1C=C(OC)N=CC=1N(S(=O)(=O)C=1C(=CC=CC=1)C)CC(=O)N(CC)CC1=CC=CN=C1 KJPHTXTWFHVJIG-UHFFFAOYSA-N 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- UGFSLKRMHPGLFU-UHFFFAOYSA-N 2-[5-(1,3-benzoxazol-2-yl)thiophen-2-yl]-1,3-benzoxazole Chemical compound C1=CC=C2OC(C3=CC=C(S3)C=3OC4=CC=CC=C4N=3)=NC2=C1 UGFSLKRMHPGLFU-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920004934 Dacron® Polymers 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- 241000506680 Haemulon melanurum Species 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229920003086 cellulose ether Polymers 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229940048084 pyrophosphate Drugs 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 1
- BHQCQFFYRZLCQQ-UHFFFAOYSA-N 4-(3,7,12-trihydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl)pentanoic acid Chemical compound OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 BHQCQFFYRZLCQQ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-M ethenesulfonate Chemical compound [O-]S(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-M 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- C11D3/3788—Graft polymers
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
Definitions
- the present invention relates to new latexes used as anti-fouling and anti-deposition agents for the aqueous washing of textile articles.
- detergent compositions currently marketed for washing synthetic or natural textile articles are complex mixtures of different products all having well-defined functions, such as, for example, metal complexing agents, surfactants, anticorrosion agents, detergents, anti-depositing agents, bleaching agents or anti-fouling agents.
- Antifouling agents are understood to mean agents which essentially have the role of reducing the affinity of textile fibers for soiling, in particular for greasy soiling, and thus facilitating their removal.
- anti-depositing agents is intended to mean agents which essentially have the role of preventing the deposition of soiling on the textile fibers, in particular to avoid the redeposition of the soiling removed during washing.
- the main object of the invention is new agents with anti-deposition and soil removal properties which are particularly effective and relatively inexpensive.
- Another subject of the invention relates to washing compositions using these new anti-fouling agents.
- latex has the usual meaning, that is to say, the aqueous dispersions of polymers forming heterogeneous systems comprising a continuous liquid phase, water and a solid discontinuous phase.
- the alkali-soluble latexes of the invention which are the subject of the patent application are latexes in the dispersion state at a certain pH, in particular acidic or neutral, and which, when the pH increases, see the above-mentioned polymerized particles disintegrate. , which thus leads to aqueous solutions of polymers.
- the latexes which are suitable in the context of the invention are those which during increases in pH are likely to undergo a variation in their configuration depending on the pH of the detergent bath.
- the alkali-soluble latexes used are generally well known products. Their preparation, their physical and chemical characteristics are considered here as part of the prior art.
- the object of the present invention has been to select, from the range of latexes described, a field of latex compositions, on the one hand, which can be synthesized at low cost and which, on the other hand, have improved anti-fouling and anti-fouling properties compared with the latexes described in the prior art.
- the latexes which are the subject of the present application are all vinyl latexes either composed of vinyl acetate-unsaturated carboxylic acid copolymers optionally grafted with sulfonic polyesters or of (meth) acrylic-carboxylic acid copolymers grafted with sulfonic polyesters.
- alkali-soluble latex which is very suitable in the context of the present invention, mention may be made of latexes based on vinyl esters. More particularly, it is possible to use the latexes based on vinyl esters, on ethylenically unsaturated mono or dicarboxylic acids and optionally either (meth) acrylic esters or of water-soluble monomers such as acrylamide or vinyl sulfonate.
- acid mention will in particular be made of maleic, crotonic, (meth) acrylic or itaconic acids. Generally, the acid level is at least 3% and preferably between 3 and 8%.
- vinyl ester particular mention will be made of vinyl acetate.
- the first type of alkali-soluble latex which is the subject of the present invention also consists of the latexes based on vinyl esters, previously described, polymerized in the presence of polyester sulfonate.
- the second type of alkali-soluble latex, object of the present invention consists of (meth) acrylic esters and of carboxylic acids grafted with polyester sulfonates.
- latexes based on (meth) acrylic esters on mono or dicarboxylic acids, ethylenically unsaturated and optionally other monomers such as styrene or butadiene.
- alkyl (meth) acrylates the alkyl chain of which preferably contains 1 to 4 carbon atoms such as methyl or ethyl (meth) acrylate.
- acids mention may be made particularly of (meth) acrylic, itaconic or maleic acids.
- the acid content (percentage by weight of monomer in the product) is at least 10% and generally it is between 10% and 20%.
- the level of polyestersulfonate relative to the monomers is preferably less than 10%.
- the sulfonated polyesters used even more preferably in the context of the present invention are those containing approximately 60% of phthalyl or succinyl group for approximately 40% of ethylene oxide group.
- Phthalic acid is distributed between its isomers approximately as follows: 80% terephthalic acid for 20% isophthalic acid. A molar quantity of sulfoisophthalic acid corresponding to approximately 15% of the previously indicated acid mixture is added to this acid mixture.
- the latexes which are the subject of the present invention are preferably chosen from those of the first group of alkali-soluble latexes which have a composition which corresponds to the following distribution: - 84 to 96% vinyl acetate, - 3 to 6% of acrylic or crotonic acid or one of its derivatives and - 1 to 10% of sulfonated polyester.
- latexes whose composition is within the following limits: - vinyl acetate 87 - 94% - crotonic or acrylic acid 4 - 5% - sulfonated polyester 2 - 8% and especially latexes whose acid is acrylic acid.
- the preceding products having undergone partial or total hydrolysis of the vinyl acetate groups, that is to say a transformation of vinyl acetate into vinyl alcohol.
- the detergent compositions containing said latex also form part of the invention, they preferably contain at least 0.1% of latex as described above and even more preferably 0.4%.
- the detergent compositions may also contain, as washing auxiliaries, pyrophosphates, metaphosphates, tripolyphosphates of alkali metals, zeolites, surfactants, a bleaching system, enzymes, optical brighteners, perfumes, silicates etc .
- the latex can also be incorporated into a rinsing composition, which of course makes it possible to add the latex to the bath during rinsing.
- the redeposition of soiling is a cumulative phenomenon which manifests itself by graying of the laundry after a significant number of washing cycles.
- the method used consists of washing tissue samples several times in the presence of the additive to be tested, and of soiled tissue.
- the experimental conditions are as follows:
- each pot of the tergotometer contains: . 4 cotton test tubes (10 ⁇ 12 cm) . 4 PE / C test pieces (10 ⁇ 12 cm) . 4 polyester test pieces (10 ⁇ 12 cm) . 4 KREFELD soiled cotton test tubes (10 ⁇ 12 cm) or: 4 KREFELD soiled cotton test tubes and 2 EMPA soiled cotton test tubes (10 ⁇ 12 cm) . 500 ml of detergent solution (the detergent concentration is 6g / l.) . Bath ratio 1/25
- the reflectance measurement R y is carried out using a GARDNER photometer filter y on 4 thicknesses of tissue.
- the products tested are particularly active on synthetic fibers, as well as on a mixture of fibers.
- the reflectance measurements presented in the tables relate only to polyester fabrics.
- the weight composition of the detergent formula used is as follows: Sodium alkybenzene sulfonate 7% Sodium stearate 3% Cémulsol® DB 6/18 2.5% Cémulsol® LA 90 2.5% Sodium tripolyphosphate 28.75% Sodium pyrophosphate 2% Sodium orthophosphate 0.5% Sodium diisilicate 9.35% Sodium sulfate 17.5% Tinopal® SOP 0.2% Tinopal® DMS X 0.2% Esperase enzyme Novo 0.3% Sodium perborate 25% Magilex® 120 1% 0.2% sodium EDTA
- test referenced white corresponds to the five washes of fabrics in the presence of soiling and in the absence of additive.
- Example 1 various tests are carried out by modifying the concentration of additive in the detergent bath. - addition in post addition at different concentrations. - detergent concentration 6g / 1. - KREFELD soiling
- the cellulose ether amplifies the redeposition while the claimed additives remain effective.
- a detergent such as TPP, ionic surfactants, sodium silicate, sodium sulfate and water are mixed to form a slurry which constitutes "the slurry". This very alkaline mixture is then spray dried to obtain a powder. Non-ionic surfactants, bleaches, enzymes and perfumes are then added.
- formula X prepared from the control slurry without additives.
- Y formula prepared from the slurry control without additive, the additive No. 5 is introduced in post addition at 0.42% of the formula
- Z formula prepared from the slurry containing 5 No. Additive, weight percent of additive No. 5 in the formula is 0.42%.
- the results obtained with the additive 5 introduced into a slurry are of the same order of magnitude as those obtained when this additive is introduced into the detergent bath.
- the product retains its anti-depositing properties when introduced into a slurry.
- the method used consists of washing tissue samples in the presence of the additive to be tested, depositing stains on these fabrics and rewashing them.
- the results obtained reflect the affinity of the textiles thus conditioned for soiling.
- the experimental conditions are as follows.
- Packaging a washing cycle is carried out in the presence of the additive to be tested.
- the additive can be introduced either into the detergent bath or during rinsing.
- Staining using a burette, 4 drops of drain oil are placed in the center of the tissue sample placed on a "watch glass”. The fabrics are then placed in an oven at 60 ° C for one hour. Half of the samples are thus soiled. .
- Measurement of the reflectance of stained fabrics (GARDNER, filter Y).
- Washing we operate in the same way as for packaging, but in the absence of additive. Each linitest jar thus contains two stained samples and two non-stained samples of each quality of fabric. . Reflectance measurement after washing (GARDNER, filter Y). The reflectance of stained fabrics indicates the anti-fouling effect.
- R s reflectance of soiled fabric, before washing
- R0 reflectance of the soiled fabric, before washing
- R1 reflectance of soiled fabric, after washing.
- the products are added to the medium at a pH such that they remain in the form of a suspension (addition on the third rinse), the solubilization of the latex only taking place during the following washing (where the pH increases).
- composition of the formula used is as follows: TPP 21.5% 2% neutral pyrophosphate 0.5% anhydrous neutral trisodium phosphate Silicate 3Na 8.6% 3.0N stearate 3.0% TINOPAL DMSX® 0.2% TINOPAL SOP® 0.2% ESPERASE NOVO® 0.3% Perborate (Air liquid) 25.0% EDTA 0.2% LABS neutral 7.0% CEMULSOL 6 / 18® 2.5% CEMULSOL LA 90® 2.5% Na sulfate 24%
- test used during the examples which follow is to evaluate the anti-redepositing properties of a given additive.
- the method used consists of washing tissue samples in the presence of the additive to be tested, and of dirt deposited on cotton wicks.
- the results obtained reflect the affinity of the textiles thus conditioned for soiling.
- the experimental conditions are as follows.
- Linitest HANAU (2 pots per test) (automated tergotometer) Each Linitest jar contains:
- a washing cycle is carried out in the presence of the additive to be tested and of soiling impregnated on cotton wicks.
- the additive can be introduced either into the detergent bath or during rinsing.
- - Measurement of the reflectance of stained fabrics GARDNER, filter Y).
- Washing the procedure is the same as for packaging, but in the absence of an additive. Each linitest jar thus contains two stained samples and two non-stained samples of each quality of fabric.
- GARDNER filter Y Measurement of reflectance after washing. The reflectance of stained fabrics indicates the anti-fouling effect.
- the purpose of this example is to demonstrate the anti-redepositing effect of an alkali-soluble latex in the presence of a formula in which the builder or the washing aid consists of tripolyphosphate (TPP) and zeolite 4A .
- TPP tripolyphosphate
- composition of the formula used is as follows: TPP 19.0% Zeolite 17.0% 9.5% Na sulfate Neutral pyrophosphate 2.0% Anhydrous Na3PO4 0.5% Silicate 3Na 8.6% BLANOSE BWS 1.5% TINOPAL DMSX® 0.2% TINOPAL SOP® 0.2% ESPERASE NOVO® 0.3% Perborate 25.0% Na 3.0 stearate LABS 7.0 CEMULSOL 6 / 18® 2.5% CEMULSOL LA 90® 2.5% EDTA 0.2% H2O 1.0%
- This example illustrates the use of different latexes at a concentration of 100 ppm in a detergent formula having a concentration of 6 g / l of bath.
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Abstract
Latex antisallissures et antiredéposants utilisables dans le lavage aqueux des matières textiles, constitués soit de copolymères acétates de vinyle acides carboxyliques insaturés éventuellement greffés par des polyesters sulfoniques soit de compolymères (méth)acrylique greffés par des polyesters sulfoniques.Anti-fouling and anti-depositing latex used in the aqueous washing of textile materials, consisting either of vinyl acetate copolymers of unsaturated carboxylic acids optionally grafted with sulphonic polyesters or of (meth) acrylic composites grafted with sulphonic polyesters.
Description
La présente invention concerne de nouveaux latex utilisés comme agents antisalissures et antiredéposants pour le lavage aqueux d'articles textiles.The present invention relates to new latexes used as anti-fouling and anti-deposition agents for the aqueous washing of textile articles.
On sait que les compositions lessivielles actuellement commercialisées pour le lavage d'articles textiles synthétiques ou naturels, sont des mélanges complexes de différents produits ayant tous des fonctions bien déterminées, tels que par exemple les agents complexants des métaux, les tensioactifs, les agents anticorrosion, les détergents, les agents antiredéposants, les agents de blanchiment ou les agents antisalissures.It is known that the detergent compositions currently marketed for washing synthetic or natural textile articles are complex mixtures of different products all having well-defined functions, such as, for example, metal complexing agents, surfactants, anticorrosion agents, detergents, anti-depositing agents, bleaching agents or anti-fouling agents.
On entend par agents antisalissures des agents qui ont essentiellement pour rôle de réduire l'affinité des fibres textiles pour les salissures, en particular pour des salissures grasses, et de faciliter ainsi leur enlèvement.Antifouling agents are understood to mean agents which essentially have the role of reducing the affinity of textile fibers for soiling, in particular for greasy soiling, and thus facilitating their removal.
On entend par agents antiredéposants des agents qui ont essentiellement pour rôle d'éviter le dépôt des salissures sur les fibres textiles, en particulier pour éviter le redépôt des salissures enlevées au cours du lavage.The term “anti-depositing agents” is intended to mean agents which essentially have the role of preventing the deposition of soiling on the textile fibers, in particular to avoid the redeposition of the soiling removed during washing.
L'objet principal de l'invention consiste en de nouveaux agents ayant des propriétés antiredéposition et d'enlèvement de la salissure qui soient particulièrement efficaces et d'un coût relativement faible.The main object of the invention is new agents with anti-deposition and soil removal properties which are particularly effective and relatively inexpensive.
Un autre objet de l'invention concerne les compositions de lavage mettant en oeuvre ces nouveaux agents antisalissures.Another subject of the invention relates to washing compositions using these new anti-fouling agents.
On donne dans ce texte et pour tout le reste de la description au terme de latex le sens habituel, c'est à dire, les dispersions aqueuses de polymères formant des systèmes hétérogènes comprenant une phase continue liquide, l'eau et une phase discontinue solide.In this text and for the remainder of the description, the term "latex" has the usual meaning, that is to say, the aqueous dispersions of polymers forming heterogeneous systems comprising a continuous liquid phase, water and a solid discontinuous phase. .
Les latex alcali-solubles de l'invention objet de la demande de brevet sont des latex à l'état de dispersion à un certain pH notamment acide ou neutre et qui, lors de l'augmentation du pH, voient les particules polymérisées précitées se déliter, ce qui conduit ainsi à des solutions aqueuses de polymères. En d'autres termes, les latex qui conviennent dans le cadre de l'invention sont ceux qui lors de l'augmentation du pH sont susceptibles de subir une variation de leur configuration en fonction du pH du bain lessiviel.The alkali-soluble latexes of the invention which are the subject of the patent application are latexes in the dispersion state at a certain pH, in particular acidic or neutral, and which, when the pH increases, see the above-mentioned polymerized particles disintegrate. , which thus leads to aqueous solutions of polymers. In other words, the latexes which are suitable in the context of the invention are those which during increases in pH are likely to undergo a variation in their configuration depending on the pH of the detergent bath.
Les latex alcali-solubles utilisés sont généralement des produits bien connus. Leur préparation, leurs caractéristiques physiques et chimiques sont considérées ici comme faisant partie de l'art antérieur.The alkali-soluble latexes used are generally well known products. Their preparation, their physical and chemical characteristics are considered here as part of the prior art.
L'objet de la présente invention a été de sélectionner, dans la gamme des latex décrits, un domaine de compositions de latex d'une part synthétisables à faible prix et présentant d'autre part des propriétés antisalissures et antiredéposantes améliorées par rapport aux latex décrits dans l'art antérieur.The object of the present invention has been to select, from the range of latexes described, a field of latex compositions, on the one hand, which can be synthesized at low cost and which, on the other hand, have improved anti-fouling and anti-fouling properties compared with the latexes described in the prior art.
Les latex, objets de la présente demande, sont tous des latex vinyliques soit composés de copolymères acétate de vinyle-acides carboxyliques insaturés éventuellement greffés par des polyesters sulfoniques soit de copolymères (méth)acryliques-acide carboxyliques greffés par des polyesters sulfoniques.The latexes which are the subject of the present application are all vinyl latexes either composed of vinyl acetate-unsaturated carboxylic acid copolymers optionally grafted with sulfonic polyesters or of (meth) acrylic-carboxylic acid copolymers grafted with sulfonic polyesters.
Comme premier type de latex alcali-solubles convenant bien dans le cadre de la présente invention, on peut citer les latex à base d'esters vinyliques. Plus particulièrement, on peut utiliser les latex à base d'esters vinyliques, d'acides mono ou dicarboxyliques éthyléniquement insaturés et éventuellement, soit d'esters (méth)acryliques, soit de monomères hydrosolubles tels qu'acrylamide ou vinylsulfonte. A titre d'acide, on mentionnera notamment les acides maléique, crotonique, (méth)acrylique ou itaconique. Généralement, le taux d'acide est d'au moins 3 % et de préférence compris entre 3 et 8 %. Comme ester vinylique, on citera particulièrement l'acétate de vinyle.As the first type of alkali-soluble latex which is very suitable in the context of the present invention, mention may be made of latexes based on vinyl esters. More particularly, it is possible to use the latexes based on vinyl esters, on ethylenically unsaturated mono or dicarboxylic acids and optionally either (meth) acrylic esters or of water-soluble monomers such as acrylamide or vinyl sulfonate. By way of acid, mention will in particular be made of maleic, crotonic, (meth) acrylic or itaconic acids. Generally, the acid level is at least 3% and preferably between 3 and 8%. As vinyl ester, particular mention will be made of vinyl acetate.
Le premier type de latex alcali-solubles, objet de la présente invention est aussi constitué par les latex à base d'esters vinyliques, précédemment décrits, polymérisés en présence de polyester sulfonate.The first type of alkali-soluble latex which is the subject of the present invention also consists of the latexes based on vinyl esters, previously described, polymerized in the presence of polyester sulfonate.
La deuxième type de latex alcalisolubles, objet de la présente invention, est constitué d'esters (méth)acryliques et d'acides carboxyliques greffés par des polyester sulfonates.The second type of alkali-soluble latex, object of the present invention, consists of (meth) acrylic esters and of carboxylic acids grafted with polyester sulfonates.
Dans ce cas, on peut utiliser les latex à base d'esters (méth)acryliques, d'acides mono ou dicarboxyliques éthyléniquement insaturés et éventuellement d'autres monomères tels que le styrène ou le butadiène.In this case, it is possible to use latexes based on (meth) acrylic esters, on mono or dicarboxylic acids, ethylenically unsaturated and optionally other monomers such as styrene or butadiene.
A titre d'esters (méth)acryliques, on citera notamment les alkyl (méth)acrylates, dont la chaîne alkyle contient de préférence 1 à 4 atomes de carbones tels que le (méth)-acrylate de méthyle ou d'éthyle.As (meth) acrylic esters, mention may in particular be made of alkyl (meth) acrylates, the alkyl chain of which preferably contains 1 to 4 carbon atoms such as methyl or ethyl (meth) acrylate.
A titre d'acides, on peut mentionner particulièrement les acides (méth)acryliques, itaconiques ou maléiques.As acids, mention may be made particularly of (meth) acrylic, itaconic or maleic acids.
En principe, le taux d'acide (pourcentage pondéral de monomère dans le produit) est d'au moins 10 % et généralement, il est compris entre 10 % et 20 %.In principle, the acid content (percentage by weight of monomer in the product) is at least 10% and generally it is between 10% and 20%.
Le taux de polyestersulfonate par rapport aux monomères est de préférence inférieur à 10%. Les polyesters sulfonés utilisés encore plus préférentiellement dans le cadre de la présente invention sont ceux contenant environ 60 % de groupe phtalyl ou succinyl pour environ 40 % de groupement éthylène oxyde. L'acide phtalique est réparti entre ses isomères approximativement de la façon suivante : 80 % d'acide téréphtalique pour 20 % d'acide isophtalique. On ajoute à ce mélange d'acide une quantité molaire d'acide sulfoisophtalique correspondant à environ 15 % du mélange d'acide précédemment indiqué.The level of polyestersulfonate relative to the monomers is preferably less than 10%. The sulfonated polyesters used even more preferably in the context of the present invention are those containing approximately 60% of phthalyl or succinyl group for approximately 40% of ethylene oxide group. Phthalic acid is distributed between its isomers approximately as follows: 80% terephthalic acid for 20% isophthalic acid. A molar quantity of sulfoisophthalic acid corresponding to approximately 15% of the previously indicated acid mixture is added to this acid mixture.
Les latex objets de la présente invention sont choisis de préférence parmi ceux du premier groupe de latex alcali-soluble qui ont une composition qui correspond à la répartition suivante :
- 84 à 96 % d'acétate de vinyle,
- 3 à 6 % d'acide acrylique ou crotonique ou de l'un des ses dérivés et
- 1 à 10 % de polyester sulfoné.The latexes which are the subject of the present invention are preferably chosen from those of the first group of alkali-soluble latexes which have a composition which corresponds to the following distribution:
- 84 to 96% vinyl acetate,
- 3 to 6% of acrylic or crotonic acid or one of its derivatives and
- 1 to 10% of sulfonated polyester.
On préfère utiliser les latex dont la composition est comprise dans les limites suivantes :
- acétate de vinyle 87 - 94 %
- acide crotonique ou acrylique 4 - 5 %
- polyester sulfoné 2 - 8 %
et tout particulièrement les latex dont l'acide est l'acide acrylique.It is preferred to use latexes whose composition is within the following limits:
- vinyl acetate 87 - 94%
- crotonic or acrylic acid 4 - 5%
- sulfonated polyester 2 - 8%
and especially latexes whose acid is acrylic acid.
Font également partie de l'invention, les produits précédents ayant subi une hydrolyse partielle ou totale des groupements acétate de vinyle, c'est à dire une transformation de l'acétate de vinyle en alcool vinylique.Also forming part of the invention, the preceding products having undergone partial or total hydrolysis of the vinyl acetate groups, that is to say a transformation of vinyl acetate into vinyl alcohol.
Les compositions détergentes contenant ledit latex font aussi partie de l'invention, elles contiennent de préférence au moins 0,1 % de latex tel que décrit précédemment et encore plus préférentiellement 0,4 %.The detergent compositions containing said latex also form part of the invention, they preferably contain at least 0.1% of latex as described above and even more preferably 0.4%.
Les compositions détergentes peuvent contenir en outre à titre d'auxiliaires de lavage, des pyrophosphates, des métaphosphates, des tripolyphosphates de métaux alcalins, des zéolites, des tensioactifs, un système de blanchiment, des enzymes, des azurants optiques, des parfums, des silicates etc.....The detergent compositions may also contain, as washing auxiliaries, pyrophosphates, metaphosphates, tripolyphosphates of alkali metals, zeolites, surfactants, a bleaching system, enzymes, optical brighteners, perfumes, silicates etc .....
Lé latex peut aussi être incorporé à une composition de rinçage ce qui permet bien sûr ainsi d'ajouter le latex au bain lors du rinçage.The latex can also be incorporated into a rinsing composition, which of course makes it possible to add the latex to the bath during rinsing.
Bien entendu, tout ce qui a été dit plus haut dans la description au sujet de la nature et des caractéristiques du latex alcali-soluble s'applique ici au sujet des compositions, les latex entrant dans leurs constitutions étant tout à fait identiques à ceux décrits pour le procédé.Of course, all that has been said above in the description concerning the nature and characteristics of the alkali-soluble latex applies here to the subject of the compositions, the latexes entering into their constitutions being completely identical to those described for the process.
Des exemples vont maintenant être donnnés.Examples will now be given.
Les tests utilisés au cours des exemples qui suivent ont pour but d'évaluer les propriétés antisalissures et antiredéposantes d'un additif donné.The tests used in the examples which follow are intended to evaluate the anti-fouling and anti-depositing properties of a given additive.
La redéposition des salissures est un phénomène cumulatif qui se manifeste par un grisaillement du linge au bout d'un nombre important de cycles de lavage.The redeposition of soiling is a cumulative phenomenon which manifests itself by graying of the laundry after a significant number of washing cycles.
Pour mesurer les propriétés antiredéposantes, la méthode utilisée consiste à laver plusieurs fois des échantillons de tissus en présence de l'additif à tester, et d'un tissue sali. Les conditions expérimentales sont les suivants :To measure the anti-depositing properties, the method used consists of washing tissue samples several times in the presence of the additive to be tested, and of soiled tissue. The experimental conditions are as follows:
Cinq cycles de lavage cumulés sont effectués selon les conditions suivants :
- Température de lavage : 60 °C
- Durée du lavage : 20 mn (7 mn de montée en température et 13 mn à 60°C. La vitesse d'agitation est de 100 coups/mn
- Dilution : ajout de 250 ml d'eau dure froide suivie de 5 mn d'agitation
- 3 rinçages de 5 mn en présence de 500 ml d'eau dure froide
- Dureté de l'eau (33°francais : 330 mg CaCO₃/l)
- Séchage des tissus par deux passages successifs sur glaceuse photo
- Mesure de réflectance : photomètre GARDNER filtre Y, 4 épaisseurs de tissus.Five cumulative washing cycles are carried out under the following conditions:
- Washing temperature: 60 ° C
- Washing time: 20 min (7 min rise in temperature and 13 min at 60 ° C. The stirring speed is 100 strokes / min
- Dilution: addition of 250 ml of cold hard water followed by 5 minutes of stirring
- 3 rinses of 5 min in the presence of 500 ml of cold hard water
- Water hardness (33 ° French: 330 mg CaCO₃ / l)
- Drying of the fabrics by two successive passes on a glazing machine photo
- Reflectance measurement: GARDNER photometer, Y filter, 4 fabric thicknesses.
Coton 405 )
Polyester coton (PE/C) 7406 ) Origine TESTFABRIC
Polyester "Dacron 54" (PE) )
Cotton 405)
Polyester cotton (PE / C) 7406) Origin TESTFABRIC
Polyester "Dacron 54" (PE))
- KREFELD WFK (Alderstrasse, 44, Lieferschein)
- EMPA (COTON Saint GALLEN EMPA, laboratoire d'essai des matériaux ; Unterstrasse 11, case postale, CH 9001, ST GALL).
- KREFELD WFK (Alderstrasse, 44, Lieferschein)
- EMPA (COTTON Saint GALLEN EMPA, materials testing laboratory; Unterstrasse 11, PO Box, CH 9001, ST GALL).
Tergotomètre (HOBOKEN, N, J, United state testing Co, Inc.)(2 pots par essai)
- chaque pot du tergotomètre contient :
. 4 éprouvettes de coton (10 × 12 cm)
. 4 éprouvettes de PE/C (10 × 12 cm)
. 4 éprouvettes de polyester (10 × 12 cm)
. 4 éprouvettes de coton sali KREFELD (10 × 12 cm) ou :
4 éprouvettes de coton sali KREFELD et
2 éprouvettes de coton sali EMPA (10 × 12 cm)
. 500 ml de solution lessivielle (la concentration lessivielle est de 6g/l.)
. Rapport de bain 1/25Tergotometer (HOBOKEN, N, J, United state testing Co, Inc.) (2 pots per test)
- each pot of the tergotometer contains:
. 4 cotton test tubes (10 × 12 cm)
. 4 PE / C test pieces (10 × 12 cm)
. 4 polyester test pieces (10 × 12 cm)
. 4 KREFELD soiled cotton test tubes (10 × 12 cm) or:
4 KREFELD soiled cotton test tubes and
2 EMPA soiled cotton test tubes (10 × 12 cm)
. 500 ml of detergent solution (the detergent concentration is 6g / l.)
. Bath ratio 1/25
La mesure de réflectance Ry est effectuée à l'aide d'un photomètre GARDNER filtre y sur 4 épaisseurs de tissus. Un additif est d'autant plus efficace que la réflectance du tissu lavé 5 fois en sa présence, selon le test décrit ci-dessus, est importante et se rapproche de celle du tissu propre (Ry = 83 %). Les produits testés sont particulièrement actifs sur fibres synthétiques, ainsi que sur mélange de fibres. Les mesures de réflectance présentées dans les tableaux sont relatives uniquement aux tissus polyester.The reflectance measurement R y is carried out using a GARDNER photometer filter y on 4 thicknesses of tissue. An additive is all the more effective as the reflectance of the fabric washed 5 times in its presence, according to the test described above, is important and approaches that of the clean fabric (R y = 83%). The products tested are particularly active on synthetic fibers, as well as on a mixture of fibers. The reflectance measurements presented in the tables relate only to polyester fabrics.
Nous avons étudié l'influence des paramètres suivants sur l'efficacité antiredéposante des produits :
- la nature et le taux de l'acide,
- le taux de polyester sulfoné,.
- l'hydrolyse des fonctions acétate.We have studied the influence of the following parameters on the anti-depositing efficacy of products:
- the nature and the level of the acid,
- the rate of sulfonated polyester ,.
- hydrolysis of acetate functions.
Dans les tableaux ci-dessous, les taux des constituants acétate de vinyle, acide crotonique ou acrylique et polyester sulfoné sont exprimés en pourcentagte pondéral. Les performances des meilleurs additifs sont comparées à celles de l'additif commercial F4M (éther de cellulose DOW CHEMICAL).In the tables below, the levels of the components vinyl acetate, crotonic acid or acrylic and sulfonated polyester are expressed in weight percentages. The performance of the best additives is compared to that of the commercial additive F4M (DOW CHEMICAL cellulose ether).
La composition pondérale de la formule lessivielle utilisée est la suivante :
Alkybenzène sulfonate de sodium 7 %
Stéarate de sodium 3 %
Cémulsol® DB 6/18 2,5 %
Cémulsol® LA 90 2,5 %
Tripolyphosphate de sodium 28,75%
Pyrophosphate de sodium 2 %
Orthophosphate de sodium 0,5 %
Diisilicate de sodium 9,35%
Sulfate de sodium 17,5 %
Tinopal® SOP 0,2 %
Tinopal® DMS X 0,2 %
Esperase enzyme Novo 0,3 %
Perborate de sodium 25 %
Magilex® 120 1 %
E.D.T.A. de sodium 0,2 %The weight composition of the detergent formula used is as follows:
Sodium alkybenzene sulfonate 7%
Sodium stearate 3%
Cémulsol® DB 6/18 2.5%
Cémulsol® LA 90 2.5%
Sodium tripolyphosphate 28.75%
Sodium pyrophosphate 2%
Sodium orthophosphate 0.5%
Sodium diisilicate 9.35%
Sodium sulfate 17.5%
Tinopal® SOP 0.2%
Tinopal® DMS X 0.2%
Esperase enzyme Novo 0.3%
Sodium perborate 25%
Magilex® 120 1%
0.2% sodium EDTA
Performance de différents latex du premier type :
Performance of different latexes of the first type:
On ajoute en post-addition les produits cités dans le tableau I, la concentration en lessive est de 6 g/l, contenant 0,42 % d'additif. Chaque échantillon de tissu est lavé 5 fois en présence de la salissure.
L'essai référencé blanc correspond aux cinq lavages de tissus en présence de salissures et en absence d'additif.The test referenced white corresponds to the five washes of fabrics in the presence of soiling and in the absence of additive.
Etude en fonction de la concentration dans la lessive :
Study according to the concentration in the detergent:
Conformément à l'exemple 1, on réalise différents tests en modifiant la concentration en additif dans le bain lessiviel.
- ajout en post addition à différentes concentrations.
- concentration en lessive 6g/1.
- salissure KREFELD
- addition in post addition at different concentrations.
- detergent concentration 6g / 1.
- KREFELD soiling
Influence de la salissure :
- ajout du latex en post addition à concentration constante dans le bain = 25 ppm.
- concentration en lessive 6g/l
- salissures KREFELD + EMPA
- addition of latex in post addition at constant concentration in the bath = 25 ppm.
- detergent concentration 6g / l
- KREFELD + EMPA soiling
Avec le mélange de salissures, l'éther de cellulose amplifie la redéposition alors que les additifs revendiqués restent efficaces.With the mixture of soils, the cellulose ether amplifies the redeposition while the claimed additives remain effective.
Introduction de l'additif 5 dans une bouillie pour atomisation ("slurry").
Introduction of the additive 5 into a spray mixture ("slurry").
Dans un "slurry", le pH alcalin, la force ionique et la température élevée tendent à dégrader les produits fragiles, par conséquent, la lessive obtenue à partie d'un slurry contenant l'additif a été testée.In a "slurry", the alkaline pH, the ionic strength and the high temperature tend to degrade the fragile products, therefore, the detergent obtained from a slurry containing the additive has been tested.
Les ingrédients habituels d'une lessive tels que le TPP, les tensio actifs ioniques, le silicate de sodium, le sulfate de sodium et l'eau sont mélangés pour former une bouillie qui constitue "le slurry". Ce mélange très alcalin est ensuite séché par atomisation pour obtenir une poudre. Les tensio actifs non ioniques, les agents de blanchiment, les enzymes et les parfums sont ensuite rajoutés.The usual ingredients of a detergent such as TPP, ionic surfactants, sodium silicate, sodium sulfate and water are mixed to form a slurry which constitutes "the slurry". This very alkaline mixture is then spray dried to obtain a powder. Non-ionic surfactants, bleaches, enzymes and perfumes are then added.
Deux slurries ont été préparés ; l'additif 5 est rajouté à l'un des slurries. Pour simuler l'hydratation du TPP et l'atomisation ces mélanges sont maintenus 1h30 à 90°C sous agitation. Dans ces conditions de pH et de température, l'additif 5 est totalement hydrolysé ; les groupements acétate de vinyle sont transformés en alcool vinylique. Trois formules ayant même composition globale que précédemment, voir formule page 7, ont été préparées à partir des slurries et testées dans les conditions expérimentales identiques à celles décrites à l'exemple 1.Two slurries have been prepared; additive 5 is added to one of the slurries. To simulate the hydration of TPP and the atomization, these mixtures are maintained for 1 hour 30 minutes at 90 ° C. with stirring. Under these pH and temperature conditions, the additive 5 is completely hydrolyzed; the vinyl acetate groups are transformed into vinyl alcohol. Three formulas having the same overall composition as above, see formula on page 7, were prepared from the slurries and tested under the experimental conditions identical to those described in Example 1.
Les caractéristiques des formules préparées sont les suivantes :
formule X : préparée à partir du slurry témoin sans additif.
formule Y : préparée à partir du slurry témoin sans additif, l'additif no 5 est introduit en post addition à raison de 0,42 % de la formule,
formule Z : préparée à partir du slurry contenant d'additif no 5, le pourcentage pondéral en additif no 5 dans le formule est de 0,42 %.The characteristics of the formulas prepared are as follows:
formula X: prepared from the control slurry without additives.
Y formula: prepared from the slurry control without additive, the additive No. 5 is introduced in post addition at 0.42% of the formula,
Z formula: prepared from the slurry containing 5 No. Additive, weight percent of additive No. 5 in the formula is 0.42%.
Les valeurs des réflectances Ry du tissu dacron obtenues avec ces formules sont reportées sur le tableau IV suivant :
Les résultats obtenus avec l'additif 5 introduit dans un slurry sont du même ordre de grandeur que ceux obtenus lorsque cet additif est introduit dans le bain lessiviel. Le produit conserve ses propriétés antiredéposantes lorsqu'il est introduit dans un slurry.The results obtained with the additive 5 introduced into a slurry are of the same order of magnitude as those obtained when this additive is introduced into the detergent bath. The product retains its anti-depositing properties when introduced into a slurry.
Cet exemple illustre qu'après hydrolyse, les polymères de l'invention conservent leur activité.This example illustrates that after hydrolysis, the polymers of the invention retain their activity.
Pour mesurer les propriétés anti-salissures, la méthode utilisée consiste à laver des échantillons de tissus en présence de l'additif à tester, à déposer des tâches sur ces tissus et à les relaver. Les résultats obtenus traduisent l'affinité des textiles ainsi conditionnés pour une salissure. Les conditions expérimentales sont les suivantes.
Linitest HANAU (2 pots par essai) Chaque pot de linitest contient :
. Température de lavage : 60°C,
. Durée du lavage : 40 mm (25 mn de montée en température et 15 mm à 60°C,
. Dilution : ajout de 150 ml d'eau dure froide suivie de 5 mn d'agitation,
. 3 rinçages de 5 mn en présence de 400 ml d'eau dure froide,
. Dureté de l'eau (33° TH),
. Séchage des tissus par deux passages successifs sur glaceuse photo,
. Mesure de réflectance : photomètre GARDNER filtre Y, 4 épaisseurs de tissus.
. Washing temperature: 60 ° C,
. Washing time: 40 mm (25 min rise in temperature and 15 mm at 60 ° C,
. Dilution: addition of 150 ml of cold hard water followed by 5 minutes of stirring,
. 3 rinses of 5 min in the presence of 400 ml of cold hard water,
. Water hardness (33 ° TH),
. Drying of the fabrics by two successive passes on a photo glazing machine,
. Reflectance measurement: GARDNER photometer, Y filter, 4 fabric thicknesses.
Huile de vidange de voiture.
Car drain oil.
. Conditionnement : on effectue un cycle de lavage en présence de l'additif à tester. L'additif peut être introduit soit dans le bain lessiviel, soit au cours du rinçage.
. Tachage : à l'aide d'une burette, on dépose 4 gouttes d'huile de vidange au centre de l'échantillon de tissu disposé sur un "verre de montre". Les tissus sont ensuite mis à l'étuve à 60°C pendant une heure. On salit ainsi la moitié des échantillons.
. Mesure de la réflectance des tissus tachés (GARDNER, filtre Y).
. Lavage : on opére de la même façon que pour le conditionnement, mais en absence d'additif. Chaque pot de linitest contient ainsi deux échantillons tachés et deux échantillons non tachés de chaque qualité de tissu.
. Mesure de la réflectance après lavage (GARDNER, filtre Y). La réflectance des tissus tachés indique l'effet antisalissure.
. Packaging: a washing cycle is carried out in the presence of the additive to be tested. The additive can be introduced either into the detergent bath or during rinsing.
. Staining: using a burette, 4 drops of drain oil are placed in the center of the tissue sample placed on a "watch glass". The fabrics are then placed in an oven at 60 ° C for one hour. Half of the samples are thus soiled.
. Measurement of the reflectance of stained fabrics (GARDNER, filter Y).
. Washing: we operate in the same way as for packaging, but in the absence of additive. Each linitest jar thus contains two stained samples and two non-stained samples of each quality of fabric.
. Reflectance measurement after washing (GARDNER, filter Y). The reflectance of stained fabrics indicates the anti-fouling effect.
Les résultats concernant l'enlèvement des salissures sont exprimés sous la forme de la valeur de la "rémission" R :
R₀: réflectance du tissu non sali, avant lavage,
R₁: réflectance du tissu sali, après lavage.The results concerning the removal of soiling are expressed in the form of the value of the "remission" R:
R₀: reflectance of the soiled fabric, before washing,
R₁: reflectance of soiled fabric, after washing.
Plus la rémission R est élevée, plus est grande l'efficacité de l'additif comme agent anti-salissure.The higher the remission R, the greater the effectiveness of the additive as an anti-fouling agent.
Cet exemple illustre l'utilisation de différents latex dont les caractéristiques sont données dans les tableaux V et VI.
Au cours des essais, les produits sont ajoutés au milieu à un pH tel qu'ils restent sous forme de suspension (ajout au troisième rinçage), la solubilisation du latex ne s'effectuant qu'au lavage suivant (où le pH augmente).During the tests, the products are added to the medium at a pH such that they remain in the form of a suspension (addition on the third rinse), the solubilization of the latex only taking place during the following washing (where the pH increases).
La composition de la formule utilisée est la suivante :
TPP 21,5 %
Pyrophosphate neutre 2 %
Phosphate trisodique neutre anhydre 0,5 %
Silicate 3Na 8,6 %
Stéarate de 3Na 3,0 %
TINOPAL DMSX® 0,2 %
TINOPAL SOP® 0,2 %
ESPERASE NOVO® 0,3 %
Perborate (Air liquide) 25,0 %
EDTA 0,2 %
LABS neutre 7,0 %
CEMULSOL 6/18® 2,5 %
CEMULSOL LA 90® 2,5 %
Sulfate de Na 24 %The composition of the formula used is as follows:
TPP 21.5%
2% neutral pyrophosphate
0.5% anhydrous neutral trisodium phosphate
Silicate 3Na 8.6%
3.0N stearate 3.0%
TINOPAL DMSX® 0.2%
TINOPAL SOP® 0.2%
ESPERASE NOVO® 0.3%
Perborate (Air liquid) 25.0%
EDTA 0.2%
LABS neutral 7.0%
CEMULSOL 6 / 18® 2.5%
CEMULSOL LA 90® 2.5%
Na sulfate 24%
Au cours de chaque groupe d'essais les produits testés (un à trois) sont comparés à un essai en absence d'additif. Les résultats obtenus sont donnés dans le tableau suivant :
Ces résultats confirme l'effet anti-salissure des différents latex alcali-solubles testés.These results confirm the anti-fouling effect of the various alkali-soluble latexes tested.
Cet exemple illustre l'utilisation de quelques latex alcali-solubles à des concentrations variables. Les conditions expérimentales sont les mêmes que pour l'exemple 5. Les résultats obtenus ont été portés sur le tableau suivant.
Ces résultats confirment l'effet anti-salissure des latex alcali-solubles pour plusieurs concentrations en additif.These results confirm the anti-fouling effect of alkali-soluble latexes for several concentrations of additive.
Le test utilisé au cours des exemples qui suivent a pour but d'évaluer les propriétés anti-redéposantes d'un additif donné.The purpose of the test used during the examples which follow is to evaluate the anti-redepositing properties of a given additive.
La méthode utilisée consiste à laver des échantillons de tissus en présence de l'additif à tester, et de salissures déposées sur des mèches de coton. Les résultats obtenus traduisent l'affinité des textiles ainsi conditionnés pour une salissure. Les conditions expérimentales sont les suivantes.The method used consists of washing tissue samples in the presence of the additive to be tested, and of dirt deposited on cotton wicks. The results obtained reflect the affinity of the textiles thus conditioned for soiling. The experimental conditions are as follows.
Linitest HANAU (2 pots par essai) (tergotomètre automatisé)
Chaque pot du Linitest contient :
Each Linitest jar contains:
. Température de lavage : 60°C,
. Durée du lavage : 40 mn (25 mn de montée en température et 15 mn à 60°C,
. Dilution : ajout de 150 ml d'eau dure froide suivi de 5 mn d'agitation,
. 3 rinçages de 5 mn en présence de 400 mnl d'eau froide,
. Dureté de l'eau : 33°TH,
. Séchage des tissus par deux passages successifs sur glaceuse photo,
. Mesure de réflectance : photomètre GARDNER filtre Y, 4 épaisseurs de tissus.
. Washing temperature: 60 ° C,
. Washing time: 40 min (25 min rise in temperature and 15 min at 60 ° C,
. Dilution: addition of 150 ml of cold hard water followed by 5 minutes of stirring,
. 3 rinses of 5 min in the presence of 400 min of cold water,
. Water hardness: 33 ° TH,
. Drying of the fabrics by two successive passes on a photo glazing machine,
. Reflectance measurement: GARDNER photometer, Y filter, 4 fabric thicknesses.
"Spangler" (sébum + particules)
"Spangler" (sebum + particles)
- Conditionnement : on effectue un cycle de lavage en présence de l'additif à tester et d'une salissure imprégnée sur des mèches de coton. L'additif peut être introduit soit dans le bain lessiviel, soit au cours du rinçage.
- Mesure de la réflectance des tissus tachés (GARDNER, filtre Y).
- Lavage : on opère de même façon que pour le conditionnement, mais en absence d'additif. Chaque pot de linitest contient ainsi deux échantillons tachés et deux échantillons non tachés de chaque qualité de tissu.
- Mesure de la réflectance après lavage (GARDNER filtre Y). La réflectance des tissus tachés indique l'effet antisalissure.
- Conditioning: a washing cycle is carried out in the presence of the additive to be tested and of soiling impregnated on cotton wicks. The additive can be introduced either into the detergent bath or during rinsing.
- Measurement of the reflectance of stained fabrics (GARDNER, filter Y).
- Washing: the procedure is the same as for packaging, but in the absence of an additive. Each linitest jar thus contains two stained samples and two non-stained samples of each quality of fabric.
- Measurement of reflectance after washing (GARDNER filter Y). The reflectance of stained fabrics indicates the anti-fouling effect.
Les résultats concernant l'anti-redéposition des salissures sont exprimés sous la forme de la valeur de la différence delta R de réflectance avant et après lavage et de l'efficacité E
Delta R : R₀ - R₂ :
R₀: réflectance du tissu, avant lavage,
R₁: réflectance du tissu blanc non lavé.
Plus la rémission delta R est faible, plus est grande l'efficacité de l'additif comme agent anti-redéposition.The results concerning the anti-redeposition of soiling are expressed in the form of the value of the difference delta R of reflectance before and after washing and of the efficiency E
Delta R: R₀ - R₂:
R₀: reflectance of the fabric, before washing,
R₁: reflectance of unwashed white fabric.
The lower the delta R remission, the greater the effectiveness of the additive as an anti-redeposition agent.
Cet exemple a pour but de mettre en évidence l'effet anti-redéposant d'un latex alcali-soluble en présence d'une formule dont le builder ou l'adjuvant de lavage est constitué par du tripolyphosphate (TPP) et de la zéolite 4A.The purpose of this example is to demonstrate the anti-redepositing effect of an alkali-soluble latex in the presence of a formula in which the builder or the washing aid consists of tripolyphosphate (TPP) and zeolite 4A .
La composition de la formule utilisée est la suivante :
TPP 19,0 %
Zéolite 17,0 %
Sulfate de Na 9,5 %
Pyrophosphate neutre 2,0 %
Na₃PO₄ anhydre 0,5 %
Silicate 3Na 8,6 %
BLANOSE BWS 1,5 %
TINOPAL DMSX® 0,2 %
TINOPAL SOP® 0,2 %
ESPERASE NOVO® 0,3 %
Perborate 25,0 %
Stéarate de Na 3,0
LABS 7,0
CEMULSOL 6/18® 2,5 %
CEMULSOL LA 90® 2,5 %
EDTA 0,2 %
H₂O 1,0 %The composition of the formula used is as follows:
TPP 19.0%
Zeolite 17.0%
9.5% Na sulfate
Neutral pyrophosphate 2.0%
Anhydrous Na₃PO₄ 0.5%
Silicate 3Na 8.6%
BLANOSE BWS 1.5%
TINOPAL DMSX® 0.2%
TINOPAL SOP® 0.2%
ESPERASE NOVO® 0.3%
Perborate 25.0%
Na 3.0 stearate
LABS 7.0
CEMULSOL 6 / 18® 2.5%
CEMULSOL LA 90® 2.5%
EDTA 0.2%
H₂O 1.0%
Cet exemple illustre l'utilisation de différents latex à une concentration de 100 ppm dans une formule lessivielle ayant une concentration de 6 g/l de bain.
Claims (16)
- de 84 à 96 % d'acétate de vinyle,
- de 3 à 6 % d'acide crotonique ou acrylique ou un de ses dérivés,
- 1 à 10 % de polyester sulfoné.6 - Latex according to claims 1 to 5 characterized in that they contain by weight
- from 84 to 96% vinyl acetate,
- from 3 to 6% of crotonic or acrylic acid or one of its derivatives,
- 1 to 10% of sulfonated polyester.
- de 87 à 94 % d'acétate de vinyle,
- de 4 à 5 % d'acide crotonique ou acrylique,
- 2 à 8 % de polyester sulfoné.7 - Latex according to claim 6, characterized in that it contains:
- from 87 to 94% vinyl acetate,
- from 4 to 5% of crotonic or acrylic acid,
- 2 to 8% of sulfonated polyester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT87402917T ATE57713T1 (en) | 1986-12-24 | 1987-12-18 | LATEX AGAINST POLLUTION WHEN WASHING TEXTILES. |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8618471A FR2609065B1 (en) | 1986-12-24 | 1986-12-24 | NOVEL WASHING AGENTS AND COMPOSITIONS CONTAINING SAME |
| FR8618471 | 1986-12-24 | ||
| FR8707279 | 1987-05-20 | ||
| FR8707279A FR2615526B1 (en) | 1987-05-20 | 1987-05-20 | LATEX ANTIFOULING AND ANTIREPOSITORS FOR AQUEOUS WASHING OF TEXTILE ARTICLES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0279134A1 true EP0279134A1 (en) | 1988-08-24 |
| EP0279134B1 EP0279134B1 (en) | 1990-10-24 |
Family
ID=26225690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87402917A Expired - Lifetime EP0279134B1 (en) | 1986-12-24 | 1987-12-18 | Antiredeposition latex for washing textiles |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4925588A (en) |
| EP (1) | EP0279134B1 (en) |
| DE (1) | DE3765773D1 (en) |
| DK (1) | DK684387A (en) |
| ES (1) | ES2018568B3 (en) |
| PT (1) | PT86467B (en) |
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- 1987-12-18 ES ES87402917T patent/ES2018568B3/en not_active Expired - Lifetime
- 1987-12-18 DE DE8787402917T patent/DE3765773D1/en not_active Expired - Fee Related
- 1987-12-18 EP EP87402917A patent/EP0279134B1/en not_active Expired - Lifetime
- 1987-12-23 PT PT86467A patent/PT86467B/en not_active IP Right Cessation
- 1987-12-23 DK DK684387A patent/DK684387A/en not_active Application Discontinuation
- 1987-12-23 US US07/137,232 patent/US4925588A/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| DE3765773D1 (en) | 1990-11-29 |
| EP0279134B1 (en) | 1990-10-24 |
| DK684387D0 (en) | 1987-12-23 |
| PT86467A (en) | 1988-01-01 |
| US4925588A (en) | 1990-05-15 |
| DK684387A (en) | 1988-06-25 |
| PT86467B (en) | 1991-02-08 |
| ES2018568B3 (en) | 1991-04-16 |
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