DE9107984U1 - Liquid, aqueous, viscous surfactant system - Google Patents

Claims (15)

LEDERER, KELLER & RIEDERER dr. &agr;. van der werth Patent Attorneys - European Patent Attorneys ₍ 1934 -1 a, 4) CR. FRAXZ LEDERER Dipl. -Ch'H-i. Minchen DR. GÜNTER KELLER Dipl.-Biol. Munich ANTON BARON RIEDERER v. PAAR Dipl.-Ing. Landshut 8000 MUNICH 80 Lucile-Grahn-Straße 22 Telephone (089) 47 29 47 Telex 524 624 leather d Fax (089) 470 57 23 28 June 1991 Joh. A. Benckiser GmbH Benckiserplatz 1
6700 Ludwigshafen 1 Liquid, aqueous, viscous surfactant system The present invention relates to a liquid, aqueous, viscous surfactant system containing a cationic surfactant, a thickener and optionally other conventional additives. Such surfactant systems are used, among other things, as textile softeners and the invention relates in particular to textile softeners. It is known that textile softeners based on cationic surfactants occasionally show instabilities - especially when they contain higher amounts of electrolyte. It is also known that textile softeners based on cationic surfactants have different viscosities at different temperatures and therefore different washing-in behavior. In addition, commercially available textile softeners with low levels of cationic surfactants have a viscosity and stability that decreases with increasing temperature. Commercially available fabric softeners with high contents of cationic surfactants can experience an increase in viscosity when stored at elevated temperatures - which prevents sufficiently good distribution in the fabric softener liquor. Systems with the lack of instability - with high contents of K-surfactants - are also known. These deficiencies impair the performance properties of textile softeners. EP-A 331 237 describes liquid, aqueous, viscous textile softeners in which the high viscosity desired for such agents is achieved by means of hydrophobic non-ionic cellulose ethers. According to EP-A 51 983, guar gum, mixtures of guar and xanthan gum, polyvinyl acetate or polyacrylamide are used as thickeners in textile softeners. According to EP-A 239 910, polymers such as hydroxy ethers of cellulose, block copolymers of terephthalic acid and polyethylene oxide or polypropylene oxide and cationic guar gums are used as soil release agents. Cellulose products and xanthan derivatives are anion-active, coagulate easily and are therefore incompatible with other components of fabric softeners. In addition, cellulose products often have long swelling times. The object of the present invention was therefore to find a thickener, in particular for textile softeners, which guarantees a viscosity that changes little with temperature, remains stable during storage, is compatible with other components and is easy to process. It has been found that polyurethane products marketed under the trademark RHEOLATE (trademark of Rheox Inc.) are excellently suited to the inventive solution of the problem. Rheolates (e.g. Rheolate 255 and Rheolate 278) are polyurethane-based rheological additives for emulsion paints. They are marketed as a polyurethane solution (25%) in a water/butyldiglycol mixture (80/20). They are recommended as additives with a high thickening effect in the medium and high shear range for emulsion paints, emulsion varnishes and emulsion paints. They are intended to increase the brush resistance and give the emulsion paints paint-like properties. It is warned that the thickening effect can be influenced by solvents, film-forming agents or surfactants. Surprisingly, it was found that these products, which are known for emulsion paints, which have a much higher viscosity, are excellently suited to setting optimal viscosities in aqueous textile softeners. They are effective in very small quantities, where they are ineffective in water, which makes them easier to handle during production, and only develop the desired viscosity when the cationic surfactants are added. The viscous viscosity of the surfactant systems adjusted with them does not change significantly with temperature and remains stable during storage, so that even pigment-like additives remain in suspension. With other thickeners, on the other hand, it is difficult to obtain stable pigment-containing dispersions. The liquid, aqueous, viscous surfactant systems according to the invention contain one or more cationic surfactants, a thickener and optionally other conventional additives and are characterized in that the thickener is a polyurethane-based rheological additive. Particularly suitable additives according to the invention are those which, like the polyurethane products known under the trademark RHEOLATE, are present as a solution in a water/butyldiglycol mixture. The polyurethane generally has a molecular weight of 30,000-70,000. To achieve optimum viscosity, the surfactant system generally contains 0.005-5% by weight, preferably 0.02-1% by weight of polyurethane. The surfactant systems according to the invention can be made acidic by adding acids. It is known that surfactant mixtures, when made acidic, have a tendency to cream and are unstable. Surprisingly, it has been shown that acidic surfactant systems with good, stable viscosity can be obtained by adding polyurethane according to the invention. The surfactant systems according to the invention therefore also include those which are acidic, in particular acidic surfactant systems for cleaning hard surfaces, furthermore rinse agents for machine washing of laundry and in particular textile softeners. The surfactant systems according to the invention generally have a viscosity of 20-250, preferably 25-40 mPas. Textile softeners preferably have a viscosity of 30-40 mPas. The surfactant systems according to the invention can also additionally contain a non-ionic surfactant. The additional use of a non-ionic surfactant and optionally also an anionic surfactant is particularly preferred for acidic surfactant mixtures for cleaning hard surfaces. Acids suitable for acidification include citric acid, adipic acid, glutaric acid, succinic acid. Acetic acid can also be used, although monocarboxylic acids are generally not preferred, since the acid should also exhibit calcium binding capacity. For this reason, citric acid is preferred. The amount of acid is not critical and is generally 3-20% by weight. In fabric softeners, 5% by weight is often sufficient; if lime-dissolving power is required, up to 20% by weight can be used. A surfactant system according to the invention can consist of 3-25 wt.% cationic surfactants, e.g. 22 wt.% tetranyl AT75
1-10 wt.% non-ionic surfactants, e.g. 1 wt.% 1618/35E 0.02-1 wt.% polyurethane, e.g. 0.13 wt.% Rheolate 50-97 wt.% water
The remainder consists of optional components. It may contain >0-5 wt.% pigment dyes. Cationic surfactants can include a) Compounds of the general formula R- wherein R ₁ and R ₂ represent hydrocarbon groups having 16 to 22 carbon atoms, R ₃ and R ₄ represent hydrocarbon groups having 1 to 4 carbon atoms, X represents an anion, e.g. chloride or methosulphate, and m represents an integer from 1-3,
or b) Imidazoline compounds of the general formula R ₁ - C N- _CH2 - _CH2 - NH - C \ O _CH2 \ _{CH2 R1} where R^ is a straight-chain or branched-chain hydrocarbon group having 8-25 carbon atoms and R ₂ is a hydrogen atom or a hydrocarbon group having 1-4 carbon atoms and X is an anion, or c) textile softening compounds such as alkylated amidoamines
the general formula R ₁ - CO - NH - CH ₂ - CH ₂ - N - R _{3 CH3} where R ₁ is a straight-chain or branched-chain hydrocarbon group with 8-25 carbon atoms, R ₂ , R3 are hydrocarbon groups with 1-4 carbon atoms and X is an anion
or d) Fatty acid derivatives such as Glycerol monostearate or mixtures of glycerol mono- and di-stearate, or e) Fatty acid amidoxyethylate of the general formula C-N- ( _CH2 - _CH2-0 ). - H in which R^ is a straight-chain hydrocarbon group with 12 to 24 carbon atoms f) Esterquats of the general formula R ₁ - COC- CH ₂ -CH ₂ R ₂ - COO- CH ₂ - CH _{2 CH2} - _CH2 - CH in which R ₁ and R2 are a straight-chain hydrocarbon group having 12 to 24 carbon atoms and R ₂ is a hydrocarbon group having 1 to 4 carbon atoms and A is an anion or g) Esterquats of the general formula - COO - CH ₂ - CH _{CH2 - CH2} -CHCH2- _CH2 -OH _{CH3SO4 ​} in which R2 is a straight-chain hydrocarbon group having 12 to 24 carbon atoms and R£ is a hydrocarbon group having 1 to 4 carbon atoms, can be used alone or in combination with one another. Pseudoquats are particularly preferred. A particularly preferred combination according to the invention consists of surfactants, which, together with the acids used, produce pseudoquats and which, according to the invention, are used together with the polyurethane. If the pseudoquats are used in rinse aids for machine washing of laundry, the additional advantage is that the rinse aid has a fabric softener effect. For acidic cleaners for hard surfaces, the use of ν,ν-dimethyloleylamine is preferred, as it also acts as a corrosion inhibitor. A preferred acidic surfactant system for cleaning hard surfaces consists of 0.5-5 % by weight cationic surfactant 1-5 % by weight non-ionic surfactant 3-20 % by weight citric acid 0.2-1 wt.% polyurethane 75-95 wt.% water rest optional components and has a viscosity of 20-250 mPas. Optional components are in particular polyacrylic acid and Polymers of acrylic acid and methacrylic acid. Examples of surfactant systems according to the invention and their properties can be found in Tables I, II and III below. Examples 1, 5 in Table I, 1, 3, 5 in Table II and A in Table III are comparative examples. Table I Concentrates 1 2 3 4 5 6 7 8th 9 10 11 Dialkyldimethyl-
ammonium chloride
(Präpagen WK)
(Prepagen WKL) 13.0 13.0 6.5 ImidazoliniummethosuHat
(Rewoquat W 7500) 6.5 6.5 6.5 Esterquats
(Tetranyl AT-7b)
(Rewoquat WE 18)
(Rewoquat WE 20)
(Tetranyl AT 1)
(Tetranyl AHT 1)
(Stepantex VS 90)
Tallow alcohol oxethylate
(Find 1618/35E)
Calcium chloride 0.2 0.2 22.3
1.5
0.2 22.3
1.5
0.2 15.0
0.07 5.0 5.0
1.0 5.0
1.0 15.0
0.07 Citric acid
acetic acid
Rheolate 278 0.10 0.08 0.25 0.13 0.17 0.22 5.0
0.07 5.0
0.07 5.0
(-.25 Pigmogol Blue 6900 0.006 0.006 0.002 0.002 0.002 0.006 0.006 0.002 0.002 0.002 0.000 Perfume 0.7 0.7 0.3 0.3 0.9 0.9 0.7 0.3 0.3 0.3 0.7 Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 1CC Viscosity after
Approach (mPas) 10 32 33 27 8th 26 27 25 40 43 30 Viscosity after
4 weeks at 40 ⁰ C Product is homogeneous
after storage no Yes Yes Yes no Yes Yes Yes Yes Yes Yes Table II 1 2 - 3 - 4 5 6 - 7 8th 9 10 11 Trialkylamine
(Armies M2HT) 2.5 2.5 15 2.5 15 2.5 15 2.5 2.5 4.5 2.5 Imidazoline
(Rewoquat V 2736) - - 0.03 - · 2.5 2.5 0.02 - - - - - Amidoamine
Rewoquat V 2748 2.5 2.5 0.3 0.3 - - - 0.3 - - - Triethanol difatty acid esters
(Rewoquat V 2843) - to 100 2.5 to 100 2.5 2.5 2.5 to 100 2.5 2.5 4.5 2.5 Fatty amine oxethylate
Ethomeen HT 60 1 1 Yes 1 no 1 1 1 Yes 1 1 1 1 1 N.N-Dimethyloleylamine
(Armies DMOD) - 34 11 - - 30 1 - - 0.5 Citric acid
acetic acid
Acid mixture
(Sokaian DCS, adipic acid
Glutaric acid, succinic acid) 15 15 15 20 7.5
7.5 15 15 15 Polyurethan
(Rheolate 278)
(Rheolate 255) - 0.15 - 0.1 0.13 0.04 0.13 0.1 Perfume 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 Storage stable no Yes no Yes Yes Yes Yes Yes viscosity 12 36 17 25 31 34 29 28 Table m Acidic surfactant mixtures for cleaning hard surfaces raw materials A B C D E F G Citric acid 6.50 6.60 6.50 3.50 18.00 - 4.50 Adipin-ZGlutar/
Succinic acid
Sokalan DCS 4.60 Copolymer
Sokalan CP5 - - - 16.00 - 2.60 2.50 Dimethyloleylamine
A'rmen DMOD 1.00 1.00 - 0.76 0.75 1.00 1.00 Amine oxide
Aronox 012 - - 1.20 - - - Non-ionic
Surfactant
Marpal 249 2.00 200 2.00 1.00 3.50 3.60 Rheolate 278 - 0.60 0.60 0.75 0.75 0.60 0.70 NaCl 0.50 050 - - - - - Sodium cumene-
sulfonate - - - 0.15 0.10 0.20 0.20 Perfume + + -I- + + + Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 viscosity 20 170 240 70 66 140 200 Protection claims 1) Liquid, aqueous, viscous surfactant system containing a cationic surfactant, a thickener and optionally other conventional additives, characterized in that the thickener is a polyurethane-based rheological additive. 2) Surfactant system according to claim 1, characterized in that the additive is a polyurethane solution in a water/butyldiglycol mixture. 3) Surfactant system according to claim 1 or claim 2, characterized in that the polyurethane has a molecular weight of 30,000-70,000. 4) Surfactant system according to one of the preceding claims, characterized in that it contains 0.005-5, preferably 0.02-1 wt.% polyurethane. 5) Surfactant system according to one of the preceding claims, characterized in that it contains >0-5 wt.% pigment dye. 6) Surfactant system according to one of the preceding claims, characterized in that it is formulated as a textile softener. 7) Surfactant system according to one of the preceding claims, characterized in that it has a viscosity of 20-250, preferably 25-40 mPas. 8) Surfactant system according to claim 6, characterized in that it has a viscosity of 30-40 mPas. 9) Surfactant system according to one of the preceding claims, characterized in that the surfactant is a pseudoquat. 10) Surfactant system according to one of the preceding claims, characterized in that it is acidic. 11) Surfactant system according to one of the preceding claims, characterized in that it additionally contains a non-ionic surfactant. 12) Surfactant system according to claim 11, characterized in that it consists of 3-25 wt.% cationic surfactants 1-10 wt.% non-ionic surfactants 0.02-1 wt.% polyurethane 50-97 wt% water Remaining optional components consists. 13) Surfactant system according to one of the preceding claims, characterized in that it is formulated as an acidic surfactant system for cleaning hard surfaces. 14) Surfactant system according to claim 13, characterized in that it consists of 0.5-5 wt.% cationic surfactant 1-5 wt.% non-ionic surfactant 3-20 wt.% citric acid 0.2-1 wt.% polyurethane 75-95 wt.% water Remaining optional components and has a viscosity of 20-250 mPas. 15) Surfactant system according to claim 14, characterized in that the cationic surfactant consists entirely or partially of N,N-dimethyloleylamine.