JPH07505181A - liquid detergent - Google Patents

Abstract

Liquid cleaning products based on an aqueous solution of surface-active agents, solvents, solubilizers, corrosion inhibitors, preservatives, thickeners, colorants and perfumes, to which is added a copolymer of acrylic or methacrylic acid esters with 1 to 8 C atoms in the alcohol residue and unsaturated aliphatic carboxylic acids with 3 to 5 C atoms, have a limiting viscosity number [n] equal to or higher than 100 ml . g?-1, measured in tetrahydrofurane at 20 C.

Description

[Detailed description of the invention] liquid detergent Liquid laundry detergents, dishwashing detergents and cleaning products are generally Aqueous solutions of ionic and/or nonionic surfactants and standard additives. Ru. A preferred use of such detergents is manual dishwashing. tableware made by hand The better the fat emulsifying power of a washing detergent, the more effective it is. For example, a certain amount of This is because the number of dishes that can be washed with detergent increases. Therefore, the present invention provides improved The present invention relates to liquid detergents with increased emulsifying power and increased cleaning power.

So-called alkyl ether sulfates, i.e. about 10 to 16 in the alkyl group. of a fatty alcohol having about 2 to 5 moles of ethylene oxide and about 2 to 5 moles of ethylene oxide. Sulfate additives are known to have both great cleaning power and mild effects on the skin. It is. Therefore, commercial hand dishwashing detergents generally contain n-alkyl Rubenzene sulfonate and/or alkanesulfonate, optionally ole Finsulfonates, alkyl sulfates or alkyl sulfosuccinates Other anionic surfactants such as, as well as nonionic surfactants, solubilizers, dyes and aqueous solutions of alkyl ether sulfates in combination with fragrances.

50% by weight C+Z alkyl ether sulfate and 50% by weight ether CI4 atom having 1 to 5, preferably 2 to 4 ethylene oxide groups as a component A mixture of alkyl ether sulfates consisting of alkyl ether sulfate Do not affect the well-known cleaning properties of the corresponding dishwashing detergent. A typically used alkali containing the same components in a weight ratio of 70:30 Unexpectedly even lower skin irritation compared to ether sulfate mixtures. It is also known (German Patent No. 3,011,550).

Finally, amphoteric surfactants of the betaine type generally have a mild effect on the skin. and a significant increase in detergency is obtained by using such surfactants. It is generally known that it is possible. Therefore, for liquids containing the above-mentioned components, Hand dishwashing detergents will be readily accepted.

The present invention relates to liquid detergents, in particular those based on aqueous solutions of anionic surfactants. , optionally nonionic and/or amphoteric surfactants, solvents, solubilizers, corrosion For manual dishwashing in combination with inhibitors, preservatives, thickeners and dyes and fragrances It relates to a detergent, the detergent further comprising: a) 1 to 8 alcohol components; a carbon atom with an ester of acrylic acid and/or methacrylic acid and b) an acyl component; Consisting of unsaturated aliphatic carboxylic acids having 3 to 5 carbon atoms in the tetra The intrinsic viscosity [η] measured at 20°C in hydrofuran (THF) is 100 or more. , a water-soluble, anionic, substantially non-crosslinked copolymer that increases cleaning power. The present invention relates to a detergent characterized by containing: Preferred copolymers are about 80-2 0% by weight, especially about 60-40% by weight of a) and 20-80% by weight, especially 4 It consists of 0 to 60% by weight of b). The alcohol component of ester a) is preferably 1 ~4 carbon atoms, more preferably 1-2 carbon atoms.

The copolymer may contain a small amount, i.e. up to 5% by weight, of e.g. acrylamide or ether. Other radical polymerization is possible, such as (meth)acrylates such as tylhexyl acrylate. It may also contain functional vinyl monomers. The copolymer is an acidic dispersion and in this form Most commonly used. Generally introduced into detergents with a neutral to slightly alkaline pH value. When the copolymers are partially or completely neutralized and dissolved, they are no longer dispersed. It does not exist in that form.

In a preferred embodiment, the aqueous detergent solution according to the invention has essentially the following composition.

5-65% by weight, especially 10-40% by weight of the following surfactants (both A mixture consisting of: 0 to 40% by weight, in particular 4 to 20% by weight, 50 parts by weight of nc+z alkano 1 to 5, preferably 2 to 4 moles of ethylene oxide. and a mixture of sulfates of the corresponding adducts of nC,4 alkanols, 0-40% by weight , in particular 5-20% by weight of one or more other anionic surfactants, 0-20% by weight , especially 1-5% by weight of surface-active betaine, 0-20% by weight, especially 0-5% by weight % of nonionic surfactant, from 0.001 to 1% by weight, especially from 0.005 to 0.05% by weight % by weight, about 80-20% by weight, especially about 60-40% by weight of alcohol component acrylic acids having from 1 to 4 carbon atoms, especially from 1 to 211 carbon atoms; and/or esters of methacrylic acid, and from about 20 to 80% by weight, especially about 40% by weight. ~60% by weight of unsaturated aliphatic carbs having 3 to 5 carbon atoms in the acyl component The intrinsic viscosity measured at 20°C in THF [η is 1001 g - 1 or more, preferably 200■z, g-1 or more, particularly preferably 400■i-g -1 or more copolymer that improves detergency, 0 to 20% by weight, especially 2 to 10% by weight % solvent, 0-10% by weight, especially 0.2-5% solubilizer, 0-10% by weight % by weight, especially 0.5-8% by weight of thickener, 0-5% by weight, especially 0.1-2% by weight % corrosion inhibitors and preservatives, 0-0.1% by weight dyes, 0-1.0% by weight of fragrance oil, and The remainder to 100 weight is water.

The water-soluble anionic copolymers used according to the invention are described, for example, in U.S. Pat. 95.772 or by emulsion polymerization as described in European Patent No. 184.785. Manufactured using known methods. The unsaturated carboxylic acid used for this purpose is preferably an acrylic acid. acid or methacrylic acid.

Similar copolymers crosslinked by polyvalent cations can be used in coating compositions and metals. It is used as a surface preservative (U.S. Pat. No. 2.754.280, U.S. Patent No. 2,7 No. 95.564, European Patent No. 14035, German Patent No. 3024727 and 3434668). Other similar copolymers are used as thickeners for aqueous liquid phases and German Patent No. 3813651 and German Patent No. 31309 No. 92). The copolymer used according to the invention neither thickens nor acts as a flocculant; We believe that it contributes to increasing the cleaning power by increasing the emulsifying power of the cleaning solution. There is nothing in the prior art to suggest this.

The intrinsic viscosity is Bollmelt (B, Voll+uert) "Grundriss" ・Dell Macromolecular Hemi (Gundri6 der makr o+1olecularen Chemie) @ Volume 3, page 55 and below, Nie Ho Determined by the method described in Rumert Verlag, Karlsruhe, 1988. do. In the case of copolymers with ionic groups, the specific viscosity is proportional to the concentration at high concentrations. For example, at low concentrations the viscosity decreases with increasing concentration. Concentration on horizontal axis These co-weights can be plotted with the help of a graph that plots the specific viscosity on the vertical axis. The limiting viscosity of the coalescence can be determined by extrapolating the linearly increasing part at high concentrations to zero concentration. It can be determined by

The sulfate of ethylene oxide adduct to alkanol is expressed by the following formula: % formula % (In the formula, R is a C11 alkyl group and a C14 alkyl group, and n is 1 to 5, preferably Preferably it is 2 to 4, and M is an alkali metal or ammonium ion. ) corresponds to

Other known alkyl ether sulfates are also present in the alkyl component, preferably 9 to 16. is an n-alkylbenzene sulfonate having 12 carbon atoms, the alkyl moiety Alkanesulfonate having 10 to 20, preferably 12 to 18 carbon atoms in 12 to 16, preferably 12 to 14 carbon atoms in the n-alkyl component Olefin sulfonates having 8 to 18 molecules in the alkyl component, preferably Individually or in the same way as alkyl sulfates with 8 to 14 carbon atoms may also be used as additional anionic surfactants in the form of mixtures.

Suitable amphoteric surfactants have the following formula: (wherein R3 is optionally interrupted by a heteroatom or a group of heteroatoms) represents a cl-3 alkyl group. ) It is a betaine compound corresponding to Cl11~1s alkyldimethylcarboxy Methylbetaine and C11-1? Alkylamidopropyldimethylcarboxy Methylbetaine is preferred.

When using a nonionic surfactant, CI-12 alkylbenzene, C3°-1 ゜, preferably CI! -11 alkanol, C3°~1. carboxylic acid alkano 4 to 20, preferably 4 to 10 moles of alkylene oxide, preferably Specifically, it is an ethylene oxide adduct, known by the name Pluronics (registered trademark). adducts of ethylene oxide and polypropylene glycol, and 1 to 5 1 to C11l-111 alkanol reacted with moles of propylene oxide All 7 mol ethylene oxide adducts are suitable. 1 to 10, preferably in the molecule Preferably 1 to 2, more preferably polyglycosides are particularly suitable.

The solvent added as necessary is a lower alkanoate having 1 to 4 carbon atoms in the molecule. ethanol, preferably ethanol and isopropanol.

For example, suitable solubilizers for dyes and fragrances include alkanolamines, alcohols, etc. Polio, such as tylene glycol, 1,2-propylene glycol, and glycerol and alkylbenzene sulfates having 1 to 3 carbon atoms in the alkyl moiety. Honate.

Preferred thickeners are urea, salt, ammonium chloride, which may be used in combination with each other. and magnesium chloride.

Suitable corrosion inhibitors and preservatives include, for example, sodium benzoate, formaldehyde and sodium sulfite. The detergent may also contain standard disinfectants.

The liquid detergent of the invention, illustrated by the following examples, can be prepared by combining the individual components in any order. The mixture was prepared by stirring together and allowing the mixture to stand until there were no bubbles. Anio The surfactant was used in the form of its sodium salt.

Example Preparation of copolymers used according to the invention 55g ethyl acrylate, 35g methacrylic acid, 10g acrylic acid, 8° 3g C+S fatty alcohol l0EO sulfonate sodium salt (30% in water) ), 8.3g nonylphenol 9.5 EO sulfosuccinate sodium salt (30% in water), 0.1 g t-butyl hydroperoxide and 378 g of distilled water was added to the stirrer, reflux condenser, internal thermometer, nitrogen inlet and and a dropping funnel. Degas the mixture and nitrogenize it The mixture was stirred using a <-zinc to prevent oxygen from being contained. Mixture 25 heated to ℃. Na formaldehyde sulfoxylate dissolved in 3 ml H,O Then, 130 mg of fluorine was added from the dropping funnel at a temperature of 25°C. Polymerization reaction starts spontaneously The temperature rose to 55°C. Polymer content of 20% by weight, measured at 20°C in THF. fine particles without agglomerates, with a limiting viscosity [η] of 525 l·gi. Mulsion was obtained.

Example B 55g ethyl acrylate, 25g methacrylic acid, 20g acrylic acid and A polymer emulsion is prepared as in Example A from the same amounts of other ingredients as in Example A. Manufactured. It has a polymer content of 20% by weight and an intrinsic viscosity of 610 ml-g-' degree [η].

Example C 55g ethyl acrylate, 20g methacrylic acid and 25g acrylic acid A 20% by weight polymer emulsion was produced in the same manner as in Example A. it is It had an intrinsic viscosity of 650 ml'g-'.

The abbreviations shown in the table below have the following meanings:

EO: Ethylene oxide As/active substance FAEO3: CI with about 2 EO! /CI4 fatty alcohol ether sulfate Na salt Betaine: C8-1 @ Alkylamidopropyldimethylammonium Betaine A PG600: C+Z~14 alkyl with 1.4 glucose units in the molecule Glucoside Polyox WSR: Polyethylene glycol molecular weight 600.000 (UCC ) Example 1 A commercial dishwashing detergent (I) to which the compounds according to the invention have been added is subjected to the so-called stirring method. Therefore, its effect on so-called fat emulsifying power was tested. In this test detergent The emulsion stability of olive oil in solution was measured. For this purpose, a test of 50 g The solution (10g detergent/40g water) was added to tap water in a 4001Il glass beaker. (hardness 10ad) and 50g of olive oil (Olio Dante (registered trademark)). ) was then poured at room temperature (20-30°C) and heated through a propeller rotating at 1200 rpm. Exactly 2 minutes using a raster roller (blade length 50, material V2A steel) Stir for a while. The stirring blade was located almost at the boundary between the two phases. Next, add the emulsion to 3. Next, pour into a 6cm diameter 2501/ graduated cylinder (2j! scale, industry standard). , aqueous phase separation was measured after 1 and 4 hours. water separated per unit time The lower the amount, the more stable the emulsion and the greater the oil/fat dispersion power of the detergent solution. This means that the cleaning power increases significantly.

FAEO311,5%---------------------- −−−−−−−−−−−−−−−−−−−>FAEO7%−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−1−−− −>Betaine 1.5%−−−−−−−−−−−−−−−−−−−1−−−− −−−−−−−−−−−−−−−−−−−−>Ethanol 5%−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− ----->1 hour later 12 10 6 0 0 0 0 0 Numbers indicate pure activity Represents the weight percent of the substance (AS).

Example 2 Other commercial applications for manual dishwashing detergents of copolymers used according to the invention The effect on the emulsifying power of the formulation (the amount expressed in weight % of AS) was the same as in Example 1. It was measured by the method.

Example No. II a b c d FAEO813%------------------ −1−−−−−−−−>APG 600 5%−−−−−−−−−−−−−− −−−−1−−−−−−−−−−−−−−−−1−−>Betaine 1.2%−1 1−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− >Ethanol 5%−−−−−−−−−−−−−−−−−−−−−−−−− -------------->Cyal H2O) 1 hour later 15 2.3 - 4 4 hours later 48 9 13 18 g The example shows that the emulsifying power of the formulation increases with increasing concentration of the compound according to the invention. Show that.

, PCT/EP 93100660 Continuation of front page

Claims (1)

[Claims] 1. Based on aqueous solutions of anionic surfactants, optionally nonionic and and/or amphoteric surfactants, solvents, solubilizers, corrosion inhibitors, preservatives, thickeners and a liquid dishwashing detergent in combination with a dye and a fragrance, the detergent further comprising: , a) acrylic acid having 1 to 8 carbon atoms in the alcohol component and/or is an ester of methacrylic acid and b) an unsaturated aliphatic carbon having 3 to 5 carbon atoms. Intrinsic viscosity measured at 20°C in tetrahydrofuran (THF) A detergent characterized by containing a copolymer that increases detergency and has [η] of 100 or more. agent. 2. about 80-20% by weight, preferably about 60-40% a) and about 2 0 to 80% by weight, preferably about 40 to 60% by weight of a copolymer consisting of b) The detergent according to claim 1, characterized in that: 3. The alcohol component of ester a) has 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms. The cleaning agent according to claim 1 or 2, having a carbon atom of agent. 4. The unsaturated aliphatic carboxylic acid component of the copolymer is acrylic acid or methacrylic acid. The detergent according to any one of claims 1 to 3, characterized in that it is derived from. 5. Approximately 5-65% by weight, especially 10-40% by weight of at least two A mixture of the following surfactants: 50 parts by weight of nC12 alkali, from 0 to 40% by weight, preferably from 5 to 20% by weight. Sulfuric acid adduct of alcohol with 1 to 5, preferably 2 to 4 moles of ethylene oxide Mixture of sulfates of salts and corresponding adducts of nC14 alkanols, 0-40 wt. % by weight, preferably 5-20% by weight of one or more anionic surfactants, 0-20% by weight %, preferably 1-5% by weight of amphoteric surfactant, 0-20% by weight, preferably 0-5% by weight nonionic surfactant, 0.001-1% by weight, preferably 0.001-1% by weight. 005-0.5% by weight, a) about 80-20% by weight, preferably about 60-40% by weight % by weight of 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, especially is an ester of acrylic acid and/or methacrylic acid having 1 to 2 carbon atoms. and b) about 20-80% by weight, preferably about 40-60% by weight of the acyl component. THF High cleaning performance with an intrinsic viscosity [η] of 100 ml・q-1 or more when measured at 20°C water-soluble anionic copolymer, 0 to 20% by weight, preferably 2 to 10% by weight % solvent, 0-10% by weight, preferably 0.2-5% solubilizer, 0-10% by weight % by weight of thickener, preferably 0.5-8% by weight, 0-5% by weight, preferably 0. 1-2% by weight of corrosion inhibitors and preservatives, 0-0.1% by weight of dyes, 0-1.0% by weight of fragrance oil, and The remainder to 100% by weight is water The cleaning agent according to any one of claims 1 to 4, characterized in that the cleaning agent is made of an aqueous solution of agent.