ES2273076T3 - DETERGENT COMPOSITIONS. - Google Patents

Abstract

Use of a water-soluble random copolymer of vinyl pyrrolidone and vinyl acetate in a laundry detergent composition, comprising an organic surfactant and, optionally, a detergency builder, to improve the oil dirt detergency of the composition.

Description

Detergent compositions.

Technical scope

The present invention relates to compositions laundry detergents containing certain vinyl pyrrolidone copolymers. The compositions show enhanced detergency on oil soils as well as reduced redeposition of dirt during washing.

Fundamentals and prior art

Polyvinyl pyrrolidone and some polymers related are known ingredients of compositions laundry detergents, which provide the benefits of reduced transfer of dyes between tissues in a load mixed.

Laundry detergent compositions containing polyvinyl pyrrolidone as an inhibitor of dye transfer are described, for example, in WO 92 18597A, WO 94 03567A, WO 95 03390A, WO 95 17496A, WO 95 27028A and WO 95 34627A (Procter & Gamble), and WO 94 06354A, WO 94 24249A and WO 97 03166A (Henkel).

GB 1 354 498 (Unilever) describes laundry detergent compositions containing vinyl pyrrolidone / vinyl acetate copolymers as agents anti-redeposition During washing, lbs polymers effectively prevent or reduce tissue redeposition Washes of dirt suspended in the wash liquor. It exposed that polyvinyl pyrrolidone by itself is ineffective.

DE 2 165 898A (Henkel) describes, also, the anti-redeposition benefits of these copolymers.

It has now been discovered that the copolymers of vinyl pyrrolidone / vinyl alcohol are equally effective for enhance the dirt detergency of oils, especially in detergent compositions containing anionic surfactants, more especially alkyl benzene sulfonate.

Definition of the invention

The present invention provides the use of a Water soluble random copolymer of vinyl pyrrolidone and acetate of vinyl in a laundry detergent composition, which comprises an organic surfactant and, optionally, an adjuvant of the detergency, to improve the dirt detergency of oils of the composition.

The random polymer of vinyl pyrrolidone / vinyl acetate

To the random copolymer of vinyl pyrrolidone and Vinyl acetate used in accordance with the present invention, is will refer hereinafter, for reasons of convenience, such as PVP / PA copolymer.

Preferably, the PVP / PA copolymer contains no more than 30 mol% of vinyl acetate monomer units (GOES). Copolymers containing higher proportions of VA units are less soluble in water and therefore are less preferred. More preferably, the copolymer contains no more than 50 mol% of VA units. Most preferably, the copolymer Contains 50 to 70 mol% of vinyl monomer units pyrrolidone (VP) and from 30 to 50 mol% of VA units.

Preferably, the copolymer has a weight molecular range from 10,000 to 100,000, more preferably from 25,000 to 75,000.

At International Specialty Products (ISP), a wide selection of PVP / PA copolymers is available. These are supplied as solutions (transparent viscous liquids) in ethanol, isopropanol or water, or as a solid (white powder). Some examples are shown in the table below.

one

The solutions have a solids content of approximately 50% by weight.

They are also available BASP PVP / PA copolymers such as the Luviskol VA series (Brand Commercial).

2

These polymers are marketed as film formers for cosmetic and personal products, and for use in hair styling formulations such as creams, gels and fixing lotions.

The laundry detergent composition

In a laundry detergent composition of according to the invention, the polymer is present in an amount enough to enhance the detergency of dirt from oils. From suitably, the polymer is present in an amount of from 0.5 to 3% by weight, preferably from 1 to 2% by weight.

Suitably, the detergent composition can understand:

(a) from 5 to 60% by weight, preferably from 10 to 40% by weight of organic surfactant,

(b) optionally, from 5 to 80% by weight, preferably from 10 to 60% by weight, of the adjuvant of the detergency,

(c) from 0.5 to 3% by weight, preferably from 1 to 2% by weight, of the random vinyl copolymer pyrrolidone and vinyl acetate,

(d) optionally, other ingredients detergents up to 100% by weight.

Organic surfactant

The detergent composition according to the invention, can contain any organic surfactant (detergent active compounds) suitable for incorporation into of laundry detergent compositions.

The detergent active compounds (surfactants) can be selected from soap and anionic, cationic, non-phonic, amphoteric and zwitterionic non-soap detergent active compounds, and mixtures thereof. Many suitable detergent active compounds are available and are fully described in the literature, for example, in Surface-Active Agents and Detergents , volumes I and II, by Schwartz, Perry and Berch. Preferred detergent active compounds that can be used are soaps and anionic and non-ionic compounds, not synthetic soaps. Suitably, the total amount of surfactant present is within the range of from 5 to 60% by weight, preferably from 5 to 40% by weight.

Anionic surfactants are well known. for those skilled in the art. Examples include alkylbenzene sulphonates, particularly alkylbenzene sulphonates linear having an alkyl chain length of C 8 -C 15; primary alkyl sulfates and secondary, particularly primary alkyl sulfates of C 8 -C 20; alkyl ether sulfates; olefin sulfonates; alkyl xylene sulfonates; dialkyl sulfosuccinates; Y fatty acid sulfonate ester. Sodium salts are the generally preferred.

The nonionic surfactants that can be used, include alcohol primary and secondary ethoxylates, especially the aliphatic ethoxylated alcohols of C_ {8} -C_ {20} with an average of 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially, the primary and secondary aliphatic ethoxylated alcohols of C_ {10} -C_ {15} with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Surfactants Nonionic non-ethoxylates include alkyl polyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).

The cationic surfactants that can be used include quaternary ammonium salts of the general formula R 1 R 2 R 3
R 4 N + X -, in which the R groups are long or short hydrocarbyl chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a solubilizing anion (for example, compounds in the which R 1 is a C 8 -C 22 alkyl group, preferably a C 8 -C 10 or C 12 -C 14 alkyl group, R 2 is a methyl group, and R 3 and R 4, which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters).

They can also be present amphoteric surfactants and / or zwitterionic surfactants.

Preferred amphoteric surfactants are amine oxides. These are materials of the general formula:

R_ {R} {2} R_ {3} N \ rightarrow OR

where R_ {1} is typically a C 8 -C 18 alkyl group, for example, C 12 -C 14 alkyl, and R 2 and R 3, which may be the same or different, are alkyl groups or C 1 -C 3 hydroxyalkyl, for example, methyl groups The most preferred amine oxide is coconut oxide dimethylamine

Preferred zwitterionic surfactants are betaines, and especially amidobetaines.

Preferred betaines are alkyl of C 8 -C 18 -amidoalkylbetains, for example, coconut amidopropyl betaine (CAPB).

According to a preferred embodiment of the invention, the composition comprises an anionic surfactant sulphonate According to an especially preferred embodiment, the anionic sulphonate surfactant comprises alkylbenzene linear sulphonate (LAS).

An interaction has been observed especially favorable between LAS and the PVP / PA copolymer, which provides enhanced primary detergency on difficult oil soils such as dirty engine oil. Without wishing to theorize, it is postulated that this benefit can be attributed to a reduction in Critical micellar concentration (CMC) of LAS.

Likewise, the benefit has been observed known of reduced redeposition of dirt on the load of washing during washing (sometimes referred to as detergency high school).

Preferably, the compositions contain from 3 to 30% by weight, more preferably from 10 to 25% by weight, of LAS.

The optional detergency builder

Preferably, the detergent compositions according to the invention, they also contain one or more detergency aids. The total amount of adjuvant of the detergency in the compositions may, suitably, vary from 5 to 80% by weight, preferably from 10 to 60% by weight.

Preferred adjuvants are aluminosilicates alkali metal, more especially metal aluminosilicates crystalline alkaline (zeolites), preferably in salt form Sodium

Zeolite adjuvants may be present, suitably, in a total amount of from 5 up to 60% by weight, preferably from 10 to 50% by weight.

Zeolites can be supplemented by other inorganic adjuvants, for example aluminosilicates amorphous, or layered silicates such as SKS-6 of Clariant

Zeolites can be supplemented by organic adjuvants, for example polycarboxylate polymers such as polyacrylates and acrylic / maleic copolymers; monomeric polycarboxylates such as citrates, gluconates, Oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethylximalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and salts of sulfonated fatty acids.

Alternatively, the compositions according with the invention may contain phosphate builders, for example, sodium tripolyphosphate.

Organic adjuvants especially Preferred are citrates, suitably used in amounts of from 1 to 30% by weight, preferably from 2 to 15% in weight; and acrylic polymers, more especially copolymers acrylic / maleic, suitably used in amounts of from 0.5 to 15% by weight, preferably from 1 to 10% in weight. The adjuvants, both organic and inorganic, are present, preferably, in the form of metal salt, especially sodium salt

According to a preferred embodiment of the invention, the detergency builder, which is present in an amount of from 5 to 80% by weight, preferably from 10 to 60% by weight, is selected from tripolyphosphate sodium, zeolites, sodium carbonate and mixtures thereof.

Other detergent ingredients

Detergent compositions according to the invention may also suitably contain a bleaching system Preferably, this will include a compound of peroxy bleaching, for example, an inorganic persalt or a organic peroxyacid, capable of providing hydrogen peroxide in aqueous solution. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate, the latter being especially preferred. Sodium percarbonate may have a protective coating against destabilization because of the humidity Suitably, the peroxy bleaching compound It is present in an amount of 5 to 35% by weight, preferably from 10 to 25% by weight.

The peroxy bleaching compound can be used in conjunction with a bleach activator (bleach precursor) to improve the bleaching action at low washing temperatures. Suitably, the bleaching precursor is present in a amount from 1 to 8% by weight, preferably from 2 to 5% by weight. Preferred bleaching precursors are precursors of peroxycarboxylic acid, more especially acid precursors peracetic and peroxibenzoic acid precursors; and precursors of peroxycarbonic acid. A bleaching precursor especially preferred suitable for use in the present invention is N, N.N'.N'-tetraacetyl ethylenediamine (TAED).

Likewise, a bleaching stabilizer (heavy metal sequestrant). The Suitable bleach stabilizers include tetraacetate ethylenediamine (EDTA), diethylenedriamine pentaacetate (DTPA), ethylenediamine disuccinate (EDDS), and such polyphosphonates such as the Dequests (Trade Mark), ethylenediamine phosphonate tetramethylene (EDTMP) and diethylenetriamine pentamethylene phosphate (DETPMP).

The compositions according to the invention may contain alkali metal carbonate, preferably sodium, in order to increase detergency and easy processing. Suitably, sodium carbonate may be present in amounts ranging from 1 to 60% by weight, preferably from 2 to 40% by weight. As previously indicated, Sodium silicate may also be present. By way of suitable, the amount of sodium silicate can vary from 0.1 Up to 5% by weight. As previously indicated, silicate sodium is introduced preferably through the second granule base.

The powder flow can be improved by incorporation of a small amount of a structuring of the powder. Examples of powder structuring agents, some of the which can play other roles in the formulation such as previously indicated, include, for example, fatty acids (or fatty acid soaps), sugars, acrylate or polymers of acrylate / maleate, sodium silicate, and dicarboxylic acids (for example, Sokolan (Trade Mark) DCS of BASF. A structuring of Preferred powder is fatty acid soap, present, so appropriate, in an amount of from 1 to 5% by weight.

Other materials that may be present in detergent compositions according to the invention, include anti-redeposition agents such as polymers cellulosics; dirt release agents; agents anti-transfer of dyes; fluorescers; inorganic salts such as sodium sulfate; enzymes (proteases, lipases, amylases, cellulases); dyes; colored macules; perfumes; and compounds for tissue conditioning. This List is not intended to be exhaustive.

Product form and preparation

The compositions according to the invention they can be of any suitable physical form, for example, particles (powders, granules, tablets), liquids, pastes, gels or bars. According to an especially preferred embodiment of The invention, the detergent composition is in the form of particles.  Low to moderate bulk density powders can be prepared by spray drying a grout, and optionally post-dosing (dry mixing) of additional ingredients "Concentrated" powders or "compact" can be prepared by means of mixing and granulation, for example, using a mixer / granulator high speed, or other procedures other than type tower.

The tablets can be prepared by powder compaction, especially powders "concentrated."

Equally preferred are the compositions. liquid detergents, which can be prepared by blend of essential and optional ingredients in any desired order to provide compositions containing the ingredients in the required concentrations.

PVPNA copolymer incorporation

The polymers can be incorporated into any suitable stage in the manufacture of the compositions according with the invention As previously indicated, the polymers are commercially available both in form of solution as in solid form.

For example, in the manufacture of compositions in spray-dried particles, the polymer in the form of powder or solution (preferably aqueous) can be incorporated into the grout. For the particulate compositions obtained by procedures other than the tower type, the powder or solution of the polymer can easily be introduced into the apparatus of mixed and granulated, either alone or mixed with other ingredients solids or liquids as appropriate.

Examples

The invention is further illustrated by the following Examples, in which the parts and percentages are by weight, unless otherwise stated.

Examples 1 to 16, examples comparisons to and b

Benefits of detergency on dirty engine oil using washing liquor models

Wash liquors containing 1 g / liter or 2.5 g / liter of an ideal detergent composition (the "product") containing linear alkylbenzene sulphonate (LAS) and sodium carbonate were prepared for the general formulation
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The polymers used, all of them products commercials from ISP supplied as 40% solutions by weight, they were the following:

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The detergency on white cotton cloth soiled with dirty engine oil, was evaluated using a Washing procedure from small to large scale. Washing it was carried out in water at 20 ° French hardness (Ca: Mg, 2: 1), to a temperature of 20 ° C for 20 minutes.

The whiteness before and after washing is determined using the color change technique by analysis of Image using a gray scale. The results are analogous to the reflectance changes at 460 nm measured by a reflectance spectrophotometer and are expressed in ΔR and Δ \ DeltaR.

Results at 1 g / liter of concentration of "product"

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Results at 2.5 g / liter concentration of "product"

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Example 17, comparative example C

Evaluation of the removal of dirt and whiteness by the polymer in a powder detergent composition

A powder detergent composition was prepared for the following formulation:

Ingredient % in weigh Linear alkylbenzene sulphonate sodium 9.31 Non-phonic surfactant 3.58 Sodium tripolyphosphate 21.32 Sodium carbonate 12.97 Sodium hydroxide 1.95 Sodium carboxymethylcellulose 0.62 Sodium Silicate (r = 2.4) 5.18 Fluorescedores 0.13 Zeolite 1.24 Perborate sodium tetrahydrate 15.00 Tetraacetyl ethylenediamine 3.80 Enzymes (protease, lipase, amylase) 2.27 Granule antifoam 2.00 Dequest 2047 0.50 Tripolyphosphate granular sodium 10.00 Fragrance 0.65 Acid citric 2.75 Water until 100.00

The removal of dirt was determined using samples of white cotton fabric fabric soiled with two different models of colored oil soils for Increase visibility: colored soybean oil with coloring violet, and mechanical grease mixed with carbon black.

The evaluations were carried out in tergotometers at a wash temperature of 20-25 ° C in water at 19 ° French hardness (Ca: Mg, 2: 1) to a liquor to cloth ratio of 8: 1. Washing regime It was as follows: 10 minutes of soaking, 15 minutes of washing, two Rinse for 2 minutes. The dosage of product for soaking and washing was 4.4 g / liter.

In Example 17, the wash liquor for both soaking as for washing additionally included a polymer PVPNA 70:30 (ISP W735 as described above). The amounts used were:

Soak: 0.20 g / I, equivalent to 4% by weight of product,

Wash: 0.05 g / I, equivalent to 1% by weight of product.

Example C was a polymer free control.

Dirt removal was measured by full spectrum reflectance spectrophotometry and it expressed as a dirt removal index (SRI), which is define as:

SRI = 100 - \Delta AND

where AE is the difference between the reflectance before and after washing. A difference of 0.6 Percent units are considered statistically significant. The results of the SRI were those shown in Table a continuation:

Dirt Example C Example 17 Soybean oil with coloring Violet 84.07 84.69 Mechanical grease / black smoke 51.24 57.08

Claims (10)

1. Use of a random copolymer soluble in water of vinyl pyrrolidone and vinyl acetate in a composition laundry detergent, comprising a surfactant organic and, optionally, a detergency aid, for Improve the dirt detergency of oil composition. 2. Use as claimed in Claim 1, characterized in that the copolymer contains no more than 30 mol%, preferably no more than 50 mol%, of vinyl acetate monomer units. 3. Use as claimed in Claim 2, characterized in that the copolymer contains from 50 to 70 mol% of monomer units of vinyl pyrrolidone and from 30 to 50 mol% of vinyl acetate units. 4. Use as claimed in any preceding Claim, characterized in that the copolymer has a molecular weight in the range of from 10,000 to 100,000, preferably from 25,000 to 75,000. 5. Use as claimed in any preceding Claim, characterized in that the laundry detergent composition contains from 0.5 to 3% by weight, preferably from 1 to 2% by weight, of the copolymer. 6. Use as claimed in any preceding Claim, characterized in that the laundry detergent composition comprises: (a) from 5 to 60% by weight, preferably from 10 to 40% by weight of organic surfactant, (b) optionally, from 5 to 80% by weight, preferably from 10 to 60% by weight, of the adjuvant of the detergency, (c) from 0.5 to 3% by weight, preferably from 1 to 2% by weight, of the random vinyl copolymer pyrrolidone and vinyl acetate, (d) optionally, other ingredients detergents up to 100% by weight. 7. Use as claimed in any preceding Claim, characterized in that the organic surfactant comprises an anionic sulphonate surfactant. 8. Use as claimed in Claim 7, characterized in that the organic surfactant comprises linear alkylbenzene sulphonate. 9. Use as claimed in Claim 8, characterized in that the laundry detergent composition contains from 3 to 30% by weight, preferably from 10 to 25% by weight, of linear alkylbenzene sulphonate. 10. Use as claimed in any preceding Claim, characterized in that the laundry detergent composition comprises from 5 to 80% by weight, preferably from 10 to 60% by weight, of the detergency aid selected from sodium tripolyphosphate, zeolites , sodium carbonate and mixtures thereof.