DE60314910T2 - LAUNDRY DETERGENT - Google Patents

Description

TECHNICAL AREA

The The present invention relates to laundry detergent compositions, which contain certain graft polymers which redeposit of dirt on textiles during of the washing process can reduce.

BACKGROUND AND STAND OF THE TECHNIQUE

During the Washing process in a household or commercial washing machine Dirt is removed from the polluted textiles by a combination the physical effect (movement) of the machine and the washing power the laundry detergent composition removed and enters the wash liquor. A similar process occurs the hand wash on. It is important to make sure that dirt does not just go back to the floor Textiles is deposited, but suspended in the wash liquor stays and finally is washed away.

Laundry detergent compositions usually contain sodium carboxymethylcellulose (SCMC) as an anti-redeposition agent. US 4,235,735 (Marco et al / Miliken) discloses cellulose acetates having a defined degree of substitution as anti-redeposition agents in laundry detergent compositions.

In Laundry detergent compositions were due to a variety of advantages, e.g. Dirt-removing and Fabric care benefits, also other cellulosic materials used.

WHERE 00 / 18861A and WO 00 / 18862A (Unilever) disclose cellulose compounds with a benefit agent attached thereto, so that the benefit agent while washing on fibers of the washed fabrics becomes.

Our International Patent Application WO-A-03010267 (PCT / EP02 / 07682) filed on July 10, 2002 discloses use in laundry compositions of grafted polysaccharides by a controlled process, the atom transfer radical polymerization process, were manufactured. The polymers can have various advantages, especially dirt release and fabric care benefits. Among the as textile care benefits The resulting disclosed polymer is a polymer having a locust bean gum backbone and grafts of styrene-4-sulfonic acid.

DEFINITION OF THE INVENTION

The The present invention provides the use of a graft polymer with a carob gum scaffold and grafts from one aromatic sulfonic acid ready for the anti-redeposition properties of a laundry detergent composition to improve.

DESCRIPTION OF THE INVENTION IN DETAIL

The graft polymer

The Graft polymer according to the invention is used to control the anti-redeposition features of a Laundry detergent composition is a polymer with a carob gum framework. Locust bean gum is a natural one galactomannan polysaccharide with a β-1,4-linked one Framework.

The Total number of sugar units is preferably 50 to 7,000 and the preferred molecular weight is 10,000 to 1,000,000.

In The graft polymer has at least one sugar unit of the polysaccharide with groups derived from an aromatic sulfonic acid, preferably styrene-4-sulfonic acid are substituted.

Consequently is that according to the invention The preferred graft polymer used was locust bean graft graft poly (4-styrenesulfonic acid).

Preparation of the graft polymer

The Graft polymer can be prepared by any suitable method become. However, according to one preferred embodiment In accordance with the invention, the polymer is made by the "living polymerization" technique of atom transfer radical polymerization (ATRP), as in our International Patent Application WO-A-03010267 described and claimed.

The laundry detergent composition

The Graft polymer is suitably used in laundry detergent compositions in an amount of 0.1 to 10% by weight, preferably 0.5 up to 5 weight percent incorporated.

• (a) 5 bis 60 Gewichtsprozent von einem organischen Waschmitteltensid, ausgewählt aus anionischen, nichtionischen, kationischen, zwitterionischen und amphoteren Tensiden und Kombinationen davon,
• (b) gegebenenfalls 0 bis 80 Gewichtsprozent eines Waschmittel builders,
• (c) 0,1 bis 10 Gewichtsprozent des Johannisbrotbaumgummipfropfpolymers,
• (d) gegebenenfalls andere Waschmittelbestandteile auf 100 Gewichtsprozent.

The laundry detergent compositions employing the graft polymer may suitably comprise:

• (a) 5 to 60% by weight of an organic detersive surfactant selected from anionic, nonionic, cationic, zwitterionic and amphoteric surfactants and combinations thereof,
• (b) optionally 0 to 80% by weight of a detergent builder,
• (c) 0.1 to 10% by weight of the locust bean gum graft polymer,
• (d) optionally, other detergent ingredients at 100 weight percent.

The organic detergent surfactant

Detergent Active Compounds (surfactants) can from soaps and anionic, cationic, nonionic, amphoteric and zwitterionic detergent non-soap compounds and mixtures selected from it become. Many suitable detergent-active compounds are available and be complete in the literature, e.g. in "Surface-Active Agents and Detergents ", Volumes I and II, by Schwartz, Perry and Berch. The preferred ones detergent-active compounds that can be used are Soaps and synthetic anionic and nonionic non-soap compounds. The total amount of surfactant present is suitably within the range of 5 to 60 weight percent, preferably 5 to 40 Weight.

Anionic surfactants are well known to those skilled in the art. Examples include alkylbenzenesulfonates, especially linear alkylbenzenesulfonates having an alkyl chain length of C ₈ -C ₁₅ ; primary and secondary alkyl sulfates, especially C ₈ -C ₂₀ primary alkyl sulfates; alkyl ether; olefin; alkylxylenesulfonates; dialkyl; and fatty acid ester sulfonates. Sodium salts are generally preferred. Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C ₈ -C ₂₀ aliphatic alcohols ethoxylated with, on average, 1 to 20 moles of ethylene oxide per mole of alcohol, and especially the primary and secondary aliphatic C ₁₀ - C ₁₅ alcohols ethoxylated with, on average, 1 to 10 moles of ethylene oxide per mole of alcohol. Nonethoxylated nonionic surfactants include alkanolamides, alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).

Cationic surfactants that may be used include quaternary ammonium salts of the general formula R ₁ R ₂ R ₃ R ₄ N ⁺ X ^- , wherein the groups R represent long or short hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X solubilizing anion (eg compounds wherein 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 are} which may be the same or different, represent methyl or hydroxyethyl groups); and cationic esters (eg, choline esters).

amphoteric and zwitterionic surfactants which may be used include alkylamine oxides, Betaines and sulfobetaines.

According to the present Invention particularly preferably comprises the detergent surfactant (a) an anionic sulfonate or sulfonate surfactant, optionally in Admixture with one or more cosurfactants selected from ethoxylated nonionic surfactants, non-ethoxylated nonionic Surfactants, ethoxylated anionic sulfate surfactants, cationic Surfactants, amine oxides, alkanolamides, and combinations thereof.

surfactants are preferably in a total amount of 5 to 60 percent by weight, more preferably 10 to 40% by weight.

The detergent builder

The The invention includes both built-up and unassembled laundry detergent compositions.

preferred Inorganic builders are alkali metal aluminosilicates, in particular crystalline alkali metal aluminosilicates (zeolites), preferably in sodium salt form.

zeolite can suitably in a total amount of 5 to 60% by weight, preferably 10 to 50 weight percent.

The Zeolites can by other inorganic builders, e.g. amorphous aluminosilicates, or phyllosilicates, such as SKS-6, by Clariant.

The Zeolites can by organic builders, e.g. Polycarboxylate polymers, such as polyacrylates and acrylic / maleic copolymers; monomeric Polycarboxylates, such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl and alkenylmalonates and -succinates, and sulfonated fatty acid salts.

alternative can the compositions of the invention Phosphate builder, e.g. Sodium tripolyphosphate.

Especially preferred organic builders are citrates, suitably in amounts of 1 to 30 weight percent, preferably 2 to 15 weight percent, be used; and acrylic polymers, especially acrylic / maleic copolymers, suitably in amounts of from 0.5 to 15% by weight, preferably 1 to 10% by weight. Builder, both inorganic as well as organic, are preferably in alkali metal salt, especially Sodium salt form, before.

Builder Suitably in total amounts of 10 to 80 weight percent, more preferably 20 to 60 weight percent, before. Builders can be inorganic or be organic.

A constructed according to the invention Composition may more preferably be 10 to 80% by weight Detergency builder (b), selected from zeolites, phosphates and citrates.

Other detergent ingredients

The Laundry detergent composition Generally, other detergent ingredients that are used on the Are well known in the art.

These can suitably bleach ingredients, enzymes, sodium carbonate, Sodium silicate, sodium sulphate, antifoaming agents, foam reinforcing agents, perfumes, Textile conditioners, soil release polymers, Dye transfer inhibitors, Be selected photobleaches, fluorescers and colored speckles.

The Laundry detergent compositions according to the invention can also suitably contain a bleach system. Preferably this will be a peroxy bleach compound, e.g. an inorganic one Persalt or an organic peroxyacid which is in aqueous solution Can yield hydrogen peroxide, lock in.

preferred Inorganic persalts are sodium perborate monohydrate and tetrahydrate and sodium percarbonate, with the latter being particularly preferred. The sodium percarbonate may be a protective coating against destabilization by moisture. The peroxy bleach compound is present suitably in an amount of 5 to 35 weight percent, preferably 10 to 25 weight percent, before.

The peroxy bleach compound can be used in conjunction with a bleach activator (bleach precursor) to enhance bleaching action at low wash temperatures. The bleach precursor is suitably present in an amount of 1 to 8 weight percent, preferably 2 to 5 weight percent. Preferred bleach precursors are peroxycarboxylic acid precursors, more specifically, peracetic acid precursors and peroxybenzoic acid precursors and peroxycarbonic acid precursors. One especially before The preferred bleach precursor is N, N, N ', N'-tetraacetylethylenediamine (TAED).

One Bleach stabilizer (heavy metal masking agent) may also available. Suitable bleach stabilizers include ethylenediaminetetraacetate (EDTA), diethylenetriamine pentaacetate (DTPA), ethylenediamine disuccinate (EDDS), and the polyphosphonates, such as the Dequests (Trade Mark), Ethylenediamine tetramethylene phosphonate (EDTMP) and diethylene triamine pentamethylene phosphate (DETPMP), a.

The Compositions of the invention in particulate form Alkali metal, preferably sodium, carbonate contained in the Increase detergency and ease of processing. Sodium carbonate can suitably in amounts ranging from 1 to 60% by weight, preferably 2 to 40% by weight.

As As indicated above, sodium silicate may also be present. The Amount of sodium silicate may suitably be in the range of 0.1 to 5 percent by weight.

product form

The Laundry detergent composition may be of any suitable form, e.g. Powder, tablet, liquid, Gel, paste or bar.

Especially preferred is the laundry detergent composition a granular or particulate Composition, in particular a powder or a tablet or a liquid.

Particulate detergent compositions are suitably spray-dried a slurry from compatible heat insensitive Ingredients in a spray-drying tower, and then spray on or postdosing those ingredients that are to be processed through the Slurry unsuitable are manufactured. The detergent formulation expert will not become Difficulty in deciding which ingredients in the slurry should be included and which not.

If a high bulk density he wishes is the spray-dried Detergent Composition Post-tower densification using e.g. a high speed mixer / granulator. Alternatively you can particulate Detergent compositions by complete non-tower blending and granulation processes are made. In both cases can a high-speed mixer / granulator in an advantageous manner be used.

EXAMPLES

The Invention is further limited by the following nonlimiting Examples explained wherein parts and percentages are by weight, if not stated otherwise.

EXAMPLE 1: SYNTHESIS OF GRAFT POLYMER

1.1 Preparation of locust bean gum macrostarter

A 9% w / v solution of lithium chloride (LiCl) in N, N-dimethylsulfoxide (DMSO) was prepared by heating 18 g of LiCl in 200 cm ^{3 of} anhydrous DMSO to 150 ° C in a 2-neck round bottom flask equipped with an overhead stirrer , Once a homogeneous solution was obtained, Jo hannisbrotbaum gum (LBG, MUD 246B from Rhodia) (10 g, 0.062 moles anhydromannose / galactose unit) was added gradually to the solution while maintaining the temperature at 150 ° C until a strong had formed viscous, clear, yellow solution. This solution was then cooled to 65 ° C.

Charakterisierung: IR: 1736 cm^–1 (s, gesättigtes Estercarbonyl) NMR(¹H-D₂O): 1,84 (d, Ester CH₃, 6 H); 3,4-4,6 (m, Mannose/Galactose CH und CH₂, 90 H) In a separate beaker, a solution of 2-bromoisobutyric acid (10 g, 0.06 mol) in anhydrous DMSO (50 cm ³ ) was prepared. To this solution was slowly added 1,1'-carbonyldiimidazole (CDI) (10 g, 0.00617 mol). Once the evolution of CO ₂ ceased, LBG / DMSO / LiCl solution was added with stirring. The reaction mixture was kept at 65 ° C for 24 hours. It was then poured into a threefold volume of methanol, causing the product to precipitate. This was collected on a sinter funnel, then redispersed in methanol, filtered and washed with copious amounts of methanol. The product was dried under vacuum at 60 ° C for 48 hours, yielding 8 g of a creamy, crystalline solid. Reaction Scheme 1:

Characterization: IR: 1736 cm ^-1 (s, saturated ester carbonyl) NMR ( ¹ HD ₂ O): 1.84 (d, ester _CH3, 6H); 3.4-4.6 (m, mannose / galactose CH and CH ₂ , 90 H)

Out In NMR, the average degree of substitution (DS) is 1 ester group for each 15 carob gum-sugar ring.

1.2 Preparation of Locust Bean Graft Poly (Sodium 4-styrenesulfonic Acid)

To a 3-neck round bottom flask equipped with an N ₂ inlet and outlet and a thermometer were carob gum macrostars (3 g, 1, 19 x 10 ^-3 mol), sodium 4-styrenesulfonic acid (12.31 g , 0.0597 mol) and a magnetic stir bar. The solids were dissolved in demineralised water (50 cm ³ ) and the resulting solution was degassed by introducing nitrogen gas within 45 minutes. A mixture of copper (I) bromide (0.1713 g, 1.19 x 10 ^-3 mol) and 2,2'-dipyridyl (0.3773 g, 2.39 x 10 ^-3 mol) was added to the reaction flask , A polymerization exotherm of 10 ° C was noted.

The Reaction was stirred for 2 hours at ambient temperature. Of the Flask contents were then diluted with demineralised water and the solution passed on a sinter funnel through a layer of silica gel, giving a water white, clear solution revealed. This was added to a threefold volume of methanol, what made the product fail. This was collected on a filter and made into a vacuum at 40 ° C Constant weight dried, giving 8 g of white, crystalline powder.

Reaction scheme 2:

Characterization:

NMR ( ¹ HD ₂ O) / ppm: 0.9-2.4 (bm, vinylic polymer backbone); 3.2-4.4 (bm, mannose / galactose CH's and CH ₂ 's); 6.1-7.0 (bm) and 7.3-7.9 (bm, aryl CHs).

EXAMPLE 2: Antistatic Deposition Benefits

The method of measuring of redeposition

The Method involved the use of a tergotometer and multiple Washing to simulate the redeposition process used in the repeated washing either under difficult washing conditions or with very low effective washing products.

The test formulations were used to wash pre-soiled "test cloths", along with clean textiles (redepositing controls) under standard conditions. The soiled fabrics were used to add soil to the system and also to measure the cleaning efficacy of the formulations were used to "collect" the soil from the liquor and were used to quantify the degree of soil redeposition. After washing, the test cloths and redeposition controls were dried and then their reflectance was measured. A new batch of test cloths was then washed along with the redeposition controls from the original wash and the process repeated to obtain information on the degree of redeposition after two washes. This procedure was then repeated for a third, fourth (and so on) wash:
Gear 1: cloths, clean anti-redeposit controls
Gear 2: cloths, anti-redeposition controls of gear 1
Gear 3: cloths, anti-segregation controls of gear 2
Gear 4: cloths, anti-redeposition controls of gear 3 ...
Gear n: cloths, anti-redeposition controls of gear n-1

This Protocol allows both the detergency and the redeposition process, as a function of the number of gears to track. The reflectivity value coincides successive courses, if more dirt is present in the system: the smaller the reflectivity decrease, the better the anti-redeposition properties of the formulation.

test formulations

A stock solution became French using water of 40 degrees Hardness, 2 g / l of the below Contains formulation (equivalent to 1.77 g / l of designated ingredients), the Balance of other detergent ingredients, such as water, enzyme, fluorescer, Perfume, etc., includes.

The following formulations were tested:

For each tested product, there were 3 repetitions.

test cloths

The soiled test cloths (detergency controls) were 7.5 cm x 7.5 cm squares, as follows:

The clean test cloths (anti-redeposition controls) were 10 cm × 10 cm squares of the following textiles:
Knitted cotton
Woven cotton
polyester

Test washing process

The Test formulations, soiled and clean test cloths 25 ° C containing Tergotometertöpfe were at 90 rpm for Moved for 15 minutes. The textile bundles were then out of the pots removed and rinsed twice in water (40 degrees French hardness). The textiles were then in the dark for dried for at least 12 hours.

The reflectance values of redeposition controls were before and after the wash measured (full spectrum with ultraviolet, excluded).

The Procedure was 8 courses repeated and the reflectance measured at the end of each gait.

Redeposition results

The table below shows reflectance values after 3 washes:

Examples 3 to 6: laundry detergent formulations

The following examples for Laundry detergent formulations according to the invention.

Example 3: Wash liquor

Example 4: Non-phosphate full wash detergent powder

Examples 5 and 6: detergent tablets

Claims (9)

Use of a graft polymer with a locust bean gum backbone and grafts of an aromatic sulfonic acid, around the anti-redeposition properties of a laundry detergent composition to improve. Use according to claim 1, characterized the graft polymer is locust bean graft graft poly (4-styrenesulfonic acid). Use according to claim 1 or claim 2, characterized characterized in that the graft polymer in the laundry detergent composition is present in an amount of 0.1 to 10 weight percent. Use according to any preceding claim, characterized characterized in that the laundry detergent composition includes: (a) 5 to 60% by weight of an organic Detergent surfactant selected from anionic, nonionic, cationic, zwitterionic and amphoteric surfactants and combinations thereof, (b) if appropriate 0 to 80% by weight of a detergency builder, (c) 0.1 to 10% by weight of the locust bean gum graft polymer, (D) optionally other detergent ingredients to 100 weight percent. Use according to claim 4, characterized the organic detergent surfactant (a) is an anionic sulfonate or sulfonate surfactant, optionally in admixture with one or more several cosurfactants selected ethoxylated nonionic surfactants, nonethoxylated nonionic surfactants Surfactants, ethoxylated anionic sulfate surfactants, cationic Surfactants, amine oxides, alkanolamides, and combinations thereof. Use according to claim 4 or claim 5, characterized characterized in that the laundry detergent composition 1.0 to 80% by weight of a detergency builder (b) selected from Zeolites, phosphates and citrates. Use according to one of Claims 4 to 6, characterized that the laundry detergent composition other detergent ingredients (d) selected from bleach ingredients, Enzymes, sodium carbonate, sodium silicate, sodium sulfate, antifoaming agents, Foam reinforcing agents, perfumes, Textile conditioners, soil release agents, Dye transfer inhibitors, Photobleaches, fluorescers and colored speckles comprises. Use according to any preceding claim, characterized characterized in that the laundry detergent composition a granular or particulate Composition is. Use according to one of claims 1 to 7, characterized that the laundry detergent composition a liquid is.