JP2620338B2 - Detergent composition - Google Patents

Description

The present invention relates to detergent compositions containing fabric softening amounts of smectite-type clays. Clay is 0.5% to 3% organic moisturizer
Present in the form of aggregates containing 0%.

GB 1,572,815 discloses detergent compositions based on soap and curd dispersants. The composition contains 4% to 25% of smectite-type clay. Clay has been agglomerated with aqueous solutions of water, electrolyte water-soluble, nonionic surfactants, or organic adhesives. Examples of such adhesives include dextrin, gelatin, carboxymethylcellulose, starch, carboxymethyl starch, and alkyl and hydroxyalkyl substituted celluloses and starches. Agglomerates are disclosed to minimize dustiness while preserving the overall softening potential of the clay.

GB 1,167,037 discloses clay treated with an alkanolamine salt and an organic humectant. It is disclosed that the treated clay hydrates faster and develops the clay in a shorter time as compared to the untreated clay.

GB 1,400,898 discloses a detergent composition comprising a smectite-type clay as a fabric softening component.

It is now well recognized in the detergent industry that clays of the type disclosed in GB 1,400,898 provide significant fabric softening benefits when used in laundry detergents. However, it is equally well recognized that the adhesion of these clays on the fabric during the washing process is by no means complete. In fact, under typical laundry conditions in Europe,
Less than half of the effective clay adheres to the fabric, and the remainder is washed away with the washing liquid in a subsequent rinsing step. In addition, the softening effect obtained as a result of clay deposition is affected by poorly understood factors.

It is therefore an object of the present invention to pre-treat a fabric softening clay to increase the softening benefits obtained.

SUMMARY OF THE INVENTION The present invention comprises (a) a conventional detergent component; and (b) 60% to 99.5% of smectite-type clay and 30% to 0.9% of organic humectant.
The present invention relates to a granular detergent composition comprising a clay aggregate containing 5%. Preferred organic humectants include: (a) an aliphatic hydrocarbon polyol having 2 to 9 carbon atoms; (b) an ether alcohol derived from the polyol of (a); (c) an ester alcohol derived from the polyol of (a); (D) monosaccharides and oligosaccharides; and mixtures thereof. Highly preferred agglomerates are by weight of the clay
It further comprises 0.005% to 20% of a clay flocculant.

Preferred clay flocculants have a weight average molecular weight of 100,000-10,
Polymers such as poly (ethylene oxide), poly (acrylamide), poly (acrylate) having 000,000. Poly (ethylene oxide) polymers having a molecular weight (weight average) of 150,000 to 5,000,000 are most preferred.

DETAILED DESCRIPTION OF THE INVENTION The detergent composition of the present invention comprises a conventional detersive surfactant, a conventional detersive builder and optionally other conventional detergent components. The composition comprises a fabric softening amount of a fabric softening clay agglomerate of the present invention, typically 1% to 35%, preferably 3 to 15%, by weight of the detergent composition, of a fabric softening clay agglomerate of the present invention. Further comprising an assembly.

In the present invention,% is% by weight of the detergent composition unless otherwise specified.

Detergent Ingredients Detersive Surfactants The compositions of the present invention will typically contain an organic surfactant to provide the usual cleaning benefits associated with use. Detersive surfactants useful in the present invention include well-known synthetic anionic, synthetic nonionic, synthetic amphoteric and zwitterionic surfactants. Alkyl benzene sulfonates, alkyl sulfates, alkyl ether sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols, alkoxylated (especially ethoxylated) alkyl phenols, amine oxides, α-sulfonates of fatty acids, fatty acids which are well known from the washing technology Esters such as α-sulfonate are representative of these. In general, such detersive surfactants contain an alkyl group in the C ₉ -C ₁₈ range. The anionic detersive surfactant can be used in the form of a sodium, potassium or triethanol ammonium salt. Nonionic surfactants generally contain from about 5 to about 17 ethylene oxide groups. U.S. Pat. No. 3,995,669 contains a detailed list of such exemplary detersive surfactants.

C ₁₁ -C ₁₆ alkyl benzene sulfonates, C ₁₂ -C ₁₈ paraffin sulfonates and alkyl sulfates, and ethoxylated alcohols and ethoxylated alkyl phenols are especially preferred in this type of composition. Also, water-soluble soaps well known in the art, such as ordinary sodium and potassium coconut or tallow soaps, are useful in the present invention as surfactants.

Surfactants can make up about 1% of the composition,
Preferably, the composition will contain from 5% to 40% of surfactant, preferably from 10% to 30%. Mixtures of ethoxylated nonionic surfactants with anionic surfactants such as alkylbenzenesulfonates, alkylsulfates, paraffinsulfonates provide a broad spectrum of stains and stains from fabrics through-the-wash.
he-wash) Preferred for cleaning.

Detergent Aids The composition can contain other components that promote cleaning performance. For example, it is highly preferred that the through-the-wash detergent composition contains a detersive builder and / or a sequestering agent. Compounds that can be classified as detergency builders and are well known in the art include nitrilotriacetate, polycarboxylates, citrates, carbonates, zeolites, water-soluble phosphates (eg, tripolyphosphate, sodium orthophosphate and sodium pyrophosphate), silicates, and And mixtures thereof. As sequestering agents,
All of the above plus substances such as ethylenediaminetetraacetate, aminopolyphosphonates (DEQUEST) and various other polyfunctional organic acids and salts that are too numerous to be described in detail in the present invention. See U.S. Pat. No. 3,579,454 for typical examples of the use of such materials in various cleaning compositions. Generally, the builder / sequestrant will comprise from about 0.5% to 45% of the composition
Will be composed. The zeolite (e.g., zeolite A) builder of 1-10 micron size disclosed in West German Patent 2,422,655 is particularly preferred for use in low phosphate compositions.

Particularly preferred phosphate-free builders include (a) structures Wherein X is H or a salt-forming cation 1% to 99% of a tartrate monosuccinate component; and (b) the structure (Where X is H or a salt-forming cation) is an ether carboxylate mixture comprising 1 to 99% by weight of a tartrate disuccinate component.

This type of builder system is described in detail in U.S. Pat. No. 4,663,071.

Typical detergent compositions contain 5% to 35% of this builder system.

Further, the laundry composition of the present invention preferably contains oxygen in order to enhance the through-the-wash cleaning performance against various stains and stains. Amylase and protease enzymes suitable for use in detergents are well known in the art and are well known in commercial liquid and granular detergents. Commercially available detersive enzymes (preferably a mixture of amylase and protease) are typically 0.001 in the composition.
It is used in amounts of 2% and higher. Detersive cellulase enzymes provide both cleaning and softening benefits, and in particular, these benefits to linen fabrics. These enzymes are highly desirable in the detergent compositions of the present invention.

The composition may contain other components that promote cleaning performance. For example, the composition advantageously comprises a bleach,
In particular, it may contain a peroxyacid bleach. In the context of the present invention, the term peroxyacid bleach encompasses both the peroxyacid itself and a system capable of producing peroxyacid in situ.

Peroxy acids themselves are meant to include their alkali metal and alkaline earth metal salts. Peroxy acids and diperoxy acids are commonly used. Examples are diperoxide decanoic acid (DPDA) or peroxyphthalic acid.

Systems that can deliver peracid in situ consist of a peroxygen bleach and its activator.

Peroxygen bleaches are those that can produce hydrogen peroxide in an aqueous solution. These compounds are well known in the art and include, for example, hydrogen peroxide, alkali metal peroxides, organic peroxide bleaches such as urea peroxide, inorganic persalt bleaches such as alkali Metal perborates, percarbonates, perphosphates, persilicates and the like.

Preferred are sodium perborate, sodium hydrogen carbonate, sodium pyrophosphate peroxide and urea hydrogen peroxide, which are commercially available in the form of monohydrate and tetrahydrate.

The liberated hydrogen peroxide reacts with the bleach activator to produce a peroxyacid bleach. Types of bleach activators include esters, imides, imidazoles, oximes, and carbonates. In these types, preferred materials include p-methylacetoxybenzoate; sodium 4-nonanoyloxybenzenesulfonate, sodium 4-octanoyloxybenzenesulfonate, sodium 4-decanoyloxybenzenesulfonate, and the like. -Sodium acetoxybenzenesulfonate; bisphenol A diacetate; tetraacetylethylenediamine; tetraacetylhexamethylenediamine; tetraacetylmethylenediamine.

Other highly preferred peroxygen bleach activators disclosed in U.S. Pat. Nos. 4,483,778 and 4,539,1300 are sodium 4- (2-chlorooctanoyloxy) benzenesulfonate, 4- (3, Α such as sodium 5,5-trimethylhexanoyloxy) benzenesulfonate
-A substituted alkyl or alkenyl ester. Suitable peroxy acids are also peroxygen bleach activators, such as those described in published European patent application 0 116 571, i.e. of the general type PXAOOH and RXAL where R is a hydrocarbyl group; X is a heteroatom, A is a carbonyl bridging group, and L is leaving
Group, especially oxybenzenesulfonate].

Other detergent ingredients highly desirable for use in detergent compositions of the present invention have the formula _{R 4 R 5 R 6 R 7} N + X - (In the formula, R ₄ is from about 8 carbon atoms
20, preferably 12 to 18 alkyl, R ₅ is alkyl having 1 to 10 carbon atoms, each R ₆ and R ₇ are C ₁ -C ₄ alkyl, preferably methyl, X ^- is anion Quaternary ammonium compounds (eg, chlorides). As the examples of the quaternary ammonium compounds such, it includes C ₁₂ -C ₁₄ alkyl trimethyl ammonium chloride and cocoalkyl trimethyl ammonium methosulfate. The quaternary ammonium compound is 0.
It can be used in an amount of 5-5%, preferably 1% -3%.

Fabric Softening Clay Smectite clay is widely used as a fabric softening component in detergent compositions. Most of these clays are
It has a cation exchange capacity of at least 50 meq / 100 g.

Montmorillonite clay is commonly used for this purpose. However, some hectorite clays appear to provide better fabric softening performance than commonly used montmorillonite. Hectorite exhibiting this excellent fabric softening performance is a hectorite of natural origin having a lath type shape.

According to the invention, the fabric softening clay is present in the form of agglomerates. These agglomerates contain, in addition to the clay, an organic humectant. The aggregate optionally further comprises a polymeric clay flocculant. Typically, the flocculant comprises, by weight of the aggregate, 60% to 99.5% clay; 0.5% to 30% humectant; and 0% to 10% clay flocculant. Preferably, the aggregate further comprises a heavy sequestering agent. Examples include heavy metal chelators such as EDTA, ethylenediaminetetramethylenephosphonic acid (EDTP). Aggregates typically contain 0.1% to 10% of a chelating agent.

Humectant The organic humectant used in the clay aggregate may be any of the various water-soluble substances utilized for such purposes. The organic humectant is preferably (a) a C 2-9 carbon atom.
(B) an ether alcohol derived from the polyol of (a); (c) an ester alcohol derived from the polyol of (a); (d) a monosaccharide and an oligosaccharide; and a mixture thereof. Selected from the group.

Highly preferred humectants include glycerol, ethylene glycol, propylene glycol and glycerol, ethylene glycol and propylene glycol dimers and trimers.

Clay agglomerates 0.5% -30% humectant, preferably 2%
Including ~ 15%.

Optional Clay Flocculants Clay flocculants are not commonly used in detergent compositions. On the contrary, there is a tendency to use clay dispersants to help remove viscosity stains from fabrics. However, flocculants are well known for flotation in other industries, such as oil well drilling and metallurgy. Most of these materials are fairly long-chain polymers and copolymers derived from monomers such as ethylene oxide, acrylamide, acrylic acid, dimethylaminoethyl methacrylate, vinyl alcohol, vinyl pyrrolidone, ethylene imine, and the like. Rubbers such as guar rubber are also suitable.

Polymers of ethylene oxide, acrylamide, or acrylic acid are preferred. These polymers have been found to dramatically increase the adhesion of fabric softening clay if the molecular weight (weight average) is in the range of 100,000 to 10,000,000. Such polymers having a weight average molecular weight of 150,000 to 5,000,000 are preferred.

The most preferred polymer is poly (ethylene oxide). The molecular weight distribution can be easily determined using gel permeation chromatography against a narrow molecular weight distribution poly (ethylene oxide) standard.

The clay agglomerates of the present invention are based on the weight of clay,
% To 20%, preferably 0.05% to 20% by weight of the clay if the molecular weight is 150,000 to 800,000, molecular weight 800,000 to 50,000
If it is 00,000, it contains 0.005-2% by weight of the clay.

Additional softening ingredients The detergent composition of the present invention may further contain other softening ingredients in addition to the clay material. A preferred example is
Formula R ₁ R ₂ R ₃ N, wherein R ₁ is C ₆ -C ₂₀ hydrocarbyl;
R ₂ is C ₁ -C ₂₀ hydrocarbyl and R ₃ is C ₁ -C ₁₀ hydrocarbyl or hydrogen). A preferred amine of this type is ditallow methylamine.

Preferably, the softening amine has the formula RCOOH, where R is C
₉ -C ₂₀ alkyl or complex with fatty acid alkenyl;) exists as (complex). The amine / fatty acid complex is desirably present, for example, in the form of ultrafine particles having a particle size of 0.1-20 μm. These amine / fatty acid complexes are described in detail in European Patent Application 0 133 804. Compositions containing 1% to 10% of the amine are preferred.

formula Wherein R ₈ and R ₉ are C ₁ -C ₂₀ alkyl, or a general formula alkyl- (OCH ₂ CH ₂ ) _y (wherein the alkyl substituent is C
₁ -C _20, preferably C ₈ -C _16, y is 1-15, phosphoric acid esters of preferably 2 to 10, an ethoxylated alkyl groups and most preferably is an integer from 2 to 5)] Complexes of the above with amines are also suitable. An amine / phosphate complex of this kind is described in detail in European Patent Application 0 168 889.

Yet another example of an optional softening component is represented by the formula R ₁₀ R ₁₁ NCOR ₁₂ , wherein R ₁₀ and R ₁₁ are independently C ₁ -C
_{22 selected from} alkyl, alkenyl, hydroxyalkyl, aryl, and alkylaryl groups; R ₁₂ is hydrogen,
Or a C ₁ -C ₂₂ alkyl or alkenyl, aryl or alkylaryl group) softened amide. Preferred examples of these amides are ditallow acetamide and ditalo benzamide. Good results are obtained when the amide is present in the composition in the form of a composite with a fatty acid or a phosphate ester as described in the case of the softening amine.

 The amide is present in the composition in an amount of 1 to 10% by weight.

Also, suitable softening components are described in UK Patent Application No. 2,173,82.
No. 7 are the amines disclosed in the specification, especially the substituted cyclic amines disclosed therein. General formula 1- (higher alkyl) amide (lower alkyl) -2- (higher alkyl) imidazoline (wherein higher alkyl is alkyl having 12 to 22 carbons, lower alkyl is alkyl having 1 to 4 carbons) The imidazolines a) are preferred.

Preferred cyclic amines are 1-taromidoethyl-2
-Taro imidazoline. Preferred compositions contain 1% to 10% of a substituted cyclic amine.

The amine and amide softening components may be added to the detergent granules as a dry powder, or may be sprayed onto the detergent granules or carrier in either a molten or dissolved form. Examples of suitable carriers are perborate
It is a monohydrate.

In addition, the composition may contain, in addition to the components described above, various other optional ingredients typically used in commercial products to provide aesthetic or additional product performance benefits. Typical ingredients include pH adjusters, fragrances, dyes, bleaches, optical brighteners, stain settling inhibitors, hydrotropes and gel control agents, freeze-thaw stabilizers, bactericides, preservatives, antifoams, Bleaching activators and the like.

In the through the wash form, the composition comprises
Typically, it is used at a concentration of at least 400 ppm, preferably 0.05% to 1.5%, in an aqueous washing bath at pH 7-11 to wash the fabric. Washing can be performed over a range from 5 ° C. to boiling, with excellent results.

Industrial Applicability The agglomeration process itself may be accomplished using any of the techniques and equipment that are conventional in the art (eg, "Review of detergent agglomeration", MJ Doran, HAPPI, April 1987). , From page 64
See page 85). The agglomeration method can be batch or continuous. Optimum operating conditions (preferred particulate size and water content) can be found by test adjustment of process parameters such as liquid spray-on volume, speed, liquid size, residence time, and the like.

Example I To 40 kg of commercially available smectite clay (CEC ≥ 50meq / 100g) was added glycerol in a Redige Drum agglomerator.
A 40% by weight aqueous solution 5 was sprayed. After drying and sieving, the following aggregate composition was obtained: smectite clay (anhydrous) 81.9% glycerol 4.1% moisture 14.0% Particle size measurement: 212 μm (65 mesh) <minimum 80% <850 μ
m (20 mesh).

A reference aggregate, ie without glycerol, was made in the same way.

The following compositions were prepared by dry blending both agglomerates with a spray-dried granular detergent: Then a clean fabric load using compositions A and B
4 kg were washed in a MIELE washing machine. Water hardness is 3.0 mmol (Ca
⁺⁺ + MG ⁺⁺ ) / and the detergent concentration was 10 g /. A clean terry towel tracer was added to allow evaluation of 1 cycle and cumulative (4 cycles) softening performance. The flexible tracer was line dried before evaluation by an expert judge. A 0-4 panel score unit (psu) scale was used for rating. 0 means no difference and 4 means very large difference.

Composition A was rated better than B with respect to flexibility: 1 cycle tracer 0.6 psu (s) 4 cycle tracer 0.8 psu (s) (s) The difference is statistically significant at the 95% confidence level is there.

Thus, it can be seen that composition A according to the present invention is superior to composition B of the prior art in fabric softening performance.

The following aggregate composition is obtained using the method outlined in Example I.

(1) It has a weight average molecular weight of about 300,000.
Alternatively, they may be incorporated into laundry additives with an insoluble carrier, such as a sheet or pouch. These agglomerates (neat or with a suitable carrier) can then be added to the wash liquor on top of a conventional detergent composition. Laundry additives
Preferably, it also contains one or more of the additional softening components described above. Thus, the additives may be used in conjunction with detergent compositions that do not themselves contain such clays and / or these other softening ingredients.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C11D 3:37) (72) Inventor Bob, Decker Strombake-Baber, Belgium, Castellstraat, 53/11 (56) References JP-A-55-112371 (JP, A) JP-A-61-97399 (JP, A)

Claims (17)

(57) [Claims] 1. An ordinary detergent component, and (b) 60% to 99.5% by weight of a smectite type clay;
Organic humectants selected from the group consisting of -9 aliphatic hydrocarbon polyols, monosaccharides and mixtures thereof from 30% to 0.5% by weight; and 0 to 20% by weight of clay consisting essentially of a polymeric clay flocculant. A granular detergent composition comprising a clay aggregate. 2. The detergent composition according to claim 1, wherein the clay aggregate comprises 2% to 15% of an organic humectant. 3. The humectant is selected from glycerol, ethylene glycol, propylene glycol; dimers and trimers of glycerol, ethylene glycol and propylene glycol; and mixtures thereof.
Or the detergent composition according to 2. 4. The detergent composition according to claim 1, wherein the clay aggregate comprises 0.005 to 20% by weight of the clay of a polymeric clay flocculant. 5. The method of claim 5, wherein the clay aggregate is a chelating agent, preferably
5. The detergent composition according to claim 4, further comprising 0.1% to 10% EDTA, EDTP, or a mixture thereof. 6. A polymer clay flocculant having a weight average molecular weight of 150,
5. The detergent composition according to claim 4, wherein the composition has from 000 to 5,000,000. 7. The detergent composition according to claim 5, wherein the polymer is derived from a monomer selected from ethylene oxide, acrylamide, and acrylic acid. 8. formula _{R 4 R 5 R 6 R 7} N + X - ( wherein, R ₄ is from about 10 carbon atoms
20 alkyl, wherein R ₅ , R ₆ and R ₇ are each C ₁ -C ₄ alkyl and X ⁻ is an anion). The detergent composition according to any one of claims 1 to 7. 9. A compound of the formula R ₁₀ R ₁₁ NCOR _{12 wherein} R ₁₀ and R ₁₁ are independently selected from C ₁ -C ₂₂ alkyl, alkenyl, hydroxyalkyl, aryl and alkylaryl groups;
₁₂ is hydrogen, or C ₁ -C ₂₂ alkyl or alkenyl,
An aryl or alkylaryl group or OR
_{13 wherein} R ₁₃ is a C ₁ -C ₂₂ alkyl or alkenyl, aryl or alkylaryl group]
The detergent composition according to any one of claims 1 to 8, further comprising 10% to 10%. 10. A formula 1- (R ₁₄₎ amido (R ₁₅₎ -2- (R
₁₆ ) The imidazoline wherein R ₁₄ and R ₁₆ are independently selected from C ₁₂ -C ₂₂ alkyl and R ₁₅ is selected from C ₁ -C ₄ alkyl, further comprising 1% to 10% of imidazoline. Item 10. The detergent composition according to any one of Items 1 to 9. 11. A formula R ₁ R ₂ R ₃ N (wherein, R ₁ is C ₆ -C ₂₀ hydrocarbyl, R ₂ is C ₁ -C ₂₀ hydrocarbyl, R ₃
C ₁ -C ₁₀ containing 1% to 10% amine hydrocarbyl or hydrogen at a) A detergent composition according to any one of claims 1 to 10. 12. The builder system further comprises 5% to 35%, wherein the builder system has the following structure: Wherein X is H or a salt-forming cation 1% to 99% of a tartrate monosuccinate component; and (b) the structure 12. The detergent composition according to any one of the preceding claims, comprising from 1 to 99% by weight of a tartrate disuccinate component wherein X is H or a salt-forming cation. 13. Smectite type clay 60% to 99.5% by weight;
30% of organic humectant selected from the group consisting of aliphatic hydrocarbon polyols having 2 to 9 carbon atoms, monosaccharides and mixtures thereof
A laundry additive characterized by comprising a clay agglomerate consisting essentially of a polymeric clay flocculant of from 0 to 0.5% by weight; and 0 to 20% by weight of the clay. 14. The additive according to claim 13, wherein the organic humectant is 2 to 15% by weight. 15. The additive according to claim 13 or 14, comprising from 0.005 to 20% by weight of the clay of a polymeric clay flocculant. 16. A method according to claim 13, further comprising an additional softening component as defined in claim 7, 8 or 9 in an amount of 2 to 50% by weight, preferably 5 to 30% by weight. Item 2. The additive according to item 1. 17. An additive according to any one of claims 13 to 16, which is deposited on / contained in a suitable water-soluble or water-insoluble carrier.