JP2001520266A - Detergent composition - Google Patents

Abstract

  (57) [Summary] The present invention relates to a detergent composition comprising an anionic mid-chain branched surfactant, a low level builder system, and an alkalinity system comprising a carbonate. The composition is particularly useful as a solid laundry detergent composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] Technical Field The present invention is anionic chain branching surfactant, low levels of builder systems, and to become a detergent composition comprising an alkalinity system comprising carbonate salts. This composition is particularly useful as a solid laundry detergent composition.

BACKGROUND OF THE INVENTION Recently, some new type of anionic chain branching surfactants have been developed. These surfactants are described in unpublished U.S. Patent Application No. 97/06485,
Nos. 97/06474, 97/06339 and 97/0647
No. 6 and 97/06338.

[0003] Hard water conditions degrade the performance of various components in detergents, especially charged surfactants, such as anionic surfactants, due to the presence of Ca and Mg ions in the wash water and on the fabric. Sometimes. To that end, builders are traditionally used in detergent compositions to trap Ca and Mg ions and thereby soften the water.
However, a disadvantage of high levels of builders is that many of these builders are insoluble or only partially soluble in water. This makes the detergent less soluble in the wash water and the builder material is washed on the fabric and / or (tableware)
It can adhere to washing machines and cause, for example, graying of fabrics. In addition, the use of high levels of builder materials can be very expensive.

[0004] It has now surprisingly been found that these special medium-chain branched surfactants have excellent surface activity and cleaning performance under severe hard water conditions. Furthermore, it has surprisingly been found that detergent compositions comprising these medium-chain branched surfactants and very low amounts of builders have excellent cleaning performance. It has also been found that mid-chain branched surfactants perform better in (slightly) alkaline environments. However, in the detergent compositions containing these medium-chain branched surfactants, when the amount of the builder material, which is a known source of alkalinity in the detergent composition, is reduced, the alkaline environment is weakened. To compensate for this, the inventor has reduced the level of builder material by introducing small amounts of alkalinity sources, preferably carbonates, while reducing the level of builder materials needed for optimal performance of medium chain branched surfactants. It has been found that alkalinity can be supplied.

[0005] In addition, it is an advantage that reducing the amount of builder material in the detergent composition lowers formulation costs.

The references cited are hereby incorporated by reference.

SUMMARY OF THE INVENTION The present invention provides a solid detergent composition having a density of from 330 grams / liter to 1400 grams / liter, comprising: (a) at least 0.5%, preferably at least 5%, by weight of the composition. %, more preferably at least 10 wt%, wherein the long alkyl chain, mid-chain branched surfactant surfactant system comprising a compound a b ^-X-B [wherein with the following, (I) a ^b Is a hydrophobic medium-chain branched alkyl moiety having a total carbon number of 9 to 22, preferably 12 to about 18, and (1) the longest carbon straight chain having a carbon number of 8 to 21 is -XB (2) one or more C ₁ -C ₃ alkyl moieties are branched from this longest carbon straight chain; and (3) at least one of the branched alkyl moieties is -XB 1-position carbon (# 1 ), From the carbon at position 2 to the position obtained by subtracting 2 carbons from the terminal carbon [(ω-2) carbon], and is directly added to the carbon of the longest carbon straight chain. , is up to (4) if there are two or more of these compounds, exceeding the average total number of carbon atoms of ^a b -X moiety in the above formulas 14.5, up to about 18, about preferably about 15-17 (II) B is sulfate, sulfonate, amine oxide, polyoxyalkylene, preferably polyoxyethylene and polyoxypropylene, alkoxylated sulfate, polyhydroxy moiety, phosphate ester, glycerol sulfonate, polygluconate, Polyphosphates, phosphonates, sulfosuccinates, sulfosuccaminates, polyalkoxylated carboxylates , Glucamide, taurinates, sarcosinate, glycinate, isethionate, dialkanolamide, monoalkanolamide, monoalkanolamide sulfate, diglycolamide, diglycolamide sulfate, glycerol ester, glycerol ester sulfate, glycerol ether, glycerol ether sulfate, Polyglycerol ether, polyglycerol ether sulfate, sorbitan ester, polyalkoxylated sorbitan ester, ammonioalkanesulfonate, amidopropyl betaine, alkylated quaternary substances (quats), alkylated / polyhydroxyalkylated quaternary substances, alkyl Quaternary material, alkylated / polyhydroxylated oxypropyl quaternary material, imida Phosphorus, 2-yl - succinate, sulfonated alkyl esters, and a selected hydrophilic moiety sulfonated fatty, (III) X is -CH 2 _- and -C (O) - is selected from, and (B) from 0.5 to 25% by weight of the composition of a builder system, and (c) from 0.0 to 50% by weight of the composition, an alkalinity system comprising carbonate. System a) is present in an amount of 3% by weight and system b) is present in an amount of 19% by weight.
The alkalinity system c) does not contain 8% by weight of sodium carbonate when present in an amount of Preferably, the surfactant system a) comprises a medium-chain branched primary alkyl sulphate or sulphonate surfactant.

[0008] The detergent composition of the surfactant system present invention including a detailed description of the chain branching surfactant compounds of the invention, at least 0.5% by weight of the composition, preferably at least 5 wt%, more preferably at least 10% by weight of a surfactant system comprising a long alkyl chain, medium chain branched surfactant compound selected from the group consisting of surfactant compounds having the above formula.

A preferred surfactant system of the present invention comprises a long alkyl chain, medium chain branched surfactant compound of the above formula, wherein the ^Ab moiety is a branched primary alkyl moiety having the formula: is there.

[0010]

Embedded image Wherein the total number of carbon atoms in the branched primary alkyl moiety (including the R, R ¹ and R ² branches) is 13-19, and R, R ¹ and R ² are each independently
Selected from hydrogen and C ₁ -C ₃ alkyl (preferably methyl), provided that R, R ¹ and R ² are not all hydrogen and when z is 0, at least R or R ¹ Not hydrogen, w is an integer from 0 to 13, x
Is an integer of 0 to 13, y is an integer of 0 to 13, z is an integer of 0 to 13, and w + x + y + z is 7 to 13.

In general, in surfactant-based mid-chain branched surfactant compounds, a particular branch point (eg, the position of the R, R ¹ and / or R ² moiety along the chain in the above formula) is defined. ,
Preferred over other branch points along the surfactant backbone. The formula below shows the mid-chain branch range (ie, the point where branching occurs), the preferred mid-chain branch range, and the more preferred mid-chain branch range for the mono-methyl branched alkyl ^Ab moieties useful in the present invention.

[0012]

Embedded image Of course, for mono-methyl substituted surfactants, these ranges will be
Excluding the terminal carbon atom and the carbon atom adjacent to the -XB group.

The formula below shows the medium chain branch range, preferred medium chain branch range, and more preferred medium chain branch range for di-methyl substituted alkyl ^Ab moieties useful in the present invention.

[0014]

Embedded image Surfactant compounds wherein the ^Ab portion in the above formula does not have a quaternary substituted carbon atom (ie, four carbon atoms directly added to one carbon atom) are preferred. The most preferred medium chain branched surfactant compound for use in the detergent composition of the present invention is a medium chain branched primary alkyl sulfonate, more preferably a sulfate surfactant.

Preferred medium chain branched primary alkyl sulfate surfactants have the formula:

Embedded image These surfactants have a linear primary alkyl sulfate chain skeleton having 12 to 19 carbon atoms (i.e., the longest carbon linear chain that includes sulfated carbon atoms) and their branched primary alkyl moieties. Has a total carbon number of at least 14, preferably 20 or less. In surfactant systems comprising two or more of these sulfate surfactants, the average total number of carbon atoms to the branched primary alkyl moiety is 14.
5 and up to about 17.5. Thus, the surfactant system comprises at least one branched primary alkyl sulfate surfactant compound, preferably having a longest carbon straight chain having 12 or more or 19 or less carbon atoms, including branched The total number of carbon atoms must be at least 14, and the average total number of carbon atoms in the branched primary alkyl moiety is greater than 14.5 and up to about 17.5.

R, R ¹ and R ² are each independently hydrogen and a C ₁ -C ₃ alkyl group (preferably hydrogen or C ₁ -C ₂ alkyl, more preferably hydrogen or methyl, most preferably methyl) Wherein R, R ¹ and R ² are not all hydrogen. Further, when z is 1, at least R
Or R ¹ is not hydrogen.

M is hydrogen or a salt-forming cation, depending on the method of synthesis. Examples of salt forming cations are lithium, sodium, potassium, calcium, magnesium, quaternary alkylamines having the formula: and mixtures thereof.

R³ ｜ R⁶-N⁺-R⁴ ｜ R⁵ Where R³, R⁴, R⁵And R⁶Is independently hydrogen, C₁~ C₂₂ Alkylene, C₄~ C₂₂Branched alkylene, C₁~ C₆Alkanol, C ₁ ~ C₂₂Alkenylene, C₄~ C₂₂Branched alkenylene, and their
It is a mixture. The preferred cation is ammonium (R³, R⁴, R⁵And
And R⁶Is hydrogen), sodium, potassium, mono-, di-, and tria
Lucanol ammonium, and mixtures thereof. Monoalkano of the present invention
Ammonium compounds are represented by R³Is C₁~ C₆An alkanol, R⁴  , R⁵And R⁶Is hydrogen, and the dialkanol ammonium of the present invention is
, R³And R⁴Is C₁~ C₆An alkanol, R⁵And R⁶  Is hydrogen, and the trialkanol ammonium compound of the present invention is represented by R³, R ⁴ And R⁵Is C₁~ C₆An alkanol, R⁶Is hydrogen.
Preferred alkanol ammonium salts of the present invention are mono-, di-
-And tri-quaternary ammonium compounds.

H ₃ N ⁺ CH ₂ CH ₂ OH, H ₂ N ⁺ (CH ₂ CH ₂ OH) ₂ , HN ⁺ (CH ₂ CH ₂ OH) ₃ Preferred M is sodium, potassium and the C ₂ alkanol ammonium salts described above, most preferably sodium.

Further, with respect to the above formula, w is an integer of 0 to 13, x is an integer of 0 to 13, y is an integer of 0 to 13, z is an integer of at least 1, and w + x + y
+ Z is an integer of 8 to 14.

Another preferred surfactant system of the present invention comprises one or more branched primary compounds having the formula:
It has a lower alkyl sulfate.

[0022]

Embedded image Wherein the total number of carbon atoms including branches is 15-18, and when two or more of these sulfates are present, the average total number of carbon atoms in the branched primary alkyl moiety having the above formula is 14.5. And up to about 17.5, wherein R ¹ and R ² are each independently hydrogen or C ₁ -C ₃ alkyl;
Is a water-soluble cation, x is 0-11, y is 0-11, z is at least 2, x + y + z is 9-13, provided that both R ¹ and R ² are It cannot be hydrogen.

Preferably, the surfactant system comprises at least 20% by weight of the system, more preferably at least 60% by weight, even more preferably at least 90% by weight of the system, medium chain branched primary alkyl sulfate. Wherein preferably R ¹ and R ² are independently hydrogen or methyl, provided that R ¹ and R ² are not both hydrogen, x + y equals 8, 9 or 10 and z is at least 2, wherein the average total number of carbon atoms in these sulfate surfactants is preferably 14-18, more preferably 15-17, and even more preferably 16-17.

Further, preferred surfactant systems comprise at least about 20%, more preferably at least 60%, even more preferably at least 90%, by weight of the system, of one or more medium chain branched alkyl having the formula: A system comprising sulfate or a mixture thereof.

[0025]

Embedded image Wherein M represents one or more cations, a, b, d, and e are integers;
+ B is 10-16, d + e is 8-14, and when a + b = 10, a is an integer of 2-9, b is an integer of 1-8, and when a + b = 11, a is a Is an integer of 2 to 10, b is an integer of 1 to 9, when a + b = 12, a is an integer of 2 to 11, b is an integer of 1 to 10, and when a + b = 13 , A is an integer of 2 to 12, b is an integer of 1 to 11, when a + b = 14, a is an integer of 2 to 13, b is an integer of 1 to 12, and a + b = 15 In the case of, a is an integer of 2 to 14, b is an integer of 1 to 13, and when a + b = 16, a is an integer of 2 to 15, b is an integer of 1 to 14, d + e When d = 8, d is an integer of 2 to 7, e is an integer of 1 to 6, when d + e = 9, d is an integer of 2 to 8, Is an integer of 1 to 7, when d + e = 10, d is an integer of 2 to 9, e is an integer of 1 to 8, and when d + e = 11, d is an integer of 2 to 10. , E is an integer of 1 to 9, when d + e = 12, d is an integer of 2 to 11, e is an integer of 1 to 10, and when d + e = 13, d is an integer of 2 to 12. And e is an integer of 1 to 11, and when d + e = 14, d is an integer of 2 to 13 and e is an integer of 1 to 12, wherein 2 of these sulfate surfactants When more than one type is present in the surfactant system, the average total number of carbon atoms in the branched primary alkyl moiety having the above formula is greater than 14.5 and up to about 17.5.

Preferred mono-methyl branched primary alkyl sulfates are 3-methylpentadecanol sulfate, 4-methylpentadecanol sulfate, 5-methylpentadecanol sulfate, 6-methylpentadecanol sulfate,
7-methylpentadecanol sulfate, 8-methylpentadecanol sulfate, 9-methylpentadecanol sulfate, 10-methylpentadecanol sulfate, 11-methylpentadecanol sulfate, 12-methylpentadecanol sulfate, 13-methylpentadecanol sulfate Methyl pentadecanol sulfate,
3-methylhexadecanol sulfate, 4-methylhexadecanol sulfate, 5-methylhexadecanol sulfate, 6-methylhexadecanol sulfate, 7-methylhexadecanol sulfate, 8-methylhexadecanol sulfate, 9-methylhexadecanol sulfate Methylhexadecanol sulfate, 10-methylhexadecanol sulfate, 11-methylhexadecanol sulfate, 12-methylhexadecanol sulfate, 13-methylhexadecanol sulfate, 14-methylhexadecanol sulfate, and mixtures thereof Selected from the group consisting of:

Preferred di-methyl branched primary alkyl sulfates are 2,3-methyltetradecanol sulfate, 2,4-methyltetradecanol sulfate,
2,5-methyltetradecanol sulfate, 2,6-methyltetradecanol sulfate, 2,7-methyltetradecanol sulfate, 2,8-methyltetradecanol sulfate, 2,9-methyltetradecanol sulfate, 2 , 10-methyltetradecanol sulfate, 2,11-methyltetradecanol sulfate, 2,12-methyltetradecanol sulfate, 2,
3-methylpentadecanol sulfate, 2,4-methylpentadecanol sulfate, 2,5-methylpentadecanol sulfate, 2,6-methylpentadecanol sulfate, 2,7-methylpentadecanol sulfate,
2,8-methylpentadecanol sulfate, 2,9-methylpentadecanol sulfate, 2,10-methylpentadecanol sulfate, 2,11-
It is selected from the group consisting of methylpentadecanol sulfate, 2,12-methylpentadecanol sulfate, 2,13-methylpentadecanol sulfate, and mixtures thereof.

The following branched primary alkyl sulfates having 16 carbon atoms and having one branch unit are examples of preferred branched surfactants useful in the compositions of the present invention.

[0029]

Embedded image The following branched primary alkyl sulfates having 17 carbon atoms and having two branching units are examples of preferred branched surfactants of the present invention.

[0030]

Embedded image Builder system The detergent composition of the present invention comprises 0.5 to 25% by weight, preferably 1.0% by weight of the detergent composition.
-20%, more preferably 5-18%, even more preferably 8-18% by weight of a builder system.

[0031] The builder system of the present invention can comprise both water-soluble and partially water-soluble or water-insoluble builder compounds.

Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylic acid salts or their acid forms, homo- or copolymeric polycarboxylic acids or their salts. Preferably, the polycarboxylic acids or salts thereof comprise at least two carboxyl groups separated from one another by no more than two carbon atoms, borates, and mixtures of any of the above.

The carboxylate or polycarboxylate builder may be monomeric or oligomeric, but monomeric polycarboxylates are generally preferred for cost and performance reasons.

Suitable carboxylate salts or their acids containing one carboxy group include lactic acid,
And water-soluble salts of glycolic acids and their ether derivatives.

Polycarboxylates containing two carboxy groups or their acids include succinic, malonic, (ethylenedioxy) diacetate, maleic, diglycolic, tartaric, tartronic and fumaric acids. Water-soluble salts, as well as ether carboxylate and sulfinyl carboxylate. Polycarboxylates containing three carboxy groups or their acids include, in particular, water-soluble citrate, aconitate and citraconic acid salts, and succinate derivatives, such as GB 1,379.
No. 1,241, carboxymethyloxysuccinate, British Patent 1,389,732, lactoxysuccinate, and Dutch Application 72050873. Aminosuccinate and oxypolycarboxylate materials such as 2-oxa-1,1,3-propanetricarboxylate described in GB 1,387,447. The most preferred polycarboxylic acid containing three carboxy groups is the monohydrate of citric acid, preferably present in an amount of 0.1 to 15%, more preferably 0.5 to 8% by weight of the composition. , Anhydrous, or, optionally, in liquid form.

[0036] Polycarboxylates containing four carboxy groups include GB 1,261,8.
No. 29, oxydisuccinate, 1,1,2,2-ethanetetracarboxylate, 1,1,3,3-propanetetracarboxylate and 1,1
, 2,3-propanetetracarboxylate. Polycarboxylates or their acids containing sulfo substituents include British Patent Nos. 1,398,421 and 1,398,422 and U.S. Pat. No. 3,936,448. And the sulfosuccinate derivatives described in British Patent No. 1,439,
000 sulfonated pyrolytic citrate. Preferred polycarboxylates or their acids are hydroxycarboxylates containing up to 3 carboxy groups per molecule, especially citrates or citric acids as described above.

Of course, the parent acid of the monomeric or oligomeric polycarboxylates or mixtures of these acids and their salts, such as citric acid or citrate / citric acid mixtures, are also useful in the builder system of the present invention. Builder compound.

The organic polymeric compound is a preferred builder compound of the builder system of the detergent composition of the present invention, and is preferably present as a component that can act to bind all the particulate components together. The organic polymer compound is a builder, a dispersant,
And substantially all polymeric organic compounds commonly used as anti-redeposition and soil dispersants, but not the polymeric or oligomeric (poly) carboxylate compounds described above.

The organic polymeric compound is used in the builder system of the present invention, typically in the builder system.
It is present in an amount of 1 to 50% by weight, preferably 0.5 to 35% by weight, most preferably 1 to 20% by weight.

Such materials include the water-soluble salts of acrylic acid and maleic / maleic anhydride copolymers. The average molecular weight of the copolymer in such an acid form is 1,000
~ 100,000, more preferably 2,000-75,000, even more preferably up to 70,000, but with an average molecular weight of 2,500-20,000, or in other preferred embodiments 60,000-75,000. 000 or 75,000 copolymers are most preferred. The ratio of acrylate to maleate moieties in such copolymers is generally between 30: 1 and 1:30, more preferably between 10: 1 and 1: 1, and most preferably between 4: 1 and 7: 3. Such water-soluble salts of acrylic acid / maleic acid copolymer include, for example, alkali metal, ammonium and substituted ammonium salts. This type of soluble acrylate / maleate copolymer is a known material,
EP-A-66915, published December 15, 1982, and EP-A-193,360, published September 3, 1986.

[0041] Other suitable polymeric carboxylate-containing builder compounds can be derived from acrylic acid. Such acrylic polymers useful herein are, for example, water-soluble salts of polymerized acrylic acid. The average molecular weight of the homopolymer in such acid form is from 1,800 to 100,000, more preferably from 2,000 to 10,000, and most preferably from 3,000 to 5,000. Such water-soluble salts of acrylic acid polymers can include, for example, alkali metal, ammonium and substituted ammonium salts. This type of soluble polymer is a known material. The use of such polyacrylates in detergent compositions is described, for example, in Diehl, US Pat. No. 3,308,
No. 067, promulgated on March 7, 1967.

Polyamino compounds are also useful herein, such as compounds derived from aspartic acid,
For example, EP-A-305282, EP-A-305
283 and EP-A-351629.

Other examples of polymeric carboxylate-containing builder compounds suitable for the purposes of the present invention include maleic / acrylic / vinyl alcohol terpolymers. Such materials are also described in EP 193,360 and include, for example, the 45/45/10 terpolymer of acrylic acid / maleic acid / vinyl alcohol.

Also suitable here are terpolymers containing monomer units selected from maleic acid, acrylic acid and polyaspartic acid, especially terpolymers having an average molecular weight of 5,000 to 20,000.

Other useful polymeric carboxylate-containing builder compounds are polyelectrolyte-containing glycols, especially those having a molecular weight of 1,000 to 10,000, more preferably 2,000.
A material that is between 00 and 8,000, most preferably about 4,000.

[0046] Other preferred polymeric carboxylate-containing builder compounds are typically compounds having a hydrophilic backbone and at least one hydrophobic side chain.

Preferably, this type of polymeric carboxylate-containing builder compound has a molecular weight of from 500 to 100,000, more preferably from 1,000 to 70,000, particularly preferably from 1,500 to 10,000, or In another preferred embodiment,
800 to 6,000. The polymeric carboxylate-containing builder compounds used herein can be prepared, for example, using conventional aqueous polymerization procedures, and suitable methods are described, for example, in GB 8924477, GB 892447.
No. 8 and British Patent No. 8924479.

In general, the hydrophilic backbone of the polymer is primarily linear (the backbone of the backbone comprises at least 50%, preferably more than 75%, and most preferably more than 90% of the backbone).
, Suitable monomer units of the hydrophilic backbone are for example unsaturated C ₁ -C ₆ acids, ethers, alcohols, aldehydes, ketones or esters, sugar units, alkoxy units, maleic anhydride and saturated polyalcohols, for example glycols, It is. Preferably, the hydrophobic side groups are alkoxy groups, such as butylene oxide and / or
Or propylene oxide and / or an alkyl or alkenyl chain having 5 to 24 carbon atoms. The hydrophobic group can be connected to the hydrophilic backbone via a relatively hydrophilic bond, such as a polyethoxy bond.

Preferred polymeric carboxylate-containing builder compounds of this type are the polymers described in WO 91/08281.

Preferred counterions for polymeric organic (carboxylate-containing) builder compounds are, for example, sodium, magnesium or calcium ions.

[0051] Borate builders, as well as builders that include borate-forming materials capable of forming borate under detergent storage or washing conditions, are useful water-soluble builders herein.

[0052] The builder system of the present invention can comprise a phosphate-containing builder material. However, it may be preferred that the builder system be substantially free of phosphate-containing builders. Preferred examples of water-soluble phosphate builders are alkali metal tripolyphosphates, pyrophosphates of sodium, potassium and ammonium, pyrophosphates of sodium and potassium and ammonium, orthophosphates of sodium and potassium, having a degree of polymerization of about 6 to No. 21 and salts of phytic acid.

The builder system can also comprise a silicate-containing builder compound. Preferred are sodium silicates, preferably SiO ₂ : Na ₂ O = 2:
It has a ratio of 1. Amorphous sodium silicate is also preferred.

Another preferred silicate-containing builder compound is a crystalline sheet silicate, preferably sodium silicate. A preferred material is a crystalline layered silicate of the formula δ-Na ₂ Si ₂ O ₅ , called NaSKS-6 (Hoechst).

Highly preferred builders included in the builder system of the present invention are aluminosilicate zeolites, preferably having the following unit cell formula:

Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ]. xH in ₂ O formula, z and y are at least 6, the molar ratio of z to y is in 1.0-0.5, x is at least 5, preferably from 7.5 to 276, more preferably 10 to 26
4. The aluminosilicate material is in a hydrated form, preferably crystalline, and contains 10% to 28%, more preferably 18% to 22%, of water in bound form. The aluminosilicate zeolite may be a naturally occurring material, but a synthetic product is preferred. Synthetic crystalline aluminosilicate ion exchange materials are commercially available as zeolite A, zeolite B, zeolite P, zeolite X, zeolite HS, and mixtures thereof. Zeolite A has the formula Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]. has xH ₂ O, x is 20 to 30, in particular 27. Zeolite X has the formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]. To have a 276H ₂ O.

Another preferred aluminosilicate zeolite is a zeolite MAP builder.

The zeolite MAP is described in EP 384070A (Unilever). This material is defined as a zeolite P-type alkali metal aluminosilicate having a silicon to aluminum ratio of 1.33 or less, preferably 0.9 to 0.95.
1.33, more preferably 0.9 to 1.2.

Of particular interest are zeolite MAPs having a silicon to aluminum ratio of 1.15 or less, especially 1.07 or less.

[0060] In a preferred embodiment, zeolite MAP detergent builder has _a particle size, expressed as _{the d 50} value is 1.0 to 10.0 micrometers, more preferably 2.0 to 7.0 micrometers, and most preferably 2. 5 to 5.0 micrometers.

The d ₅₀ value indicates that 50% by weight of the particles have a diameter smaller than that value. In particular, particle size can be measured using conventional analytical techniques, for example microscopy using a scanning electron microscope or a laser granulometer. Another method of determining the the d ₅₀ value is described in EP 384070A.

[0062] alkalinity detergent composition of the present invention, preferably up to 50% by weight of the composition, more preferably 5 to 30 wt%, more preferably 8-20 wt%, more preferably 10 to 15
% By weight, comprising an alkalinity system comprising a carbonate.

Examples of preferred carbonates are alkaline earth and alkali metal carbonates, sodium carbonate, bicarbonate and sesquicarbonate, and German Patent Application No. 2,32
No. 1,001, published Nov. 15, 1973, mixtures of these salts with ultrafine calcium carbonate. Alkali metal percarbonates can also be included in the alkalinity system of the detergent composition, are also suitable carbonates and are described in more detail below.

A very suitable carbonate may be anhydrous sodium carbonate. Carbonate has a particle size of 20
0 μm to 900 μm particles, and anhydrous sodium bicarbonate has a particle size distribution of 400 μm.
It is preferably from μm to 1200 μm.

Other Detergent Components The detergent composition of the present invention can also include other detergent components. The exact nature of these other components and their loading will depend upon the physical form of the composition and the nature of the cleaning operation using the composition.

The composition of the present invention or a component thereof may contain other surfactants, bleaching agents, bleaching catalysts, other organic polymeric compounds, enzymes, foam inhibitors, lime soaps, dispersants, and soil dispersants. And preferably comprises one or more additional detergent components selected from anti-redeposition agents, soil release agents, fragrances, brighteners, photobleaches, and additional corrosion inhibitors. Other surfactants Anionic, zwitterionic, amphoteric and amphoteric (ampholytic) as desired.
teric) There may be other surfactants selected from the group consisting of surfactants.

The total amount of surfactant is preferably 1 to 95% by weight of the detergent composition, preferably 3%.
It is preferably from 70 to 70% by weight, more preferably from 5 to 40% by weight, still more preferably from 10 to 30% by weight, and most preferably from 12 to 25% by weight.

A preferred embodiment of the present invention is a granular detergent composition. One or more surfactants make up the base composition and can optionally include a hydrophobic peracid bleaching component and / or a hydrophilic nonionic surfactant. The base composition can be made by spray drying and dry mixing / agglomeration as disclosed herein.

Anionic Surfactant The detergent composition of the present invention further comprises one or more anionic surfactant. All anionic surfactants useful for cleaning purposes are suitable. Examples include salts of anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants (e.g., sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts). Anionic sulphate surfactants are preferred.

Other anionic surfactants include isethionates such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, sulfosuccinates monoester (particularly saturated and unsaturated _C 12 _{-C 18} monoesters), diesters of sulfosuccinate (especially saturated and unsaturated _C 6 _{-C 14} diesters), include N- acyl sarcosinates. Resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin,
Also suitable are resin acids and hydrogenated resin acids which are present in or derived from tallow oil.

The anionic surfactant preferably comprises from 0.5 to 60%, preferably from 3 to 50%, more preferably from 5 to 35%, most preferably from 6 to 20% by weight of the composition. Present in quantity.

[0072]Anionic sulfate surfactant Other anionic sulfate surfactants suitable for use herein include linear surfactants.
Primary and secondary alkyl sulfates, alkyl esters
Toxic sulfate, fatty oleoyl glycerol sulfate, alkyl phe
Nor ethylene oxide ether sulfate, C₅~ C₁₇Acyl-N- (
C₁~ C₄Alkyl) and -N- (C₁~ C₂Hydroxyalkyl)
Glucamine sulfate, and sulfates of alkyl polysaccharides, such as alkyl
Sulfates of polyglucosides (non-ionic non-sulfated compounds described herein),
Is mentioned. The alkyl sulphate surfactant is preferably linear,
And branched, first class C₉~ C₂₂Alkyl sulfate, more preferably C ₁₁ ~ C_FifteenBranched alkyl sulphate and C₁₂~ C₁₄Straight chain alkyl
Selected from sulfate. Alkyl ethoxy sulfate surfactants are good
More preferably, ethoxylate with 0.5 to 20 moles of ethylene oxide per molecule.
Done C₁₀~ C₁₈Select from the group consisting of alkyl sulfates. More preferred
In other words, the alkyl ethoxy sulfate surfactant is used in an amount of 0.5 to 7 per molecule.
Moles, preferably 1 to 5 moles of C ethoxylated with ethylene oxide.₁₁~ C ₁₈ , Most preferably C₁₁~ C_FifteenIt is an alkyl sulfate.

In a particularly preferred embodiment of the invention, a mixture of the preferred alkyl sulphate and alkyl ethoxy sulphate surfactants is used. Such a mixture is PC
It is described in T patent application WO 93/18124.

Anionic Sulfonate Surfactants Other anionic sulfonate surfactants suitable for use herein include C ₅ -C ₂₀ linear alkylbenzene sulfonates, alkyl ester _sulfonates, C 6 _{-C 22} primary or secondary alkane _sulfonates, C 6 _{-C 24} olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, Fatty oleyl glycerol sulfonate, and mixtures thereof.

Anionic Carboxylate Surfactants Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylate, alkyl polyethoxy polycarboxylate surfactants and soaps ("alkyl carboxyls"), in particular The particular secondary soaps mentioned are mentioned.

Suitable alkylethoxycarboxylates include those having the formula:

RO (CH ₂ CH ₂ O) _x CH ₂ COO ⁻ M ^{+ wherein} R is a C ₆ -C ₁₈ alkyl group, x is 0-10, and x is 0 in the ethoxylate. The amount of substance is distributed such that it is less than 20% by weight, and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula:

RO— (CHR ₁ —CHR ₂ —O) _x —R ₃ wherein R is a C ₆ -C ₁₈ alkyl group, x is 1 to 25, and R ₁ and R ₂ are hydrogen, methyl groups, succinic acid, hydroxy succinic acid, and is selected from the group consisting of a mixture thereof, R ₃ is hydrogen, has been or unsubstituted, substituted, hydrocarbons having a carbon number 1 to 8, And mixtures thereof.

Suitable soap surfactants include secondary soap surfactants that contain a carboxyl unit attached to a secondary carbon. Preferred secondary soap surfactants for use herein are 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octane. A water-soluble substance selected from the group consisting of acids and water-soluble salts of 2-pentyl-1-heptanoic acid. Certain soaps can also be included as foam inhibitors.

Alkali Metal Sarcosinate Surfactants Other suitable anionic surfactants are the alkali metal sarcosinates of the formula

R-CON (R ¹ ) CH ₂ COOM wherein R is a C ₅ -C ₁₇ linear or branched alkyl or alkenyl group, and R ¹ is a C ₁ -C ₄ alkyl group. And M is an alkali metal ion. Preferred examples are myristyl and oleylmethyl sarcosinate in the form of the sodium salt.

Nonionic surfactant When present in the detergent composition of the present invention, the nonionic surfactant is preferably present in an amount of 0.5 to 20% by weight, more preferably 1 to 15% by weight, and still more preferably Is 1.5
Present at low levels of ８8% by weight. When present, the ratio of nonionic surfactant to surfactant system is preferably 5: 1 to 1:20, more preferably 5: 1 to 1.
: 10, more preferably 1: 1 to 1:10.

Alkoxylated nonionic surfactants Almost all alkoxylated nonionic surfactants are preferred here.
Ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants include alkylphenols, nonionic ethoxylated alcohols, nonionic condensates of nonionic ethoxylated / propoxylated fatty alcohols, nonionic ethoxylates / propoxylates with propylene glycol It can be selected from the group of condensates and non-ionic ethoxylate condensation products with propylene oxide / ethylenediamine adducts.

Nonionic alkoxylated alcohol surfactants Condensation products of aliphatic alcohols with 1 to 25 moles of alkylene oxides, especially ethylene oxide and / or propylene oxide, are preferred for use herein. The alkyl chain of the aliphatic alcohol may be linear or branched, primary or secondary, and generally has from 6 to 22 carbon atoms. Particularly preferred is a condensation product of an alcohol having an alkyl group having 8 to 20 carbon atoms, or more preferably 9 to 15 carbon atoms, and 3 to 12 moles of ethylene oxide per mole of alcohol.

Nonionic polyhydroxyfatty acid amide surfactants Suitable polyhydroxyfatty acid amides for use herein are those having the following structural formula:

R²CONR¹In the formula, R1 is H, C₁~ C₄Hydrocarbyl, 2-hydroxyethyl, 2-
Hydroxypropyl, ethoxy, propoxy, or mixtures thereof, preferably
Is C1 -C4 alkyl, more preferably C1 -C4 alkyl₁Or C₂Alkyl, most preferred
Or C₁Alkyl (ie, methyl);₂Is C₅~ C₃₁Hid
Locarbyl, preferably linear C₅~ C₁₉Alkyl or alkenyl, more preferred
Preferably straight chain C₉~ C₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁ ~ C₁₇Alkyl or alkenyl, or a mixture thereof, wherein Z is
Has a hydrocarbyl straight chain with at least three hydroxyls directly attached to the chain
Polyhydroxyhydrocarbyls or their alkoxylation (preferably
Toxylated or propoxylated) derivatives. Z is preferably a reducing amino
It is obtained from a reducing sugar in a nomination reaction, more preferably Z is glycityl.

Nonionic Fatty Acid Amide Surfactants Suitable fatty acid amide surfactants include those having the formula: R ⁶ CON (R ⁷ ) _{2 In the} formula, R ⁶ is an alkyl group having ^{7 to} 21, preferably 9 to 17 carbon atoms, and each R ⁷ is hydrogen, C _{1 to} C ₄ alkyl, C ₁ to C _4. Selected from the group consisting of C ₄ hydroxyalkyl, and — (C ₂ H ₄ O) _x H, wherein x is 1-3
Is an integer.

Nonionic Alkyl Polysaccharide Surfactants Alkyl polysaccharides suitable for use herein are described in US Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986. Has 6 carbon atoms
And a hydrophilic group of a polysaccharide having 1.3 to 10 saccharide units, for example, a polyglycoside.

Preferred alkyl polyglycosides have the following formula:

R ² O (C _n H _2n O) _t (glycosyl) _{x wherein} R ² is an alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl having an alkyl group having 10 to 18 carbon atoms, and Wherein n is 2 or 3; t is 0-10; x
Is from 1.3 to 8. Glycosyl is preferably derived from glucose.

Amphoteric surfactants Suitable amphoteric surfactants for use herein include amine oxide surfactants and alkyl amphoteric carboxylic acids.

[0093] Suitable amine oxides include compounds having the formula:

R³(OR⁴)_xN⁰(R⁵)₂ Where R³Is an alkyl, hydroxyalkyl, a having 8 to 26 carbon atoms
Choose from silamidopropyl and alkylphenyl groups or mixtures thereof
And R⁴Is an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms
Or a mixture thereof, wherein x is 0-5, preferably 0-3, and each R⁵  Is an alkyl or hydroxyalkyl group containing 1 to 3, or
It is a polyethylene oxide group having 1 to 3 lenoxide groups. C₁₀~ C ₁₈ Alkyldimethylamine oxide, and C_10-18Acyl amido al
Killed dimethylamine oxide is preferred.

A good example of an alkyl amphoteric dicarboxylic acid is Miranol C2M Conc. Manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic Surfactants Zwitterionic surfactants can also be included in the detergent composition of the present invention.
These surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Can be roughly described as:
Betaine and sultaine surfactants are representative of the zwitterionic surfactants used herein.

Suitable betaines are compounds having the formula:

R (R ′)₂N⁺R²COO⁻ Where R is C₆~ C₁₈A hydrocarbyl group, each R¹Is typically C ₁ ~ C₃Alkyl, R²Is C₁~ C₅It is a hydrocarbyl group. Like
The new betaine is C_12-18Dimethyl-ammoniohexanoate and C_{1 0-18} Acylamidopropane (or ethane) dimethyl (or diethyl)
Betaine. Complex betaine surfactants are also suitable for use herein.

Cationic Surfactants Suitable cationic surfactants for use in the detergents of the present invention include quaternary ammonium surfactants. Preferably, the quaternary ammonium surfactant is mono C ₆ -C _16, preferably _C 6 _-C 10 N-alkyl or alkenyl ammonium surfactants, the remaining N positions are substituted methyl, the hydroxyethyl or hydroxypropyl groups. Monoalkoxylated and bis-alkoxylated amine surfactants are also preferred.

Another suitable group of cationic surfactants that can be used in the detergent compositions or components thereof are cationic ester surfactants. The cationic ester surfactant comprises at least one ester (i.e., -COO-) linkage and at least one ester bond.
It is a compound having surfactant properties, preferably water-dispersible, comprising two cationically charged groups.

Suitable cationic ester surfactants, including choline ester surfactants, are described, for example, in US Pat. Nos. 4,228,042, 4,239,660 and 4,260,529.

In a preferred embodiment, the ester linkage and the cationically charged group are at least 3 atoms (ie 3 chain length), preferably 3 to 8 atoms, more preferably 3 to 5 atoms within the surfactant molecule. Are separated from each other by spacer groups consisting of a chain comprising atoms, most preferably 3 atoms. The atoms forming the chain of the spacer group are selected from the group consisting of carbon, nitrogen and oxygen atoms and mixtures thereof, provided that any nitrogen or oxygen in the chain is only associated with carbon in the chain. Are combined. Thus, for example, -OO- (i.e., peroxide), -NN-, and-
Although spacer group having a N-O-bonds are excluded, for example, _-CH 2 -O-C
H ₂ - and _{-CH 2} -NH-CH 2 - spacer group having a bond are included. In a preferred embodiment, the chain of the spacer group comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.

Cationic mono-alkoxylated amine surfactants Cationic mono-alkoxylated amine surfactants having the general formula I below are preferred.

[0104]

Embedded image Wherein R ¹ is an alkyl or alkenyl moiety having from about 6 to about 18, preferably from 6 to about 16, most preferably from about 6 to about 14 carbon atoms, and R ² and R ³ Are each independently an alkyl group having 1 to about 3 carbon atoms, preferably methyl, most preferably both R ² and R ³ are methyl groups, R ⁴ is hydrogen (preferred), X ⁻ is selected from methyl and ethyl, and X ⁻ is an anion for providing electric neutrality, for example, chloride, bromide, methyl sulfate, sulfate,
And A is an alkoxy group, especially an ethoxy, propoxy or butoxy group, and p is 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8, provided that A is ethoxy. And when R ⁴ is hydrogen, p is 1 and R ¹ Not a _C 12 _{-C 14} alkyl group.

Preferably, the ApR ⁴ group in Formula I is a hydroxyalkyl group having p = 1 and having 6 or less carbon atoms, wherein the —OH group is a quaternary group having 3 or less carbon atoms. It is separated from quaternary ammonium nitrogen atoms. Particularly preferred ApR ⁴ groups are-
_{CH 2 CH 2 OH, -CH 2} CH 2 CH 2 OH, -CH 2 CH (C
H ₃₎ OH and _-CH (CH 3) a _{CH 2} OH, _-CH 2 _CH 2 OH is particularly preferred. Preferred R ¹ groups have 10 or fewer carbon atoms, or 8 or 9 carbon atoms or less. Preferred R ¹ groups are linear alkyl groups. With 8 or more carbon atoms
A linear R ¹ group which is 11, or 8 to 10 is preferred. Such highly preferred cationic surfactants have the formula wherein R ¹ is a C ₈ -C ₁₀ alkyl group, p is 1, A is ethoxy, and R ² and R ³ are methyl groups. Having.

Another highly preferred cationic mono-alkoxylated amine surfactant for use herein is a material having the formula:

[0107]

Embedded image Wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof;
Especially C ₁₀ -C ₁₄ alkyl, preferably C ₁₀ and C ₁₂ alkyl,
X is a convenient anion to balance the charge, preferably chloride or bromide.

As noted above, compounds of the above class include ethoxy (CH ₂ CH ₂ O) units (EO) with butoxy, isopropoxy [CH (CH ₃ ) CH ₂ O] and [CH ₂ CH ( CH ₃ ) O] unit (i-Pr) or n-propoxy unit (
Pr), or EO and / or Pr and / or i-Pr units.

The amount of the cationic mono-alkoxylated amine surfactant used in the detergent composition of the present invention is preferably 0.1 to 20% by weight of the composition, more preferably 0.4 to 20%.
7% by weight, most preferably 0.5-3.0% by weight.

Cationic bis-alkoxylated amine surfactant The cationic bis-alkoxylated amine surfactant preferably has the following general formula II:

[0111]

Embedded image Wherein R ¹ is an alkyl or alkenyl moiety having from about 8 to about 18, preferably from about 10 to about 16, most preferably from about 10 to about 14, and R ² has from 1 to 3 carbon atoms. Certain alkyl groups, preferably methyl, R ³ and R ⁴ can be independently varied and are selected from hydrogen (preferred), methyl and ethyl, and X ⁻ is one that provides electrical neutrality. Sufficient anions, such as chloride, bromide, methylsulfate, sulfate, etc., and A and A ′ can vary independently and are each C ₁ -C ₄ alkoxy, especially ethoxy (ie, ethoxy) −
CH ₂ CH ₂ O-), propoxy, selected from butoxy and mixtures thereof, p is from 1 to about 30, preferably from 1 to about 4, q is from 1 to about 30, preferably in from 1 to about 4 , Most preferably, both p and q are 1.

Highly preferred cationic bis-alkoxylated amine surfactants for use herein are those having the formula:

[0113]

Embedded image Wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof;
Preferably C ₁₀ , C ₁₂ , C ₁₄ alkyl and mixtures thereof, X is a convenient anion to balance the charge, preferably chloride. Respect general cationic bis alkoxylated amine structure noted above, since in a preferred compound ^{R 1} is derived from _(coconut) C 12 _{-C 14} alkyl fraction fatty acids, ^{R 2} is methyl, ApR ³ and A ' qR ⁴ is each monoethoxy.

Other cationic bisalkoxylated amine surfactants suitable for use herein include compounds having the formula:

[0115]

Embedded image Where R¹Is C₁₀~ C₁₈Hydrocarbyl, preferably C₁₀~ C₁₄A
And independently p is 1 to about 3; q is 1 to about 3;²Is C ₁ ~ C₃X is alkyl, preferably methyl, and X is an anion, especially chloride.
Or bromide.

Other compounds of the above type include ethoxy (CH ₂ CH ₂ O) units (EO)
But butoxy (Bu), isopropoxy _{[CH (CH 3) CH 2} O] and _{[CH 2 CH (CH 3)} O] units (i-Pr) or n- propoxy units (
Pr), or EO and / or Pr and / or i-Pr units.

The amount of the cationic bis-alkoxylated amine surfactant used in the detergent composition of the present invention is preferably from 0.1 to 20% by weight of the composition, more preferably from 0.4 to 20%.
7% by weight, most preferably 0.5 to 30% by weight.

Optional Surfactants Suitable optional surfactants include secondary soap surfactants containing a carboxyl unit attached to a secondary carbon. Preferred secondary soap surfactants for use herein are 2-methyl-1-undecanoic acid, 2-ethyl-1
A water-soluble substance selected from the group consisting of water-soluble salts of decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as foam inhibitors.

Other optional additional anionic surfactants are carboxylate anionic surfactants known in the art and alkali metal sarcosinates of the formula:

R-CON (R ¹ ) CH ₂ COOM wherein R is a C ₅ -C ₁₇ linear or branched alkyl or alkenyl group, and R ¹ is a C ₁ -C ₄ alkyl group. And M is an alkali metal ion. Preferred examples are myristyl and oleylmethyl sarcosinate in the form of the sodium salt.

Other preferred components of the perhydrate bleach detergent are perhydrate bleach, such as metal perborates, metal percarbonates, especially sodium salts. The perborate may be a mono- or tetrahydrate. Sodium percarbonate is 2Na ₂ CO ₃ . Having a formula corresponding to 3H ₂ O ₂ ,
It is commercially available as a crystalline solid.

Potassium peroxymonopersulfate, sodium per, is another inorganic perhydrate salt optionally used in the detergent compositions of the present invention.

[0123] Preferred embodiments of the organic peracid bleach detergent composition is an organic peracid bleaching system. In a preferred embodiment, the bleaching system comprises a hydrogen peroxide source and an organic peracid bleach precursor compound. Organic peracids are formed by the in situ reaction of a precursor and a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the claimed perborate bleaches of the present invention. In another preferred embodiment, the preformed organic peracid is incorporated directly into the composition. Compositions comprising a mixture of a hydrogen peroxide source and an organic peracid precursor in combination with a preformed organic peracid are also contemplated.

Peracid bleach precursor Precursor bleach precursor is a compound that reacts with hydrogen peroxide in a perhydrolysis reaction to form peracid. Generally, the peracid bleach precursor is represented as O ＯX-C-L, where L is a leaving group and X is the structure of the peracid formed by perhydrolysis, O ＯX-C-L. Substantially all functional groups such as OOH.

The peracid bleach precursor compound is preferably present in an amount of 0.5 to 20%, more preferably 1 to 15%, most preferably 1.5 to 10% by weight of the detergent composition. Suitable peracid bleach precursor compounds typically contain one or more N- or O-acyl groups, and these precursors can be selected from a wide range of groups. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials falling into these categories are described in GB-A-1586789. Suitable esters are described in GB-A-836988, GB-A-8647.
No. 98, GB-A-1147871, GB-A-21432
No. 31 and EP-A-0170386.

[0126] leaving group leaving group (hereinafter, referred to as L group) must have a sufficient reactivity as the reaction occurs within the optimum time frame (e.g. wash cycle). However, if the reactivity of L is too high, the activator becomes difficult to stabilize for use in bleaching compositions.

Preferred L groups are selected from the group consisting of the following materials, and mixtures thereof:

[0128]

Embedded image In the formula, R ¹ is an alkyl, aryl, or alkaryl group having 1 to 14 carbon atoms, R ³ is an alkyl chain having 1 to 8 carbon atoms, R ⁴ is H or R ³ , Y is H or a group imparting solubility. Any of R ¹ , R ³ and R ⁴ may be substituted by substantially all functional groups including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.

[0129] groups that impart desirable _{^{solubility, -SO 3 - M +, -CO}} 2 - M +, -S
_{^{O 4 - M +, -N +}} (R 3) 4 X - and O <- ^{N (R} _{3) 3} and most preferably -SO ₃ ^- M ⁺ and _-CO ² - a ^{M +,} R ³ is an alkyl chain having 1 to 4 carbon atoms; M is a cation for imparting solubility to the bleach activator;
Are anions that impart solubility to the bleach activator. Preferably M is an alkali metal, ammonium or substituted ammonium cation, most preferably sodium and potassium, and X is a halide, hydroxide, methyl sulfate or acetate anion.

Alkyl percarboxylic acid bleach precursor The alkyl percarboxylic bleach precursor forms percarboxylic acid by perhydrolysis. Preferred precursors of this type form peracetic acid by perhydrolysis.

Preferred imide-type alkyl percarboxylic acid precursor compounds are N-, N, N ¹ N ¹ tetraacetylated alkylenediamines having 1 to 6 carbon atoms in the alkylene group, particularly 1 in the alkylene group having 1 carbon atom. 2 and 6. Tetraacetylethylenediamine (TAED) is particularly preferred. TAED is preferably not present in the agglomerated particles of the present invention, but is preferably present in the detergent composition comprising the particles.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), acetoxybenzene Sodium sulfonate (ABS) and pentaacetylglucose. Amide-Substituted Alkyl Peracid Precursors Amide-substituted alkyl peracid precursors are preferred herein and include those having the general formula:

[0133]

Embedded image Wherein R ¹ is an alkyl group having 1 to 14 carbon atoms, and R ² is an alkyl group having 1 carbon atom.
An alkylene group of １４14, R ⁵ is H or an alkyl group of 1-10 carbon atoms, and L may be substantially any leaving group. Amide-substituted bleach activator compounds of this type are described in EP-A-0170386.

Perbenzoic acid precursor The perbenzoic acid precursor gives perbenzoic acid by perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyl oxybenzenesulfonates, and products of benzoylation of sorbitol, glucose, and all saccharides with benzoylating agents, and Examples include imide-type perbenzoic acid precursor compounds including N-benzoylsuccinimide, tetrabenzoylethylenediamine and N-benzoyl-substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyroglutamic acid.

Cationic Peracid Precursor The cationic peracid precursor compound forms a cationic peracid by perhydrolysis.

Typically, the cationic peracid precursor is a compound in which the peracid moiety of a suitable peracid precursor compound is converted to a positively charged functional group, such as an ammonium or alkyl ammonium group, preferably an ethyl or methyl ammonium group. , And is formed by substitution. Cationic peracid precursors are typically included in solid detergent compositions in suitable anions,
For example, it exists as a salt with a halide ion.

The peracid precursor compound so cationically substituted may be perbenzoic acid or a substituted derivative thereof, a precursor compound described above. Alternatively, the peracid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peracid precursor described below.

Cationic peracid precursors are described in US Pat. No. 4,904,406, US Pat.
No. 751,015, No. 4,988,451, No. 4,397,75
No. 7, No. 5,269,962, No. 5,127,852,
Nos. 5,093,022 and 5,106,528, British Patent No. 1
382,594, EP 475,512, 45.
8,396 and 284,292, and Japanese Patent No. 87
-318,332.

Examples of preferred cationic peracid precursors are described in UK Patent Application No. 9407944.9.
And U.S. patent application Ser. Nos. 08 / 298,903, 08/2986.
Nos. 50, 08 / 298,904 and 08 / 298,906.

Suitable cationic peracid precursors include all ammonium or alkyl ammonium substituted alkyl or benzoyloxybenzene sulfonates,
N-acylated caprolactam, and monobenzoyltetraacetylglucosebenzoyl peroxide. Preferred cationic peracid precursors of the N-acylated caprolactam group include trialkyl ammonium methylene benzoyl caprolactam and trialkyl ammonium methylene alkyl caprolactam.

Benzoxazine organic peracid precursors, for example EP-A-332,294 and EP-A
Also suitable are benzoxazine-type precursor compounds as described in -482,807, especially compounds having the formula:

[0142]

Embedded image Wherein R ₁ is H, alkyl, alkaryl, aryl, or arylalkyl.

Preformed Organic Peracids The organic peracid bleaching system employs a preformed organic peracid, typically in one of the compositions, in addition to or instead of the organic peracid bleach precursor compound. -15% by weight, more preferably 1-10% by weight.

A preferred class of organic peracid compounds are amide substituted compounds having the general formula:

[0145]

Embedded image Wherein R ¹ is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R ² is an alkylene, arylene or alkarylene group having 1 to 14 carbon atoms, and R ⁵ is H Or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms. Such amide-substituted organic peracid compounds are described in EP-A-0170386.

Other organic peracids include diacyl and tetraacyl peroxides, especially diperoxidedecandionic acid, diperoxytetradecandionic acid and diperoxyhexadecandionic acid. Mono- and diperazelaic acids, mono- and diperbracyl acids and N-phthaloylaminoperoxycaproic acid are also suitable for the present invention.

The bleach-catalyzed detergent composition can include a transition metal-containing bleach catalyst.

Suitable types of bleach catalysts include transition metal cations with defined bleach catalytic activity, such as copper, iron or manganese cations, auxiliary metal cations with little or no bleach catalytic activity, such as Including zinc or aluminum cations, and sequestering agents having well-defined stability constants for catalysts and auxiliary metal cations, especially ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and their water-soluble salts. Catalyst system. Such catalysts are described in U.S. Pat. No. 4,430,243.

Another type of bleach catalyst is disclosed in US Pat. No. 5,246,621 and US Pat.
Includes manganese-based complexes described in Japanese Patent No. 5,244,594.
. Preferred examples of these catalysts include Mn^IV ₂(uO)₃(1,4,7-trim
Tyl-1,4,7-triazacyclononane)₂-(PF₆)₂ , Mn^III ₂(u-
O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂−
(ClO₄)₂ , Mn^IV ₄(uO)₆(1,4,7-triazacyclononane) ₄ -(ClO₄)₂ , Mn^IIIMn^IV ₄(uO)₁(u-OAc)₂(1,4,7
-Trimethyl-1,4,7-triazacyclononane)₂-(ClO₄)₃ , And mixtures thereof. Other catalysts are disclosed in published European patent application 549,2.
No. 72. Other suitable ligands here include 1,5,9-tooth
Limethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-to
Riazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2
, 4,7-Tetramethyl-1,4,7-triazacyclononane, and their
Mixtures are mentioned.

The bleach catalyst useful herein can be appropriately selected for the present invention. See U.S. Pat. Nos. 4,246,612 and 5,227,084 for examples of suitable bleaching catalysts. Mononuclear manganese (IV) complexes, such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononane)-(OC
Referring (PF _6), U.S. Patent No. 5,194,416 which discloses a - H _{3) 3.} Yet another type of bleach catalyst described in U.S. Pat. No. 5,114,606 comprises a ligand that is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Manganese (III), and / or
It is a water-soluble complex of (IV). Preferred ligands include sorbitol, iditol, dulcitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof. U.S. Pat. No. 5,114,611 discloses a bleaching catalyst comprising a complex of a transition metal, including Mn, Co, Fe or Cu, with a non- (large) cyclic ligand. The ligand has the following formula:

[0151]

Embedded image Wherein R ¹ , R ² , R ³ and R ⁴ are each R ¹ -N = C-R ² And R ³ -C = N-R ⁴ form a 5- or 6-membered ring, respectively.
, Substituted alkyl and aryl groups. The ring may be further substituted. B is a bridge group selected from O, S, CR ⁵ R ⁶ , NR ⁷ and C ＝ O, wherein R ⁵ , R ⁶ , and R ⁷ are each H
, Or an alkyl or aryl group, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. If desired, the ring may be substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. Particularly preferred is the ligand 2,2'-bispyridylamine. Preferred catalysts include Co, Cu, Mn, Fe, -bispyridylmethane and bispyridylamine complexes. Highly preferred catalysts include Co (2,2 '
-Bispyridylamine) Cl ₂ , di (isothiocyanato) bispyridylamine-cobalt (II), trisdipyridylamine-cobalt (II) perchlorate, Co (2
, _{2-bispyridylamine)} 2 _O 2 ClO _4, perchloric acid bis (2,2'
Bispyridylamine) copper (II), tris (di-2-pyridylamine) iron perchlorate (I)
I), and mixtures thereof.

Other examples include N ₄ Mn ^III (u—O) ₂ Mn ^IV N ₄ ) ⁺ and [Bipy ₂ Mn ^{II I} (u—O) ₂ Mn ^IV Bipy ₂ ] — (ClO ₄ ) ₃ . And dinuclear Mn complexes with 4-N- and 2-N-dentate ligands.

Other bleaching catalysts are described, for example, in published European patent application 408,131 (
Cobalt complex catalysts), published European patent applications 384,503 and 306,089 (metallo-porphyrin catalysts), U.S. Pat.
8,455 (manganese / polydentate catalyst), U.S. Pat. No. 4,711,7
No. 48 and published European patent application 224,952 (manganese absorbed on aluminosilicate catalyst), U.S. Pat. No. 4,601,845 (aluminosilicate support with manganese and zinc or Magnesium salt), U.S. Pat. No. 4,626,373 (manganese / ligand catalyst), U.S. Pat.
, 119,557 (ferric complex catalyst), German Patent 2,054,019
US Pat. No. 4,430,243 (with manganese cations and non-catalytic metal cations). Chelating substances), and US Pat.
No. 28,455 (manganese gluconate catalyst).

The bleach catalyst is typically used in the compositions and methods of the present invention in a catalytically effective amount.
By "catalytically effective amount" is meant an amount sufficient to bleach and remove the soil of interest from the target substrate using any of the comparative test conditions. The test conditions vary depending on the type of washing device used and the habits of the user. Some users use very hot water for the washing operation, while others use hot or cold water. Of course, the catalytic performance of the bleaching catalyst is affected by such conditions, and the amount of bleaching catalyst used in a well-formulated detergent composition and bleaching composition can be adjusted as appropriate. In practice, but not by way of limitation, the compositions and methods of the present invention may comprise at least one
It can be adjusted to provide on the order of one tenth of a million parts active bleaching catalyst material in the wash water, preferably from about 1 ppm to about 200 ppm of the catalyst material in the wash liquor. To further illustrate this point, 3 micromoles of manganese catalyst is effective at 40 ° C., pH 10, under European conditions using perborates and peracids. Under US conditions, concentrations would need to be increased 3-5 fold to achieve the same result.

Other preferred ingredients useful in enzyme detergents are one or more additional enzymes.

Preferred additional enzyme materials include commercially available lipases, cutinases, amylases, neutral or alkaline proteases, cellulases, endases, esterases, pectinases, lactases and peroxidases conventionally formulated in detergent compositions. Suitable enzymes are described in U.S. Patent Nos. 3,519,570 and 3,533,139.

[0157] Preferred commercially available protease enzymes include Novo Industries A / S (Denmark).
From Alcalase, Savinase, Primase, Durazym, and the enzyme sold under the trade names Esperase, Gist-Brocades from the enzymes sold under the trade names Maxatase, Maxacal and Maxapem, the enzyme commercially available from Genencor International, and Examples include enzymes commercially available from Solvey Enzymes under the trade names Opticlean and Optimase. Protease enzymes are present in the detergent compositions of the present invention at 0.0% of the composition.
001 to 4% by weight of the active enzyme can be added.

Preferred amylases are, for example, α-α obtained from a special strain of B. licheniformis.
Amylase, which is disclosed in GB 1,269,839 (Novo).
In more detail. Preferred commercially available amylase include, for example, Gist-B
enzyme sold by rocades under the trade name Rapidase, and Novo Industries
There are enzymes sold by A / S under the trade names Termamyl and BAN. Amylase enzymes can be incorporated into the detergent compositions of the present invention in amounts of 0.0001 to 2% active enzyme by weight of the composition.

The lipolytic enzyme is present in an amount of 0.0001 to 2% by weight of the composition, preferably 0.001 to 2%.
It can be present in an amount of 1% by weight, most preferably 0.001 to 0.5% by weight active lipolytic enzyme.

[0160] Lipase may be those derived from fungi or bacteria, for example, Humicola sp., Obtained from Th ermomyces sp. Or Pseudomonas sp. Lipase production line comprising a Pseudomonas pseudoalcaligenes or Pseudomonas Fluore scence. Lipases obtained from chemically or genetically engineered mutants of these strains are also useful herein. Preferred lipases are obtained from Pseudomonas pseudoalcaligenes ,
It is disclosed in EP-B-0218272.

Another preferred lipase is to clone a gene obtained from Humicola lanuginosa and express the gene using Aspergillus oryza as a host, as disclosed in European Patent Application EP-A-0258068. And marketed under the trade name Lipolase from Novo Industries A / S, Bagsvaerd, Denmark. This lipase is disclosed in U.S. Pat. No. 4,810,414, Hu.
It is also disclosed in ge-Jensen et al., promulgated March 7, 1989.

Antifoaming System When the detergent composition of the present invention is formulated for a machine cleaning composition, it is preferably 0.01 to 15% by weight of the composition, preferably 0.05 to 10% by weight, and most preferably. 0
. Comprising a foam control system present in an amount of 1 to 5% by weight.

[0163] Suitable foam control systems for use herein can comprise substantially all known antifoam compounds, including, for example, silicone antifoam compounds and 2-alkylalkanol antifoam compounds. .

By defoaming compounds is meant here all compounds or mixtures of compounds which act by means of a solution of the detergent composition, in particular the foaming or foaming which occurs when the solution is stirred.

Particularly preferred antifoam compounds for use herein are the silicone antifoam compounds defined herein as all antifoam compounds containing a silicone component. Such silicone antifoam compounds typically also include a silica component. The term "silicone" as generally used in the present invention and throughout the industry encompasses a variety of relatively high molecular weight polymers containing various types of siloxane units and hydrocarbyl groups. Preferred silicone antifoam compounds are siloxanes, especially polydimethylsiloxanes having trimethylsilyl endblock units.

Other suitable defoaming compounds include monocarboxylic fatty acids and their soluble salts. These materials are described in U.S. Pat. No. 2,954,347, issued Sep. 27, 1960 to Wayne St. John. Monocarboxylic fatty acids and their salts used as foam inhibitors typically have 10 to 24 carbon atoms.
, Preferably 12 to 18 hydrocarbyl chains. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (eg, fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C ₁₈ -C ₄₀ ketones (eg, stearone), N-alkylated aminotriazines E.g. tri- to hexa-alkylmelamine or di-tetra-alkyldiamine formed as a reaction product of cyanuric chloride with 2 or 3 moles of a primary or secondary amine having 1 to 24 carbon atoms having 1 to 24 carbon atoms Chlorotriazine, propylene oxide, bisstearic acid amide and monostearyl dialkali metal (eg, sodium, potassium, lithium) phosphates and phosphates are mentioned.

Preferred foam control systems include (a) an antifoam compound, preferably a silicone antifoam compound, most preferably (i) an amount of 50-99%, preferably 75-95%, by weight of the silicone antifoam compound. A polydimethylsiloxane and (ii) a combination of silica in an amount of 1 to 50% by weight, preferably 5 to 25% by weight of the silicone / silica antifoam compound, said silica / silicone antifoam compound comprising 5 to 50%. (B) a dispersant compound in an amount of 0.5 to 10% by weight, preferably 1 to 10% by weight, most preferably poly A silicone glycol rake copolymer having an oxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of 1: 0.9 to 1: 1.1 (this Particularly preferred silicone glycol rake copolymers are commercially available from DOW Corning under the trade name DCO544), (c) an inert carrier fluid compound in an amount of 5 to 80% by weight, preferably 10 to 70% by weight (most preferably ethoxylated degree 5 to 50, preferably comprise comprising _C 16 _{-C 18} ethoxylated alcohol is 8-15).

[0169] Highly preferred particulate foam control systems are described in EP-A-02107.
No. 31 and comprising a silicone antifoam compound and an organic carrier material having a melting point of 50 ° C. to 85 ° C., wherein the organic carrier material has glycerol and a carbon chain having 12 to 20 carbon atoms. It comprises a monoester of a fatty acid. EP-A-0210721 discloses another preferred particulate foam control system wherein the organic carrier material comprises a fatty acid or alcohol having a carbon chain having 12 to 20 carbon atoms, Or a mixture thereof, having a melting point of 45 ° C to 80 ° C.

Polymeric Dye Transfer Inhibitor The present detergent composition is used in an amount of 0.01 to 10% by weight, preferably 0.05 to 0.5% by weight.
A polymeric dye transfer inhibitor.

[0171] The polymeric dye transfer inhibitor is preferably a polyamine N-oxide polymer, N-
It is selected from copolymers of vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof, wherein these polymers may be crosslinked.

A ) Polyamine N-Oxide Polymers Polyamine N-oxide polymers suitable for use herein comprise units having the following structural formula:

P | (I) Ax | R In the formula, P is a polymerizable unit, and OO O ‖ Ａ A is NC, CO, C, —O—, —S—, or —N—. , X is 0 or 1,
R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or a combination thereof, to which the nitrogen of the NO group can be added, or the nitrogen of the NO group Is a part of these groups.

The NO group is represented by the following general structure.

OO ↑ ↑ (R ₁ ) _x N- (R ₂ ) _y or ＮN- (R ₁ ) _x | (R ₃ ) _{z wherein} R ₁ , R 2 and R 3 are an aliphatic group, an aromatic group , A heterocyclic or alicyclic group or a combination thereof, wherein x and / or y and / or z are 0 or 1
And the nitrogen of the NO group can be added, or the nitrogen of the NO group forms part of these groups. The NO group may be part of the polymerizable unit (P) or may be added to the polymeric backbone, or a combination of both.

Suitable polyamine N-oxides in which the N—O group forms part of a polymerizable unit include those polyamines N-oxide in which R is selected from aliphatic, aromatic, cycloaliphatic or heterocyclic groups.
Comprising an oxide. One group of the polyamine N-oxides comprises the polyamine N-oxides wherein the nitrogen of the NO group forms part of the R group. Preferred polyamine N-oxides are those in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are those in which the N—O group is attached to a polymerizable unit. A preferred group of these polyamine N-oxides has the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group and the nitrogen of the NO functional group is a part of the R group. Or a polyamine N-oxide. Examples of these groups are polyamine oxides in which R is a heterocyclic compound, such as pyridine, pyrrole, imidazole and derivatives thereof.

The polyamine N-oxides can be obtained with almost all degrees of polymerization. The degree of polymerization is not critical as long as the material has the desired water solubility and dye dispersing power. Typically, the average molecular weight is between 500 and 1,000,000.

B) Copolymer of N-vinylpyrrolidone and N-vinylimidazole Suitable here are those having a preferred average molecular weight of 5,000 to 50,000,
It is a copolymer of N-vinylimidazole and N-vinylpyrrolidone. Preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1 to 0.5.
2.

C) Polyvinylpyrrolidone The detergent composition of the present invention may use polyvinylpyrrolidone (“PVP”) having an average molecular weight of 2,500 to 400,000. Suitable polyvinylpyrrolidone is a product name from ISP Corporation, New York, NY and Montreal, Canada
PVP K-15 (viscosity molecular weight 10,000), PVP K-30 (average molecular weight 40,000),
PVP K-60 (average molecular weight 160,000) and PVP K-90 (average molecular weight 360,
000). PVP K-15 is also available from ISP Corporation. BA
Other suitable polyvinylpyrrolidones commercially available from SF Corporation include Sokalan HP 165 and Sokalan HP 12.

D) Polyvinyloxazolidone In the detergent composition of the present invention, polyvinyloxazolidone can be used as a polymeric dye transfer inhibitor. The polyvinyl oxazolidone has an average molecular weight of 2,
500-400,000.

E) Polyvinylimidazole In the detergent composition of the present invention, polyvinylimidazole may be used as a polymeric dye transfer inhibitor. The polyvinyl imidazole preferably has an average molecular weight of 2,500 to 400,000.

Optical Brighteners The detergent compositions of the present invention can also optionally contain from about 0.005 to 5% by weight of certain hydrophilic optical brighteners.

The hydrophilic optical brighteners useful in the present invention include those having the following structural formula:

[0185]

Embedded image Wherein R ₁ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl, and R ₂ is N-2-bis-hydroxyethyl, N-
Selected from 2-hydroxyethyl-N-methylamino, morpholino, chloro and amino, M is a salt-forming cation, such as sodium or potassium.

In the above formula, when R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl, and M is a cation, for example, sodium, the brightener is 4,4 ′ -Bis [(4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and disodium salt. This special brightener substance is Ciba-Geigy Cor
It is commercially available from poration under the trade name Tinopal-UNPA-GX. Tinopal-UNPA-GX is a preferred hydrophilic optical brightener useful in the detergent compositions of the present invention.

In the above formula, R ₁ is anilino and R ₂ is N-2-hydroxyethyl-
N-2-methylamino, where M is a cation, such as sodium;
The brightener is 4,4'-bis [(4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2.
2'-Stilbene disulfonic acid disodium salt. This special brightener is commercially available from Ciba-Geigy Corporation under the trade name Tinopal 5BM-GX.

In the above formula, when R ₁ is anilino, R ₂ is morpholino, and M is a cation, for example, sodium, the brightener is 4,4′-bis [(4-anilino -6-morpholino-s-triazin-2-yl) amino]
-2,2'-stilbene disulfonic acid, sodium salt. This special brightener is commercially available from Ciba-Geigy Corporation under the trade name Tinopal AMS-GX. Polymeric Soil Release Agent The detergent composition of the present invention may optionally contain a known polymer soil release agent (hereinafter referred to as “SR”).
A "). If used, the SRA generally represents 0.01 to 10.0% by weight of the composition, in particular 0.1 to 5% by weight, preferably 0.2 to 3%.
. Accounts for 0% by weight.

Preferred SRAs are hydrophilic moieties for imparting hydrophilicity to the surface of hydrophobic fibers, such as polyester and nylon, and are deposited on hydrophobic fibers and remain there until the wash and rinse cycle is completed. And generally has a hydrophobic moiety that acts as an anchor for the hydrophilic moiety. As a result, dirt generated after the treatment with SRA is more easily washed in a later washing step.

Preferred SRAs are oligomeric terephthalic acids typically prepared by processes involving at least one transesterification / oligomerization (often using metal catalysts such as titanium (IV) alkoxides) And esters. Such esters are of course made using additional monomers that can be incorporated into the ester structure through one, two, three, four or more positions, without forming a tightly crosslinked overall structure. be able to.

Suitable SRAs are, for example, terephthaloyl and oxyalkyleneoxy repeats, as described in US Pat. No. 4,968,451, issued Nov. 6, 1990 to JJ Scheibel and EP Gosselink. Includes a substantially linear ester oligomer sulfonation product comprising an oligomeric ester backbone of the unit and a sulfonated end moiety derived from allyl covalently attached to the backbone. Such ester oligomers include (a) ethoxylating allyl alcohol and (b) converting the product of (a) to a two-stage ester with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG"). It can be produced by reacting in an exchange reaction / oligomerization step and reacting the products (c) and (b) with sodium metabisulfite in water. Another SRA is disclosed in U.S. Pat.
Non-ionic end-capped 1,2-propylene / polyoxyethylene terephthalate polyesters from Gosselink et al., Dec. 8, 1987, December 8, 1987, such as poly (ethylene glycol) methyl ether, DMT,
Includes materials made by transesterification / oligomerization of PG and poly (ethylene glycol) ("PEG"). Other examples of SRA include partially and fully anionic end-capped oligomeric esters of US Pat. No. 4,721,580, Jan. 26, 1988, Gosselink, such as ethylene glycol (" EG "), PG, DMT and oligomers obtained from Na-3,6-dioxa-8-hydroxyoctanesulfonate, U.S. Pat. No. 4,702.
No. 857, Oct. 27, 1987, Gosselink, nonionic capped block polyester oligomeric compounds such as DMT, methyl (Me
) Materials made from capped PEG and EG and / or PG, or DMT, EG and / or PG, a combination of Me-capped PEG and Na-dimethyl-5-sulfoisophthalate, and US Pat. No. 4,877. No. 896, Oct. 31, 1989, Maldonado, Gosselink et al., Anionic systems, especially sulfoalloyl end-capped terephthalates, the latter being useful in both laundry and fabric conditioning products. Is a typical material of SRA
Examples are ester compositions made from m-sulfobenzoic acid monosodium salt, PG and DMT, but optionally, but preferably, added PEG,
For example, PEG3400 is further included.

SRA includes simple copolymer blocks of ethylene terephthalate or propylene terephthalate and polyethylene oxide or polypropylene oxide terephthalate (US Pat. No. 3,959,230, Hays, May 2, 1976).
5th, and U.S. Pat. No. 3,893,929, Basadur, July 1975
Month 08, reference), cellulosic derivatives, such as the commercially available hydroxy ether cellulosic polymer as METHOCEL from _Dow, C 1 -C ₄ alkylcelluloses and _{C 4} hydroxyalkyl celluloses (US Pat. No. 4,000,093 , Dec. 28, 1976, Nicol, et al.) And the average degree of substitution (methyl) per anhydroglucose unit is about 1.6 to about 2.3, measured as a 2% aqueous solution at 20 ° C. Methyl cellulose ethers having a solution viscosity of about 80 to about 120 centipoise. Such materials are available as METOLOSE SM100 and METOLOSE SM200, trade names of methylcellulose ether manufactured by Shin-Etsu Chemical Co., Ltd.

Another group of SRAs are (I) nonionic terephthalates which use a diisocyanate coupling agent to link the polymeric ester structure (US Pat. No. 4,201,8).
No. 24, Violland et al. And U.S. Pat. No. 4,240,918, Lagasse et al.), And (II) trimellitic anhydride is added to a known SRA, and the terminal hydroxyl group is trimellitate. And SRA containing carboxylic acid ester end groups. By selecting an appropriate catalyst, trimellitic anhydride forms a bond at the end of the polymer through an isolated carboxylic acid ester of trimellitic anhydride, rather than opening an anhydride bond. Either nonionic or anionic SRAs can be used as starting materials, as long as they have an esterifiable hydroxyl end group. U.S. Pat. No. 4,525,524, Tu
See ng et al. Other types include (III) SRA based on anionic terephthalate having various urethane bonds (US Pat. No. 4,201,824, Vi
olland et al.).

Other Optional Ingredients Other optional optional ingredients suitable for incorporation into the compositions of the present invention include colorants and filler salts, with sodium sulfate being the preferred filler salt.

Highly preferred compositions comprise about 2 to about 10% by weight of an organic citric acid, preferably citric acid. Preferably, a small amount (about 20% by weight) is combined with a carbonate.
) Neutralizers, buffers, phase modifiers, hydrotropes, enzyme stabilizers, polyacids,
Foam control agents, opacifiers, antioxidants, bactericides, dyes, fragrances, such as U.S. Pat.
285,841, Barrat et al., Promulgated August 25, 1981, incorporated herein by reference.

Composition Forms The detergent compositions of the present invention can be manufactured in a variety of ways, including dry mixing and agglomeration of the various compounds contained in the detergent compositions.

The compositions of the present invention can take a variety of physical forms, such as tablets, flakes, pastels and bars, with a granular form being preferred.

Alternatively, the detergent composition should be compatible with the chlorine bleach to ensure that the user can add the chlorine bleach to the detergent composition at or during the start of the washing process. It can also be prescribed.

In general, the granular detergent compositions of the present invention can be manufactured in various ways, including dry mixing, spray drying, agglomeration and granulation.

The medium-chain branched surfactant system of the present invention preferably comprises other surfactants and is present in a granular composition in the form of surfactant agglomerated particles, preferably free of bleach precursors Flakes, prills, marumes, noodles and ribbons, but preferably in the form of granules. The most preferred method of processing the particles is to agglomerate the powder (eg, aluminosilicate, carbonate) with a highly active surfactant paste and adjust the particle size of the resulting agglomerates within certain limits. In such a process, one or more agglomerators, such as a pan agglomerator, a Z-blade mixer, or more preferably an in-line mixer, such as Schugi (Holland) BV, 29 Chroomstra
at 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH,
D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany, Mixer mixes an effective amount of powder with highly active surfactant paste. Most preferably, a high shear mixer, for example Lodige CB (trade name), is used. Typically, a highly active surfactant paste comprising 50-95%, preferably 70-85% by weight of a surfactant, including medium chain surfactants, is used. The paste can be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to prevent degradation of the anionic surfactant used. it can. The operating temperature of the paste is typically between 50C and 80C.

The average particle size of the components of the granular composition of the present invention is preferably such that particles having a diameter of more than 1.8 mm are 25% or less, and particles having a diameter of less than 0.25 mm are 25% or less. Should. Preferably, the average particle size is such that 10-50% of the particles are 0.2 mm-0.
. It should have a diameter of 7 mm.

The term average particle size as defined herein is calculated by passing a sample of the composition through a series of Tyler sieves to divide it into multiple fractions (typically five fractions). The weight fraction obtained is plotted against the sieve mesh size. The average particle size is 50% by weight of the sample
Is the size of the eye that passes.

The bulk density of the solid detergent composition of the present invention is from 330 g / l to 1240 g / l, more preferably from 380 g / l to 1200 g / l, most preferably 4 g / l to 1200 g / l.
20 g / liter to 850 g / liter. Bulk density is measured using a simple funnel and cup apparatus consisting of a conical funnel rigidly mounted on a foundation. The lower end of the funnel is equipped with a flap valve so that the contents of the funnel can be emptied into an axially aligned cylindrical cup located below the funnel. The height of the funnel is 130 mm and the inner diameter at the upper and lower ends is 130 mm and 40 mm, respectively. The funnel is mounted so that its lower end is 140 mm above the upper surface of the foundation. The overall height of the cup is 90 mm, the inside height is 87 mm and the inside diameter is 84 mm. The nominal volume of the cup is 500 ml.

During the measurement, the funnel is filled with powder by hand, the flap valve is opened and the cup is overfilled with powder. Remove the filled cup from the frame and pass an instrument with a straight blade, such as a knife, across the top edge of the cup to remove excess powder. The filled cup is then weighed and the value obtained for the weight of the powder is doubled, indicating the bulk density in g / l. Repeat the measurement as needed.

Washing Methods Machine washing methods typically involve cleaning soiled laundry with an effective amount of an aqueous washing solution in a washing machine in which an effective amount of the machine laundry detergent composition of the present invention has been dissolved or dispensed. Processing. An effective amount of the detergent composition is 10 g to 300 g dissolved or dispersed in a washing solution having a volume of 5 to 65 liters, which is a typical product usage amount and a washing solution volume generally used in a normal machine washing method. Means the product.

In a preferred mode of use, the detergent composition is formulated to be suitable for manual washing. In another preferred mode of use, the detergent composition is a pre-treatment or dipping composition used to pre-treat or soak soiled, dyed fabrics.

In the abbreviation detergent compositions used in the examples, the abbreviated components have the following meanings. LAS: sodium linear C ₁₂ alkyl benzene sulfonate TAS: sodium tallow alkyl sulfate C45AS: sodium C ₁₄ -C ₁₅ linear alkyl sulfate MES: C ₁₈ sulfomethyl ester of fatty acid CxyEzS: sodium C _1x -C _1y condensed with z mole of ethylene oxide branched alkyl sulfates MBASx, y: sodium chain branched alkyl sulfates, average number of carbon atoms x, carbon number y _C 48 SAS in branching units: sodium _C 14 _{-C 18} secondary alcohol sulfates SADE2S: formula 2- (R). _{C 4 H 7 -1,4- (SO 4} -) 2 Sodium _C 14 _{-C 22} alkyl disulfate _{(wherein, R} = C 10 _{OC 18)}
Ethylene oxide z moles condensation C45E7: primarily linear primary alcohol CxyEz of _{C 14-15} condensed with an average of 7 moles of ethylene oxide: sodium condensed with an average z moles of ethylene oxide _{C 1x-1y} branched primary alcohol QASII : R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), where R ₂ = 50% to 60% C ₉ , 40% to 50% C ₁₁ QASIV: R ₁ N ⁺ (CH ₃ ) (C ₂ H _{4 OH) 2,} where ^{_{R 1 = C 12 ~C 14 QASV}} : R 2 (C 2 H 4 OH) X ( _{glycosyl) 2,} wherein ^{R 2} is _C 8 _{-C 10} alkyl group, t Is from 2 to 8 Soap: sodium linear alkyl carboxylate TFAA from an 80/20 mixture of tallow and coconut oil TFAA: C ₁₆ -C ₁₈ Alkyl N- methyl glucamide _{TPKFA: C 12 ~C 14 topped whole} cut fatty acids STPP: Anhydrous sodium tripolyphosphate Zeolite A: formula _{Na 12 (AlO 2 SiO 2)} 12. 27H ₂ O hydrated sodium aluminosilicate, primary particle size 0.1 to 10 μm NaSKS-6: crystalline layered silicate of formula δ-Na ₂ Si ₂ O ₅ Carbonate: anhydrous sodium carbonate, particle size 200 μm -900 μm bicarbonate: anhydrous sodium bicarbonate, particle size distribution 400 μm-1200 μm silicate: amorphous sodium silicate (SiO ₂ : Na ₂ O, 2.0 ratio) sodium sulfate: anhydrous sodium sulfate citric acid: anhydrous citrate Acid Citrate: trisodium citrate dihydrate, activity 86.4%, particle size distribution 425 μm-850 μm MA / AA: copolymer of maleic acid / acrylic acid 1: 4, average molecular weight about 70,000 MA / AA2: maleic acid / acrylic acid 4: 6 copolymer, average molecular weight about 3,000 MA / AA3: maleic acid / acrylic acid 4: 6 Copolymer, average molecular weight about 12,000 AA: sodium polyacrylate polymer, average molecular weight 4,500 CMC: sodium carboxymethylcellulose protease: proteolytic enzyme, activity 4KNPU / g, trade name of Savinase from NOVO Industries A / S Sale Alcalase: Proteolytic enzyme, activity 3AU / g, sold from NOVO Industries A / S Cellulase: Cellulose degrading enzyme, activity 1000CEVU / g, NOVO Industries A / S
Amylase: amylolytic enzyme, active 60 KNU / g, sold by NOVO Industries A / S from Termoyl 60T Lipase: lipolytic enzyme, active 100 KLU / g, from NOVO Industries A / S Endolase: Endoglucanase enzyme, activity 3000 CEVU / g, sold by NOVO Industries A / S PB4: Nominal NaBO ₂ . 3H ₂ O. Sodium perborate tetrahydrate of H ₂ O ₂ PB1: Nominal formula NaBO ₂ . H ₂ O ₂ anhydrous sodium perborate monohydrate bleach percarbonate: nominal formula 2Na 2 CO 3. Sodium percarbonate of 3H2 O2 NAC-OBS: (nonanamidocaproyl) oxybenzenesulfonate in the form of sodium salt NOBS: nonanoyloxybenzenesulfonate in the form of sodium salt DPDA: diperoxide decandionic acid PAP: N-phthaloylamide Peroxycaproic acid NAPAA: Nonanoylamide peroxo-adipic acid NACA: 6 Nonylamino-6-oxocaproic acid TAED: Tetraacetylethylenediamine DTPMP: Diethylenetriaminepenta (methylenephosphonate), Monsanto
Light activated: Encapsulated sulfonated zinc or aluminum phthalocyanine brightener 1: disodium 4,4'-bis (2-sulfostyryl) biphenyl brightener 2: disodium 4,4 '-Bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino) stilbene-2: 2'-disulfonate HEDP: 1,1-hydroxyethanediphosphonic acid PVNO: polyvinylpyridine N- oxide PVPVI: copolymer of polyvinyl pyrrolidone and vinyl imidazole QEA: bis _{((C 2 H 5 O)} (C 2 H 4 O n) (CH 3) -N + -C 6 H 12 -N + - ( CH ₃₎ bis _{((C 2 H 5 O)} - (C 2 H 4 O) n), n = 20~30 SRP1: oxyethylene oxy and terephthaloyl Sulfobenzoyl end-capped ester having a skeleton SRP2: Diethoxylated poly (1,2 propylene terephthalate) short block polymer Silicone defoamer: Polydimethylsiloxane foam modifier containing siloxane-oxyalkylene copolymer as dispersant Ratio of cell regulator to dispersant 10
: 1 to 100: 1

[0208]

【Example】

In the examples below, all amounts are given as parts by weight of the composition or% by weight of the composition.

Example 1 The following high-density granular laundry detergent compositions AF for use under machine wash conditions, especially in Europe, were prepared according to the present invention.

[0210] A B C D E F LAS 12.0 12.0 10 8.0 18.0 8.0 TAS 1.0 0 2.0 0 0 2.0 C25E9 3.4 - - 3.4 5.4 2.4 C25E7 - 3.0 4.5 - - - C46AS 2.0 2.0 - - - 4.0 C24AS - - 5.0 5.0 4.0 0.5 SADS - --- 1.0- MBAS 16.5, 1.7 6.0 3.0 8.0 10.5 4.0 2.0 QASII--0.8--0.8 Zeolite A 10.1 5.7 8.0 12.0 16.0 18.1 Carbonate 13.0 13.0 13.0 20.0 20.0 20.0 Citric acid 2.0 1.0 2.0 --- Silicate 1.4 1.4 1.4 3.0 3.0 1.0 Sulfate 26.1 26.1 26.1 26.1 26.1 26.1 MA / AA 0.3 2.0 ---- AA--- 0.5 2.0- CMC 0.2 0.2 0.2 0.2 0.2 0.2 PB4 9.0 9.0 9.0--- Percarbonate --- 18.0 15.0 20.0 TAED--1.0 1.5-- NAC-OBS 4.0 2.5 0.5 1.0 2.0 5.0 DTPMP 0.25 0.25 0.25 0.25 0.25 0.25 EDDS--0.25 0.4-- HEDP 0.3 0.3 0.3 0.3 0.3 0.3 QEA 0.5 1.0--0.5- Protease 0.26 0.26 0.26 0.26 0.26 0.26 Amylase 0.1 0.1 0.1 0.1 0.1 0.1 Photoactivated bleach (ppm) 15p p 15pp 15pp 15ppm 15ppm 15pp Brightener 1 0.09 0.09 0.09 0.09 0.09 0.09 Fragrance 0.3 0.3 0.3 0.3 0.3 0.3 Silicone defoamer 0.5 0.5 0.5 0.5 0.5 0.5 Density g / l 850 850 850 850 850 850 850

Example 2 The following granular laundry detergent compositions GI having a bulk density of 750 g / l are compositions of the present invention.

[0212] G H I LAS 18.0 8.0 11.5 TAS 1.25 2.86 1.57 C45AS 3.5 3.24 2.0 C25E3S - 3.0 1.0 C45E7 3.25 - - C25E3 - 3 5.5 3.5 QASI 0.8 2.0- MBAS 17, 1.5 7.0 10.0 5.0 STPP 10.5 Zeolite A-12.0 5.0 NaSKS-6 / silicate-5.5 10 6.6 (79:21) citric acid / citrate 2.0 2.0 1.0 carbonate 6.1 21.4 21.4 bicarbonate-2.0 2.0 silicate 2.0- - sodium sulfate 10.0 - 7.0 PB4 5.0 12.7 - TAED 0.5 0.2 - NAC OBS 1.0 2.2 - DTPMP 0.25 0.2 0.2 HEDP - 0.3 0.3 protease 0.26 0.85 0.85 lipase .15 0.15 0.15 Cellulase 0.28 0.28 0.28 Amylase 0.1 0.1 0.1 MA / AA 0.8 1.6 1.6 CMC 0.2 0.4 0.4 PVP--0.8 Light activated bleach (ppm) 15 ppm 27 ppm 27 ppm Brightener 1 0.08 0.19 0.19 Brightener 2-0.04 0.04 Fragrance 0.3 0.30 .3 silicone antifoam 0.5 2.4 2.4 total 100% not applicable without other / minor ingredients appropriate

Example 3 In the following detergent composition of the present invention, J is a phosphorus-containing detergent composition, K is a zeolite-containing detergent composition, and L is a compact detergent composition.

[0214] J K L M blown Powder STPP 8.0 - 12.00 - Zeolite A - 14.0 - 7.0 C45AS 4.0 - 4.0 5.0 QASI - 1.0 - - MBAS17, 1.5 4.0 11.0 10.0 6.0 SASDE2S 2.0 - - - C 25 AE 3 S - 1.0 - 1.0 MA / AA- 1.0-1.0 MA / AA2 2.0-1.0- LAS 14.0 2.0 3.0 1.6 TAS-4.0 2.0- Silicate 1.0 3.0 3.0- CMC 1.0 1.0 0.5 1.0 Brightener 2 0.2 0.2 0.2 0.2 Soap 1.0--1.0 DTPMP 0.4 0.4 0.2 0.4 Spray C45E7-2.5-- C25E3 2.5-4.0 1.5 Silicone defoamer 0.3 0.3 0.3 0.3 Fragrance 0.3 0.3 0.3 0.3 Dry additive QEA-0.5 1.0- Carbonate 6.0 13.0 15.0 13.0 PB4 18.0 18.0 10.0- PB1 4.0 4.0- - NOBS 3.0 4.2 1.0 - photoactive bleach 0.02 0.02 0.02 0.02 manganese catalyst - - 0.5 - protease 1.0 1.0 1.0 1.0 lipase 0.4 0.4 0.4 0.4 amylase 0.25 0.30 0.15 0.3 dry mixed sodium sulfate 3.0 3.0 5.0 3.0 remainder (water and 100.0 100.0 100.0 100.0 minor component) density (g / l) 630 670 670 670

Example 4 The following detergent composition is in accordance with the invention.

[0216] N O P Q LAS - 14.0 8.0 12.0 TAS - 1.0 4.0 - MBAS16.5, 1.8 15.0 10.0 6.0 8.0 C45AS 4.0 4.0 6.0 6.0 MES 3.0 - - - QASII 0.4 - 1.0 - TFAA - 1.0 - - C25E5 / C45E7 / C 25 E ₃ - 2.0 - 1.0 STPP 16.0 18.0 8.0 12.0 Silicate 2.0 1.0 5.0 6.0 Carbonate 13.0 7.5 4.0 5.0 Bicarbonate-7.5 -- DTPMP 0.7 1.0-- SRP1 0.3 0.2-0.1 MA / AA 2.0 1.0-1.0 AA--2.0- CMC 0.8 0.4 0.4 0.2 Protease 0.8 1.0 0.5 0.5 Amylase 0.8 0.4-0.25 Lipase 0.2 0.1 0.2 0.1 Cellulase 0.15 0.05-- Photoactive bleach (ppm) 70 ppm 45 ppm-10 ppm Brightener 1 0.2 0.2 0.08 0.2 PB1 6.0 2.0-- NACA---3.0 NAC OBS 2.0 1.0 0.9 3.1 remaining (moisture and 100 100 100 100 minor components)

Example 5 The following detergent composition is in accordance with the invention.

[0218] R S T blown powder MBAS16.5, 1.8 - 10.0 3.0 MBAS17, 2.6 6.0 - 4.0 Zeolite A 8.0 12.0 6.0 Sodium sulfate 19.0 5.0 7.0 MA / AA 1.0 3.0 1.0 MES - 5.0 - LAS 10.0 9.0 13.5 C45AS 3.0 4.0 7.0 silicate - 1.0 1.0 soap - - 2.0 Brightener 1 0.2 0.2 0.2 Carbonate 8.0 16.0 20.0 Spray C45E5 1.0 1.0- Dry additive PPVVI / PVNO 0.5 0.5 0.5 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.1 0.1 0.1 Cellulase 0.1 0.1 0.1 NOBS-6.1- NAC OBS-- 4.5 sodium sulfate - 6.0 - rest (moisture and 00 100 100 minor component)

Example 6 The following high density, bleach-containing detergent composition is in accordance with the invention.

[0220] U V W blown Powder Zeolite A - 7.0 10.0 Sodium sulfate 0.0 5.0 0.0 LAS 10.0 - 10.0 C45AS 3.0 2.0 4.0 QAS - - 1.5 DTPMP 2. 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA / AA 4.0 2.0 2.0 MBAS 6.5, 1.8 5.0 8.0 4.0 Aggregate LAS 0 1.0 1.0 TAS 2.0 2.0 1.0 silicate 3.0 3.0 4.0 Zeolite A 8.0 5.0 5.0 carbonate 8.0 8.0 4.0. 0 spray capsules contained perfume 0.3 0.3 0.3 C25E3 2.0 - 2.0 dry additives QEA - - 0.5 citrate 5.0 - 2.0 bicarbonate - 3.0 - carbonate 8.0 15.0 10.0 NAC OBS 6.0 - 5.0 manganese catalyst - - 0.3 N OBS-2.0- PB1 14.0 7.0 10.0 Polyethylene oxide-0.2 Molecular weight 5,000,000 Bentonite clay-10.0 10.0 Citric acid-1.0 0.5 Protease 1.0 1.0 0 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone defoamer 5.0 5.0 5.0 Dry additive Sodium sulfate 0 0.0 3.0 0.0 Residual (moisture and minor components 100.0 100.0 100.0 ) Density (g / liter) 850 850 850

Example 7 The following high-density detergent composition is in accordance with the invention.

[0222] XY aggregate MES-12.0 LAS 12.0- TAS-2.0 C45AS 6.0 4.0 MBAS 16.5, 1.6-9.0 MBAS 16.5, 2.8 10.0- Zeolite A 10.06 0.0 carbonate 4.0 8.0 MA / AA 1.0 2.0 CMC 0.5 0.5 DTPMP 0.4 0.4 spray --- C25E3 1.0 1.0 perfume 0.5 0.5 Drying additive HEDP 0.5 0.3 SKS6 5.0 6.0 citrate-1.0 citric acid 2.0- NAC OBS 4.1- TAED 0.8 2.0 percarbonate 20.020 .0 SRP1 0.3 0.3 protease 1.4 1.4 lipase 0.4 0.4 cellulase 0.6 0.6 amylase 0.6 0.6 QEA 1.0 - silicone antifoam 5.0 5 .0 brightener 1 0.2 0.2 Brightener 0.2 - Density (g / liter) 850 850

Example 8 The following granular detergent composition is an example of the present invention.

[0224] AH AI AJ Blown powder MES-2.0- LAS 2.0-3.0 C45AS-1.0- C46AS 4.0- C45AE35 7.0 5.0 3.0 MBAS 14.5, 1.7 8.0- - zeolite A 6.0 4.0 6.0 MA / AA2 1.0 - - sodium sulfate 3.3 24.0 13.3 silicate 1.0 2.0 1.0 carbonate 9.0 15. 0 8.0 QEA 0.4-0.5 PEG 4000-1.0 1.5 Brightener 0.3 0.3 0.3 Spray C25E5 0.5 1.0- Fragrance 0.3 1.0 0. 3 Aggregate C45AS 5.0 2.0 5.0 LAS 4.0 11.0 2.0 MBAS17, 2.0 15.0 6.0- Zeolite A 7.5-7.5 HEDP 1.0-2.0 Carbonate 4.0-4.0 PEG 4000 0.5- 0.5 Other (water, etc.) 2.0-2.0 Dry additive NOBS 4.0-- TAED--2.0 PB4 1.0-2.0 Carbonate 5.3-2.5 Cumene sulfone Acid 2.0-2.0 Lipase 0.4 0.1 0.05 Cellulase 0.2-0.2 Amylase 0.3-- Protease 1.6-1.6 PVPVI 0.5-- PVNO 0.5 − − SRP1 0.5 − − Silicone defoamer 0.2 − 0.2

Example 9 AK AL AM AN AO AP C45AS 11.0 5.1 4.0 8.5 4.1 9.8 C25 AES 1.3 1.0-1.3 1.0- LAS 9.4 6.6 23.5 3.7 1.7 4.3 C25E3 / C25E5 1.5 4.7 3.3 1.5 4.7 3.3 MBAS 16.5, 1.7 9.0 5.0 10.0 12.2 5.9 14.1 QAS-1.15 0.7 - 1.7 - zeolite A 16.0 10.7 8.0 7.7 16.7 10.0 SKS -6 - 9.0 6.0 - 3.0 5.0 citric acid - 1.5 - - 1.5 - MA / AA - 0.6 - - 0.6 - MA / AA3 - - 3.0 - - 2.0 AA 2.2 - -2.6 -- EDDS-0.3--0.3- HEDP-0.5--0.5- Carbonate 26.0 12.5 14.9 26.0 12.5 14.9 Silicate 0.8 0.8 3.0 0.8 0.8 3.0 PB1 1.0-3.9 1.0-3.9 NACA-OBS-2.75--2.7 - PC - 17.3 - - 17.3 - NOBS - 2.7 4.0 - - 4.0 TAED - 3.5 - - 3.5 - protease 0.26 0.3 0.2 0.6 0.3 0.2 lipase - - - - - - cellulase 0.3 0.2 - 0.3 0.3 - amylase - 0.3 - - 0.3 - Brightener 0.17 0.06 0.30 0.17 0.06 0.3 SRP1 0.41 0.2 0.5 0.41 0.2 0.5 PEG 1. 6 - 0.19 1.6 - 0.19 Sulfate 5.8 6.4 3.0 5.5 6.0 3.8 CMC - 0.5 - - 0.5 - MgSO4 - 0.13 - - 0.13 - photobleach - 0.0026 - - 0.0026 - Silicone antifoam 0.02 0.21 0.17 0.02 0.21 0.17 Perfume 0.42 0.55 0.25 0.42 0.55 0.25

Example 10 The following laundry detergent compositions AQ-AT are prepared according to the present invention.

[0227] AQ AR AS AT MBAS 16.5, 1.7 22 16.5 11 5.5 C45AS 8 10 11 4 C45E1S 43-1 LAS 814-4 C16SAS--3- MES--12- C23E6.5 1.5 1.5 1.5 1.5 Zeolite A 7.0 10.0 12.0 14.0 AA 2.3 2.3 2.3 2.3 Carbonate 7.0 15.0 27.0 25.0 Silicate 0.6 0.6 0.6 0.6 Perborate 1.0 1.0 1.0 1.0 Protease 0.3 0.3 0.3 0.3 Cellulase 0.3 0.3 0.3 0.3 SRP1 0.4 0.4 0.4 0.4 Brightener 0.2 0.2 0.2 0.2 PEG 1.6 1.6 1.6 1.6 Sulfate 5.5 5.5 5.5 5.5 Silicone defoamer 0.42 0.42 0.42 0.42 Moisture and minor components --- Remainder-- Density (g / L) 660 660 660 660

Example 11 The following laundry detergent compositions AU to AY are prepared according to the present invention.

[0229] AU AV AW AX AY MBAS 16.5, 1.7 14.8 16.4 12.3 8.2 4.1 C45AS 5 7 6 4 12 C45E3S 2-4-5 LAS 148-18 5 C16SAS--1-1 MES--10-- TFAA 1.600 0 C24E3 4.9 4.9 4.9 4.9 4.9 Zeolite A 10 5 7 11 15 NaSKS-6 69 5 2.0 4.6 Citrate / citric acid 1.0 1.0 2.0-0.5 MA / AA 4.8 2.8-1.0 1.0 HEDP 0.5 0.5 0.5 0.5 0.5 Carbonate 8.5 8.5 8.5 8.5 8.5 PB1 13.0-15.0 -- Percarbonate-20.7-20.7 20.7 NACAOBS 4.0 3.0 1.0-- TAED--4.8 4.8 4.8 QEA 1.0 1.0--- QAS 1.0 --- 1.0 Protease 0.9 0.9 0.9 0.9 0.9 Lipase 0.15 0.15 0.15 0.15 0.15 Cellulase 0.26 0.26 0.26 0.26 0.26 Amylase 0.36 0.36 0.36 0.36 0.36 SRP 0.2 0.2 0.2 0.2 0.2 Brightener 0.2 0.2 0.2 0.2 0.2 Sulfate 2.3 2.3 2.3 2.3 2.3 Silicone defoamer 0.4 0.4 0.4 0.4 0.4 Water and minor components- - remaining - density g / L) 850 850 850 850 850

Example 12 The following laundry detergent compositions AZ-Ee are prepared according to the present invention.

[0231] AZ Aa Bb Cc Dd Ee MBAS 16.5, 7.1 32 24 12 16 16 8 C45AS 5 8 6.5 5.0 12.0- C45E1S----2.5 7.2 LAS-2.0 8 23 12 16 C16SAS 1.0----- MES 14 --- - - C23E6.5 3.6 3.6 3.6 3.6 3.6 3.6 QAS - 0.5 - - 0.5 - zeolite A 9.0 5.0 12.0 3.0 9.0 8.0 polycarboxylate 2.0 5.0 3.0 7.0 6.0 5.0 carbonate 18.4 18.4 18.4 18.4 18.4 18.4 silicate 1.0 10 5.0 10 4.5 3.0 Perborate 3.9 3.9 3.9 3.9 3.9 3.9 NOBS 4.1 4.1 4.1 4.1 4.1 4.1 Protease 0.9 0.9 0.9 0.9 0.9 0.9 SRP1 0.5 0.5 0.5 0.5 0.5 0.5 Brightener 0.3 0.3 0.3 0.3 0.3 0.3 PEG 0.2 0.2 0.2 0.2 0.2 0.2 Sulfate 5.1 5.1 5.1 5.1 5.1 5.1 Silicone defoamer 0.2 0.2 0.2 0.2 0.2 0.2 Moisture and minor components -Remains- Density (g / L) 810 810 810 810 810 810

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (GH, KE, LS, MW, SD, SZ, UG, ZW) , EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR , LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW (71) Applicant ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventor Gabor, Hertvics-UK New Zealand Appon-Tyne, Kenton, Bellingham, Court, 38 (72) Inventor Francisco, Ramon, Figurore, United Kingdom Tyne, And, Ware, North, Shields, Preston, Wood, 35 (72) Inventor Kenneth, William, Willman Williamsva, Fairfield, Ohio, United States , 5603 (72) Inventor Michael, Alan, John, Moss Northern England, Stocksfield, Painshawfield, Road, UK, 13 (72) Inventor Tomoko Katsuta Minatojima, Chuo-ku, Kobe, Hyogo Prefecture 6-2-1 Kobe Park City C507 F-term (reference) 4H003 AB19 AB27 AC08 AE06 BA10 DA01 EA12 EA15 EA16 EA20 EA28 EB08 EB12 EB19 EB22 EB23 EB24 EB26 EB30 EB32 EB37 EB42 EC01 EC02 EE05 FA32

Claims (10)

[Claims] 1. A solid detergent composition having a density of from 330 g / l to 1400 g / l, comprising: a) at least 0.5%, preferably at least 5%, more preferably at least 0.5% by weight of the composition. 10 wt%, long alkyl chain having the formula, and a surfactant system comprising medium chain branching surfactant compounds, a b ^-X-B [in the above formula, (I) a ^b is a carbon A hydrophobic medium chain branched alkyl moiety having a total number of 9 to 22, preferably 12 to about 18, and (1) the longest carbon straight chain having 8 to 21 carbon atoms is added to the -XB moiety. and which, (2) is branched is C ₁ -C ₃ alkyl moiety of 1 or more from this longest linear carbon chain, (3) adding at least one is, -X-B moiety of the branched alkyl moiety Counting from the carbon at position 1 (# 1) (4) at the position within the range from the position of carbon 2 to the position obtained by subtracting two carbons from the terminal carbon [(ω-2) carbon], to the longest carbon straight chain carbon; when two or more of these compounds is present, a ^b -X in the above formula
The average total number of carbons in the moiety is greater than 14.5 to about 18, preferably about 15 to about 17, and (II) B is sulfate, sulfonate, amine oxide, polyoxyalkylene, preferably polyoxyethylene and polyoxyethylene. Oxypropylene, alkoxylated sulfate, polyhydroxy moiety, phosphate ester, glycerol sulfonate, polygluconate, polyphosphate ester, phosphonate, sulfosuccinate, sulfosuccinate, polyalkoxylated carboxylate, glucamide, taurinate, sarcosinate, glycinate , Isethionate, dialkanolamide, monoalkanolamide, monoalkanolamide sulfate, diglycolamide, diglycolamide sulfate, glycerol ester, Serol ester sulfate, glycerol ether, glycerol ether sulfate, polyglycerol ether, polyglycerol ether sulfate, sorbitan ester, polyalkoxylated sorbitan ester, ammonium alkane sulfonate, amidopropyl betaine, alkylated quaternary substance, alkylated / polyhydroxy Hydrophilicity selected from alkylated quaternary substances, alkylated quaternary substances, alkylated / polyhydroxylated oxypropyl quaternary substances, imidazolines, 2-yl-succinates, sulfonated alkyl esters, and sulfonated fatty acids And (III) X is selected from —CH ₂ — and —C (O) —. ”B) 0.5-25% by weight of the composition of the builder system; and c) the composition. of From 0.0 to 50% by weight of an alkalinity system comprising carbonate, wherein system a) is present in an amount of 3% by weight and system b) in an amount of 19% by weight. Wherein the alkalinity system c) is free of 8% by weight of sodium carbonate when present. 2. A surfactant system according to claim 1, wherein the surfactant compound of the surfactant system a) comprises a branched first compound having an ^Ab moiety having the formula:
The detergent composition according to claim 1, having the above formula which is a lower alkyl moiety. Embedded image Wherein the total number of carbon atoms in the branched primary alkyl portion of the formula, including the R, R ¹ and R ² branches, is 13-19, and R, R ¹ and R ² are each independently , Hydrogen and C ₁ -C ₃ alkyl, preferably methyl, provided that R, R ¹ and R ² are not all hydrogen and when z is 0, at least R Or R ¹ is not hydrogen, w is an integer of 0-13, x is an integer of 0-13, y is an integer of 0-13, z is an integer of 0-13, w + x + y + z 7 to 13] 3. The surfactant system a) according to claim 1, wherein the surfactant system a) comprises at least 20% by weight, preferably at least 90% by weight, of one or more medium-chain branched alkyl sulphates having the formula: Detergent composition. Embedded image [Wherein M represents one or more cations, a, b, d, and e are integers, a + b is 10-16, d + e is 8-14, and a + b = In the case of 10, a is an integer of 2 to 9, b is an integer of 1 to 8; When a + b = 11, a is an integer of 2 to 10; b is an integer of 1 to 9; When a + b = 12, a is an integer of 2 to 11, b is an integer of 1 to 10, and when a + b = 13, a is an integer of 2 to 12, and b is an integer of 1 to 11. When a + b = 14, a is an integer of 2 to 13, b is an integer of 1 to 12, and when a + b = 15, a is an integer of 2 to 14, and b is 1 to 13. When a + b = 16, a is an integer of 2 to 15, b is an integer of 1 to 14, and when d + e = 8, d is E is an integer of 1 to 6; e is an integer of 1 to 6; if d + e = 9, d is an integer of 2 to 8; e is an integer of 1 to 7; Is an integer of 2 to 9, e is an integer of 1 to 8, when d + e = 11, d is an integer of 2 to 10, e is an integer of 1 to 9, and when d + e = 12 , D is an integer of 2 to 11, e is an integer of 1 to 10, and when d + e = 13, d is an integer of 2 to 12, e is an integer of 1 to 11, d + e = 14 Wherein d is an integer from 2 to 13 and e is an integer from 1 to 12, wherein the average total number of carbon atoms in the branched primary alkyl moiety is 14.5 to
17.5] Surfactant compounds of 4. A surfactant system a) is a carbon number of 16-18 A ^b -
The detergent composition according to any one of claims 1 to 3, having an X moiety, wherein B has a sulfate group. 5. The builder system comprises an amorphous silicate, a crystalline layered silicate, an aluminum silicate,
5. A composition as claimed in any one of claims 1 to 4, comprising one or more builder materials selected from polymeric or monomeric polycarboxylates and their acids and optionally phosphates. Detergent composition. 6. The detergent composition according to claim 1, wherein the builder system is substantially free of a phosphate builder material. 7. The detergent composition according to claim 1, wherein the amount of the builder material is 5 to 18% by weight of the composition. 8. The detergent composition according to claim 1, wherein the alkalinity system comprises sodium carbonate present in an amount of 4 to 20% by weight. 9. The method of claim 1, wherein the density is between 550 grams / liter and 900 grams / liter.
A detergent composition according to any one of claims 8 to 13. 10. A nonionic surfactant, preferably a C _9-15 primary alcohol ethoxylate containing 3 to 12 moles of ethylene oxide per mole of alcohol, having a ratio of 10: 1 to anionic surfactant. Detergent composition according to any of the preceding claims, wherein the detergent composition is present at from 1 to 1:10, preferably from 1: 1 to 1:10.