JP2003507532A - How to improve foaming of detergent products - Google Patents

Abstract

  (57) [Summary] Use of aluminosilicate ion exchange materials to impart foaming properties in detergent products, methods of making laundry detergent products exhibiting a combination of foaming and builder properties, methods of washing laundry detergent products, and methods of washing dirty cloth Is disclosed. In one embodiment, the use of an aluminosilicate ion exchange material to provide foaming in a detergent product comprises preparing an aluminosilicate ion exchange material having pores, drying the aluminosilicate ion exchange material, In the pores of the aluminosilicate ion-exchange material, adding the gas-trapped aluminosilicate ion-exchange material to the detergent composition, and preparing a detergent product that exhibits foaming properties when the detergent product is placed in an aqueous medium. Include.

Description

Detailed Description of the Invention

[0001]

【Technical field】

The present invention relates generally to detergent products, and in particular to aluminosilicate ion exchange materials that not only serve as builders, but also as a means to improve the foamability of detergent products when the product is placed in an aqueous medium. It relates to a granular or non-granular detergent product containing.

[0002]

[Background technology]

Non-granular detergents are attractive alternatives to granular or granular detergents from the standpoint of simplifying dosing of such detergents for automatic washing machines or dishwashers. Non-granular detergents are not usually delivered in the form of solids, tablets or briquettes and prevent spillage of the detergent composition, but also eliminate the need for the consumer to calculate the exact dosage of the detergent composition for cleaning. .

There is a consumer desire to have non-granular detergent products such as detergent tablets that are foamable when placed in an aqueous cleaning medium. Typically, foamability is provided by incorporating acid and carbonate forms such as citric acid and sodium bicarbonate into the detergent composition. However, this does not provide a significant weight benefit, eg improved builder properties, to the detergent composition. Thus, there has been a demand for a method for giving not only the foaming property but also a useful by-product. In particular, it was desirable to have a method for improving both foamability and builder properties.

The present invention not only serves as a builder, but also as a means for improving the foamability of detergent products when the product is placed in an aqueous medium. Providing a detergent product provides both of the above desirable characteristics. The present invention also provides a method for achieving the above object. The method involves using an aluminosilicate ion exchange material, such as zeolite, to drive water out of the zeolite so that the pores are substantially empty. Carbon dioxide or some other suitable gas is then trapped in the pores. When the zeolite is thrown into the aqueous cleaning medium, carbon dioxide gas effervesces,
Creates a foaming property. The present invention thus takes advantage of the use of aluminosilicate ion exchange materials such as zeolites, which are useful builders and useful foaming agents. These objects, features and attendant advantages of the present invention, as well as other objects, features and attendant advantages, will be apparent to those skilled in the art from reading the following detailed description of the preferred embodiments.

[0005]

DISCLOSURE OF THE INVENTION

The present invention relates to the use of an aluminosilicate ion exchange material to provide foamability in detergent products, a method for producing laundry detergent products which exhibits a combination of foamability and builder properties, laundry detergent products, and soiled cloths. The need is met by disclosing a class of laundry methods.

In one aspect of the invention, the use of an aluminosilicate ion exchange material to provide foaming properties in a detergent product comprises providing an aluminosilicate ion exchange material having pores. This method is to dry the aluminosilicate ion exchange material, trap the gas in the pores of the aluminosilicate ion exchange material, add the gas trapped aluminosilicate ion exchange material to the detergent composition, and put the detergent product in an aqueous medium. Preparing a detergent product that exhibits foamability when exposed. Another aspect of the present invention is a method for producing a laundry detergent product showing a combination of foaming property and builder property, in which an aluminosilicate ion exchange material having pores is prepared, and gas is used as a fine powder of the aluminosilicate ion exchange material. The method comprises the steps of adding an aluminosilicate ion exchange material trapped in the pores and gas to a laundry detergent composition to prepare a laundry detergent product that exhibits foaming and builder properties when the detergent product is placed in an aqueous medium.

[0007]   Yet another aspect of the invention is a laundry detergent product comprising a surfactant and a builder.
Laundry detergent composition (builders combine laundry detergent and foaming properties into laundry detergent
Suitable for application to the composition). The builder uses the formula Mm / n [(AlO ₂ ) M (SiO₂) Y] ・ xH₂O (where n is the valence of the cation M, x
Is the number of water molecules per unit cell, m and y are tetra
The total number of Dora, y / m is 1 to 100, M is sodium, potassium,
Aluminosilicate selected from the group consisting of magnesium and calcium)
Includes a ion exchange material. Aluminosilicate ion exchange materials have pores
In addition, the aluminosilicate ion exchange material has gas trapped in the pores.
To do. Detergent products exhibit foaming properties when placed in an aqueous medium.

In yet another aspect of the invention, a method of laundering dirty cloth is disclosed. This method consists of immersing the soiled fabric in an aqueous medium containing an effective amount of a laundry detergent product prepared by the method as described above.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION

In a preferred embodiment of the present invention, the method of using an aluminosilicate ion exchange material to provide foamability in detergent products comprises the step of providing an aluminosilicate ion exchange material having pores.

[0010] The structural formula of the aluminosilicate material aluminosilicate materials, crystal unit cell, Mm / n _{[(AlO 2) m (SiO 2} ) y ] · xH in ₂ O (wherein, n is the valence of the cation M Yes, x is the number of water molecules per unit cell, m and y are the total number of tetrahedra per unit cell, and y / m is 1 to
Based on the smallest unit of the structure represented by 100). Most preferably y / m is 1-5
Is. The cation M can be a Group IA and Group IIA element, such as sodium, potassium, magnesium, and calcium. The preferred aluminosilicate material is zeolite. The most preferred zeolites are zeolite A, zeolite X, zeolite Y, zeolite P, zeolite MAP and mixtures thereof.

The aluminosilicate ion exchange material used herein preferably has both a high calcium ion exchange capacity and a high exchange rate. Without wishing to be bound by theory, it is believed that such high calcium ion exchange rates and capacities are a function of several correlative factors resulting from the aluminosilicate ion exchange material process. In that regard, the aluminosilicate ion exchange materials used herein are preferably those disclosed in Colkill et al. US Pat. No. 4,605,509 (
Procter End Gamble), the disclosure of which is incorporated herein by reference.

[0012] Preferably, the aluminosilicate ion exchange material is in the "sodium" form. The reason is that the potassium and hydrogen forms of the present aluminosilicates do not show as high exchange rates and capacities as provided by the sodium form. Additionally, the aluminosilicate ion exchange material is preferably in the overdried form to facilitate the production of the free-flowing detergent agglomerates as described herein. The aluminosilicate ion exchange material used herein preferably has a particle size that optimizes effectiveness as a detersive builder. As used herein, the term "particle size" refers to the average particle size of a given aluminosilicate ion exchange material as measured by common analytical techniques such as microscopy and scanning electron microscopy (SEM). The preferred particle size of the aluminosilicate is from about 0.1 μm to about 10 μm, more preferably about 0.1 μm.
It is 5 μm to about 9 μm. Most preferably, the particle size is from about 1 μm to about 8 μm. In a preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula
It has Na ₁₂ [(AlO ₂ ) ₁₂ · (SiO ₂ ) ₁₂ ] · xH ₂ O, where x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0-10) may also be used here. Preferably,
Aluminosilicates have a particle size of about 0.1-10 μm in diameter. In a preferred embodiment, the aluminosilicate ion exchange material is a zeolite and the zeolite acts as a builder.

In a preferred embodiment, the aluminosilicate ion exchange material has pores having a pore size in the range of about 2 Å to about 12 Å. Further, desirably, the aluminosilicate ion exchange material has a total porosity of at least 2.
With 5%.

In a preferred embodiment, the method also includes drying the aluminosilicate ion exchange material. This is accomplished by heating the aluminosilicate ion exchange material to a temperature of at least 20 ° C.

In a preferred embodiment, the method also includes trapping the gas in the pores of the aluminosilicate ion exchange material. The preferred gas is carbon dioxide. The method also includes placing the aluminosilicate ion exchange material in a pressurizable container and trapping the gas at a gas pressure of at least 1 atmosphere in the pores of the aluminosilicate ion exchange material.

In a preferred embodiment, the method also includes adding a gas-trapped aluminosilicate ion exchange material to the detergent composition to prepare a detergent product that exhibits foamability when the detergent product is placed in an aqueous medium. To do. The gas trapped aluminosilicate ion exchange material is added to the detergent composition in an amount within the range of about 1 to about 25% by weight of the detergent composition.

In a preferred embodiment, the detergent composition is free of citric acid and bicarbonate.

Non-granular detergent product detergent tablets can be produced by simply mixing the solid ingredients together and compressing the mixture in a conventional tablet press such as is used in the pharmaceutical industry.

A given detergent tablet can be prepared in any size or shape. Prior to compaction, the detergent particles may be surface treated with a flow aid according to the present invention. A given detergent tablet may be manufactured by using compaction methods, such as tableting methods, briquetting, or extrusion methods, preferably tableting methods. Suitable devices, standard single stroke or a rotary press include [Kotoi (Courtoy ^R), coaches (Korch ^R), Manesuti (Manesty ^R), Bonaruzu (Bonals ^R), etc.]. The term "non-granular detergent product" as used herein includes physical forms such as tablets, blocks, solids and the like.

Non-Granular Detergent Product Coating In one embodiment, the tablets are coated with a coating to provide mechanical strength and impact and chipping resistance to the compressed tablet core. The tablets are coated with a coating that is substantially insoluble in water so that the tablets do not absorb water or absorb water only at a very slow rate. The coating is strong such that moderate mechanical shocks applied to the tablet during handling, packaging and shipping result in only very low levels of breakage or wear. Furthermore, the coating is preferably brittle so that it will break when the tablet is subjected to a stronger mechanical shock. In addition, it is advantageous if the coating material dissolves under alkaline conditions or is easily emulsified with a surfactant. This avoids depositing undissolved particles or lumps of coating material on the wash load. This may be important when the coating material is completely insoluble in water (eg less than 1 g / l).

As defined herein, “substantially insoluble” means having a very low solubility in water. This means that the solubility in water at 25 ° C. is less than 20 g / liter, preferably 5
It should be understood to mean having less than g / liter, more preferably less than 1 g / liter. Solubility in water is measured according to ASTM E1148-87 test protocol "Standard Test Method for Determination of Solubility in Water".

Suitable coating materials are fatty acids, adipic acid and C8 to C13 dicarboxylic acids, fatty alcohols, diols, esters and ethers. Preferred fatty acid is C
Those having a carbon chain length of 12 to C22, most preferably C18 to C22. Preferred dicarboxylic acids are adipic acid (C6), suberic acid (C8) and azelaic acid (C).
9), sebacic acid (C10), undecanedioic acid (C11), dodecanedioic acid (C12) and tridecanedioic acid (C13). Preferred fatty alcohols are C12-C22,
Most preferably, it has a carbon chain length of C14 to C18. Preferred diols are 1,2-octadecanediol and 1,2-hexadecanediol.
Preferred esters are tristearin, tripalmitin, methyl behenate, ethyl stearate. Preferred ethers are diethylene glycol monohexadecyl ether, diethylene glycol monooctadecyl ether, diethylene glycol monotetradecyl ether, phenyl ether, ethylnaphthyl ether, 2-methoxynaphthalene, β-naphthylmethyl ether and glycerol monooctadecyl ether. Other preferred coating materials include dimethyl 2,2-propanol, 2-hexadecanol, 2-octadecanone, 2-hexadecanone, 2,15-hexadecanedione and 2-hydroxybenzyl alcohol. The coating is a hydrophobic material having a melting point, preferably 40 ° C to 180 ° C.

In the preferred embodiment, the coating can be applied in a number of ways. Two preferred coating methods are (a) coating with a molten substance and (b) coating with a solution of the substance. In (a), the coating material is applied at a temperature above its melting point and solidifies on the tablet. In (b) the coating is applied as a solution (solvent is dried to leave a coherent coating). The substantially insoluble substance can be applied to the tablets by, for example, spraying or dipping. Normally, when the molten material is sprayed onto the tablet, it will rapidly solidify to form a coherent coating. When the tablets are dipped into the molten material and then removed, rapid cooling again causes rapid solidification of the coating material. It has been found that substantially insoluble substances having a melting point of less than 40 ° C. are not sufficiently solid at room temperature and substances having a melting point above about 180 ° C. cannot be used. Preferably the material is between 60 ° C and 160 ° C.
C., more preferably in the range of 70.degree. C. to 120.degree.

“Melting point” means, for example, the temperature at which a substance becomes a clear liquid when slowly heated in a capillary. For most purposes, the coating is 1% to 10% of the tablet weight.
, Preferably 1.5% to 5%.

[0025]Surfactant   Anionic surfactantA preferred anionic surfactant is C₁₁~ C₁₈Al
Killbenzene sulfonate (LAS) and primary, branched and random C_Ten ~ C₂₀Alkylsulfate (AS), formula CH₃(CH₂)_x(CHOSO₃ ^- M⁺) CH₃And CH₃(CH₂)_y(CHOSO₃ ^-M⁺) CH₂CH₃ Where x and (y + 1) are integers of at least about 7, preferably at least about 9.
And M is a water-solubilizing cation, especially sodium)_Ten~ C₁₈Second grade
(2,3) alkyl sulphate, unsaturated sulphate, eg oleyl sulphate
Fate, C_Ten~ C₁₈Alkylalkoxy sulphate ("AE_xS "; especially E
O1-7 ethoxysulfate), C_Ten~ C₁₈Alkylalkoxycarboxylate
(Especially EO1-5 ethoxycarboxylates), C_10-18Glycerol a
Tell, C_Ten~ C₁₈Alkyl polyglycosides and their corresponding sulfated polyglycosides
Cid and C₁₂~ C₁₈Examples include α-sulfonated fatty acid esters.

Generally, anionic surfactants useful herein are those disclosed in Barat et al., US Pat. No. 4,285,841 issued Aug. 25, 1981 and Dec. 30, 1975.
It is disclosed in US Pat. No. 3,919,678 issued to Lorin et al. Examples of useful anionic surfactants include water-soluble salts, particularly alkali metal salts, of organic sulfuric acid reaction products having an alkyl group having about 10 to about 20 carbon atoms and a sulfonic acid ester group or a sulfuric acid ester group in the molecular structure, Ammonium salts and alkylol ammonium salts (eg, monoethanolammonium salt or triethanolammonium salt) are included (the term “alkyl” includes the alkyl portion of aryl groups). Examples of synthetic surfactants of this group, resulting alkyl sulfates, especially higher alcohols (C ₈ -C ₁₈ carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil by sulfating It is what is done.

Other anionic surfactants of the present invention include alkylphenol ethylene oxide ether sulfates containing from about 1 to about 4 units of ethylene oxide per molecule and having from about 8 to about 12 carbon atoms in the alkyl group. It is a water-soluble salt.

Other anionic surfactants useful herein include α-sulfones having about 6-20 carbon atoms in the fatty acid groups and about 1-10 carbon atoms in the ester groups. Water-soluble salts of esters of epoxidized fatty acids; of 2-acyloxyalkane-1-sulfonic acids having about 2 to 9 carbon atoms in the acyl group and about 9 to about 23 carbon atoms in the alkane moiety. Water-soluble salts; water-soluble salts of olefin sulfonic acids having about 12-24 carbon atoms; and having about 1-3 carbon atoms in the alkyl group and about 8-20 carbons in the alkane moiety. And β-alkyloxyalkane sulfonates having atoms.

[0029] Here, other useful anionic surfactants of the formula _{RO (C 2 H 4 O)} x SO 3 - M + ( wherein, R represents a saturated or unsaturated alkyl of from about 10 to about 22 carbon atoms Is a chain, M is a cation that renders the compound water soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x averages from about 1 to about 15) alkyl polyethoxylate sulphate.

Other alkyl sulphate surfactants are non-ethoxylated C _12-15 primary and secondary alkyl sulphates. Cold water wash conditions, ie about 65 ° F. (18.
It is preferred that below 3 ° C.) there is a mixture of such ethoxylated alkyl sulphates with non-ethoxylated alkyl sulphates. Examples of fatty acids include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid. Other fatty acids include palmitoleic acid, oleic acid, linoleic acid, linolenic acid and ricinoleic acid.

Nonionic Surfactants- Conventional nonionic and amphoteric surfactants include C ₁₂ -C ₁₈ alkyl ethoxylates (AE) such as the so-called narrow peaked alkyl ethoxylates and C ₆ -C. ₁₂ alkylphenol alkoxylates (especially ethoxylates and mixed ethoxy / propoxy). C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include C ₁₂ -C ₁₈ N-methyl glucamides. WO 9,206,15
See specification No. 4. Other sugar-derived surfactants include N- alkoxy polyhydroxy fatty acid amides, such as C ₁₀ ~C ₁₈ N- (3- methoxypropyl) glucamide. From N- propyl C ₁₂ -C ₁₈ glucamides to N- hexyl C ₁₂ -C ₁₈ glucamides can be used for low sudsing. Normal C ₁₀ -C ₂₀ soaps may also be used. If high sudsing is desired, the branched-chain C ₁₀ -C ₁₆ soaps may be used. Examples of nonionic surfactants are described in Barat et al., US Pat. No. 4,285,841 issued Aug. 25, 1981.

Examples of the surfactant include the formula R (OC ₂ H ₄ ) _n OH (wherein R is an aliphatic hydrocarbon group having about 8 to about 15 carbon atoms and about 8 to about 12 alkyl groups). Ethoxylated alcohols and ethoxylated alkylphenols selected from the group consisting of alkylphenyl groups having 5 carbon atoms and an average value of n of from about 5 to about 15). These surfactants are more fully described in US Pat. No. 4,284,532 to Lake Him et al., Issued Aug. 18, 1981. Other surfactants include ethoxylated alcohols having an average of about 10 to about 15 carbon atoms in the alcohol and an average degree of ethoxylation of about 6 to about 12 moles of ethylene oxide per mole of alcohol. . Mixtures of anionic and nonionic surfactants are especially useful.

[0033]   Polyhydroxy fatty acid amide, alkyl glucoside, polyalkyl glucoside
, C₁₂~ C₁₈Other common, including betaine and sulfobetaine (sultaine)
Useful surfactants are described in standard texts. For example, C₁₂~ C ₁₈ N-methyl glucamide is mentioned. See WO 9,206,154
. Other sugar-derived surfactants include C_Ten~ C₁₈N- (3-methoxypropyl) g
Examples include N-alkoxy polyhydroxy fatty acid amides such as Lucamide. N-
Propyl C₁₂~ C₁₈Glucamide to N-hexyl C₁₂~ C₁₈Up to glucamide,
Can be used for low foaming.

Cationic Surfactants One class of useful cationic surfactants is the monoalkyl quaternary, although any cationic surfactant useful in the detergent composition is suitable for use herein. It is an ammonium surfactant.

[0035]   Cationic surfactants that can be used here include those of the formula

[Chemical 1] [In the formula, R₁And R₂Is individually C₁~ C_FourAlkyl, C₁~ C_FourHydroxya
Rukyl, benzyl, and-(C₂H_FourO)_xH (where x is a value of about 2 to about 5)
X) is an anion; (1) R₃And R_FourIs
Each C₆~ C₁₄Alkyl or (2) R₃Is C₆~ C₁₈Alkyl and R _Four Is C₁~ C_TenAlkyl, C₁~ C_TenHydroxyalkyl, benzyl, and-
(C₂H_FourO)_xSelected from the group consisting of H, where x has a value of 2-5
] The quaternary ammonium surface active agent of these is mentioned.

Other useful quaternary ammonium surfactants are chlorides, bromides, and methylsulfates. Examples of desirable mono long chain alkyl quaternary ammonium surfactants are those in which R ₁ , R ₂ and R ₄ are each methyl and R ₃ is C ₈ -C ₁₆ alkyl, or R ₃ is C _{8-. 18} alkyl, wherein R ₁ , R ₂ and R ₄ are selected from methyl and hydroxyalkyl moieties. Lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, palmityltrimethylammonium chloride, coconut trimethylammonium chloride, coconut trimethylammonium methylsulfate, coconut dimethylmonohydroxyethylammonium chloride, coconut dimethylmonohydroxyethylammonium methylsulfate, steryldimethylmonohydroxyethyl ammonium chloride, steryl dimethyl mono-hydroxyethyl ammonium methyl sulfate, di -C ₁₂ -C ₁₄ alkyl dimethyl ammonium chloride, and mixtures thereof, desirable. ADOGEN 4 marketed by Witco
12 ^™ , lauryl trimethyl ammonium chloride is also desirable. Other desirable surfactants are lauryl trimethyl ammonium chloride and myristyl trimethyl ammonium chloride.

[0037]   Another group of suitable cationic surfactants are those of the formula

[Chemical 2] [In the formula, R¹Is C_10-18Can be alkyl or substituted or unsubstituted phenyl
Yes; R²Is C₁₄Alkyl, H, or (EO)_y(In the formula, y is about 1 to about 5
And Y is O or -N (R³) (R^Four) Is; R³Is
H, C₁₄Alkyl or (EO)_yWhere y is from about 1 to about 5
Can be; R^FourIs C if it exists₁₄Alkyl or (EO)_y(In the formula
, Y is from about 1 to about 5); each n is independently from about 1 to about 6, preferably
Selected from about 2 to about 4; X is hydroxyl or -N (R^Five) (R⁶) (R ⁷ ) (Where R is^Five, R⁶, R⁷Is independently C₁₄Alkyl, H, or (EO) _y  (Wherein y is from about 1 to about 5)) Is an alkanol amidal quaternary surfactant.

Amine Oxide Surfactant --Also, the composition has the formula R ¹ (EO) _x (PO) _y (BO) _z N (O) (CH ₂ R ') ₂ .qH ₂ O (I
) Amine oxide surfactant.

In general, structure (I) is found to give one long chain moiety R ¹ (EO) _x (PO) _y (BO) _z and two short chain moieties CH ₂ R ′. R 'is preferably selected from hydrogen, methyl and -CH ₂ OH. In general, R ¹ is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably R ¹ is a primary alkyl moiety. When x + y + z is 0, R ¹ is about 8
Is a hydrocarbyl moiety having a chain length of about 18. When x + y + z is different from 0, R ¹ may be slightly longer and has a chain length in the range C _{12 to} C ₂₄ .
In general formula, x + y + z = 0 , R 1 = C 8 ~C 18, R '= H, q = 0~2,
It includes amine oxides which are preferably 2. These amine oxides include C _12-14 alkyl dimethyl amine oxides, hexa hexa, as disclosed in US Pat. Nos. 5,075,501 and 5,071,594 (incorporated herein by reference). It is exemplified by decyldimethylamine oxide, octadecylamine oxide and their hydrates, especially the dihydrate.

In the present invention, x + y + z is different from 0, specifically, x + y + z is about 1 to about 10, and R ¹ is a ^{primary group} having 8 to about 24 carbon atoms, preferably about 12 to about 16 carbon atoms. It includes amine oxides that are alkyl groups. In these aspects, y + z is
Preferably 0, x is preferably from about 1 to about 6, more preferably from about 2 to about 4, EO represents ethyleneoxy, PO represents propyleneoxy and BO
Represents butyleneoxy. Such an amine oxide can be produced by a conventional synthetic method, for example, by reacting an alkyl ethoxy sulfate with dimethylamine and then oxidizing the ethoxylated amine with hydrogen peroxide.

Preferred amine oxides here are solids at room temperature, more preferably a melting point of 3
It has 0 ° C to 90 ° C. Suitable amine oxides for use herein are Akzo.
Manufactured commercially by a number of suppliers including Chemie, Ethyl Corporation, and Procter End Gamble. For other amine oxide manufacturers see McCacheon compilation and Kirk-Othmer review article. Other desirable commercial amine oxides are solid dihydrate Admox 16 and Admox 18, Admox 1 from Ethyl Corporation.
2 and especially Admox 14.

In another embodiment, dodecyldimethylamine oxide dihydrate, hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris (ethyleneoxy) dimethylamine oxide, tetradecyl Dimethylamine oxide dihydrate, and mixtures thereof. In some embodiments, R'is H, but there is some latitude in having R'slightly larger than H. In another embodiment, R'is CH ₂ OH, such as hexadecylbis (2-hydroxyethyl) amine oxide, tallowbis.
Includes (2-hydroxyethyl) amine oxide, stearylbis (2-hydroxyethyl) amine oxide and oleylbis (2-hydroxyethyl) amine oxide.

Enzymes Enzymes are incorporated into the formulation for a variety of fabric laundering purposes including, for example, removal of protein-based stains, carbohydrate-based stains, or triglyceride-based stains, and fabric repair. it can. Enzymes to be included include proteases, amylases, lipases and cellulases, and mixtures thereof. Other types of enzymes may also be included. They may have any suitable origin, for example plant, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors, such as pH activity and / or stability optima, thermal stability, stability to active detergents, builders and the like. In this respect, bacterial or fungal enzymes, such as bacterial amylases and proteases, and fungal cellulases are preferred.

The enzyme is typically incorporated in an amount sufficient to provide up to about 5 mg (weight) of active enzyme per gram of composition, more typically about 0.01 mg to about 3 mg. In other words, the composition typically comprises from about 0.001 to about 5% by weight of a commercially available enzyme preparation, preferably 0.
It will contain from 0 to 1% by weight. Protease enzymes are typically present in such commercial formulations in an amount sufficient to provide 0.005-0.1 Anson Units (AU) of activity per gram of composition.

A preferred example of a protease is subtilisin obtained from Bacillus subtilis and certain strains of B. licheniforms. Another suitable protease is obtained from a strain of Bacillus that has maximum activity over the pH range of 8-12 developed by Novo Industries A / S and sold under the registered trade name ESPERASE. The preparation of this and similar enzymes is described in Novo's British Patent 1,243,7.
No. 84. Commercially available proteolytic enzymes suitable for removing protein-based stains are commercially available from Novo Industries A / S (Denmark) under the trade names ALCALASE and SAVINASE.
) And sold by International Bio-Synthetics Incorporated (Netherlands) under the trade name Maxatase.
The ones sold at. Other proteases include Protease A (see European Patent Application No. 130,756 published Jan. 9, 1985) and Protease B (European Patent Application No. 873037 filed April 28, 1987).
No. 11.8 and European Patent Application No. 1 of Bot et al. Published on January 9, 1985
No. 30,756).

As the amylase, for example, α-amylase described in British Patent No. 1,296,839 (Novo), International Bio-synthetics
RAPIDASE made by Incorporated and TERMAMYL made by Novo Industries are listed.

Cellulases that can be used in the present invention include both bacterial and fungal cellulases. Preferably, they will have a pH optimum of 5-9.5. Suitable cellulases are Humicola insolens and Humicola strain DSM
1800 or a fungus cellulase produced from a cellulase 212-producing fungus belonging to Aeromonas sp. It is disclosed in US Pat. No. 4,435,307. Also,
Suitable cellulases are described in British Patent No. 2.075.028, British Patent No. 2.
No. 095.275 and DE-OS No. 2.247.832. CAREZYME (Novo) is particularly useful.

Suitable lipase enzymes for detergent use include Pseudomonas stutzeri ATCC 19.154, such as Pseudomonas stutzeri ATCC 19.154 as disclosed in British Patent 1,372,034.
Those produced by the monas group of microorganisms. See also lipase in JP-A-53-20487, published Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co., Ltd. of Nagoya, Japan under the trade name Lipase P "Amano" (hereinafter referred to as "Amano-P"). Other commercially available lipases include Amano-CES, Chromobacter viscosum, such as Chromobacter viscosum var. Lipolyticum NRRLB367 commercially available from Toyo Brewery Co., Ltd.
Lipase from U.3; and U.S.A. S. Biochemical Corporation and yet another Chromobacter viscosu from the Desoint Company of the Netherlands
m lipase, and lipase from Pseudomonas gladioli. Humico
The LIPOLASE enzyme from La lanuginosa and commercially available from Novo (see also EPO 341,947) is the preferred lipase for use herein.

A wide range of enzyme substances and means for blending into synthetic detergent compositions are also available in McCartie etc.
It is disclosed in U.S. Pat. No. 3,553,139 issued Jan. 5, 971. The enzyme is further described in Place et al., U.S. Pat. No. 4,1, issued July 18, 1978.
No. 01,457 and Hughes U.S. Pat. No. 4,507,219 issued Mar. 26, 1985. Enzymatic materials useful in liquid detergent formulations and methods of incorporation into such formulations are disclosed in Hora et al., U.S. Pat. No. 4,261,868, issued Apr. 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. The enzyme stabilization technique is described in US Pat. No. 3,600,319 issued August 17, 1971 to Judge et al.
European Patent Application Publication No. 0 199 405 of Venegas published October 29, 986
No. 86200586.5, application No. 86200586.5. The enzyme stabilization system is described in, for example, US Pat. No. 3,519,570.

The enzyme used herein may be stabilized by the presence of a source of water-soluble calcium and / or magnesium ions in the finished composition that donates ions to the enzyme (calcium ions are generally slightly more effective than magnesium ions). Present and preferred if only one cation should be used). Additional stability can be provided by the presence of various other technically disclosed stabilizers, especially borate species. See Severson U.S. Pat. No. 4,537,706. Typical detergents, especially liquid detergents, range from about 1 to about 30 millimoles per liter of finished composition, preferably about 2 to about 20 millimoles, more preferably about 5 to about 15 millimoles, most preferably about 8 to about 12 milliliters. It will contain millimolar calcium ions. It can vary slightly depending on the amount of enzyme present and the response to calcium or magnesium ions. The amount of calcium or magnesium ions should be chosen such that there is always some minimal amount available for the enzyme in the composition after complexing with builders, fatty acids and the like. Any water-soluble calcium or magnesium salt,
For example, without limitation, calcium chloride, calcium sulfate, calcium malate,
Calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the corresponding magnesium salts can also be used as sources of calcium or magnesium ions. Small amounts of calcium ions (generally about 0.05 to about 0.4 millimoles per liter) are also often present in the composition due to calcium in the enzyme slurry and formulation water. In solid detergent compositions, the formulation may include a source of water-soluble calcium ions sufficient to provide such amounts in the wash liquor. Alternatively, natural water hardness may be sufficient.

It should be understood that said amount of calcium and / or magnesium ions is sufficient to confer enzyme stability. More calcium and / or magnesium ions can be added to the composition to provide an additional measure of degreasing performance. Thus, as a general proposition, the composition typically comprises a source of water-soluble calcium or magnesium ions, or both about 0.
05 to about 2% by weight. The amount can, of course, vary depending on the amount and type of enzyme used in the composition.

The composition may optionally but preferably also contain various additional stabilizers, especially borate-type stabilizers. Typically, such stabilizers are from about 0.25 to about 10% by weight boric acid or other borate compound (calculated on the basis of boric acid) capable of forming boric acid in the composition, preferably Will be used in the composition in an amount of about 0.5 to about 5% by weight, more preferably about 0.75 to about 4% by weight. Boric acid is preferred (although other compounds such as boron oxide, borax and other alkali metal borates (eg sodium orthoborate, sodium metaborate, sodium pyroborate, and sodium pentaborate) are preferred). . Substituted boric acids such as phenylboronic acid, butaneboronic acid, and p-bromophenylboronic acid can also be used in place of boric acid.

Polymeric Antifouling Agents Any polymeric antifouling agent known to those skilled in the art can optionally be used in the compositions and methods of the present invention. The polymeric antifoulant adheres to the hydrophilic segment for hydrophilizing the surface of the hydrophobic fiber, such as polyester, nylon, etc., on the hydrophobic fiber and remains adhered throughout the washing and rinsing cycle. As well as having both a hydrophobic segment to serve as an anchor for the hydrophilic segment. This may allow the stains that occur after treatment with the antifouling agent to be more easily cleaned in a subsequent washing method.

Examples of polymeric antifoulants useful herein include Gosseling, Jan. 26, 1988.
U.S. Pat. No. 4,721,580 issued to Nichol et al., U.S. Pat. No. 4,000,093 issued Dec. 28, 1976 to Nichol et al.
European Patent Application No. 0 219 048 published April 22, 1995, U.S. Pat. No. 4,702,857 issued October 27, 1987 to Gosseling, J
． J. U.S. Pat. No. 4,968,451 issued to Schabel on November 6, 1990.
No. specification. Examples of commercially available antifouling agents include SOKALAN type substances available from BASF (West Germany), for example, Socalan HP-22. See also US Pat. No. 3,959,230 issued May 25, 1976 to Haze and US Pat. No. 3,893,929 issued July 8, 1975 to Bather. An example of this polymer is the commercially available substance ZELCON 5126.
(Made by DuPont) and MILEASE T (made by ICI). Other suitable polymeric antifouling agents include terephthalate polyesters of U.S. Pat. No. 4,711,730 issued Dec. 8, 1987 to Gosselink et al., Issued Jan. 26, 1988 to Gosselink. Anionic end-capped oligomeric esters of U.S. Pat. No. 4,721,580, and Gosseling 1987 10
The block polyester oligomer compound of U.S. Pat. No. 4,702,857 issued on May 27, may be mentioned. Preferred polymeric antifouling agents also include the antifouling agents of US Pat. No. 4,877,896, issued October 31, 1989 to Maldonado et al.

If utilized, the antifouling agent generally comprises from about 0.01 to about 1 part of the detergent composition of the present invention.
0.0% by weight, typically about 0.1 to about 5% by weight, preferably about 0.2 to about 3.
It will account for 0% by weight.

Chelating Agents The detergent compositions of the present invention may also optionally contain one or more iron and / or manganese chelating agents. Such chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents as defined below and mixtures thereof. Without intending to be bound by theory, it is believed that the benefit of these materials is due, in part, to their exceptional ability to remove iron and manganese ions from the wash liquor by the formation of soluble chelates.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate and ethanoldiamine. Glycine, its alkali metal salts, ammonium salts, and substituted ammonium salts and mixtures thereof.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least a small amount of total phosphorus is allowed in the detergent composition and as an example of them as DEQUEST. Examples include ethylenediamine tetrakis (methylene phosphonate). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms. Polyfunctionally substituted aromatic chelating agents are also useful in the present compositions. See US Pat. No. 3,812,044 issued May 21, 1974 to Conner et al. A preferred compound of this type in the acid form is dihydroxydisulfobenzene, such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use herein is ethylenediamine disuccinate as described in US Pat. No. 4,704,233 issued Nov. 3, 1987 to Hartmann and Perkins. (“EDDS”), especially [S, S
] It is an isomer.

If utilized, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent composition of the present invention. More preferably, if utilized, chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.

Clay Soil Removal / Redeposition Agents The compositions of the present invention can also optionally include a water soluble ethoxylated amine having clay soil removal and antiredeposition properties. Liquid detergent compositions typically have about 0.
． It contains from 01% to about 5%. The most preferred antifoulant / antiredeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in Vandermeal U.S. Pat. No. 4,597,898 issued July 1, 1986. Another group of preferred clay soil removal / antiredeposition agents are the cationic compounds disclosed in Oh and Gosselling European Patent Application No. 111,965, published Jun. 27, 1984. Other clay stain removal / redeposition agents that can be used include June 2, 1984.
Ethoxylated amine polymers disclosed in Gosselling European Patent Application No. 111,984, published 7th; disclosed in Gosselling European Patent Application 112,592, published July 4, 1984. Zwitterionic polymers; and the amine oxides disclosed in Connor U.S. Pat. No. 4,548,744 issued Oct. 22, 1985. Other clay stain removers and / or anti-redeposition agents known in the art may also be used
It can be used in the present composition. Another type of preferred anti-redeposition agent includes carboxymethyl cellulose (CMC) materials. These materials are well known in the art.

Polymeric Dispersants Polymeric dispersants are advantageously utilized in the composition in amounts of from about 0.1 to about 7% by weight, especially in the presence of zeolites and / or layered silicate builders. Suitable polymeric dispersants include polymeric polycarboxylates and polyethylene glycols, although others known in the art may be used. While not wishing to be limited by theory, polymeric dispersants are used by other builders (including low molecular weight polycarboxylates) in combination with crystal growth inhibition, particle soil release peptization, and anti-redeposition. It is believed to enhance overall detergency builder performance.

The polymeric polycarboxylate material is a suitable unsaturated monomer (preferably in acid form).
Can be produced by polymerizing or copolymerizing. Unsaturated monomeric acids that can be polymerized to produce suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and Examples include methylene malonic acid. The presence of monomer segments that do not contain a carboxylate group, such as vinyl methyl ether, styrene, ethylene, etc., in the polymeric polycarboxylates of the present invention means that if such segments do not constitute greater than about 40% by weight. It is suitable.

A particularly suitable polymeric polycarboxylate can be derived from acrylic acid. Such acrylic acid-based polymers useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in acid form is preferably about 2,000 to 10,000, more preferably about 4,000 to 7,000, and most preferably about 4,000 to 5,000. Examples of such water-soluble salts of acrylic acid polymers include alkali metal salts, ammonium salts and substituted ammonium salts. Soluble polymers of this kind are known substances. The use of this type of polyacrylate in detergent compositions is disclosed, for example, in Deal, US Pat. No. 3,308,067, issued Mar. 7, 1967. Copolymers based on acrylic acid / maleic acid may also be used as a preferred component of the dispersant / anti-redeposition agent. Examples of such a substance include a water-soluble salt of a copolymer of acrylic acid and maleic acid. The average molecular weight of such copolymers in acid form is preferably about 2,000-100,000, more preferably about 5 ,.
000-75,000, most preferably about 7,000-65,000. The ratio of acrylate segment to maleate segment in such a copolymer will generally be from about 30: 1 to about 1: 1 and more preferably from about 10: 1 to 2: 1. Examples of such water-soluble salts of acrylic acid / maleic acid copolymers include alkali metal salts, ammonium salts and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are known substances described in European Patent Application No. 66915, published Dec. 15, 1982, as well as 19
The known substances described in EP 193,360 published Sep. 3, 1986 (which also describes such polymers containing hydroxypropyl acrylate). Still other useful dispersants include maleic acid / acrylic acid / vinyl alcohol terpolymers. Such materials, such as acrylic acid / maleic acid / vinyl alcohol 45/45/10 terpolymers, are disclosed in EP 193,360.

Another polymeric material that can be incorporated is polyethylene glycol (PEG). P
EG exhibits dispersant performance and can act as a clay soil remover / antiredeposition agent. Typical molecular weight ranges for these purposes are about 500 to about 100,000, preferably about 1,000 to about 50,000, more preferably about 1,500 to about 10,
It is 000.

Polyaspartate and polyglutamate dispersants may also be used, especially with zeolite builders. Dispersants such as polyaspartate are preferably
It has a molecular weight (average) of about 10,000.

Brightener Any optical brightener or other brightener or whitening agent known in the art is typically present in the detergent compositions of this invention in an amount of from about 0.05 to about 1.2% by weight. Can be blended with. Commercially available optical brighteners that may be useful in the present invention can be divided into subgroups, including, but not necessarily limited to, stilbene, pyrazoline, coumarin,
Included are carboxylic acids, methinecyanine, dibenzothiophene-5,5-dioxide, azoles, derivatives of 5- and 6-membered heterocyclic compounds, and other miscellaneous agents. Examples of such brighteners are described in "Production and Application of Optical Brighteners", M. et al. The Radonic, published by John Willie End Sons in New York (198
2).

Specific examples of optical brighteners useful in the composition are those identified in US Pat. No. 4,790,856 issued Dec. 13, 1988 to Wixon. These brighteners include PHORWHITE series brighteners from Verona. Other brighteners disclosed in this document include Tinopal UNPA, Tinopal CBS and Tinopal 5BM available from Ciba Geigy.
Artic White CC and Artic White CWD available from Hilton-Davis, Italy; 2- (4-styrylphenyl) -2H-naphthol [1,2-d] triazole; 4 , 4'-bis- (1,2,3-triazol-2-yl) -stilbene; 4,4'-bis (styryl) bisphenyl; and aminocoumarin. Specific examples of these brighteners include 4-methyl-7-diethylaminocoumarin; 1,2-bis (benzimidazol-2-yl) ethylene; 1,3-diphenylfurazoline;
5-bis (benzooxazol-2-yl) thiophene; 2-styryl-naphtho- [1,2-d] oxazole; and 2- (stilben-4-yl) -2H-.
Examples include naphtho [1,2-d] triazole. See also U.S. Pat. No. 3,646,015 issued Feb. 29, 1972 to Hamilton. Anionic brighteners are preferred here.

The compounds for inhibiting or reducing the formation of foam inhibitors bubbles can be incorporated into the compositions of the present invention. Foam suppression is described in U.S. Patents 4,489,455 and 4,489,574.
It may be of particular importance in so-called "high-concentration cleaning methods" and front-loading European washing machines as described in the specification.

Various substances may be used as suds suppressors, and suds suppressors are known to those skilled in the art. For example, Kirk Othmer Encyclopedia of Chemical Technology, 3rd edition,
Vol. 7, pp. 430-447 (John Willie End Sands Incorporated, 1979). One category of suds suppressors of particular benefit includes monocarboxylic fatty acids and their soluble salts. See Wayne St. John, US Pat. No. 2,954,347, issued Sep. 27, 1960. The monocarboxylic fatty acids and their salts used as suds suppressors typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts, such as sodium salts, potassium salts, and lithium salts, and ammonium salts and alkanol ammonium salts.

The detergent composition of the present invention may also contain a non-surfactant suds suppressor. These include, for example, high molecular weight hydrocarbons such as paraffins and fatty acid esters.
(E.g., fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C ₁₈ -C ₄₀ ketones (e.g., stearone), and the like. Other foam suppressors include N-alkylated aminotriazines, such as trialkylmelamines formed as a product of 2 or 3 moles of a primary or secondary amine having 1 to 24 carbon atoms and cyanuric chloride. Up to hexaalkylmelamine, or from dialkyldiamine chlorotriazines to tetraalkyldiamine chlorotriazines, propylene oxide, and monostearyl phosphates, such as monostearyl alcohol phosphates and monostearyl dialkali metals (eg, K, Na,
And Li) phosphates and phosphate esters. Hydrocarbons such as paraffin and haloparaffin are available in liquid form. Liquid hydrocarbons will be liquid at room temperature and atmospheric pressure and will have a pour point of about -40 ° C to about 50 ° C and a minimum boiling point of about 110 ° C or higher (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably those having a melting point of less than about 100 ° C. Hydrocarbons constitute a preferred category of suds suppressors for detergent compositions. Hydrocarbon suds suppressors are described, for example, in US Pat. No. 4,265,779 issued May 5, 1981 to Gandolfo et al. As the hydrocarbon, as described above, the carbon number is about 12 to about 7.
And 0 aliphatic, cycloaliphatic, aromatic and heterocyclic saturated or unsaturated hydrocarbons. The term "paraffin" as used in this foam suppressant discussion is intended to include mixtures of true paraffins and cyclic hydrocarbons.

Another preferred category of non-surfactant suds suppressors consists of silicone suds suppressors. This category includes polyorganosiloxane oils such as polydimethylsiloxanes, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxanes and silica particles (polyorganosiloxanes are chemisorbed on silica or Fusion). Silicone suds suppressors are well known in the art and are described, for example, in US Pat. No. 4,265,779 issued May 5, 1981 to Gandolfo et al. S. 1990 2 by Starch
It is disclosed in European Patent Application No. 89307851.9, published on May 7.

Other silicone suds suppressors are disclosed in US Pat. No. 3,455,839 for methods for defoaming aqueous solutions by incorporating the composition and a small amount of polydimethylsiloxane fluid into the aqueous solution. ing.

Mixtures of silicone and silanized silica can be obtained, for example, from German patent application DOS No. 2
, 124,526.

In the preferred silicone suds suppressors for use herein, the solvent for the continuous phase is
It consists of a specific polyethylene glycol or polyethylene-polypropylene glycol copolymer or a mixture thereof (preferred), or polypropylene glycol. The primary silicone suds suppressor is branched / crosslinked and preferably not linear. In the case of detergent compositions to be used in automatic washing machines, the foam should not form so much that it overflows the washing machine. When used, the foam suppressor is preferably
Exists with "foam suppression amount". By "foam level" is meant that the formulator of the composition can select the amount of this foam control agent that will adequately control the foam to produce a low foam laundry detergent for use in an automatic washing machine. Means

The composition will generally contain 0% to about 5% suds suppressor. When utilized as suds suppressors, monocarboxylic fatty acids and their salts will typically be present in amounts up to about 5% by weight of the detergent composition. Although large amounts may be used, silicone suds suppressors are typically utilized in amounts up to about 2.0% by weight of the detergent composition.
This upper limit is practical in nature primarily due to concerns about small amounts of effectiveness to keep costs to a minimum and effectively control foam. Preferably, about 0.01% to about 1% of silicone suds suppressor is used, more preferably about 0.25% to about 0.5%. As used herein, these weight percent values include silica that may be used in combination with the polyorganosiloxane, as well as adjunct materials that may be utilized. Monostearyl phosphate suds suppressors are generally utilized in amounts of about 0.1 to about 2% by weight of the composition.
Although high amounts can be used, hydrocarbon suds suppressors are typically about 0.01% to about 5.0%.
Used in the amount of%. Alcohol suds suppressors typically range from 0.2 to 0.2% of the finished composition.
Used at 3% by weight.

Dye Transfer Inhibitors The compositions of the present invention may also include one or more substances effective in inhibiting dye transfer from one fabric to another during the cleaning process. Generally, such dye transfer inhibitors include polyvinylpyrrolidone polymers, polyamine N-
Oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanines, peroxidases, and mixtures thereof. If used, these agents typically comprise about 0.01 to about 10% by weight of the composition, preferably about 0.01 to about 5%, more preferably about 0.05 to about.
It accounts for about 2% by weight.

[0078] More specifically, where the preferred polyamine N- oxide polymers for use bodies, in the structural formula R-A _x -P [the following formula, P is a polymerizable unit (and N-O group bonds Or the N-O group can form part of the polymerizable unit, or the N-O group can be bound to both units); A is of the structure -NC (O)-, -C (O) O
-, -S-, -O-, -N =; x is 0 or 1; R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or those. (Wherein the nitrogen of the NO group can be attached, or the NO group is part of these groups). Preferred polyamine N-oxides are those in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine,
Piperidine and derivatives thereof.

[0079]   The N-O group has the following general structure

[Chemical 3] (Wherein R ₁ , R ₂ and R ₃ are aliphatic, aromatic, heterocyclic or alicyclic groups or a combination thereof; x, y and z are 0 or 1; The nitrogen of can be bonded or can form part of any of the above groups). The amine oxide unit of polyamine N-oxide has pKa <10,
It preferably has pKa <7, more preferably pKa <6.

Any polymer backbone can be used as long as the resulting amine oxide polymer is water soluble and dye transfer inhibiting. Examples of suitable polymer backbones are polyvinyl,
Polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers in which one monomer type is an amine N-oxide and the other monomer type is an N-oxide. Amine N-oxide polymers typically have an amine to amine N-oxide ratio of 10: 1 to 1: 1,000,0.
Has 00. However, the number of amine oxide groups present on the polyamine oxide polymer can be varied by suitable copolymerization or by a suitable degree of N-oxidation. Polyamine oxides can be obtained with almost any degree of polymerization. Typically, the average molecular weight is 500 to 1,000,000, more preferably 100
It is in the range of 0 to 500,000, most preferably 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".

The most preferred polyamine N-oxide useful in the detergent compositions of the present invention is poly (4-vinylpyridine-N-) having an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1: 4. Oxide).

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as “PVPVI” as a class) are also preferred for use herein. Preferably, the PVPVI has an average molecular weight range of 5,000 to 1,000,000, more preferably 5,000 to 200,000, and most preferably 10,000 to 20,000.
[The average molecular weight range is determined by light scattering as described in Berth et al., Chemical Analysis, Vol. 113, "Modern Methods of Polymer Characterization", the disclosure of which is incorporated herein by reference]. The PVPVI copolymer is typically a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1, most preferably Is from 0.6: 1 to 0.4: 1
Have. These copolymers can be either linear or branched. The composition of the present invention has an average molecular weight of about 5,000 to about 400,000, preferably about 5,000 to about 200,000, more preferably about 5,000 to about 50,000.
Polyvinylpyrrolidone (“PVP”) having 0 may also be used. PVP is known to those skilled in the detergent art. See, for example, EP-A 262,897 and EP-A 256,696 (incorporated herein by reference).
Compositions containing PVP include polyethylene glycol ("PEG") having an average molecular weight of about 500 to about 100,000, preferably about 1,000 to about 10,000.
) Can also be included. Preferably, the ratio of PEG to PVP (ppm) delivered to the wash solution
By weight) from about 2: 1 to about 50: 1, more preferably from about 3: 1 to about 10: 1.
Is.

Optical Brighteners The detergent compositions of the present invention may also optionally contain from about 0.005 to 5% by weight of a specific type of hydrophilic optical brightener which also provides a dye transfer inhibiting effect. If you use
The composition will preferably contain from about 0.01 to 1% by weight of such optical brightener.

Bleaching Compounds- Bleaches and Bleach Activators The detergent compositions of the present invention optionally contain a bleaching agent, or a bleaching composition containing a bleaching agent and one or more bleaching activators. Good. The bleaching agent, when present, will typically be in an amount of about 1% to about 30%, more typically about 5% to about 20% of the detergent composition, especially for fabric laundering. The amount of bleach activator, if present, is
Typically, from about 0.1% to about 60% of the bleaching composition containing a bleach and a bleach activator.
, More typically about 0.5% to about 40%.

The bleaching agent used herein can be any of the bleaching agents useful in detergent compositions for cloth cleaning, hard surface cleaning, or other cleaning purposes now known or known. . These include oxygen-based bleaches as well as other bleaches. Perborate bleaches such as sodium perborate (eg monohydrate or tetrahydrate) and percarbonate bleaches can be used here.

Another category of bleaches that can be used without limitation includes percarboxylic acid bleaches and their salts. Suitable examples of this type of bleaching agent include magnesium monoperoxyphthalate hexahydrate, magnesium salt of m-chloroperbenzoic acid, 4-
Nonylamino-4-oxoperoxybutyric acid and diperoxide decanedioic acid are mentioned. Such bleaching agents are disclosed in Hartman, U.S. Pat. No. 4,483,781, issued Nov. 20, 1984, and Burns et al., U.S. Pat. No. 740,446, Jun. 3, 1985. , Banks et al., European Patent Application No. 0,133,354, published Feb. 20, 1985, and Chang, et al., US Pat. No. 4,412,934, issued Nov. 1, 1983. Has been done.
Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described by Burns et al. In US Pat. No. 4,634,551 issued Jan. 6, 1987.

Peroxygen bleaches can also be used. Suitable peroxygen bleaching compounds include sodium carbonate hydrogen peroxide and equivalent "percarbonate" bleaches, sodium pyrophosphate hydrogen peroxide, urea hydrogen peroxide, and sodium peroxide. Persulfate bleach (eg OXONE, commercially produced by DuPont) can also be used. Mixtures of bleaching agents can also be used.

Peroxygen bleaches, perborates, percarbonates, etc. are preferably combined with a bleach activator, which corresponds to the bleach activator in situ in an aqueous solution of the peroxyacid (ie a washing process). Time). Various non-limiting examples of activators are disclosed in Mao et al., US Pat. No. 4,915,854 issued Apr. 10, 1990 and US Pat. No. 4,412,934. . Nonanoyloxybenzene sulfonate (NOBS) and tetraacetylethylenediamine (TAED) activators are typical and mixtures thereof can also be used. For other typical bleaches and activators useful herein, see US Pat. No. 4,634.
, 551.

Highly preferred amide-derived bleach activators are of the formula R ¹ N (R ⁵ ) C (O) R ² C (O) L or R ¹ C (O) N (R ⁵ ) R ² C
(O) L (In the formula, R ¹ is an alkyl group having about 6 to about 12 carbon atoms, and R ² is 1 to about 6 carbon atoms.
Is an alkylene, R ⁵ is H or an alkyl, aryl or alkaryl having from about 1 to about 10 carbons, and L is a suitable leaving group). A leaving group is a group that is displaced from a bleach activator as a result of a nucleophilic attack on the bleach activator by a perhydrolyzed anion. A preferred leaving group is phenyl sulfonate.

Preferred examples of bleach activators of the above formula include US Pat. No. 4,634,551
(6-octanamidocaproyl) oxybenzene sulfonate, (6-nonanamidocaproyl) oxybenzene sulfonate, (6-decanamidocaproyl) oxybenzene as described in the specification (incorporated herein by reference). Sulfonates, and mixtures thereof.

Another type of bleach activator is a benzoxazine type activity disclosed in Hodge et al., US Pat. No. 4,966,723, issued Oct. 30, 1990, which is incorporated herein by reference. It consists of agents. Yet another class of preferred bleach activators includes acyl lactam activators, especially acyl caprolactam and acyl valerolactam. Highly preferred lactam activators include benzoylcaprolactam, octanoylcaprolactam, 3,5,5-trimethylhexanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, benzoylvalerolactam, octanoylvalerolactam, Examples include decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. 19 to Sanderson, which discloses acylcaprolactams, including benzoylcaprolactam adsorbed on sodium perborate.
See also U.S. Pat. No. 4,545,784, issued October 8, 1985, incorporated herein by reference.

Bleaching agents other than oxygen-based bleaching agents are known in the art and can be utilized herein. One class of non-oxygen bleaches of particular benefit includes photoactivated bleaches such as sulfonated zinc phthalocyanine and / or aluminum phthalocyanine. U.S. Pat. No. 4,033,71 issued July 5, 1977 to Holcombe et al.
See specification 8. If used, detergent compositions will typically contain from about 0.025 to about 1.25% by weight of such bleaching agents, especially sulfonated zinc phthalocyanine.

If desired, the bleaching compound can be catalyzed by a manganese compound. Such compounds are well known in the art, eg US Pat. No. 5,246,621, US Pat. No. 5,244,594, US Pat. No. 5,194,416, U.S. Pat. No. 5,114,606 and European Patent Application Publication No. 54
9,271A1 Specification, 549,272A1 Specification, 544,440A
2 and manganese-based catalysts disclosed in 544,490A1. Practically, without limitation, the compositions and methods of the present invention can be adjusted to provide at least about 1 part / million active bleach catalyst species in an aqueous wash liquor, and preferably in the wash liquor about 0. It will provide from 1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm.

Antistatic Agents The present compositions may also include antistatic agents such as those exemplified in US Pat. No. 4,861,502. Preferred examples of the antistatic agent include an alkylamine-anionic surfactant ion pair, for example, a distearylamine-cumenesulfonate ion pair. The antistatic agent, if present, is about 0.5 of the detergent composition.
To about 20% by weight, preferably about 1 to about 10% by weight, more preferably about 1 to about 5% by weight.

[0095]

EXAMPLES In the abbreviated detergent compositions used in the examples , the abbreviation component identification has the following meanings.

LAS: linear C _11-13 sodium alkylbenzene sulfonate TAS: sodium tallow alkylsulfate CxyAS: C _1x -C _1y sodium alkylsulfate C 46 SAS: C ₁₄ -C ₁₆ secondary (2,3) sodium alkylsulfate CxyEzS : z moles of ethylene oxide condensed with C _1x -C _1y sodium alkyl sulfate CxyEz: mean z moles of engaged ethylene oxide condensed C _1x -C _1y predominantly linear primary alcohol ^{_{QAS: R 2 · N + (}} CH 3 ) ₂ (C ₂ H ₄ OH) (wherein R ₂ = C ₁₂ ~
C ₁₄ ) QAS1: R ₂ · N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH) (wherein R ₂ = C ₈ ~
_{C 11) APA: C 8 ~C} 10 amidopropyl dimethylamine Soap: tallow and sodium linear alkyl carboxylate derived from a 80/20 mixture of coconut fatty acids STS: Sodium toluene sulfonate CFAA: C ₁₂ ~C ₁₄ (here ) alkyl N- methyl glucamide TFAA: C ₁₆ ~C ₁₈ alkyl N- methyl glucamide TPKFA: C ₁₂ ~C ₁₄ Topputo total cut fatty STPP: anhydrous sodium tripolyphosphate TSPP: tetrasodium pyrophosphate zeolite A: primary particle size 0 The formula Na ₁₂ (AlO ₂ S having the formula
iO ₂ ) ₁₂ · 27H ₂ O hydrated sodium aluminosilicate (weight expressed on an anhydrous basis) NaSKS-6: crystalline layered silicate of the formula δ-Na ₂ Si ₂ O ₅ citric acid: citric anhydride borate: boric acid Sodium carbonate: Anhydrous sodium carbonate having a particle size of 200 μm to 900 μm Bicarbonate: Anhydrous sodium bicarbonate having a particle size distribution of 400 μm to 1200 μm Silicate: Amorphous sodium silicate (SiO ₂ : Na ₂ O = 2.0: 1) Sulfate: anhydrous sodium sulphate Mg sulphate: anhydrous magnesium sulphate citrate: activity 86.4% with a particle size distribution of 425 μm to 850 μm
Trisodium citrate dihydrate MA / AA: copolymer of maleic acid / acrylic acid 1: 4, average molecular weight about 70
2,000 MA / AA (1): copolymer of maleic acid / acrylic acid 4: 6, average molecular weight of about 10,000 AA: sodium polyacrylate polymer having average molecular weight of 4,500 CMC: sodium carboxymethylcellulose cellulose ether: Methyl cellulose ether protease with a degree of polymerization of 650 available from Shin-Etsu Chemical: Proteolytic enzyme with 3.3% by weight of active enzyme sold under the trade name Sabinase by Novo Industries A / S Protease I: by Genencor Into Inc. W for sale
Proteolytic enzyme with 4% by weight of active enzyme described in O 95/10591 Alcalase: Proteolytic enzyme with 5.3% by weight of active enzyme sold by Novo Industries A / S Cellulase: Novo. Cellulolytic enzyme having 0.23% by weight of active enzyme sold under the trade name Carezyme by Industries A / S Amylase: trade name Termamyl 12 by Novo Industries A / S
Amylolytic enzyme lipase with 1.6% by weight of active enzyme sold at 0T: Lipase (1) with 2.0% by weight of active enzyme sold under the trade name Lipolase by Novo Industries A / S. ): Lipid-degrading enzyme Endolase with 2.0 wt% active enzyme sold under the trade name Lipolase Ultra by Novo Industries A / S: 1.5 wt active enzyme sold by Novo Industries A / S % Endoglucanase enzyme PB4: sodium perborate 4 of the nominal formula NaBO ₂ .3H ₂ O.H ₂ O ₂
Hydrate PB1: Nominal formula NaBO ₂ · H ₂ O ₂ anhydrous sodium perborate bleach Percarbonate: Nominal formula 2Na ₂ CO ₃ · 3H ₂ O ₂ sodium percarbonate NOBS: Nonanoyloxy in the form of the sodium salt Benzenesulfonate NAC-OBS: (6-nonanamidocaproyl) oxybenzenesulfonate TAED: Tetraacetylethylenediamine DTPA: Diethylenetriaminepentaacetic acid DTPMP: Diethylenetriaminepenta (methylenephosphonate) EDDS: sodium salt marketed by Monsanto under the trade name Dequest 2060. Ethylenediamine-N, N'-disuccinic acid in the form of
(S, S) isomer Photo-activated bleach (1): Sulfonated zinc phthalocyanine encapsulated in dextrin-soluble polymer Photo-activated bleach (2): Sulfonated alumino encapsulated in dextrin-soluble polymer Phthalocyanine Whitening agent 1: 4,4'-bis (2-sulfostyryl) biphenyl disodium Whitening agent 2: 4,4'-bis (4-anilino-6-morpholino-1,3,5-
Triazin-2-yl) amino) stilbene -2: Sodium 2'-disulfonate, disodium HEDP: 1,1-hydroxyethane diphosphonic acid PEG _x: polyethylene glycol having a molecular weight x (typically 4,000 to) PEO: Polyethylene oxide having an average molecular weight of 50,000 TEPAE: Tetraethylene pentaamine ethoxylate PVI: Polyvinylimidazole having an average molecular weight of 20,000 PVP: Polyvinylpyrrolidone polymer having an average molecular weight of 60,000 PVNO: Having an average molecular weight of 50,000 polyvinylpyridine N- oxide polymers PVPVI: average molecular copolymer of polyvinyl pyrrolidone and vinyl imidazole having a weight 20,000 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 ( wherein n is 20 to 30) SRP1: anionic end-capped polyester SRP2: Diethoxylated poly (1,2-propylene terephthalate) short block polymer PEI: Polyethyleneimine having an average molecular weight of 1800 and an average degree of ethoxylation of 7 ethyleneoxy residues per nitrogen Silicone antifoam: Antifoam pair Polydimethylsiloxane antifoam with siloxane-oxyalkylene copolymer as a dispersant having a dispersant ratio of 10: 1 to 100: 1 Emulsifier: sold by BASF Corporation under the trade name Lytron 621. Water Based Monostyrene Latex Mixture Wax: Paraffin Wax In the examples below, all amounts were It cited as the percent by weight of the thing.

Example 1 In this example, 400 g of activated zeolite X is placed in a high pressure vessel. Evacuate the container. The vessel is then charged with CO ₂ at a pressure of 10 bar G. Hold this pressure for 10 minutes. The pressure is then released and the CO ₂ loaded zeolite is removed and stored in a glass jar.

Upon the addition of 10 g of CO ₂ loaded zeolite to a beaker of water, there is a rapid release of CO ₂ to create bubbles and to generate significant localized heat.

Example 2 The following laundry detergent compositions AF are prepared and 10% by weight of the material prepared in Example 1 is added to each of the formulations. Gas bubbles are observed according to the invention upon addition of each of the resulting formulations to water. ABCDEF LAS 8.0 8.0 8.0 2.0 6.0 6.0 TAS-0.5-0.5 1.0 0.1 C46 (S) AS 2.0 2.5----C25AS---7.0 4.5 5.5 C68AS 2.0 5.0 7.0---C25E5--3.4 10.0 4.6 4.6 C25E7 3.4 3.4 1.0---C25E3 S---2.0 5.0 4.5 QAS-0.8----QAS (I)---0.8 0.5 1.0 Zeolite A 18.1 18.0 14.1 18.1 20.0 18.1 Citric acid---2.5-2.5 Carbonate 13.0 13.0 27.0 10.0 10.0 13.0 SKS-6---10.0-10.0 Silicate 1.4 1.4 3.0 0.3 0.5 0.3 Site rate-1.0-3.0--Sulfate 26.1 26.1 26.1 6.0--Mg sulfate 0.3--0.2-0.2 MA / AA 0.3 0.3 0.3 4.0 1.0 1.0 CMC 0.2 0.2 0.2 0.2 0.4 0.4 PB4 9.0 9.0 5.0---Percarbonate----18.0 18.0 1TAED 1.5 0.4 1.5-3.9 4.2 NAC-OBS-2.0 1.0---DTPMP 0.25 0.25 0.25 0.25-- SRPI---0.2-0.2 EDDS-0.25 0.4-0.5 0.5 CFAA-1.0-2.0-- EDP 0.3 0.3 0.3 0.3 0.4 0.4 1 QEA---0.2-0.5 Protease I--0.26 1.0--Protease 0.26 0.26--1.5 1.0 Cellulase 0.3--0.3 0.3 0.3 Amylase 0.1 0.1 0.1 0.4 0.5 0.5 Lipase (1) 0.3-- 0.5 0.5 0.5 Photo-activated bleach (ppm) 15ppm 15ppm 15ppm-20ppm 20ppm PVNO / PVPVI----0.1--Whitening agent 1 0.09 0.09 0.09-0.09 0.09 Perfume 0.3 0.3 0.3 0.4 0.4 0.4 Silicone defoamer 0.5 0.5 0.5 -0.3 0.3 Miscellaneous / minor components Remainder (100%) Density (g / l) 850 850 850 850 850 850

Thus, although the present invention has been described in detail above, various modifications may be made without departing from the scope of the present invention and the present invention is not limited to those described in the specification. It should be obvious to those skilled in the art that it should not be considered.

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, MZ, SD, SL, SZ, TZ, UG , ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, BZ, C A, CH, CN, CR, CU, CZ, DE, DK, DM , DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, K E, KG, KP, KR, KZ, LC, LK, LR, LS , LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT, RO, R U, SD, SE, SG, SI, SK, SL, TJ, TM , TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Adrian, John, Waynefor             Su, Angel             West, Chi, Ohio, United States             Esther, Hidden, Ridge, Drive,             6837 (72) Inventor Eugene, Joseph, Pancelli             Montgomery, Ohio, United States             ー, Sunberina, Rain, 7420 (72) Inventor Frank, Andre, Kubituk             Cincinnati, Ohio, USA             Richwood, Avenue, 1103 (72) Inventor Diane, Parry             Cincinnati, Ohio, USA             Blame, road, 9568 (72) Inventor Harold, Fisher, Stouffer,             Junior             Cincinnati, Ohio, USA             Lake, thames, drive, 10820, apa             Statement, ray F-term (reference) 4H003 AB19 AB27 AC08 BA01 BA17                       EA12 EA28 EA31 EB32 EB42                       EC01 EC02 EC03 EE05 FA06                       FA09 FA12 FA18 FA20 FA22                       FA26 FA38

Claims (16)

[Claims] 1. An aluminosilicate ion exchange material having pores is prepared, the aluminosilicate ion exchange material is dried, gas is trapped in the pores of the aluminosilicate ion exchange material, and the gas trapped alumino A silicate ion exchange material is added to a detergent composition to prepare a detergent product that exhibits foamability when the detergent product is placed in an aqueous medium. Usage of aluminosilicate ion exchange material. 2.   The aluminosilicate ion exchange material has the formula Mm / n [(AlO₂) M (SiO ₂ ) Y] ・ xH₂O (where n is the valence of the cation M and x is the unit cell)
Is the number of water molecules, and m and y are the total number of tetrahedra per unit cell.
Yes, y / m is 1 to 100, M is sodium, potassium, magnesium,
And is selected from the group consisting of: and calcium). 3. The method according to claim 1, wherein the aluminosilicate ion exchange material is zeolite. 4. The method according to claim 1, wherein the aluminosilicate ion exchange material further acts as a builder in the detergent product. 5. The method according to claim 1, wherein the aluminosilicate ion exchange material has pores having a pore size in the range of 2 Å to 12 Å. 6. The method of any one of claims 1-5, wherein the aluminosilicate ion exchange material has a total porosity of at least 25%. 7.   7. The method according to any one of claims 1-6, wherein the gas is carbon dioxide. 8. The method of claim 1 comprising heating the aluminosilicate ion exchange material to a temperature of at least 20 ° C. prior to trapping the gas in the pores of the aluminosilicate ion exchange material. The method according to any one of items. 9. The method comprises placing the aluminosilicate ion exchange material in a pressurizable container and trapping the gas in the pores of the aluminosilicate ion exchange material at a gas pressure of at least 1 atmosphere. The method according to any one of 1 to 8. 10. The gas trapped aluminosilicate ion exchange material is added to the detergent composition in an amount in the range of 1 to 25% by weight of the detergent composition. The method described. 11. The detergent composition is free of citric acid and bicarbonate.
The method according to any one of 1. 12. A laundry detergent composition comprising a surfactant and a builder, said builder being suitable for providing said laundry detergent composition with a combination of builder and foaming properties, said builder comprising: , Mm / n [(AlO ₂ ) m (SiO ₂ ) y] .xH ₂ O (where n is the valence of the cation M, x is the number of water molecules per unit cell, m And y is the total number of tetrahedra per unit cell, y / m is 1 to 100, M is selected from the group consisting of sodium, potassium, magnesium and calcium) aluminosilicate ion exchange material , The aluminosilicate ion exchange material has pores, the aluminosilicate ion exchange material has gas trapped in the pores, and the detergent product is an aqueous solution of the detergent product. Shows a foaming when placed in the body, characterized by, laundry detergent products. 13. A carbon dioxide gas trapped zeolite is included, wherein said zeolite is present in said laundry detergent composition in an amount in the range of 1 to 25% by weight. Laundry detergent product as described. 14. The laundry detergent product according to claim 1, wherein the laundry detergent product is in a granular form. 15. The laundry detergent product according to claim 1, wherein the laundry detergent product is in a non-granular form. 16. A group consisting of an enzyme, an antifouling agent, a dispersant, an optical brightener, a foam suppressor, a fabric softener, an enzyme stabilizer, a fragrance, a dye, a filler, a dye transfer inhibitor, and a mixture thereof. A laundry detergent product according to any one of claims 1 to 15, further characterized by an auxiliary detergent ingredient selected from: