JPS6116314B2 - - Google Patents

Abstract

A detergent composition contains as builder a combination of an aluminosilicate cation-exchange material, for example, Zeolite A, with an organic precipitant builder having the formula I <CHEM> wherein: R1 is C10-C24 alkyl or alkenyl, or an arylalkyl or alkylaryl group of equivalent chain length; X is CH, CR2, N or CON; R2 is C1-C3 alkyl; Y is hydrogen or a solubilising cation: n and m, which may be the same or different, are O or integers from 1 to 4; and Z is COOY or SO3Y. Preferred organic precipitant builders are the alkyl or alkenyl malonates and succinates. The inorganic phosphate content is desirably less than 10% by weight, and zerophosphate compositions are preferred.

Description

[Detailed description of the invention]

The present invention relates to additives for detergent compositions and detergent compositions containing the additives. These compositions are particularly suitable, but not exclusively, for textile cleaning. In particular, the present invention relates to detergent compositions that are substantially phosphate-free. Textile cleaning compositions typically contain a phosphate detergency builder such as sodium tripolyphosphate. Under certain circumstances, the use of phosphates in detergent compositions was thought to cause wastewater to cause environmental pollution. It is therefore desirable to reduce or eliminate the amount of phosphorus in detergent compositions. Water-insoluble aluminosilicate ion exchange materials have been suggested as alternative builders to phosphates (see, for example, GB 1473201 and GB 1473202 (Henkel)). However, the inventors have found that in practice these aluminosilicate materials undesirably tend to slow down the exchange of these cations, especially at low temperatures, even when used in large quantities, resulting in a reduction in detergency. I discovered that. It has therefore been suggested that supplementary water-soluble builders should be used in conjunction with these aluminosilicates to achieve acceptable levels of detergency. These supplemental builders are generally materials that are themselves effective sequestrant builders, such as alkali metal tripolyphosphates, nitrotriacetates, and poly-alpha-hydroxy acrylates. However, the use of large amounts of these substances in detergent compositions
Generally undesirable for reasons of cost or environmental pollution. Surprisingly, we have shown that the cleaning power of aluminosilicate-builder detergent products can be substantially increased by replacing a portion of the aluminosilicate with an organic precipitant builder having divalent anions. I discovered that. It has been found that replacing 15 to 30% of the aluminosilicate by such an organic precipitant builder provides detergency comparable to the combination of zeolite and sodium tripolyphosphate as the builder. It is known that the detergency builder properties of aluminosilicates can be improved by adding water-soluble complexing agents such as sodium tripolyphosphate. This effect is explained by the so-called “carrier molecule model”.
(e.g. Peebels (P.
Berth), J. Am. Oil Chemists' Soc., 55, 52−
53 (1978)). Complexing agents can dissolve polyvalent hard water ions (notably Ca ⁺⁺ , but also Mg ²⁺ ) from solid surfaces, such as those of textile fibers;
It can then be transferred to an aluminosilicate ion exchanger after being transported through an aqueous medium. The complexing agent forms a chelate complex with hard water ions that have reached the surface of the aluminosilicate dissociated product. It is reasonable to consider a similar mechanism with precipitant builders, since precipitant builders remove hard water ions from wash liquors by forming a virtually irreversible precipitate (insoluble calcium or magnesium salts). It's not easy. It is thus surprising that an arsinosilicate/precipitating agent combination can impart builder properties comparable to an aluminosilicate/complexing agent combination. Attempts have been made to use the most common organic precipitant builder soaps as supplementary builders for zeolites, but detergency benefits were obtained only at impractically high builder concentrations (8 g/and above). This is a result of the soap's low effectiveness when used as a builder. That is, since soap anions are monovalent, two moles of soap are consumed by each gram ion Ca ²⁺ or Mg ²⁺ . British Patent No. 1,545,801 [Procter _{& Gamble} ] discloses that the organic detergent component is ₁ to ₄₀ % by _weight ; A spray-dried granular detergent composition comprising 3 to 25% by weight of a water-insoluble crystalline aluminosilicate ion exchange material (representing an integer of 30); 5 to 35% by weight of a phosphate builder and 5 to 25% by weight of an alkali metal silicate. is disclosed. The organic detergent component can in particular be a water-soluble salt of an alpha-sulfocarboxylic acid having 6 to 20 carbon atoms. (a) from about 3 to about 90% by weight of one or more detergent actives;
(b) essentially (i) from about 25 to about 97% by weight of the detergent additive of a crystalline or amorphous aluminosilicate cation exchange material; and (ii) of the formula: (In the formula, R ₁ represents an alkyl or alkenyl group having 10 to 24 carbon atoms or an arylalkyl or alkylaryl group with an equivalent chain length, X represents CH, OR ₂ , N or CON, and R ₂
represents an alkyl group having 1 to 3 carbon atoms, Y represents a hydrogen atom or a solubilizing cation, preferably an alkyl metal, especially sodium, n and m may be the same or different; represents an atom or an integer from 1 to 4,
And Z represents COOY or SO ₃ Y. ), wherein the detergent composition comprises from about 10 to about 97% by weight of a detergent additive comprising from about 3 to 75% by weight of an organic precipitant builder, with the proviso that the organic precipitant builder is an α- sulfocarboxylic acid and the aluminosilicate material is crystalline, the composition preferably contains up to 5% and preferably 3%
An object of the present invention is to provide a detergent composition containing an inorganic phosphate or less. Organic precipitant builders are water-soluble substances that react with Ca ²⁺ ions and preferably also Mg ²⁺ ions in a stoichiometric ratio of 1:1 to form insoluble salts. The solubility of the calcium salt product of the organic precipitant builder is preferably 10 ^-8 or less. A preferred group of compounds within the general formula is X
represents CH, n represents 0, and m represents 0
or a compound representing 1. According to a first preferred embodiment of the invention, the organic precipitant builder has the formula: (In the formula, R ₁ , Y and Z have the above-mentioned meanings, and P represents 0 or 1.) Among the compounds represented by the general formula, the following compounds are particularly preferred: (i) The following formula: A substituted malonate represented by and (ii) the following formula: Substituted succinates of the formula and compounds of the formula are described, for example, in GB 1293753, GB 1342247 and GB 1342347 (Unile-ver). . Such compounds include, for example, disodium dodecyl malonate ( _C12 -AKM), disodium hexadecenyl succinate (C16:1-AKS), and disodium mixed _C15 - _C18 succinate ( _{C15- 18} −
AKS) is included. According to a second preferred embodiment of the invention, the organic precipitant builder has the formula: A compound represented by or the following formula: It is a compound represented by In the above formula, R ₁ and Y have the above meanings, and v and w each represent 1 to 4, preferably 1 or 2. Compounds in which v and w both represent 1, ie N-alkyliminodiacetates, are of particular interest. The compound represented by formula V in which v and w both represent 2, ie β-iminodipropionate, is a known amphoteric surfactant as disclosed, for example, in British Patent No. 1296793 (General Mills). be. These substances are also used as foam enhancers in bar soaps, e.g.
No. 0025242 (Procter & Gamble) and as a rust inhibitor, for example from US Pat. No. 2,926,108 (General Mills).
Compounds of the formula V in which v and w both represent 1, i.e. iminodiacetates, are described, for example, in U.S. Pat.
It is also disclosed in US Pat. No. 3,630,927 (Monsanto) as a scum dispersant in soap products and as a rust inhibitor in US Pat. No. 2,368,604 (Shell).
U.S. Pat. No. 3,981,779 (Grace) discloses a water-based “chelant” that reduces metal fouling.
GB 761384 [California Research Corporation] discloses compounds of the formula and for use as chelant-surfactants.
Research Corporation)] contains 10 to 50% by weight of alkylbenzene sulfonate and N-( _C8 to _C18
5 to 20 water-soluble salts of alkyl)-iminodiacetic acid
% by weight.
The latter component acts as a foam enhancer. Similarly, GB 761,383 (California Research Corporation) discloses the combination of alkyl sulfates and N-( _C8 - _C18 alkyl)-iminodicarboxylic acids. Other specifications relating to the use of compounds of formula V in detergent compositions include GB 446737 and GB 446813 (I G Farben). . Compounds similar to those of the formula but with shorter alkyl chains (C ₈ or less) are described in British Patent No. 1383025
Chemische Werke Hu¨
It is well known as a sequestering agent builder, as described in U.S. Pat. Aluminosilicate cation ^exchange _materials have _the ^following _{formula :} (Cat _{2 /o} O ₎ represents an exchangeable n-valent cation, x represents a number from 0.7 to 1.5, y represents a number from 1.3 to 4, and Z represents an amount such that the bound water content is 10 to 28% by weight.) It is a crystalline or amorphous substance represented by The following formula: Na _x [(AlO ₂ ) _x・(SiO ₂ ) _y ]ZH ₂ O (wherein x and y represent an integer of at least 6, and the ratio of x to y is 1:1 to 1:2 It is preferable to use crystalline materials which can be described by the unit cell content (within the range of 10 to 28 wt. . The aluminosilicate preferably has a particle size of 0.1 to 100 micrometers, ideally 0.1 to 10 micrometers, and at least 200 micrometers per gram of aluminosilicate (on anhydrous basis).
It has an ion exchange capacity of _mgCaCO3 . In a preferred embodiment, the water-insoluble aluminosilicate has the formula: Na ₁₂ (AlO ₂ ) ₁₂ ·(SiO ₂ ) ₁₂ ·ZH ₂ O, where Z represents 20 to 30, preferably about 27. is a crystalline material described by the unit cell inclusions represented by For example, this substance is typically represented by the following formula: Na ₂ O.Al _{2 O} 3.2SiO _{2.4.5H 2} O, and the following formula: Na ₁₂ [(AlO ₂ ) _12. (SiO ₂ ) Mention may be made of commercial products known as zeolite type A, also described by the unit cell content represented by ₁₂ ].27H ₂ O. The detergent compositions of the present invention contain about 100% of the specified detergent additives.
10 to about 97% by weight, preferably about 12 to about 80%
% by weight, more preferably from about 15 to about 70% and especially from about 16 to about 67%. Since the detergent additive contains from about 25% to about 97% by weight aluminosilicate, the aluminosilicate content in the detergent composition ranges from about 2.5% to about 94% by weight.
Weight percentages may vary. Particularly preferred is an aluminosilicate content of about 10 to about 60% by weight, especially about 12 to about 55% by weight. Similarly, the content of organic precipitant builder is approximately 0.3
Although it can vary from about 1% to about 73% by weight, a range of about 1% to about 30% by weight, especially about 3% to about 17% by weight is particularly preferred. Preferably, the detergent compositions of the present invention are substantially free of inorganic phosphates. This is highly desirable for the environmental pollution reasons mentioned above. It has been found that the compositions of the present invention, which do not contain inorganic phosphates, exhibit detergency properties comparable to products with sodium tripolyphosphate builder. However, if desired, the compositions of the invention can contain inorganic phosphates, preferably in an amount not exceeding 10%, based on the total weight of the composition.
The phosphates present can be, for example, in the form of alkali metal (preferably sodium) tripolyphosphates, orthophosphates, pyrophosphates or phosphate polymers. However, as mentioned above, when the organic precipitant builder is a special α-sulfocarboxylic acid salt, the phosphate content is preferably 5% or less, preferably 3%.
% or less. Although malonates and succinates of the above formulas are preferred, the following formulas: The α-sulfocarboxylic acid salt represented by the formula (wherein R ¹ and Y have the above-mentioned meanings) is of interest as an organic precipitant builder for use in the present invention.
The compound represented by the formula is, for example,
1368736 and UK Patent No. 1380390 (Unilever). A typical example is disodium α-sulfostearate (C ₁₈ -SFAS). Mixtures of compounds of different chain lengths such as α-sulfo salts of coconut oil fatty acids (coco-SFAS) or α-sulfo salts of beef fatty acids (tallow-SFAS) or α-salts of coconut oil and tallow fatty acids mixtures. Sulfo salts can also be used advantageously. The present invention essentially comprises (i) about 25 to about 97% by weight of a crystalline or amorphous aluminosilicate cation exchange material; and (ii) about 3% by weight of an organic precipitant builder having polyvalent, preferably divalent anions. and about 75% by weight, and when the aluminosilicate material (i) is crystalline, the organic precipitant builder contains 6 carbon atoms.
The present invention also provides detergent additives that are not water-soluble salts of α-sulfocarboxylic acids. The organic precipitant builder constitutes from about 3 to about 75% by weight of the builder mixture (detergent additive) of the present invention, preferably from about 10 to about 60%, especially from about 15 to about 30%. The detergent additives of the present invention are effective builder systems that provide good detergency when mixed with detergent actives in detergent compositions. The detergent compositions of the present invention can optionally further contain non-phosphate builders.
The composition of the present invention can be applied, for example, to a co-related application filed by the present applicant (Case C) entitled "Detergent Additive and Detergent Composition Containing the Additive" and filed on the same date.
For example, an organometallic sequestering agent builder can be included in addition to the organic precipitant as disclosed in 1303). The organometallic sequestrant is preferably a water-soluble substance that forms a soluble complex with calcium with a pK _Ca of 3.0 or higher, more preferably 4.0 or higher and even more preferably 45 or higher. Certain sequestering agent builders preferably have a
It also forms a complex with magnesium with pK _Mg . Such substances include, for example, the alkali metal (especially sodium) salts of the following acids: nitrilotriacetic acid, ethylenediaminetetraacetic acid,
Polyacrylic acid, poly(alpha-hydroxyacrylic) acid, carboxymethyloxymalonic acid, carboxyoxysuccinic acid, oxydiacetic acid, oxydisuccinic acid, citric acid, dipicolinic acid and many others. U.S. Patent No. 4144126 and U.S. Patent No.
Polyacetal carboxylate disclosed in Specification No. 4146495 (Monsanto) and British Patent No.
The oxidized polysaccharides disclosed in GB 1330121, GB 1330122 and GB 1330123 (Unilever) can also be used advantageously. The detergent compositions of the present invention necessarily contain from about 3 to about 90% by weight, preferably from about 5 to about 40% by weight of synthetic anionic, nonionic, amphoteric or zwitterionic detergent compounds or mixtures thereof. contains about 10 to about 25% by weight. Many suitable detergent active compounds are commercially available and are available in the literature such as "Surface Active Agents and Detergents" by Schwartz, Perry and Berch.
Preferred detergent compounds that may be used include synthetic anionic and nonionic compounds. are water-soluble alkali metal salts of organic sulfates and sulfonates having alkyl moieties of higher aryl groups).Suitable synthetic anionic detergent compounds include, for example, sodium and potassium alkyl sulfates, especially e.g. tallow. or compounds obtained by sulfating higher ( _C8 - _C18 ) alcohols produced from coconut oil; sodium and potassium alkyl ( _C9 - _C20 ) benzene sulfonates, especially sodium linear secondary alkyl (C10 ₎ ~ _C15 )
Benzene sulfonate; sodium alkyl
Glyceryl ether sulfates, especially these ether compounds of higher alcohols obtained from oilseed or coconut oil and synthetic alcohols obtained from petroleum; sodium coconut fatty acid monoglycerides sulfates and sulfonates; higher ( _C9 - _O18 ) fatty alcohols - alkylene oxides, especially ethylene oxide) sodium and potassium salts of sulfuric esters of reaction products; esterified with isethionic acid;
Reaction products of fatty acids such as coconut oil fatty acids neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyltaurine; by reaction of α-olefins (C ₈ -C ₂₀ ) with sodium hydrogen sulfate Alkane monosulfonates such as random sulfonates obtained by reacting the resulting compounds and paraffins with SO ₂ and Cl ₂ and then hydrolyzing with base; and olefin sulfonates (the term refers to olefins, especially C ₁₀ to C ₂₀ - used to describe substances produced by reacting elefin with _SO3 , then neutralizing and hydrolyzing the reaction product). A preferred anionic detergent compound is sodium (C ₁₁
~ _C15 ) alkylbenzene sulfonate and sodium ( _C16 - _C18 ) alkyl sulfate. Suitable nonionic detergent compounds that can be used include:
For example, in particular, reaction products of alkylene oxide (usually ethylene oxide) and alkyl (C ₆ -C ₂₂ )phenols, each having an EO of 5 to 25 or 5 to 25 ethylene oxide units per molecule; aliphatic (C ₈ -C _{16 )} ) Condensation products of primary or secondary straight-chain or branched-chain alcohols with ethylene oxide, generally prepared by the condensation of ethylene oxide with compounds of EO 6 to 30 and the reaction products of propylene oxide with ethylene diamine products. Other so-called nonionic detergent compounds include long-chain tertiary amine oxides,
Included are long chain tertiary phosphoxides and dialkyl sulfoxides. Mixtures of detergent compounds, such as anionic compound mixtures or mixtures of anionic and nonionic compounds, can be used in detergent compositions, particularly in the latter case to impart controlled low foaming properties. This is beneficial for compositions intended for use in automatic washing machines where air bubbles are detrimental. The anionic and nonionic detergent compounds are preferably 3:1
It is commonly used in a ratio of 1.5:1 to 1.5:1. Although it is possible to use certain amounts of amphoteric or zwitterionic detergent compounds in the compositions of the present invention, this is usually undesirable due to the relatively high cost of these compounds. When an amphoteric or zwitterionic detergent compound is used, it is used in smaller amounts in the composition than the much more commonly used synthetic anionic and/or nonionic detergent compounds. If desired, the compositions of the invention can also contain soap. The presence of small amounts of soap is beneficial in terms of bubble control and cleaning power. Soaps that can be used are especially the sodium or, less preferably, potassium salts of _C10 to _C24 fatty acids. Soaps based primarily on longer chain fatty acids within this range, ie soaps with at least half of the chain lengths of C ₁₆ or greater, are particularly desirable. Preferred chain length distributions include soaps from natural sources such as tallow, palm oil or rapeseed oil, which may optionally be hydrogenated, and small amounts of soaps made from nut oils such as coconut oil or palm kernel oil. can be conveniently obtained by using short chain soaps. According to a preferred embodiment of the invention, the detergent composition also contains a bleaching system. The bleaching system consists of a peroxy bleaching compound, preferably an inorganic persalt, preferably in combination with an activator of this compound. The persalt can be, for example, sodium perborate (either monohydrate or tetrahydrate) or sodium percarbonate. Activators make bleaching more effective at lower temperatures, ie in the range of room temperature to about 60°C. Such bleaching systems are therefore commonly known as low temperature bleaching systems and are well known in the art. The inorganic persalt acts to release active oxygen in solution, and the activator is usually an organic compound with one or more reactive acyl groups, which causes the formation of the peracid. The latter activator provides more effective bleaching action at lower temperatures than can be obtained by the use of peroxy bleach compounds alone. The weight ratio of peroxy bleach compound to activator is generally from about 20:1 to about 1:1, preferably from about 15:1 to about 2:1. Detergent compositions of the present invention preferably contain about 5% to about 30% by weight peroxy bleach compound and about 0.1 to about 15% by weight activator. The total amount of bleaching system components preferably ranges from 5% to 35% by weight, especially from 6% to about 30% by weight. Typical examples of suitable peroxy bleaching compounds include alkali metal perborate (tetrahydrate and mono
hydrates), alkali metal percarbonates, persilicates and perphosphates, with sodium perborate being preferred. Activators for peroxy bleach compounds are described in the literature, for example GB 836,988, GB 855,735, GB 907,356, GB 907,358;
Specification No. 970950, Specification No. 1003310 and No.
1246339, US Pat. No. 3,332,882 and US Pat. No. 4,128,497, Canadian Patent No. 844481 and South African Patent No. 68/6344. Particularly suitable activators include the following compounds: (a) N-diacylated and N,N'-polyacylated amines such as N,N,N',N'-tetraacetylmethylenediamine and N,N, N',N'-tetraacetylethylenediamine, N,N-diacetylaniline, N,N-diacetyl-P-toluidine; 1,3-diacylated hydantoins such as 1,3-diacetyl-5,5-dimethylhydantoin and 1, 3-dipropionylhydantoin; α-acetoxy-(N,N')-polyacylmalonamide e.g. α-acetoxy-
(N,N')-Diacetylmalonamide (b) N-alkyl-N-sulfonylcarbonamide such as N-methyl-N-mesylacetamide, N-methyl-N-mesyl-benzamide,
N-Methyl-N-mesyl-p-nitrobenzamide and N-methyl-N-mesyl-p-methoxybenzamide (c) N-acylated cyclic hydrazides, acylated triazones or urazoles, such as monoacetylmaleic hydrazide; (d ) O,N,N-trisubstituted hydroxylamines, such as O-benzoyl-N,N-succinylhydroxylamine, O-acetyl-N,N-succinylhydroxylamine, O-p-methoxybenzoyl-N,N-succinyl- Hydroxylamine, O-p-nitrobenzoyl-N,N
-succinyl-hydroxylamine and O,
N,N-triacetyl hydroxylamine (e) N,N'-diacyl-sulfurylamide e.g. N,N'-dimethyl-N,N'-diacetyl-
Sulfurylamide and N,N'-diethyl-
N,N'-dipropionylsulfurylamide (f) Triacyl cyanurates such as triacetyl cyanurate and tribenzoyl cyanurate (g) Carboxylic anhydrides such as benzoic anhydride, m-chlorobenzoic anhydride, phthalic anhydride, 4 -Chloro-phthalic anhydride (h) Sugar esters such as glucose pentaacetate (i) 1,3-diacyl-4,5-diacyloxy-imidazolidine such as 1,3-diformyl-
4,5-diacetoxy-imidazolidine, 1,
3-Diacetyl-4,5-diacetoxy-imidazolidine, 1,3-diacetyl-4,5-dipropionyloxy-imidazolidine (j) Tetraacetyl glycoluril and tetrapropionyl glycoluril (k) Diacylated 2,5- Diketopiperazines such as 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-diketopiperazine and 1,4-dipropionyl-3,
6-Dimethyl-2,5-diketopiperazine (l) Propylene diurea or 2,2-dimethyl. Propylene diurea (2,4,6,8-tetraaza-bicyclo-(3,3,1)-nonane-
3,7-diones or their 9,9-dimethyl derivatives), in particular tetraacetyl- or tetrapropionyl-propylene diureas or their dimethyl derivatives (m); carboxylic acid esters such as p-(ethoxy sodium salts of p-(propoxy-carbonyloxy)-benzoic acid and p-(propoxy-carbonyloxy)-benzenesulfonic acid (n) α-acyloxy-(N,N′) polyacylmalonamides such as α-acetoxy-(N,
N') diacetylmalonamide N-diacylation as described in (a) and N,
N'-polyacylated amines especially N,N,N',
Of particular interest is N'-tetraacetylethylenediamine (TAED). Granulation activator It is preferred to use a finely divided activator, preferably as described in the Applicant's British Patent No. 8,021,979. especially
It is preferred to have an activator with an average particle size of 150 micrometers or less, which provides a significant improvement in bleaching performance. Sedimentation losses are substantially reduced when using activators with an average particle size of 150 μm or less. Even excellent bleaching performance is obtained when the average particle size of the activator is less than 100 μm. However, if the particle size is too small, it can lead to increased decomposition, fines formation and handling problems;
The activator uses particles with a size of 50 μm or less, although particle sizes below can serve for improved bleaching performance.
It is desirable not to have more than 20% by weight. On the other hand, the activator may contain a certain amount of particles larger than 150 μm, but should not contain more than 5% by weight of particles larger than 300 μm,
Particles larger than 200 μm, preferably larger than 150 μm should contain no more than 20% by weight. It is to be understood that these particle sizes refer to the activator present in the granules and not to the granules themselves. Most of the granules themselves are 100 or less.
It has a particle size of 2000 μm, preferably 250 to 1000 μm. 5% by weight of granules with a particle size larger than 1700μm
and up to 10% by weight of granules smaller than 250 μm are permitted. The granules incorporating the activator, preferably in finely divided form, are prepared by combining a suitable carrier material such as sodium, tripolyphosphate and/or potassium tripolyphosphate with the activator particles of the required size. It can be obtained by converting Other granulation methods may also be usefully applied, for example using organic and/or inorganic granulation aids. The granules can then be dried if desired. As long as the granules contain the activator, essentially any granulation method can be applied, provided that other substances present in the granules do not have a negative effect on the activator. It is particularly preferred that the detergent compositions contain bleach-based stabilizers such as ethylenediaminetetramethylenephosphonate and diethylenetriaminepentamethylenephosphonate. These stabilizers can be used in acid or salt form, particularly calcium, magnesium, zinc or aluminum salts, as described in the applicant's GB 2048930. Apart from the ingredients already mentioned, the detergent compositions of the invention can contain any conventional additives in the amounts normally used for such additives in textile detergent compositions. Such additives include, for example, foam boosters such as alkanolamides, especially monoethanolamides obtained from palm kernel oil fatty acids and coconut oil fatty acids; alkyl phosphates, alkylphosphonic acids incorporated into silicones or petroleum jelly. anti-redeposition agents such as sodium carboxymethyl cellulose and cellulose ethers;
Fabric softeners; inorganic salts such as sodium sulfate and sodium carbonate; and fluorescent agents, fragrances, enzymes such as proteases and amylases, which are usually present in very small amounts. It may be desirable to contain significant amounts of alkali metal silicates in the composition, particularly sodium ortho, meta or preferably neutral or alkaline silicates. The presence of such alkali metal silicates in an amount of at least about 1% by weight, preferably from about 5 to about 15% by weight of the composition, reduces corrosion of the mechanical parts of washing machines and also improves processing. and generally improved powder properties. The more highly alkaline ortho- and metasilicates are used only in small amounts within this range, usually in admixture with neutral or alkaline silicates. The composition of the present invention is preferably alkaline, but not too alkaline, as too much alkalinity may damage textiles or be harmful for household use. In practice, the compositions of the present invention desirably, when used in an aqueous wash, have a composition of approximately
It should give a PH of 8.5 to about 11. Household products should have a PH of about 9.0 to about 10.5, since lower PH tends to reduce the effectiveness of optimal cleaning compositions, and higher alkaline products can also be harmful if used incorrectly. is particularly preferred. PH was measured in water at 12°H (Ca) (French Permanent Hardness Calcium only) at the minimum normal use concentration of the product of 0.1% W/V, so that it is a satisfactory alkaline condition for use at all normal product concentrations. degree can be ensured. Up to 10% by weight of an alkali metal carbonate, preferably sodium carbonate, can be included if necessary to increase the pH and maintain adequate buffering capacity in the presence of acidic soils. When carbonates or phosphates are present, it is desirable to include one or more anti-fouling agents in the compositions of the invention in order to also reduce the tendency for inorganic deposit formation on washed textiles. could be. The amount of such anti-adherent agents is usually from about 0.1 to about 5%, preferably from about 0.2 to about 1.5% by weight, based on the weight of the composition. Preferred antifouling agents are anionic polyelectrolytes, especially high molecular weight aliphatic carboxylates or organic phosphonates. The detergent compositions of the invention should preferably be free-flowing particles, for example in powder or granule form, and may be prepared by any technique normally used for the manufacture of such cleaning compositions, for example slurry making and spray drying methods. It can be manufactured by The method used to form the composition has a moisture content of approximately 12
It is preferred to produce less than 4% by weight product, preferably from about 4 to about 10% by weight. The detergent composition of the invention may be in bar or tablet form or in liquid form. Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples. EXAMPLES In the following examples, the cleaning power of wash solutions mixed with various builder systems is evaluated and the reflectance of clay-stained polyester/cotton test cloths before and after washing in a Tergotometer is evaluated. Measured and compared. Reflectance was measured using a Carl Zeiss Elrepho reflectometer.
The increase in reflectance (ΔR) during cleaning was used as a measure of cleaning power. Examples 1 to 3 The washing liquid in each case was 40°FH (Ca) or 20°
FH(Ca) was prepared using the ingredients listed below at the concentrations listed below in water. The wash solution was allowed to equilibrate for 15 minutes. Then test cloth pieces (each 76.2mm x
Add 76.2mm test cloth (4 pieces per liter),
Washing was carried out for 20 minutes at 80° C., PH 10.0 and stirring at 55 rpm, followed by rinsing with water of the same hardness as that used to prepare the washing solution. The ingredients and concentrations are as follows:

[Table] (specified)
The detergent additive according to the invention has a concentration of 0.50 to 5.00
used at a concentration of
It will be appreciated that a constant total concentration of 2.495 g/ is used, so that the total concentration is within the range of 2.995 to 7.495 g/. The proportions of each concentration of detergent additive to the total composition constituted by the detergent additive of the present invention are as follows:

[Table] Example 1 The detergency of compositions containing two zeolite/precipitant systems according to the invention is evaluated: one containing only zeolite and one containing zeolite/sodium tripolyphosphate (STP). The detergency was compared at various concentrations in water at 20°FH (Ca ²⁺ ). The organic precipitants used were disodium dodecyl malonate ( _C12 AKM) and disodium ( _C15 - _C18 ) alkyl succinate ( _C15 - _C18) .
AKS) and the zeolite was Zeolite A. The results were as follows.

[Table] Example 2 The detergency of a composition containing zeolite/disodium hexadecenyl succinate (C16:1AKS) was compared with that of a composition containing only zeolite and a composition containing zeolite/STP. and 40°
Various concentrations of FH (Ca ²⁺ ) in water were compared.

[Table] Example 3 The detergency of compositions containing other detergent additives according to the invention was evaluated using zeolite alone and zeolite/
Compositions containing STP were compared at various concentrations in water at 40°FH (Ca ²⁺ ). The organic precipitant used was disodium alpha-sulfostearate (C18 _- SFAS). The results were as follows.

【table】

[Table] Example 4 Zeolite disodium dodecyliminodiacetate (C ₁₂ IMA) and zeolite/disodium tetradecyliminodiacetate (C ₁₄ IMA)
The detergency of a composition containing zeolite alone and a composition containing zeolite/STP was compared at a total builder concentration of 4.0 g/STP in water at 40° FH (Ca ²⁺ ). The results were as follows.

Table: Example 5 A detergent product was prepared from the following ingredients. Percentages are based on total solids.

【table】

Table: _{The builder systems used were zeolite alone, zeolite/C 15-18 AKS} and zeolite/cured tallow soap. In water at 35°H (Ca ²⁺ ), 60°C, PH
The cleaning power was compared by washing for 20 minutes in a tergotometer with product dosages of 3.0, 5.0 and 8.0 g/10.0. The results were as follows.

【table】

Claims (1)

Claims: 1. (a) 3 to 90% by weight of one or more detergent actives; (b) essentially (i) a crystalline or amorphous aluminosilicate cation exchanger with a detergent additive; 25~ as standard
97% by weight and (ii) the following formula: (In the formula, R ₁ represents an alkyl or alkenyl group having 10 to 24 carbon atoms or an arylalkyl or alkylaryl group with an equivalent chain length, X represents CH, CR ₂ , N or CON, and R ₂
represents an alkyl group having 1 to 3 carbon atoms, Y represents a hydrogen atom or a solubilizing cation, n and m may be the same or different, and represent an oxygen atom or an integer of 1 to 4. and Z represents COOY or SO ₃ Y. ) A detergent composition comprising 10 to 97% by weight of a detergent additive comprising 3 to 75% by weight of an organic precipitant builder, provided that the organic precipitant builder has 6 to 20 carbon atoms.
of an α-sulfocarboxylic acid and, when the aluminosilicate material is crystalline, the composition contains not more than 5% of an inorganic phosphate. 2 The organic precipitant builder has the following formula: (In the formula, R ₁ , Y and Z are
p represents 0 or 1. ) The detergent composition according to claim 1, which is a compound represented by: 3 The organic precipitant builder has the following formula: The detergent composition according to claim 2, which is a compound represented by the formula (wherein R ₁ and Y have the meanings defined in claim 1). 4 The organic precipitant builder has the following formula: The detergent composition according to claim 2, which is a compound represented by the formula (wherein R ₁ and Y have the meanings defined in claim 1). 5 The organic precipitant builder has the following formula: (In the formula, R ₁ and Y have the meanings described in claim 1, and V and W each independently represent an integer within the range of 1 to 4.) A detergent composition according to claim 1. 6 The organic precipitant builder has the following formula: (In the formula, R ₁ and Y have the meanings given in claim 1, and V and W have the meanings given in claim 5.) A detergent composition according to claim 1. 7. The detergent composition according to claim 5 or 6, wherein the organic precipitant builder is a compound represented by the formula or formula in which V and W each represent 1 or 2. 8. A detergent composition according to any of claims 1 to 7, wherein the organic precipitant builder provides a calcium salt solubility product of 10 ^-8 or less. 9 The aluminosilicate cation exchange material has the following formula: (Cat _2/o O) _x・Al ₂ O ₃ (SiO ₂ ) _y・^ZH ₂ ^O () represents an n-valent cation exchangeable with calcium, x represents a number from 0.7 to 1.5, y represents a number from 1.3 to 4, and Z represents a bound water content of 10 to 28% by weight.
represents the amount. ) Claims 1 to 9 are crystalline or amorphous substances represented by
The detergent composition according to any one of paragraphs. 10 The aluminosilicate cation exchange material has the following formula: Na _x (AlO ₂ ) _x (SiO ₂ ) _y ZH ₂ O () where x and y represent an integer of at least 6, and is within the range of 1:1 to 1:2, and Z represents a number such that the crystal water content is 10 to 28% by weight. Detergent composition according to item 9. _{11 The} aluminosilicate cation exchange _material has _a unit cell _{( unit} 11. The detergent composition according to claim 10, which is a crystalline material having cells. 12. The detergent composition according to claim 11, wherein the aluminosilicate material has a unit cell represented by the formula where Z represents 27. 13 Aluminosilicate cation exchange material
15. A detergent composition according to claim 14 having a particle size in the range of 0.1 to 10 μm. 14 Aluminosilicate cation exchange material is
At least 200mg per gram of anhydrous aluminosilicate
14. A detergent composition according to any one of claims 1 to 13, having an ion exchange capacity of _CaCO3 . 15. A detergent composition according to any one of claims 1 to 14, containing 5% by weight or less of an inorganic phosphate. 16. The detergent composition according to any one of claims 1 to 15, containing 15 to 70% by weight of detergent additives. 17 Aluminosilicate cation exchange material 10
Claims 1 to 1 containing ~60% by weight
The detergent composition according to any one of Item 6. 18. The detergent composition according to any one of claims 1 to 17, containing 1 to 30% by weight of an organic precipitant builder.