JPS5823894A - Detergent composition - Google Patents

Abstract

A low phosphate, alumino-silicate built cleaning composition having improved bleach performance is described comprising a) 15-50% by weight of a water-insoluble alumino-silicate cation exchange material; b) 3-30% by weight of a peroxide bleach; c) 0.5-15% by weight of an activator for said peroxide bleach; and d) 1-15% by weight of a nitrilotriacetic acid compound, wherein the percentage quantities of (a) + 2(d) is between 30 and 55.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to cleaning compositions, and more particularly to cleaning compositions and articles particularly, but not exclusively, suitable for cleaning textiles, and furthermore IP! The present invention relates to a cleaning composition containing fK aluminosilicate C.

Bleaching systems consisting of a peroxide bleach, such as IJum, and a peracid bleach precursor, also called an activator. It is known to mix. Such cleaning compositions typically contain a phosphate detergent builder such as sodium triphosphate. It is believed that under certain circumstances, the use of phosphate Y in cleaning compositions can lead to environmental pollution problems in wastewater.

It is desirable to eliminate phosphorus or reduce the amount of phosphorus in effluent cleaning compositions. .

Water-insoluble alkinosilicate cation exchange materials have been proposed as builders to replace phosphorus (e.g. British Patent I
I! No. 1429143, UK iFF@1470
Specification No. 250, British Patent No. 1504211,
British Patent No. 1529454 and US Patent No. 4064062
(see specification). However, in compositions containing aluminosilicate builders.

Having found that the performance of this bleaching system is significantly reduced, we have surprisingly found that aluminosilicate III can be used.

Therefore according to the invention.

a) 15 to 50% by weight of a water-insoluble aluminosilicate cation exchange material; b) 6 to 3031% by weight of a peroxide bleach; C) 0.5 to 15% by weight of an activator for said peroxide bleach; and d) nitrilotriacetic acid compound 1 to 15% by weight, (a) + 2 (the amount of dJ is 60 to 55% by weight).

An al(]silicate bibilder edge cleanser composition is provided which preferably comprises 40 to 55% by weight.

Generally, the cleaning compositions of the invention contain at least one organic soap or synthetic detergent-active substance. Preferably containing from about 5 to 40% by weight of an organic, anionic, nonionic, amphoteric or zwitterionic detergent compound, a soap, or mixtures thereof.Many suitable detergent-active compounds are commercially available, and Literature such as Schwartz (8chwartz), Berry (Parr)
y ) and BerCkt
Detergenta)'', Vol.

Preferred detergent-active compounds that may be used in the present invention include synthetic anionic soaps and nonionic compounds. The first thing to be allocated is 1, usually an aryl group (the term alkyl used here is ``alkyl'').

(including the alkyl sY of the higher aryl group) has about 8 carbon atoms.
Water-soluble alkali metal salts of organic sulfates and sulfonates having a molecular weight of 1 to 22V.

Suitable anionic detergent compounds include, for example, sodium and potassium alkyl sulfates % KIQ, compounds obtained by sulfating higher (Co to C 8) alcohols obtained from beef tallow or coconut oil. ;
Sodium and potassium alkyl (C,~C,.)benzenesulfonates, especially sodium linear ni-alkyl ('
-10~6) Benzene sulfonate; sodium alkyl glyceryl ether sulfate; especially the above-mentioned ether compounds of higher alcohols obtained from beef tallow or coconut oil and synthetic alcohols obtained from petroleum; sodium coconut oil fatty acid monoglyceride sulfate and sulfonate - ; higher (09~Czs) fat IFF alcohol-alkylene y oxide (ethylene oxide to the butt) sodium and potassium salts of sulfate esters of reaction products; coconut oil fatty acid real fat a! Ashite products esterified with Y isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyltaurine; alkane monosulfonates such as α-olefins (C, ~C
, o) with sodium hydrogen oxide and a compound obtained by reacting with parafubun and 80. and lantum sulfonate obtained by Y reaction with Cjl and then hydrolyzed with a base; olefin sulfonate, this term refers to y% olefin with 80% α-olefin of CIO”””2°
The substances produced by reacting S with Y, then neutralizing and hydrolyzing the reaction product Y were used in the description; and beef tallow, coconut oil.

Long chain C8 like sodium soaps of palm kernel oil, palm oil, particularly hydrogenated rapeseed oil fatty acids or mixtures thereof
~' J11 Alkali metal salts of fatty acids can be mentioned. Preferred anionic detergent compounds include sodium (C, ~C)
0,) alkylbenzene sulfonate and sodium (
'16 NC11! ) is an alkyl sulfate.

Suitable nonionic detergent compounds that can be used in the present invention include, for example, the reaction products of alkylene oxides (usually ethylene oxide) and alkyl (C, to C□)phenols, generally having a concentration of 0.5 to 25 ethylene oxide per molecule. Compounds of 5 to 25 units; aliphatic (C, ~CX
S)! - or a condensation product of a second straight or branched alcohol and ethylene oxide, generally 1!0
6 to 60 and the product obtained by condensing the reaction product of brolene oxide and ethylenediamine with ethylene oxide.

Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary amine oxides, and dialkyl sulfoxides.

Mixtures of detergent active compounds, such as mixed anionic compounds and mixed compounds of anionic and nonionic compounds, can be used in detergent compositions. Particularly in the case of the latter mixing tube, it can be used to impart a suppressed low foaming property. This is beneficial for compositions intended for use in automatic flushing machines where soap suds are detrimental.

Although significant amounts of amphoteric or zwitterionic detergent active compounds may be used in the compositions of the present invention.

This is usually undesirable since they are relatively expensive. When used, amphoteric or zwitterionic detergent-active compounds Y are generally used in small amounts in compositions based on the much more commonly used synthetic anionic and/or non-ionic detergent-active compounds.

The alinosilicate cation exchange material has a linear formula: % formula % [In the formula, Cut is an n-valent cation that can be exchanged with calcium (e.g. Na+ or X+) W. Representation; I is 0
．． y represents a number from 1.6 to 4; and 2 represents a number Y such that the bound water content is 10 to 28% by weight. It is an amorphous substance.

Preferably, the following formula: %formula% (21. I and y are small (both represent the integer Y of 6.

The ratio of X to y is within the range of 1:1 to 1:2,
A crystalline material is used which can be described by a unit cell having a content expressed by 2 (represented by a number r, -f,) such that the content of bound water is 10 to 28.

Aluinosilicate is preferably 1 grain KO01 to 100
A micrometer, ideally from 0.1 to 10 micrometers, whose ion-exchange capacity is at least 200 CaC0 per 5 kg of alinosilicate (anhydrous Y basis)
, is.

In a preferred embodiment, the water-insoluble aluminosilicate is a crystalline material described by a unit cell having the following formula: This substance is, for example, typically represented by the following formula: % formula %, and the following formula:
27 Tyzo A is a zeolite which can be expressed by a unit cell with a content represented by Ht*0.[Known commercial products are listed.

The target thread used in the present invention consists essentially of a peroxy bleaching compound, which is an inorganic peracid, and an activator for this compound.
It is more effective within the range of

Such bleaching systems are therefore commonly known as conventional low temperature bleaching systems and are well known in the art.

Inorganic peracids such as sodium perborate are 1i! The action of releasing active oxygen Y in the liquid YL, and the activator of this compound, is usually an organic compound containing one or more reactive acyl groups, which causes the formation of a peracid. The latter activators provide more effective bleaching action at lower temperatures than peroxy bleaching compounds.

The weight ratio of peroxy bleach compound lamp activator in the composition of the present invention is from about 60=1 to about 1:1, preferably 1:1.
The ratio can be varied from 5:1 to 2:1. A particularly preferred ratio is between 5:1 and 2:1.

On the other hand, the amounts of the bleach system, i.e., peroxy bleach compound and activator, may vary from about 6.5% to as much as about 45% by weight of the cleaning composition. , approximately 5 of the components forming bleaching system Y
Preferably, from about 351% to about 351% is used.

As a typical example of a suitable peroxy bleaching compound.

Supernatural alkali metal salts (tetrahydrate and monohydrate).

Alkali metal belkarzanate, 5. Mention may be made of persilicate and perphosphate, with sodium perborate being preferred.

Activators of peroxy bleaching compounds are described in the literature, for example British Patent Nos. 836,988 and 855,735.

No. 907556, No. 907558, No. 970950
Nos. 1003310 and 1246339, U.S. Pat. No. 5,552,882 and I! Specification No. 4128494.

Canadian patent @844481 specification and South African patent! It is described in detail in the specification of No. 68/6344. Suitable timed activators include the following compounds: N-diacylated and H,N/-bolyacylated amines such as y,N,N-diacetylaniline and N,N-diacetyl-p-toluidine; e.g. 1,6-di,acetyl-5,5-dimethylhydantoin and 1,3-diacylated hydantoins such as 1,3-dizolopionylhydantoin; (b) N-alkyl-N-sulfonylcarbonamides such as wing-methyl-N-mesyl-acetamide.

N-methyl-N-mesyl-benzamide, N-methyl-
N-Mesyl-p-nitropenzaide and N-methyl-N-mesyl-p-methoxybenzaide; (c) N-acylated cyclic hydrazides, acylated triazones or urazoles, such as monoacetylmaleic hydrazide; (a ) On ' e '-trisubstituted hydroxyl i
7 For example, 0-benzoyl-N, N-succinylhydroxyl(n, 0-acetyl-N, N-succinylhydro-Φsylua("*0-p-metho-dibenzoyl-N, N-
succinylhydroxyl], 0-p-nitrobeyf
Iru N, N-succinylhydroxylain and O,
N,N-triacetylhydroxylazun;
, N'-dimethyl-N, )i'-diacetyl-sulfurylide and N,N'-diethyl-N,M'-dif
(f) triadyl cyanurates such as doriacetyl cyanurate and trivea, fyl cyanurate; (g) carboxylic anhydrides such as benzoic anhydride, m-chlorobenzoic anhydride! ! ! ,
Heptatalic anhydride and 4-chloro heptatalic anhydride; (hl Sugar ester, e.g. glycose pentaacetate; (1) 1,3-diacyl-4,5-diacyloxy-imidateridine, e.g. 1,6-cyformyl-4°5-diacetate Φcyimidazolidiy, 1,5-diacetyl-4,
5-Diacetoxy-imidazoly.

1,3-diacetyl-4,5-dizoloC onyloxy-imidacillin; ljl tetraacetyl glycoluril and tetrazoag onyl glycoluril; (k) diacylated 2,5-diketozeperazine e.g. ifl
, 4-diacetyl-2,5-diketopiperazine.

1,4-dizologionyl-2,5-diketobipera 9 y
& T) 1 a 4-9 f-bi 4 aL sa
-5,6-(/1 tyl-2,5-3'ketoC pelagy
; 11) f Robile ν diurea or 2,2-y methyl-zolozerenediurea (2,4,6,8-tetraazo-
Ccyclo-(5,3,)-nonaV-5,7-sion or its 9,9-dimethyl derivative], especially tetraaceter- or tetraprobioel-propylene diurea or its dimethyl derivative; (Elm) α-acyl-benzoic acid and sodium salt of p-(zoropo-dicarzanyloxy)-benzoic acid; (Elm) α-acyl-benzoic acid-N, N')
-Polyacylmalonide e.g. α-acetoΦcy(”
sN/) - Shea heptylmalonoid.゛(
The mono-diacetylated and N,N'-bolyacylated iy% M,M,f,N'-tetraacetylenecyano (τAID) described in al. is a compound of particular interest.

It is preferred to use the activator Y in granular form and preferably the activator is present in finely divided form as described in the applicant's UK TF#2055998 Specification 11FK. It is particularly preferred to use activators with an average particle size of less than 150 micrometers, which gives a considerable improvement in bleaching efficiency. Average particle size 150μm
Sedimentation losses are substantially reduced when the following activators are used: Better bleaching performance is obtained when the average particle size of the activator is less than or equal to 100 μm. However, if the particle size is too small, increased decomposition, formation of fines, and handling problems occur. Particle sizes below 100 .mu.m may provide improved bleaching efficiency, but the activator is irritating as particles below 50 .mu.m in size do not have a weight up to 20 g. On the other hand, the activator may contain particles larger than 150 μm, but may contain particles larger than 300 μm, and 150 μm.
There should be no more than 20% by weight of larger particles.

If needle-shaped crystalline activator particles are used, these particle sizes correspond to the diameter of the needles. It is to be understood that these particle sizes refer to the activator present in the granules and not to the granules themselves. The granules themselves are
Generally, the majority of the granules are between 100 and 2000 μm, preferably between 250 and 1000 μm [)! - have.

Granules [up to 5% by weight of granules larger than 1600 μm and 2
Up to 10 weight pieces of granules smaller than 50 μm are allowed. The activator-loaded granules, preferably in finely divided form, can be obtained by granulation with the activator and a suitable carrier material such as sodium tripolyphosphate and/or potassium tripolyphosphate.

Other granulation methods using organic and/or inorganic granulation aids can also be usefully applied. The granules can then be dried if necessary. Essentially any granulation method can be applied as long as the granules contain an activator and as long as other substances present in the granules do not have a negative effect on the activator. The desired nitrilotriacetic acid compound has the following formula: e.g. sodium, potassium and ammonium cations Y
represent. ). These compounds contain carbon atoms of inert and non-hazardous nature such as alkyl groups such as methyl, ethyl, etc., haloalkyl groups such as chloromethyl, etc.
-bonding substituent Y can further contain. The properties of these compounds are not limited, although there is an implicit restriction that the substituents must not have a tendency to affect the desired properties of the nitrilotriacetic acid compound.

Preferred compounds within the above definitions and formulas include nitrilotriacetic acid, trisodium nitrilotriacetate, tripotassium nitrilotriacetate, disodium nitrilotriacetate and dipotassium nitrilotriacetate.

The nitrilotriacetic acid compound (hereinafter NT
1 to 15 of l/jl, measured with trisodium nitrilotriacetate.
The weight can vary within the range and will depend on the amount of alinosilicate cation exchange material. The proportion of the amount of the nitrilotriacetic acid compound (N) and the proportion of the amount of the alinosilicon salt cationic y-exchange material (A) are such that the sum of A+2N is about 60 to about 55% by weight, preferably 40 to 55% by weight. It is a percentage. The preferred range of NTA useful in this invention is 265 to 10% by weight of the composition.

Preferably, the cleaning composition of the present invention is substantially free of inorganic phosphate trilide. However, if desired, the compositions of the present invention may contain inorganic phosphates such as alkali metal (preferably sodium) rephosphates, pyrophosphates, orthophosphates or polymeric phosphates, the amount of which may vary depending on the composition. However, only in amounts below 12.5 lbs.

Apart from the components already mentioned, the cleaning compositions according to the invention can contain any customary additives in the amounts customary for these additives in cleaning compositions for cleaning textiles. These additives include, for example, foam boosters such as alkanolamides, in particular palm oil fatty acids and monoethanolamides obtained from coconut oil fatty acids; foam reducers such as alkyl phosphates and silicones; sodium carboxymethylcellulose, polyvinyl Anti-resettling agents such as pyrrolidone and cellulose ethers (such as methylcellulose and hyethylhydroxyethylcellulose); ethylene cyabantetra vinegar.

Stabilizers such as ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate; fabric softeners; Moths include proteases, and amylases; fungicides and colorants.

The cleaning compositions of the present invention desirably contain one or more deposit inhibitors to reduce the tendency of inorganic deposits to form on washed and cleaned fabrics. The amount of the agent is usually about 0.1 to 5% by weight per composition.
Preferably it is about 0.2 to 2.5 gw. Preferred anti-deposition agents are anionic polyelectrolytes, especially polyaliphatic carboxylates or organic phosphonates.

Other non-phosphate detergency builders may be incorporated as well, if desired, only in small amounts, preferably up to 10% by weight of the cleaning composition. It may also be desirable to include significant amounts of alkali metal silicates in the composition of sodium ortho-, meta- or preferably neutral or alkaline silicates. The presence of an alkali metal silicate in an amount of at least about 1% and preferably about 5 to 15% by weight of the composition provides processing advantages and generally improved powder properties, as well as reduced corrosion of the metal parts of the washing machine. It is advantageous in this respect. The higher alkaline ortho- and meta-silicates are used in admixture with neutral or alkaline silicates 1 usually only in small amounts within this range.

The composition of the present invention needs to be alkaline, but if it is too strongly alkaline, it will damage the fabric, and it may be dangerous for household use, so it should not be too alkaline. The composition of the invention can be used in an aqueous stream #
For use in solution, a pH of about 8.5 to about 11
Y should be shown.

In the case of household products, about 9.0 to 10. 5 - is preferable for things.

- is 50℃, 12"H (Ca) (:y lance permanent hardness,
Calcium only) in water 1. It was measured at the minimum use concentration of 0.1% v/v of product a. The result is a satisfactory alkali vmm for use at all standard concentrations.

The cleaning compositions of the present invention are preferably provided in free-flowing particle form, such as powder or granules, although the manufacture of such cleaning compositions can be carried out by any commonly used technique.

Preferably, a slurry is prepared and spray-dried to form a detergent-based powder, to which heat-sensitive ingredients such as bleaching systems and optionally other desired ingredients are added. It has been found that lower moisture levels are beneficial to the stability of the bleaching systems used. The method used to form the composition has a moisture content of less than about 12% by weight, more preferably about 4 to 10% by weight. It is preferable to produce a product that weighs less than or equal to the weight factor.

Invention %: This invention will be explained by the following examples, but the present invention is not limited to these examples.

Example 1. -... The following cleaning powder Y was prepared by spray drying the detergent slurry IJ-' and then adding the hypersensitivity component Y containing the bleaching system Y afterward.

The composition contains 30% zeolite and 0% NT.

Composition B contains 40% zeolite) and NT Ots.

Composition 1 contains 30% zeolite and MTAloqb (post-added).

The composition contains 30g6 of zeolite and 0% NTAl (slurry).

The bleaching action of these powders was tested in a Tergotomater on standard test cloths with black tea stains using 65°H water and 28 wash cycles at a product dosage of 511/l. .

(1) Extended wash at 16°C to 90°C for 80 minutes (It) Extended wash at 16°C to 55°C
), 60 minutes (heated to 55℃ for 28 minutes, then heated to 55℃ for 3
2 minutes) After each wash, use a 420nm Uv interference filter Y and a Zeiaa GLREHO filter.
) The bleaching performance against standard specimens was determined by measuring the reflectance (R460”)v at 460 nm with a photometric needle and comparing with the reflectance of the sample before cleaning.The results were as follows: ΔR460 (1)
Rise to 90°C - Wash A zeolite) 30% 9.2 (8,
7) B zeolite 40chi 12.5 (7,'
8) l Zeolite 30ts + NTA10ts 17.8
Zeolite for (17,5)) 30% + NT person 10% 1
9.3(18,8)(Ml Temperature raised to 55°C, extended washing, t5() 301 3.8(1
,3) B Zeolide 401 6.4(3,
1) l Zeolite 30 pieces + w TA 10 * 1
2. Ri (9,9) ■ Zeolite 50% + N T A
1016 14.1 (12,0) Note: The numbers in parentheses are ethylenecyazine tetramethylphosphonate) (
IDTMP) These are the results obtained with a washed powder that does not contain Y.

The above results demonstrate that the compositions of the present invention and B have superior performance compared to the control samples A and B which do not contain HT.

Examples ■~X 1 except that the builder mixture Y was changed! Example 1-1 was prepared using a composition similar to that used in Example 1-1.
The following bleaching test Y was carried out in the same manner as described in 1. The results of H were as follows.

Composition 90℃ gradient temperature (ΔR460”)
at”, tyito so* included! 19.8
ill SE*54 50%+yr2.511b included W
23.5D zeolite 40g/BTp(
Contains 117.5 14.7■'tt54t40
Contains fb/5rp75fb/NTh11
19.01138TP-Sodium Triphosphate Composition
Temperature raised to 55℃, extended washing (ΔR460”) 8 Contains 40% zeolite 4,5? Contains 5096 zeolite 7.5 ■ Zeola 4
) 50% / Contains 2.5% NTA 15.0■ Zeolite 40% / Contains 5.0% NTA 16.
1■ Zeolite 20%/NIrA15. Cl-containing
15.6G Zeolite 40cm/8TP 7.5% Contains 8.2H Zeolite 30cm/8TP 2mat Contains 5.9■Se*94) 3096/
Contains NTA 1s 9.2X Zeolite 30'j/5Tp 4% Contains 7.4
X Contains Zeolite 3096/arp29G/NTA196 9.5 Notes: Compositions C and 2 contain ED11''MPO, 3 hours. Compositions D-K and -X do not contain IEDTMP Y.

The above results again demonstrate the surprisingly superior performance of the composition (III-X) of the present invention compared to each control sample C-X.

Implementation ipHM This example demonstrates the importance of NTA amount and NTA/aluminum silicate ratio.

Sodium perborate 6 pieces and tetraacetyl ethylene cyanide (activator, same as used in Examples 41-II)
16 kinds of detergent compositions Y, which do not contain BDTMl't', were prepared by changing the Vivilu mixture, using water of French hardness FrL65@, and extended cleaning at a temperature of 16 to 55°C. The bleaching performance of this detergent was tested. The results were as follows.

Composition of Zeolite 60・C, 9.7 Example Karitsugu 21111 @1tlI! ! Remains, Example 1~
A comparative extended cleaning at elevated temperature to 55° C. was carried out as described in Section B.

The results were as follows.

Reflectance (ΔR460) Composition)Ql114.8 Composition'ItlxI1m 14.1・
Composition L111.8 Composition L3 9.8 These results once again clearly demonstrate the improvement in bleaching performance resulting from the use of NT according to the invention.

Agent Hao Mura 4 other people

Claims (1)

[Scope of Claims] (15 to 50 parts by weight of an IJ-type arunnosilicate cation exchange material; b) 3 to 30 parts by weight of one peroxide standard; C) the above-mentioned persaponified whitening agent activator of 0.5 to 15 heavy molecules; and a) = 1 to 15 heavy molecular weight of 1-lilotriacetic acid compound; Phosphate Content Detergent Composition with Alinosilicate Builder 6(2)(a)
+ 2 (Cleaning composition according to claim 111, wherein the amount of 11 is from 40 to 55% by weight. The cleaning composition according to claim 111 or 2. (4) The cleaning composition according to any one of claims 1 to 3, wherein the nitrilotriacetic acid compound is sodium nitrilotriacetate. (5) A cleaning composition according to any one of claims 1 to 4, wherein the weight ratio of peroxide bleach to activator in the composition is from 5=1 to 2:1. ) The cleaning composition according to any one of claims 1 to 5, which contains at least one organic cleaning agent active substance. (8) The cleaning composition according to claim 6, wherein the amount of slFFm is present in an amount of 12.5% by weight or less. Item 1 or IN
The cleaning composition according to any one of Item 7. (9) The cleaning composition according to claim 8, which does not substantially contain inorganic phosphate c-ruder.