JPH01132695A - Aqueous liquid phosphorus free or low detergent composition - Google Patents

Abstract

PURPOSE: To obtain a detergent compsn. having superior cleaning performance although it does not contain a phosphate builder at all by blending water with an org. detergent, an alkali metal silicate, a chlorine bleach and a specified detergent builder.

CONSTITUTION: The detergent compsn. contains water, a bleach-stable water- dispersible org. detergent, an alkali metal silicate, a chlorine bleach and a detergent builder contg. a mixture of aluminosilicate zeolite and a bleach-stable carboxyl group-contg. water-soluble polymer. The detergent compsn. is used as an aq. detergent for washing dishes particularly in an automatic dishwasher and it consists generally of, by weight, 5-35% aluminosilicate zeolite, >25% sodium silicate, 0-9% alkali metal carbonate, 0.1-5% org. detergent active material, a chlorine bleach compd. enough to give about 0.2-4% available chlorine, 0-0.5% long-chain fatty acid or its salt, 0-5% thickener, 0-8% sodium hydroxide and the balance water.

COPYRIGHT: (C)1989,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application: The present invention relates to an aqueous cleaning composition, particularly for cleaning dishes etc. in automatic dishwashers. More particularly, the present invention relates to such compositions that are completely free of phosphate builders, yet have comparable or superior cleaning performance compared to similar phosphorus-containing liquid automatic dishwasher detergent compositions.

BACKGROUND OF THE INVENTION: The present invention particularly exhibits enhanced cleaning performance despite having viscoelastic properties, improved chemical and physical stability, and is free of phosphate builders, and is easily incorporated into cleaning media. Distributed tableware, glassware, pottery, etc.? This invention relates to a thickened liquid automatic dishwashing detergent composition that cleans effectively.

Supplied in powder form. Commercially available household dishwasher detergent compositions are, for example, non-uniform in composition, require expensive operations to produce, tend to cake during storage at high temperatures, and produce clumps that are difficult to disperse. Form.

It has several disadvantages, such as having a tendency to cake in the dishwasher dispenser, having a dusting property that causes particular irritation to users with allergies. However, liquid forms of such compositions generally cannot be used in automatic dishwashing machines due to high suds levels, unacceptably low viscosities, and extremely high alkalinity.

Recent research and development activities have focused on the development of such compositions as gels or
``Chickentrope'' type 1 concentrates on abrasive cleansers and automatic dishwashing products characterized as eg thixotropic liquids or pastes. Dishwasher refills manufactured in this way do not have sufficient viscosity to "stay" in the dispenser cup of the dishwasher, and may also leave spots on dishes, glassware, ceramics, etc. This is mainly undesirable because it causes

Thus, the production of gel-like automatic dishwashing compositions with sufficient dispersion stability and detergency has proven to be a problem, particularly for compositions used in domestic dishwashers. For effective use, an automatic dishwashing detergent (hereinafter abbreviated as ADD) must contain the following ingredients: il+ to soften or combine with hard water minerals to emulsify and/or thaw dirt; sodium tripolyphosphate (NaTPP); (2) sodium silicate to provide the necessary alkalinity for effective cleaning and also to protect the luster of the desired porcelain; (3) carbonic acid for alkalinity 7 enhancement. Sodium (generally considered optional); (4) Chlorine release agent to help remove stain spots that cause water stains; It is generally desirable to include agents/surfactants.

For example, details of SDA detergent, [Dishwasher formulation (FOr
mulatiOnS ASpeCtS Of MaCh
inel Dishwa-shingJJ Totus,
Operation A/ (Thomas 0berleJ (197
See 4J. Cleansers that approximate the above compositions are mostly liquids or powders. Combining such ingredients into an effective thickened form for household wash walls presents difficulties. Generally, such compositions do not contain hypochlorite bleach, which bleach reacts with other chemically active ingredients, especially surfactants, to form suspending or thickening agents. This is because it decomposes and reduces its effectiveness.

U.S. Pat. No. 4,115,308 contains a suspending agent 1 such as CMC1 synthetic clay; inorganic salts including silicates, phosphates and polyphosphates; small amounts of surfactants and foam suppressants. , discloses a thixotropic automatic dishwashing wall paste. Bleach is not disclosed. On the other hand, U.S. Pat. The patentee discloses a composition of matter.
Tests have been described showing that various types of organic polymeric thickeners are unstable or cannot be thickened for adequate thickening, resulting in loss of available chlorine. It has been found that polyacrylates give thickening for several weeks at room temperature, but then decompose.

U.S. Pat. No. 3,985,668.

('') Suspending agents, preferably smectite and attapulgite type clays; (2) Abrasive agents 1, such as silica sand or perlite; and +S+ fillers, including density powder polymers, extract bump powder perlite, etc., the fillers being increased Discloses an abrasive cleanser having a gel-like consistency that has a flotation and stabilizing effect on the composition in addition to serving as an agent and eliminates water that is used to form undesirable supernatants due to leaching or phase separation. . The above ingredients are essential ingredients. Optional ingredients are hyposalt salt bleaches, bleach-stable surfactants, and buffers such as silicates, carbonates, and phosphates. N
Builders such as aTPP may also be included as an optional ingredient to provide or augment detergency-enhancing functions not provided by buffering agents, but the amount of such builders, according to this patent, can be added to the overall composition. does not exceed 5% of Preferred p) l l O level (or pH 10
(above) is maintained by buffer/builder components. High pH is said to minimize the degradation of chlorine bleach and the interaction of surfactants with bleach. NaTPP
, if present, is limited to 5% as described above.

Antifoaming agents are not disclosed.

Colgate-Pal
UK Patent Application No. 2, assigned to mo-1iVeJ
．． No. 116,199A and No. 2,140.450A disclose liquid ADD ( A typical gel-like aqueous automatic dishwasher detergent composition with thixotropes has the following components by weight: (a) 5-35% alkali metal tripolyphosphate;
Sodium silicate 2.5-20%; fcl Alkali metal silicate 0-9%; fdl 0.1-5% water-dispersible organic detergent active, stable to chlorine bleach; tel chlorine bleach-stable origin. Foam suppressant O~5%;+
f) an amount of chlorine bleach in an amount sufficient to release about 0.2 to 4% available chlorine; (g) an amount of chlorine bleach in an amount sufficient to give the composition a Chickentropy Index of about 2.5 to 10; a chickentrope thickener of lhl; optionally sodium hydroxide to adjust the pH; and (i) water.The LADD composition thus formulated has low foaming properties;
It is readily soluble in cleaning media and is most effective at alkaline pH values. These compositions usually have a gel consistency, ie, are very viscous.

It is an opaque, jelly-like substance with Bingham plasticity and a relatively high yield point. Therefore, a pronounced shear force, such as that obtained in the agitated dispenser cup of an energized automatic dishwasher, is required to initiate or enhance flow. Under such conditions the two compositions fluidize quickly and are easily dispensed. When the shear force is discontinued, the fluid composition quickly returns to high viscosity. The Bingham plastic state closely approximates the initial consistency of the composition.

U.S. Patent No. 4.511.487 (April 16, 1985)
The date mentions a low-foaming detergent paste for dishwashing walls. This patented Chicken Trope cleaning agent is 5 r.
It has a viscosity of at least 30 pa-s at 20° C. as measured in a rotational viscometer at a spindle speed of pm. The composition consists of a mixture of pulverulent hydrated sodium tripolyphosphate and hydrated sodium metasilicate, an active chlorine compound and a thickening agent which is a thin layer silicate of the hectorite type. Small amounts of nonionic surfactants and alkali metal carbonates/hydroxides may be used.

Recently, the Applicant has developed various modifications and improvements to the liquid dishwasher detergent compositions of British Patents Nos. 2.116,199A and 2.140,450A. For example, US Pat. Discloses a liquid cleaning composition that does not contain.

Commonly Assigned Co-pending Application No. 903.924 describes the physical stability of clay-based thixotropic liquid builder automatic dishwashing detergent compositions.

These disclosed commercial liquid automatic dishwashers may be modified by adding a small amount, e.g., about 0.02 to 1% by weight, of a polyvalent metal salt of a long chain fatty acid (e.g., aluminum 5 stearate). Most detergent compositions and similar compositions rely on phosphate builder salts, such as sodium tripolyphosphate, to enhance their cleaning performance. Phosphate builder salts are very expensive to engineer. However, their use has a major drawback; phosphate builder salts are generally harmful to aquatic life and waterways. In fact, many jurisdictions do not use phosphate-containing cleaning detergent products. are generally opposed to or are considering banning.

Many attempts are made to provide alternative builders.
Although many such phosphate-free inorganic or organic detergent builder salts are known, only a few can actually provide detergency improvements comparable to phosphate builder salts. Additionally, since the alternative builder must be compatible with chlorine bleach.

Selecting a suitable builder is even more difficult in the current environment of bleach-containing aqueous compositions.

In addition to its function as a detergent builder, the inorganic alkali metal phosphate builder is
No. 2,140,450A, thickened thixotropic gel-like fluids have an important function in contributing to the rheology of aqueous detergent compositions. Therefore, replacing phosphate builders with non-phosphate builders is not an easy task as many different factors have to be considered in order to fulfill all the multi-functional effects of phosphate builders. I know that.

Problem to be Solved by the Invention: Therefore, to provide a bleach-containing aqueous cleaning composition that avoids the use of phosphate builders and does not contain phosphorus from other sources or only at environmentally acceptable levels. This is the first object of the present invention.

It is another object of the present invention to provide phosphate-free or low phosphate thickened liquid ADD compositions with improved physical stability and rheology.

It is an object of the present invention to provide a phosphorus-free and low valine level thickened liquid ADD composition with particularly low spot and film formation without adversely affecting or with improved cleaning performance. Yet another object of the invention.

SUMMARY OF THE INVENTION The above and other objects of the present invention, which will be more readily understood from the following detailed description of the present invention and its preferred embodiments, are to provide a water- and chlorine bleach-stable water-dispersible organic detergent. Aqueous liquid low-phosphorus or phosphorus-free cleaning, consisting of chlorine bleach, an alkali metal silicate and a detergent builder, where the detergent builder consists of a mixture of an aluminosilicate zeolite and a bleach-stable water-soluble polymer containing carboxyl groups or its salts. This is achieved by the composition. More particularly, according to certain preferred embodiments of the invention, the present invention is free of phosphate builder salts, contains no or very low levels of phosphorus, contains water-based materials such as aluminosilicate zeolite builders, bleach particles, etc. Provided is a thickened viscoelastic liquid automatic dishwasher detergent composition that can effectively prevent sedimentation of suspended particles insoluble in water.

The composition may include clays and other thickeners as well as other stabilizers and other conventional ADD additives.

According to this particular embodiment, the invention comprises the following components on a weight basis: (a) Aluminosilicate zeolite 5-35
%lbl Sodium silicate 25-4
0% (C1 alkali metal carbonate 0-9%
(Mountain) Moisture-friendly organic detergent active substance stable to chlorine bleach 0.1-5%lfl
Chlorine whitening agent compound in sufficient amount to provide 0.2-4% available chlorine+gl Long-chain fatty acids or salts thereof 0-0.5
%+hl Clay thickener O~5%(i)
Sodium hydroxide 0-8% and tj+
Water Residual In connection with this particular aspect, the present invention provides a method of cleaning dishes in an automatic dishwashing machine with a wash water bath comprising a compositional amount of a liquid automatic dishwasher detergent (LADDJ composition) as described above. According to this aspect of the invention, the LADD composition can be easily poured into the dispensing cup of an automatic dishwasher and subjected to a shear force above the yield value of the composition, such as by a water spray from the dishwasher, and the composition is It is sufficiently viscous to remain safely in the dispensing cup until it flows.

The invention will now be described in more detail by means of specific embodiments thereof.

In view of the environmental problems caused by pollution of lakes, rivers and other waterways due to deposition in waterways from detergents and other products, great emphasis has been placed on phosphate removal from detergent products.

However, clay thickeners of the type used by the assignee of the present application (generally 0-3% smectite water-swellable type, 10-25% alkali metal silicates, 0-0.5% fatty acid stabilizers)
, a little bleach, ? Chickentrope liquid dishwashing rack typically contains bleach-stable detergents, bleach-stable antifoam agents (sodium carbonate, caustic soda, etc.) and about 20-25% alkali metal phosphates as detergent builders. Attempts to replace phosphate builders from compositions result in decreased thixotropy and usually a deterioration in cleaning performance.The exact mechanism of rheological disruption leading to decreased thixotropy is not fully understood. but not suspended phosphate builder particles and other ingredients of the formulation, especially clay thickeners,
It appears that there is at least some interaction between the fatty acid or fatty acid salt that contributes to the increase in yield stress and plastic viscosity of the composition.

The present invention includes aluminosilicate zeolite V composition as an inorganic water-insoluble detergent builder in a mixture of a bleach-stable water-soluble carboxyl group-containing polymer as a multifunctional rheology agent and a detergent builder. Increasing the level of alkali metals to 25% by weight or higher provides similar rheology and physical stability (-f'', i.e., resistance to phase separation, sedimentation, etc.)
This is based on the surprising discovery that .

At the same time, improved smearing and film-forming properties (ie, less smearing and reduced film-forming properties) are achieved.

The compositions of the present invention do not exhibit chickentrope properties, but do have viscoelastic properties and have a sufficiently high yield point (maximum of the shear core force versus shear rate curve) that they do not flow under the pressure exerted by their own weight, i.e. gravity. stress). Accordingly, the compositions of the present invention can be easily poured into the dispenser cup of an automatic dishwasher and flowed out of the cup until a shear core force, such as a water jet force, is exerted on the cup during a detergent dispensing cycle. do not. At the same time, improved staining and film forming properties (ie, less staining and lower film forming properties) are achieved.

The compositions of the invention do not exhibit thixotropic properties, but are viscoelastic and have a sufficiently high yield point (maximum stress in the shear core force versus shear rate curve) that they do not flow under the pressure exerted by their own weight, i.e. gravity. ). Accordingly, the compositions of the present invention can be easily poured into the dispenser cup of an automatic dishwasher and drained from the cup until subjected to shear core forces, such as the water jet forces exerted on the cup during the detergent dispensing cycle. do not.

Clay thickeners and/or fatty acids or fatty acids when long-term physical stability, such as weeks or months, is not required and there is no need to provide highly thickened solutions, high levels of silicates. Salt stabilizer? , aluminosilicate zeolite builder and water-soluble carboxyl group (or its salt)
It will of course be appreciated that they can be omitted from the composition without adversely affecting the cleaning performance provided by the bleach-stable polymers included.

Useful builders in this case are water-insoluble aluminosilicates, both crystalline and amorphous. Various crystalline zeolites are described in British Patent No. 1.504.168, US Patent No. 4.409,136 and Canadian Patent No. 1,07.
No. 2,835 and No. 1,087,477, all of which are incorporated herein by reference for such description.

Amorphous zeolites useful in the present invention are described in Belgian Patent No. 83
No. 5.3s1, which patent is also incorporated herein by reference. Zeolite generally has the formula: % [X is 1, Y is 0.8 to 1.2. Preferably it is 1, Z is 1.5 to 3.5 or more, preferably 2 to
3, and W is 0 to 9. Preferably 2.5-6 and 1
M is an alkali metal, preferably sodium or potassium, preferably sodium. Typical zeolites are of type A or similar structure, with type 4A being particularly preferred.

Preferred aluminosilicate is about 200 meQ, /P
For example, it has a calcium ion exchange capacity t of 400 meq/ml.

The aluminosilicate zeolite builder is present in the composition in the same amount as has been found to be useful with respect to the alkali metal polyphosphates, generally in the range of about 5 to 35 weight percent, preferably about 20 to 30 weight percent.

Bleach-stable, carboxyl group-containing water-soluble polymers useful in this case include, for example, acrylic acid homopolymers, copolymers and their salts. These materials are commonly commercially available and are described below.

Polyacrylic acid polymers and their salts that can be used have the formula: [wherein R1, R2 and R3 are the same or different groups and are hydrogen, 01-C4 lower alkyl or a combination thereof; n is 5-25o , preferably a number from 10 to 150 and %M represents hydrogen or an alkali metal such as sodium or potassium. A preferred substituent of 5M is sodium.

Preferred R1, R2, R3 groups are hydrogen, methyl, ethyl and propyl. Preferred acrylic monomers are monomers where Ro and R3 are hydrogen, such as acrylic acid, or monomers where R and R3 are hydrogen and R2 is methyl, such as methacrylic acid monomers.

The degree of polymerization, or value of n, is generally determined by a limit value that generally corresponds to the solubility of the polymer or copolymer in water. The end groups of the polymer or copolymer are not critical and can be H, OH, CH3 or low molecular weight hydrocarbons.

Polyacrylic acid copolymers typically include, for example, copolymers of acrylic acid or methacrylic acid, and polycarboxylic acid anhydrides or acids such as succinic anhydride, succinic acid, maleic acid, maleic anhydride, citric acid, and the like. Copolymers of acrylic acid or methacrylic acid and maleic anhydride are preferred.

Acrylic acid or methacrylic acid monomers account for 40 to 60% by weight of the copolymer with polycarboxylic acid or anhydride, for example about 50% by weight.

Polyacrylic acid polymer is 500)"!1000 ~
25,000, preferably 1,500-15,000.
Particularly preferably, the copolymer has a molecular weight of 2,000 to 10.00.0.
They can also have molecular weights as high as 00,000.

Special examples of polyacrylic acid polymers that can be used include:
o - A 77 )' Haas (ROhm and H
Acrysol (ACrySO1)LMW from aaSJ
Acrylic acid polymers include Acrisol LMW-45NX, a neutralized sodium salt with a molecular weight of about 4.500, and Acrisol LMW-2ONX, a neutralized sodium salt with a molecular weight of about 2.000.

Specific examples of polyacrylic acid copolymers that can be used include:
7:I ly is the reaction product of approximately equimolar amounts of methacrylic acid and maleic anhydride, completely neutralized to form its sodium salt, and has a molecular weight of about 70,000.
(Sokolan) CPS (from BASF).

The polymers and copolymers described above can be made using methods well known in the art. For example, U.S. Patent No. 4.203
．． See No. 858.

Bleach-stable, water-soluble, carboxyl-containing polymers have been found to serve three primary functions in liquid automatic dishwashing detergent compositions: rheology control, calcium ion sequestration, soil dispersion, and soil dispersion.

As a rheology modifier, this polymeric additive apparently acts similar to a thickener, with high levels of alkali metal silicates, clays (if present) and fatty acids or salts (if present). Gives bullets, about 200-1
0.000 centipoise.

It preferably provides a plastic viscosity in the range of 2.000-s, o ocps (eg 5.000 cps). Molecular weight is 10.000 or less, '# is 2,000 to 10,00
0, for example, about 4.000 to about 4.000 s, ooo, a desirable viscoelasticity and plastic viscosity range can be obtained.

As a calcium ion sequestrant, it is important that the polymer is particularly well water-soluble. In this case too, the polymer has a molecular weight of 10,000 or less, especially 2,000 to 10,000
Best results are obtained with a molecular weight of 0.

Similarly, it is preferred that the molecular weight of the polymeric additive be within the range of 2,000 to 10.000 as a soil dispersant contributing to the desired improvement in stain and film resistance.

The amount of polyacrylic acid polymer or copolymer required to preferably enhance physical stability and cleaning performance is determined by the amount and nature of the fatty acid or salt (if present), clay thickener (if present). ), depending on the amount and nature of detergent active compounds, bleaching agents and anticipated storage and transportation conditions.

However, generally the amount of polyacrylic acid polymer or copolymer additive that can be used is about 0.5 to 10% by weight, preferably
It is preferably in the range of about 0.80 to 8.0% by weight, particularly preferably about 2 to 6% by weight.

Detergent actives useful in this invention must be stable in the presence of chlorine bleaches, especially chlorite-deficient bleaches, organic anions, amine oxides, phosphine oxides, sulfoxides or betaine water-hostile interfaces. Active agent type detergent materials are preferred, with the first mentioned anionic agents being most preferred.

These are about 0.1-5%, preferably about 0.3-2.0
Used in amounts ranging from % to %. Particularly preferred surfactants in this case are linear or branched mono- and/or di(
08~C□4 Noalkyl diphenyl oxide mono and/
or disulfate alkali metal salts, such as those commercially available as DOWFAX® 3B-2 and DOWFAX® 3B-2.In general, paraffin sulfonates tend to increase viscosity too much. In addition, the surfactant must be compatible with the other components of the composition.Other suitable surfactants include primary alkyl sulfates, alkyl sulfonates, Alkylaryl sulfonates and secondary alkyl sulfates. Examples include 0□ to C18 sodium alkyl sulfates, such as sodium dodecyl sulfate and sodium tallow alcohol sulfate; C1o-C□8 sodium alkanesulfonates, such as hexadecyl-1- Sodium sulfonate;
and sodium 01□-C18 alkylbenzenesulfonates, such as sodium dodecylbenzenesulfonate. The corresponding potassium salts can also be used.

As other suitable surfactants or detergents, amine oxide surfactants typically have the structure R2R''N.

wherein R represents a lower alkyl group, such as methyl, and R1 represents a long-chain alkyl group having 8 to 22 carbon atoms, such as lauryl, myristyl, palmityl or cetyl. Instead of the amine oxide, the corresponding surfactant phosphine oxide
Fl"SO can also be used. Betaine surfactants typically have the structure R2R"N-R11Co〇-.
In the formula, each R represents a lower alkylene group having 1 to 5 carbon atoms. Specific examples of these surfactants are lauryl dimethylamine oxide and sulfoxide and the corresponding betaines, including dodecyl dimethyl ammonium acetate, tetradecyl diethylammonium pentanoate, hexadecyl dimethyl ammonium hexanoate, and the like. Because of their primary degradability, the alkyl groups in these surfactants must be linear, and such compounds are preferred.

All of the above types of surfactants are well known in the art and are described, for example, in U.S. Pat.
It is stated in the issue.

Compositions of the invention include, for example, dichloroisocyanurate, dichlorodimethylhydantoin, or chlorinated TSP.
Although any chlorine bleach may be used, hypochlorites of alkali metals such as potassium, lithium, magnesium, and especially sodium are preferred. The composition has an available chlorine content of about 0.2 as determined, for example, by acidifying 100 parts of the composition with excess hydrochloric acid.
It should contain enough chlorine bleach compound to release ~4.0% by weight. Sodium hypochlorite approximately 0.2~
Solutions containing 40% by weight contain or release approximately the same percentage of available chlorine. Particularly preferred is about 0.8 to 1.6 weight percent available chlorine. Available chlorine in an amount of about 3-20%, preferably about 7
~12% amount of about 11 to about 13% sodium hypochlorite (
Preference is given to using NaOC; t) solutions.

Sodium or potassium silicates, which provide alkalinity and protect hard surfaces, such as fine porcelain polishes or patterns, are usually used in amounts of about 2.5 to 20 or 25% by weight. Silicates also enhance antistaining action at levels greater than about 10% by weight.

However, the preferred viscoelastic, physically stable, liquid aqueous dishwasher detergent compositions of the present invention contain an excess of 1% by weight or more, based on the weight of the composition, over a normal usage period, e.g. It is important to include an amount of alkali metal silicate of 40% by weight, especially about 30-38% by weight.

Sodium silicate is generally preferably Na2O:S
r02 ratio about 1:2.2 to l:2.8. For example, 1:2.
It is added as an aqueous solution with 4. Most of the other ingredients of the composition are also added as aqueous dispersions or solutions, particularly NaOH, sodium hypochlorite and suds suppressants.

To increase the efficiency of the dishwasher and to minimize the destabilizing effect caused by the presence of excess foam in the dishwasher during use, it is the main foam generator. Detergent actives By appropriately selecting the type and/or amount of NaTPP, foam can be sufficiently reduced.The degree of foaming depends to some extent on the hardness of the washing water in the north washing machine, so NaTPP, which also has a water softening effect, Appropriate adjustment of the proportions can help provide the desired degree of suds control. However, it is generally preferred to add a stable suds suppressant or inhibitor to the chlorine bleach. If the content is permissible.

Alkyl phosphonic acid esters having the formula: % Formula %, especially alkyl acidic phosphoric esters having the formula HO-P-OR OR are particularly effective. In the above formula, one or both of the B groups in each type of ester independently represent 01□-C12-C20 alkyl m. Ethoxylated derivatives of various esters, fAl
A condensation product of 1 mole of ester and 1 to 10 moles, preferably 2 to 6 moles, more preferably 3 to 4 moles of ethylene oxide can also be used. Some examples of the above compounds include, for example, Knapp (S) from Hooker (HOOkerJ).
AP, l products and napsac f y / (Knapsac
It is commercially available as LPKn-158 from K.K. A mixture of the above two types, other types that are stable to chlorine bleach,
Alternatively, a mixture of monoesters and diesters of the same type can also be used. Particularly preferred are monostearyl/distearyl acidic phosphate esters 1.2/1 and their 3-4 mole ethylene oxide condensates.
and di-016-C□8 alkyl acid phosphate. When used, 0.01-0.5%,
A proportion of suds suppressant in the composition, preferably from 0.02 to 0.4% by weight, particularly preferably from about 0.1 to 0.2% by weight, is typical; The weight ratio is generally about 20=1 to 4:1. Preferably G'! Approximately 10:1-5
: The range is 1. At such low levels of antifoam, the total phosphorus content in the composition is generally and preferably less than 0.01% by weight, based on the total composition.

If total phosphorus removal is desired, known bleach compatible silicone consumables can be used.

Preferred thickened LADD compositions of the present invention are thickened with inorganic water-swellable colloid-forming clays of the smectite and/or attapulgite type. These materials generally contain about 0.1 to 10
It is used in an amount of % by weight, preferably 1 to 5% by weight. However, in the presence of fatty acids or fatty acid metal salt stabilizers,
Smaller amounts of smectite and/or attapulgite type inorganic colloid-forming clays are used. For example, about 0.1 to 3
%, preferably from 0.1 to 2.5%, especially from 0.1 to 2%, when used in combination with fatty acid (or fatty acid salt) stabilizers and other specific components, provides favorable viscoelastic properties. Enough to get.

Smectite clays include montmorillonite (including montmorillonite, hectorite, attapulgite, smectite, sabonite, etc.), and montmorillonite clay is preferred;
Georgia Kaolincampa = - (Georgia
Kaolin Company Nokara 0> Chi*Sogel (
ThiXOgelJ (registered trademark) AI and gel white (Gelwhite (registered trademark)) GP, H, etc. and Ruthern Clay Products (Luthern C1a)
yProducts) to Noyokka Gum (ECCAG)
UMJ (registered trademark JGP, H, etc.).

Attapulgite clay is produced by Engelhard Minerals and Chemicals Corporation (Engel-ha
rd Mir+erals and Chemi
There are materials available commercially under the trade names Actagel (Attags LJ) from Cals Corporation under the registered trademarks Actagel 40, Actagel 50 and Actagel 150.

Smectite/atapulgite type mixtures with an it ratio of 4:1 to 1:5 are also useful in this case. Thickening or suspending agents of the above type are well known in the art.

The physical stability, ie, resistance to phase separation, sedimentation, etc., of these liquid aqueous ADD compositions is significantly improved by the addition to the compositions of small but effective amounts of long chain fatty acids or metal salts thereof. In fact, the preferred alkaline pH conditions for LADD compositions, ie pH 10.5-13.
In 5, fatty acids are converted to the corresponding alkali metal salts.

Preferred long chain fatty acids have a carbon number of about 8 to about 22, preferably about 10 to about 22 °C, including the number of carbon atoms in the carboxyl group of the fatty acid.
Approximately 20. Particularly preferred are higher aliphatic fatty acids of about 12-18. Fat daughter radicals can be saturated or unsaturated;
Straight chain saturated fatty acids are preferred, although they can be straight chain or branched. Fatty acid mixtures, such as fatty acids derived from natural sources, such as tallow fatty acids, coconut oil fatty acids, soybean fatty acids, etc., or fatty acids from synthetic sources obtained from industrial manufacturing processes? Can be used.

Examples of such fatty acids include, for example, decanoic acid, dodecanoic acid, balmitic acid, myristic acid, stearic acid, oleic acid, eicosanoic acid, tallow fatty acids, coconut oil fatty acids,
Preferred are stearic acid and mixed fatty acids such as soybean fatty acids, mixtures of these acids, and the like.

Metal salts of fatty acids can also be used, and either monovalent or polyvalent metals can be used. Monovalent metals include 2, for example alkali metals, especially sodium or potassium. Particular preference is given to sodium salts.

Preferred polyvalent metals are polyvalent metals of Groups [A, [B and 1B] of the Periodic Table of the Elements, such as magnesium, calcium, aluminum and zinc;
Group A, Group 1V Group A, Group VA, Group 1B, Group 1'QB, Group VIB, Group IB, and Group 1 metals were included.

Other polyvalent metals can also be used. Specific examples of such other polyvalent metals include Ti, Zr, V, Nb, Mn,
Fe, Co, Ni, cd.

There are Sn, Sb, Bi, etc. These metals are generally 2
It exists in a valent to pentavalent state. It is preferred to use polyvalent metal salts in their higher oxidation state.

For LADD compositions, the compositions of the present invention may also be used in applications where the compositions of the invention come into contact with products used in food handling, storage, or service, or products that come into contact with or are to be consumed by humans or animals. Metals should be selected taking into account their toxicity. For this purpose, calcium and magnesium salts are particularly highly preferred as generally safe food additives.

Many metal salts are commercially available. For example, aluminum salts are obtained in the triacid form as 9A1, e.g. aluminum tristearate t"!, A/, (CHCo0]3.
Acid salts (e.g. aluminum monostearate, diacids (e.g. aluminum distearate and -acid salts, diacid salts and mixtures of two or three of the diacid salts, such as At with a valence of +3) For metals with a valence of +2, such as Zn,
- Mixtures of acid and diacid acids can be used. a diacid acid salt of a metal with a valence of +2 and a diacid acid salt of a metal with a valence of +3;
Tetrate salts of +4 metals and diacid salts of +5 valent metals are used in major amounts.

The above-mentioned metal salts are generally commercially available; for example, treatment with tallow, fatty acids such as stearic acid, or corresponding fatty acid esters with hydroxides or oxides of polyvalent metals;
For example, in the case of aluminum salts, they can be easily obtained by treatment with alum, alumina, etc. or by reaction of soluble metal salts with soluble fatty acid salts.

Calcium stearate (i.e. calcium distearate), magnesium stearate (i.e. magnesium distearate), aluminum stearate (
Aluminum tristearate and zinc stearate (zinc distearate) are the preferred polyvalent fatty acid salt stabilizers.

Mixed fatty acids such as naturally occurring acids (eg coconut oil fatty acids) as well as mixed fatty acids obtained from commercial manufacturing processes are also advantageously used as inexpensive and effective sources of long chain fatty acids.

Furthermore, dimers or trimers of these acids can also be used.

A fatty acid or fatty acid salt stabilizer cap that preferably enhances physical stability depends on the nature of the fatty acid (or its salt),
Clay thickeners, detergent active compounds, inorganic salts, and other LADs
It depends on the nature and amount of component D and the expected storage and transport conditions.

However, generally about 0.02 to 1%, preferably about 0.0
Amounts of polyvalent metal fatty acid salt stabilizer in the range of 6-0.8%, particularly preferably about 0.08-0.4%, provide long-term stability and are suitable for commercially acceptable products. Ensures no phase separation during storage or transportation at both desired low and high temperatures.

Without wishing to be bound to any particular theory regarding the mechanism of action of fatty acid (metal salt) stabilizers, it is important to note that these stabilizers, which are anionic salts under alkaline conditions, are used as cationic clays as thickening agents. It is hypothesized that the fatty acid component helps to maintain the clay particles suspended by interacting with the surface of the particles. Furthermore, depending on the proportion and type of physical stabilizer and clay thickener, the addition of fatty acids (or their salts) may not only increase the physical stability (but also increase the apparent viscosity). Fatty acid (salt)/clay thickener ratios in which the thickener is in the range of about 0.08 to 0.4 wt% are usually sufficient to provide such simultaneous benefits; Most preferably, these components are used.

Generally, the LADD effect is (al available chlorine level, (b)
Alkalinity, Ic) is directly related to solubility and 1 dl residue suppression in the cleaning medium. In this case, the pH of the LADD composition
is at least about 9.5, preferably about 10.5 to 13.
5. Particularly preferably at least about 11.5. At relatively low pH values, LADDM products are often too viscous, i.e., solid-like, and difficult to fluidize at the shear level that occurs in the dispenser cup under normal dishwasher operating conditions. be. The composition essentially loses most (if not all) of its viscoelastic properties. Therefore, addition of NaOH is often necessary to raise the pH within the above range and to improve fluidity. The presence of carbonate is also present, as carbonate acts as a buffer that helps maintain a favorable pH level.

This is often necessary in this case. However, excess carbonate may result in the formation of carbonate needles, impairing the stability, tropism and/or detergency of the LADD product and impairing the dispensability of the product from, for example, a squeeze tube bottle. Should be avoided. Caustic soda (NaOH) has the additional function of neutralizing vanillic acid or phosphonate ester suds suppressants, if present. About 0.5-3% by weight NaOH and about 2 to 2-3% sodium carbonate in the LADD composition.
Although 9% by weight is typical, it should be noted that sufficient alkalinity is often provided by alkali metal silicates.

The amount of water included in these compositions should of course not be so high as to result in unduly low viscosity and flowability.

The viscosity must not be so low that it leads to unduly high viscosity and low flow properties, in which case the viscoelasticity is reduced or destroyed. Such amounts are readily determined in a particular case by routine testing, but generally total from about 25 to 75% by weight from all °C sources.

Preferably it ranges from about 55 to 65% by weight. Preferably, the water is deionized or soft water.

Other conventional ingredients such as perfumes, hydrotropes such as sodium benzene, toluene, xylene and cumene sulfonates, preservatives, dyes and pigments, etc. are generally present in these compositions at about 3% by weight. It can be included in small amounts as low as %. All ingredients must naturally be stable to chlorine bleach compounds and high alkalinity (nature of all ingredients).For coloring, chlorinated phthalocyanines, which give bright green and blue hues, respectively; Polysulfides of aluminosilicates are particularly preferred. T i O2 is used for whitening and neutralization of discoloration, since abrasives or polishes will scratch the surface of delicate tableware, crystal, etc.

Its use in LADD compositions should be avoided.

According to a preferred method of manufacturing these compositions, all of the inorganic salts, such as carbonates (if used), silicates and zeolites, are first dissolved or dispersed in an aqueous medium. The carboxyl group-containing polymer and clay (if used, nona included) are added last. The foam suppressant (if used) is formed in advance as an aqueous thickening dispersion.

The antifoam dispersion, caustic soda (if used) and inorganic salts are first mixed into an aqueous solution (deionized water) at elevated temperature;
Cool using thorough stirring.

Next, bleach,
Add surfactant, fatty acid (or metal salt stabilizer thereof) and thickener dispersion at room temperature.

Total C salt concentration excluding chlorine bleach compounds (e.g. sodium silicate and sodium carbonate are generally about 20°C in the composition)
-50% by weight, preferably about 25-40% by weight.

Another highly preferred method of mixing the components of the LADD composition is to first form a mixture of water, suds suppressant, detergent, carboxyl-containing polymer, fatty acid or salt thereof, and clay. This mixture is introduced into a mixer under high renewal conditions to form a homogeneous dispersion, preferably starting at room temperature. The remaining ingredients are introduced into this premix portion under low shear mixing conditions. For example, the required amount of premix is introduced into a low shear mixer and then the remaining ingredients are added sequentially or simultaneously while mixing. Although it is preferable to add the ingredients sequentially, do all additions of one ingredient occur before starting the addition of the first ingredient? There's no need to end it. Additionally, one or more ingredients can be divided into portions and added at different times.

Remaining ingredients 2nd order: sodium hydroxide, alkali metal carbonate, sodium silicate, aluminosilicate zeolite, ? Favorable results have often been obtained by adding 4-day preparations (preferably sodium hypochlorite and sodium hydroxide in that order).

The liquid ADD compositions of the present invention can be readily used in a known manner for cleaning dishes, other kitchen utensils, etc. in a wash water bath containing an effective amount of the composition in an automatic dishwasher equipped with a suitable detergent dispenser. It will be done.

In connection with the application of the present invention to a liquid automatic dishwashing rack detergent,
In particular, we have described bleach-stable detergents, with or without improvements in viscoelasticity and physical stability obtained by supplemental amounts of alkali metal silicates and interactions between clays and fatty acids; g A combination of whitening agent, zeolite builder and bleach-stable water-soluble carboxyl group-containing polymer.

It will be readily appreciated by those skilled in the art that cleaning improvements are provided as general type liquid cleaning compositions for glassware, cutlery, pots, pans, etc.

The cleaning performance of the compositions of the present invention in terms of removing a wide range of food stains is superior to that of the regular polyphosphate alkali metal builder.
For example, sodium tripolyphosphate builder is comparable to or slightly inferior to detergents. For example, eggs, peanut butter, tea, coffee, milk, chocolate milk, tomato juice, rice, rice/cheese mixtures, white sauce, oatmeal, and various food residues, including spinach (some of which may be baked onto dishes) In cleaning tests for 14 to 16 food stains on various substrates (glass tops, cutlery, plates, bottles), the LADD compositions of the present invention showed moderately good cleaning for 14 to 16 food stains on various substrates (glass tops, cutlery, plates, bottles); Showed rather poor cleaning on chocolate milk and burnt rice.

Additionally, as shown in the examples below, the compositions of the present invention are generally superior to similar phosphate builder compositions in terms of staining and film formation.

The invention can be implemented in various ways, and the following examples illustrate the invention with reference to some specific embodiments.

All amounts and proportions herein are by weight of the composition, unless otherwise indicated.

EXAMPLE In order to compare the properties of the compositions of this invention with similar phosphate builder compositions, two primary acid complexes are prepared.

Present invention Comparative deionized water 16.44 30.44
Stearic acid 0.10 0.1
0 smectite clay (VanGetESJl, 50
1.50 Sodium silicate (Na zO: S 10
47.5% solution with z ratio 1:2.4] 35.0
0 25.00 Sodium tripolyphosphate (substantially anhydrous, i.e. approximately 3% water) ----12,
00 Sodium tripolyphosphate hexahydrate---12,
00 Aluminosilicate Zeolite 24.00 -
--Sodium monoanhydride 6.00
6.00 Sodium hypochlorite (available chlorine 1% J 9
．． 00 9.00 Surfactant (Dowfax 3B
-12~C2045% mono-/didecyldisulfonic acid Na aqueous solution) 0.80 0
．． 80 antifoaming agent (Natsupsack LPKn1ss.

Mono-/di-stearyl phosphate (C16'18 noalkyl ester mixture 1 molar ratio approximately 1:1.3 0.16 0.
16 Caustic sorter solution (50% NaOH) 3.00 3
．． 00bo IJ 7 Sodium acrylate (MW=4.500) (
45% solution L+ 4.00 --
-- Each composition of Run &1 and A2 was poured into a glassware (1005
The cleaning performance (stain formation and thin film formation on glassware) was tested using Kenmore (K6nnmOr6J) at a dishwasher tap water temperature of 1307 mm and hardness of 120 ppm.The test method was ASTM D 3566-7.
9, but in this case only four wash cycles are used. Filming and blot formation are evaluated according to the following scale: Film Rating Scale 1, best, no obvious thinning 2, mild thinning, discernible 3, noticeable thinning, increasing 4, marked thinning, continuously increasing 5 , overly filmed 6, highly filmed, excessively deposited 7, excessively filmed, continuously increasing stain rating school A, best - no stains B, very slight stains, discernible C1 obvious stains, significant stain coverage 50% area results are shown below.

Performance evaluation l A, B B 1,2 1,22 A,
B B 1,2 1,23 A, B-B
B-01,21,248B-022 Results similar to those described above are believed to be obtained when a methacrylic acid/maleic anhydride copolymer, such as Socolan OP5, is used in place of the polyacrylate.

1. Indication of the case Patent Application No. 239576 filed in 1988 2. Name of the invention Aqueous liquid phosphorus-free or low-phosphorus detergent composition 3. Relationship with the case Patent applicant address Name Colgate Vermolib φ Company 4 , Agent 5, Specification written by type stamp subject to amendment

Claims (1)

[Claims] 1. A water- and chlorine bleach-stable and water-dispersible organic detergent, an alkali metal silicate, a chlorine bleach, and a detergent builder, the detergent builder being aluminosilicate zeolite and a bleach. An aqueous liquid phosphorus-free or low-phosphorus detergent composition comprising a mixture with a stable carboxyl-containing water-soluble polymer. 2. The bleach-stable polymer is a polyacrylic acid or polyacrylate polymer, and has a molecular weight of about 1000 to about 25.
A composition according to claim 1 having a molecular weight within the range of 0.000. 3. The bleach-stable polymer has a molecular weight of about 2,000 to about 10,
3. The composition of claim 2 having a molecular weight of 0.000. 4. The composition of claim 1, wherein the detergent builder comprises about 5 to about 35 weight percent aluminosilicate zeolite and about 0.5 to 10 weight percent bleach-stable polymer. 5. Claim 1 further comprising an inorganic colloid-forming clay thickener.
Compositions as described. 6. The composition according to claim 5, further comprising a C_8 to C_2_2 aliphatic carboxylic acid or a salt thereof. 7. The composition of claim 1 further comprising a bleach-stable suds suppressant. 8. C_1_2 to C_2 containing one or two foaming inhibitors
8. The composition of claim 7, comprising an alkyl acid phosphate or alkyl phosphonate containing an alkyl group or a mixture thereof. 9. The composition according to claim 1, which does not contain phosphorus. 10. The composition of claim 9 further comprising a silicone suds suppressor. 11. An aqueous thickened liquid automatic dishwasher detergent composition containing not more than about 0.01% by weight of phosphorus, comprising: (a) 5-35% aluminosilicate zeolite; (b)
more than 25% sodium silicate; (c) 0-9% alkali metal carbonate; (d) 0.1-5% bleach-stable, water-dispersible organic detergent active; (e) bleach-stable origin. (f) a chlorine bleach compound in an amount to provide about 0.2-4% available chlorine; (g) an inorganic colloid-forming clay thickener 0-3%; (h) a carbon number of 8 to 3%; 22 aliphatic fatty acids, their dimers, trimers or their metal salts 0-0.5% (i) Sodium hydroxide 0-8% (j) Bleach-stable water-soluble carboxyl group-containing polymers 0.5-10% and (k) a composition comprising water and having a pH of at least 9.5. 12. The bleach-stable polymer is polyacrylic acid or polyacrylate, and has a molecular weight of about 1,000 to about 25,000
12. The composition of claim 11 having a molecular weight of 0. 13. Bleach-stable polymers range from about 2,000 to about 10
13. The composition of claim 12 having a molecular weight of ,000. 14. The aliphatic fatty acid or its salt (h) 0.03~
12. A composition according to claim 11, comprising 0.5% and 0.1-3% of said clay thickener (g). 15. The composition according to claim 14, wherein the fatty acid is stearic acid or a salt thereof, and the clay is smectite clay or attapulgite clay. 16. The composition according to claim 11, wherein the chlorine bleach (f) is sodium hypochlorite. 17. The composition of claim 11, comprising at least about 0.1% by weight of suds suppressant (e). 18. The composition according to claim 17, wherein the suds suppressant is an alkyl acid phosphate or an alkyl phosphonate having one or more C_1_2 to C_2_0 alkyl groups, or a mixture thereof. 19, having a pH of about 10.5 to about 13.5.
1. The composition according to item 1. 20. A method for cleaning soiled dishes in an automatic dishwasher, comprising contacting the soiled dishes with an aqueous cleaning bath containing dispersed therein an effective amount of the composition of claim 11. .