JPH01163299A - Detergent composition for automatic tableware washer composed of thixotropic aqueous solution - Google Patents

Abstract

PURPOSE: To provide the composition having improved properties for preventing the formation of silica films and dirty spots and containing water, an organic detergent or the like, an agent for preventing formation of silica films, polymer of acrylic acid or the like and a thixotropic thickening agent.

CONSTITUTION: The composition comprises (A) water, (B) one or more components selected from a group consisting of organic detergents, bleaching agents containing chlorine, builders for detergents, sequestering agents for metallic ions and antifoaming agents, (C) about 0.5-5% of agents for preventing the formation of silica films, (D) about 2-14% of the polymer of acrylic acid or its salt and (E) about 2.5-10% of a thixotropic thickening agent.

COPYRIGHT: (C)1989,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a thixotropic aqueous liquid automatic dishwashing detergent composition with improved anti-filming and anti-spotting properties and a composition for cleaning dishes, glassware, china, etc. The present invention relates to a method of using a detergent composition. The dishwashing area composition includes silica as an anti-filming agent, a polyacrylic acid polymer builder, an inorganic builder salt, a chlorine bleach, a bleach-stable detergent, and a thixotropic thickener.

The detergent dishwashing compositions of the present invention reduce film formation and spotting on dishes, glassware, china, etc., especially in hard water, and remain stable to phase separation.

More specifically, the present invention uses silica as a film-forming agent and a polyacrylic acid polymer builder in a thixotropic aqueous liquid dishwashing detergent composition to reduce film formation and spotting.

The detergent composition does not require the addition of rinse aids, is storage stable, non-settling, easily dispersible, and pourable.

The invention also relates to thixotropic aqueous suspensions with improved physical stability.The invention also relates to stable gel-like liquid suspensions suitable for use as liquid automatic dishwashing detergent compositions. To form the body, long chain fatty acids,
It concerns the use of metal salts of fatty acids and clays as thixotropic agents.

Specifically, the present invention has thixotropic properties, improved anti-filming and anti-spotting properties, and improved physical stability, and is easily dispersible in cleaning media and is suitable for cleaning dishes, glassware, etc. Provides effective cleaning of ceramics, etc.
The present invention relates to an aqueous liquid automatic dishwashing detergent composition.

Domestic dishwashing detergents provided in commercially available powders suffer from several drawbacks, such as inhomogeneous composition, costly operations required during production, and a tendency to solidify during high-humidity storage. It has a tendency to form clumps that are difficult to disperse, is dusty which is a source of irritation for users suffering from allergies, and has a tendency to solidify in dishwasher dispensing equipment. Liquid forms of such compositions, however, cannot be used in automatic dishwashing machines because of the high foam levels within the membrane, the unacceptably low viscosity and the excessively high alkalinity.

Moreover, the currently used formulated powder detergents are designed to avoid undesirable traces or film residues of precipitated calcium and magnesium salts on dishes, glassware, etc.
Separate processes for wiping and drying ceramics, etc. are required. The use of liquid detergent compositions presents other problems. builder salts settle during storage and are not easily redispersed;
These compositions also often thicken on storage and are not easily pourable.

Recent research and development activity has focused on gel-type or "thixotropic" forms of these types of compositions, but these compositions generally have insufficient viscosity to be suitable for dishwashers. Anc that got stuck in the dispenser cup
It has been found that the liquid can remain "hored" and also produce a spotty residue on dishes, glassware, china, etc. Ideally, a thixotropic cleaning composition should be highly viscous at rest, Bingham plastic in nature, and have a relatively high yield value.

However, when subjected to shear stress, such as when shaken in a container or squeezed through an orifice, they should fluidize rapidly and return rapidly to a high viscosity/Bingham plastic state when shear application is stopped. be. Stability is also of primary importance, ie there should be no significant signs of phase separation or leakage after prolonged standing.

For effective use, - ultimately, automatic dishwashing detergents, hereinafter referred to as ADD, must contain (1) sodium tripolyphosphate (NaTPP) to soften or trap hard water minerals and emulsify and/or decoagulate soils; ), (2) sodium silicate to provide the alkalinity necessary for effective washability and protection of fine ceramic glazes and patterns; (3) an optional ingredient to enhance alkalinity. (4) a chlorine release agent to aid in the removal of dirt spots that lead to water spotting; and (5) a chlorine release agent to reduce suds thereby increasing machine efficiency and providing the required washability. For example, SDA Detergent J (SD
A Detergents in Depth), “
``Preparation status of machine dishwashing'', Thomas Orbel, (19
74), see. A cleanser approximating the aforementioned composition'
- is mostly liquid or powder. - Within the membrane, such compositions omit hypochlorite bleach, since it reacts with other chemically active ingredients, especially surfactants, thereby or because it degrades the thixotropic agent and impairs its effectiveness.

Thus, U.S. Patent No. 3,985,668 (
1) suspending agents, preferably clays of the smectite and attapulgite type, (2) abrasives, such as silica sand or perlite, and (3) light density cast polymers, expanded perlite, etc., in addition to serving as fillers. A gel-like consistency comprising a filler, which has a buoyant force on the material and thus has a stabilizing effect, thereby displacing the water available for leakage and the formation of undesirable supernatant layers due to phase destabilization. Describes a cleaning agent for polishing and refining.

Optional formulation ingredients include hypochlorite bleach, bleach-stable surfactants, and buffers such as silicates, carbonates, and monophosphates; builders such as NaTPP are not provided by buffers. It can be included as another optional ingredient to supply or supplement the function, and the amount of such builder is according to the patent to be 5% of the total composition.
Do not exceed. Maintenance of the desired pH 10 level (greater than pH 10) is achieved by the buffer/builder component.

High pH is said to minimize chlorine bleach degradation and undesirable interactions between surfactants and bleach.

When present, NaTPP is limited to 5% as described above. Antifoaming agents are not disclosed.

British Patent Application GB 2,116,199^ and G[2,1
No. 40,450^, both of which are assigned to Colgate-Palmolive, discloses a liquid ADD composition desirably having properties characterizing a chickentropic gel-type structure and having effectiveness with respect to an automatic dishwasher. Contains each of the various ingredients necessary for target cleansing,
A normally gel-like, aqueous automatic dishwashing detergent composition of thixotropic nature contains, on a weight basis, the following ingredients:

(a) 5 to 35% alkali metal tripolyphosphate; (b) 2.5 to 20% sodium silicate; (C)
0 to 9% alkali metal carbonate, (d) 0.1
(e) from 0 to 5% chlorine bleach-stable suds suppressor; (f) from about 0.2 to 4% effective. a chlorine bleach compound in an amount to provide chlorine; (g) a thixotropic thickener in an amount sufficient to provide a composition with a thixotropic index of about 2.5 to 10; (h) adjust the pH if necessary. Sodium hydroxide.

The ADD composition so formulated has low foaming properties;
Easily soluble in the cleaning medium and the most favorable pH value for improved cleaning performance, i.e. pH 10.5-1
3.5 is most effective. The compositions usually have gel properties, ie, highly viscous, opaque jelly-like materials with Bingham plastic properties and, therefore, relatively high yield values. A certain shear force is therefore required to initiate or increase flow, such as is achieved in the agitator dispensing cup of a running automatic dishwasher. Under such conditions, the composition becomes rapidly fluidized and easily dispersed.

When the shear is discontinued, the fluid composition rapidly returns to a highly viscous, Bingham plastic state approaching its original consistency.

U.S. Patent 4,511,487 dated April 16, 1985
describes a low-foaming detergent paste for dishwashers. This composition is based on a mixture of finely divided aqueous sodium metasilicate, an active chlorine compound, and a thickening agent which is a phyllosilicate of the hectorite type. non-ionic tenside and alkali metal carbonates and/or
Alternatively, small amounts of hydroxide may be used.

There are 19 related jointly pending patent applications that will be assigned to a common assignee.
Application number 816.535 filed on January 7, 1987,
This is incorporated herein in its entirety as a document. That co-pending patent application discloses thixotropic aqueous automatic dishwashing detergent compositions containing long chain fatty acids as thixotropic thickeners.

Another related co-pending patent application, also assigned to the common assignee, is incorporated by reference.

Application number 924,385 filed on October 29, 1986
It is.

This co-pending patent application discloses an aqueous liquid thixotropic clay dishwashing detergent composition comprising a metal salt of a long chain fatty acid and a polyacrylic acid polymer or salt stabilizer.

BACKGROUND OF THE INVENTION 1. The thixotropic aqueous liquid detergent compositions of the present invention overcome many of the problems of the prior art with respect to powder and liquid detergents. Since a small amount of a silica film-forming inhibitor and a polyacrylic acid polymer or salt builder are added to the composition,
The addition of rinse aids is not required, and no toweling and drying is required to obtain dry, wonderfully clean dishes, glasses, cups, and utensils; this thixotropic aqueous liquid detergent composition is stable and shelf-stable. It has the additional advantage that it sometimes does not settle and can be easily redispersed. The liquid composition of the present invention is easy to pour, easy to measure,
Easily placed in the dishwasher.

An additional and unexpected benefit of adding hesilica anti-filming agents in detergent formulations is that silica inhibits the formation of brown stains in dishwashers.

This brown stain is formed by the deposition of iron and/or manganese oxides in the dishwasher. This brown stain formation is a particularly serious problem in areas with hard water.

The silica in the formulation acts on iron and/or manganese in the wash water and prevents their deposition in the dishwasher as iron and/or manganese oxides.

SUMMARY OF THE INVENTION One object of the present invention is to provide a thixotropic aqueous liquid dishwashing detergent composition with improved anti-filming and anti-spotting properties.

Another object of the present invention is to provide a thixotropic aqueous liquid detergent composition that is stable on storage, easily pourable, and easily dispersible in dishwashing water.

Another object of the invention is a method for washing dishes, glassware, china, etc. in an automatic dishwashing machine using a thixotropic aqueous detergent composition without the addition or need of a separate rinse aid. The goal is to provide the following.

Yet another object of the present invention is to provide a method for cleaning dishes, glassware, china, etc. in an automatic washing machine using an aqueous liquid detergent composition, the method comprising: Tableware, china, etc. are machine dried without leaving any marks or films.

Another object of the present invention is to provide stable, aqueous, thixotropic liquid compositions, particularly An object of the present invention is to provide an automatic dishwasher detergent composition. Also added are small amounts of fatty acids, metal salts of fatty acids, and/or clay thixotropic thickeners effective to prevent settling of suspended particles and prevent phase separation.

These and other objects of the present invention will become more readily understood from the following detailed description of the present invention and its preferred embodiments, but these and other objects of the present invention will become more readily understood from the following detailed description of the present invention and its preferred embodiments. This is accomplished by incorporating a but effective amount of a silica anti-filming agent and a polyacrylic acid polymer or salt builder.

The physical stability of the composition is determined by the fatty acids, fatty acid metal salts and/or
or improved by the addition of clay thixotropic thickeners. More particularly, in accordance with a preferred and specific embodiment of the present invention, about 0.5 to 5% silica film inhibitor and about 2 to 14% water soluble polyacrylic acid polymer or acid builder. Automatic dishwasher detergent compositions, typically in gel form, are provided that incorporate. The silica anti-filming agent has a particle size of about 0.1 to 10 microns.

Water-soluble polyacrylic acid or salt is about 500 to 100.0
It has a molecular weight of 0.00. In a preferred embodiment of the invention, a sufficient amount of a long chain fatty acid or a metal salt of a long chain fatty acid or any of the foregoing together with a clay thixotropic thickening agent is added to the composition, It provides a thixotropic index of about 2.5 to 10 and prevents settling of suspended particles such as alkali gold layer builder salts and the like.

According to this aspect, the present invention may provide a typically gel-like aqueous liquid automatic dishwashing detergent composition having chickentrope properties, which contains, by weight, (a) from 5 to 35% alkali; metal tripolyphosphate, (b) 2.5 to 40% sodium silicate, (c)
0.5 to 5% silica film formation inhibitor, (d) 2 to 14% polyacrylic acid polymer or salt builder, (e) 0 to 9% alkali metal carbonate, (f)
0.1 to 5% chlorine bleach-stable water-dispersible organic detergent active, (g) 0 to 5% chlorine bleach-stable suds suppressor, (?l) about 0.2 to 4 % of available chlorine, (i) a thixotropic thickener in an amount sufficient to provide a thixotropic index of about 2.5 to 10, (j) 0 to 8% sodium hydroxide, and , <k) including water to balance the remainder.

In connection with this particular aspect, the present invention provides a method for cleaning dishes in an automatic dishwasher with an aqueous wash bath comprising an effective amount of a liquid automatic dishwashing detergent (LADD) 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 within a few seconds of dispensing, the LADD composition can be poured into a conventional gel-like or rapidly thickens to a paste state and remains secure within the dispensing cup until shear is applied again, such as by water spray from a dishwasher.

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

For example, the aforementioned CB2, 116, 199^ and CB2,
The conventional LADD product at 140,4508 is
Shows the hisological properties as assessed by testing product viscosity as a function of shear rate. The composition exhibits high viscosity at low shear rates and low viscosity at high shear rates, with data indicating fully efficient fluidization and gelling within the shear rate range within a standard dishwasher. In a practical sense, this means improved pouring and handling properties and less leakage in mechanical dispensing cups compared to conventional liquid or gel ADD products. For applied shear rates corresponding to 3 to 30 rpm, the viscosity (Brookfield) is correspondingly approximately No. 10, measured at room temperature by an LVT Brookfield viscometer after 3 minutes using a 4 spindle. They ranged from 000 to 30,000 centiboise to about 3,000 to 7,000 centiboise fs. The shear rate of 7.4 s−1 is approximately 3 spindle rp
Corresponds to m. An approximately 10-fold increase in shear rate increases the viscosity by approximately 3
resulting in a nine-fold decrease from The compositions of this assignee's prior invention exhibit a significantly greater degree of critical fluidization at lower shear forces and with respect to incremental increases in shear rate versus incremental decreases in viscosity. This property of prior patent LADD products is summarized as the thixotropic index (TI), which is the ratio of the apparent viscosity at 3 and 30 rpm. Conventional compositions have a TI of 2 to 10.

The LADD composition exhibits a substantial and rapid return to its original resting consistency upon discontinuation of the shear force.

Regarding the apparent viscosity, No. 4 at 2 Orpm.
The viscosity at room temperature (22° ± 1°C) measured using a spindle in a Brookfield viscometer HATD is approximately 2.
As long as the thixotropic composition is smaller than 0, OOO centivoise, it is easy to "fluidize" or "liquefy" the thixotropic composition.
It has been found that the composition can be easily shaken so that the product can be dispensed through a conventional swab tube or other convenient dispenser.

The present invention provides that substantially improved anti-filming and anti-spotting properties can be obtained by incorporating small effective amounts of a silica anti-filming agent and a polyacrylic acid polymer or salt builder into a thixotropic aqueous liquid detergent composition. It is based on the surprising discovery that it can be obtained by igniting it. Physical stability, ie, resistance to phase separation, sedimentation, etc., can be achieved by adding to the composition small amounts of thixotropic thickeners and stabilizers.

The silica film-forming inhibitor materials that can be used in the anal plate are fumed or precipitated synthetic silica or natural silica.

The silica may be amorphous or crystalline.

The silica material used is approximately 0, based on the weight of silica.
．． It may contain from 1 to 5% alumina, usually about 0.5 to 3%, and more usually about 1%.

A preferred silica material is Thyroid 244, which is an amorphous silica supplied by.

Another preferred silica material is Hyperze No. 49
, which is an amorphous silica supplied by J.M. Huber Corporation and contains about 1% alumina (^I203). 1% is a small amount ^120
It has been found that the presence of No. 3 helps reduce hydrolysis, and thus helps reduce the subsequent solubility of silica in highly alkaline automatic dishwashing detergent compositions.

The particle size of the silica material used is important in achieving the desired anti-filming properties.

The silica particles used are finely divided and approximately 0.10
The particle size can be from about 10 microns to 10 microns, preferably from 0.50 to 8 microns, and more preferably from about 1.0 to 5.0 microns.

Silica particles of this size and in the amounts used herein are not abrasive.

The finely divided silica material particles in the dishwashing liquid act to coagulate proteinaceous particulate contaminants and keep them in suspension, and, together with the polyacrylic acid polymer or salt, act as anti-redeposition agents. It acts to prevent dirt from settling on clean glasses and dishes.

The amount of silica anti-filming agent that can be used to achieve the desired improvement in film formation and spotting depends on the water hardness, detergent active compounds, inorganic salts, and other ADD formulation ingredients. Silica film formation inhibitors are particularly effective in hard water, such as wash liquors with hardness of 300 ppm or more.

The amount of the silica film formation inhibitor used is about 0.5 to 5% by weight, preferably about 1 to 4%, based on the weight of the entire composition.
More preferably, it may be about 1.5 to 3%.

Polyacrylic Polymers and Salts Polyacrylic polymers and their salts that can be used are generally commercially available and are summarized as follows.

The polyacrylic acids and salts thereof that can be used consist of water-soluble low molecular weight polymers with the formula R,R2CCR,C00Mn, where R1
, R2 and R1 can be the same or different and can be hydrogen, C, -C, lower alkyl, or a combination thereof. The value of n is 5 to 100
0, preferably 10 to 500, more preferably 20
It is 100 from M represents hydrogen or an alkali metal such as sodium or potassium. A preferred substituent for M is sodium.

Preferred R1, R2, and R1 groups are hydrogen, methyl, ethyl, and propyl. Preferred acrylic acid monomers are those in which R, through Rs are hydrogen, such as acrylic acid, or R1 and R1 are hydrogen and R2
is methyl, such as methyl acrylic acid monomer.

The degree of polymerization, ie the value of n, is determined - ultimately by the limit compatible with the solubility of the polymer in water. The terminal groups on the polymer are not critical and can be H5OH, CH, or low molecular weight hydrocarbons.

Polyacrylic acid and its salts are 500 or 1.000 to 100,000 preferably 1.500 to 50,000
0, particularly preferably from 2,000 to 10,000.

Particular polyacrylic acid polymers that can be used include Acrisol LMW acrylic acid polymers from Rohm and Haas, such as Acrisol LMW-45NX, a neutralized sodium salt with a molecular weight of about 4.500, and Acrisol LMW-45NX, a neutralized sodium salt with a molecular weight of about 2. ,000 neutralized sodium salt of Acrisol LMW2ONX. These low molecular weight acrylic acid polymers have, for example, a molecular weight of about 1000 to 10,000. Another polyacrylic acid polymer that can be used is Alco Bars 110 (manufactured by Alco), which is a sodium salt of an organic polycarboxylate. and about 1
It has a molecular weight of 00,000.

The polyacrylic acid polymers and salts thereof described above can be made using procedures known in the art, see, for example, US Pat. No. 4,203,858. The amount of polyacrylic acid polymer or salt builder that can be used to achieve the desired improvement in anti-filming and anti-spotting properties depends on water hardness, detergent active compounds, inorganic salts, and other A
Depends on the DD ingredients.

Builders of polyacrylic acid or salts are e.g. 300 p.
It is particularly effective in reducing spotting in hard water with a hardness of 100 ps or above.

-i-wise, the amount of polyacrylic acid polymer or salt that can be used ranges from about 2.0 to 14%, preferably from about 3.0 to 12%, particularly preferably from about 4 to 10%.

The thixotropic thickening or suspending agent that can be used according to the invention to impart thixotropic properties to a thixotropic aqueous medium can be organic, such as fatty acids or fatty acid polyvalent metal salts, or inorganic, colloid-forming clay minerals. The thixotropic thickener should be stable to high alkalinity and stable to chlorine bleach compounds such as sodium hypochlorite. Preferred thixotropic thickeners are fatty acids, fatty acid polyvalent metal salts,
and an inorganic colloid-forming clay of the smectite and/or attapulgite type. The amount of thixotropic thickener used depends on the specific thickener used;
However, sufficient thickening agent is added to the formulation to give the composition a thixotropic index of about 2.5 to 10.

Preferred fatty acid thixotropic thickeners are higher fatty acid thixotropic thickeners having about 8 to about 22 carbon atoms, more preferably about 10 to 20 carbon atoms, and particularly preferably about 12 to 18 carbon atoms, including the carbon atoms of the carboxyl group of the fatty acid. It is an aliphatic monocarboxylic acid. The aliphatic group may be saturated or unsaturated and may be linear or branched, preferably a straight chain saturated fatty acid. Mixtures of fatty acids may be used, for example those derived from natural sources such as beef tallow fatty acid, coco fatty acid, soybean fatty acid, etc., or from synthetic sources available from industrial manufacturing processes.

Thus, examples of fatty acids that can be used are, for example, decanoic acid, lauric acid, dodecanoic acid, valmitic acid, myristic acid, stearic acid, oleic acid, eicosanoic acid, tallow acid, coco fatty acid, soybean fatty acid, and Contains mixtures. Stearic acid and mixed fatty acids such as coco fatty acids are preferred.

The amount of fatty acid thickener to achieve the desired thixotropic properties and physical stability depends on the nature of the fatty acid, detergent active compounds, inorganic salts, especially TPP, other LADD formulation ingredients,
and the expected storage and shipping conditions.

Generally, however, the amount of fatty acid thixotropic agent that can be used is about 0.03 to 0.5%, preferably about 0.03%
to 0.2%, particularly preferably about 0.05 to 0.15
% to provide the desired long-term stability and avoid phase separation.

Polyvalent metal salts of the above fatty acids can also be used as thixotropic thickeners in the present invention. A suitable metal salt thixotropic thickener is described by Dravinil et al. in 1986.
No. 903.924, filed September 5, 2005, which is incorporated herein in its entirety.

Preferred metals are polyvalent metals such as magnesium, calcium, aluminum and zinc.

Generally, the metal may be present in a divalent or pentavalent state, preferably the metal salt is used in its higher oxidation state. It will be appreciated that for LADD compositions, the compositions of the present invention may come into contact with or come into contact with articles used for the handling, storage or presentation of food or products that come into contact with or are consumed by humans or animals. As with other applications in which metals may be used, the metal salt should be selected by taking metal toxicity into account.

For this purpose, calcium and magnesium salts are particularly preferred as overall safe food additives.

Many of these metal salts are commercially available.

For example, aluminum salts are available in the form of triacids, such as aluminum stearate as aluminum tristearate^I(C+J*5COO)*. −
Acid salts, such as aluminum monostearate, ^1(
OH)z(C+tLsCOO) and diacid salts, such as aluminum distearate, ^I(OH)(C+tH
zsC00)2, and mixtures of two or three of -acids, diacids and diacids can be used for metals with a valence of +3, e.g.
- a mixture of acid salts and diacid salts of a metal with a valence of +2;
For example, it can be used for Zn. More preferably, diacids of +2 valence metals, triacids of +3 valence metals, tetraacids of +4 metals, and pentaacids of +5 valence metals are used in predominant amounts. For example, at least 30% of the total metal salts, preferably at least 50%, particularly preferably 8%
100% of the o should be in the highest possible oxidation state, ie each possible valence site is occupied by one fatty acid residue.

Metal salts, as mentioned above, are generally commercially available;
It can be easily produced by subsequent treatment with a hydroxide or oxide of a polyvalent metal, such as alum or alumina in the case of an aluminum salt.

Calcium stearate or calcium distearate, magnesium stearate or magnesium distearate, aluminum stearate or aluminum tristearate, and zinc stearate or zinc distearate are preferred polyvalent fatty acid salt stabilizers. Mixed fatty acid metal salts such as naturally occurring acids such as coco acid as well as mixed fatty acids resulting from commercial manufacturing processes are also advantageously used as inexpensive and effective sources of long chain fatty acids.

The amount of fatty acid salt stabilizer that achieves the desired increase in physical stability depends on the nature of the fatty acid salt, the nature and amount of the thixotrope agent, the detergent active compounds, the inorganic salts, particularly TPP, other LADD formulation ingredients, and the anticipated storage. - Exists in factors such as shipping conditions.

However - ultimately, the polyvalent metal fatty acid salt stabilizer ranges from about 0.02 to 1%, preferably from about 0.06 to 0.8%, particularly preferably from about 0.08 to 0.4%. The amount of
It provides long-term stability and does not undergo phase separation, on storage or during transportation, at both the low and high temperatures required for commercially acceptable products.

Conventional inorganic thixotropic clay thickeners may also be used in the present invention; clay thickeners may be used in small amounts in combination with fatty acid thickeners or in combination with fatty acid polyvalent metal salt thickeners. It's fine.

However, clay thickeners may be used in their own right as thixotropic thickeners.

Preferred clay thickeners consist of inorganic colloid-forming clays of the smectite and/or attapulgite type.

Smectite clay is montmorillonite (bentonite)
, hectorite, attapulgite, smectite, sabonite, etc. Montmorillonite clays are preferred, such as "Sixogel"® NOll and "Gel White" from the Josiah Kaolin Company.
(registered trademark) GP, Hl, etc., and Lucerne (Lu
(thern) available under trade names such as Etsuki Gum® GP, H, etc. from Clay Products.

Attapulgite clay is produced by Engelhardt Minerals.
and Chemicals: Corporation under the trade name "Atagel"®, ie, Atagel 40, Atagel 50, and Atagel 150. Mixtures of smectite and attapulgite types in a weight ratio of 4=1 to 1:5 are also useful in the present invention. Thickening or suspending agents of the above type are well known in the industry and are described, for example, in US Pat. No. 3,985,668, cited above.

Abrasives or abrasives scratch the surfaces of precision ceramics, crystals, etc. and should be avoided in LADD compositions.

When used in combination with fatty acids or fatty acid polyvalent metal salts, the clay thixotropic thickener may contain from 0.1 to 3%;
Preferably 0.1 to 2.5%, more preferably 0.1
It is used in an amount of 2%.

When clay thixotropic thickeners are used alone as thixotropic thickeners, the weight of the formulation is about 1.
It can be used in amounts of 5 to 8%, preferably 2 to 5%.

Generally, the effectiveness of LADD is determined by (a) the available chlorine level;
It is directly related to (b) alkalinity, (C) solubility in the cleaning medium, and (d) suds suppression. In the present invention, the pH of the LADD composition is at least about 9.5, more preferably about 10.5 to 13.5, and most preferably about 11.
．． It is preferable that it is 5. At relatively low pH values, the LADD product is too viscous, i.e., solid, and is therefore easily dissipated under the shear levels created in the dispensing device cup under normal mechanical operating conditions. is not liquidized. Addition of NaOH is thus often required to increase the pH within the above range and increase flow properties. The presence of carbonate is also often required in the present invention, as carbonate acts as a buffer to help maintain the desired pH level. However, excess carbonate causes the formation of carbonate needles,
Excess carbonate should be avoided, as it thereby impairs the stability, thixotropy and/or washability of the LADD product, and at the same time impairs the dispensing properties of the product, for example from a dispensing tube. Caustic soda (NaOH) further serves the function of neutralizing the phosphoric or phosphonic acid ester suds suppressant when present, approximately 0.5 to 3% by weight of NaO in the LADD composition.
H and about 2 to 9% by weight sodium carbonate are typical, although it should be noted that sufficient alkalinity may be provided by NATPP and sodium silicate.

NaTPP may be used in the LADD composition in the range of about 8 to 35% by weight, preferably about 20 to 30% by weight, and preferably decomposes or decomposes the preferred sodium hypochlorite and other chlorine bleach compounds. It should not contain heavy metals, which tend to be inert. NaTPP may be anhydrous or hydrated and includes a stable water salt or higher with a degree of hydration of 6, corresponding to about 18% water by weight. In fact, considering the stability of the hexahydrate salt, the presence of some aqueous phase water is extremely beneficial, as it forms seeds of stable hole water salts that promote hydration and solubilization of the remaining NaTPP particles. It is considered useful. If only hexahydrate is used, the detergent product will be too liquid but not runny. Conversely, if only anhydrous NaTPP is used, it may be too viscous and therefore unsuitable in some cases. A particularly preferable LADD compound is, for example, 0.5
: 1 to 2:1 weight ratio of anhydrous NaTPP to hexahydrate N
A value of about 1:1 obtained when using aTPP is particularly preferred.

Foam control is important to increase dishwasher efficiency and to minimize destabilizing effects due to the presence of excessive suds within the washer during use. Foaming can be significantly reduced by appropriate selection of the type and/or amount of detergent actives that are the main foam-forming components.

The degree of foaming also depends somewhat on the hardness of the washing water in the machine,
Appropriate adjustment of the proportion of water softening NaTPP may help provide the desired degree of foam control. However, it is generally preferred to include chlorine bleach-stable suds suppressants or inhibitors, particularly effective are e.g.
alkylphosphonic acid esters of the formula % formula % available from Wyandotte (PCUK-PAE) and, in particular, for example Hookah (SAP) and Natpsack (LPKn
-158), wherein one or both R groups in each type of ester are independently 012-2
These two types may represent 0 alkyl groups,
or any other chlorine bleach-stable mixtures, or mixtures of mono- and di-esters of the same type;
may be used. Particularly preferred are mixtures of mono- and di-C+S-+a alkyl acid phosphate esters, such as monostearyl/distearyl phosphate 1.2/1 (Knapsack). When used, the composition contains 0
．． 01 to 5% by weight, preferably 0.1 to 5% by weight,
In particular, about 0.1 to 0.5% by weight of suds suppressor is typical, with the weight ratio of detergent active ingredient (d) to suds suppressant (e) generally being about 10; 1=1, preferably about 4
=1 to 1:1. Other defoamers that can be used include, for example, the known silicones.

Any chlorine bleach compound such as dichloro-isocyanurate, dichlorodimethylvidantoin, or chlorinated TSP may be used in the compositions of the present invention, as well as alkali metals such as potassium, lithium, magnesium and especially Sodium hypochlorite is preferred. The composition should contain enough chlorine bleach compound to provide about 0.2 to 4.0% by weight by acidifying 100 parts of it with excess hydrochloric acid. Approximately 0.2 to 4
．． Solutions containing 0% by weight sodium hypochlorite contain or provide approximately the same percentage of available chlorine. Solutions containing about 0.8 to 1.6% by weight hypochlorite contain about 0.8 to 1.6% available chlorine, and are particularly preferred, such as from about 11 to about 13% available. A solution of chlorine in sodium hypochlorite (NaOCI) may advantageously be used in an amount of about 3 to 20%, preferably about 7 to 12%.

Sodium silicate, which provides alkalinity and protection of hard surfaces such as fine china glazes and patterns, ranges from about 2.5 to 40% by weight in the composition, preferably from about 10 to 35% by weight. used in amounts of At the higher levels specified herein, such as greater than about 10% by weight,
Silicates also increase the anti-spot effect. Sodium silicate is generally preferably Na2O:SiO□
It is added in the form of an aqueous solution in a ratio of approximately 1=2.2 to 1+2.8, for example 1:2.4. Other components of the composition, especially N
The majority of the aOH1 sodium hypochlorite and suds suppressant may also be added in the form of an aqueous dispersion or solution.

Detergent actives to be useful here must be stable in the presence of chlorine bleaches, especially hypochlorite bleaches, and be organic anionic, amine oxide, phosphine oxide, sulfoxide or betaine water dispersible. Surfactant types are preferred, and the anionic substances mentioned at the beginning are most preferred. They are about 0.1 to 5%
, preferably in an amount ranging from about 0.3 to 2.0%. Particularly preferred surfactants here are linear or branched alkali metal mono- and/or di(Cm-
+4) Alkyldiphenyl oxide mono- and/or disulfates, commercially available e.g. Dowfax® 3B-2 and Dowfax 2A-
Available as 1.

Additionally, the surfactant should be compatible with the other ingredients of the composition. Other suitable surfactants include primary alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, and secondary alkyl sulfates such as sodium dodecyl sulfate and sodium tallow alcohol sulfate. , alkyl sulfate; sodium-
Sodium C such as hexadecyl-1-sulfonate
+o-+s alkane-sulfonates; and sodium C, such as sodium dodecylbenzenesulfonate
Corresponding potassium salts, including alkylbenzene sulfonates, may also be used.

As other suitable surfactants or detergents, amine oxaf surfactants are typically those with the structure R2R'NO, where each R represents a lower alkyl group, such as methyl, and R ' has a carbon atom number of 8 to 2
Instead of amine oxides representing two long-chain alkyl groups, for example lauryl, myristyl, valmityl or cetyl groups, the corresponding surfactants phosphine oxide R2R'PO or sulfoxide RR'SO
can be used. Betaine surfactants are typically of the structure R,R'N-R''C00: where each R represents a lower alkylene/group of 1 to 5 carbon atoms; Specific examples of surfactants are lauryl dimethylamine oxide, myristyl dimethylamine oxide, the corresponding phosphine oxides and sulfoxides, and dodecyldimethylammonium acetate, tetradecyldimethylammonium pentanoate, hexadecyldimethylammonium hexanoate, It is an equivalent betaine containing such as.

For biodegradability, the alkyl groups in these surfactants should be linear, and such compounds are preferred.

Surfactants of the above type, all well known in the industry, are described, for example, in US Pat. Nos. 3,985.668 and 4,271,030.

The amount of water included in these compositions must, of course, not be so high as to result in unreasonably low viscosity and low flow, nor must it be so low as to result in unreasonably high viscosity and low flow. , in both cases the thixotropic properties are reduced or destroyed. Although such amounts are readily determined by routine experimentation in any particular instance, - about 25 to 75% by weight, preferably about 50 to 6
It is in the range of 5% by weight. The water should also preferably be deionized or softened. These amounts of water in the composition include water added as part of a liquid solution of other ingredients, but do not include water added as part of a liquid solution of other ingredients, such as in NaTPP hexahydrate. Contains no bound water such as water.

Other conventional formulation ingredients may be included in small amounts, generally less than about 3% by weight, such as hydrotropes such as sodium benzene, toluene, xylene and cumene sulfonates, preservatives, etc. agents, dyes and pigments, all of which are of course stable to chlorine bleach compounds and high alkalinity (nature of all ingredients). Particularly preferred for coloring are chlorinated phthalocyanine and aluminosilicate polysulfides, which provide pleasant green and blue hues, respectively.

The liquid ADD compositions of the present invention can be used to wash dishes, glasses, cups, cutlery, etc. in an automatic dishwasher equipped with a suitable detergent dispenser in an aqueous wash bath containing an effective amount of the composition. can be easily used in known ways to

Preferred implementation of the invention Ra! In , an aqueous liquid dishwashing detergent composition is formulated using the ingredients listed below.

LU Rinen χ Alkali metal tripolyphosphate 10-25 Sodium silicate (47.5%) 20-
40 Silica film formation inhibitor
1-4 polyacrylic acid polymer or salt
3-12 Alkali metal carbonate
2-8 Chlorine bleach stable water-dispersible organic detergent actives 0.5-3 Chlorine bleach stable suds suppressor
0.10-3 chlorine bleach compound
0.2-4 fatty acid thixotropic thickener 0.03-0.5 sodium hydroxide 2-6 remaining water The thixotropic aqueous liquid automatic dishwashing detergent compositions of the present invention can be prepared by adding conventional dishwashing detergent compositions. can contain agents. The formulations can be made with commercially available solid powder builders and/or the formulation ingredients can be mixed and the formulations can be ground to the desired particle size.

The invention may be implemented in various ways and a number of specific embodiments are set forth to illustrate the invention with reference to the accompanying examples.

The amounts and proportions referred to herein are by weight percent of the composition, unless otherwise specified.

The invention is further illustrated by the following examples.

An aqueous, aqueous, liquid automatic dishwashing detergent composition is prepared from the following ingredients in the amounts specified.

LU Kamemi% Deionized Water 24.05 Natsupzak LPKN-158 Foaming Inhibitor NI
Q, 15 Sodium hydroxide (50%)
5.00 Sodium carbonate (anhydrous)
5.00 Sodium tripolyphosphate (anhydrous) 20.00 Silica film formation inhibitor = 21 2.5 Sodium polyacrylate polymer builder 131 (^4.)
s, o.

Stearic acid thixotropic thickener 0.
10 Daufax 3B-2 Surfactant '4'
0.80 Sodium hypochlorite (11%)
9.10 Sodium silicate (1/2.23
．． 47%) 25.29100.00 (1) Mono- and di-stearyl phosphoric acid (C+ s
C+ s ) mixture of alkyl esters, molar ratio 1:
1.3°(2) Silica Thyroid 244 has a particle size of approximately 4 microns and is available from the company.

(3) 7) L, :7 Subers 149, molecular weight approximately 2000, available as a 40% solution.

(4) Sodium Seven-No and Di-decyl diphenyl ether disulfonate (45% solution) These ingredients are added to water, generally in the order listed, and stirred gently until a homogeneous mixture is obtained.

The formulation was tested by washing glassware and dishes in an automatic dishwasher in hard water (300 ppm hardness) at a temperature of 120°F, and clean, dry dishes had a clear film. There are almost no obvious spots.

K1 Dish - To demonstrate the effect of adding a silica anti-filming agent, formulations are made with and without a silica anti-filming agent and compared to commercially available powder detergent compositions.

The composition is formulated to contain the following ingredients.

These ingredients are added to water, generally in the order listed, and stirred gently until a homogeneous mixture is obtained. The formulation is tested by washing glassware at 120°F in hard water (300 ppm hardness).

Three of the above formulations (A), (B), and (C) were tested and compared to commercially available powder automatic dishwasher detergent formulations. These formulations were tested in a Kenmore automatic dishwasher using the procedure described in STM D3566-79, but using only 4 clean cycles. Film formation and spotting are evaluated according to the following scale:

Ryomin Chuen Toho x1 1. Best, no clear film, 2. Film formation is weak and becoming clear.

3. The number of recognizable films is increasing.

4. Continuous increase in remarkable film thickness 5. Film formation gets worse 6. Severe film formation and accumulation.

7. Continuous increase in severe film formation Hikihi 1”j11 Tanhama A1 Best, no spots.

B. There are almost no clear spots.

C9 clear, D. Remarkable coverage, approximately 50% The results obtained are reported in Table 1 below.

Table-1 (A) Silica/Polyacrylate B 1-
2(B) No silica/polyacrylate B-C5-6
(C) No silica/polyacrylate B-C2 (D)
Commercially available powder detergent B-CB-4 Kawagawa" L
- A utilixotropic aqueous liquid automatic dishwashing detergent composition is prepared from the following ingredients in the amounts specified.

Each ingredient is added to the water, generally in the order listed, and stirred until a homogeneous mixture is obtained. These formulations are tested by washing glassware at 130° F. in hard water (300 ppm hardness).

Two formulations were tested and compared to commercial powder automatic dishwasher detergent composition H. The formulation was tested in a Kenmore automatic dishwasher using the procedure described in STM [1356B-79, but using only 4 washes.

Spot occurrence and film formation were evaluated in the same manner as in Example 2, and the results obtained are reported in Table 2 below.

Table-) (E) Silica/Polyacrylate) A 2 (F)
No Silica/Polyacrylate A4 (G) No Silica/Polyacrylate B 2-3 (H) Commercial Powder Detergent B-C5-6K1 Dish-A A thixotropic aqueous liquid automatic dishwashing detergent composition defined from the following ingredients. Mix in the amount
Kamei% deionized water
34.7! Sodium tripolyphosphate (anhydrous) 12.01
Sodium tripolyphosphate (hexahydrate)
12.0 Silica film formation inhibitor
2.0 Sodium polyacrylate
) (MW 2000) 6.0 Dowfax 3B-2 Surfactant
0.8 graphitol green
-Vehicle 100.0 The ingredients are mixed according to the procedures of common assignee's co-pending patent application No. 903,924, filed September 5, 1986, which application is incorporated herein in its entirety. ).

Mix the mixture in glassware at 130°F with hard water (300 hardness).
ppm) by washing in an automatic dishwasher.

The thixotropic aqueous liquid automatic dishwashing detergent compositions of the present invention provide improved film-forming properties.

The invention is not to be limited by the above disclosure and examples, which are given by way of example only. The invention is to be construed in accordance with the scope of the following claims.

Procedural Amendment December 22, 1988 Patent Application No. 272849 2 Title of Invention Thixotropic Aqueous Liquid Cleaning Dish Composition for Automatic Dishwashing Machine 3
, Relationship with the case of the person making the amendment Patent applicant address Name: Colgate Vermolive Company 4, Agent address: Shin-Otemachi Building 206-ku 5, 2-2-1 Otemachi, Chiyoda-ku, Tokyo, Application subject to amendment Application form stating the person's representative name

Claims (1)

[Claims] 1. Water; at least one component selected from the group consisting of organic detergents, chlorine bleaches, detergent builders, sequestering agents, foam inhibitors, and mixtures thereof; from about 0.5 to 5
% silica anti-filming agent; about 2% to 14% polyacrylic acid polymer or salt; and a sufficient amount of a thixotropic thickener to provide a thixotropic index of about 2.5 to 10; Aqueous liquid automatic dishwasher detergent composition. 2. the silica film formation inhibitor in an amount of about 1 to 4%;
The composition of claim 1, wherein the polyacrylic acid polymer or salt is in an amount of about 3 to 12%. 3. By weight, about (a) 5 to 35% detergent builder, (b) 2.5 to 40% sodium silicate, and (c) 0.5 to 5% with a particle size of about 0.1 to 10 microns. Silica film formation inhibitor, (d) 1000 to 1
(e) 0 to 9% alkali metal carbonate; (f) 0.1 to 5% chlorine bleach stable. a water-dispersible organic detergent active; (g) 0 to 5% chlorine bleach-stable suds suppressor; (h) a chlorine bleach compound in an amount to provide about 0.2 to 4% available chlorine; (i ) a thixotropic thickening agent in an amount sufficient to provide a thixotropic index of about 2.5 to 10; (j) 0 to 8% sodium hydroxide; (k) the balance water; Automatic dishwasher composition. 4. The polyacrylic acid polymer or salt has the formula ▲mathematical formula, chemical formula, table, etc.▼, where R_1, R_2, and R_3 can be the same or different, and hydrogen, C_1
-C_4 lower alkyl, M represents hydrogen or an alkali metal, n=5 to 1000,
4. The composition of claim 3, wherein the polymer has a molecular weight of 1000 to 100,000. 5. Approximately 0.03 to 0.5% thixotropic thickener
4. The composition of claim 3, comprising an amount of long chain fatty acids. 6. Approximately 0.02 to 1.0% thixotropic thickener
4. The composition of claim 3, comprising a polyvalent metal salt of a long chain fatty acid in an amount of . 7. The composition of claim 5 further comprising a clay thixotropic thickener in an amount of about 0.1 to 3.0. 8. The composition of claim 6 further comprising a clay thixotropic thickener in an amount of about 0.1 to 3.0%. 9. The composition of claim 3, wherein the silica anti-filming agent has a particle size of about 0.5 to 8.0 microns. 10, by weight, about (a) 5 to 35% alkali metal tripolyphosphate, (b) 2.5 to 40% sodium silicate, (c) 1 to 4%, particle size of about 0.5 to 8.0 micron silica film formation inhibitor, (d)3
(e) from 0 to 9% alkali metal carbonate; (f) from 0.1 to 5% of a chlorine bleach-stable water-dispersible organic detergent active. (g) 0 to 5% chlorine bleach stable suds suppressant; (h) a chlorine bleach compound in an amount to provide about 0.2 to 4% available chlorine; (i) about 2.5 to 10% chlorine bleach compound; A thixotropic aqueous liquid automatic dishwashing composition comprising: a thixotropic thickener in an amount sufficient to provide a thixotropic index; (j) 0 to 8% sodium hydroxide; (k) the balance water. 11. A polyacrylic acid polymer or salt has the formula ▲mathematical formula, chemical formula, table, etc.▼, where R_1 and R_3 are hydrogen, and R_2 is hydrogen or methyl, and M is hydrogen, sodium or potassium. 11. The composition of claim 10, wherein n=10 to 500 and the polymer has a molecular weight of 1500 to 50,000. 12. The composition of claim 10, wherein the polyacrylic acid polymer or salt has a molecular weight of about 2000. 13. The composition of claim 10, wherein the polyacrylic acid polymer or salt has a molecular weight of about 4,500. 14. The composition of claim 10, wherein the silica anti-filming agent comprises about 0.1 to 5% alumina, based on the weight of silica. 15. The composition of claim 10, wherein the silica has a particle size of about 1 to 5 microns. 16. The thixotropic thickener is about 0.03 to 0.2
Composition according to claim 10, consisting of long chain fatty acids with C_1_6 to C_2_0 carbon atoms in an amount of 0%. 17. The thixotropic thickener is about 0.06 to 0.8
11. The composition of claim 10, comprising a polyvalent metal salt of a long chain fatty acid having from C_1_6 to C_2_0 carbon atoms in an amount of %. 18. The composition of claim 17, wherein the polyvalent metal is one of aluminum, calcium, zinc, and magnesium. 19. The composition of claim 16 further comprising a clay thixotropic thickener in an amount of about 0.1 to 2.5%. 20. The composition of claim 17 further comprising a clay thixotropic thickener in an amount of about 0.1 to 2.5%. 21. Soiled glassware in an automatic dishwasher, comprising contacting the soiled dishes in an automatic dishwasher in an aqueous wash bath having an effective amount of the composition of claim 3 dispersed therein; How to clean dishes. 22. Contacting the soiled glassware and dishes in an automatic dishwasher in an aqueous washing bath having an effective amount of the composition of claim 10 dispersed therein. How to clean dishes.