JP2766064B2 - Stable thickening liquid cleaning composition containing bleach - Google Patents

Abstract

Liquid cleaning compositions displaying enhanced physical stability in the presence of bleach are provided, comprising a chlorine bleach ingredient, cross-linked polycarboxylate polymer, a rheology stabilizing agent, and a buffering agent to maintain the pH of the composition above about 10. Preferred liquid automatic dishwashing detergent compositions containing builder and optional surfactant and metalate, and displaying shear thinning behavior, are disclosed.

Description

Description: TECHNICAL FIELD The present invention incorporates a chlorine bleach component, a cross-linked polycarboxylate polymer, a rheological stabilizer and a buffer, and exhibits enhanced physical stability in the presence of the bleach. It relates to a liquid cleaning composition. One particular application is for builder and optional surfactants and metalates (metala
liquid dishwashing detergent compositions additionally containing te) and exhibiting shear thinning behavior, i.e. high viscosity at low shear rates, low viscosity at high shear rates.

BACKGROUND OF THE INVENTION A thickened aqueous cleaning composition is disclosed in U.S. Patent No. 3,843,54.
No. 8, 3,558,496, 3,684,722, 4,005,027, and 4,116,851 are known and known.

The use of bleach in cleaning household items is disclosed and known in U.S. Pat.Nos. 3,928,065, 3,708,429, 3,058,917, and 3,671,440. .

The use of polycarboxylate polymers in cleaning compositions is disclosed in U.S. Pat.
71,440, 4,392,977, 4,147,650 and 4,836,949, UK Patent 1527706
As disclosed in US patent application Ser.

The use of benzoic acid or a salt or derivative thereof in a cleaning composition is disclosed in U.S. Pat.Nos. 4,810,409, 4,810,413, 4,576,728, 3,
Known as taught in 932,316 and 4,333,862.

However, none of the above patents disclose the present compositions containing a crosslinked polycarboxylate polymer, a chlorine bleach component, a rheology stabilizer and a buffer.

SUMMARY OF THE INVENTION The composition of the present invention comprises, by weight: (a) a chlorine bleach component that provides 0.2% to 2.5% available chlorine; (b) about 0.1% of a crosslinked polycarboxylate polymer thickener.
~ 10%; formula (c) (Wherein each of X, Y, and Z is -H, -COO ^- M ⁺ , -Cl,
_{^{-Br, -SO 3 - M +,}} -NO 2, a -OCH ₃ or C ₁ -C ₄ alkyl,, M is rheology stabilizers or mixtures thereof 0.05% having an a) H or an alkali metal
５5%; and (d) a liquid cleaning composition comprising sufficient alkaline buffering agent to provide the composition with a pH greater than about 10.

 Particularly preferred embodiments of the invention include: (a) 0% to about 5% of a detergent surfactant; (b) about 5% to about 50% of a detersive builder substance; % To about 1% of a liquid automatic dishwashing detergent composition.

DETAILED DESCRIPTION OF THE INVENTION The composition of the present invention comprises four essential components: a chlorine bleach component, a crosslinked polycarboxylate polymer thickener, a rheology stabilizer, and an alkaline buffer.

Chlorine bleach component The composition contains a bleach component that produces hypochlorite species in an aqueous solution. Hypochlorite ion is
Chemically formula OCl ^- represented by. The hypochlorite ion is a strong oxidizing agent and the substance that produces this species is considered a strong bleaching agent.

The strength of the aqueous solution containing hypochlorite ions is
Measured by available chlorine. This is the oxidizing power of the solution as measured by the ability of the solution to release iodine from the acidified iodide solution. One hypochlorite ion has an oxidizing power of two atoms of chlorine, that is, one molecule of chlorine gas.

At lower pH levels, aqueous solutions prepared by dissolving the hypochlorite-generating compound contain active chlorine, partially in the form of hypochlorite moieties, partially in the form of hypochlorite ions. Above a pH level of about 10, ie, at the pH level of the composition, essentially all (more than 99%) of the active chlorine is reported to be in the form of hypochlorite ions.

Bleaches that produce hypochlorite species in aqueous solution include hypochlorites, hypochlorite addition products of alkali metals and alkaline earth metals, chloramine, chlorimine, chloramide, and chlorimide. Specific examples of such compounds include sodium hypochlorite,
Potassium hypochlorite, monobasic calcium hypochlorite,
Dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate, sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3
-Dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, dichloramine T, chloramine B and dichloramine B. Preferred bleaches for use in the compositions of the present invention are sodium hypochlorite, potassium hypochlorite, or mixtures thereof.

Most of the hypochlorite-forming bleaches are available in solid or thick form and dissolve in water when preparing the compositions of the present invention. Some of the above substances are available as aqueous solutions.

The bleach dissolves in the aqueous liquid component of the composition.
Bleach is available chlorine from about 0.2 to about 2.5% by weight of the total composition,
Preferably about 0.5-1.5% by weight of available chlorine can be provided.

Polymeric Thickener The thickener in the composition of the present invention is a crosslinked polycarboxylate polymer thickener. The polymer preferably has a molecular weight of from about 500,000 to about 5,000,000, more preferably about 5,000,000.
It has from 750,000 to about 4,000,000.

The polycarboxylate polymer is preferably a carboxyvinyl polymer. Such compounds are disclosed in U.S. Pat.
It is disclosed in the specification of 2,798,053. The preparation of carboxyvinyl polymers is also disclosed in the aforementioned U.S. Pat. No. 2,798,053.

The carboxyvinyl polymer is a polyether of a monomeric olefinically unsaturated carboxylic acid and a polyhydric alcohol from about 0.1 to about 10% by weight of the total monomers (the polyhydric alcohol has at least 4 carbon atoms, Polyethers have at least three hydroxyl groups attached to these carbon atoms and the polyether contains more than one alkenyl group per molecule). Other monoolefinic monomeric materials, if desired, may be present in the monomer mixture, even in major proportions. Carboxyvinyl polymers are substantially insoluble in liquid volatile organic hydrocarbons and are dimensionally stable upon exposure to air.

Preferred polyhydric alcohols used to form the carboxyvinyl polymer include oligosaccharides, reduced derivatives of carbonyl groups converted to alcohol groups, and polyols selected from the group consisting of pentaerythritol. Sucrose or pentaerythritol is most preferred. Preferably, the hydroxyl groups of the modified polyol are etherified with allyl groups (the polyol has at least two allyl ether groups per polyol molecule). When the polyol is sucrose, it preferably has at least about 5 allyl ether groups per sucrose molecule. Preferably, the polyol polyether comprises from about 0.1% to about 4%, more preferably from about 0.2% to about 2.5% of the total monomer.

Preferred monomeric olefinically unsaturated carboxylic acids for use in producing the carboxyvinyl polymer used herein include monomeric polymerizable α-β monoolefinically unsaturated lower aliphatic carboxylic acids. Can be Construction Wherein R is a substituent selected from the group consisting of hydrogen and a lower alkyl group.
Acrylic acid is most preferred.

 Various carboxyvinyl polymers are available from New York, NY
Product name from B.F.Goodrich Company of New York
Carbopol ). these
Polymers are carbomer or polyacrylic
Also known as luic acid. Cals useful in the formulations of the present invention
It has a molecular weight of about 750,000 as a boxy vinyl polymer
Carbopol 910, a carbohydrate having a molecular weight of about 1,250,000
Paul 941, and molecular weights of about 3,000,000 and 4, respectively.
Carbopol 934 and 940 with 000,000
You.

Preferred polycarboxylate polymers of the present invention are crosslinked with a polyalkenyl polyether and have a molecular weight of about 750,
Non-linear, water-dispersible polyacrylic acid having from 000 to about 4,000,000.

 These polycarboxylates for use in the present invention
A highly preferred example of a polymer is Sokalan P
HC-25 Poria available from BASF Corporation
Crylic acid, obtained from 3-V Chemical Corporation
Polygel DK and B.F.
From the Carbopol 600 family of resins, especially
Lubopol 614, 616 and 617. These are 900
Higher cross-linking than Rubopol series polymers, molecular weight
It is believed to have about 1,000,000 to 4,000,000. here
Mixtures of polycarboxylate polymers as described also
It may be used in the present invention.

The polycarboxylate polymer thickener is preferably
Used essentially without clay thickener. The reason for this is that the presence of clay usually results in less desirable products having phase instability. In other words, the polycarboxylate polymer is preferably used as a thickener in the present composition instead of clay.

The polycarboxylate polymer thickener in the compositions of the present invention is present in an amount from about 0.1% to about 10%, preferably from about 0.25% to about 5%, and most preferably from about 0.5% to about 2%.

In a preferred liquid automatic dishwashing detergent composition, the polycarboxylate polymer thickener has an apparent viscosity at high shear of about 500 centipoise or more and an apparent yield value of about 40 to about 8
00, most preferably from about 60 to about 600 dynes / cm ^{2 is provided} to the composition.

Yield number is an indication of the shear stress at which gel strength is exceeded and flow begins. The yield value is about 77 ° F (25 ° C) using a Helipath drive at the time of the related reading in the present invention.
Measured with a Brookfield RVT model viscometer having a T-bar B spindle. The system was set to 0.5 rpm,
Torque readings are taken after 30 seconds for the composition under test or after the system has stabilized. System stops, rpm is
Reset to 1.0 rpm. Torque readings are taken after 30 seconds for the same composition or after the system has stabilized.

 Apparent viscosity is measured using a Brookfield viscometer.
Calculate from torque readings using a factor. Then
The apparent or Brookfield yield value is calculated as follows:
Calculate: Brookfield yield value = (apparent at 0.5 rpm)
Viscosity-apparent viscosity at 1 rpm) / 100. This is B.F.
Carboball from the Drich Company Literature and
This is a common calculation method published in other publications. here
In most cases of the cited formulation, this apparent yield value
Is the shear rate and stress in more demanding rheology equipment
It is approximately four times higher than the yield value calculated from the measurements.

The apparent viscosity at high shear, reading the torque in 30 seconds,
Brookfield RVT with spindle # 6 at 0 rpm
Measure with a viscometer.

Rheological stabilizers Rheological stabilizers useful in the present invention have the formula (Wherein each of X, Y, and Z is -H, -COO ^- M ⁺ , -Cl,
_{^{-Br, -SO 3 - M +,}} -NO 2, a -OCH ₃ or C ₁ -C ₄ alkyl,, M has a a) H or an alkali metal. Examples of this component include pyromellitic acid (i.e., where X, Y and Z are -COO ^- H ⁺ ), hemimellitic acid and trimellitic acid (i.e. X and Y are -COO ^- H ^+).
And Z is -H).

Preferred rheology stabilizing agents of the present invention, sulfophthalic acid (i.e., X is -SO ₃ ^- is H ^+, Y is -COO ^- a H ^+,
Z is -H), other monosubstituted phthalic and disubstituted benzoic acids, and alkyl-, chloro-, bromo-,
Sulfo -, nitro - and carboxy - benzoate (i.e., Y and Z are -H, X each C ₂ -C _{4 ^{alkyl, -Cl, -Br, -SO 3 -}} H +, -NO 2, and the case is -OCH _3).

Highly preferred examples of rheology stabilizers useful in the present invention are benzoic acid (i.e., where X, Y and Z are -H); phthalic acid (i.e., X is -COO ^- H ⁺ , Y and If Z is -H); and toluic acid (X is -CH ₃
And Y and Z are -H) and mixtures thereof.

All of the above rheological stabilizers are in the acidic form of the species, ie, M is H. The invention also seeks to cover salt derivatives of these species (ie M is an alkali metal, preferably sodium or potassium). In fact, since the pH of the composition of the invention is in the alkaline range, the rheology stabilizer is present in the aqueous composition of the invention mainly as an ionized salt. Also, certain of the above-mentioned anhydrous derivatives, such as pyromellitic dianhydride, phthalic anhydride, sulfophthalic anhydride, etc., are intended to be included in the present invention.

Mixtures of rheology stabilizers as described herein may also be used in the present invention.

This component is present in an amount from about 0.05 to about 2%, preferably from about 0.1 to about 1.5%, most preferably from about 0.2 to about 1% by weight of the composition.

Crosslinked polymers such as those used in the bleach-containing compositions of the present invention, especially those of high molecular weight, are susceptible to bleach-initiated degradation, resulting in unacceptable loss of rheology for some applications. Some small percentage of chlorine bleach components are present in solution in the form of free radicals, ie, molecular fragments having one or more unpaired electrons. These free radicals have a short lifetime but are highly reactive and may initiate some other types of degradation, including crosslinked polycarboxylate polymers, in solution via a growth mechanism. The polymers of the present invention are susceptible to this degradation due to putative oxidative sites present in the crosslinked structure.

The addition of a small amount of a rheological stabilizer substantially increases the physical stability of the composition of the present invention, ie, the rheological stability when added. Without being limited by theory,
Rheology stabilizers are believed to function as free radical scavengers to tie up the highly active species in the composition and prevent them from attacking the degradation sensitive structure of the polycarboxylate polymer.

However, surprisingly, other free radical scavengers cannot react with the chlorine bleach or interfere with the interaction between the bleach component and the polymer thickener, so the present invention provides a rheologically stable agent. Ineffective as an agent. One preferred rheology stabilizer here is benzoic acid. Benzoates have been technically characterized as weak radical scavengers and almost ineffective in alkaline media. However, phthalic and toluic acids, which have not been characterized as radical scavengers, function effectively as rheology stabilizers.

Buffer In this composition, the undiluted composition ("as is")
It is also desirable to include one or more buffers which can generally maintain the pH of the composition within the alkaline range when measured with a pH meter as the pH of the composition. It is within this pH range that the optimum performance and stability of the bleach is achieved, and it is also within this pH range that the optimal chemical and physical stability of the composition is achieved. .

Maintaining the pH of the composition above about 10, preferably above about 11.5 minimizes the undesirable chemical degradation of active chlorine, hypochlorite-forming bleach. Maintaining this particular pH range also minimizes the chemical interaction between the strong hypochlorite bleach and the surfactant compound present in the composition. Finally, as noted above, high pH values, such as those maintained by optional buffers, help to enhance soil removal and stain release when utilizing the present compositions.

The composition pH should be within the alkaline pH range, preferably 10 to about 13
Any compatible substance or mixture of substances that has the effect of keeping within the range can be used as a buffer in the present invention. Such materials include, for example, various water-soluble inorganic salts, such as carbonates, bicarbonates, sesquicarbonates, silicates, pyrophosphates, phosphates, tetraborate, and mixtures thereof. Can be

Examples of substances that can be used as a buffer alone or in combination here include sodium carbonate, sodium bicarbonate, potassium carbonate, sodium sesquicarbonate, sodium silicate, potassium silicate, sodium pyrophosphate, tetrapotassium pyrophosphate, phosphoric acid Tripotassium, trisodium phosphate, anhydrous sodium tetraborate, sodium tetraborate 5
Hydrates, potassium hydroxide, sodium hydroxide, and sodium tetraborate decahydrate. Combinations of these buffers, including both sodium and potassium salts, may be used. This includes a mixture of tetrapotassium pyrophosphate and trisodium phosphate at a weight ratio of pyrophosphate / phosphate of about 3: 1, tetrapotassium pyrophosphate and tripotassium phosphate at a weight ratio of pyrophosphate / phosphate of about 3: 1. And a carbonate / silicate weight ratio of about 1: 3 to about 3: 1, preferably about
Mixtures of 1: 2 to about 2: 1 anhydrous sodium carbonate and sodium silicate are included.

If present, the buffer substance is dissolved or suspended in the aqueous liquid component. Buffering agents generally comprise one of the total compositions.
To about 25% by weight, preferably about 2.5 to about 20% by weight.

Detergent Surfactant The composition of the present invention comprises a bleach-stable detergent surfactant at 0%
To about 5%, preferably about 0.1% to about 2.5%.

Desirable detergent surfactants generally include non-ionic detergent surfactants, anionic detergent surfactants, amphoteric detergent surfactants, zwitter detergent surfactants and mixtures thereof.

Examples of nonionic surfactants include: (1) 1 mole of a saturated or unsaturated straight or branched chain alcohol or fatty acid having about 10 to about 20 carbon atoms and about 4 to about 50 moles of ethylene oxide. Condensate with Specific examples of such compounds include condensates of 1 mol of coconut or tallow fatty acids with 10 mol of ethylene oxide; condensates of 1 mol of oleic acid and 9 mol of ethylene oxide;
Condensates of moles and 25 moles of ethylene oxide; the condensation products of tallow fatty alcohol 1 mole of ethylene oxide of about 9 moles; the condensation of C ₁₉ alcohol 1 mole of ethylene oxide 8 mol; condensation products of oleic alcohol 1 mol of ethylene oxide 10 mol And a condensate of 1 mol of C ₁₈ alcohol and 9 mol of ethylene oxide.

Condensates of fatty alcohols having 17 to 19 carbon atoms with about 6 to about 15 moles, preferably 7 to 12 moles, and most preferably 9 moles of ethylene oxide provide excellent spotting and film forming performance. More particularly, the fatty alcohol has 18 carbon atoms and ethylene oxide from about 7.5 to about 12,
It is desirable to condense with preferably about 9 moles. These various specific C ₁₇ -C ₁₉ ethoxylates, minor amounts (e.g., 2.5% to 3%) even at, and give a very good performance in large amounts (less than 5%), in particular low molecular weight _{(C. 1 to 5} ) When foamed with acid or alcohol moieties, the foaming properties are low enough to minimize or eliminate the need for foam inhibitors. Foam inhibitors generally act as loads on the composition and tend to impair long term spotting and film forming properties.

(2) Molecular weight of about 1,400 to about 30,000, for example, 20,000, 9,5
Polyethylene glycol or polypropylene glycol having 00, 7,500, 6,000, 4,500, 3,400, and 1,450. All of these materials are available from 110 ° F (about 43 ° C) to 20 ° C.
A waxy solid that melts at 0 ° F (about 93 ° C).

(3) 1 mole of an alkyl phenol having an alkyl chain having about 8 to about 18 carbon atoms and about 4 to about 50 ethylene oxide.
Condensate with mole. Specific examples of these nonionic surfactants include the condensate of 1 mole of decylphenol and 40 moles of ethylene oxide; the condensate of 1 mole of dodecylphenol and 35 moles of ethylene oxide; the condensation of 1 mole of tetradecylphenol with 25 moles of ethylene oxide. Condensates: Condensates of 1 mol of hectadecylphenol with 30 mol of ethylene oxide.

(4) _{HO (C 2 H 4 O)} x (C 3 H 6 O) y (C 2 H 4 O) x H or _{HO (C 3 H 6 O)} x (C 2 H 4 O) x (C ₃ H ₆ ) _y H (where the sum y is at least 15 and the sum (C ₂ H
₄ O) is equal to the total weight of 20% to 90% of the compound, molecular weight of about 2,000 to about 10,000, preferably polyoxypropylene polyoxyethylene condensates having from about 3,000 to about 6,000). These substances are, for example, Pluronics, which are well known in the art.

(5) propylene oxide, butylene oxide and / or
Or compounds of (1) or (4) blocked with short-chain alcohols and / or short-chain fatty acids, for example those having 1 to about 5 carbon atoms, and mixtures thereof.

Useful surfactants in detergent compositions has the formula _{RO- (C 2 H 4 O)} x R 1 [wherein, R is an alkyl or alkylene group having 17 to 19 carbon atoms, x is from about 6 to about 15 , Preferably from about 7 to about 12, and R ¹ is preferably hydrogen, C
_1-5 alkyl _{group, C 2 to 5} acyl group and the formula _{- (C y H 2y O)} n H ( wherein, y is 3 or 4, n is from 1 to about 4
Selected from the group consisting of groups having the following formulas:

Particularly suitable surfactants are the low foaming compounds of (4),
(5) Other compounds and _C17-19 substances of (1) having a narrow ethoxy distribution.

In addition to the above surfactants, other surfactants suitable for detergent compositions are described in U.S. Pat.Nos. 3,544,473, 3,630,9.
No. 23, 3,888,781 and 4,001,132.

Some of the surfactants are bleach stable, but some are not. When the composition contains hypochlorite bleach, the detergent surfactant is preferably bleach stable. Such surfactants desirably do not contain functional groups susceptible to oxidation by hypochlorite, for example, unsaturated and some aromatic, amide, aldehyde, methyl keto or hydroxyl groups.

Bleach-stable anionic surfactants, which are particularly resistant to hypochlorite oxidation, fall into two main groups. One such type of bleach-stable anionic surfactant is a water-soluble alkyl sulfate and / or sulfonate having about 8 to 18 carbon atoms in the alkyl group.
Alkyl sulfates are water-soluble salts of sulfated fatty alcohols. They are formed from natural or synthetic fatty alcohols having about 8 to 18 carbon atoms. Natural fatty alcohols include those produced by reducing the glycerides of naturally occurring oils and fats. Fatty alcohols can be produced synthetically, for example, by the oxo method. Examples of suitable alcohols that can be used in the production of alkyl sulfates include decyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol and mixtures of fatty alcohols derived by reducing the glycerides of tallow and coconut oil. Can be

Specific examples of alkyl sulfates that can be used in the detergent composition of the present invention include sodium lauryl alkyl sulfate, sodium stearyl alkyl sulfate, sodium palmityl alkyl sulfate, sodium decyl sulfate, sodium myristyl alkyl sulfate, potassium lauryl alkyl sulfate,
Potassium stearyl alkyl sulfate, potassium decyl sulfate, potassium palmityl alkyl sulfate, potassium myristyl alkyl sulfate, sodium dodecyl sulfate, potassium dodecyl sulfate, potassium tallow alkyl sulfate, sodium tallow alkyl sulfate, sodium coconut alkyl sulfate, magnesium coconut alkyl sulfate, coconut alkyl Calcium sulfate, coconut potassium alkyl sulfate and mixtures of these surfactants. Highly preferred alkyl sulfates are sodium coconut alkyl sulfate, potassium coconut alkyl sulfate, potassium lauryl alkyl sulfate and sodium lauryl alkyl sulfate.

Preferred sulfonated anionic surfactants are the alkali metal salts of secondary alkanesulfonic acids, examples of which are Hostapur SAS from Hoechst Celanese.
It is.

A second type of bleach-stable surfactant material that can be used in the present invention is a water-soluble betaine surfactant. These substances have the general formula: Wherein R ₁ is an alkyl group having about 8 to 18 carbon atoms; R ₂ and R ₃ are each a lower alkyl group having about 1 to 4 carbon atoms;
R ₄ is an alkylene group selected from the group consisting of methylene, propylene, butylene and pentylene) (propionate betaine decomposes in aqueous solution and is therefore not incorporated into the composition).

Examples of suitable betaine compounds of this type include dodecyldimethylammonium acetate, tetradecyldimethylammonium acetate, hexadecyldimethylammonium acetate, alkyldimethylammonium acetate (the alkyl groups are on average about 14.8 carbon atoms in length) , Dodecyl dimethyl ammonium butanoate, tetradecyl dimethyl ammonium butanoate,
Hexadecyl dimethyl ammonium butanoate, dodecyl dimethyl ammonium hexanoate, hexadecyl dimethyl ammonium hexanoate, tetradecyl diethyl ammonium pentanoate and tetradecyl dipropyl ammonium pentanoate. Particularly preferred betaine surfactants include dodecyldimethylammonium acetate, dodecyldimethylammonium hexanoate, hexadecyldimethylammonium acetate, and hexadecyldimethylammonium hexanoate.

 A useful nonionic surfactant is ethoxy.
And / or propoxylated nonionic surfactants, eg
For example, from BASF Corporation in New Jersey
Available ones are listed. Examples of such compounds include BA
Product name Pluronic available from SF Corporation
And Tetronic ) Sold in
Polyethylene oxide polypropylene oxide block
It is a copolymer.

Preferred of this type are blocked oxyalkylene oxide block copolymer surfactants of the following structure: Wherein I is the residue of a mono-, di- or polyhydroxyl compound; AO ₁ , AO ₂ and AO ₃ are oxyalkyl groups and _one of AO ₁ and AO ₂ is propylene oxide ( The corresponding x or y is greater than zero), the other of AO ₁ and AO ₂ is ethylene oxide (the corresponding x or y is greater than zero), and the molar ratio of propylene oxide to ethylene oxide is from about 2: 1 to about 2: 1.
8: 1; R and R ′ are hydrogen, alkyl, aryl,
Alkylaryl, arylalkyl, carbamate,
Or butylene oxide; w is equal to zero or one; z, x ', y' and z 'are greater than or equal to zero].

Other bleach-stable surfactants include amine oxides, phosphine oxides, and sulfoxides. However, such surfactants are usually high foaming. The disclosure of bleach-stable surfactants is disclosed in published UK Patent Application No. 2,116,199A, U.S. Pat.
No. 7, U.S. Pat.No. 4,116,851, U.S. Pat.
It can be found in 3,985,668, U.S. Pat. No. 4,271,030 and U.S. Pat. No. 4,116,849.

Other desirable bleach-stable surfactants are described in U.S. Pat.
Alkyl phosphonates as taught in 4,150,573.

Still other preferred bleach-stable anionic surfactants include Dowfax 3B-2 (n-
Sodium or decyl diphenyl oxide disulfonate) and the linear or branched alkali metal mono- and / or di-
( _C8-14 ) alkyl diphenyl oxide mono- and / or disulfonates. These and similar surfactants are disclosed in published UK Patent Application No. 2,
No. 163,447A, No. 2,163,448A, No. 2,164,35
It is disclosed in specification 0A.

Detergency builder A detergency builder is any substance that reduces the concentration of free calcium and / or magnesium ions in a surfactant-containing aqueous solution. In preferred liquid automatic dishwashing detergent compositions, the detersive builder comprises from about 5% to about 50%,
Preferably it is used in an amount of about 15% to about 40%. In general,
Detergent builders for use in liquid automatic dishwashing detergent compositions such as those of the present invention comprise from about 10% to about 40%, preferably from about 15%.
% To about 30% of sodium tripolyphosphate. Generally, some percentage of sodium tripolyphosphate is in the form of undissolved particulates suspended in the remainder of the detergent composition. The phosphate ester, if present in the composition, operates to keep such solid particles suspended in an aqueous solution.

The detersive builder substance can be any detersive builder substance known in the art. For example,
Trisodium phosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, potassium pyrophosphate, potassium tripolyphosphate, potassium hexametaphosphate, weight ratio of SiO ₁ : Na ₂ O from about 1: 1 to about 3.6:
Sodium silicate, sodium carbonate, sodium hydroxide, borax, sodium nitrilotriacetate, sodium carboxymethyloxysuccinate, sodium carboxymethyloxymalonate, polyphosphonates, salts of low molecular weight carboxylic acids, polycarboxylates having 1, Includes polymeric carboxylate such as polyacrylate or polymaleate, copolymers and mixtures thereof.

Some of the buffer substances additionally serve as builders. The buffer preferably contains at least one compound that can additionally act as a builder.

Alkali metal amphoteric metallate The optional component of the present invention is an alkali metal amphoteric metal anion (hereinafter referred to as metalate). This component,
Additional structuring can be provided to the polycarboxylate polymer thickener in preferred liquid automatic dishwashing detergent compositions.

The metalate in the liquid automatic dishwashing detergent composition of the present invention is present in an amount of 0% to about 1%, preferably about 0.01% to about 0.1%.

Amphoteric metals, such as aluminum, zinc, beryllium, tin, zirconium, metalates such as titanium,
Acting similarly in the present invention would provide this polymer structuring benefit. These materials are intended to be covered by the present invention. Preferred metalate is sodium potassium aluminate or aluminates, for example, a _{xM 2 O · yAl 2 O 3} · zH 2 O ( wherein, M is K or Na).

One method of incorporating the metalate into a preferred liquid automatic dishwashing detergent composition is to dissolve the amphoteric metal oxide in the aqueous alkali metal hydroxide in an amount greater than the molar equivalent of the hydroxide or to disperse it in a colloidal form. . Some metalates,
For example, sodium aluminate is commercially available.

The metalate has a pH of the mixture of about 10 or more, preferably about 10%.
It can be added to the composition at any time above 11.5.
A preferred method of incorporating the metalate into a preferred liquid automatic dishwashing detergent composition is to blend the metalate with an aqueous solution of an alkali metal silicate and then incorporate the other components of the liquid automatic dishwashing detergent composition into the resulting colloid. It is. Preferred structuring benefits are seen when the metallate is finely dispersed in the silicate such that the increased turbidity is little or nothing visible in the mixture.

Formulating a metalate such as aluminate in these compositions ensures that a cationic metal ion such as Al ⁺³ is not present for precipitating the silicate under such mixing conditions.

The lack of suspended solids or visible solids in the colloidal silicometallate (i.e., a particle size of about 1 micron or less) requires that the finished composition use sufficient potassium salt to ensure dissolution of the other components. Sometimes (i.e., a molar ratio of potassium to sodium ions of greater than about 1: 1, preferably about 3: 2
Greater molar ratio of potassium to sodium ions) allows for a transparent or translucent gel.

About 0% to about 15%, preferably about 3% to about
10% silicometallate is added to the polyacrylate polymer thickener to obtain additional structuring. The molar ratio of aluminum metal to SiO ₂ in the preferred colloidal dispersion to be prepared, about in order to benefit the best structured 0.01: 1
To about 0.1: 1, preferably from about 0.02: 1 to 1 to about 0.06: 1.

Other Optional Materials The compositions of the present invention may optionally include certain esters of phosphoric acid (phosphate esters). Phosphate esters have the general formula: (Wherein, R and R 'are C ₆ -C ₂₀ alkyl or ethoxylated alkyl group) material. Preferably, R and R 'have the general formula alkyl _{- (OCH 2 CH 2) Y} ( wherein the alkyl substituent is C ₁₂ ~
_C18 , Y has 0 to about 4). Most preferably, the alkyl substituent of the above formula is C ₁₂ -C ₁₈ and Y is from about 2 to about 4
It is. Such compounds are formed by known methods from phosphorus pentoxide, phosphoric acid, or phosphorus oxyhalides and alcohols or ethoxylated alcohols.

It will be appreciated that the above formulas represent mono- and di-esters, and commercially available phosphate esters will generally consist of a mixture of monoester, diester and some proportion of triester. Typical commercially available esters are trade names "Phospnolan" PDB3 (Diamond Shamrock), [Servoxil (Servoxil)
yl) ”VPAZ (Selvo), PCUK-PAE
(BASF Wyandotte), Sapuku (SAPC) (Hooker)
Available at KNH340N and KL340L (Hoechst) and monostearyl acid phosphate (Oxydental Chemical Corporation) are preferred for use in the present invention. Hostophat-TP-2253 (Hoechst) is most preferred for use in the present invention.

The phosphate esters useful herein provide protection for silver and silver plated household items surfaces. The phosphate component also acts as a foam inhibitor in the anionic surfactant-containing detergent compositions disclosed herein.

If used in the compositions of the present invention with a phosphate component, the phosphate component generally will comprise from about 0.1 to about 0.1% of the composition.
It is present at about 5% by weight, preferably about 0.15 to about 1.0% by weight.

Metal salts of long-chain hydroxy fatty acids have been found to be useful in automatic dishwashing detergent compositions to reduce fogging caused by repeated exposure of pure silver or silver plated dishes to bleach-containing automatic dishwashing detergent compositions. (US Patent No.
4,859,358). "Long chain hydroxy fatty acids" refer to fatty acids such as about 8 to about 22 carbon atoms, including the carbon atom of the carboxyl group of hydroxystearic acid;
Preferably about 10-20 carbon atoms, most preferably about 12
Higher aliphatic hydroxy fatty acids having 1818 carbon atoms are meant. "Metal salts" of long-chain hydroxy fatty acids
Both monovalent and polyvalent metal salts, especially sodium salts,
Potassium, lithium, aluminum and zinc salts are meant, for example, lithium salts of hydroxy fatty acids. Particular examples of this material are potassium hydroxystearate, sodium hydroxystearate, and especially lithium hydroxystearate. If a metal salt of a long chain hydroxy fatty acid is incorporated into the automatic dishwashing detergent composition of the present invention, this component will generally comprise from about 0.05 to about 0.05% of the composition.
It comprises about 0.3% by weight, preferably about 0.05 to about 0.2% by weight.

Conventional colorants and flavors may also be added to the composition to enhance aesthetic appeal and / or consumption tolerance. These substances should, of course, be of the type of dyes and fragrances which are particularly stable against degradation due to high pH and / or strong active chlorine bleach.

If present, the other optional materials generally comprise up to about 10% by weight of the total composition and dissolve in the composition.
Suspended or emulsified.

All percentages, parts and ratios used herein are by weight unless otherwise indicated.

The following examples illustrate the invention and facilitate its understanding.

EXAMPLES Example I A liquid automatic dishwashing detergent composition of the present invention is as follows. Ingredient weight% Sodium tripolyphosphate (STPP) 4.67 Tetrapotassium pyrophosphate (TKPP) 12.60 Sodium silicate (ratio 2.4) 3.27 Potassium carbonate (K ₂ CO ₃ ) 3.91 Sodium carbonate (Na ₂ CO ₃ ) 2.61 Available chlorine (added as NaOCl) 0.93 Potassium hydroxide (KOH) 0.84 Monostearyl acid phosphate (MSAP) 0.03 Polyacrylic acid (Socaran PHC-25) 1.07 Al ₂ O ₃ (added as sodium aluminate) 0.03 Rheological stabilizer (if added) 0.47 Adjusted KOH (pH 12.2 to 12.3) 0 to 0.3 Perfume, dye, water balance (100) Slurry polyacrylic acid at 3.4% by weight in demineralized water. While stirring with a paddle blade mixer, add all other ingredients in the following order: additional active conditioning water, 40
% TKPP as an aqueous solution, about 5% sodium aluminate in water (nominally 46.8% Al ₂ O ₃ ) and KOH (45% in water added before or premixed with colloidal aluminate dispersion). %), Solids in water 4
Silicate, sodium and potassium carbonate as 7.3% and STPP as a dry powder (dissolves essentially within 5 minutes), heated 2.6% aqueous dispersion of MSAP defoamer, rheology stabilizer. The acid or anhydride is neutralized by excess caustic already present in the composition. The heat is about the temperature of the mixture
Add to the mix by this point so that it is at least 130 ° F (54 ° C). This temperature is maintained for at least 5 minutes to facilitate sample equilibrium. After the composition cools below about 90 ° F (32 ° C), the aqueous sodium hypochlorite is reduced to about 13% available chlorine
Add as Optional flavors and colorants are added last. The composition is transparent or translucent and has no visible particles or turbidity. The balance water is added along with sufficient KOH adjustment to adjust the pH of the composition "as is" to 12.2 to 12.3 and additional KOH cook is used if necessary after equilibration overnight.

After about 1-3 days of equilibrium, a sample of the composition had an apparent Brookfield yield of about 250-450 dynes / cm ² , an apparent viscosity at high shear (100 rpm, Brookfield RVT # 6) of about 1300-2000 cps, and a medium It shows an apparent viscosity of about 4000-7000 cps at shear (20 rpm, Brookfield RVT # 6).

Record the physical properties and place the sample in a light-shielded bottle at 100 ° F under ambient conditions.
(38 ° C) and 120 ° F (49 ° C). Brookfield apparent viscosity is measured on a Brookfield RVT model with a # 6 spindle at 100 rpm. 120 ゜ F (49
C), the following viscosity readings are taken at weekly intervals. The day after the composition adjustment is the first day.

It can be seen that a benzene ring having one or two carboxylic acid groups can be more than twice the rheological life of the composition under such storage conditions. Obviously, the four carboxyl functions on the ring show reduced benefit and more than four carboxyls result in essentially no stability benefit. Note that the viscosity usually increases early in the week and is believed to be due to continuous polymer swelling with caustic and bleach.

Addition of benzoic acid or substituted benzoic acid usually results in lower initial viscosity compared to formulations without additives,
Dramatically improved storage stability formulations are achieved.

Example II Benzoic acid and benzoates have been identified as potential free radical scavengers in the published literature. Other liquid automatic dishwashing detergent compositions using known free radical scavengers are prepared generally according to the methods described in the preceding examples. In the case of the addition of benzoic acid or benzoate, the available chlorine decays at about the same rate or less compared to the control without additive.
Most other free radical scavengers reduce the activity of hypochlorite bleach when placed in storage tests in the formulation context of the above examples.

As can be seen from the above examples, most free radical scavengers have a chemical structure that is either a reducing agent (reactive with available chlorine) or hypochlorite. Even phytic acid, which is said to be a hydroxyl group scavenger in the sense of benzoic acid, is not readily reactive with hypochlorite, but does not show rheological stabilization of benzoic acid or sodium benzoate.

Example III Various amounts of benzoic acid (a potential rheology stabilizer) are tested using the procedure of Example I. Also, these samples are selected by the rapid aging stability test as described above. Figure 4 shows viscosity stability as a function of storage time.

The desired increase in rheological stability in the composition can be achieved by adjusting the amount of benzoate compound added to the formulation, and it can be appreciated that large amounts can adversely affect the viscosity of the initial composition.

Example IV The following liquid automatic dishwashing detergent composition is as follows.

A storage test as described in Example I is performed on the formulation. 12
Summarizes viscosity stability as a function of time at 0 ° F (49 ° C).

Adding benzoic acid to the A-1 and B-1 compositions results in a dramatic increase in rheological stabilization of the A-2 and B-2 compositions under stress test conditions.

Example V Various cross-linked polyacrylate polymers from several sources are incorporated into the approximate composition of Example I. A sample of the composition
Place in 0 ° F (49 ° C) storage test. The following results are obtained.

The degree of stabilization benefit achieved with the addition of benzoic acid depends on the type of polymer used in the composition. It is believed that both the degree of benefit without the benzoate additive and the rate of viscosity reduction depend on the amount or type of crosslinkable component and / or the presence of other minor components in the particular polymer stock. Nevertheless, there is some improvement in rheological stability seen with all polymer stocks tested.

Example VI The composition of Example I (lacking MSAP) of a substituted benzoic acid is placed as a candidate rheology stabilizer and subjected to the same stress stability test in a light tight bottle at 120 ° F (49 ° C).

All of the above monosubstituted benzoic acids (other than those having a hydroxyl substituent) are effective in increasing the rheological stability of a composition that substantially exceeds the rheological stability provided by the composition without the rheological stabilizer. (See Examples I-III). A reading of less than about 80% of the initial viscosity can be considered to reflect a significant decrease in viscosity for the purpose of this test (Brookfield viscosity values for such thickening compositions have considerable variability).

The hydroxybenzoic acid sample loses all available chlorine in just one day and therefore the viscosity reading is not considered relevant beyond this point.

Successful viscosity stabilization with 4-sulfophthalic acid and 5
Failure with sulfosalicylic acid indicates that disubstituted benzoic or monosubstituted phthalic acids follow the same pattern.

Of the compositions, only those containing toluic acid and m-chlorobenzoic acid are higher than 80% of the initial viscosity in 4 weeks and only those with m-toluic acid are still higher than 80% in 6 weeks. high. Thus, it appears that toluic acid is the preferred rheology stabilizer and the meta isomer is in the preferred configuration.

Example VII A liquid cleaning composition of the present invention is as follows.

All of the above compositions are clear to translucent gels and are useful for hard surface cleaning and similar applications. Compositions containing benzoic acid as a rheology stabilizer can retain viscosity and yield value over time under stress storage conditions (greater than 80% of the initial value) than compositions without the stabilizer. The benzoic acids and other rheological stabilizers of the present invention produce lower initial viscosities as described above, but the stabilizing effect over a longer period of time compensates for the lower initial viscosities.

Claims (12)

(57) [Claims] 1. A chlorine bleaching component which provides, by weight, 0.2% to 2.5% of available chlorine; and (b) 0.1% to 1% of a crosslinked polycarboxylate polymer thickener.
0%; and (c) a liquid cleaning composition comprising sufficient alkaline buffer to provide the composition with a pH above 10. (Wherein each of X, Y, and Z is -H, -COO ^- M ⁺ , -Cl,
_{^{-Br, -SO 3 - M +,}} -NO 2, a -OCH ₃ or C ₁ -C ₄ alkyl,, M is rheology stabilizers or mixtures thereof 0.05% having an a) H or an alkali metal
A liquid cleaning composition, further comprising about 5%. 2. The method according to claim 1, wherein said chlorine bleach component is 0.5% to 1.5% effective chlorine.
The alkaline buffer provides the composition with a pH greater than 11.5; the crosslinked polycarboxylate polymer thickener is present at 0.5% to 2.0%; and the rheology stabilizer is 0.2% to 1.0%. The composition of claim 1, wherein the composition is present in percent. (3) 0% to 5% of a detergent surfactant; (b) 5% to 50% of a detersive builder substance; and (c) 0% to 1% of an alkali metal salt of an amphoteric metal anion. The liquid cleaning composition according to claim 1, comprising and having an apparent yield value of 40 to 800 dynes / cm ² . 4. The method according to claim 1, wherein (a) said detergent surfactant is 0.1% to 2.5%.
(B) the detersive builder substance is present in an amount of 15% to 40%; (c) the alkali metal salt of the amphoteric metal anion is 0.01% or less.
4. The liquid cleaning composition according to claim 3, wherein the composition is present in an amount of from 0.1% to 0.1%. 5. The composition according to claim 1, wherein the chlorine bleach component is selected from the group consisting of sodium hypochlorite, potassium hypochlorite, and mixtures thereof. 6. The composition according to claim 1, wherein the molecular weight of the polycarboxylate polymer thickener is from 750,000 to 4,000,000. 7. The composition according to claim 1, wherein Z in the rheology stabilizer is H. 8. The composition according to claim 1, wherein the rheology stabilizer is benzoic acid, phthalic acid, toluic acid, or a salt or a mixture thereof. 9. The method according to claim 1, wherein the alkaline buffer is selected from the group consisting of alkali metal silicates, alkali metal carbonates, alkali metal hydroxides, and mixtures thereof. Composition. 10. The surfactant is a blocked propylene oxide-ethylene oxide block copolymer; a condensate of ethylene oxide and propylene oxide with a mono-, di- or poly-hydroxyl compound (residual hydroxyl is blocked); Or an alkali metal salt of di- (C _8-14 ) alkyldiphenyl oxide mono- and / or di-sulfonic acid; C _8-18 alkyl sulfate;
_{10. A} compound as claimed in any one of claims 1 to 9 selected from the group consisting of _8-18 alkyl sulfonates; and mixtures thereof.
The composition according to Item. 11. The builder according to claim 1, wherein the builder is selected from the group consisting of alkali metal tripolyphosphates, alkali metal pyrophosphates, alkali metal silicates, alkali metal carbonates, polycarboxylates and mixtures thereof. A composition according to any one of the preceding claims. 12. An alkali metal salt of an amphoteric metal anion,
Sodium or potassium aluminate, sodium or potassium zincate, sodium or potassium stannate (IV), sodium or potassium titanate (IV), or a mixture thereof A composition according to any one of claims 1 to 11.