JPH0680999A - Liquid composition for automatic dish washer - Google Patents

Abstract

PURPOSE: To improve the hypochlorite resistance and biodegradability a composition by making the composition contain a certain biodegradable ether carboxylate, chlorine donor, thickening agent and inorganic builder.

CONSTITUTION: By mixing from 3 to 30% by weight of ether a carboxylate compound which is selected from the group consisting of oxydisuccinates, is both hypochlorite resistant and biodegradable as defined by the modified SCAS test, a chlorine donor providing from 0.2 to 1.5% by weight of available chlorine, from 0.1 to 6% by weight of thickening agent having from 500,000 to 1,000,000 of molecular weight, from 3 to 30% by weight of one or more than 2 kinds of inorganic builder selected from alkali metal silicate, alkali metal carbonate, hydrogencarbonate, and sesquicarbonate, from 0.5 to 15% by weight of antiscale agent when necessary, and from 0.5 to 4% by weight of foamless surfactant, the above composition is provided.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an organic detergent builder having both hypochlorite resistance and biodegradability for use in a liquid detergent for an automatic dishwashing machine. In particular, certain ether carboxylates are used in the preparation of phosphate-free or low phosphate detergent compositions.

[0002]

Liquid detergents for automatic dishwashers have been commercially available since the mid-1980s and have overcome many of the problems associated with powder detergents. In particular, powder detergents become insoluble over time, forming cakes in the dispenser cups and producing fine particles during dispensing.

Since the late 1960s, there has also been an effort to replace the high content of phosphate builders in both powder and liquid detergent products with non-phosphate components which fulfill the builder function without harming the environment. Builders in automatic dishwashing products impart alkalinity, sequester hardness ions, disperse dirt and prevent redeposition on clean dish surfaces.

Unfortunately, many organic or environmentally friendly builders are hypochlorite-sensitive and unstable in the presence of chlorine bleach, especially in liquid detergent compositions.

US Pat. No. 4,933,101 (Pro
Cter & Gamble) disclose a number of polycarboxylic acid salts as suitable for preparing detergent compositions in combination with a chlorine source. However, this patent only exemplifies a powder composition and states that builders such as citrate are particularly good at dishwashing performance. However, citrate is unstable in the presence of free hypochlorite and decomposes in liquid detergent compositions.

US Pat. No. 4,689,167 (P &
G), U.S. Pat. No. 4,687,592, discloses ether carboxylates as useful detergent builders. However, in these patent specifications, neither the hypochlorite resistance of these organic builder liquid detergent compositions nor their biodegradability is described.
Surprisingly, certain ether carboxylates are readily biodegradable while having chlorine bleach stability, and are useful in providing phosphate-free or low-phosphate liquid detergent compositions. all right. Ether carboxylates have ether bonds similar to those present in ethoxylated nonionic surfactants. Shell In
c. It is well known that ethoxylated nonionic surfactants, such as the Neodol® series manufactured by K.K., are unstable in the presence of chlorine bleach.

Ethylene glycol disuccinate (EG
DA) and propylene glycol disuccinate (PG
It has also been found that ether carboxylates such as DS) are chlorine stable but not biodegradable. The present invention relates to certain ether carboxylates which not only have surprisingly good chlorine bleach resistance even at high temperatures, but which are also readily biodegradable.

[0008]

Accordingly, it is an object of the present invention to provide an automatic dishwasher containing a non-phosphate builder that is not only readily biodegradable, but surprisingly chlorine bleach resistant. It is to provide a liquid detergent composition.

[0009]

SUMMARY OF THE INVENTION It is an object of the invention to have from about 3 to about 30% by weight of an ether carboxylate builder selected from the group of compounds known as oxydisuccinates; from about 0.2 to about 1. A chlorine source providing 5% by weight of available chlorine; about 0.1 to about 6% by weight thickener; about 3 to about 30% by weight inorganic builder; optionally an anti-scale agent (a
nti-scalant agent) about 0.5 to about 1
This is accomplished by providing an automatic dishwasher liquid composition comprising 5% by weight and about 0.5 to about 4.0% by weight of a low foaming surfactant.

Also included are other optional ingredients such as colorants, dyes, pigments, fragrances, antifog agents, soil suspending agents, hydrotropes and mixtures thereof.

Ether Carboxylate Builder The aqueous composition according to the present invention comprises from about 3 to about 30% by weight, preferably from about 5 to about 20% by weight of an ether carboxylate or a mixture thereof selected from the compounds known as oxydisuccinates. % Included.

Suitable oxydisuccinates within the scope of the present invention include 2,2'-oxydisuccinates.

The oxydisuccinate of the present invention can be produced by any conventional means well known in the art.

Modified SCAS Test The Semi-Continuous Activated Sludge Test (SCAS), which measures the biodegradability of nonionic linear detergent components, is the American Soci.
ety for Testing and Mater
als (ASTM) D2667, p386-389. This test is carried out at the concentrations used in the test: (1) Water-soluble (dissolved organic carbon 20 mg / l or more); (2) Poor vapor pressure; (3) Inhibition against microorganisms (4) hardly adsorbed on the glass surface; (5) not lost from the test solution by foaming; modified to measure the biodegradability of the organic test substance.

Therefore, the "modified SCAS test" is Org
animation for Economic Co
operation and Development
(OECD) was found to be suitable for measuring the innate biodegradability of organic chemicals under aerobic conditions, OECD Guideline for Test.
ing of Biodegradability C
chemicals Test 302A (May 1981)
12). This document is hereby incorporated by reference.

In this test, carbon decomposition loss (D
Test substances with an OC) higher than 70% are considered biodegradable. Biodegradability can also be measured by complex and specific analytical methods using ¹⁴ C-labeled test substances.

The modified SCAS test method is based on Soap and
Detergent Association's Semi-Continuous Activated Sludge (SCAS) method modified to evaluate the primary biodegradation of alkylbenzene sulfonates. This method consists of exposing the chemicals to relatively high concentrations of microorganisms for extended periods of time (preferably months). During this period, standing sewage is fed daily to maintain microbial viability.

Due to the long detention time (36 hours) and the intermittent addition of nutrients, this test does not simulate those conditions experienced in a sewage treatment plant. The results obtained with the test substance show that it has a high biodegradability and is therefore most useful as a natural biodegradability test.

Since the conditions given by the tests are very favorable for the selection and / or adaptation of the microorganisms capable of degrading the test compound, this procedure has also been used to make acclimated inoculum for use in other tests. Can be used. This test is applicable to water-soluble, non-volatile organic chemicals that are non-inhibitory to microorganisms at the concentrations tested.

Method Activated sludge from a sewage treatment plant is placed in an aeration (SCAS) unit. Add test compound and static domestic sewage,
The mixture is aerated for 23 hours. Then stop the aeration and let the sludge stand and remove the supernatant. Sludge remaining in the aeration tank
Mix with another aliquot of test compound and sewage and repeat this cycle.

Biodegradation is established by measuring the dissolved organic carbon content of the supernatant. This value is compared with the value of the liquid obtained from the control tube containing static sewage only.

Description of test procedure Preparation Clean the aeration unit and fix it on a suitable support. Connect the air inlet tube to the supply manifold. The unit is aerated using a small laboratory scale air compressor and the air is pre-saturated with water to reduce evaporation losses from the unit.

A mixed liquid sample is obtained from an activated sludge plant which mainly treats domestic sewage. About 150 ml of mixed solution is required for each aeration unit.

Calibrate the organic carbon analyzer with potassium hydrogen phthalate.

Prepare a stock solution of test compound: Usually the required concentration is 400 mg / l organic carbon, at which concentration the test compound concentration at the beginning of each aeration cycle, if no biodegradation occurs. Is 20 mg / l.

Determine the organic carbon content of the stock solution.

Test conditions A high concentration of aerobic microorganisms was used, and the effective detention period was 3
6 hours. The carbon-containing material in the sewage feed is fully oxidized within 8 hours of the start of each aeration cycle. afterwards,
The sludge breathes endogenously during the remaining aeration time, during which the test substance is the only available substrate, unless the test substance is also easily metabolized. Together with daily re-inoculation of the test using domestic sewage as the medium, these features provide very favorable conditions for acclimatization and biodegradation.

Conducting the Test A mixed liquid sample obtained from a suitable activated sludge plant is obtained and aerated while being carried to the laboratory. Fill each aeration unit with 150 ml of the mixture and start the aeration. After 23 hours, stop the aeration and let the sludge stand for 45 minutes. Open the stopper and 100 supernatant
Remove ml. A static household sewage sample is obtained just before use and 100 ml is added to the sludge remaining in each aeration unit. Aeration is newly started. At this stage, the test substance is not added and the unit is fed daily with domestic sewage until a clear supernatant is obtained. This usually ends within 2 weeks by which time the supernatant liquid at the end of each aeration cycle should have a dissolved organic carbon of less than 12 mg / l.

At the end of this period, the sludges left to stand are mixed and 50 ml of the resulting composite sludge is added to each unit.

100 ml of static sewage was added to the control unit and the appropriate test compound stock solution (400 ml / l) 95 was added.
Add ml + 5 ml to the test unit. Start aeration again,
Continue for 23 hours. The sludge is allowed to stand for 45 minutes, the supernatant is drained and analyzed for dissolved organic carbon content.

The above addition sampling operation is repeated every day during the test.

To prevent solids from accumulating above the liquid level,
It may be necessary to clean the walls of the unit before standing. Use a separate scraper or brush for each unit to prevent cross-contamination.

Ideally, the dissolved organic carbon of the supernatant is measured daily, although less frequent analysis is possible. Prior to analysis, the supernatant is filtered through a washed 0.45 μm membrane filter and centrifuged. During centrifugation, the sample temperature should not exceed 40 ° C.

Test times have not been established for compounds that are poorly or not degraded, but empirically suggest that they should be 12 weeks or longer.

Resulting Treatment The dissolved organic carbon results of the test unit and control unit supernatants are plotted against time. As it biodegrades, the concentration in the test unit approaches that in the control unit. When the difference between the two concentrations becomes constant in three or more consecutive measurements, the measurement is repeated three more times, and the biodegradation rate (%) of the test compound is calculated according to the following formula.

[0036]

[Equation 1]

Here, O _T is the concentration of the test substance added to the sewage left standing at the start of aeration as organic carbon; O _t is the concentration of dissolved organic carbon in the supernatant of the test unit at the end of aeration;

O _c is the concentration of dissolved organic carbon in the supernatant of the control unit.

Therefore, the degree of biodegradation is the removal rate (%) of organic carbon.

If there is no difference between the start and the control and the test,
Or, if the difference between the two continues to be less than would be expected when biodegradation is not occurring, further testing is needed to clearly distinguish between biodegradation and adsorption.
This is Sturm Test or Closed Bot
tle Test (OECD Test Guidel
The supernatant is used as the inoculum for tests such as ines 301 B and 301 D).

Bleach A wide variety of bleaching agents can be used in these automatic dishwashing liquid detergent compositions. Both halogen type and peroxy type are included in the present invention.

Among the suitable halogen donor bleaches are the heterocyclic compounds such as trichlorocyanuric acid, tribromocyanuric acid, dibromocyanuric acid, dichlorocyanuric acid and their salts with water-soluble cations such as potassium and sodium. N-bromoimide and N-chloroimide.
An example of a hydrated dichlorocyanuric acid is Olin Cor
p. Manufactured by Clearon® CDB56. These bleaching agents may be used in admixtures of two or more separate chlorine donors. Examples of commercially available mixed systems are:
Monsanto Chemical Company
Made under the registered trademark "ACL-66" (ACL stands for "available chlorine", the number "66" indicates parts per pound of available chlorine), which is potassium dichloroisocyanurate (4 parts). And trichloroisocyanuric acid (1 part).

Other N-bromoimides and N-chloroimides such as N-brominated and N-chlorinated succinimides, malonimides, phthalimides and naphthalimides can also be used. Other compounds include 1,3-dibromo- and 1,
3-dichloro-5,5-dimethylhydantoin, N-monochloro-C, C-dimethylhydantoin, methylenebis (N-bromo-C, C-dimethylhydantoin);
There are hydantoins such as 1,3-dibromo- and 1,3-dichloro-5-methyl-5-n-amylhydantoin. Other useful hypohalous acid liberators include tribromomelamine and trichloromelamine.

Dry particulate water soluble anhydrous inorganic salts such as lithium, sodium or calcium salts of hypochlorous acid and hypobromite are also suitable for use herein.

Suitable chlorinating agents include potassium and sodium dichloroisocyanurate dihydrate, trisodium chlorinated phosphate and calcium hypochlorite. Particularly preferred is the dihydrate of potassium and sodium dichloroisocyanurate. Suitable concentrations for all of these materials are those that provide about 0.2 to about 1.5% available chlorine. The hypohalous acid free compound is usually used in the automatic dishwashing detergent at a concentration of 0.5 to 5% by weight, preferably 0.5 to 3% by weight.

Suitable chlorine releasing agents are also "Chlorine-"
It's Manufacture, Propertie
ACS monograph entitled "s and Uses" (Scone, Reinhold Publishing, 1962).
Is disclosed in.

The chlorine bleach source of this invention may be encapsulated by the method described in EP 0,510,761.

It will be appreciated that the oxygen bleaching agents that may be included in the compositions of the present invention are alkali metal and ammonium salts of inorganic peroxy compounds such as perboric acid, percarbonic acid, persulfuric acid, dipersulfuric acid. Generally, the inorganic oxygen compounds are activators such as TAED (tetraacetylethylenediamine), sodium nonyloxybenzene sulfonate or choline sulfophenyl carbonate, or manganese or other transition metal, as is well known in the bleach industry. Used with such catalysts (see US Pat. No. 5,041,232, which describes organic catalysts of Batal et al., US Pat.
45,223, U.S. Pat. No. 5,047,163). Insoluble organic peroxides such as diperoxide decanedioic acid (DPDA), phthalimidoperoxycaproic acid (PAP) and lauroyl peroxide, benzoyl peroxide can also be used. Many others known in the art can also be used. Usually, the peroxy compound is present at a concentration of 0.5 to 20% by weight, 0.005 to 5% of catalyst and / or 0.5.
Present with ~ 3% activator.

Surfactants A wide variety of alkoxylates can be used if the encapsulated chlorine bleach is used in the present invention. Particularly, the defoaming nonionic substance as described in U.S. Pat. No. 4,973,419 is suitable.

It is also clear that low foaming bleach resistant surfactants may also be included in the liquid detergent compositions of the present invention, as is well known in the art. The preferred range of surfactants useful in the present invention is from about 0.5 to about 4%.

Inorganic builder An amount of about 3 to about 30%, preferably 3 to 10%, of an inorganic builder may also be present in the composition as a water hardness sequestrant or builder. When a sequestrant is used above its solubility limit in the composition, the solid is
must be present as fine particles suspended in the ructuring system. Since the presence of solids affects the viscosity of the liquid, the range of structuring agents needed to provide the proper rheology can be modified. Inorganic builders which can be used are the sodium and potassium salts of polyphosphoric acid, orthophosphoric acid, carbonic acid, bicarbonate, sesquicarbonate and boric acid.

Water-insoluble aluminosilicate ion exchange materials can be used as further builders (eg Henkel, GB 1,473,201 and GB 147).
No. 3,202). These are the general formulas:

[0053]

[Chemical Formula 1] (Cat _{2 / n} O) _x Al ₂ O ₃ (SiO ₂ )
_y · zH ₂ O [where Cat is a calcium-exchangeable n-valent cation (eg, Na ⁺ or K ⁺ ); x is a number of 0.7 to 1.5; y is a number of 1.3 to 4 Z has a bound water content of 1% by weight to
28% by weight] is a crystalline or amorphous substance. Suitable commercial products Zeolite type A:

[0054]

## STR2 ## is a _{Na 2 O · Al 2 O 3} · 2SiO 2 · 4.5H 2 O.

Of the alkali metal silicates, sodium silicate having a SiO ₂ : Na ₂ O ratio of from about 1.0 to about 3.3, preferably from about 2 to about 3.2 is used. Useful for invention. Liquid form of silicic acid is preferred. Solid silicates can also be used alone or in combination with liquid silicates.

Thickeners and Stabilizers Thickeners that can be used in the compositions of the present invention are described in US Pat.
36,948 (Corring),
It is included herein by reference. A particularly preferred thickening agent is a cross-linked polymer having a molecular weight in the range of about 500,000 to about 10,000,000, preferably 500,000 to 4,000,000. Examples of commercially available crosslinked polymers include B.I. F. Goodrich Chemical
Carbopol® resin from Company. These materials include Carbopol 94
1 (registered trademark) (molecular weight 1,250,000), Car
bopol 934 (registered trademark) (molecular weight 3,000,
000), Carbopol 940® (molecular weight 4,000,000) and Carbopol 617.
(Registered trademark) (molecular weight 4,000,000). Similar products marketed by other manufacturers can also be used. When encapsulated with chlorine bleach, US Pat. No. 4,260,528 (Fox et al.).
Polymers such as those described in can also be used.

The thickening polymer is present in the composition in the range of 0 to about 3.0% by weight, preferably about 0.4% to about 1.5% by weight.

Co-structuring agent
t) or stabilizers can also be used in combination with thickeners.
Examples of such suitable costructuring or stabilizing agents include:
(1) Alumina described in U.S. Pat. No. 4,836,948, (2) Alkali metal salt of silicoaluminic acid described in U.S. Pat. No. 4,941,988, (3) U.S. Pat. No. 4,752, 409, and (4) Laporte, Inc. Is a subsidiary of Wav
ery Mineral Products Co.
Laponite® marketed by
There are synthetic hectorite clays such as XLS.

Suitable costructuring agents are alumina and hectorite clay. The co-structuring agent is about 0.005 to 1%, preferably about 0.1 to about 0.5%, and particularly preferably about 0.01.
Can be used in the range of about 0.1%.

Scale Inhibitors and Antiscale Agents Antiscale agents prevent fine nuclei from growing to a critical size and then redisperse to act on other nuclei. Antiscale agents are also useful in a wide range of applications such as industrial boilers, water purification, evaporators and the like. Any conventional anti-scale agent used to prevent the deposition of sparingly soluble salt scales such as CaCO ₃ in aqueous systems (sometimes described as dispersants)
Are also considered to be within the scope of this invention.

The anti-scale agent can be used in a powder form or a solution form, but a solution form is usually used, and an acid,
It may be supplied as a partially neutralized acid, or otherwise comprises the free acid. Suitable phosphorus-containing scale inhibitors include methylenephosphonate, methylenephosphonic acid,
And McCutcheon's Functional Ma
terials (North America Edi
region, Volume 2, McCutcheon
Division Publishing, Glen Rock, New
There are other phosphates and phosphonates described in Jersey, 1991).

Suitable methylene phosphonates include aminotris 5 sodium, hexamethylene diamine tetra,
There are 6 potassium and 8 sodium diethylenetriaminepenta.

A particularly suitable methylenephosphonic acid is diethylenetriaminepentanoic acid. Aquaness
Chemicals to Arquest® 7
As 10 or from Monsanto Dequest
Hydroxyethylenediphosphonic acid in an aqueous solution marketed as (registered trademark) 2010 is particularly suitable.
A similar diphosphonic acid is in powder form, as Dequest® 2016D from Mansanto, or from Arqueshes Chemicals Arquee.
It is available as aminotri (methylenephosphonic acid) commercially available as st (R) 709. Suitable polymeric anti-scaling agents for the present invention include Ciba-Ge.
polymaleic acid and its sodium salt (Be
lcrene® 200 and 201), BAS
Polycarboxylate polymers prepared by copolymerization of acrylic acid and maleic acid, commercially available from F as Sokalan® CP series, and polyacrylics commercially available from BASF as Sokalan® PA series. There are sodium acid and polyacrylic acid.

Alco Chemical Cor
p. , Division of National S
Alco from tarch and Chemicals
sperse (registered trademark) series, Rhone-Po
ulenc Corp. Sold by
Oids, B.I. F. Good-r made by Goodrich
ite (registered trademark) series and Rohm & Haa
Also suitable are polyacrylic acids and sodium or ammonium polyacrylates such as products such as the Acusol® series manufactured by s.

Particularly suitable anti-scale agents include Collo
id (R) 117/50; Colloid (R) 211, 223 (D) and 274; Good-r.
ite (registered trademark) K-732, K-7058, KG
00N; Acusol® 445 and Alco
sperse (registered trademark) 602N.

Additional antiscale agents suitable for the present invention include
Kirk-Othmer Encyclopedia
of Chemical Technology , 3
Edition, Volume 7 (John Wiley & Sons, N
Y, 1979), which describes anti-nucleating or anti-scaling agents as dispersant substances.

Sulfonated styrene maleic anhydride copolymers are also suitable as the anti-scaling agent of the present invention, and Na
Commercially available from Regional Starch as Versa® TL 7. Other copolymers include Narlex from National Starch
®-D-82 and sodium lignosulfonate commercially available from ITT Rayonier as Orzans ®.

Optional Ingredients Direct Yellow as described in British Patent Application No. 2,233,662 (licensed Aug. 9, 1991).
Bleach stable colorants such as w 28 can also be used in the present invention. Bleach sensitive dyes such as those described in US Pat. No. 4,446,281 can also be used in embodiments containing oxygen bleaches or encapsulated bleaches. Or
Ultramarine Blue 5151 and Ul
Dyes such as tramarine Blue 17 can also be used. Since chlorine destabilization is not a factor, the perfume ingredients can be chosen very freely.

If it is preferable to add an antifoaming agent, D
ow Corning to Antifoam DB-1
Silicones such as polydimethylsiloxane containing 6% hydrophobized silica, commercially available as 00®, can be used. Other ingredients such as minor amounts of antifog agents, soil suspending agents, hydrotropes and the like may be included in the compositions of this invention. The amount of each optional additive is less than or equal to about 0.5% by weight.

[0070]

The following examples will clarify the difference between the present invention and the prior art, and will more fully illustrate the embodiments of the present invention.
All parts, percentages and ratios are by weight unless otherwise indicated.

Example 1 The hypochlorite stability of the sequestering agent was measured. A standard thiosulfate titration was performed on residual hypochlorite. A pH 12 solution containing a 5% sequestrant and a hypochlorous acid bleach providing 1% available chlorine was prepared. The solution was stored in an oven at 40 ° C to accelerate the decomposition of the bleach. The results are shown in the table below. The structure is shown in Table 2.

[0072]

[Table 1] Table 1 Type Effective chlorine% after 40 ° C, 8 days Oxydisuccinate (ODS) ^I 96 (48% in 32 days) Ethylene glycol disuccinate (EGDS) ^II 97 Propylene glycol disuccinate (PGDS) ^III 98

[0073]

[Chemical 3]

[Where X is COOH].

From Table 1 above, it was found that none of the ether carboxylates (ODS, EGDS, PGDS) decomposes available chlorine in the sample solution. However, only ODS is biodegradable (see Example 2).

Example 2 The solution of Example 1 was tested by the modified semi-continuous activated sludge test described above to determine the biodegradability of selected ether carboxylate builders. A sludge sample containing each builder was placed in a 1,500 ml aeration unit and tested as described in the OECD guidelines. Modified SCA
The acclimatization time of each builder obtained from the S test is shown below.

[0077]

Table 2 Type Modified SCAS Acclimation Time DOC (%) ODS 2-3 weeks> 80% EGDS 7 weeks> 80% PGDS 9 weeks> 80% Examples 3-6 Compositions useful as liquid detergent compositions are listed below. Enumerate in.

A composition containing sodium tripolyphosphate as a builder is shown for comparison.

[0079]

[Table 3] ADL composition components 3 4 5 6 sodium disilicate 15.0 15.0 15.0 15.0 (ratio 2.0) Carbopol 940 ^a 1.2 1.2 1.2 1.2 encapsulated CDB Wax 3.6 3.6 3.6 3.6 (effective) Chlorine 1.0% donation) SLF-18 ^b 2.0 2.0 2.0 2.0 Chlorine donor − − − − (donation of available chlorine 1.0%) Alcosperse 602N (AA) ^c − 5.0 − 5.0 Sokalan CP-7 ^d − − 5.0 − (2 1 AA / MA) STPP (anhydrous) 25.0 --- ODS-10.0 --- EGDS-10.0-PGDS --- 10.0 All components are shown as active components (percentage), and the builder is shown as the concentration of sodium salt.

A) B. F. Goodrich Chem
ical Co. Cross-linked polymer having a molecular weight of 4,000,000 manufactured by b) BASF low-foaming surfactant c) Anti-scale agent manufactured by National Starch d) Copolymerized product of acrylic acid and maleic acid manufactured by BASF.

Examples 7-10 One of the criteria for judging the performance of the dishwashing detergent is the appearance of the glass product after washing. In this example, 10 glass tumblers were placed in a Sears Kenmore dishwasher. 40 g of a mixture of margarine and milk powder (4: 1) was introduced into the dishwasher. 40g of each compound shown below
Was added to the dishwasher dispenser cup. After repeating the test for 4 wash cycles, visually inspect the glassware,
evaluated. The speckle formation and the thin film formation were evaluated numerically on a scale of 0 to 4 (0 = best, 4 = worst) and 0-5 (0 = best, 5 = worst) for thin film formation. Differences of about 0.5 for speckle formation and about 1.0 for thin film formation were considered significant as compared to the 25% liquid STPP composition. The lipstick stained glass was placed in the dishwasher as a builder sensitivity monitor. Removal of pigment fatty acids in lipstick compositions was sensitive to both builders and surfactants.

The results are shown below:

[0083]

Table 4 Example Formulation Spot formation Thin film formation Lipstick residue (%) 7 10% ODS 0 1.4 Trace 8 10% PGDS 0 1.8 Trace 9 10% EGDS 0.2 2.0 Trace 10 25% STPP 0.3 0.9 A trace amount of ODS prevents spotting, thin film formation and lipstick residue on the tableware, and the overall performance is EGDS and ST.
It showed much better performance than PP. ODS and PGDS
Had almost the same performance, but PGDS was modified SCAS
Not biodegradable by testing.

Example 11 As described in Examples 3-6 except that 1% hypochlorite which donates 1% of available chlorine was used as the chlorine source and the surfactant SLF-18 was omitted. , An ODS-containing liquid detergent composition can be prepared.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C11D 7:12 7:14)

Claims (8)

[Claims] 1. A hypochlorite resistant and modified SCA selected from the group consisting of (a) oxydisuccinates.
From about 3% to about 30% by weight of an ether carboxylate compound that is biodegradable by definition of the S test; and (b) from about 0.2 to about 1.5% by weight of a chlorine donor that donates available chlorine. A liquid detergent composition for an automatic dishwasher, comprising (c) about 0.1 to about 6% by weight of a thickening agent; and (d) about 3 to about 30% by weight of an inorganic builder. 2. A composition according to claim 1, wherein the oxydisuccinate is 2,2'-oxydisuccinate. 3. The thickener is from about 500,000 to about 10.0.
A polymer having a molecular weight of 0,000.
The composition according to. 4. The inorganic builder is an alkali metal silicate,
The composition of claim 1 selected from the group consisting of alkali metal carbonates, bicarbonates, sesquicarbonates, aluminosilicates and mixtures thereof. 5. The composition according to claim 4, wherein the inorganic builder is selected from the group consisting of alkali metal carbonates and alkali metal bicarbonates. 6. The composition of claim 1, further comprising about 0.5 to about 15% by weight antiscale agent. 7. The composition according to claim 6, wherein the anti-scale agent is selected from the group consisting of phosphonates, polyacrylic acids, sodium polyacrylates and ammonium polyacrylates. 8. The composition of claim 1, further comprising about 0.5 to about 4% by weight of low foaming surfactant.