U.S. patent number 3,899,436 [Application Number 05/305,596] was granted by the patent office on 1975-08-12 for machine dishwashing detergent having a reduced condensed phosphate content.
This patent grant is currently assigned to Economics Laboratory, Inc.. Invention is credited to James L. Copeland, William G. Mizuno.
United States Patent |
3,899,436 |
Copeland , et al. |
August 12, 1975 |
Machine dishwashing detergent having a reduced condensed phosphate
content
Abstract
Machine dishwashing detergents having a low condensed phosphate
content and characterized by the presence therein of a metallic
salt of citric acid (e.g. sodium citrate). An alkaline machine
dishwashing detergent (e.g. pH at 1% concentration above 10.5)
containing less than 30 weight percent on a dry basis of sodium
tripolyphosphate and at least 5 weight percent of an alkali metal
citrate.
Inventors: |
Copeland; James L.
(Bloomington, MN), Mizuno; William G. (St. Paul, MN) |
Assignee: |
Economics Laboratory, Inc. (St.
Paul, MN)
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Family
ID: |
26751226 |
Appl.
No.: |
05/305,596 |
Filed: |
November 10, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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70528 |
Sep 8, 1970 |
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Current U.S.
Class: |
510/223; 510/229;
510/370; 510/469; 510/477; 510/379 |
Current CPC
Class: |
C11D
3/044 (20130101); C11D 3/08 (20130101); C11D
3/10 (20130101); C11D 3/2086 (20130101); C11D
3/06 (20130101) |
Current International
Class: |
C11D
3/00 (20060101); C11D 3/20 (20060101); C11d
007/38 () |
Field of
Search: |
;252/99,135,256,DIG.19,DIG.11,103 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1,300,699 |
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Jun 1962 |
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FR |
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1,197,446 |
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Jul 1970 |
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GB |
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Primary Examiner: Padgett; Benjamin R.
Assistant Examiner: Nelson; P. A.
Attorney, Agent or Firm: Meshbesher; Thomas M.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of our application Ser.
No. 70,528 filed Sept. 8, 1970, which was copending with this
application and is now abandoned.
Claims
What is claimed is:
1. In the process of preparing a low-foaming or nonfoaming machine
dishwashing detergent composition from the components
comprising:
1. an alkaline condensed phosphate salt generally characterized by
the structural formula ##SPC2##
wherein M is hydrogen or an alkali metal, at least one M being an
alkali metal, and
n is an integer ranging from 1 to 60; and
2.
2. 2 - 80% by weight, on a dry basis, of a nonsequestering,
alkaline, pH-adjusting or buffering detergent builder salt;
said detergent Composition having a pH of about 10.0 to 12.8 and a
Ross-Miles foam height, determined at a concentration of 0.1
percent by weight of said detergent composition in water, of less
than 45 mm initially and less than 15mm after five minutes in a
column of water maintained at 50.degree.C.; the improvement which
comprises:
substituting into said detergent composition at least 5 - 60 parts
by weight per 100 parts by weight of said detergent composition, of
a water soluble metal salt of citric acid;
whereby said salt of citric acid substitutes for part of said
condensed phosphate; whereby the amount of said condensed phosphate
in the resulting detergent composition is in the range of 0.5 to 35
percent by weight of the resulting detergent composition; and
whereby the amount of said detergent builder salt in the resulting
detergent composition is within the range of 2 - 80% by weight;
all of the foregoing parts by weight and percentages by weight
being on a
dry basis. 2. Improved process according to claim 1, wherein said
salt of citric acid substitutes for at least one-third by weight,
on a dry basis, said alkaline condensed phosphate, whereby the
ratio of said salt of citric acid to said condensed phosphate in
said resulting detergent composition, on a dry weight basis, is in
the range of from 1:3 to 20:1.
3. Improved process of claim 2 wherein said salt of citric acid is
an alkali metal citrate; the amount of said citrate is 10 - 30
percent by weight and the amount of said alkaline condensed
phosphate on the same basis is less than 30 percent by weight, all
on a dry basis.
4. Improved process according to claim 1, wherein said detergent
composition consists essentially of solids including a
chlorine-releasing agent selected from the group consisting of
chlorinated trisodium phosphate, potassium dichloroisocyanurate,
sodium dichloroisocyanurate, trichloroisocyanuric acid, double
salts or crystalline complex salts or hydrated salts of
trichloroisocyanuric acid, trichloromelamine, and Chloramine T.
5. Improved process according to claim 1, wherein said detergent
composition is a liquid concentrate containing a chlorine releasing
agent comprising an alkali metal hypochlorite.
6. Improved process according to claim 5 wherein said salt of
citric acid is formed in situ.
7. A machine dishwashing detergent composition which, in 0.1 weight
percent concentration in water, has Ross-Miles foam heights, using
a water column maintained at 50.degree.C., of less than 45mm
initially and less than 15mm after five minutes, and which has a
pH, determined at 1 weight percent solution in water, of about 10
to 12.8, said composition consisting essentially of:
a. 2 - 70 percent by weight of at least one nonsequestering,
alkaline, pH adjusting or buffering, water soluble detergent
builder salt,
b. 0 - 5 percent by weight of a surfactant which, in 0.1 weight
percent concentration in water, has the said Ross-Miles foam
heights, using a water column maintained at 50.degree.C.,
c. from 5 to 60 percent by weight of a water soluble metal salt of
citric acid, and
d. 0.5 to 35 percent by weight of water soluble alkaline condensed
phosphate of the formula ##SPC3##
wherein M is hydrogen or an alkali metal, at least one M being an
alkali metal, and
n is an integer from 1 to 6, all of the said percentages being on a
dry basis.
8. Composition according to claim 7 wherein the ratio, on a dry
weight basis, of said component (c) to said component (d) is in the
range of 1:2 to 20:1, and total of said components (c) and (d) does
not exceed 65 percent by weight of said composition on a dry
basis.
9. Composition according to claim 7 wherein said component (c) is
the product of the in situ reaction of citric acid and an alkali
metal hydroxide.
10. Composition according to claim 7 wherein said detergent
composition consists essentially of solids including a
chlorine-releasing agent selected from the group consisting of
chlorinated trisodium phosphate, potassium dichloroisocyanurate,
sodium dichloroisocyanurate, trichloroisocyanuric acid, double
salts or crystalline complex salts or hydrated salts of
trichloroisocyanuric acid, trichloromelamine, and Chloramine T.
11. Composition according to claim 7 wherein said detergent
composition is a liquid concentrate containing a chlorine releasing
agent comprising an alkali metal hypochlorite.
12. Composition according to claim 7 wherein said water soluble
detergent builder salt is capable of precipitating hardness from
water in the form of calcium carbonate in water having a pH of
about 10 to 12.8.
13. Composition according to claim 12 wherein said water soluble
detergent builder salt is sodium carbonate.
14. Composition according to claim 7 wherein said component (c)
comprises an alkali metal citrate and said component (d) comprises
an alkali metal tripolyphosphate.
15. Composition according to claim 14 wherein said composition
comprises 10-30 percent by weight of said citrate and 2-20 percent
by weight of sodium tripolyphosphate.
16. In the process of machine dishwashing, the improvement which
comprises using as the dishwashing detergent added to the wash
water the composition of claim 7.
17. The process of claim 16 wherein the wash water used in said
process, after addition of said composition, comprises 0.1-1
percent by weight of said composition on a dry basis.
18. In the process of machine dishwashing, the improvement which
comprises using as the dishwashing detergent the composition of
claim 15.
19. Treated wash water useful for machine dishwashing having a pH
in the range of about 10 - 12.8 and being substantially free of
stable foam comprising:
1. a machine detergent composition comprising:
a. 5 - 60 percent by weight of an alkali metal citrate,
b. 0.5 - 35 percent by weight of an alkali metal condensed
phosphate of the formula ##SPC4##
wherein M is hydrogen or an alkali metal, at least one M being an
alkali metal, and
n is an integer from 1 to 6, and
c. 2 - 70 percent by weight of a non-sequestering, alkaline,
pH-adjusting or buffering alkali metal detergent builder salt, all
on a dry basis, and
2. 99 - 1,000 parts by weight of water for each part by weight of
dry solids contained in component (1), said component (1) being
totally dissolved in said water.
20. Treated wash water according to claim 19 wherein said machine
dishwashing detergent composition further contains up to 5 percent
by weight of a surfactant which, in 0.1 percent by weight
concentration in water, has Ross-Miles foam heights, using a water
column maintained at 50.degree.C., of less than 45 mm initially and
less than 15 mm after five minutes and a cloud point, determined in
distilled water at a concentration of 1 percent by weight of less
than 45.degree.C.
21. Improved process according to claim 1 wherein all surfactants
included in said dishwashing detergent composition, when tested
individually at a concentration of 0.1% by weight in water, have
said Ross-Miles foam height characteristics.
Description
BACKGROUND OF THE INVENTION
Machine dishwashing detergents constitute a generally recognized
class of detergent compositions. Machine dishwashing detergents are
mixtures of ingredients whose purpose, in combination, is to
emulsify and remove food soils, to inhibit the foam caused by
certain food soils, to promote the wetting of dinnerware to thereby
minimize or eliminate visually observable spotting, to remove
stains such as those caused by coffee and tea, to prevent a buildup
of soil films on dinnerware surfaces, to reduce or eliminate
tarnishing of flatware, and to destroy bacteria. Additionally,
machine dishwashing detergents must possess these characteristics
without substantially etching or corroding or otherwise damaging
the surfaces of dinnerware and flatware.
Machine dishwashing detergents are often highly alkaline (a pH
above 10.0 and frequently above 12.5 at concentrations of 1 weight
% in water). Machine dishwashing detergents are often formulated by
mixing or otherwise combining alkaline detergent salts and alkaline
condensed phosphate salts. Frequently, chlorine releasing agents
and low-foaming or non-foaming organic surface active agents (e.g.
nonionic surfactants) are optionally and preferably included in
such compositions.
In recent years, increasing attention has been focused upon
environmental pollution problems (e.g. water pollution). Phosphates
have been identified as a contributing factor to water pollution
(e.g. by promoting the growth of algae) and considerable effort has
been devoted to attempts at replacing all or at least some
significant part of the alkaline condensed phosphates used in
machine dishwashing detergents with chemicals that are more
ecologically acceptable. Of the numerous compounds that have been
tested as substitutes for alkaline condensed phosphates
(particularly as substitutes for sodium tripolyphosphate), very few
chemicals have given promising results. Many chemicals lack the
desired cleansing ability. Other chemicals lack a threshold effect,
i.e, the ability to sequester hard water metal ions beyond their
stoichiometric presence (contrary to sodium tripolyphosphate which
has such an ability). Still others create foam problems and still
others are as much or more ecologically undersirable as the
alkaline condensed phosphates.
Among the many chemicals tested for use as a substitute for sodium
tripolyphosphate, nitrilo triacetic acid appears to be one of the
most promising candidates. However, one disadvantageous effect of
nitrilo triacetic acid (often call "NTA") is its tendency to
de-stabilize chlorine in use solutions of machine dishwashing
detergents. Other disadvantages of NTA at the present time include
cost, lack of general availability, and lack of a threshold
effect.
SUMMARY OF THE INVENTION
The present invention is based upon the discovery that metallic
salts of citric acid (e.g. sodium citrate) are effective partial
substitutes for alkaline condensed phosphates in machine
dishwashing detergents. The use of citrates in combination with
reduced amounts of alkaline condensed phosphates (e.g. reduced
amounts of sodium tripolyphosphate) produces dishwashing results
that are commercially acceptable by today's industrial and home
standards. By retaining some alkaline condensed phosphate in the
detergent, effective sequestration and deflocculation of hard water
metal ions can be obtained. Additionally, the citrates are very
stable in the presence of chlorine releasing agents (e.g. potassium
di-chloroisocyanurate).
DETAILED DISCUSSION
Machine dishwashing detergents of the present invention can be
formulated as a solid detergent or as single or multiple package
liquid detergents.
Solid or dry detergents can be formed by blending together the
various detergent-forming ingredients to form a powdered or
granular product, or they can be agglomerated, pelletized or the
like.
Multiple package liquid detergents are those machine diswashing
detergents which are formulated into two or more separate liquid
components, each component being packaged separately. In the
dishwashing operation, the separate components are dispensed from
their separate containers into the dishwashing tank by suitable
dispensing apparatus.
Although the present invention can be applied to or embodied in any
of these various types of machine dishwashing detergents, its
greatest advantage is associated with the production of solid
detergent compositions and single package liquid detergent
compositions. Of these, the formulation and use of solid machine
dishwashing detergents is of particular significance.
The machine dishwashing detergent compositions of the present
invention will normally contain at least one alkaline detergent
salt other than an alkaline condensed phosphate salt, at least one
alkaline condensed phosphate salt, at least one citrate, and,
optionally, a chlorine releasing agent and various surfactants. If
desired, other ingredients can be included in the detergent
compositions of the present invention.
The pH of these machine dishwashing detergents will normally be at
least 10.0 and generally not above about 12.8 at a concentration of
1 weight percent in water. The effectiveness of the present
compositions at these high pH's is unexpected since alkali metal
citrates are not normally used to sequester calcium, magnesium, or
ferric ions in alkaline aqueous media having a pH above 9. When the
present compositions are to be used for institutional machine
dishwashing, they will generally be used to form an alkaline wash
water with a pH which is not in excess of 12.8, and a pH of
11.0-12.7 is ordinarily adequate for such institutional use. For
home machine dishwashing use, a pH range of 10.0-11.0 for the wash
water, particularly 10.0-10.5 is preferable. These pH values can be
obtained by calculating the negative of the logarithm of the
hydroxyl ion concentration but are preferably determined by pH
measuring instruments which can accurately determine the negative
of the logarithm of the hydroxyl ion activity, e.g. Corning Model
12, Research pH meter, with Beckman 39099 E- 3 glass electrode
(0.degree.-100.degree.C., pH 0-14 range) and matched calomel
reference electrode. Additionally, nomographs can be used for
sodium ion error correction.
A sufficient amount of the dry or liquid detergents formulations of
this invention should be used to provide wash water containing at
least 0.1 percent by weight of detergent solids in water. It is
preferred that the wash water contain these solids in stable
aqueous solution. In liquid machine dishwashing detergent
compositions of this invention, the condensed alkali metal
phosphate content is preferably near the lower end of the ranges
defined herein for greater water solubility and hydrolytic
stability of the liquid composition. It is permissible and even
preferred for these liquid detergent compositions to contain an
aqueous diluting medium which acts as a solvating phase rather than
the continuous phase of an emulsion or dispersion. In solid
detergent formulations of this invention, the ingredients and/or
their proportions are selected for good water solubility so as to
permit at least one part by weight of the solid formulation to be
totally dissolved in 99 (and preferably no more than 1,000,
typically no more than 500) parts by weight of water.
In use, the amount of liquid or solid detergent composition added
to the wash water will preferably be limited so that the dissolved
solids of the composition do not exceed 1 percent by weight of the
wash water, the preferred concentration in the wash water being
0.25-0.75 weight percent. Concentrations of less than 0.5 percent
by weight are typically sufficient for good machine
dishwashing.
The solid, high pH detergent compositions of this invention (e.g.
for institutional use) typically contain fairly substantial amounts
of sodium carbonate and caustic soda (sodium hydroxide) or other
alkali metal hydroxides, e.g. KOH. However, the amount of caustic
soda should preferably not exceed about 20 or 30 percent by weight
so that the wash water will contain only a fraction of 1 percent by
weight of caustic and will exhibit a pH measurement less than 12.8.
The lower pH formulations of this invention typically contain a
metasilicate as a non-sequestering builder salt, the same or
smaller amounts of caustic, and a relatively small amount of sodium
carbonate.
All the ingredients of either of the solid or liquid compositions
of this invention should be selected so as to provide a detergent
which produces little or no foam during machine dishwashing, even
in interaction with foamable food soils such as egg or milk
residues. Low-foaming or non-foaming ingredients can be used to
help provide this freedom from excessive foaming, and, as will be
pointed out in more detail subsequently, surfactants with low
foaming or even de-foaming properties can be added to reduce or
control foaming. A realistic test for low foaming detergent
compositions containing builder salts, condensed phosphates,
surfactants, etc. is the commercial dishwashing machine test
described in column 2, line 59 et seq. and Table III and IV of U.S.
Pat. No. 3,444,242 (Rue et al), issued May 13, 1969. Detergent
formulations of this invention do not unduly reduce either the
r.p.m. of the spray arm or the wash pressure in this test.
ALKALINE DETERGENT SALTS
Alkaline detergent salts or detergent builder salts as they are
sometimes called (other than alkaline condensed phosphate salts)
are well known to those engaged in the detergent industry and
include such chemicals as di and tri-sodium orthophosphates, sodium
carbonate, sodium bicarbonate, sodium silicates, sodium
metasilicate, sodium borate, caustic soda, caustic potash, and the
like. These salts are used primarily to adjust the pH of the wash
water and/or to minimize corrosion. These salts may have a water
conditioning effect, but this effect is characterized by the
precipitation of hardness rather than by a sequestration or soluble
complex formation or other solubilization effect. In machine
dishwashing, sequestration is the preferred means for reducing
hardness, since precipitated calcium carbonate or the like can form
a film upon dishes or glassware. Thus, another way of
characterizing these salts would be to describe them as the
non-sequestering detergent builder salts, and they are included
primarily for their pH-adusting and/or buffering rather than their
water conditioning properties. The sodium silicates inhibit
corrosion of glass, ceramic and metal surfaces in addition to
buffering and adjusting the pH.
The combined amount of these non-sequestering detergent builder
salts will generally but not always be less than 80 weight percent
of the total dishwashing detergent formula (on a dry basis). More
usually, the total amount of such detergent salts will range from 2
to 70 weight percent on the same basis.
ALKALINE CONDENSED PHOSPHATE SALTS
Alkaline condensed phosphate salts are also well known to those
engaged in the detergent industry. These salts are generally
characterized by the structural formula: ##SPC1##
wherein M is hydrogen or an alkali metal (at least one M being an
alkali metal) and n is an integer ranging from 1 to about 60. The
lower numerical values of n are preferred, e.g. 1-6. It is
permissible to use condensed polyphosphates wherein n is larger
than 60; however, such high molecular weight phosphates are less
preferred, due to their relative lack of availability and lower
water solubility. Cyclic condensed phosphates (wherein a plurality
of --PO.sub.3 M-- units join to form a ring) can also be used.
Typical alkaline condensed phosphates include tetrasodium
pyrophosphate, tetra potassium pyrophosphate, sodium
tripolyphosphate, other sodium polyphosphates and the like.
These alkaline condensed phosphate salts have a number of
properties which make them particularly suitable for use in machine
dishwashing detergent compositions. Other classes of compounds
investigated by detergent chemists have equal or even superior
sequestering capabilities but often lack the buffering,
de-flocculation, solubilizing or peptizing, and other desirable
effects provided by these condensed phosphate salts. The socalled
threshold effect (the ability to sequester hard water metal ions
beyond the stoichiometric presence of the sequestering agent) has
already been alluded to and is observed with sodium
tripolyphosphate at the levels of about 5 to about 20 parts per
million. It is also known that these condensed phosphate salts are
active sequestering agents in aqueous alkaline media.
As used in the compositions of the present invention, the amount of
alkaline condensed phosphate in the detergent compositions will be
less than 35 weight percent on a dry basis, typically less than 30
weight percent on the same basis. To provide a reasonable assurance
that the threshold effect will be obtained, more than 0.5 weight
percent of the alkaline condensed phosphate (dry basis) is used in
the composition. Normally, the amount of alkaline condensed
phosphate used in these compositions will be from 2-20 percent,
e.g. 2-10 percent, on the same basis.
THE CITRATES
Any of the water soluble metal salts of citric acid can be used in
the practice of the present invention. However, all salts do not
serve with equal effectiveness, and the alkali metal salts,
particularly the sodium and potassium citrates, are preferred.
There are three COOH radicals on the citric acid molecule.
Commercial "sodium citrate" is fully neutralized and is more
accurately described as trisodium citrate. Trisodium citrate is
available as white crystals or granular powder. It is odorless,
stable in air, and has a pleasant saline taste. Each molecule of
trisodium citrate dihydrate loses two molecules of water of
hydration when heated to 150.degree.C. Commercial potassium citrate
also exists as white crystals or powder. It is normally available
as the monohydrate (as contrasted to sodium citrate which exists as
the dihydrate).
As used in the present invention, the amount of citrate employed
will be above 5 percent and will generally fall within the range of
5-60 weight percent on a dry basis (expressed as trisodium
citrate). Water of hydration can be considered to be part of the
salt. More usually, the amount of citrate (whether hydrated or not)
employed will be from 5-40 weight percent, e.g. 10-30 percent on
the same basis.
If desired, mixtures of citrates can be used. Although it is not
preferred, a citrate can be formed in situ from, for example, the
combination of citric acid with sodium or potassium hydroxide. The
use of a pre-formed alkali metal citrate or a mixture thereof is
particularly preferred with dry blended solid detergents.
The combination of the citrate and the condensed phosphate salt
(e.g. sodium tripolyphoshate) appears to cooperate in some fashion,
and the total of the citrate and the condensed phosphate salt will
be in the range of 7-90 weight percent on a dry basis and will
generally not exceed 65 weight percent (dry basis) of the total
composition. Excellent results can be obtained from the combination
of sodium tripolyphosphate and sodium citrate when the ratio on a
dry weight basis of polyphosphate to citrate is less than about 2:1
but greater than about 0.05:1, i.e., 1:2 to 20:1
citrate:polyphosphate. One preferred method for formulating a
detergent composition of this invention is to modify a conventional
machine dishwashing detergent formula by replacing more than
one-third of the condensed phosphate salt with citrate; provided,
of course, that the condensed phosphate content is reduced below 35
percent on a dry weight basis. A typical elemental analysis for
phosphorus in compositions of this invention shows less than 8.7%
(e.g. less than 5%) by weight phosphorus. Orthophosphates are
preferably not used as builder salts (or used in very small
amounts), so that this low phosphorus level can be maintained.
Although the alkali metal citrates can be chelating agents and are
known to have some water conditioning effects, these compounds are
not particularly effective sequestering agents at alkaline pH
levels. Nor are the citrates themselves known to be particularly
outstanding in performing the variety of functions, in addition to
sequestering, attributed to sodium tripolyphosphate (buffering,
de-flocculation, solubilizing or peptizing, etc.)
However, one-third, one-half, or even nine-tenths or more of the
polyphosphate can be replaced by citrate with little or no
significant loss in overall performance characteristics of the
detergent composition. Although this invention is not bound by any
theory, it appears that so long as sufficient condensed alkali
metal phosphate is present to preserve the threshold effect, the
citrate is an effective substitute for the remainder of the
polyphoshate that would normally be present in a machine
dishwashing detergent. However, partial replacement of condensed
alkali metal phosphate with other carboxylic acid salt water
conditioning agents (e.g. gluconate salts) does not appear to
provide the same performance as the partial replacement with
citrates.
When citrates are formed in situ from citric acid in compositions
of the present invention, either solid or dissolved citric acid can
be used. Commercially available aqueous citric acid solutions at
concentrations of about 25-40 percent by weight are suitable.
CHLORINE RELEASING AGENTS
Among the various chlorine releasing agents are chlorinated
trisodium phosphate, potassium and sodium dichloroisocyanurate,
trichloroisocyanuric acid and "double salts" or crystalline complex
salts or hydrated salts thereof (See U.S. Pat. No. 3,272,813),
trichloromelamine, "Chloramine T," alkali metal and alkaline earth
metal hypochlorites (e.g. sodium or potassium salt). These agents
are not always required for good dishwashing, and, in any event,
less than 5 or 10 percent by weight (e.g. 0.1-3%), based on the dry
solids of the total composition, is ordinarily effective.
In solid machine dishwashing compositions of the invention, the
preferred chlorine-releasing agents are the chlorinated cyanurates
and their salts. In liquid formulas, the alkali metal hypochlorites
are also particularly useful.
LOW FOAMING, NON-FOAMING OR DE-FOAMING SURFACTANTS
Although surfactants are useful in many types of detergent
compositions, those which have a tendency to produce stable foam
are preferably excluded or used in minimum amounts in machine
dishwashing compositions. The preferred surfactants of this
composition have a cloud point of about 45.degree.C. or less
(preferably less than 35.degree.C, e.g. 20.degree.-30.degree.C.)
determined in distilled water at a concentration of 1 percent.
These preferred surfactants, at 0.1 weight percent concentration in
water, have Ross-Miles test values indicating the formation of very
little stable foam after several minutes. The Ross-Miles test is
performed by pipetting the 0.1 percent detergent solution into a
column of water, measuring the height of foam immediately after
pipetting and measuring again after 5 minutes. Water hardness is
preferably specified for the test, but foam height values for
nonionic surfactants tend to be independent of the hardness of the
test water. In a column of water maintained at 50.degree.C.,
non-foaming or low-foaming detergents used in this invention have
Ross-Miles foam height values of less than 45 mm/15 mm (initial
value/ 5 minute value). Typical of these preferred surfactants are
nonionic surfactants containing oxyethylene and, if desired, some
oxypropylene units. See for example U.S. Pat. No. 3,048,548, issued
Aug. 7, 1962, and U.S. Pat. No. 3,444,242, issued May 13, 1969.
Another useful low foaming surfactant system is a blend of low
foaming oxyethylene-oxypropylene adduct and alkyl (C.sub.12
-C.sub.18) phosphate ester as described in U.S. Pat. Nos. 3,314,891
(Schmolka et al) and 3,595,968 (Groves).
The aforementioned commercial machine dishwashing test of the Rue
et al U.S. Pat. No. 3,444,242 provides a criterion for the low
foaming characteristics of completely formulated compositions of
this invention. The compositions of this invention control foam to
the extent that when used at 0.25 to 0.75 percent by weight (dry
basis) in 6.5 liters of 140.degree.F. wash water, the r.p.m. of the
wash arm with detergent alone, or with detergent plus 0.1 percent
by weight of mixed whole raw egg soil is greater than 80 percent of
the r.p.m. measured with water alone.
The aforementioned surfactants are used in limited amounts, e.g.
0-5 percent by weight of the total formulation.
OTHER ADDITIVES
Depending upon the end use and desired performance characteristics
of compositions of the invention, bases such as sodium and
potassium hydroxide, filler, corrosion inhibitors, anti-caking
agents, coloring agents and the like can be included in machine
dishwashing detergents of this invention. If desired, neutral salts
such as sodium sulfate and sodium chloride can be used as
fillers.
Generally speaking, all ingredients of compositions of this
invention, other than the aforementioned surfactants, anti-caking
agents and chlorine release agents, are water soluble. By "water
soluble" is meant the ability to form at least a 10 weight percent
solution in deionized water.
The present invention is further illustrated by the following
specific examples. Unless otherwise indicated, all parts and
percentages are by weight.
EXAMPLE I
This example illustrates the preparation of a solid or dry
detergent according to this invention.
The following dry ingredients are mixed together in the proportions
indicated. pH of the resulting composition is above 10.0.
______________________________________ Ingredient Amount (%)
______________________________________ sodium citrate dihydrate
25.0 sodium tripolyphosphate (anhydrous) 5.1 caustic soda
(anhydrous) 21.0 sodium metasilicate (anhydrous) 25.0 sodium
carbonate 21.9 sodium dichloroisocyanurate 2.0 100.0%
______________________________________
EXAMPLE II
This example illustrates the preparation of a single package liquid
machine dishwashing detergent concentrate having a pH above
10.0
Ingredient Amount (%) ______________________________________ citric
acid 10.0 tetra potassium pyrophosphate 5.0 liquid KOH (45%) 55.0
NaOCl (added as 10-15% NaOCl solution) 1.5 water 28.5 100.0%
______________________________________
The above-noted ingredients are mixed in the following manner.
Citric acid is dissolved in part or all of the water. Next, the KOH
is added to neutralize the citric acid (i.e., form a citrate in
situ). After the solution cools, the remaining ingredients are
added.
EXAMPLES III-V
Solid detergent compositions for machine dishwashing were prepared
by blending soda ash (anhydrous sodium carbonate), caustic soda
(anhydrous sodium hydroxide), the low foaming nonionic surfactant
described in U.S. Pat. No. 3,048,548, various amounts of sodium
tripolyphosphate (STP) and sodium citrate (i.e. trisodium citrate
dihydrate), the citrate and the STP each being varied over the
range of 0-33.40 parts by weight. The detergent composition
containing no citrate was referred to as the "Standard;" the
detergent containing no STP was referred to as the "All-Citrate"
sample. The low foaming nonionic surfactant was pre-mixed with
sodium carbonate to form an 85/15 (weight/weight) Na.sub.2 CO.sub.3
/surfactant composition hereinafter referred to as the
"pre-mix."
The resulting formulations were:
INGREDIENTS IN PARTS BY WEIGHT
__________________________________________________________________________
Chlorine Soda Caustic Dry Sodium Example Ash Soda Pre-Mix Bleach
STP Citrate
__________________________________________________________________________
Standard 30.80 21.40 12.00 2.40 33.40 0.0 III 30.80 21.40 12.00
2.40 16.70 16.70 IV 30.80 21.40 12.00 2.40 5.56 27.74 V 30.80 21.40
12.00 2.40 3.04 30.36 All-Citrate 30.80 21.40 12.00 2.40 0.0 33.40
__________________________________________________________________________
The pH of the Standard was measured with a Corning glass electrode
pH meter at 1.0 percent by weight and 0.1 percent by weight
concentration in aqueous solution. The results were:
Concentration pH ______________________________________ 1% 12.65
0.1% 11.55 ______________________________________
The detergent formulations were tested and compared to the
"Standard" as to their performance in machine dishwashing. In the
test, glasses were washed in a Hobart C-44 dishwasher using well
water of 13 grains hardness heated to 160.degree.F. The glasses
were cycled ten times in the dishwasher, during which time the
detergent concentration was maintained at a level of 2,000 parts
per million (plus or minus 5 percent). Following completion of the
test, the glasses were inspected for filming and spotting. The
results reported subsequently in Table I were based upon an average
rating of three glasses. The detergents were ranked in order of
performance from the least film (1) to the heaviest film (5).
Essentially no foaming was observed in the wash tank in connection
with any of the detergent formulations tested.
Table I ______________________________________ Performance of
Examples III-V vs. Standard and All-Citrate Example Glass Film
Results ______________________________________ V 1 (Slight)
Standard 2 (Very light) III 3 (Very light) IV 4 (Light) All-Citrate
5 (Light) ______________________________________
EXAMPLES VI-VIII
Solid detergent compositions were prepared substantially as in
Examples III-V except that no premix was included, and amounts of
caustic soda were different, and sodium metasilicate was used in
place of soda ash. The resulting formulations were:
Parts by Weight Sodium Other Example STP Citrate Ingredients*
______________________________________ Standard 52.60 0.0 47.40 VI
26.30 26.30 47.40 VII 8.80 43.80 47.40 VIII 4.80 47.80 47.40
All-Citrate 0.0 52.60 47.40 ______________________________________
*Metasilicate: 23.70 parts, chlorine dry bleach: 2.40 parts, and
caustic soda: 21.30 parts.
The above Standard was also measured for pH in the same manner as
the Standard of Examples III-V with the following results:
Concentration pH ______________________________________ 1% 12.75
0.1% 11.55 ______________________________________
Results of the glass film test are shown in Table II. Again,
essentially no foaming was observed in the wash tank when these
formulations were used. The test method was the same as that of
Examples III-V.
Table II ______________________________________ Performance of
Examples VI-VIII vs. Standard and All-Citrate Example Glass Film
Results ______________________________________ Standard 1 (Extra
Slight) VIII 2 (Extra Slight) VI 3 (Slight) VII 4 (Slight)
All-Citrate 5 (Light) ______________________________________
EXAMPLE IX
As a further comparison with Examples V and VIII, the performance
of low tripolyphosphate formulations containing no citrate were
investigated. In comparison Examples V-A and VIII-A, the
formulations were the same as Examples V and VIII except that the
citrate was simply omitted so that the total parts used were only
69.64 and 52.20, respectively. In comparison Examples V-B and
VIII-B, the citrate was replaced with 30.36 parts and 47.80 parts,
respectively, of soda ash. Test results were determined as in
Examples III-VIII and are set forth in Table III.
Table III ______________________________________ Comparison
Examples Example Glass Film Results
______________________________________ V-A 3 (Slight) V-B 4
(Slight) VIII-A 5 (Light) VIII-B 6 (Light) (Ratings 1 and 2 applied
to Examples V and VIII.) ______________________________________
* * * * *