U.S. patent application number 11/570425 was filed with the patent office on 2008-10-30 for stable nonaqueous bleaching detergent composition dispersion.
Invention is credited to Evert Peter Ids Baars, Lali Pataridze, William E. Simpson.
Application Number | 20080263778 11/570425 |
Document ID | / |
Family ID | 34929295 |
Filed Date | 2008-10-30 |
United States Patent
Application |
20080263778 |
Kind Code |
A1 |
Baars; Evert Peter Ids ; et
al. |
October 30, 2008 |
Stable Nonaqueous Bleaching Detergent Composition Dispersion
Abstract
The invention pertains to a nonaqueous bleaching detergent
composition comprising: a) a solid bleaching agent in an amount
from 20% to 85% by weight, said solid bleaching agent being a
hypochlorite-liberating agent, b) a thickening agent in an amount
from 0.1 to 10% by weight, wherein the thickening agent is a
mixture of clay and polymer in a ratio of clay:polymer of 1:10 to
10:1, c) a thickening agent activator in an amount of up to 0.3% by
weight, d) an auxiliary compound in an amount from 0 to 23% by
weight, and e) a nonaqueous liquid in an amount of at least 14.9%
by weight which is chemically inert to the bleaching agent and
wherein the solubility of the bleaching agent is less than 10 mg/l,
said nonaqueous liquid being selected from vegetable oils, mineral
oils, synthetic oils, or animal oils including fish oils, and
admixtures thereof.
Inventors: |
Baars; Evert Peter Ids;
(Wijk bij Duurstede, NL) ; Pataridze; Lali;
(Woerden, NL) ; Simpson; William E.; (New Berlin,
WI) |
Correspondence
Address: |
JohnsonDiversey, Inc.
8310 16TH STREET, M/S 509, PO BOX 902
STURTEVANT
WI
53177-0902
US
|
Family ID: |
34929295 |
Appl. No.: |
11/570425 |
Filed: |
June 15, 2005 |
PCT Filed: |
June 15, 2005 |
PCT NO: |
PCT/US05/21160 |
371 Date: |
January 7, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60585619 |
Jul 6, 2004 |
|
|
|
Current U.S.
Class: |
8/108.1 |
Current CPC
Class: |
C11D 3/3765 20130101;
C11D 3/3956 20130101; C11D 3/3749 20130101; C11D 3/2093 20130101;
C11D 3/18 20130101; C11D 17/0004 20130101; C11D 3/382 20130101;
C11D 11/0094 20130101; C11D 3/3955 20130101; C11D 3/1266 20130101;
C11D 3/3947 20130101; C11D 3/3707 20130101 |
Class at
Publication: |
8/108.1 |
International
Class: |
D06L 3/08 20060101
D06L003/08 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 6, 2004 |
EP |
04103183.2 |
Claims
1. A nonaqueous bleaching detergent composition comprising a
dispersion of: a) a solid bleaching agent in an amount from 20% to
85% by weight, said solid bleaching agent being a
hypochlorite-liberating agent, b) a thickening agent in an amount
from 0.1 to 10% by weight, wherein the thickening agent is a
mixture of clay and polymer in a ratio of clay:polymer of 1:10 to
10:1, c) a thickening agent activator in an amount of 0 to 0.3% by
weight, d) an auxiliary compound in an amount from 0 to 23% by
weight, and e) a nonaqueous liquid in an amount of at least 14.9%
by weight which is chemically inert to the bleaching agent and
wherein the solubility of the bleaching agent is less than 10 mg/l,
said nonaqueous liquid being selected from vegetable oils, mineral
oils, synthetic oils, or animal oils including fish oils, and
admixtures thereof.
2. The bleaching detergent composition of claim 1 wherein the
bleaching agent is selected from a salt of dihaloisocyanurate,
trihaloisocyanurate, chloramine-T, N-halosuccinimide,
N-halomalonimide, N-halophthalimide, N-halonaphthalimide,
1,3-dihalo-5,5-dimethylhydantion; N-monohalo-C,C-dimethylhydantion;
methylene-bis(N-halo-C,C-dimethylhydantoin);
1,3-dihalo-5-methyl-5-isobutylhydantoin;
1,3-dihalo-5-methyl-5-ethylhydantoin;
1,3-dihalo-5,5-diisobutylhydantoin;
1,3-dihalo-5-methyl-5-n-amylhydantoin; trihalomelamine, and
mixtures thereof, wherein halo stands for chloro.
3. The bleaching detergent composition of claim 1 or 2 wherein the
bleaching agent has a particle size less than 400 .mu.m, preferably
10 to 200 .mu.m, most preferably 30-110 .mu.m.
4. The bleaching detergent composition of any one of claims 1 to 3
wherein said clay is organically modified smectite, organically
modified bentonite, or synthetic hectorite.
5. The bleaching detergent composition of any one of claims 1 to 4
wherein said polymer is a block(co)polymer styrene/ethylene
oxide/propylene oxide or triblockcopolymer
styrene-ethylene/butylene-styrene.
6. The bleaching detergent composition of any one of claims 1 to 5
wherein the auxiliary compound is selected from surfactant, bleach
activator, enzyme, colorant, perfume, phosphate, anti-foam agent,
inorganic carbonate or hydrogen carbonate, gloss enhancer,
sequestering agent, and nonaqueous builder, or mixtures
thereof.
7. The bleaching detergent composition of any one of claims 1 to 6
which comprises 25 to 50%, preferably 35 to 45% by weight, of said
bleaching agent.
8. The bleaching detergent composition of any one of claims 1 to 7
which comprises 0.1 to 6%, preferably 0.1 to 4%, more preferably
0.5 to 3% by weight, of said thickening agent.
9. The bleaching detergent composition of claim 1-8 wherein said
thickening agent is in a ratio of clay:polymer of 1:3 to 2:1.
10. The bleaching detergent composition of any one of claims 1 to 9
wherein the nonaqueous liquid is paraffin oil.
11. The bleaching detergent composition of any one of claims 1 to
10 wherein the thickening agent activator is propylene
carbonate.
12. A closed package comprising the bleaching detergent composition
of any one of claims 1-11.
13. A method for preparing the bleaching detergent composition of
any one of claims 1-11, comprising the steps: i) making at elevated
temperature a pre-gel of a polymer and a nonaqueous liquid, which
is chemically inert to the bleaching agent and wherein the
solubility of the bleaching agent is less than 10 mg/l; ii) making
a pre-gel of a clay, the nonaqueous liquid, and, optionally, a
thickening agent activator, in a high-shear mixer; iii) adding
under stirring the pre-gel of ii) to the pre-gel of i), and iv)
adding a solid bleaching agent, and, optionally, an auxiliary
compound.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention pertains to a nonaqueous bleaching
detergent composition comprising a dispersion, a method of
manufacturing said composition, and to a closed package containing
the same.
[0003] 2. Description of the Prior Art
[0004] Commercially available detergents for washing machines and
dishwashing applications provided in powder dispersion or slurry,
or in liquid form have the disadvantage of not being stable in high
concentrations.
[0005] Stable nonaqueous bleaching detergent composition have been
developed, for instance the composition of U.S. Pat. No. 5,164,106,
wherein a dishwasher detergent composition having improved cleaning
performance against difficult to remove soils was disclosed. The
disclosure of this patent was directed to a stable nonaqueous
liquid composition containing a dual bleach system for use in an
automatic dishwasher to clean dishware, glassware, cookware, and
the like. It discloses a nonaqueous bleaching detergent composition
comprising a dispersion of a carrier liquid, a bleaching agent
selected from a hypochlorite-liberating compound, a nonaqueous
builder salt, sodium silicate, alkali metal carbonate, and a
bromine compound. Typical bleaching compositions contain an amount
to provide 0.5 to 10% chlorine, corresponding to the use of
hypochlorite-liberating compounds of 1 to 18 wt. %, and preferably
of 2 to 12 wt. %. According to the examples concentrations of the
bleaching agent of 2.5 to 5.36% by weight could be obtained.
[0006] Aqueous bleach compositions are known in the art, for
instance in U.S. Pat. No. 4,992,194. This patent describes a method
wherein a nonaqueous peroxide acid is kept water insoluble by using
a low pH. At higher pH the peroxide acid dissolves and thereby
becomes inactivated. The disadvantage of this method is the
restricted numbers of suitable peroxide acids. In fact one of the
few acids that can be used according to this prior art method are
compounds of the group PAP (phthaloyl aminoperoxocaproic acids).
This method therefore is certainly not generally applicable.
SUMMARY OF THE INVENTION
[0007] It was found that compositions of U.S. Pat. No. 5,164,106
are not stable at amounts of bleaching agent above 18% by weight.
This is a considerable problem because there is a need for more
concentrated bleaching compositions, which are effective in
removing proteinaceous and starchy carbohydrate soils in
dishwashing and stubborn stains in laundry washing, and which are
also effective in cleaning hard surfaces in CIP (cleaning in place)
applications, such as in the food and beverage industry. For
economic reasons it is particularly important to obtain
compositions that are stable enough to be stored for longer periods
of time at higher temperatures. The latter is of particular
importance when using oxygen-generating bleaching agents because on
decomposition they can release oxygen, or chlorine in the case of
hypochlorite-releasing agents. In general, bleaching agents
including peroxide- and hypochlorite-releasing agents, ultimately
release oxygen, and decomposition of the bleaching agent will lead
to decrease of activity and build up of oxygen pressure (in
non-vented packages), which can lead to hazardous conditions when
stored in (non-vented) bottles and other packaging types which are
opened after decomposition has commenced.
[0008] Thus there is a need for stable dispersions containing much
higher concentrations of bleaching agent than known in the art.
[0009] An object of the present invention is to obtain a stable
dispersion containing at least 20% by weight, preferably about 40%
by weight or higher of a bleaching agent, which can be selected
from a large group of bleaching agents, particularly form
oxygen-generating bleaching agents. It is further an object of the
invention that such compositions can be packed and stored for long
periods of time without decomposition or formation of oxygen.
[0010] The problem to be solved is to formulate a concentrated
nonaqueous liquid detergent composition that is stable in storage
and effective as bleach in automatic dishwashing, laundering and
other bleaching applications. In particular, the composition should
easily remove coffee, tea, and wine stains. Typical stains, such as
originating from blood, starch and proteins should also be easily
removed. The composition should be made at substantially higher
concentrations than compositions known from the prior art, while
maintaining stability under long term storage conditions.
[0011] Another object of the invention is to provide a nonaqueous
liquid detergent concentrate composition which is stable under
storage conditions, does not degrade or decompose (even at elevated
temperatures), is easily pourable, and is readily dispersible in
the wash water.
The present invention is directed to a nonaqueous bleaching
detergent composition comprising a dispersion of:
[0012] a) a solid bleaching agent in an amount from 20% to 85% by
weight, said solid bleaching agent being a hypochlorite-liberating
agent,
[0013] b) a thickening agent in an amount from 0.1 to 10% by
weight, wherein the thickening agent is a mixture of clay and
polymer in a ratio of clay:polymer of 1:10 to 10:1,
[0014] c) a thickening agent activator in an amount of 0 to 0.3% by
weight,
[0015] d) an auxiliary compound in an amount from 0 to 23% by
weight, and
[0016] e) a nonaqueous liquid in an amount of at least 14.9% by
weight which is chemically inert to the bleaching agent and wherein
the solubility of the bleaching agent is less than 10 mg/l, said
nonaqueous liquid being selected from vegetable oils, mineral oils,
synthetic oils, or animal oils including fish oils, and admixtures
thereof.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0017] It was found that the compositions according to this
invention are stable for at least 6 months, usually for at least 1
year, and in most cases even for an unlimited time period, and
nevertheless contain very concentrated bleaching agent. It is
possible to obtain stable compositions having 25 to 50%, preferably
35 to 45% by weight of the bleaching agent. Compositions within the
most preferred range, i.e. containing 35 to 45% by weight of the
bleaching agent, can be used in conventional washing machines,
dishwashers, and the like. At higher concentrations, particularly
those close to 85% by weight, the compositions become more viscous
but can be used in adapted machines that use higher pressures to
pump the bleaching composition. Concentrations higher than 85% by
weight are possible, but due to the substantial increase of
viscosity they are not commercially useful.
[0018] Surprisingly, the compositions of this invention can be used
for liquid automatic dishwasher detergent composition having
improved cleaning performance on protein and carbohydrate soils in
automatic dishwashing, and on coffee, tea, and wine stains in
textile laundering. They can also be used in food and beverage
industries for cleaning hard surfaces. More generally, the bleach
can be used as destainer but also for sanitizing purposes in dish
wash and laundry. The liquid detergent composition contains an
bleach source, particularly an oxygen-generating bleach source, and
more particularly contains a source of hypochlorite.
[0019] The present invention specifically relates to liquid
automatic dishwashing detergent concentrate compositions having
improved cleaning performance against proteinaceous and starchy
carbohydrate soils on dishware, glassware, cookware, and the like,
particularly cooked on and baked on soils, and improved cleaning
capacity for coffee, tea and wine stains. Such stains are removed
in laundry applications.
[0020] The nonaqueous liquid compositions are stable in storage, do
not settle, are preferably pourable and are readily dispersed in
water.
[0021] The nonaqueous liquid detergent compositions of the present
invention have the advantages of being stable, non-settling and
non-gelling in storage, and are readily-dispersible in
(dish)washing machines. The preferred liquid compositions of the
present invention are easily poured, easily measured, and easily
put into (dish)washing machines and are readily dispersed in the
wash water in the (dish)washing machines.
[0022] These and other objects of the invention will become more
readily understood from the following detailed description of the
invention and preferred embodiments thereof.
[0023] In accordance with the present invention there is provided a
nonaqueous liquid automatic dishwasher detergent composition which
includes at least a bleaching agent preferably selected from an
oxygen-generating compound, a thickening agent, a nonaqueous
liquid, and optionally a thickening agent activator, and auxiliary
compound(s). The term "nonaqueous" throughout this invention means
a composition or liquid containing less than 5% by weight of free
water. Thus the compositions and liquids of the invention at the
most only contain minor amounts of free water, and preferably do
not contain any free water.
[0024] The present invention also provides a method for cleaning
dishware, glassware, and cookware in a household or industrial
automatic dishwashing machine and a method for cleaning laundry in
a washing machine with an aqueous wash bath containing an effective
amount of the nonaqueous liquid composition as described above.
According to this aspect of the invention, the composition is
stable in storage, is easily measured and can be readily poured or
dispersed into automatic (dish)washing machines.
1 Bleaching Agents
[0025] Oxygen-generating compounds suitable for use in bleaching
compositions are those water soluble solid materials which generate
oxygen on contact with, or dissolution in, water. Such oxygen
release can be obtained by direct oxygen release or release via
hypochlorite, hypobromite, or hypoiodite ions, ozone, perhydroxy
ions, or halodioxide, such as chlorodioxide. Examples of solid
bleaching agents are particulate heterocyclic N-haloimides such as
trihalocyanuric acid, dihalorocyanuric acid and salts thereof such
as sodium dihalocyanurate and potassium dihalocyanurate, wherein
the term "halo" stands for chloro, bromo, or iodo. The preferred
halo group is chloro. The corresponding dihaloisocyanuric and
trihaloisocyanic acid salts can also be used. Other N-halomides may
be used such as N-halosuccinimide, N-halomalonimide,
N-halophthalimide and N-halonaphthalimide. Additional suitable
N-haloroimides are the hydantoins such as
1,3-dihalo-5,5-dimethylhydantion; N-monohalo-C,C-dimethylhydantion;
methylene-bis(N-halo-C,C-dimethylhydantoin);
1,3-dihalo-5-methyl-5-isobutylhydantoin;
1,3-dihalo-5-methyl-5-ethylhydantoin;
1,3-dihalo-5,5-diisobutylhydantoin;
1,3-dihalo-5-methyl-5-n-amylhydantoin; and the like.
[0026] Preferred solid bleaching agents are hypochlorite-liberating
agents. Useful hypochlorite-liberating agents are trichloromelamine
and dry, particulate, water soluble anhydrous inorganic salts such
as calcium and lithium hypochlorite. The hypochlorite-liberating
agent may, if desired, be a stable, solid complex or hydrate such
as sodium p-toluene-sulfo-chloramine-trihydrate (choramine-T),
sodium benzene-sulfo-chloramine-dihydrate, calcium hypochlorite
tetrahydrate, or chlorinated trisodium phosphate containing 0.5 to
4% available chlorine produced by combining trisodium phosphate in
its normal Na.sub.3PO.sub.4.12H.sub.2O form and an alkali metal
hypochlorite (e.g., sodium hypochlorite). Apart for potassium,
sodium and calcium, also other salts may be used, such as lithium,
magnesium, and ammonium salts.
[0027] In compositions in which the alkali and alkaline earth metal
hypochlorites are used as the chlorine source, these compounds can
be used in the form of anhydrous dispersed solids in order to
prevent deterioration of the nonionic surfactants in the
composition.
[0028] The preferred sources of hypochlorite are dichloro- and
trichloroisocyanurates and chloramine-T
(p-toluenesulfochloramine).
[0029] Source of hydrogen peroxide is selected from the group
percarbonate, persilicate, persulfate, perborate, peroxyacids,
dialkyl peroxides, diacyl peroxides, preformed percarboxylic acids,
nonaqueous peroxides, inorganic peroxides, hydroperoxides, and
mixtures thereof. Specific examples include peroxyformic acid,
peroxyacetic acid, monoperphthalate, monoperoxysuccinate,
monoperoxysulfate, monoperoxy phosphate, peroxyoctanoic acid,
peroxybenzoic acid, ethylperoxycarbonic acid,
phthalimidoperoxyhexanoic acid, sodium perborate, and sodium
percarbonate.
[0030] Typically, the oxygen-generating agents are employed in a
proportion of about 20 to 85% by weight of the composition,
preferably about 25 to 50%, and more preferably 35 to 45% by
weight.
[0031] It was found that the best dispersions were obtained with
solid bleaching agents having a particle size less than 400 .mu.m,
preferably 10 to 200 .mu.m, most preferably 30-110 .mu.m. According
to the examples the bleaching particles have a particle size of
about 70 .mu.m.
2. Thickening Agents
[0032] The composition also includes conventional thickening agents
in amounts from 0.1 up to 10% by weight to obtain a product
consistency of a cream or a paste.
[0033] The thickening agents, i.e. thickeners or suspending agents
which provide thickening properties, are known in the art and may
be water soluble or insoluble, dispersible or colloid-forming, and
monomeric or polymeric, and should of course be stable in these
compositions, e.g., stable to alkalinity and bleaching agents, such
as sodium hypochlorite and peroxide. The preferred thickeners
generally comprise the inorganic, colloid-forming clays of smectite
and/or attapulgite types. These materials are generally used in
amounts of about 1.5 to 10 wt. %, preferably 2 to 5 wt. %, to
confer the desired thickening properties to the formulation.
[0034] Smectite clays include montmorillonite (bentonite),
hectorite, attapulgite, smectite, saponite, and the like.
Montmorillonite clays are preferred and are available under trade
names such as Tixogel.RTM. MP100, Tixogel.RTM. VP, Tixogel.RTM. MIO
from Sud-chemie, Bentone.RTM. 34, Bentone.RTM. Gel, Bentone.RTM.
SD-1 from Water Ingredients, Thixogel.RTM. No. 1 and Gelwhite.RTM.
GP, H, etc., from Georgia Kaolin Company; and ECCAGUM.RTM. GP, H,
etc., from Georgia Kaolin Company; and ECCAGUM.RTM. GP, H, etc.,
from Luthern Clay Products. Attapulgite clays include the materials
commercially available under the trade name Attagel.RTM., i.e.
Attagel.RTM. 40, Attagel.RTM. 50 and Attagel.RTM. 150 from
Engelhard Minerals and Chemicals Corporation. Mixtures of smectite
and attapulgite types in weight ratios of 4:1 to 1:5 are also
useful. Thickening or suspending agents of the foregoing types are
well known in the art, being described, for example in U.S. Pat.
No. 3,985,668, which is incorporated herein by reference. Preferred
clays are organically modified bentonite, organically modified
smectite, and synthetic hectite.
[0035] The conventionally used organic polymeric thickening agents,
such as the polyacrylates, e.g. powdered polyacrylates having a
molecular weight of 1,000-20,000 can be used. Suitable
polyacrylates, e.g. sodium, are Alcosperse.RTM. 130D, MW 15,000,
available from Alco Chem. Co. Alcosperse.RTM. 149D, MW 2000,
available from Alco Chem. Co., and Alcrysol.RTM. 45N, MW 4500,
available from Rohm & Haas Co., Polymer WSP 10 (butene
copolymer), WSP 01 (blockcopolymer S-E/P (styrene/ethylene
oxide/propylene oxide)), WSP 52 (triblockpolymer
styrene-ethylene/butylene), WSP 50 (triblockcopolymer
styrene-ethylene/butylene-styrene), WSP 22 (polybutene),
PEO-1(polyethyleneoxide) from Water Ingredients.
[0036] The composition preferably comprises 0.1 to 6%, preferably 1
to 4%, more preferably 2 to 3% by weight of thickening agent.
[0037] It was further found that apart from the chemical stability
as obtained with these compositions, also a high physical stability
could be obtained (i.e. stabile dispersions without phase
separation) when a mixture of both a clay and a polymer was used as
thickening agent. Such mixtures are effective for increasing the
physical stability when the ratio clay:polymer is 1:10 to 10:1,
preferably 1:3 to 2:1. Most preferably, these mixtures are used in
combination with paraffin oil as nonaqueous liquid (see herein
below).
3. Thickening Agent Activator
[0038] The compositions may contain up to 0.3% by weight of a
thickening agent activator. Such activators improve the dispersing
properties of the clay thickening agents, and are well known in the
art. Suitable activators for use with clays include lower alcohols,
such as ethanol, and propylene carbonate.
4. Auxiliary Compounds
[0039] The composition may further contain up to 23% by weight of
an auxiliary compound. Auxiliary compounds are for instance
surfactant detergents, builder salts such as phosphates, silicates,
and carbonates, foam inhibitors, perfumes, gloss enhancers,
colorants, sequestering agents, and the like.
[0040] Surfactants that can be used linear or branched alkali metal
mono- and/or di-(C8-14)alkyl diphenyl oxide mono- and/or
disulfonates, which are commercially available for example as
DOWFAX.RTM. 3B-2 and DOWFAX.RTM. 2A-1. Other suitable surfactants
include the primary alkyl sulfates, alkyl sulfonates, alkylaryl
sulfates, sec-alkyl sulfates, alkyl phosphonates. Examples include
sodium (C10-18)alkyl sulfates such as sodium dodecyl sulfate;
sodium (C10-18)alkyl sulfonates such as sodium
hexadecyl-1-sulfonate and sodium (C12-18)alkylbenzene sulfonates,
such as sodium dodecylbenzene sulfonates. The corresponding
potassium salts may also be employed.
[0041] Sodium carbonate can be added as a builder salt to act as a
buffer to maintain the desired pH level. The compositions of the
present invention can also contain inorganic builder salts such as
NaTPP or organic builder salts such as the alkali metal salts of
polycarboxylic acids.
[0042] A preferred inorganic builder salt is an alkali metal
polyphosphate such as sodium tripolyphosphate (TPP). In place of
all or part of the alkali metal polyphosphate one or more other
detergent builder salts can be used. Suitable other builder salts
are alkali metal borates, phosphates and hydrogencarbonates.
Specific examples of such builders are sodium tetraborate, sodium
pyrophosphate, potassium pyrophosphate, sodium bicarbonate, sodium
hexametaphosphate, sodium sesquicarbonate, sodium mono- and
di-orthophosphate, potassium bicarbonate, and sodium or potassium
zeolites.
[0043] Since the compositions of this invention are generally
highly concentrated, and therefore may be used at relatively low
dosages, it is desirable to supplement any phosphate builder (such
as sodium tripolyphosphate) with an auxiliary builder such as an
alkali metal polycarboxylic acid. Suitable alkali metal
polycarboxylic acids are alkali metal salts of citric and tartaric
acid, e.g., monosodium and disodium citrate (anhydrous). The sodium
salts of citric and tartaric acids are preferred.
[0044] Addition of foam inhibitors is important to increase
dishwasher machine efficiency and minimize destabilizing effects
which might occur due to the presence of excess foam within the
washer during use. Foam may be sufficiently reduced by suitable
selection of the type and/or amount of detergent active material,
the main foam-producing component. The degree of foam is also
somewhat dependent on the hardness of the wash water in the machine
whereby suitable adjustment of the proportions of NaTPP which has a
water softening effect may aid in providing the desired degree of
foam inhibition. However, it is generally preferred to include a
chlorine bleach stable foam depressant or inhibitor. Particularly
effective are alkyl phosphonic acid esters which are available, for
example, from BASF-Wyandotte (PCUK-PAE), and alkyl acid phosphate
esters which are available, for example, from Hooker (SAP) and
Knapsack (LPKN-158). Other foam inhibitors which may be used
include, for example, the known silicones such as Dow Corning 1400
and 1500, which are polysiloxanes mixed with dispersed silica.
[0045] Alkali metal silicates, e.g. sodium silicate, which provide
alkalinity and protection of hard surfaces, such as fine china, may
be employed. Sodium silicate also protects the washing machine from
corrosion. The preferred silicates are sodium disilicate and sodium
metasilicate.
[0046] Most of the components of the composition can be added to
the nonaqueous liquid composition in the form of dry powders or
nonaqueous dispersions or solutions.
[0047] Sequestering agents can be employed in higher quantities
when necessary. Preferred sequestering agents are compounds that
have a strong complexation with or bonding to calcium and
magnesium. Most preferred are sodium or potassium salts of NTA
(nitrilotriacetic acid), MGDA (methylglycinediacetic acid), EDTA
(ethylenediamine tetraacetic acid), and (S,S)-EDDS
(ethylenediamine-N,N'-disuccinic acid), or mixtures thereof.
Preferred amounts of the sequestering agent amount to 10-23 wt.
%.
[0048] Various other conventional ingredients may be included in
these compositions in small amounts, generally less than about 4
wt. %, such as perfume and hydrotropic agents, preservatives, gloss
enhancers, dyestuffs, and pigments and the like, all of course
being stable to chlorine bleaching agent and high alkalinity
(properties of many of the components). Especially preferred for
coloring are the chlorinated phthalocyanines and polysulfides of
aluminosilicate which provide, respectively, pleasing green and
blue tints.
5. Nonaqueous Liquids
[0049] The nonaqueous liquids that can be used in accordance with
the present invention are in general vegetable oils, mineral oils,
synthetic oils, or animal oils including fish oils, and mixtures
thereof. Specific but not exhaustive examples are paraffin oil,
coconut oil, salad oil, and olive oil.
[0050] The above discussed nonaqueous liquids can be used alone or
in admixture in order to obtain a desired viscosity and stability
of the product liquid. It may be preferred to use a nonaqueous
liquid that is a mixture of at least two liquids. Preferred
mixtures contain in addition to the above liquids 0.1 to 5% by
weight of a saturated or unsaturated fatty acid having 12 to 24
carbon atoms as co-liquid. Examples of such co-liquids are for
instance silicone oil, low alkanes such as hexanes, heptanes,
octanes, soybean oil methyl esters (e.g. Steposol.RTM. SB-W),
methyl soyate/ethyl lactate blend (e.g. Steposol.RTM. SC), isobutyl
ester (Rodiasolve.RTM. DIB, ex. Rhodia), and other types of liquids
such as ethylene glycol ethers.
[0051] The component only partially dissolve or do not dissolve at
all in the liquids and co-liquids, and form an emulsion,
dispersion, or suspension in the liquid.
[0052] The compositions of the present invention have good
viscosity and stability characteristics and remain stable at room
temperature and higher, and are pourable at low temperatures. A
particularly useful composition contained 35-45 wt. % of solid
sodium dihaloiscyanuric acid (NaDCCA) having a mean particle size
of about 60-80 .mu.m, 0.5-3 wt. % of a clay thickener such as
Tixogel.RTM. MP100, 0.02 to 0.04 wt. % ethanol, and 64.48 to 51.96
wt. % up to 100 wt. % of paraffin oil. It was found that the
stability was excellent in that no oxygen formation occurred. The
stability of the compositions of the invention is expressed as less
than 5% decrease of activity of the bleaching agent after 6 months
storage at 40.degree. C., as measured by thiosulfate titration
according to ASTM D 2022. For that reason the composition can be
stored in close packages for months under normal storage conditions
between 0 and 40.degree. C. It is therefore also an object of the
invention to obtain storage stable packages (or containers)
containing the composition of the invention.
Method of Preparation of Liquid Composition
[0053] The compositions of the present invention can be prepared by
conventional means. In a suitable manner to make the compositions
of the invention the method comprising the steps: [0054] i) making
at elevated temperature a pre-gel of a polymer and a nonaqueous
liquid, which is chemically inert to the bleaching agent and
wherein the solubility of the bleaching agent is less than 10 mg/l;
[0055] ii) making a pre-gel of a clay, the nonaqueous liquid, and,
optionally, a thickening agent activator, in a high-shear mixer;
[0056] iii) adding under stirring the pre-gel of ii) to the pre-gel
of i), and [0057] iv) adding a solid bleaching agent, and,
optionally, an auxiliary compound.
[0058] Suitable elevated temperatures as used in step i) are above
100.degree. C., preferably about 150.degree. C. High-shear mixers
as used in step ii) are known in the art and comprise mixtures such
as Silverson, ULTRA TURRAX T25, and Heidolph DIAX 600.
[0059] The invention may be put into practice in various ways and a
number of specific embodiments will be described to illustrate the
invention.
[0060] The viscosity profile was determined for a structured liquid
containing 55% of paraffin oil, 3% of fractionated coconut oil, 2%
of Tixogel.RTM. MP100, and 40% of sodium dichloroisocyanuric acid
(NaDCCA).
[0061] The following examples of formulations according to the
invention illustrate the invention and are not intended to restrict
the invention
Pre-Gels
[0062] Pre-gel Polymer (WSP01):
A mixture of 96 wt. % paraffin oil and 4 wt. % WSP.RTM. 01
(blockcopolymer styrene-ethylene/propylene, ex Water Ingredients,
Zeist, The Netherlands) was stirred and heated above 160.degree. C.
for about 60 min. After WSP01 was completely dissolved it was
slowly cooled down under stirring. Pre-gel WSP 50 was made
according to the above procedure wherein 99 wt. % paraffin oil and
1 wt. % WSP.RTM. 50 (triblock polymer
styrene-ethylene/butylene-styrene, ex Water Ingredients, Zeist, The
Netherlands) solution was stirred and heated above 160.degree. C.
for about 60 min. When WSP50 was dissolved it was slowly cooled
down under stirring.
[0063] Pre-Gel Clay:
A mixture of 88 wt. % paraffin oil and 10 wt. % Tixogel.RTM. MP 100
(ex Sud-Chemie, Munich, Germany) was brought into a plastic beaker
and stirred with a high shear mixer (Ultra Turrax) during 5 to 10
min (speed: 16000 rpm), after which 2 wt. % ethanol were added to
the blend and stirred with a high shear mixer for another 10 min at
16000 rpm.
Procedure
[0064] Paraffin oil (32.5%) and the pre-gel clay (15%) were mixed
for 5 min, after which the pre-gel polymer (12.5%) was added and
mixing was continued for 20 min. Then NaDCCA powder (40%) (ex.
Clearon, Terneuzen, The Netherlands) was added and the mixture was
stirred for another 30 min.
Formulations
[0065] The following formulations according to the invention were
prepared.
A) 50% Pre-gel WSP 01+10% Pre-gel MP 100+40% NaDCCA
B) 45% Pre-gel WSP 01+15% Pre-gel MP 100+40% NaDCCA
[0066] C) 32.5% Paraffin oil+15% Pre-gel MP 100+12.5% Pre-gel WSP
01+40% NaDCCA D) 42.5% Paraffin oil+15% Pre-gel MP 100+12.5%
Pre-gel WSP 01+30% NaDCCA E) 57% Paraffin oil+2% Pre-gel WSP 01+1%
Pre-gel MP 100+40% NaDCCA F) 58% Paraffin oil+0.5% Pre-gel WSP
50+1.5% Pre-gel MP 100+40% NaDCCA. The above compositions were
tested for their stability by measuring the phase separation as
follows. The products were brought into a measuring cylinder and
kept at 40.degree. C. for 40 days. The volume of the separated oil
was read out from the measuring bars and expressed as percentage of
the total volume. None of the compositions of the invention showed
phase separation (oil volume 0%), whereas comparison compositions
made of the pre-gel of the clay only, showed substantial phase
separation (oil volume in the range from 5 to 15%).
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