Note: Descriptions are shown in the official language in which they were submitted.
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I
COATED PARTICLE-CONTAININ~;;, NON-AQUEOUS
LIQUID CLEANING COMPOSITIONS
FIELD OF TH~ INVENTION
This invention }elates to liquid cleaning products for fabric laundering. Such
products are nonaqueous in nature and are in the form of stable dispersions of
particulate material that includes peroxygen bleaching agents and specific types of
coated peroxygen bleach activators
BACKGROUND OF THE INVENTION
Liquid cleaning, e.g. bl~ hin~ products are often considered to be more
convenient to use than are dry powdered or particulate cleaning products. Liquidcleaners have therefore found substantial favor with consumers. Such liquid
detergent products are readily measurable, speedily dissolved in the wash water,capable of being easily applied in conce~ dl~d solutions or dispersions to soiled
areas on g~rment~ to be laundered and are non-dusting. They also usually occupy
less storage space than granular products. Additionally, liquid cleaning products
may have incorporated in their formulations materials which could not withstand
drying operations without deterioration, which operations are often employed in the
m~n~ ture of particulate or granular detergent or bleach products.
Although liquid cleaners have a number of advantages over granular cleaning
products, they also inherently possess several disadvantages. In particular, detergent
or bleach composition components which may be compatible with each other in
granular products may tend to interact or react with each other in a liquid, andespecially in an aqueous liquid, environment. Thus such components as enzymes,
surf~ct~nt~, perfumes, brighten~rs, solvents and especially bleaches and bleach
activators can be especially difficult to incorporate into liquid cleaning products that
have an acceptable degree of chemi~l stability.
One approach for enhancing the chemical compatibility of detergent o~ bleach
composition components in liquid cleaning products has been to formulate
nonaqueous (or anhydrous) liquid detergent compositions. In such nonaqueous
products, at least some of the normally solid cleaning composition components tend
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to remain insoluble in the liquid product and hence are less reactive with each other
than if they had been dissolved in the liquid matrix. Nonaqueous liquid detergent
compositions, including those which contain reactive materials such as peroxygenble~ching agents, have been disclosed for example, in Hepworth et al., U.S. Patent
4,615,820, Issued October 17, 1986; Schultz et al., U.S. Patent 4,929,380, Issued
May 29, 1990; Schultz et al., U.S. Patent 5,008,031, Issued April 16, 1991; Elder et
al., EP-A-030,096, Published June 10, 198~; Hall et al., WO 92/09678, Published
June 11, 1992 and Sanderson et al., EP-A-565,017, Published October 13, 1993.
Even in non-aqueous liquid products, a problem of chemical stability can arise
when peroxygen ble~hing agents and peroxygen bleach activators are incl~(led
Bleach activators, in particular, tend to react with nucleophilic components such as
ethoxylated alcohol nonionic srlrf~t~nt~ that are frequently used to form the liquid
phase of such non-aqueous cleaning products. Such nucleophilic materials can
attack conventional bleach activators, e.g., cross-esterifying with them, and can
thereby deactivate such activators before they can be delivered to aqueous washing
or blea~hing solution.
One approach which has historically been used to perrnit formul~tic~n of
chemically incompatible components into a single detergent or bleach compositionhas been to coat or encapsulate one or more of these components. Karnel et al; U.S.
Patent 5,230,822; Issued July 27, 1993, for example, discloses the encoding or
encapsulation of certain types of peroxygen ble~ching agents and bleach activators
in various types of bleach-cont~inin~ products. Notwith~tz-n~lin~ the general
availability of component coating as a means For enhancing cleaning composition
chemical stability, there remains a continllin~ need to identify specific combinations
of ble~hin~ agents, bleach activators, coating technology and cleaning composition
matrices that can be used to realize bleach-cont~ining cleaning products of especially
desirable cleaning performance and chemical/physical stability.
SUMMARY OF THE INVENTION
The present invention relates to a certain type of coated particulate material
which contains a peroxygen bleach activator and which is especially suitable forincorporation into certain types of peroxygen bleach-cont~ining non-aqueous liquid
cleaning compositions. Such coated particulate material comprises a plurality ofindividual particles ranging in average particle size from about 20 to 800 microns.
Each particle c~ t~ s from about 20% to 95% by weight of a solid core material
and from about 5% to 80% by weight of a coating material which substantially
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completely encapsulates the solid core material. The solid core material comprises a
norrnally solid bleach activator capable of reacting with a peroxygen compound in
aqueous solution to thereby forrn in situ a peroxyacid corresponding to the bleach
activator; and preferably also comprises an inert carrier material for the bleach
activator. The coating material which surrounds this solid core material is selected
from those citrates, sl~lf~te~, carbonates, silicates, halides and chromates, which are
soluble in water, but insoluble in non-aqueous liquids.
The present invention also relates to certain types of non-aqueous liquid
bleach-cont~ining cleaning compositions which are in the form of a suspension ofsolid, substantially insoluble particulate m~t~l dispersed throughout a non-
aqueous liquid phase. Such compositions comprise:
A) from about 30% to 80% by weight of one or more non-aqueous organic
liquids;
B) from about 2% to 15% by weight of particles of peroxygen ble~rhing
agent dispersed throughout these non-aqueous organic liquids; and
C) from about 2% to 20% by weight of coated particles of peroxyen bleach
activator material also dispersed through the non-aqueous organic
liquids.
The particles of the peroxygen ble~chin~ agent range in average particle size
from about 10 to 800 microns. The coated bleach activator particles range in
average size from about 20 to 800 microns. The coated activator particles are coated
~,vith a solid salt material that is soluble in water but insoluble in the non-aqueous
organic liquid component of the compositions herein.
DETAILED DESCRIPTION OF THE INVENTION
The coated bleach activator particles of this invention, as well as non-aqueous
liquid, fabric cleaning compositions which contain these coated bleach activatorparticles, are described in greater detail as follows. All concentrations and ratios are
on a weight basis unless otherwise specified.
COATED BLEACH ACTIVATOR PARTICLES
The bleach activator particles of this invention comprise bleach activator
m~teri~l, optionally coextruded, agglomerated or otherwise combined with an inert
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carrier material, which has been coated with a certain type of coating material
having specific solubi~ity characteristics in non-aqueous fabric cleaning products.
These particles, compositions as well as the particle and composition preparation
processes, are described hereinafter.
(A) Activator Material
The bleach activators employed in this invention are those normally solid
materials which are capable of reacting with a peroxygen compound in aqueous
solution to form in situ a peroxyacid corresponding to the bleach activator structure.
Such reacting and in situ peracid generation will generally occur during use of
activator-con~ining products to form fabric ble~elling and/or laundering solutions.
Various non-limiting examples of activators are disclosed in U.S. Patent
4,915,854, Issued April 10, 1990 to Mao et al.; and U.S. Patent 4,412,934 IssuedNovember 1, 1983 to Chung et al. The nonanoyloxybenzene sulfonate (NOBS) and
tetraacetyl ethylene ~ minf- (TAED) activators are typical. Mixtures of these
activators can also be used. Burns et al, U.S. Patent 4,634,551; Issued January 6,
1987 also discloses typical bleach activators useful in this invention. All of these
patents are incorporated herein by reference.
Other useful amido-derived bleach activators are those of the forrnulae:
RIN(R5)C(O)R2C(O)L or RlC(O)N(R5)R2C(O)L
wherein Rl is an alkyl group co~ from about 6 to about 12 carbon atoms, R2
is an alkylene cont~inin~ from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or
alkaryl cont~inin~ from about 1 to about 10 carbon atoms, and L is any suitable
leaving group. A leaving group is any group that is displaced from the bleach
activator as a consequence of the nucleophilic attack on the bleach activator by the
perhydrolysis anion. A preferred leaving group is phenol sulfonate.
Preferred exarnples of bleach activators of the above formulae include (6-
octanamido-caproyl)oxyben7~n~sulfonate, (6-nonanarnidocaproyl)
oxybenzenesulfonate, (6-dec~n~mi(lc--caproyl)oxybenzenesulfonate and mixtures
thereof as described in the hereinbefore referenced U.S. Patent 4,634,551. Such
mixtures are characterized herein as (6-C8-Cl0 alkarnido-
caproyl)oxyben7~nesll1 fonate.
Another class of useful bleach activators comprises the benzoxazin-type
activators disclosed by Hodge et al. in U.S. Patent 4,966, 723, Issued October 30,
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s
1990, incorporated herein by reference~ A highly preferred activator of the
benzoxazin-type is:
~l
~N~C~
Still another class of useful bleach activators includes the acyl lactarn
activators, especially acyl caprolactarns and acyl valerolactams of the formulae:
O O
l1 l1
O Cl- CH2 CH2 ~ Cl - CH2 CH2
R6_C N \ R6 C--N
CH2 CH2 CH2 CH2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group cont~ining from 1 to
about 12 carbon atoms. Highly preferred lactam activators include benzoyl
caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoylcaprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam,octanoyl valerolactam, decanoyl valerolactarn, undecenoyl valerolactam, 3,5,5-
trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent
4,545,784, Issued to Sanderson, October 8, 1985, inc~ o~ d herein by reference,
which discloses acyl caprol~ct~mc, including benzoyl caprolactam, adsorbed into
sodium perborate.
Of all the foregoing peroxygen bleach activators, the plcr~..ed ones for use in
this invention are nonanoyloxybenzene sulfonate ~NOBS), tetraacetyl ethylene
~ min~ (TAE~) and (Cg 1 0 alkamido-caproyl) oxybenzene sulfonate. Sodiurn
NOBS is the most ~left;lled.
(B) Inert Carrier Material
The bleach activator m~t~n~l may optionally be combined with an inert carrier
material. An "inert" material is one which does not chemically react with the
activator material.
Suitable inert carrier materials can include non-reactive nonionic surfactants,
polyethylene glycols, e.g., PEG 4000, fatty acids, anionic surfactants such as C10 16
linear alkyl benzene sulfonates (LAS), solid polyacrylate polymers and copolymers,
solid organic acids such as citric acid, citrates, e.g., sodium citrate, and mixtures of
these inert materials. Such inert materials are described in greater detail in Murphy
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et al; U.S. Patent 4,486,327; lssued December 4, 1984, which patent is incorporated
herein by reference.
The activator and inert carrier material can be combined by any technique
which forms an intim~te combination of activator and carrier. This can be, for
example, via simple dry mixing or blending, co-extrusion, agglomeration, and thelike.
If lltili7~1 the inert carrier material can comprises up to about 80% by weight
of the activator/carrier combination that serves as the core material for the coated
activator particles herein. More preferably, the inert carrier will comprises from
about 10% to 50% by weight of the activator/carrier combination.
(C) Activator Particle Coatin~e Material
The activator material as hereinbefore described, optionally in combination
with inert carrier m~teri~, is coated with a coating m~t~ l which completely
encapsulates the particles cont~ining activator material. The coating material must
be one which is insoluble in the non-aqueous solvents used to form the non-aqueous
fabric cleaning compositions herein. Though insoluble in non-aqueous solvents, the
coating material should be readily soluble in aqueous solutions such as the fabric
laundering and/or ble~hin~ solutions which are formed from the non-aqueous fabric
cleaning products herein.
Typically the coating material will be an organic or inorganic salt. Such salts
are those selected from the water soluble citrates, sulfates, carbonates, silicates,
halides, chromates and the like. Alkali metal salts, e.g., sodium and potassium of
these anionic moieties are preferred. Calcium and m~gne~iurn salts may also be
used. The most preferred coating materials are sodium citrate and sodium sulfate.
~D) Coated Particle P~ Ltion
Coating of the solid core material comprising bleach activator can be
accomplished using any conventional coating techniques which provide a
continuous, unbroken coating around the core m~teri~l However applied, the
coating material must completely surround the activator-cont~i..i.~g core and insulate
the activator m~teriz.~ therein from contact with the non-aqueous solution in the non-
aqueous cleaning products in which such coated activator particles are employed.Coating of this type is thus distinct from agglomeration or other forms of particle
p~dLion which would not necessarily result in complete encapsulation of the
activator-co.~ g particle with a protective coating.
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Complete coating of the activator-cont~ining core material is best
accomplished by a fluidized bed coating/drying operation. In such a procedure~ an
aqueous solution of the particle coating material is sprayed onto the particles to be
coated in a fluidized bed arrangement such as for example in a Wurster coater. The
sprayed particles in the fluidized bed are then dried with dehumidified air
m~int~ined at a tenl~cldl-lre below the melting point of the activator, e.g., below
about 60~C for NOBS. In this manner, a coating which comprises from about 5% to
80% by weight of the coated particles, more preferably from about 10% to 40% by
weight of the coated particles, can be obtained.
The coated activator particles which result will frequently range in size from
a~out 20 to 800 microns. More preferably, the coated activator particles of from 20
to 400 microns can be re~li7e-l Very small coated particles ranging in size fromabout 20 to 80 microns, are especially advantageous for suspension in liquid non-
aqueous detergent and bleach compositions in that they minimi7:~ the suspension
requirement for the particles in the liquid compositions and in that they produce
improved consumer aesthetics.
NON-AOUEOUS CLEANING COMPOSITIONS
The coated bleach activator particles as hereinbefore described are utilized in
non-aqueous liquid fabric cleaning compositions which are formed from one or
more non-aqueous organic solvents in which are suspended particles of inorganic
peroxygen blc~ching agent, the coated bleach activator particles and optionally a
number of other types of solid insoluble particle materials. Such non-aqueous
compositions will generally include one or more structurant m~tt?ri~l~, generally
surf~ct~nt~, which serve to enhance the ability of the compositions to keep
particulate material suspended and dispersed therein and throughout. The severales~.?nti~l and optional components of such compositions, in addition to the coated
activator particles hereinbefore described, are described in detail as follows:
(A) Non-aqueous Or~anic Diluents
The major component of the liquid phase of the detergent compositions herein
comprises one or more non-aqueous organic diluents. The non-aqueous organic
diluents used in the fabric cleaning compositions of this invention may be either
surface active, i.e., surfactant, liquids or non-aqueous, non-surfactant liquids referred
to herein as non-aqueous solvents. The term "solvent" is used herein to connote the
non-aqueous liquid portion of the compositions herein. While some of the ~?ssenti~l
and/or optional components of the compositions herein may actually dissolve in the
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"solvent"-cont~ining liquid phase, other components will be present as particulate
material dispersed within and throughout the "solvent"-cont~ining liquid phase.
Thus the term "solvent" is not meant to require that the solvent material be capable
of actually dissolving all of the cleaning composition components added thereto.Preferably, the liquid phase of the compositions herein, i.e., the non-aqueous
liquid diluent component, will comprise both non-aqueous liquid surfactants and
non-surfactant non-aqueous solvents.
i) Non-aqueous Surfactant Li~uids
Suitable types of non-aqueous ~llrf~- t~nt liquids which can be used to form
the liquid phase of the compositions herein include the allcoxylated alcohols,
ethylene oxide (~O)-propylene oxide (PO) block polymers, polyhydroxy fatty acid
arnides, alkylpolysaccharides, and the like. Such normally liquid surfactants are
those having an HLB ranging from 3 to 17. Most preferred of the surfactant liquids
are the alcohol alkoxylate nonionic surfactants.
Alcohol alkoxylates are materials which correspond to the general formula:
Rl (CmH2mO)nOH
wherein Rl is a C8 - C16 alkyl group, m is from 2 to 4, and n ranges from about 2 to
12. Preferably R1 is an alkyl group, which may be primary or secondary, that
contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14
carbon atoms. Preferably also the alkoxylated fatty alcohols will be ethoxylatedmaterials that contain from about 2 to 12 ethylene oxide moieties per molecule,
more preferably from about 3 to 10 ethylene oxide moieties per molecule.
The alkoxylated fatty alcohol materials useful in the liquid phase will
frequently have a hydlophilic-lipophilic balance (HLB) which ranges from about 3to 17. More preferably, the ~ILB of this material will range from about 6 to 15, most
preferably ~om about 8 to 15.
Examples of fatty alcohol alkoxylates useful in or as the non-aqueous liquid
phase of the compositions herein will include those which are made from alcohols of
12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such
materials have been commercially marketed under the trade names Neodol 25-7 and
Neodol 23-6.5 by Shell Chemical Company. Other useful Neodols include Neodol
1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with
about 5 moles of ethylene oxide, Neodol 23-9, an ethoxylated primary C12 - C13
alcohol having about 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated
Cg - C11 primary alcohol having about 10 moles of ethylene oxide. Alcohol
ethoxylates of this type have also been marketed by Shell Chemical Company under
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the Dobanol tradename. Dobanol 91-5 is an ethoxylated Cg-Cl l fatty alcohol withan average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxy~ated C12-C1s
fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7 and
Tergitol 15-S-9 both of which are linear secondary alcohol ethoxylates that havebeen cornmercially marketed by Union Carbide Corporation. The former is a mixed
ethoxylation product of Cll to Cls linear secondary alkanol with 7 moles of
ethylene oxide and the latter is a similar product but with 9 moles of ethylene oxide
being reacted.
Other types of alcohol ethoxylates useful in the present compositions are
higher molecular weight nonionics, such as Neodol 45-11, which are similar
ethylene oxide condensation products of higher fatty alcohols, with the higher fatty
alcohol being of 14-15 carbon atoms and the number of ethylene oxide groups per
mole being about 11. Such products have also been com~nercially marketed by
Shell Chemical Company.
If alcohol alko~ylate nonionic surfactant is utilized as part of the non-
aqueous liquid phase in the cleaning compositions herein, it will preferably be
present to the extent of from about 1% to 60% of the composition liquid phase.
More preferably, the alcohol alkoxylate component will comprise about 5% to 40%
of the liquid phase. Most preferably, the essentially utilized alcohol alkoxylate
component will comprise from about 5% to 35% of the cleaning composition liquid
phase. Utilization of alcohol alkoxylate in these concentrations in the liquid phase
corresponds to an alcohol alkoxylate concentration in the total composition of from
about 1% to 60% by weight, more preferably from about 2% to 40% by weight, and
most preferably from about 5% to 25% by weight, of the composition.
Another type of non-aqueous surfactant liquid which may be utilized in this
invention are the ethylene oxide (EO~ - propylene oxide (PO) block polymers.
M~t~ri~l~ of this type are well known nonionic surf~ct~ntc which have been
mzlrkete~1 under the tr~-l.sn~me Pluronic. These materials are formed by adding
blocks of ethylene oxide moieties to the ends of polypropylene glycol chains to
adJust the surface active ~r~ ies of the resulting block polymers. EO-PO block
polymer nonionics of this type are described in greater detail in Davidsohn and
Milwidsky, Synthetic D~lcl~ellts. 7th Ed.; Longman Scientific and Technical (1987)
at pp. 34-36 and pp. 189-191 and in U.S. Patents 2,674,619 and 2,677,700. All ofthese publications are incorporated herein by reference. These Pluronic type
nonionic surfactants are also believed to function as effective suspending agents for
-
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the particulate material which is dispersed in the liquid phase of the detergentcompositions herein.
Another possible type of non-aqueous surfactant liquid useful in the
compositions herein comprises polyhydroxy fatty acid amide sur~f~t~nt~. Materials
of this type of nonionic surfactant are those which conform to the forrnula:
1~l I pH2p+1
R--C--N--Z
wherein R is a Cg 17 alkyl or alkenyl, p is from 1 to 6, and Z is glycityl derived
from a reduced sugar or alkoxylated derivative thereof. Such materials include the
C 12-c 18 N-methyl glucatnides. Examples are N-methyl N- 1 -deoxyglucityl
cocoamide and N-methyl N-l-deoxyglucityl ole~mide. Processes for making
polyhydroxy fatty acid, amides are know and can be found, for example, in Wilson,
U.S. Patent 2,965,576 and Schwartz, U.S. Patent ~,703,798, the disclosures of which
are incorporated herein by reference. The mz~tt?ri5ll~ themselves and their ple~aldlion
are also described in greater detail in ~onsa, U.S. Patent 5,174,937, Issued
December 26, 1992, which patent is also incorporated herein by reference.
The amount of total liquid surfactant in the non-aqueous liquid phase herein
will be detl-tmin~l by the type and amounts of other composition components and
by the desired composition properties. Generally, the liquid surfactant can comprise
from about 35% to 70% of the non-aqueous liquid phase of the compositions herein.
More preferably, the liquid surfactant will comprise from about 50% to 65% of the
non-aqueous liquid phase. This corresponds to a non-aqueous liquid surfactant
concentration in the total composition of from about 15% to 70% by weight, more
preferably from about 20% to 50% by weight, of the composition.
ii) Non-surfactant Non-aqueous Or~anic Solvents
The liquid phase of the cleaning compositions herein may also comprise one
or more non-surfactant, non-aqueous organic solvents. Such non-surfactant non-
aqueous liquids are preferably those of low polarity. For purposes of this invention,
"low-polarity" liquids are those which have little, if any, tendency to dissolve one of
the essential types of particulate material used in the compositions herein, i.e., the
peroxygen blç~hin~ agents, sodiurn perborate or sodium percarbonate. Thus
relatively polar solvents such as ethanol are preferably not l~tili7Pd Suitable types of
low-polarity solvents useful in the non-aqueous liquid detergent compositions herein
do include non-vicinal C4-Cg alkylene glycols, alkylene glycol mono lower alkyl
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Il
ethers, lower molecular weight polyethylene glycols~ lower molecular weight methyl
esters and amides, and the like.
A pl~r~ d type of non-aqueous, low-polarity solvent for use in the
compositions herein comprises the non-vicinal C4-Cg branched or straight chain
alkylene glycols. Materials of this type include hexylene glycol (4-methyl-2,4-
pentanediol), 1,6-hexanediol, 1,3-butylene glycol and 1,4-butylene glycol. Hexylene
glycol is the most preferred.
Another l l~f~l-ed type of non-aqueous, low-polarity solvent for use herein
comprises the mono-, di-, tri-, or tetra- C2-C3 alkylene glycol mono C2-C6 alkylethers. The specific examples of such compounds include diethylene glycol
monobutyl ether, tetraethylene glycol monobutyl ether, dipropolyene glycol
monoethyl ether, and dipropylene glycol monobutyl ether. Diethylene glycol
monobutyl ether, dipropylene glycol monobutyl ether and butoxy-propoxy-propanol
(BPP) are especially preferred. Compounds of the type have been commercially
marketed under the tr~ n~mes Dowanol, Carbitol, and Cellosolve.
Another preferred type of non-aqueous, low-polarity organic solvent useful
herein comprises the lower molecular weight polyethylene glycols (P~Gs). Such
materials are those having molecular weights of at least about 150. PEGs of
molecular weight ranging from about 200 to 600 are most ~l~r~ d.
Yet another ~ .,ed type of non-polar, non-aqueous solvent comprises lower
molecular weight methyl esters. Such materials are those of the general formula:Rl-C(O)-OCH3 wherein Rl ranges from 1 to about 18. Examples of suitable lower
molecular weight methyl esters include methyl acetate, methyl propionate, methyloct~no~te~ and methyl dodPr~no~te
The non-aqueous, generally low-polarity, non-surfactant organic solvent(s)
employed should, of course, be compatible and non-reactive with other composition
components, e.g., bleach and/or coated activators, used in the liquid detergent
compositions herein. Such a solvent component is preferably utilized in an amount
of from about 1% to 70% by weight of the liquid phase. More preferably, a non-
aqueous, low-polarity, non-surfactant solvent will comprise from about 1 Q% to 60%
by weight of the liquid phase, most lJrer~ lably from about 20% to 50% by weight, of
the liquid phase of the composition. Utilization of non-surfactant solvent in these
concentrations in the liquid phase corresponds to a non-surfactant solvent
concentration in the total composition of from about 1% to 50% by weight, more
preferably from about 5% to 40% by weight, and most preferably from about 10% to30% by weight, of the composition.
. --
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iii) Blends of Surfactant and Non-surfactant Solvents
In systems which employ both non-aqueous surfactant liquids and non-
aqueous non-surfactant solvents, the ratio of surfactant to non-surfactant liquids,
e.g., the ratio of alcohol alkoxylate to low polarity solvent, within the liquid phase
can be used to vary the rheological properties of the detergent compositions
eventually formed. Generally, the weight ratio of surfactant liquid to non-surfactant
organic solvent will range about 50:1 to 1:50. More preferably, this ratio will range
fromabout3:1 to 1:3.
(B) PeroxY~en Bleaching A~ent Particles
The non-aqueous fabric cleaning compositions of this invention ess~onti~lly
comprise from about 2% to 15% by weight of the composition of particles of
peroxygen bleaching agent suspended in the non-aqueous liquid phase. More
preferably, particles of peroxygen ble~hing agent will comprise from about 2% to10% by weight of the composition. The peroxygen ble~ching agents which are
generally used in combination with the essentially present bleach activator particles
are inorganic compounds.
Suitable inorganic peroxygen compounds include alkali metal perborate and
percarbonate materials, most preferably the percarbonates. For example, sodium
perborate ~e.g. mono- or tetra-hydrate) can be used. Suitable inorganic blç~hingagents can also include sodium or potassiurn c~u bullale peroxyhydrate and
equivalent "~clc~bonate" bleaches, sodium pyrophosphate peroxyhydrate, urea
peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE,
manufactured conl~ cially by DuPont) can also be used. Frequently inorganic
peroxygen bleaches will be coated with silicate, borate, sulfate or water-soluble
~ulra~ . For example, coated percarbonate particles are available from various
co~ ial sources such as FMC, Solvay Interox, Tokai Denka and Degussa.
Peroxygen blearhing agents are suspended in the non-aqueous liquid phase of
the cleaning compos;tions herein in the form of solid insoluble par~icles. Such
particles generally range in average size from about 10 to 800 microns. More
preferably, the dispersed and suspended particles of inorganic peroxygen bleaching
agents will range in average size from about 10 to 400 microns.
(C) Coated Bleach Activator Particles
The non-aqueous cleaning compositions herein also essentially contain the
coated bleach activator particles hereinbefore described. Such coated bleach
activators can comprise from about 2% to 20%, more preferably ~om about 4% to
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13
10%, by weight of the composition. Frequently, activators are employed such thatthe molar ratio of bleaching agent to activator ranges from about 1:1 to 10:1, more
preferably from about 1.5:1 to 5:1.
(D) Optional Composition ComPonents
In addition to the hereinbefore-described f~cf-nti~l non-aqueous solvent,
peroxygen bleaching agent and coated bleach activator particles, the non-aqueouscleaning compositions of the present invention can, and preferably will, contain a
wide variety of optional ingredients. Such optional components may be in either
liquid or solid form. The optional components may either dissolve in the liquid
phase or may be dispersed within the liquid phase in the form of fine particles or
droplets. Some of the materials which may optionally be utilized in the compositions
herein are described in greater detail as follows:
(a) Optional Surfactants
Besides the liquid non-aqueous surfactant materials hereinbefore described as
possible components of the composition liquid phase, the cleaning compositions
herein may also contain other types of surfactant materials. Such additional optional
surfactants must, of course, be compatible with other composition components andmust not subst~nt;~lly adversely affect composition rheology, stability or
performance. Surfactants in general çnh~n~e the stain and soil remove performance
of the cleaning compositions to which they are added. Surf~-t:~nt~ can also be
selected to add structure to the non-aqueous cleaning compositions herein. Optional
surfactants can be of the anionic, nonionic, cationic, and/or amphoteric type.
Preferred optional surfactants are the anionic surfactants such as the alkyl
s~llf~tec, the alkyl polyethoxylene sulfates and the linear alkyl benzene sulfonates.
Another common type of anionic surfactant material which may be optionally addedto the deL~ L compositions herein comprises carboxylate-type anionics.
Carboxylate-type anionics include the C 1 o-C l 8 alkyl alkoxy carboxylates
(especially the EO 1 to 5 ethoxycarboxylates) and the C 1 o-C 18 sarcosinates,
especially oleoyl sarcosinate. Yet another common type of anionic surfactant
material which may be optionally employed comprises other sulfonated anionic
surf~t~nt~ such as the Cg-C 18 paraffm sulfonates and the Cg-C 1 y olefin sulfonates.
Anionic surf~t~nts can optionally comprise from about 1% to 30% by weight of thecompositions herein.
_
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14
As indicated, one preferred type of optional anionic surfactant comprises
primary or secondary alkyl sulfate anionic surfactants. Such surfactants are those
produced by the sulfation of higher Cg-C20 fatty alcohols.
Conventional primary alkyl sulfate surfactants have the general forrnula
ROSO3-M+
wherein R is typically a linear C8 - C20 hydrocarbyl group, which may be straight
chain or branched chain, and M is a water-solubilizing cation. Preferably R is a C 10
- C14 alkyl, and M is alkali metal. Most preferably R is about C12 and M is
sodium.
Conventional secondary alkyl sl-lf~tt-c may also be utilized as an optional
anionic sur~actant component of the solid phase of the compositions herein.
Conventional secondary alkyl sulfate surfactants are those materials which have the
sulfate moiety distributed randomly along the hydrocarbyl "backbone" of the
molecule. Such materials may be depicted by tne structure:
CH3(CH2)n(cHOs03-M+) (CH2)mCH3
wherein m and n are integers of 2 or greater and the surn of m + n is typically about
9 to 15, and M is a water-solubilizing cation.
If lltili7~-1, alkyl sulfates will generally comprise from about 1% to 30% by
weight of the composition, more preferably from about 5% to 25% by weight of thecomposition. Non-aqueous liquid dl:Le~ compositions contAining alkyl ~l~lf,.t~s,peroxygen ble~ in~ agents, and bleach activators are described in greater detail in
Kong-Chan et al., WO 96/10073; Publiched April 4, 1996, which application is
incorporated herein by reference.
Another ~,er~l,ed type of anionic surfactant material which may be optionally
added to the non-aqueous cleaning compositions herein comprises the alkyl
polyalkoxylate sll1fAtl~s Alkyl polyalkoxylate sulfates are also known as
alkoxylated alkyl sulfates or alkyl ether sulfates. Such materials are those which
c~ cs~o~1d to the forrnula
R2-0-(CmH2mO)n-S03M
wherein R2 is a C lo-C22 alkyl group, m is from 2 to 4, n is from about 1 to 15, and
M is a salt-forming cation. Preferably, R2 is a C12-Clg alkyl, m is 2, n is fromabout 1 to 10, and M is sodium, potassiurn, amrnonium, alkylammonium or
alkanolarnrnonium. Most preferably, ~2 is a C12-C16, m is 2, n is from about 1 to
6, and M is sodium. Ammonium, alkylarnmoniurn and alkanolarnmoniurn
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counterions are preferably avoided when used in the compositions herein because of
incompatibility with the peroxygen bleaching agent.
If l]ti~i7t'(l, alkyl polyalkoxylate sulfates can also generally comprise from
about 1% to 30% by weight of the composition, more preferably from about 5% to
25% by weight of the composition. Non-aqueous liquid detergent compositions
cont~ining peroxygen blç~hing agents, bleach activators and alkyl polyalkoxylatesulfates, in combination with polyhydroxy fatty acid amides~ are described in greater
detail in Boutique et al; PCT Application No. PCT/US96/04223, which application
is incorporated herein by reference.
The most preferred type of anionic surfactant for optional use in the
compositions herein comprises the linear alkyl benz¢ne sulfonate (LAS) sllrf~ct~ntc
In particular, such LAS surfactants can be forrn~ te(~ into a specific type of anionic
surfactant-cont~ining powder which is especially useful for incorporation into the
non-aqueous liquid cleaning compositions of the present invention. Such a powdercomprises two distinct phases. One of these phases is insoluble in the non-a~ueous
organic liquid diluents used in the compositions herein, the other phase is soluble in
the non-aqueous organic liquids. It is the insoluble phase of this anionic surfactant-
cont~inin~ powder which can be dispersed in the non-aqueous liquid phase of the
compositions herein and which forms a network of aggregated small particles thatallows the final product to stably suspend other additional solid particulate materials
in the composition.
Such a preferred anionic surfactant-corlt~ining powder is forrned by co-drying
an aqueous slurry which essenti~lly contains a) one of more alkali metal salts of
C10-l6 linear alkyl benzene sulfonic acids; and b) one or more non-surfactant
diluent salts. Such a slurry is dried to a solid material, generally in powder form,
which comprises both the soluble and insoluble phases.
- The linear alkyl benzene sulfonate (LAS) materials used to form the preferred
anionic surfactant-cont~inin~ powder are well known materials. Such surf~t~nt~
and their ~lc~iuaLion are described for example in U.S. Patents 2,220,099 and
2,477,383, incorporated herein by reference. Especially ~ler~ d are the sodiLlm
and potassium linear straight chain alkylbenzene sulfonates in which the averagenumber of carbon atoms in the alkyl group is from about 11 to 14. Sodiurn Cl 1~
C14, e.g., C~12~ LAS is especially preferred. The alkyl benzene surfactant anionic
surfactants are generally used in the powder-forming slurry in an amount from about
20 to 70% by weight of the slurry, more preferably from about 30% to 60% by
weight of the slurry.
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16
The powder-forming slurry also contains a non-surfactant, organic or inorganic
salt component that is co-dried with the LAS to form the two-phase anionic
surfactant-cont~ining powder. Such salts can be any of the known sodium,
potassium or m~gne~ium halides, sulfates, citrates, carbonates, sulfates, borates,
succinates, sulfo-succinates and the like. Sodium sulfate, which is generally a bi-
product of LAS production, is the preferred non-surfactant diluent salt for use
herein. Salts which function as hydrotropes such as sodium sulfo-succinate may
also usefully be included. The non-surfactant salts are generally used in the aqueous
slurry, along with the LAS, in amounts ranging from about 1 to 12% by weight of
the slurry, more preferably from about 2% to 1~% by weight of the slurry. Salts that
act as hydrotropes can preferably comprise up to about 3% by weight of the slurry.
The aqueous slurry cont~ining the LAS and diluent salt components
hereinbefore described can be dried to form the anionic surfactant-contS~ining
powder preferably added to the non-aqueous solvents in order to prepare a structured
liquid phase within the compositions herein. Any conventional drying technique,
e.g., spray drying, drum drying, etc., or combination of drying techniques, may be
employed. Drying should take place until the residual water content of the solidmaterial which forms is within the range of from about 0.5% to 4% by weight, more
preferably from about 1% to 3% by weight.
The anionic surfactant-cont~ining powder produced by the drying operation
constitutes two distinct phases, one of which is soluble in the inorganic liquiddiluents used herein and one of which is insoluble in the diluents. The insoluble
phase in the anionic surfactant-cont~inin~ powder generally comprises from about10% to 25% by weight of the powder, more preferably from about 15% to 25% by
weight of a powder.
After it is dried to the requisite extent, the combined LAS/salt material can beconverted to flakes or powder form by any known suitable milling or comminl1tionprocess. Generally at the time such material is combined with the non-aqueous
organic solvents to forrn the structured liquid phase of the compositions herein, the
particle size of this powder will range from 0.1 to 2000 microns, more preferably
from about 0.1 to 1000 microns.
A structured, surfactant-cont~ining liquid phase of the preferred detergent withbleach compositions herein can be ~lcparcd by combining the non-aqueous organic
diluents hereinbefore described with the anionic surfactant-cont~ining powder ashereinbefore described. Such combination results in the formation of a structured
surfactant-cont~ining liquid phase. Conditions for making this combination of
preferred structured liquid phase components are described more fully hereinafter in
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17
the "Composition Preparation and Use" section. As previously noted, the formation
of a structured, surfactant-cont:~ining li~uid phase permits the stable suspension of
the peroxygen bleaching agent and coated bleach activator particles as well as
~ additional functional particulate solid materials within the preferred cleaning
compositions of this invention.
(b) Optional Builder Materials
Another possible type of optionally utilized particulate material which can be
suspended in the non-aqueous liquid cleaning compositions herein comprises an
organic or inorganic det~r~ l builder material which serves to counteract the effects
of calcium, or other ion, water hardness encountered during laundering/blç,q~hing
use of the compositions herein. Exarnples of such organic materials include the
alkali metal citrates (in addition to those used as activator coating or inert material),
succinates, malonates, fatty acids, carboxymethylsuccinates, carboxylates,
polycarboxylates and polyacetyl carboxylates. Specific examples include sodium,
potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene
polycarboxylic acids and citric acid. Other examples of organic phosphonate typesequestering agents such as those which have been sold by Monsanto under the
Dequest tr~(lçn~rne and s-lk~n~hydroxy phosphonates. Citrate salts are highly
preferred.
Other suitable organic builders include the higher molecular weight polymers
and copolymers known to have builder ~lv~ellies. For example. such materials
include a~o~.;ate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic
acid copolymers and their salts, such as those sold by BAS~ under the Sokalan
tr~ m~rk
Another suitable type of organic builder comprises the water-soluble salts of
higher~atty acids, i.e., "soaps". These include alkali metal soaps such as the sodium,
pO~ , ammonium, and alkylolammonium salts of higher fatty acids Cont~inin~
from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18
carbon atoms. Soaps can be made by direct saponification of fats and oils or by the
neutralization of free fatty acids. Particularly useful are the sodium and potassiurn
salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodiurn
or potassiurn tallow and coconut soap.
The cleaning compositions herein may also optionally contain one or more
types of inorganic de~ ellt builders beyond those listed hereinafter that also
function as alkalinity sources. Such optional inorganic builders can include, for
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18
exarnple, aluminosilicates such as zeolites. Aluminosilicate zeolites, and their use as
detergent builders are more fully discussed in Corkill et al., U.S. Patent No.
4,605,509, Issued August 12, 1986~ the disclosure of which is incorporated herein
by reference. Also crystalline layered silicates, such as those discussed in this '509
U.S. patent, are also suitable for use in the detergent compositions herein.
If utilized as optionally added particulate material, insoluble orgar~ic or
inorganic detergent builders can generally comprise from about 2% to 20% by
weight of the compositions herein. More preferably, such builder material can
comprise from about 4% to 15% by weight of the composition.
(c)OPtional Inor~anic Alkalinity Sources
Another possible type of optionally added particulate material which can be
suspended in the non-aqueous liquid cleaning compositions herein can comprise a
material which serves to render aqueous washing and bleaching solutions forme~d
from such compositions generally ~lk~ in nature. Such materials may or may not
also act as detergent builders, i.e., as materials which counteract the adverse effect of
water hardness on delelg~,ncy perforrnance.
Examples of suitable alkalinity sources include water-soluble alkali metal
carbonates, bic~l,ol1~LLes, borates, ~ilic~tes and metasilicates. Although not p,~e~l.~d
for ecological reasons, water-soluble phosphate salts may also be utilized as
~Ik~linity sources. These include alkali metal pyrophosphates, orthophosphates,
polyphosphates and phosphonates. Of all of these ~Ik~linity sources, alkali metal
carbonates such as sodium carbonate are the most preferred.
The ~lk~1inity source, if in the form of a hydratable salt, may also serve as a
desiccant in the non-aqueous liquid d~ gelll compositions herein. The presence of
an ?Ik~linity source which is also a desiccant may provide benefits in terrns ofchtomi~lly stabilizing those composition components such as the peroxygen
ble~ ing agent which may be susceptible to deactivation by water.
If utilized an optionally added particulate material component, the ~Ik~linity
source will generally comprise from about 1% to 25% by weight of the compositions
herein. More preferably, the alkalinity source can comprise from about 2% to 15%by weight of the composition. Such materials, while water-soluble, will generally be
insoluble in the non-aqueous cleaning compositions herein. Thus such materials
will generally be dispersed in the non-aqueous liquid phase of the compositions
herein in the form of discrete particles.
(d) Optional Enz~,rmes
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19
The cleaning compositions herein may also optionally contain one or more
types of detergent enzymes. Such enzymes can include proteases, amylases,
cellulases and lipases. Such materials are known in the art and are commerciallyavailable. They may be incorporated into the non-aqueous liquid detergent
compositions herein in the form of suspensions, "marumes" or "prills". Another
suitable type of enzyme comprises those in the form of slurries of enzymes in
nonionic surfactants, e.g., the enzymes marketed by Novo Nordisk under the
tr:~-len~me "SL" or the micro encapsulated enzymes marketed by Novo Nordisk
under the trafl.on~me "LDP."
Enzymes added to the compositions herein in the form of conventional enzyme
prills are especially preferred for use herein. Such prills will generally range in size
from about 100 to 1,000 microns, more preferably from about 200 to 800 microns
and will be suspended throughout the non-aqueous liquid phase of the composition.
Prills in the compositions of the present invention have been found, in comparison
with other enzyme forms, to exhibit especially desirable enzyme stability in terrns of
retention of enzymatic activity over time. Thus, compositions which utilize enzyme
prills need not contain conventional enzyme stabilizing such as must frequently be
used when enzyrnes are incorporated into aqueous liquid d~L~I~,en~.
If employed, enzymes will normally be incorporated into the non-aqueous
liquid compositions herein at levels sufficient to provide up to about 10 mg by
weight, more typically from about 0.01 mg to about 5 mg, of active enzyme per
gram of the composition. Stated otherwise, the non-aqueous liquid cleaning
compositions herein will typically comprise from about 0.001% to 5%, preferably
from about 0.01% to 1% by weight, of a commercial enzyme ~le~a~tion. Protease
enzymes, for example, are usually present in such commercial ~lepaldLions at levels
sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of
compositlon.
(e) Optional Chelatin~ A~ents
The cleaning compositions herein may also optionally contain a chelating
agent which serves to chelate metal ions, e.g., iron and/or mzingf~n~se, within the
non-aqueous d~ ,elll compositions herein. Such chelating agents thus serve to
form complexes with metal impurities in the composition which would otherwise
tend to deactivate composition components such as the peroxygen ble~ching agent.Useful rh~l~fing agents can include amino carboxylates, phosphonates, arnino
phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures
thereof.
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Amino carboxylates useful as optional chelating agents include
ethylene~ rninetetraacetates, N-hydroxyethyl-ethylene~ minetriacetates,
nitrilotri~cet~t~c,ethylene-~ mine tel~lvL)ionates,
triethylenetetr~minehexacetates, diethylenetriaminepentaacetates,
ethyleneAi~minedisuccinates and ethanol diglycines. The alkali metal salts of these
materials are preferred.
Amino phosphonates are also suitable for use as chelating agents in the
compositions of this invention when at least low levels of total phosphorus are
permitt~l in detergent compositions, and include ethylent?~ min~tetrakis
(methylene-phosphonates) as DEQUEST. Preferably, these amino phosphonates do
not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Preferred chelating agents include hydroxy-ethyldiphosphonic acid (HEDP),
diethylene triamine penta acetic acid (DTPA), ethylen.~ mine disuccinic acid
(EDDS) and dipicolinic acid (DPA) and salts thereof. The chelating agent may, ofcourse, also act as a d~Lc~e-lt builder during use of the compositions herein for
fabric laundering/bleaching. The chelating agent, if employed, can comprise fromabout 0.1% to 4% by weight of the compositions herein. More preferably, the
chelating agent will comprise from about 0.2% to 2% by weight of the cleaning
compositions herein.
(f) Optional Thickenin~. Viscositv Control and/or
Dispersin~ As~ents
The non-a~lueous cleaning compositions herein may also optionally contain a
polymeric m~t~?rizll which serves to l?nh~nre the ability of the composition to
m~int~;n its solid particulate components in suspension. Such materials may thusact as thickeners, viscosity control agents and/or dispersing agents. Such m~teri~l~
are frequently polymeric polycarboxylates but can include other polymeric m~t~n~l~
such as polyvinylpyrrolidone (PVP). Insoluble materials like fumed silica and
titanium dioxide may also be used to enhance the elasticity of any structured liquid
phase that is present.
Polymeric polycarboxylate materials can be prepared by polymerizing or
copolymerizing suitable unsaturated monomers, preferably in their acid form.
Unsaturated monomeric acids that can be polymerized to form suitable polymeric
polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric
acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and
methylenem~lonic acid. The presence in the polymeric polycarboxylates herein of
monomeric segment~, cont~inin~ no carboxylate radicals such as vinyl methyl ether,
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21
styrene. ethylene, etc. is suitable provided that such segments do not constitute more
than about 40% by weight of the polymer.
Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid. Such acrylic acid-based polymers which are useful herein are the water-
soluble salts of polymerized acrylic acid. The average molecular weight of such
polymers in the acid form preferably ranges from about 2,000 to 10,000, more
preferably from about 4,000 to 7,000, and most preferably from about 4,000 to
5,000. Water-soluble salts of such acrylic acid polymers can include, for example,
the alkali metal, salts. Soluble polymers of this type are known materials. Use of
polyacrylates of this type in detergent compositions has been disclosed, for example,
Diehl, U.S. Patent 3,308,067, issued March 7, 1967. Such m~t~ .c may also
perform a builder function.
If lltili7erl the optional thic~ning, viscosity control and/or dispersing agentsshould be present in the compositions herein to the extent of from about 0.1% to 4~/.o
by weight. More preferably, such materials can comprise from about 0.5% to 2% byweight of the cleaning c~mpositions herein.
(g) Optional Clay Soil Removal/Anti-redeposition Agents
The compositions of the present invention can also optionally contain water-
soluble ethoxylated amines having clay soil removal and anti-redeposit;on
properties. If used, soil materials can contain from about 0.01% to about 5% by
weight of the compositions herein.
The most ~ler~.led soil release and anti-redeposition agent is ethoxylated
tetraethylenepen~min~. Exemplary ethoxylated amines are fLlrther described in U.S.
Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay
soil removal-anti-redeposition agents are the cationic compounds disclosed in
European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
Other clay soil removal/anti-redeposition agents which can be used include the
ethoxylated amine polymers disclosed in European Patent Application 111,984,
Gosselink, published June 27, 1984, the zwitterionic polymers disclosed in
European Patent Application 112,592, Gosselink, published July 4, 1984; and the
amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985.
Other clay soil removal and/or anti-redeposition agents known in the art can also be
utilized in the compositions herein. Another type of ~l. r.;.l~d anti-redeposition
agent includes the carboxy methyl cellulose (CMC) materials. These materials arewell known in the art.
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(h) Optional Liquid Bleach Activators
The cleaning compositions herein may also optionally contain bleach
activators which are liquid in form at room temperature and which can be added as
liquids to the non-aqueous liquid phase of the cleaning compositions herein. Onesuch liquid bleach activator is acetyl triethyl citrate ~ATC). Other exarnples include
glycerol triacetate and nonanoyl valerolactam. Liquid bleach activators can be
dissolved in the non-aqueous liquid phase of the compositions herein.
(i) Optional Bri~hteners. Suds Suppressors~ DYes and/or Perfumes
The cleaning compositions herein may also optionally contain conventional
brighten~rs, suds suppressors, bleach catalysts, dyes and/or perfume materials. Such
brighteners, suds suppressors, silicone oils, bleach catalysts, dyes and perfurnes
must, of course, be compatible and non-reactive with the other composition
components in a non-aqueous environment. If present, bri~htPnPrs suds suppressors,
dyes and/or perfumes will typically comprise from about 0.0001% to 2% by weight
of the compositions herein. Suitable bleach catalysts include the m~ng~nt?se based
complexes disclosed in US 5,246,G21, US 5,244,594, US 5,114,606 and US
5,114,611.
NON-AOUEOUS COMPOSITION FORM
As indicated, the non-aqueous liquid cleaning compositions herein are in the
form of ble~ching agent, coated bleach activator and possibly other materials inparticulate form as a solid phase suspended in and dispersed throughout a preferably
~ r*.~ co..~;-in;..~, non-aqueous liquid phase. Generally, the structured non-
aqueous liquid phase will comprise from about 45% to 95%, more preferably from
about 50% to 90%, by weight of the composition with the dispersed additional solid
materials comprising from about 5% to 55%, more preferably from about 10% to
50%, by weight of the composition.
The particulate-co.~t~ g liquid cleaning compositions of this invention are
substantially non-aqueous (or anhydrous) in C~ . While very small arnounts of
water may be incorporated into such compositions as an impurity in the es,~nti~l or
optional components, the amount of water should in no event exceed about 5% by
weight of the compositions herein. More preferably, water content of the non-
aqueous cleaning compositions herein will comprise less than about 1% by weight.The particulate-cont~ining non-aqueous liquid cleaning compositions herein
will be relatively viscous and phase stable under conditions of commercial
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23
marketing and use o~ such compositions. Frequently the viscosity of the
compositions herein will range from about 300 to 5,000 cps, more preferably fromabout 500 to 3,000 cps. For purposes of this invention, viscosity is measured with a
Carrimed CSL2 Rheometer at a shear rate of 20 sec~ 1
COMPOSITION PREPARATION AND USE
The non-aqueous liquid cleaning compositions herein can be plc~pal~d by first
forming a non-aqueous liquid phase which is preferably structured and surfactant-
cont~ining and by thereafter adding to this structured phase the additional particulate
components in any convenient order and by mixing, e.g., ~itzltin~ the r~s~lting
component combination to form the phase stable compositions herein. In a typicalprocess for preparing compositions, e~ePnti:~l and certain preferred optional
components will be combined in a particular order and under certain conditions.
In a first step of a ~-- r~ d p.e~alalion process, an anionic surfactant-
cont~inin~ powder used to form a structured, surfactant-cont~ining liquid phase is
prepared. This pre-p~ dLion step involves the forrnation of an aqueous slurry
contz-ining from about 30% to 60% of one or more alkali metal salts of linear Clo
16 alkyl benzene sulfonic acid and from about 2% to 10% of one or more diluent
non-sl-rf~ct~nt salts. In a subsequent step, this slurry is dried to the extent necessary
to form a solid material co~ g less than about 4% by weight of residual water.
After pr~d dlion of this solid anionic ~--rf~ct~nt-co..i;~ material, this
m~t~ l can be combined with one or more of the non-aqueous organic diluents to
form a structured, surfactant-cont~ining liquid phase of the cleaning compositions
herein. This is done by reducing the anionic surfactant-co~ i..g material formedin the previously described pre-p~ udlion step to powdered forrn and by combining
such powdered material with an agitated liquid medium comprising one or more of
the non-aqueous organic diluents, either surfactant or non-surfactant or both, as
hereinbefore described. This combination is carried out under agitation conditions
which are sufficient to form a thoroughly mixed dispersion of particles of the
insoluble fraction of the co-dried LAS/salt material throughout a non-aqueous
organic liquid diluent.
In a subsequent processing step, the non-aqueous liquid dispersion so prepared
can then be subjected to milling or high shear agitation under conditions which are
sufficient to provide a structured, surfactant-cont~ining liquid phase of the detergent
compositions herein. Such milling or high shear agitation conditions will generally
include m~int~n~n~e of a temperature between about 10~C and 90~C, preferably
between about 20~C and 60~C; and a processing time that is sufficient to fonn a
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24
network of aggregated small particles of the insoluble fraction of the anionic
surfactant-cont~ining powdered material. Suitable equipment for this purpose
includes: stirred ball mills, co-ball mills (Fryma), colloid mills, high pressure
honogenizers, high shear mixers, and the like. The colloid mill and high shear
mixers are preferred for their high throughput and low capital and maintenance
costs. The small particles produced in such equipment will generally range in size
from about 0.4 to 2 microns. Milling and high shear agitation of the liquid/solids
combination will generally provide an increase in the yield value of the structured
liquid phase to within the range of from about 1 Pa to 8 Pa, preferably from about 1
Pa to 4 Pa.
After formation of the dispersion of LAS/salt co-dried material in the non-
aqueous liquid, either before or after such dispersion is milled or agitated to increase
its yield value, any optionally added particulate material to be used in the cleaning
compositions herein can be added. Such components which can be added under
high shear agitation include any optional surfactant particles, particles of
sl-hst~nti~lly all of an organic builder, e.g., citrate and/or fatty acid, and/or an
alkalinity source, e.g., sodium carbonate, can be added while continuing to m:~int~in
this ~lrnixtllre of composition components under shear agitation. Agitation of the
mixture is continlle~i~ and if necessary, can be increased at this point to form a
uniform dispersion of ;nsoluble solid phase particulates within the liquid phase.
After some or all of the foregoing solid materials have been added to this
agitated mixture, the particles of the peroxygen ble~hing agent with coated bleach
activator particles can be added to the composition, again while the mixture is
m~ints~ined under shear agitation. By adding the peroxygen bleaching agent material
and coated activator particles last, or after all or most of the other components, and
especially after ~lk~linity source particles, have been added, desirable stability
benefits for the peroxygen bleach can be realized. If enzyme prills are incorporated,
they are preferably added to the non-aqueous liquid matrix last.
As a final process step, after addition of all of the particulate material, agitation
of the mixture is continued for a period of time sufficient to form compositionshaving the requisite viscosity, yield value and phase stability characteristics.Frequently this will involve agitation for a period of from about 1 to 30 minlltes
In adding solid coll~ollents to non-aqueous liquids in accordance with the
foregoing procedure, it is advantageous to m~int~in the free, unbound moisture
content of these solid m~tt~ below certain limits. Free moisture in such solid
materials is frequently present at levels of 0.8% or greater. By reducing free
moisture content, e.g., by fluid bed drying, of solid particulate materials to a free
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moisture level of 0.5% or lower prior to their incorporation into the cleaning
composition matrix, significant stability advantages ~or the resulting composition
can be realized.
The compositions of this invention, prepared as hereinbefore described, can be
used to form aqueous washing and/or bleaching solutions for use in the laundering
~ and bleaching of fabrics. Generally, an effective arnount of such compositions is
added to water, preferably in a conventional fabric laundering automatic washingmachine, to forrn such aqueous laundering/bleaching solutions. The aqueous
washing/ble~f hing solution so forrned is then cont~c tt?~l preferably under agitation,
with the fabrics to be laundered and bleached therewith.
An effective amount of the liquid cleaning compositions herein added to water
to form aqueous laundering/bleaching solutions can comprise amounts sufficient to
forrn from about 500 to 7,000 ppm of composition in aqueous solution. More
preferably, from about 800 to 3,000 ppm of the detergent compositions herein will
be provided in aqueous washing/bleaching solution.
The following examples illustrate the p~ ~dlion and performance advantages
of non-aqueous liquid cleaning compositions of the instant invention. Such
examples, however, are not nt?cess~rily meant to limit or otherwise define the scope
of the invention herein.
EXAMPLE I
PreParation of Citrate-~oated Bleacl~ Activator Particles
Citrate coated powdered sodium nonanoyloxybenzene sulfonate (NOBS) is
produced by discretely coating NOBS powder (p.s. 3-100 microns) using a Wurster
fluid bed coating d~aldL-Is (Wurster HS 18" bottom spray coating unit). NOBS
powder is charged to the fluid bed coating a~p~dL,ls. The fluidizing ~ir is ~ct~l~ted
to fluidize the NOBS powder within the Wurster a~pa,dlus. Thereafter, a solution of
sodium citrate dihydrate (40% by weight) is applied to the NOBS powder through atwo-fluid nozzle as it recirculates in the fluidized bed. Once the target level of
coating is applied, the nozzle is switched off and the product is dried in the fluidized
bed for 5 minutes. Eight batches of 54.5 kg. (120 Ib.) each are produced and used
in the prel ~dLion of a non-aqueous liquid detergent product as hereinafter described
in Example III.
EXAMPLE II
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Preparaltion of LAS Powder
Sodium C12 linear alkyl benzene sulfonate (NaLAS) is processed into a
powder contz~ining two phases. One of these phases is soluble in the non-aqueousliquid phase of the detergent composition hereinafter described in Example III and
the other phase is insoluble. It is the insoluble fraction which serves to add structure
and particle suspending capability to the non-aqueous phase of the Example ~II
composition.
NaLAS powder is produced by taking a slurry of NaLAS in water
(approximately 40-50% active) combined with dissolved sodium sulfate (3-15%)
and a hydrotrope, sodium sulfosuccinate (1-3%). The hydrotrope and sulfate are
used to improve the characteristics of the dry powder. A drum dryer is used to dry
the slurry into a flake. When the NaLAS is dried with the sodium sulfate, two
distinct phases are created within the flake. The insoluble phase creates a network
structure of aggregate small particles (V.4-2 um) which allows the finished non:aqueous dct~ ,el-L product to stably suspend solids.
The NaLAS powder prepared according to this example has the following
makeup shown in Table I.
TABLE I
LAS Powder
Component Wt. %
NaLAS 85%
Sulfate 1 1%
- Sulfosuccinate 2%
Water 2.5%
Unreacted, etc. balance to 100%
% insoluble LAS 17%
# of phase (via X-ray diffraction) 2
EXAMPLE III
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Preparation of Non-Aqueous Liquid Deter~ent Compo~ition
1) Butoxy-propoxy-propanol (BPP) and a Cl 1 IsEO(5) ethoxylated alcohol
nonionic surfactant (Neodol 1-5) are mixed for a short time (1-2 minutes)
using a pitched blade turbine impeller in a mix tank into a single phase.
2) NaLAS powder as ~ ~.,d in Example II is added to the BPP/Neodol solution
in the mix tank to partially dissolve the NaLAS. Mix time is approximately
one hour. The tank is bl~nketec~ with nitrogen to prevent moisture pickup from
the air. The soluble phase of NaLAS powder dissolves, while the insoluble
NaLAS aggregates and forms a network struct,ure within the BPPlNeodol
solution.
3) Liquid base (LAS/BPP/NI) is pumped out into drums. Molecular sieves (type
3A, 4-8 mesh) are added to each drum at 10% of t_e net weight of the liquid
base. The molecular sieves are mixed into the liquid base using both single
blade turbine mixers and drum rolling techniques. The mixing is done under
nitrogen blanket to prevent moisture pickup from the air. Total mix time is 2
hours, after which 0.1-0.4% of the moisture in the liquid base is removed.
4) Molecular sieves are removed by passing the liquid base through a 20-30 mesh
screen. Liquid base is returned to the mix tank.
5) Additional solid ingredients are prepared for addition to the composition.
Such solid ingredients include the following:
Sodium carbonate (particle size 10-40 microns)
Sodium citrate dihydrate
Maleic-acrylic copolymer (BASF Sokalan CP5 moisture
content 4. 1-5.0%)
Brighten.or
Diethyl triamine pent~cetic acid (DTPA)
Tit,anium dioxide particles ( 1-5 microns)
These solid m~teri~l~, which are all millable, are added to the mix tank through- a 20-30 mesh screen and mixed with the liquid base until smooth. This
approximately 1 hour after addition of the last powder. The tank is blanketed
wit,h nikogen after addition of the powders. No particular order of addition forthese powders is critical.
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28
6) The batch is pumped once through a Fryma colloid mill, which is a simple
rotor-stator confi~uration in which a high-speed rotor spins inside a stator
which creates a zone of high shear. This serves to disperse the insoluble
NaLAS aggregates and partially reduce the particle size of all of the solids.
This leads to an increase in yield value (i.e. structure). The batch is then
recharged to the mix tank.
7) Still additional solid materials which should not be milled or subjected to high
shear agitation are then prepared. These include the following/
Sodiurn nonanoyloxybenzene sulfonate (NOBS) coated with
Sodium citrate dihydrate as prepared in Exarnple I. Such material is
NOBS 60%
Citrate 40%
Sodium perborate (20-40 microns)
Protease and arnylase enzyme prills ( 100-1000 microns)
These non-millable solid materials are then added to the mix tank followed by
liquid ingredients (perfume and silicone-based suds suppressor). The batch is
then mixed for one hour (under nitrogen blanket). The resulting composition
has the formula set forth in Table II.
TABLE II
Non-Aqueous Liquid D~tc~ ,..t Composition with Bleach
Component Wt % Active
LAS Powder 20.26
C12-14E0=5 alcohol ethoxylate 18.82
BPP 1 8.82
Sodium citrate dihydrate 4.32
Citrate Coated NOBS 8.49
Sodium Carbonate 11 .58
Maleic-acrylic copolymer 11 .58
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DTPA 0.77
Protease Prills 0.77
Amylase Prills 0.39
Sodium Perborate2.86
Suds Suppressor 0.03
Perfume 0.46
Titanium Dioxide0.54
Brightener 0.3 1
100.00%
The resulting Table II composition is a stable, anhydrous heavy-duty liquid
laundry detergent which provides excellent stain and soil removal perforrnance
when used in normal fabric laundering operations.
EXAMPLE IV
Non-ac~ueous Liquid DetersJents with Coated Bleach Activators
Several non-aqueous liquid detergent compositions are prepared Cont~ining
sodium pelL,oldte bleach and sodium nonanoyloxybenzene sulfonate (NOBS) bleach
activator. Co,ll~d,dli~e formulas use uncoated NOBS powder. Similar formulas arethen prepared wherein the NOBS is coated in accordance with this invention with
sodiurn citrate or sodiurn sulfate. The formulas so p,~ ,d are then evaluated for
percent of peracid retained after two weeks of aging at 1 00~F (3 8~C).
Formulas and test results are set forth in Table III.
TABLE III
Forrnula No. ~Wt. %)
- Component A B C D E F
NOBS Form uncoatedcitrate sulfate uncoated citrate sulfate
powder coated coated powder coated coated
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C12 15 AE3S 22.9 21.8 21.9
C12_14 AS 28.5 28.1 27.5
C12 Glucose10.0 9.5 9.6
Amide
1,2-Propandiol 31.6 31.2 30.6
C12 13 E05 21.4 20.5 20.5 17.1 16.9 16.5
BPP 24.3 23.2 23.3
Sodium 14.3 13.6 13.7 9.0 8.8 8.7
Carbonate
NOBS powder 7.1 5.6
Coated NOBS 6.8 6.8 5.6 5.4
Sodium Citrate 2.9 2.3
(as coating)
Sodium Sulfate 2.7 2.2
(as coating)
NOBS particle 1.6 1.4 1.4 1.1
material
Sodium Citrate 4.3 1.9 4.3
Sodium 3.2 3.1 3.1
o~
DTPA 0.4 0.4 0.4
BrightPnl-r O 3 Qt3 Q.3
100% 100% 100% 100% 100% 100%
% Peracid 0% 65% 52% 0% 20% 20%
retained after 2
wks. at 100~F.
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31
The Table III data illustrate the importance of bleach activator coating in terms
of retention of activator effectiveness upon product storage.
EXAMPLE V
Non-Aqueous Liquid Deter~ents with Small Coated Activator Particles
Two additional non-aqueous liquid detergents are prepared cont~ining a
peroxygen bleaching agent and a sodiurn nonanoyloxybenzene sulfonate (NOBS)
bleach activator. One product uses uncoated NOBS powder (3-100 microns), the
other product uses a sodium citrate-coated NOBS powder (20-150 microns).
The products prepared are evaluated for percent of peracid retained after four
weeks of aging at 100~F (38~C). These products are also observed and evaluated for
rheology changes, i.e, thickening, upon storage. Product formulas and tests results
are set forth in Table IV.
TABLE IV
Formula No. (Wt. %)
Component A B
NaLAS 22.0 22.0
Neodol 1-5 22.0 22.0
Butoxy-propoxy propanol 18.8 18.8
Sodium Citrate dihydrate5.8 5.8
Sodiurn Carbonate 17.3 17.3
DTPA 0.8 0.8
Brightener 0 5 0 5
~ Sodiurn Percarbonate 5.2 5.2
(Degussa Q20)
NOBS powder* 7.6 0
Coated NOBS powder 0 12.7
100% 100%
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3:~!
Percent Peracid Retained at4 78% 90%
weeks of 100%
Rheology Solid after 4Liquid after 4
weeks at 100~Fweeks at 100~F
or 8 weeks at
80~F
* The coated NOBS powder is 40% active NOBS, 60% sodium citrate. Tl1e,~fole,
dosing it at 12.7% results in 7.6% active NOBS.
I he Table IV data indicate that the use of small particle, citrate-coated NOBS
can provide both bleach stability and physical stability benefits in non-aqueousliquid detergent products.
