Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02232341 1998-03-13
RINSE AID FOR PLASTICWARE
Field of the Invention
The invention relates to warewashing processes
and chemicals used in washing plastic cookware, dishware
and flatware. More particularly, the invention relates
to primarily organic materials that can be added to
water to promote a sheeting action in an aqueous rinse
used after an alkalirie detergent cycle. Such aqueous
rinse aids promote effective sheeting to result in
removal of aqueous rinse materials and solids contained
therein from plastic cookware, dishware and flatware in
acceptable drying time without cracking the plasticware.
Backc-round of the Invention
Mechanical warewashing machines have been
common in the institutional and household environments
for many years. Such automatic warewashing machines
clean dishes u::ing two or more cycles which can include
initially a wash cycle followed by a rinse cycle. Such
dishwashers can also utilize soak cycle, prewash cycle,
scrape cycle, second wash cycle, a rinse cycle, a
sanitizing cycle and a drying cycle, if required. Such
cycles can be repeated if needed and additional cycles
can be used. After passing through a wash, rinse and
dry cycle, dishware, cups, glasses, etc., can exhibit
spotting that arises from the uneven draining of the
water from the surface of the ware after the rinse step.
Spott:ing is aesthetically unacceptable in most consumer
and institutional environments.
In order to substantially prevent the
formation of spotting rinse agents have commonly been
CA 02232341 1998-03-13
added to water to form an aqueous rinse which is sprayed
on the dishware afte.r cleaning is complete. The precise
mechanism through wh_Lch rinse agents work is not
established. One theory holds that the surfactant in
the rinse aid is absorbed on the surface at temperatures
at or above its clouci point, and thereby reduces the
solid-liquid interfacial energy and contact angle. This
leads to the formation of a continuous sheet which
drains evenly from the surface and minimizes the
formation of spots. Generally, high foaming surfactant-s
have cloud points above the temperature of the rinse
water, and, accordincf to this theory, would not promote
sheet formation, thereby resulting in spots. Moreover,
high foaming materials are known to interfere with the
operation of the warewashing machine. Common rinse aid
formulas are used in an amount of less than about 1,000
parts preferably less than 500 parts, commonly 50 to 200
parts per million of active materials in the aqueous
rinse. Rinse agents avai].able in the consumer and
institutional markets comprise liquid or solid forms
which are typically added to, dispersed or dissolved in
water to form an aqueous rinse. Such dissolution can
occur from a rinse agent installed onto the dish rack.
The rinse agent can be diluted and dispensed from a
dispenser mounted on or in the machine or from a
separate dispenser that is mounted separately but
cooperatively with the dish machine.
Commonly available commercial rinse agents
typically comprise a low foaming surface active agent
made from homopolymers or copolymers of an alkylene
oxide such as ethylene oxide or propylene oxide or
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mixt:ures thereof. Typically, the surfactants are formed
by reacting an alcohol, a glycol, a carboxylic acid, an
amirie or a substituted phenol with various proportions
and combinations of ethylene oxide and propylene oxide
to f:orm both random and block copolymer substituents.
The commonly available rinse agents have
priniarily focused on reducing spotting and filming on
surfaces such as glass, ceramics, china and metal.
However, plastic dishware is more commonly used now,
especially in the institutional market. A special
problem for rinse aicl surfactants used for plasticware
is the attack and crazing of the ware. Block copolymer
surfactants do not seem to attack plastics as strongly
as fatty alcohol or alkyl phenol-based nonionic
surfactants. Linear alkoxylates show they do not attack
plexiglass, polystyrene, or Tupperware , common utensil
plastics. Nevertheless, current surfactants have not
provided the desired sheeting in an acceptable drying
time following the rinse cycle.
U.S. Patent 5,298,289 describes the treatment
and after-treatment of surfaces, especially metals, with
derivatives of polyphenol compounds. These compositions
are also said to be useful in treating plastic and
painted surfaces to improve rinsability without water
breaks. The surfactants employed are a combination of
previously known anionic.and nonionic surfactants.
Liquid dishwashing detergent compositions are
described in U.S. Patent 4,492,646 containing highly
ethoxylated nonionic surfactants to reduce spotting and
film_ing on surfaces such as glass, ceramics and metal.
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European Patent Publication 0,432,836
describes the use of alkyl polyglycoside surfactants in
rinse aid compositions on polycarbonate.
Fluorinated surfactants are described in U.S.
Patent 4,089,804 where a non-ethoxylated fluoroaliphatic
sulf:onamide alcohol is added to typical fluorinated
hydrocarbon surfactarlts as a synergist. The
compositions are described as useful in a wide variety
of industries, e.g., household cosmetic and personal
proclucts. Rinse aid for dishwashing is mentioned.
Certain orqanosilanes have been described in
rinse aid compositions where the organosilane contains
either a nitrogen, phosphorous or sulfur cationic group
in combination with an anion, e.g. a monofunctional
organic acid. U.S. Patent 4,005,024 describes such
compounds in a rinse aid composition to attract specific
soil particles.
Aminosilanes have been described with a low
foaming ethoxylated nonionic surfactant in rinse aid
compositions in automatic dishwashing machines.
None of the fluorinated surfactants or silanes
described in rinse aid compositions have focused on
their use in plasticware.
Surprisingly, we have found that by adding a
polyi=ther or polybetaine polysiloxane nonionic or
amphoteric surfactant alone or in combination with a
fluorinated hydrocarbon surfactant, especially an
ethoxylated fluorinated aliphatic sulfonamide alcohol,
to a conventional rinse aid compositiori containing
hydrocarbon surfactants, the resulting rinse agent
provides excellent sheeting properties on plasticware
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without attacking or crazing the plastic and, more
importantly, providing dried, non-spotted plasticware in
acceptable time following the rinse cycle.
Summary of the Invention
Accordingly, the present invention is a rinse
aid composition for plasticware, formulated as a
dilutable liquid, gel or solid concentrate and, when
diluted, forming an aqueous rinse, and including in
addition to conventional rinse aid surfactants, e.g.
hydrocarbon surfactarits, about 0.1 to 10 wt-% of a
polyalkylene oxide-modified polydimethylsiloxane or a
polybetaine-modified polysiloxane, alone or in
combination with about 0.1 to 10 wt-% of a fluorinated
hydrocarbon nonionic surfactant.
A second aspect of the present invention is a
method of cleaning plasticware by: (a) first contacting
the ware with an alkaline aqueous cleaning agent in a
warewashing machine at 100-180 F to produce cleaned
plasticware, and (b) contacting the cleaned plasticware
with an aqueous rinse containing a major proportion of
an aqueous diluent having about 2 to 100 parts per
million of hydrocarbon surfactants, and about 0.01 to 10
parts per million of a polyalkylene oxide-modified
polydimethylsiloxane or polybetaine-modified
polysiloxane, optionally in combination with about 0.01
to 10 parts per million of a fluorinated hydrocarbon
surfactant, e.g. an ethoxylated fluoroaliphatic
sulfonamide alcohol.
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Detailed Description of the Invention
For the purpose of this invention, the term
"ririse agent" includes concentrate materials that are
diluted with an aqueous stream to produce an aqueous
rinse. Accordingly, an aqueous rinse agent is an
aqueous material that is contacted with ware in a rinse
cycl.e. A sheeting agent is the polymeric material used
to promote the even draining of the aqueous rinse.
Sheeting is defined as forming a continuous, evenly
draining film, leavirig virtually no spots or film upon
the evaporation of water. For the purpose of this
invention, the term "dish" or the term "ware" is used in
the broadest sense of the term to refer to various types
of articles used in the preparation, serving,
consumption, and disposal of food stuffs including pots,
pans, trays, pitchers, bowls, plates, saucers, cups,
glasses, forks, knives, spoons, spatulas, and other
glass, metal, ceramic, plastic composite articles
commonly available in the institutional or household
kitchen or dining room.
Since the present invention focuses on plastic
articles, the term "plasticware" includes the above
articles made from, e.g., polycarbonate, melamine,
polypropylene, polyester resin, polysulfone, and the
like.
The siloxane surfactant employed as an
additive in the present invention alone or in
combination with a fluorochemical surfactant described
below is a polyalkylene oxide-modified
polydimethylsiloxane, nonionic surfactant or a
polybetaine-modified polysiloxane amphoteric surfactant.
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Both, preferably, are linear polysiloxane copolymers to
which polyethers or polybetaines have been grafted
through a hydrosilation reaction. This process results
in an alkyl-pendant (AP type) copolymer, in which the
polyalkylene oxide groups, for example, are attached
alor)g the siloxane backbone through a series of
hydrolytically stable Si-(-' bonds. These products have
the general formula:
C H 3 CHa
( C H 3 ) 3 S i O O i_ p S I ( C H 3) a
[L3 n m
wherein R is -(CHz) 3-()- (EO) X- (PO) y-Z or
CH3
1
- ( CHz ) 3-0-CH2CH ( OH ) CH2 -N+-CH2C00 ;
I
CH3
EO is ethyleneoxy, PO is 1,2-propyleneoxy, Z is hydrogen
or alkyl of 1-6 carbon atoms, and the weight ratio in %
of EO:PO may vary from 100:0 to 0:100. A broad range of
surfactants have been developed varying x and y above
and coefficients n and m. Preferably, n is 0 or _ 1 and
m is at least 1. More preferred are the siloxanes where
Z is hydrogen, methyl or butyl and the weight ratio of
EO:PO is 100:0 to 40:00, or in the polybetaines where n
is 0 to 200 and m is :1 to 50. Particularly valuable are
the siloxane surfactants herein described and known as
SILWET surfactants available from Union Carbide or ABIL
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polyether or polybetaine polysiloxane copolymers
available from Goldschmidt Chemical Corp. and described
in U.S. Patent No. 4,654,161. The particular siloxanes
usecl in the present :-nvention are described as having,
e.g., low surface terision, high wetting ability and
excellent lubricity. For example, these surfactants are
said to be among the few capable of wetting
polytetrafluoroethylene surfaces.
The fluorochemical surfactant employed as an
additive in the present invention in combination with a
silane, defined above, is a nonionic fluorohydrocarbon,
such as, for example, fluorinated alkyl polyoxyethylene
ethanols, fluorinatec. alkyl alkoxylate and fluorinated
alkyl esters. These FluoradTM surfactants are available
from 3M. As a fluorinated alkyl polyoxyethylene
ethanol, included as a preferred surfactant is a
polyoxyethylene adduct of a fluoroaliphatic sulfonamide
alcohol which has excellent wetting, spreading and
leveling properties. These surfactants may be described
as having the formula:
RfSOzN ((--2H5) (CHZCH2O) xH
wherein Rf is CnF2n+1 in which n is 6-10 and x may vary
from 10 to 20. Particularly valuable is the surfactant
where n is 8 and x is 14. This particular surfactant
iden-:ified as FC-170C is available from 3M.
Although fluorocarbon surfactants and silicone
surfactants have been known to be good wetting agents
and used individually in rinse aid formulations, there
is no description of their being used effectively in
plasticware as rinse aids. We have found in the present
invention that the use of certain polysiloxane
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copolymers in a mixture with hydrocarbon surfactants
provide excellent rinse aids on plasticware. We have
alsc> found that the combination of certain silicone
polysiloxane copolymers and fluorocarbon surfactants
with conventional hydrocarbon surfactants also provide
excellent ri_nse aids on plasticware. This combination
has been found to be better than the individual
components except with certain polyalkylene oxide-
modified polydimethylsiloxanes and polybetaine
polysiloxane copolymers of the present invention where
the effectiveness is about equivalent. Therefore, the
preferred embodiments of the present invention encompass
the polysiloxane copolymers alone and the combination
with the fluorocarbori surfactant preferably involves
polyether polysiloxaries, the nonionic siloxane
surfactants. The amphoteric siloxane surfactants, the
polybetaine polysiloxane copolymers may be employed
alone as the additive in t:he conventional rinse aids to
provide the same results.
Since the use of: the above siloxane additives
alone or in combination with the fluorocarbon are
applicable to all conventional rinse aid formulations,
the following description of ingredients and rinse aid
formulations is illustrative only and not limiting of
the present invention.
An example of hydrocarbon surfactants in
conventional rinse aid formulations are nonionic
surfactants, typically a polyether compound prepared
from ethylene oxide, propylene oxide, in a homopolymer
or a block or heteric copolymer. Such polyether
compounds are known as polyalkylene oxide polymers,
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polyoxyalkylene polymers, or polyalkylene glycol
polymers. Such sheeting or rinse agents have a
molecular weight in t:he range of about 500 to about
15,000. Certain types of polyoxypropylene-
polyoxyethylene glycol polymer rinse aids have been
found to be particularly useful. Those surfactants
comprising at least one block of a polyoxypropylene and
having at least one other block of polyoxyethylene
attached to the polyoxypropylene block. Additional
blocks of polyoxyethylene or polyoxypropylene can be
present in a molecule. These materials having an
average molecular weight in the range of about 500 to
about 15,000 are commonly available as PLURONIC
manufactured by the BASF Corporation and available under
a variety of other trademarks of their chemical
suppliers. In addition, r.inse aid compositions called
PLURONIC R (reverse pluronic structure) are also useful
in the rinse aids of the invention. Additionally, rinse
aids made by reacting ethylene oxide or propylene oxide
with an alcohol anion and an alkyl phenol anion, a fatty
acid anion or other such anionic material can be useful.
One particularly useful rinse aid composition can
comprise a capped polyalkoxylated C6_29 linear alcohol.
The rinse aids can be made with polyoxyethylene or
polyoxypropylene units and can be capped with common
agents forming an ether end group. One particularly
useful species of this rinse aid is a benzyl ether of a
polyethoxylated. C12_14 linear alcohol; see U.S. Patent No.
3,444,247. Alcohol ethoxylates having EO and PO blocks
can be particularly useful since the stereochemistry of
CA 02232341 1998-03-13
these compounds can permit occlusion by urea, a feature
useful in preparing solid rinse aids.
Particularly useful polyoxypropylene
polyoxyethylene block polymers are those comprising a
center block of polyoxyprcpylene units and blocks of
polyoxyethylene units to each side of the center block.
These copolymers have the formula shown below:
(EO)n -- (PO)m - (EO)n
wherein m is an integer of 21 to 54; n is an integer of
7 to 128. Additional useful block copolymers are block
polymers having a center block of polyoxyethylene units
and blocks of polyoxypropylene units to each side of the
center block. The copolymers have the formula as shown
below:
(PO)n - (EO)m - (PO)n
wher-ein m is an integer of 14 to 164 and n is an integer
of 9 to 22.
In the preparation of conventional rinse aid
compositions, a hydrotropic agent is often employed in
the formulation. Such an agent may also be used in the
present invention.
Hydrotropy is a property that relates to the
ability of materials to improve the solubility or
miscibility of a substance in liquid phases in which the
substance tends to be insoluble. Substances that
provide hydrotropy are called hydrotropes and are used
in relatively lower concentrations than the materials to
be solubilized.
A hydrotrope modifies the solvent to increase
the solubility of an insoluble substance or creates
micellar or mixed micellar structures resulting in a
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stable suspension of the insoluble substance in the
solvent. The hydrotropic mechanism is not thoroughly
understood. Apparently either hydrogen bonding between
primary solvent, in this case water, and the insoluble
substance are improved by the hydrotrope or the
hydrotrope creates a micellar structure around the
insoluble composition to maintain the material in a
suspension/solution. In this invention, the hydrotropes
are inost useful in maintaining a uniform solution of the
cast rinse composition both during manufacture and when
dispersed at the use location. The combination of the
polyalkylene oxide materials and the casting aids tends
to be partially incompatible with aqueous solution and
can undergo a phase change or phase separation during
storage of the solution. The hydrotrope solubilizer
maintains the rinse composition in a single phase
solution having the nonionic rinsing agent uniformly
distributed throughout the composition.
Preferred hydrotrope solubilizers are used at
about 0.1 to 20 wt-% and include, for example, small
molecule anionic surfactants and semi-polar nonionic
surfactants. The most preferred range of hydrotrope
solubilizers is about 1 to 10 wt-%.
The small molecule anionic surfactants include
aromatic sulfonic acid or sulfonated hydrotropes such as
C1_5 substituted benzene sulfonic acid or naphthalene
sulfonic acid. Examp:Les of such a hydrotrope are xylene
sulfonic acid or naph--halene sulfonic acid or salts
thereof.
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The semi-polar type of nonionic surface active
agents _include amine oxide hydrotropes such as tertiary
amine oxides corresponding to the general formula:
R2
R1 -( OR4 ) n- N-3 0
~3
wherein the arrow is a conventional representation of a
semi-polar bond; and, R1, R2, and R3 may be aliphatic,
aromatic, heterocyclic, alicyclic, or combinations
thereof. Generally, for amine oxides of detergent
interest, R' is an alkyl radical of from about 8 to about
24 carbon atoms; R2 and R3 are selected from the group
consisting of alkyl or hydroxyalkyl of 1-3 carbon atoms
and mixtures thereof; R4 is an alkylene or a
hydroxyalkylene group containing 2 to 3 carbon atoms;
and n ranges from 0 to about 20.
Useful water soluble amine oxide hydrotropes
are selected from alkyl di--(lower alkyl) amine oxides,
specific examples of which are n-decyldimethylamine
oxide, dodecyldimethylamine oxide, tridecyldimethylamine
oxide, tetradecyldimethylamine oxide,
pentadecyldimethylamine oxide, hexadecyldimethylamine
oxide, heptadecyldimethylamine oxide,
octadecyldimethylamine oxide, dodecyldipropylamine
oxide, tetradecyldipropylamine oxide,
hexadecyldipropylamine oxide, tetradecyldibutylamine
oxide, octadecy.Ldibutylamine oxide, bis(2-
hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-3-
dodecoxy-l-hydroxypropylamine oxide, dimethyl-(2-
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hydroxydodecyl)amine oxide, 3,6,9-
trioctadecyldimethylamine oxide and d-dodecoxy-2-
hydroxypropyldi-(2-hydroxyethyl)amine oxide. The most
preferred of the above is n-decyldimethylamine oxide.
Such materials do not provide any pronounced
surfactant or sheeting activity but significantly
improve the solubility of the organic materials of the
rinse aid in the aqueous rinse compositions.
Thus, a preferred embodiment of a rinse aid
composition for plasticware, which is suitable for
dilution to form an aqueous rinse includes: (a) about 2
to 90 wt-% of one or more nonionic surfactants;
(b) about 1 to 20 wt-% of a hydrotrope; (c) about 0.1 to
10 wt-o of a polysiloxane copolymer of the formula
CH3 CH3
(CH3)3510 LO 1i_o SI(CH3)a
I L. n m
wherein R is -(CH2) 3-0- (EO) X- (PO)Y-Z or
CH3
-( CH2 ) 3-O-CH2CH ( OH ) CHZ-N+-CH2C00 ;
I
CH3
n is 0 or _ 1; m is at. least 1, Z is hydrogen or alkyl
of 1-6 carbon atoms, and the weight ratio in % of EO:PO
may vary from 100:0 to 0:100, and, optionally, (d) about
0.1 to 10 wt-% of an ethoxylated fluoroaliphatic
sulfonamide alcohol.
Another embodimer)t of the rinse aid
composition of the present invention is the above-
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described siloxane surfactant with a rinse aid
composition containing a nonionic block copolymer and a
defoamer composition, and, optionally, in combination
with the above-described fluorocarbon surfactant. The
nonionic ethylene oxide propylene oxide block copolymer
in t:ais case would not have been expected to provide
effective sheeting action and low foam in an aqueous
rinse due to its high cloud point and poor wetting
properties. However, rinse agents diluted into an
aqueous rinse providing effective sheeting and low
foaming properties have been prepared from high cloud
point, high foaming surfactants with an appropriate
defoamer as described in U.S. Patent No. 5,589,099.
Illustrative but non-limiting examples of
various suitable high cloud point nonionic surface
active agents for these rinse agents include
polyoxyethylene-polyoxypropylene block copolymers having
the formula:
(EO)x(PO)y(EO)Z
wherein x, y and z reflect the average molecular
proportion of each alkylene oxide monomer in the overall
block: copolymer composition. x typically ranges from
about: 30 to 130, y typically ranges from about 30 to 70,
z typically ranges from about 30 to 130, and x plus y is
typically greater thari aboiit 60. The total
polyoxyethylene comporient of the block copolymer
constitutes typically at least about 10 wt-% of the
block. copolymer and commonly 20 wt-% or more of the
block copolymer. The material preferably has a
molecular weight great.er than about 1,000 and more
preferably greater than about 2,000.
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Defoaming agents (defoamers) include a variety
of different materials adapted for defoaming a variety
of compositions. Defoamers can comprise an anionic or
nonionic material such as polyethylene glycol,
polypropylene glycol, fatty acids and fatty acid
derivatives, fatty acid sulfates, phosphate esters,
sulfonated materials, silicone based compositions, and
othe,_ s .
Defoarners may include food additive defoamers
including silicones and other types of active anti-foam
agents.
Silicone foam suppressers include
polydialkylsiloxane preferably polydimethylsiloxane.
Such silicone based foam suppressers can be combined
with silica. Such silica materials can include silica,
fumed silica, derivat:ized silica, silanated silica, etc.
Commonly available anti-foaming agents combine a
polydimethylsiloxane and silica gel. Another food
additive defoaming agent comprises a fatty acid
defoamer. Such defoarner compositions can comprise
simple alkali metal or alkaline earth metal salts of a
fatty acid or fatty acid derivatives. Examples of such
derivatives include mono, di- and tri- fatty acid esters
of polyhydroxy compourids such as ethylene glycol,
glycerine, propylene glycol, hexylene glycol, etc.
Preferably such defoaming agents comprise a fatty acid
monoester of glycerol. Fatty acids useful in such
defoaming compositions can include any CB_24 saturated or
unsaturated, branched or urlbranched mono or polymeric
fatty acid and salts thereof, including for example
myristic acid, palmitic acid, stearic acid, behenic
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acid, lignoceric acid, palmitoleic acid, oleic acid,
linoleic acid, arachidonic: acid, and others commonly
available. Other food additive anti-foam agents
available include water insoluble waxes, preferably
microcrystalline wax, petroleum wax, synthetic petroleum
wax, rice base wax, beeswax having a melting point in
the range from about 35 to 125 C with a low
saponification value, white oils, etc. Such materials
are used in the rinse agents at a sufficient
concentration to prevent the accumulation of any
measurable stable foam within the dish machine during a
rinse cycle. The defoaming composition may be present
in the composition of the present invention from about
0.1-30 wt-%, preferably 0.2-25 wt-%.
Thus, as another embodiment, a rinse aid
composition for plasticware, suitable for dilution to
form an aqueous rinse also includes: (a) about 5 to 40
wt-% of a nonionic block copolymer composition of
ethylene oxide and propylene oxide, having a molecular
weight of _> 2000 and a cloud point, measured with a 1
wt-% aqueous solution, greater than 30 C; (b) about 0.2
to 25 wt-% of a food additive defoamer composition; (c)
about 0.1 to 10 wt-% of a polysiloxane copolymer of the
formula
CH3 CH3
(CH3)3S10 31 _ O I LH3 n [ [ i m
wherein R is -(CH2) 3-0-- (EO) X- (PO) y-Z or
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CH3
- (CH2) 3-0-CH2CH ( OH ) CH2-N+-CH2COO ;
1
CH3
n is 0 or _ 1; m is at least 1, Z is hydrogen or alkyl
of 1--6 carbon atoms, and the weight ratio in % of EO:PO
may vary from 100:0 to 0:100, and, optionally, (d) about
0.1 to 10 wt-% of an ethoxylated fluoroaliphatic
sulfonamide alcohol.
Still another embodiment of the present
inverition is a rinse aid composition containing the
above-described siloxane surfactant with a rinse aid
composition containinq solely food additive ingredients
and, optionally, in combination with the above-described
fluorocarbon surfactarlt. 'rhe compositions include a
class of nonionic surfactants, namely, the polyalkylene
oxide derivatives of sorbitan fatty acid esters, which
exhibit surprising levels of sheeting action, with a
careful selection of defoarner compositions. The
effective defoamer compositions are selected from the
group consisting of a silicone defoamer, an alkali metal
(e.g. sodium, potassium, etc.) or alkaline earth fatty
acid salt defoamer or a glycerol fatty acid monoester
defoamer described above. Preferably, silicone based
materials are used to defoam the sorbitan material.
Sorbitol ancl sorbitan can be derivatized with
an alkylene oxide such as ethylene oxide or propylene
oxide or derivatized with fatty acids or with both using
conventional technology to produce nonionic surfactant
sheeting agent materials. These sheeting agents are
typically characterized by the presence of from 1 to
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3 moles of a fatty acid, in ester form, per mole of
surfactant and greater than 15 moles of alkylene oxide,
preferably 15 to 40 moles of alkylene oxide and most
preferably 15 to 25 moles of ethylene oxide per mole of
surfactant. The composition of the surfactant is a
mixture of a large nurnber of compounds characterized by
the molar proportion of alkylene oxide and the molar
proportion of fatty acid residues on the sorbitol or
sorbi_tan molecules. The compositions are typically
characterized by average concentrations of the alkylene
oxide (typically ethylene oxide) and the fatty acid on
the overall compositions. Examples of preferred
nonionic surfactants are Polysorbate 20 , also known as
TweerL 20 (ICI), typically considered to be a mixture of
laureate esters of sor.bitol and sorbitan consisting
predominantly of the mono fatty acid ester condensed
with approximately 20 moles of ethylene oxide.
Polysorbate 60 is a nlixture of stearate esters of
sorbitol and sorbitan consisting predominantly of the
mono fatty acid ester condensed with approximately 20
moles of ethylene oxide. Selected polysorbate nonionic
surfactant materials are approved for direct use in food
intended for human consumption under specified
conditions and levels of use.
Alkoxylated sorbitan or sorbitol aliphatic
esters suitable for use in the rinse aid composition
include any sorbitan or sorbitol aliphatic ester
derivatized with an alkylerie oxide capable of providing
effective sheeting action or rinsing performance in
cooperation with the ether components of the rinse agent
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composition. The preferred compositions are the
ethylene oxide condensates with sorbitan or sorbitol
fatty acid esters. In addition to providing superior
sheeting and rinsing performance, these materials are
approved food additives, in the form of a liquid or waxy
solid, that can be easily formulated into concentrated
liquid or solid rinse agents. Alkoxylated sorbitan or
sorbitol fatty acid esters suitable for use in the rinse
agent include mono, di- and tri-esters and mixtures
thereof. Sorbitan fatty acid esters may be derivatized
by esterification of sorbitol or sorbitan with such
fattv acids as lauric, myristic, palmitic, stearic,
oleic, linoleic, and other well known similar saturated,
unsaturated (cis or trans), branched and unbranched
fatty acid. Preferred food additive or GRAS fatty acids
are the sorbitaii esters approved as direct food
additives (e.g. sorbitan monostearate, POE 20 Sorbitan
monolaurate, POE 20 Sorbitan monostearate, POE 20
Sorbitan tristearate, POE 20 Sorbitan monooleate and
mixtures thereof. Based on their cost availability and
ability to provide excellent sheeting action and rinsing
performance, the preferred useful ethoxylated sorbitan
or sorbitol fatty acid ester include monoesters
derivatized with ethylene oxide.
Thus, a preferred rinse aid composition for
plasticware, suitable for ciilution to form an aqueous
rinse, further includes: (a) about 5 to 50 wt-% of a
sorbitan fatty acid ester containing greater than about
15 moles of alkylene oxide per mole of sorbitan; (b)
about 0.2 to 25 wt-% ef a clefoamer composition selected
from the group consisting of an alkali metal or alkaline
CA 02232341 1998-03-13
earth metal salt of a fatty acid, a silicone, a fatty
acid ester of glycerol, and mixtures thereof; (c) about
0.1 to 10 wt-% of a polysiloxane copolymer of the
formula
r CH3 C H 3
(CH3)3Si0 I Si _ Si(CH3)~
I H, n m
wherein R is -(CHZ) 3-0- (EO) X- (PO) y-Z or
CH,3
1
- (CHZ) 3-0-CH2CH (OH) CHz-N+-CH2C00 ;
I
CH3
n is 0 or _ 1; m is at least 1, Z is hydrogen or alkyl
of 1-6 carbon atoms, and the weight ratio in % of EO:PO
may vary from 100:0 to 0:100, and, optionally, (d) about
0.1 to 10 wt-% of an ethoxylated fluoroaliphatic
sulfonamide alcohol.
The rinse agents of the invention can, if
desired, contain a polyvalent metal complexing or
chelating agent that aids in reducing the harmful
effects of hardness components in service water.
Typically calcium, magnesium, iron, manganese, etc.,
ions present in service water can interfere with the
action of either washing compositions or rinsing
compositions. A chelat_Lng agent can effectively complex
and remove such ions from inappropriate interaction with
active ingredients increasing rinse agent performance.
Both organic and inorgaizic chelating agents are common.
21
CA 02232341 1998-03-13
Inorganic chelating agents include such compounds as
sodium tripolyphosphate and higher linear and cyclic
polyphosphate species. C)rganic chelating agents include
both polymeric and small molecule chelating agents.
Polymeric chelating agents commonly comprise polyanionic
compositions such as polyacrylic acid compaunds. Small
molecule organic chelating agents include salts of
ethylenediaminetetraacetic acid and
hydroxyethylenediaminetetraacetic acid, nitrilotriacetic
acid, ethylenediaminetetrapropionates,
tri.ethylenetetraminehexacetates, and the respective
alkali metal ammonium and substituted ammonium salts
thereof. Amino phosphates are also suitable for use as
chelating agents in the composition of the invention and
include ethylenediamine(tetramethylene phosphates),
nitrilotrismethylenephosphonates, diethylenetriamine
(pentamethylenephosphonates). These amino phosphonates
cornmonly contain alkyl or alkyl groups with less than
8 carbon atoms. Preferred chelating agents include
approved food additive chelating agents such as disodium
salt of ethylenediaminetetraacetic acid.
The liquid rinse agent compositions of the
invention have a liquid base component which can
function as a carrier with various aqueous diluents to
form the aqueous rinse. Liquid bases are preferably
water or a solvent compatible with water to obtain
compatible mixtures thereof. Exemplary nonlimiting
solvents in addition to water include low molecular
weight C1_6 primary and secondary mono, di-, and
trihydrate alcohol such as ethanol, isopropanol, and
polyols containing from two to six carbon atoms and from
22
CA 02232341 1998-03-13
two to six hydroxyl groups such as propylene glycol,
glycerine, 1,3-propane diol, propylene glycol, etc.
The compositioris of the invention can be
formulated using conventional formulating equipment and
techniques. The compositions of the invention typically
can comprise proportions as set forth in Table I.
In the manufacture of the liquid rinse agent
of the invention, typically the materials are
manufactured in commonly available mixing equipment by
charging to a mixing chamber the liquid diluent or a
substantial proportion of a liquid diluent. Into a
liquid diluent is added preservatives or other
stabilizers. Care must be taken in agitating the rinse
agent as the formulation is completed to avoid
degradation of polymer molecular weight or exposure of
the composition to elevated temperatures. The materials
are typically agitated urltil uniform and then packaged
in commonly available packaging and sent to storage
before distribution.
The liquid materials of the invention can be
adapted to a solid block rinse by incorporating into the
composition a casting agent. Typically organic and
inorganic solidifying materials can be used to render
the composition solid. Preferably organic materials are
used because inorganic compositions tend to promote
spotting in a rinse cycle. The most preferred casting
agents are polyethylene glycol and an inclusion complex
comprising urea and a nonionic polyethylene or
polypropylene oxide polymer. Polyethylene glycols (PEG)
are used in melt type solidification processing by
uniformly blending the sheeting agent and other
23
CA 02232341 1998-03-13
components with PEG at a temperature above the melting
point of the PEG and cooling the uniform mixture. An
inclusion complex solidifying scheme is set forth in
Morganson et al., U.S. Patent No. 4,647,258.
The organic nature of the rinse agents of the
invention can be subject to decomposition and microbial
attack. Preferred stabi:Lizers that can limit oxidative
decomposition or microbial attack include food grade
stabilizers, food grade antioxidants, etc. Most
preferred materials for use in stabilizing the
conlpositions of the invention include C1_lo mono, di- and
tricarboxylic acid compounds. Preferred examples of
such acids include acetic acid, citric acid, lactic,
tartaric, malic, fumaric, sorbic, benzoic, etc.
Optional ingredients which can be included in
the rinse agents of the invention in conventional levels
for use include solvents, processing aids, corrosion
inhibitors, dyes, fillers, optical brighteners,
germicides, pH adjusting agents (monoethanol amine,
sodium carbonate, sodium hydroxide, hydrochloride acid,
ph(Dsphoric acid, etc.), bleaches, bleach activators,
perfumes and the like.
The range of actives in the solid and liquid
concentrate compositions of the invention are set forth
in Table I and the ranges in the aqueous rinse in
Table II. Although the actives in the Tables include
fluorocarbon surfactants, the Tables may also be read in
the absence of such surf'actant.
24
CA 02232341 1998-03-13
TABLE I
Preferred (wt-%)
Actives Useful (wt-%) Liquid Solid
Hydrocarbon surfactant 2-90 8-60 5-75
Fluorocarbon surfactant 0.1-10 0.5-5 0.5-5
Siloxane surfactant 0.1-10 0.5-5 0.5-5
TABLE II
Actives Useful (ppm) Preferred (ppm)
Hydrocarbon surfactant 2-200 20-150
Fluorocarbon surfactant 0.01-10 0.1-1.0
Siloxane surfactant 0.01-10 0.1-3.0
Liquid rinse agents of the invention are
typically dispensed by iricorporating compatible
packaging containing the liquid material into a
dispenser adapted to diluting the liquid with water to a
final use concentration wherein the active material is
present in the aqueous rinse as shown in Table II above
in parts per million parts of the aqueous rinse.
Examples of dispensers for the liquid rinse agent of the
invention are DRYMASTER-P sold by Ecolab Inc., St. Paul,
Minnesota.
Solid block products may be conveniently
dispensed by inserting a solid block material in a
cor.Ltainer or with no enclosure into a spray-type
dispenser such as the volume SOL-ET controlled ECOTEMP
Rinse Injection Cylinder system manufactured by Ecolab
Inc., St. Paul, Minnesota. Such a dispenser cooperates
CA 02232341 1998-03-13
with a warewashing machine in the rinse cycle. When
demanded by the machine, the dispenser directs a spray
of water onto the solid block of rinse agent which
effectively dissolves a portion of the block creating a
concentrated aqueous rinse solution which is then fed
directly into the rinse water forming the aqueous rinse.
The aqueous rinse is then contacted with the dishes to
affect a complete rinse. This dispenser and other
similar dispensers are capable of controlling the
effective concentration of the active block copolymer
anci the additives in the aqueous rinse by measuring the
volume of material dispensed, the actual concentration
of the material in the rinse water (an electrolyte
measured with an electrode) or by measuring the time of
the spray on the solid block.
The following examples and data further
illustrate the practice of the invention. These should
noz be taken as limiting the invention and contain the
best mode.
26
CA 02232341 1998-03-13
EXAMPLE I
The following four liquid formulations were
prepared by routine mixing of the ingredients.
Item Raw Material Formula No. (wt. %)
1 2 3 4
1 EO/PO Block Terminated with PO 19.300 19.720 19.633 19.461
(32% EO)
2 EO/PO Block Terminated with PO 52.309 54.147 53.908 53.436
(39% EO)
3 FluoradT" FC-170C 0.887 0.875
4 Silwet L_77* 1.325 1.313
C14_15 linear primary alcohol 5.000 5.067 5.044 5.000
ethoxylate
6 Inerts to 100%
5
* Siloxane of the formula described above where Z is
methyl, n is 0, m is 1 and the weight ratio in o of
EO:PO is 100:0.
These formulations were evaluated in a
modified Champion 1 KAB dishwash machine modified to
replace the front stainless panel with a glass window
and to conduct rinsing tests using the machine pump and
wash arms.
The test procedure is first to select
appropriate test substrates to evaluate the test
formulations. These substrates are typical pieces of
plasticware commonly used in institutional accounts. In
preparation for the sheeting test, the test substrates
are conditioned with 0.2% Hotpoint soil in softened
water at 160 F for three minutes in the modified Champion
1 KAB dishmachine. The test procedure is to add test
rinse aid in increments of 10 ppm actives, to the
27
CA 02232341 1998-03-13
machine pump, circulate the test solution at 160 F for 30
seconds, turn off the machine and observe the type of
water break on each test substrate. There are three
types of water break. These are:
0. No Sheeting. The test solution runs off
the test substrate leaving discrete droplets behind.
1. Pinhole Sheeting. The test solution
drains off of the test substrate to leave a continuous
film. The film contains pinholes on the surface of the
film. No droplets remain on the test substrate after
the film drains and dries.
2. Complete Sheeting. The test solution
drains off the test substrate to leave a continuous film
with no pinholes. No droplets remain on the test
substrate after the filnt drains and dries.
The type of water used in this test is
softened well water. After each evaluation of test
rinse aid per 10 ppm active increment, the results are
recorded for each test substrate. The test continues
until a good performance profile is obtained that allows
a judgment to be made regarding the relative performance
of the test formulations.
Results are given below in table form for each
of the four formulations noted above.
Tables 1-4
Table 1 contains results for a commercially
available rinse aid. Note that none of the plastic
substrates exhibit complete sheeting until 70 ppm
actives are used.
28
CA 02232341 1998-03-13
Table 2 contains results for the same set of
actives containing FluoradTM FC-170C. It performs
marginally better at 60 ppm to complete sheet on some of
the plastic substrates.
Table 3 contains results for the same set of
actives containing Silwet L-77. It also performs
marginally better at 60 ppm to complete sheet on some of
the plastic substrates.
Table 4 contains results for the invention.
This contains both Silwet L-77 and FluoradTM FC-170C.
It performs much better at 40 ppm to complete sheet on
several of the plastic substrates.
The invention represented as Formulation 4 was
also evaluated in four institutional test accounts
relative to the commercially available rinse aid
represented as Formulation 1. In each account at either
the same or even at a lower concentration, there has
been a significant improvement in drying results on
plasticware. With the commercially available product
large residual droplets of rinse water remained on the
plasticware so that the dry time was much too long,
i.e., the plasticware was stacked wet. With the
invention, the dry time was greatly reduced and the
plasticware was stacked dry.
29
CA 02232341 1998-03-13
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CA 02232341 2005-07-26
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CA 02232341 1998-03-13
These formulations were evaluated in a modified Champion
1 KAB dishwash machine as described in Example I.
Results are given below in table form for each of the
ten formulations noted above.
Tables 8-17
Table 8 contains results for a commercially available
rinse aid. Note that none of the plastic
substrates exhibit complete sheeting until 70
ppm actives are used. This is that standard
formulation that the next nine are compared
to.
Table 9 contains results for the same set of actives
containing ABIL B-9950. It performs much
better at 40 ppin to complete sheet on some of
the plastic substrates. This formulation
represents the invention.
Table 10 contains results for the same set of actives
containing ABIL--Quat 3272. It performs
marginally worse at 80 ppm to complete sheet
on some of the plastic substrates.
Table 11 contains results for the same set of actives
containing ABIL--B-8878. It performs
marginally better at 60 ppm to complete sheet
on some of the plastic substrates.
Table 12 contains resultS for the same set of actives
containing ABIL--B-8847. It performs
marginally better at 60 ppm to complete sheet
on some of the plastic substrates.
Table 13 contains results for the same set of actives
containing ABIL-B-8842. It performs at 50 ppm
to complete sheet on some of the plastic
substrates. This is a second embodiment of
the invention.
Table 14 contains results for the same set of actives
containing Tegopren-5840. It performs much
worse with no complete sheeting on any plastic
substrates up to 150 ppm.
CA 02232341 1998-03-13
Table 15 contains results for the same set of actives
containing PECOSIL SMQ-40. It performs much
worse with no complete sheeting on any plastic
substrates up to 150 ppm.
Table 16 contains results for the same set of actives
containing PECOSIL SPB-1240. It performs
radically worse with no sheeting on any
substrates up to 150 ppm.
Table 17 contains results for the same set of actives
containing PECOSIL CAP-1240. It performs
marginally worse at 90 ppm to complete sheet
on some of the plastic substrates.
The nature of the silicone additive can radically affect
results. Some additives provide much better results
when added to the basic set of rinse aid ingredients,
some do not affect results much, and some detract from
results.
The invention represented as Formulation 9 was also
evaluated in eight institutional test accounts relative
to the commercially available rinse aid represented as
Formulation 1. In each account at either the same or
even at a lower concentration, there has been a
significant improvement in drying results on
plasticware. With the commercially-available product
large residual droplets of rinse water remained on the
plasticware so that the dry time was much too long.
With the invention either there were very small residual
droplets of rinse water or the rinse water sheeted from
the plasticware. The dry time was greatly reduced and
results were judged as acceptable.
41
CA 02232341 2005-07-26
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CA 02232341 1998-03-13
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CA 02232341 1998-03-13
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CA 02232341 1998-03-13
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CA 02232341 1998-03-13
TABLE 26
A Key to the Dishware Substrates used for the Plastic Rinse
Additive Sheeting Test
Abbreviated Title Type of Dishware
PC Tile Polycarbonate Tile
PC Bowl Polycarbonate Bowl
Glass Glass Tumbler
China Plt China Plate
Mel Plt Melamine Plate
P3 Plt Polypropylene Plate
P3 Plt Polypropylene Cup
Dnx Cup Filled Polypropylene Cup
Dnx Bowl Filled Polypropylene Bowl
P3 Jug Polypropylene Jug
Poly Try Polyester Resin Tray
PS (dish) Polysulfone Dish
PS Spoon Polysulfone Spoon
SS Knife Stainless Steel Knife
61
CA 02232341 1998-03-13
EXAMPLE V
The following formulations are illustrative of
the most preferred embod_Lments of the invention.
Formulations 25-29 are to the concentrate, and refer to
the components by wt-%. Formulations 30-34 are
illustrative of the use concentrations at which the
products were tested as plasticware rinse aids.
Formulations 30-34 are recommended use concentrations
which depend on the type of machine being used and thus
do not illustrate the miriimum dose concentration. All
of these formulations were tested as previously
described and all performed satisfactorily in accordance
with the objects of the present invention.
The following glossary identifies the
materials used and referred to by trade name in the
formulations.
Glossary
DO-97 EO/PO block copolymer terminated with PO
from Ecolab Inc. (32 wt-% EO)
LDO-97 EO/PO block copolymer terminated with PO
from Ecolab Inc. (39 wt-% EO)
Neodol 45-13 Alcohol ethoxylate from Shell Chemical
Co.
Neodol 25-12 Alcohol ethoxylate from shell Chemical
Co.
SLF 18B 45 Alkyl capped alcohol ethoxylate from Olin
Corp.
Barlox 10 S n-decyldimethylamine oxide
62
CA 02232341 1998-03-13
TABLE 27
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2 D 097 9.6500 7.7500 14.4750 14.4700 11.3500
3 DL 097 26.1550 19.6600 39.2325 40.2325 30.7590
4 Neodol 45-13 2.5000 3.7500 3.5000 5.0000
Neodol 25-12 1.8300
6 SLF 18B 45 17.5000
7 Barlox 10 S 2.4000 2.1000 2.4000
8 ABIL B 9950 0.6000 0.3690 0.5250 0.6000 0.7521
9 Urea 28.0000
Inerts to 100% to 100% to 100% to 100% to 100%
TABLE 2 8
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Gal. per rack 1.2 1.2 1.2 1.2 1.2
1.5 1.2 1.5 1.5 1.5
Spec. grav 1.0375 1.033 1.049 1.049 1.000
Dose Range Mls 0.75 1.00 0.50 0.50 1.00
1.25 1.50 1.00 1.00 2.00
Sump Conc. 0.05
1 D 097 13.2257 17.6260 13.3723 13.3677 0.9996
2 DL 097 35.8465 44.7133 36.2439 37.1677 2.7089
3 Neodol 45-13 3.4264 3.4643 3.2334 0.4403
4 Neodol 25-12 4.1620
5 SLF 18B 45 1.5412
6 Barlox 10 S 3.2893 1.9400 2.2172
7 ABIL B 9950 0.822---: 0.8392 0.4850 0.5543 0.0662
8 Urea 2.4659
9 Inerts < 0.5 < 0.5 < 0.5 < 0.5 < 0.5
5 t Inerts include dyes and preservatives.
63
