Note: Descriptions are shown in the official language in which they were submitted.
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METHOD FOR SANITIZING MEDICAL EQUIPMENT USING
MICROWAVES
TECHNICAL FIELD
The invention generally relates to the field of cleaning compositions. More
specifically, the invention rel<~tes to a method for cleaning, sanitizing
and/or
otherwise removing stains, odors, particulate matter and microbes from medical
equipment surfaces by contacting the equipment with a cleaning composition and
subjecting the equipment to microwaves. The composition is a liquid, gel,
foam, or
trigger-spray detergent composition. This method provides a convenient way in
which medical equipment such that which is used in surgical operations can be
sanitized on-site, for example at the hospital, in the operating room, or at a
doctor's
office. The detergent composition comprises water, surfactant, and optionally,
a
bleaching agent such as a peroxide in a liquid or gel formulation.
BACKc3ROUND OF THE INVENTION
Historically, doctors, surgeons, nurses and other medical personnel routinely
use a variety of medical equipment to practice medicine on patients requiring
an
assortment of medical treatments. For example, surgical equipment including
forceps, scalpels, bone chisels., drills and the like are used to perform
medical
operations on patients. In such cases, the equipment must be disinfected, and
preferably sterilized, prior to use on a new patient. As used herein, the term
"sanitize" broadly encompasses both disinfecting and sterilization, whereas
disinfecting and sterilizing each refer to different levels of microbe removal
as
described in detail hereinafter. Quite often, equipment such as mirrors that
are not
particularly used to penetrate tissue, but nevertheless are contacted with
tissue and
the like when used during surgical operations or other medical procedures will
therefore require disinfecting and/or sterilization prior to use on the next
patient. Of
the numerous pieces of medical equipment used, certain equipment such as
scalpels,
sealers, burs, and forceps, must be sterilized prior to re-use so as to
prevent the
transmission of disease from patient to patient.
Currently, doctors, surgeons, and other medical personnel employ either heat,
cold or chemical vapor disinfc:ction and sterilization techniques for which
relatively
expensive equipment is required in addition to time-consuming procedures using
such equipment to disinfect mdlor sterilize the medical equipment. By way of
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2
example, private doctors offices must employ personnel on overage of two to
four
hours per day just to disinfect and/or sterilize used medical equipment, and
hospital
40 require exponentially larger ~unounts of time. Moreover, governmental
agencies in
most countries require proper disinfection and/or sterilization of medical
equipment,
and doctors' offices and hospitals are routinely inspected for compliance with
the
agency's guidelines. In the tJ.S., for example, the Organizational Safety and
Health
Agency (OSHA), Public Health Service (CDC), and the American Medical
45 Association (AMA) have relatively stringent guidelines on the
sterilization/disinfection of medical equipment prior to use.
Unfortunately, conventional relatively inexpensive detergents used for
washing tableware (i.e., glassware, china, silverware, plastic, etc.) or
kitchenware in
the home or institution are not particularly effective in obtaining
disinfection, and
50 particularly inef~'ective in obtaining sterilization of medical equipment.
The
particular requirements of cleansing tableware and leaving it in a sanitary,
essentially
stainless, residue-free state has indeed resulted in so many particular
compositions
that the body of art pertaining; thereto is now recognized as quite distinct
from other
cleansing product art. Additionally, the body of art pertaining to fabric
cleaning is
55 immense and encompasses many formulations designed for stain removal, many
including bleaches. However, medical offices and hospitals simply cannot
effectively sterilize and/or disinfect their used medical equipment with such
detergent compositions if used alone.
Accordingly, there is a need for method by which medical equipment can be
60 efficiently and effectively disinfected and/or sterilized without the use
of relatively
expensive equipment and time-consuming techniques. There is also a need for
such
a method which can be conveniently employed in small private doctors' offices
and
the like.
SUMMARY OF THE INVENTION
65 The invention providea a method by which medical equipment, such as
surgical scalpels, can be sanitized using detergent or treating composition
containing
a surfactant and a solvent such as water. The method involves placing used
medical
equipment in a non-metal container and contacting it with the treating
composition,
and subjecting both the equipment and composition to microwaves. The
70 composition foams during miicrowaving and/or immerses the equipment such
that
microwave arcing is avoided, and such that the medical equipment is sanitized,
preferably to the point of sterilization.
In accordance with one aspect of the invention, a method of sanitizing
medical equipment containing microbes is provided. The method comprises the
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75 steps of: (a) contacting the medical equipment with an effective amount of
a treating
composition containing a suriFactant and a solvent which generates heat under
microwave radiation; (b) subjecting the medical equipment and the treating
composition to microwaves fir an effective amount of time such that a
sanitizing
amount of the microbes are removed from the medical equipment.
80 In accordance with another aspect of the invention, a medical equipment
sanitizing product is providedl. The medical equipment sanitizing product
comprises
a treating composition containing a surfactant and a solvent which generates
heat
under microwave radiation. ~l'he product further includes instructions for
using of the
treating composition comprising the steps of: (a) contacting the medical
equipment
85 with the treating composition; and (b) subjecting the medical equipment and
treating
composition to microwaves for an effective amount of time such that a
sanitizing
amount of microbes are removed from the medical equipment.
All percentages and proportions herein are by weight, and all references cited
are hereby incorporated by reference, unless otherwise specifically indicated
90 Accordingly, it is an advantage of the invention to provide a method by
which medical equipment can be efficiently and effectively sanitized using an
inexpensive treating composition. This and other features and attendant
advantages
of the present invention will become apparent to those skilled in the art from
a
reading of the following detailed description of the preferred embodiment and
the
95 appended claims.
DETAILED DESCRII?'TION OF THE PREFERRED EMBODIMENT
The method of the invention essentially includes the steps of contacting
microbe-containing medical equipment with a treating composition and
subjecting
both the composition and equipment to microwaves. Preferably, the treating
100 composition contains a solvent which generates heat upon exposure to
microwaves
and is generally responsible for killing the microbes on the medical
equipment. The
treating composition preferably also contains a surfactant which aides in the
sanitization of the equipment.
By "effective amount" of a treating composition, it is meant any amount
105 capable of measurably removiing microbes, tissue and other particulate
matter from
the surface of medical equipment. In general, this amount may vary quite
widely,
but typically will include from about S ml to about 20 ml per piece of medical
equipment, but the amount must be sufficient to at least partially immerse the
equipment to be sanitized. By "sanitizing amount", it is meant an amount of
microbe
110 removal which amounts to at least about 50% removal of the microbes on the
dental
equipment, more preferably at least about 90% removal, and most preferably at
least
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about 99.9% removal of the microbes. As used herein, the term "disinfection"
means
removal of at least about 90°,% of the microbes, and the term
"sterilization" means
removal of at least about 99.!9% of the microbes. The term "microbes" means
any
115 type of germ, bacteria, virus, parasite, including but not limited to,
spore (e.g., B.
sutilis or C. sporogenes), ye~~st (e.g., C. albicans), anaerobes (e.g., P.
gingivalis),
proteins/bugs (e.g., plaque), ;gram (+) (e.g., S. mutans), gram (-) (e.g., E.
coli) and
fungi (A. meger).
The treating composition is preferably a detergent composition which
120 contains a surfactant, solvent, and optionally, also contains a bleaching
agent.
Preferably, the surfactant is present in an amount of from about 0.01 % to
about SO%,
more preferably from about '( % to about 10%, and most preferably from about
2% to
about 5% by weight. In preferred embodiments of the method invention, the
treating
composition further comprises an ingredient selected from the group consisting
of
125 clay, polycarboxylate thickeners, baking soda, carbonates, phosphates,
hydrobenzoic
acid, dicarboxylic acid, siloxanes, perfumes, bleach catalysts, and mixtures
thereof.
The treating composition carp be in a variety of forms including a liquid, gel
or
granules.
The medical equipment is preferably placed in a non-metal container into
130 which the treating composition can be dispensed. It is important for the
medical
equipment to be totally immersed in the treating composition, or at least
partially
immersed such that the composition will be able to foam and substantially
immerse
the equipment with liquid and foam such that arcing does not occur during
microwaving. A variety of containers can be used to help provide a place for
the
135 medical equipment to be placed and contacted with the treating
composition. For
example, a "boat-shaped" container having a false or grated bottom much like a
broiling pan can be used such that the treating composition is placed in the
false
bottom and the equipment on top of the grating. Upon microwaving, the treating
composition foams up from the grating so as to immerse the medical equipment
to
140 both sanitize the equipment and to prevent arcing. Other dispensing
procedures can
be used without departing from the scope of the invention so long as arcing is
prevented during microwaving and such that a sanitizing amount of microbes are
removed from the medical equipment.
The treating or deter~;ent composition and dental equipment are subjected to
145 microwaves for an effective .amount of time to sanitize the equipment to a
point that
it is suitable for re-use on other patients. Typically an "effective amount of
time" is
from about 30 seconds to about 5 minutes, preferably from about 30 seconds to
about
3 minutes, and most preferably from about 1 minute to 2 minutes. During this
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effective amount of time, the treating composition foams as described above
and
I 50 delivers the treating composition to substantially all exposed surfaces
of the
equipment. Optionally, the medical equipment can be rinsed with fresh solvent
once
it is removed from the microwave and allowed to dry. The drying time can be
enhanced by placing the sanitized medical equipment into a conventional oven.
Thereafter, the sanitized medical equipment is stored in a sanitary fashion
(e.g.
155 handling the sanitized medical equipment with rubber gloves and storing it
in
sealable plastic bags or the like) before use on the next patient.
Preferred aspects of tlhe treating composition described herein include having
the bleaching agent selected :from the group consisting of diacyl peroxide, a
source of
hydrogen peroxide and bleach activator, a source of hydrogen peroxide, a
chlorine
160 bleach, and mixtures thereof. Another highly preferred treating
composition is a gel
or liquid detergent composition comprising by weight: (a) from about 0.1 % to
about
60% of said bleaching agent which is selected from the group consisting of i)
diacyl peroxide having the general formula:
RC(O)00(O)CR1
165 wherein R and R1 can be the same or different; ii) a source of hydrogen
peroxide; iii)
a source of hydrogen peroxidle and a bleach activator; iv) a chlorine bleach;
and v)
mixtures thereof; (b) from 0°.% to about 95% of a solvent; {c) from
0.01% to about
50% of a surfactant; and (d) i~rom 0% to about 7% of a thickener. Another
highly
preferred treating composition is a gel detergent composition comprising by
weight:
170 (a) from about 0.1 % to about 10% of a diacyl peroxide having the general
formula:
RC(O)00(O)CR1
wherein R and Rl can be the same or different; (b) from 0.01 % to about 50% of
a
surfactant; and (c) from 0% to about 7% of a thickener; the composition having
a
neat pH of from about 3 to about 10; and such that said diacyl peroxide
remains
175 undissolved in said composition.
Microwaves - By mic:rowaving herein is meant exposing said surface treated
with said compositions to microwave electromagnetic radiation. This is by any
conventional means such as by placing the surface in a typical microwave such
as
used in homes and microwaving the surface for a sufficient time. Microwaves
have
180 an electromagnetic radiation wavelength of from about 1 cm to about 1 m,
preferably
from about 3cm to about 30cm, more preferably from about 1 lcm to about l3cm.
See Aust. J. Chem., 1995, 48 [10], 1665-1692, Developments in Microwave-
Assisted
Organic Chemistry, by Strauss and Trainor.
Bleaching A eats
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185 Suitable bleaching for use herein are listed below:
Diacyl Peroxide Bleaching Species - The composition of the present
invention preferably contain diacyl peroxide of the general formula:
RC(O)00(O)CR1
wherein R and R1 can be the same or different and are hydrocarbyls, preferably
no
190 more than one is a hydrocarb;yl chain of longer than ten carbon atoms,
more
preferably at least one has an aromatic nucleus.
Examples of suitable ~diacyl peroxides are selected from the group consisting
dibenzoyl peroxide, dianisoylL peroxide, benzoyl gluaryl peroxide, benzoyl
succinyl
peroxide, di-(2-methybenzoy:l) peroxide, diphthaloyl peroxide, dinaphthoyl
peroxide,
195 substituted dinaphthoyl peroxide, and mixtures thereof, more preferably
dibenzoyl
peroxide, dicumyl peroxide, ciiphthaloyl peroxides and mixtures thereof. A
particularly preferred diacyl peroxide is dibenzoyl peroxide.
Hydrogen Peroxide Source - The compositions of the present invention rnay
comprise a source of oxygen bleach, preferably a source of hydrogen peroxide
with
200 or without a selected bleach activator. The source of hydrogen peroxide is
typically
any common hydrogen-peroxide releasing salt, such as sodium perborate or
sodium
percarbonate. Hydrogen peroxide sources are illustrated in detail in Kirk
Othmer
Review on Bleaching and include the various forms of sodium perborate and
sodium
percarbonate and modified forms. An "effective amount" of a source of hydrogen
205 peroxide is any amount capable of measurably improving stain removal
(especially
of tea and tomato stains) from the soiled surface compared to a hydrogen
peroxide
source-free composition when the soiled surface is washed by the consumer.
The preferred source of hydrogen peroxide used herein can be any convenient
source, including hydrogen peroxide itself. For example, perborate, e.g.,
sodium
210 perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium
carbonate
peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxy-
hydrate, urea peroxyhydrate, .or sodium peroxide can be used herein. Sodium
perborate monohydrate and sodium percarbonate are particularly preferred.
Mixtures
of any convenient hydrogen peroxide sources can also be used.
215 Another source of hydlrogen peroxide is enzymes. Examples include
Lipoxidase, glucose oxidase, peroxidase, alcohol oxidases, and mixtures
thereof.
Bleach Activators - Numerous conventional bleach activators are known. See
for example activators referenced hereinabove in the background as well as
U.S.
Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent
4,412,934.
220 Nonanoyloxybenzenesulfonat:e (HOBS) or acyl lactam activators may be used,
and
mixtures thereof with TAED can also be used. See also U.S. 4,634,551 for other
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typical conventional bleach activators. Also known are amido-derived bleach
activators of the formulae: R»N(RS)C(O)R2C(O)L or R1C(O)N(RS)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms,
R2
225 is an alkylene containing from 1 to about 6 carbon atoms, RS is H or
alkyl, aryl, or
alkaryl containing from about 1 to about 10 carbon atoms, and L is anysuitable
leaving group. Further illustration of bleach activators of the above formulae
include
(6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)-
oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, and mixtures
230 thereof as described in U.S. P'atent 4,634,551. Another class of bleach
activators
comprises the benzoxazin-type activators disclosed by Hodge et al in U.S.
Patent
4,966,723, issued October 30, 1990. Still another class of bleach activators
includes
acyl lactam activators such as, octanoyl caprolactam, 3,5,5-trimethylhexanoyl
caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl
caprolactam,
235 octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam,
nonanoyl
valerolactam, 3,5,5-trimethyl-hexanoyl valerolactam, t-
butylbenzoylcaprolactam, t-
butylbenzoylvalerolactam and mixtures thereof. The present compositions can
optionally comprise aryl ben2:oates, such as phenyl benzoate, and acety
triethyl
citrate.
240 Quaternary Substituted Bleach Activators - The present compositions can
also comprise quaternary substituted bleach activators (QSBA). QSBA's herein
typically have the formula E-~[Z]n-C(O)-L, wherein group E is referred to as
the
"head", group Z is referred to as the "spacer" (n is 0 or 1, i.e., this group
may be
present or absent, though its presence is generally preferred) and L is
referred to as
245 the "leaving group". These compounds generally contain at least one
quaternary
substituted nitrogen moiety, vvhich can be contained in E, Z or L. More
preferably, a
single quaternary nitrogen is present and it is located in group E or group Z.
In
general, L is a leaving group, the pKa of the corresponding carbon acid (HL)
of
which can lie in the general range from about 5 to about 30, more preferably,
from
250 about 10 to about 20, depending upon the hydrophilicity of the QSBA. pKa's
of
leaving groups are further defined in U.S. Pat. No. 4,283,301.
Preferred QSBA's herein are water-soluble but have a tendency to partition to
a definite extent into surfactant micelles, especially into micelles of
nonionic
surfactants.
255 Leaving groups and solubilizing tendencies of quaternary moieties which
can
be present in the QSBA's are :further illustrated in U.S. 4,539,130, Spt. 3,
1985
incorporated by reference. 'this patent also illustrates QSBA's in which the
quaternary moiety is present in the leaving group L.
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British Pat. 1,382,594, published Feb. 5, 1975, discloses a class of QSBA's
260 found suitable for use herein. In these compounds, Z is a poly(methylene)
or
oligo(methylene) moiety, i.e., the spacer is aliphatic, and the quaternary
moiety is E.
U.S. 4,818,426 issued Apr. 4., 1989 discloses another class of QSBA's suitable
for
use herein. These compounds are quaternary ammonium carbonate esters wherein,
with reference to the above formula, the moiety Z is attached to E via a
carbon atom
265 but is attached to the carbonyl moiety through a linking oxygen atom.
These
compounds are thus quaternary ammonium carbonate esters. The homologous
compounds wherein the linking oxygen atom is absent from Z are likewise known
and are useful herein. See, for example, U.S. 5,093,022 issued March 3, 1992
and
U.S. 4,904,406, issued Feb. 2.7, 1990. Additionally, QSBA's are described in
EP
270 552,812 A1 published July 28, 1993, and in EP 540,090 A2, published May 5,
1993.
Chlorine Bleach - Amy chlorine bleach typically known in the art is suitable
for use herein. Preferred chlorine bleaches for use herein include sodium
hypochlorite, lithium hypochlorite, calcium hyposhlorite, chlorinated
trisodium
phosphates, and mixtures thereof. For more about chlorine bleaches see
Surfactant
275 Science Series, Vol. 5, Part II, pages 520-26.
Other Ingredients - Dcaersive ingredients or adjuncts optionally included in
the instant compositions can iinclude one or more materials for assisting or
enhancing
cleaning performance, treatment of the surface to be cleaned, or designed to
improve
the aesthetics or ease of manufacture of the compositions. Other adjuncts
which can
280 also be included in compositions of the invention at their conventional
art-
established levels, generally fiom 0% to about 20% of the composition,
preferably at
from about 0.1 % to about I 0°,'io, include one or more processing
aids, color speckles,
dyes, fillers, bleach-compatible enzymes, germicides, alkalinity sources,
hydrotropes,
stabilizers, perfumes, solubilizing agents, earners. In general, materials
used for the
285 production of detergent compositions herein are preferably checked for
compatibility
with the essential ingredients used herein.
Exemplary germicides suitable for use include triclosan, triclocarbon,
hydrogen peroxide and other oxygen bleaches, para-chloro-meta-xylenol,
iodine/iodophors, selected alcohols, chlorohexidine, phenols, phospholipids,
thymol,
290 eugeniol, geraniol, oil of lemon grass, and limonene. Additionally,
certain
quaternary surfactants may also show antimicrobial action and may be included
as an
adjunct germicide.
In the preferred embodiments, additional ingredients such as water-soluble
silicates (useful to provide allsalinity and assist in controlling corrosion),
dispersant
295 polymers (which modify and inhibit crystal growth of calcium and/or
magnesium
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salts), chelants (which control transition metals), builders such as citrate
(which help
control calcium and/or magncaium and may assist buffering action), and alkalis
(to
adjust pH) are present. Additional bleach-improving materials such as bleach
catalysts may be added.
300 Solvent - The solvent of the present invention is of the type in which the
diacyl peroxide will dissolve. The preferred solvents are selected based upon
the
solubility parameter value of the diacyl peroxide employed. The solubility
parameter
value of a compound is available from literature sources such as Polymer
Handbook.
Values obtained by experiments are preferred. If the solubility parameter
value is
305 not available in the literature, the value can be calculated by using any
of the
methods described by Robert F~ . Fedor's article "A Method of Estimating Both
the
Solubility Parameters & Mol<~r Volumes of Liquids", Polymer Engineering &
Science, February, 1974, Vol 14, No. 2. Once the solubility parameter value is
obtained of the diacyl peroxide, solvents are selected having a solubility
parameter
310 which fall within the diacyl peroxide solubility parameter.
Said solvent is preferably selected from the group consisting of N-alkyl
pyrrolidones, such as N-ethyl pyrrolidone, diacetone alcohol, long chain
(greater than
C6) alkyl ethers, cyclic alkyl ketones, and mixtures thereof. Amines, ethers
and
short chain (less than C6) primary and secondary alcohols are preferably not
present.
315 Without being limited by theory, it is believed that the presence of these
compounds
may introduce stability problems. Thus, when diacyl peroxide and solvent are
present in the compositions of this invention, it is further preferable that
the amount
of amine, ether, or primary or secondary alcohol be limited to no more than
about
S%, preferably no more than .about 3%, by weight of the composition.
320 Surfactants - Nonlimiting examples of surfactants useful herein include
the
conventional C 11-C 1 g alkyl benzene sulfonates ("LAS") and primary, branched-
chain and random C10-C20 alkyl sulfates ("AS"), the C 10-C 1 g secondary (2,3)
alkyl
sulfates of the formula CH3((:H2)x(CHOS03-M+) CH3 and CH3
(CH2)y(CHOS03-M+) CH2CH3 where x and (y + 1 ) are integers of at least about
7,
325 preferably at least about 9, and M is a water-solubilizing cation,
especially sodium,
unsaturated sulfates such as oleyl sulfate, the C 10-C 1 g alkyl alkoxy
sulfates
("AEXS"; especially EO 1-7 eahoxy sulfates), C 10-C 1 g alkyl alkoxy
carboxylates
(especially the EO 1-5 ethoxycarboxylates), the C 10-CI g glycerol ethers, the
C 10-
C 1 g alkyl polyglycosides and their corresponding sulfated polyglycosides,
and C 12-
330 C 1 g alpha-sulfonated fatty acid esters.
If desired, the conventional nonionic and amphoteric surfactants such as the
C 12-C 1 g alkyl ethoxylates (",AE") including the so-called narrow peaked
alkyl
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ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and
mixed
ethoxy/propoxy), C 12-C 1 g betaines and sulfobetaines ("sultaines"), and the
like, can
335 also be included in the overalll compositions. The C 10-C 1 g N-alkyl
polyhydroxy
fatty acid amides can also be used. Typical examples include the C 12-C 1 g N-
methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include
the
N-alkoxy polyhydroxy fatty acid amides, such as C 10-C 1 g N-(3-methoxypropyl)
glucamide. The N-propyl through N-hexyl C 12-C I g glucamides can be used for
low
340 sudsing. C 1 p-C2p conventional soaps may also be used. If high sudsing is
desired,
the branched-chain C 1 p-C 16 soaps may be used. Mixtures of anionic and
nonionic
surfactants are especially useful. Other conventional useful surfactants are
listed in
standard texts.
Preferably, anionic surfactants are used herein. Without being limited by
345 theory, it is believed that the use of anionic surfactants maximizes both
cleaning
performance and removal of residual bleach from the surface being treated.
One example of a group of surfactants suitable for use herein are those
selected from the group consisting of alkyl ether sulfate, long chain (greater
than
about C~) alkyl ethoxylate, linear alkyl benzene sulfonate (LAS), alkyl
(ether)
350 carboxylates, alkyl polyglucasi.de (APG), and mixtures thereof.
Thickeners - Thickeners for use herein can be selected from clay,
polycarboxylates, such as Pol,ygel~, gums, carboxymethyl cellulose,
polyacrylates,
and mixtures thereof. The preferred clay type herein has a double-layer
structure.
The clay may be naturally occurring, e.g., Bentonites, or artificially made,
e.g.,
355 Laponite~. Laponite~ is supplied by Southern Clay Products, Inc. See The
Chemistry and Physics of C.'l~rys, Grimshaw, 4th ed., 1971, pages 138-155,
Wiley-
Interscience.
Bleach catalysts - If desired, detergent compositions herein may additionally
incorporate a catalyst or accelerator to further improve bleaching or starchy
soil
360 removal. Any suitable bleach catalyst can be used. The compositions will
comprise
from about 0.0001 % to about 0.1 % by weight of bleach catalyst.
Typical bleach catalysts comprise a transition-metal complex, for example
one wherein the metal coordinating ligands are quite resistant to labilization
and
which does not deposit metal oxides or hydroxides to any appreciable extent
under
365 the conditions of cleaning herein. Such catalyst compounds often have
features of
naturally occurring compounds such as enzymes but are principally provided
synthetically. Highly preferred accelerators include, for example, the cobalt
3+
catalysts, especially {Co(NH:;)SCI}2+or equivalents thereof with various
alternate
donor ligands. Such complex:es include those formerly disclosed for use in
laundry
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370 compositions in U.S. Pat. 4,810,410 to Diakun et al, issued March 7, 1989.
The
active species thereof is believed to be {Co(NH3)5(OOH)}2+ and is disclosed in
J.
Chem. Soc. Faraday Trans., 1994, Vol. 90, 1105-1 i 14. Alternate catalysts or
accelerators are the noncobalt transition metal complexes disclosed in this
reference,
especially those based on Mo(VI), Ti(IV), W(VI), V(V) and Cr(VI) although
375 alternate oxidation states and metals may also be used. Such catalysts
include
manganese-based catalysts diisclosed in U.S. Pat. 5,246,621, U.S. 5,244,594;
U.S.
5,194,416; U.S. 5,114,606; and EP Nos. 549,271 Al, 549,272 A1, 544,440 A2, and
544,490 Al; preferred examples of these catalysts include MnIV2(p-O)3(TACN)2-
(PF6)2~ MnIII2(I~-O)1(w-OAc)2(TACN)2(C104)2~ MnIV4(N~-O)6(TACN)4(C104)4~
380 MnIIIMnIV4_(~_O)1(p,-OAc)2-(TACN)2-(C104)3, MnIV-(TACN)-(OCH3)3(PF6),
and mixtures thereof wherein. TACN is trimethyl-1,4,7-triazacyclononane or an
equivalent macrocycle; though alternate metal-coordinating ligands as well as
mononuclear complexes are also possible and monometallic as well as di- and
polymetallic complexes and complexes of alternate metals such as iron or
ruthenium
385 are all within the present scope. Other metal-based bleach catalysts
include those
disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of manganese
with various complex ligands to enhance bleaching is also reported in the
following
United States Patents: 4,728.,455; 5,284,944; 5,246,612; 5,25b,779; 5,280,117;
5,274,147; 5,153,161; and 5,227,084.
390 Transition metals may be precomplexed or complexed in-situ with suitable
donor ligands selected in function of the choice of metal, its oxidation state
and the
denticity of the ligands. Other complexes which may be included herein are
those of
U.S. Application Ser. No. 081210,186, filed March 17, 1994. Other suitable
transition metals in said transition-metal-containing bleach catalysts include
iron,
395 cobalt, ruthenium, rhodium, iridium, and copper.
Builders - Detergent builders can optionally be included in the compositions
herein to assist in controlling mineral hardness. Inorganic as well as organic
builders
can be used. Builders are typically used in fabric laundering compositions to
assist
in the removal of particulate soils.
400 The level of builder can vary widely depending upon the end use of the
composition and its desired physical form. When present, the compositions will
typically comprise at least about 1% builder. Liquid formulations typically
comprise
from about 5% to about 50%, more typically about S% to about 30%, by weight,
of
detergent builder. Lower or higher levels of builder, however, are not meant
to be
405 excluded.
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Inorganic or P-containing detergent builders include, but are not limited to,
the alkali metal, ammonium and alkanolammonium salts of polyphosphates
(exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric
meta-
phosphates), phosphonates, phytic acid, silicates, carbonates (including
bicarbonates
410 and sesquicarbonates), sulphates, and aluminosilicates.
Examples of silicate builders are the alkali metal silicates, particularly
those
having a Si02:Na20 ratio in l:he range 1.6:1 to 3.2: l and layered silicates,
such as
the layered sodium silicates described in U.S. Patent 4,664,839, issued May
12, 1987
to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate
marketed
415 by Hoechst (commonly abbreviated herein as "SKS-6"). NaSKS-6 can be
prepared
by methods such as those described in German DE-A-3,417,649 and DE-A-
3,742,043. Other layered silicates, such as those having the general formula
NaMSix02x+1'YH20 wherein M is sodium or hydrogen, x is a number from 1.9 to
4, preferably 2, and y is a number from 0 to 20 can be used herein. Various
other
420 layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-1 l, as
the
alpha, beta and gamma forms.
Examples of carbonate; builders are the alkaline earth and alkali metal
carbonates as disclosed in German Patent Application No. 2,321,001 published
on
November 15, 1973.
425 Aluminosilicate builds;rs may be useful in the present invention.
Aluminosilicate builders include those having the empirical formula:
Mz(zA102)y] ~xH20
wherein z and y are integers of at least 6, the molar ratio of z to y is in
the range from
1.0 to about 0.5, and x is an integer from about 15 to about 264.
430 Useful aluminosilicate ion exchange materials are commercially available.
A
method for producing aluminosilicate ion exchange materials is disclosed in
U.S.
Patent 3,985,669, Krummel, ea al, issued October 12, 1976. Preferred synthetic
crystalline aluminosilicate ion exchange materials useful herein are available
under
the designations Zeolite A, Ze;olite P (B), Zeolite MAP and Zeolite X. In an
435 especially preferred embodiment, the crystalline aluminosilicate ion
exchange
material has the formula:
Na~l2[(A102)12(Si02)121'xH20
wherein x is from about 20 to about 30, especially about 27. This material is
known
as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein.
Preferably,
440 the aluminosilicate has a particle size of about 0.1-10 microns in
diameter.
Organic detergent builders suitable for the purposes of the present invention
include, but are not restricted to, a wide variety of poiycarboxylate
compounds. As
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13
used herein, "polycarboxylate" refers to compounds having a plurality of
carboxylate
groups, preferably at least 3 c~arboxylates. Polycarboxylate builder can
generally be
445 added to the composition in acid form, but can also be added in the form
of a
neutralized salt. When utilized in salt form, alkali metals, such as sodium,
potassium, and lithium, or alk.anolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of
useful materials. One important category of polycarboxylate builders
encompasses
450 the ether polycarboxylates, including oxydisuccinate, as disclosed in
Berg, U.S.
Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent
3,635,830,
issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071,
issued to Bush et al, on May _'i, 1987. Suitable ether polycarboxylates also
include
cyclic compounds, particularly alicyclic compounds, such as those described in
U.S.
455 Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypolycarboxylates,
copolymers of malefic anhydride with ethylene yr vinyl methyl ether, 1, 3, 5-
trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic
acid, the
various alkali metal, ammonium and substituted ammonium salts of polyacetic
acids
460 such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as
well as
polycarboxylates such as mell.itic acid, succinic acid, oxydisuccinic acid,
polymaleic
acid, benzene 1,3,5-tricarboxylic acid, carboxyrnethyloxysuccinic acid, and
soluble
salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium
465 salt), are polycarboxylate builders of importance for liquid detergent
formulations
due to their availability from renewable resources and their biodegradability.
Oxydisuccinates are also especially useful in such compositions and
combinations.
Also suitable in the compositions of the present invention are the 3,3-
dicarboxy-4-oxa-1,6-hexaned:ioates and the related compounds disclosed in U.S.
470 Patent 4,566,984, Bush, issued January 28, 1986. Laurylsuccinates are the
preferred
builders of this group, and are: described in European Patent Application
86200690.5/0,200,263, published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226,
Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl,
issued
475 March 7, 1967. See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C 12-C 1 g monocarboxylic acids, can also be incorporated
into the compositions alone, or in combination with the aforesaid builders,
especially
citrate and/or the succinate builders, to provide additional builder activity.
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Various alkali metal plhosphates such as the well-known sodium
480 tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be
used.
Phosphonate builders such as ethane-I-hydroxy-1,1-diphosphonate and other
known
phosphonates (see, for examplle, U.S. Patents 3,159,581; 3,213,030; 3,422,021;
3,400,148 and 3,422, I 37) can also be used.
Enzymes - Suitable enzymes include proteases, amylases, lipases, cellulases,
485 peroxidases, and mixtures thereof of any suitable origin, such as
vegetable, animal,
bacterial, fungal and yeast origin. Preferred selections are influenced by
factors such
as pH-activity and/or stability optima, thermostability, and stability to
active bleach,
detergents, builders and the like. In this respect bacterial or fungal enzymes
are
preferred, such as bacterial amylases and proteases, and fungal cellulases.
490 Enzymes are normally incorporated into detergent or detergent additive
compositions at levels sufficient to provide a "cleaning-effective amount".
The term
"cleaning effective amount" refers to any amount capable of producing a
cleaning,
stain removal, soil removal, whitening, deodorizing, or freshness improving
effect on
surfaces such as dishware and the like. In practical terms for current
commercial
495 preparations, the compositions herein may comprise from 0.001 % to 5%,
preferably
0.01 %-1 % by weight of a commercial enzyme preparation. Protease enzymes are
usually present in such commercial preparations at levels sufficient to
provide from
0.005 to 0. I Arson units (AU) of activity per gram of composition.
The preparation of protease enzyme and analogous enzymes is described in
500 GB 1,243,784 to Novo. Other suitable proteases include ALCALASE~ and
SAVINASE~ from Novo and MAXATASE~ from International Bio-Synthetics,
Ire., The Netherlands; as well as Protease A as disclosed in EP 130,756 A,
January
9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP
130,756
A, January 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338
505 described in WO 9318140 A to Novo. Enzymatic detergents comprising
protease,
one or more other enzymes, arid a reversible protease inhibitor are described
in WO
9203529 A to Novo. Other preferred proteases include those of WO 9510591 A to
Procter & Gamble . When desired, a protease having decreased adsorption and
increased hydrolysis is available as described in WO 9507791 to Procter &
Gamble.
510 A recombinant trypsin-like protease for detergents suitable herein is
described in WO
9425583 to Novo.
Amylases suitable herein, especially for, but not limited to automatic
dishwashing purposes, include., for example, a-amylases described in GB
1,296,839
to Novo; RAPIDASE~, International Bio-Synthetics, Inc. and TERMAMYL~,
515 Novo. FUNGAMYL~ from Novo is especially useful. Engineering of enzymes for
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IS
improved stability, e.g., oxidative stability, is known. See, for example J.
Biological
Chem., Vol. 260, No. 11, June 1985, pp 6518-6521 Preferred amylases include
(a)
an amylase according to the hereinbefore incorporated WO 9402597, Novo, Feb.
3,
1994. Other amylases include variants having additional modification in the
520 immediate parent as described in WO 9510603 A and are available from the
assignee, Novo, as DURAM'~L~. Other particularly preferred oxidative stability
enhanced amylase include those described in WO 9418314 to Genencor
International
and WO 9402597 to Novo.
Cellulases usable herein include those disclosed in U.S. 4,435,307,
525 Barbesgoard et al, March 6, 1984. Suitable cellulases are also disclosed
in GB-A-
2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME~ (Novo) is
especially useful. See also WO 9117243 to Novo.
Suitable lipase enzymes for detergent usage include those produced by
microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC
530 19.154, as disclosed in GB 1,372,034. See also lipases in Japanese Patent
Application 53,20487, laid open Feb. 24, 1978. Other suitable commercial
lipases
include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter
viscosum var. lipolyticum NR;RLB 3673 from Toyo Jozo Co., Tagata, Japan;
Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth
535 Co., The Netherlands, and lipases ex Pseudomonas gladioli. LIPOLASE~
enzyme
derived from Humicola lanu~~inosa and commercially available from Novo, see
also
EP 341,947, is a preferred lipase for use herein. Lipase and amylase variants
stabilized against peroxidase enzymes are described in WO 9414951 A to Novo.
See
also WO 9205249 and RD 94359044.
540 Cutinase enzymes suitable for use herein are described in WO 8809367 A to
Genencor.
Peroxidase enzymes rnay be used in combination with oxygen sources, e.g.,
percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or
prevention of transfer of dyes. or pigments removed from surfaces during the
wash to
545 other surfaces present in the wash solution. Known peroxidases include
horseradish
peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-
peroxidase.
Peroxidase-containing detergent compositions are disclosed in WO 89099813 A,
October 19, 1989 to Novo and WO 8909813 A to Novo.
A range of enzyme materials and means for their incorporation into synthetic
550 detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A
to
Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January S,
1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place
et al,
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16
July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials
useful for liquid detergent formulations, and their incorporation into such
555 formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981.
Enzymes
for use in detergents can be stabilized by various techniques. Enzyme
stabilization
techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971,
Gedge
et al, EP 199,405 and EP 200.,586, October 29, 1986, Venegas. Enzyme
stabilization
systems are also described, for example, in U.S. 3,519,570. A useful Bacillus,
sp.
560 AC13 giving proteases, xylanases and cellulases, is described in WO
9401532 A to
Novo.
Enzyme Stabilizing S~ sY tem - Enzyme-containing, including but not limited
to, liquid compositions, herein may comprise from about 0.001% to about 10%,
preferably from about 0.005°io to about 8%, most preferably from about
0.01% to
565 about 6%, by weight of an enzyme stabilizing system. Such stabilizing
systems can,
for example, comprise calcium ion, boric acid, propylene glycol, short chain
carboxylic acids, boronic acids, and mixtures thereof, and are designed to
address
different stabilization problenns depending on the type and physical form of
the
detergent composition. See Severson, U.S. 4,537,706 for a review of Borate
570 stabilizers.
Stabilizing systems may further comprise from 0 to about 10%, preferably
from about 0.01 % to about 6~% by weight, of chlorine bleach scavengers, added
to
prevent chlorine bleach species present in many water supplies from attacking
and
inactivating the enzymes, especially under alkaline conditions. Suitable
chlorine
575 scavenger anions are widely lcnown and readily available, and, if used,
can be salts
containing ammonium cations with sulfite, bisulfate, thiosulfite, thiosulfate,
iodide,
etc. Antioxidants such as carbamate, ascorbate, etc., organic amines such as
ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof,
monoethanolamine (MEA), and mixtures thereof can likewise be used. Other
580 conventional scavengers such as bisulfate, nitrate, chloride, sources of
hydrogen
peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate
and
sodium percarbonate, as well as phosphate, condensed phosphate, acetate,
benzoate,
citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures
thereof can be
used if desired.
585 Material Care Ads - The present compositions may optionally contain as
corrosion inhibitors and/or anti-tarnish aids one or more material care agents
such as
silicates. Material Care Agents are preferred especially in countries where
electroplated nickel silver and sterling silver are common in domestic
flatware, or
when aluminium protection is a concern and the composition is low in silicate.
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590 Material care agents include bismuth salts, transition metal salts such as
those of
manganese, certain types of paraffin, triazoles, pyrazoles, thiols,
mercaptans,
aluminium fatty acid salts, and mixtures thereof and are preferably
incorporated at
low levels, e.g., from about 0.01 % to about 5% of the composition. A
preferred
paraffin oil is a predominantly branched aliphatic hydrocarbon comprising from
595 about 20 to about 50, more preferably from about 25 to about 45, carbon
atoms with
a ratio of cyclic to noncyclic lhydrocarbons of about 32 to 68 sold by
Wintershall,
Salzbergen, Germany as WINOG 70~. Bi(N03)3 may be added. Other corrosion
inhibitors are illustrated by bc~nzotriazole, thiols including thionaphtol and
thioanthranol, and finely divided aluminium fatty acid salts. All such
materials will
600 generally be used judiciously so as to avoid producing spots or films on
glassware or
compromising the bleaching action of the compositions. For this reason, it may
be
preferred to formulate without mercaptan anti-tarnishes which are quite
strongly
bleach-reactive or common fatty carboxylic acids which precipitate with
calcium.
Chelating Agents - 'The detergent compositions herein may also optionally
605 contain one or more iron and/or manganese chelating agents. Such chelating
agents
can be selected from the group consisting of amino carboxylates, amino
phosphonates, polyfunctionally-substituted aromatic chelating agents and
mixtures
therein, all as hereinafter defined.
Amino carboxylates useful as optional chelating agents include
610 ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,
nitrilo-
triacetates, ethylenediamine tetraproprionates, triethylenetetra-amine-
hexacetates,
diethylenetriaminepentaacetal:es, and ethanoldiglycines, alkali metal,
ammonium,
and substituted ammonium salts therein and mixtures therein.
Polyfunctionally-substituted aromatic chelating agents are also useful in the
615 compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to
Connor et
al. Preferred compounds ofthis type in acid form are dihydroxydisulfobenzenes
such as 1,2-dihydroxy-3,5-dis~ulfobenzene. A preferred biodegradable chelator
for
use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S]
isomer as
described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
620 If utilized, these chelating agents will generally comprise from about 0.1
% to
about 10% by weight of the detergent compositions herein. More preferably, if
utilized, the chelating agents will comprise from about 0.1 % to about 3.0% by
weight
of such compositions.
Polymeric Dispersing Agents - Polymeric dispersing agents can
625 advantageously be utilized at levels from about 0.1 % to about 7%, by
weight, in the
compositions herein, especially in the presence of zeolite and/or layered
silicate
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18
builders. Suitable polymeric dlispersing agents include polymeric
polycarboxylates
and polyethylene glycols, although others known in the art can also be used.
It is
believed, though it is not intended to be limited by theory, that polymeric
dispersing
630 agents enhance overall detergent builder performance, when used in
combination
with other builders (including lower molecular weight polycarboxylates) by
crystal
growth inhibition, particulate soil release peptization, and anti-
redeposition.
Product/Instructions - ~Chis invention also encompasses the inclusion of
instructions on the use of a product either on or in with the package or with
other
635 forms of advertising associated with the sale or use of the product. The
instructions
may be included in any manner typically used by consumer product manufacturing
or supply companies. Examples include providing instructions on a label
attached to
the container holding the medical equipment; on a sheet either attached to the
container or accompanying it when purchased; or in advertisements,
demonstrations,
640 and/or other written or oral instructions which may by connected to the
purchase or
use of a product containing a substrate and the treating composition.
Specifically the instructions will include a description of the use of the
treating composition and microbe-containing medical equipment in connection
with
microwaving. The instructions, for instance, may additionally include
information
645 relating to the length of microwaving time; the recommended settings on
the
microwave; the recommended positioning of the medical equipment, container and
the like, or whether soaking or rubbing is appropriate; the recommended amount
of
water, if any, to apply to the swface before and after treatment; other
recommended
treatment to accompany the microwave application.
650 Process - Methods for producing diacyl peroxide particles for use in the
compositions herein wherein an abrasive particle is desired may include any
particle
making process commonly known in the art, including shear mixing. The diacyl
particles for use herein can range in size from sub-micron (0.1 ) to about I
00 microns.
A preferred range is from about 1 to about 20 microns. Another process for
making
655 particles follows:
Process Descn~tion - 7'he diacyl peroxide raw material particles are dissolved
in an appropriate solvent (n-ethylpyrrolidone) and added to the rest of the
formulation (primarily water, surfactant and thickener) with stirnng. This
procedure
results in the in situ precipitation of the diacyl peroxide particles,
resulting in a
660 dispersion of small homogeneous particles ranging in size of from about 1
to about
20 microns. Optionally, commercially available diacyl peroxide raw material
particles can be used which have particle sizes on the order of 800 microns or
more,
although these are not preferred.
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Procedure for preparation of in situ,particles: Laponite (33g, 6% active) is
66S dispersed in tap water (100g) with stirring. Sodium Alkylethoxy sulfate
(14g, 70%
active) is stirred into the Laponite dispersion and Sodium bicarbonate (Ig,
100%
active) is added. In a separate container, Benzoyl peroxide (2g, 7S% active)
is
dissolved in N-ethylpyrrolidone (IOg, 100% active) with stirring. This benzoyl
peroxide solution is then poured into the Laponite and surfactant solution
with
670 stirring. The mixture immediately turns cloudy and results in a
homogeneous
dispersion of 10-SO micron be:nzoyl peroxide particles.
In order to make the present invention more readily understood, reference is
made to the following examples, which are intended to be illustrative only and
not
intended to be limiting in scope.
67S EXAMPLE
The following compositions are prepared for use as a treating composition.
Each of the compositions are dispensed into "boat-shaped" containers, after
which
microbe-containing medical equipment is immersed in the compositions. The
container containing the medical equipment and composition is then placed into
a
680 conventional household microwave and operated at the highest setting for
the noted
times, respectively.
Ingredient A B C
C 12-13 alkyl ether3.0 3 .0 2.0
sulfate (avg. ethoxy
of 1 )
Magnesium chloride0.3 0.3 -
hexahydrate
Magnesium silicate2.0 2.0 2.0
1
Potassium bicarbonate1.0 1.0 -
Acyl peroxides 2.0 2.0 -
Perfume 0.2 0.2 -
Hydrogen peroxide - - 3.0
Mint flavor 0.1 0.1 0.1
Other (water, dye to 100% to 100% to 100%
etc.)
Microwave Time 1 minute 30 seconds 2 minutes
Microbe removal 4-log reductionS-log reduction4-log reduction
(ASTM
method)
1 Commercially available as L,aponite RD~
2Acy1 Peroxides selected from dibenzoyl peroxide, dianisoyl peroxide, benzoyl
68S gluaryl peroxide, benzoyl succinyl peroxide, di-(2-methybenzoyl) peroxide,
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diphthaloyl peroxide, dinaphth.oyl peroxide, substituted dinaphthoyl peroxide,
and
mixtures thereof.
All the medical equiprr~ent is then rinsed with fresh solvent such as water
and
allowed to dry, either by air or in a conventional oven. The percent microbe
removal
690 is determined by standard techniques (ASTM). As can be seen in this
Example, all
of the compositions A, B and (~ unexpectedly remove a sanitizing amount of
microbes from the medical equipment in inexpensive and timely manner.
Having thus described the invention in detail, it will be clear to those
skilled
in the art that various changes may be made without departing from the scope
of the
695 invention and the invention is not to be considered limited to what is
described in the
specification.
