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Patent 2205585 Summary

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(12) Patent: (11) CA 2205585
(54) English Title: CLEANING COMPOSITIONS AND METHODS OF USING THE SAME
(54) French Title: COMPOSITIONS NETTOYANTES ET LEURS PROCEDES D'UTILISATION
Status: Term Expired - Post Grant Beyond Limit
Bibliographic Data
(51) International Patent Classification (IPC):
  • C11D 3/16 (2006.01)
  • C9D 9/04 (2006.01)
  • C11D 3/18 (2006.01)
  • C11D 3/20 (2006.01)
  • C11D 3/28 (2006.01)
  • C11D 3/43 (2006.01)
  • C11D 17/00 (2006.01)
(72) Inventors :
  • PURCELL, KAREN (United States of America)
  • HAWES, CHARLES L. (United States of America)
  • HARRY, DAVID R., JR. (United States of America)
  • LA COSSE, GERALD E. (United States of America)
(73) Owners :
  • KAY CHEMICAL COMPANY
(71) Applicants :
  • KAY CHEMICAL COMPANY (United States of America)
(74) Agent: SMART & BIGGAR LP
(74) Associate agent:
(45) Issued: 2007-01-23
(86) PCT Filing Date: 1995-11-17
(87) Open to Public Inspection: 1996-05-30
Examination requested: 2002-07-10
Availability of licence: N/A
Dedicated to the Public: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/US1995/015114
(87) International Publication Number: US1995015114
(85) National Entry: 1997-05-16

(30) Application Priority Data:
Application No. Country/Territory Date
08/342,037 (United States of America) 1994-11-17

Abstracts

English Abstract


Cleaning compositions are disclosed that economically and effectively remove a
variety of marking materials from many coated or
uncoated substrate surfaces. The compositions contain a terpene compound, a
pyrrolidone compound, an emulsifying surfactant, and water,
the compositions being in the form of a microemulsion. Also disclosed are
methods of cleaning marked surfaces with the microemulsion
compositions.


French Abstract

La présente invention concerne des compostions nettoyantes éliminant de façon économique et efficace diverses matières marquantes de surfaces de substrat enduites ou non enduites. Ces compositions contiennent un composé terpénique, un composé pyrrolidonique, un agent tensioactif émulsionnant et de l'eau, les compositions se présentant sous la forme d'une micro-émulsion. L'invention concerne également des procédés d'utilisation des compositions en micro-émulsion pour nettoyer des surfaces portant des marques.

Claims

Note: Claims are shown in the official language in which they were submitted.


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WHAT IS CLAIMED IS:
1. A cleaning composition characterized as forming
a microemulsion, the microemulsion cleaning composition
comprising:
1% to 60% by weight of a terpene compound comprising
alpha-pinene and beta-pinene;
1% to 60% by weight of a pyrrolidone compound;
1% to 35% by weight of a surfactant effective to form
a microemulsion;
9.5% to 20% by weight of a solvent extender; and
at least 20% by weight water.
2. The cleaning compositions of claim 1, wherein
the solvent extender is selected from the group consisting
of small chain alcohols, alkylene carbonates, monoglycols,
and glycol ethers, with the proviso that the solvent
extender is not ethyleneglycolmonobutylether.
3. The cleaning composition of claim 1, wherein the
solvent extender is selected from the group consisting of
small chain alcohols, alkylene carbonates, ethylene
glycol, propylene glycol, butylene glycol, hexylene
glycol, diethyleneglycolmonobutylether,
diethyleneglycolmonoethylether,
diethyleneglycolmonohexylether,
diethyleneglycolmonomethylether,
diethyleneglycolmonopropylether,
dipropyleneglycolmonobutylether,
dipropyleneglycolmonomethylether,
dipropyleneglycolmonopropylether,
ethoxypropyleneglycolmonobutylether,
ethyleneglycolmonoethylether,

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ethyleneglycolmonohexylether,
ethyleneglycolmonomethylether,
ethyleneglycolmonopropylether,
propyleneglycolmonobutylether,
propyleneglycolmonomethylether,
propyleneglycolmonopropylether, propyleneglycolmono-t-
butylether, triethyleneglycolmonoethylether,
triethyleneglycolmonomethylether,
triethyleneglycolmonopropylether, and
tripropyleneglycolmonomethylether.
4. The cleaning composition of claim 1, comprising:
5% to 40% by weight of the terpene compound;
5% to 40% by weight of the pyrrolidone compound;
5% to 20% by weight of the surfactant effective to
form a microemulsion;
9.5% to 20% by weight of the solvent extender; and
25% to 60% by weight water.
5. The cleaning composition of claim 2, comprising:
10% to 20% by weight of the terpene compound;
10% to 20% by weight of the pyrrolidone compound;
10% to 15% by weight of the surfactant effective to
form a microemulsion;
9.5% to 20% by weight of the solvent extender; and
40% to 50% by weight water.
6. The cleaning composition of claim 5, comprising
from 10% to 15% by weight of the solvent extender.
7. The cleaning composition of claim 5, wherein the
surfactant effective to form a microemulsion comprises at

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least one of a nonionic surfactant and a cationic
surfactant.
8. The cleaning composition of claim 5, wherein the
pyrrolidone compound is N-methylpyrrolidone.
9. The cleaning composition of claim 6, wherein the
solvent extender comprises at least one of propylene
glycol, hexylene glycol, and propylene glycol monomethyl
ether.
10. The cleaning composition of claim 4, wherein
said composition has a flash point of at least 105°F.
11. The cleaning composition of claim 4, wherein
said composition has a pH of 2 to 12.
12. The cleaning composition of claim 8, wherein
said composition has a pH of 5.5 to about 8.
13. The cleaning composition according to claim 9,
wherein said composition has a pH of 6 to 8.
14. A cleaning composition characterized as forming
a microemulsion, the microemulsion cleaning composition
comprising:
10% to 20% by weight of a terpene compound comprising
alpha-pinene and beta-pinene;
10% to 20% by weight of N-methylpyrrolidone;
10% to 15% by weight of a surfactant effective to
form a microemulsion, said surfactant comprising a
nonionic surfactant and a cationic surfactant;
40% to 50% by weight of water; and

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10% to 15% by weight of a solvent extender comprising
at least one of propylene glycol monomethyl ether and
hexylene glycol;
said composition having a flash point of at least
105°F and a pH of 6 to 8.
15. A method for removing markings from a surface,
the method characterized by using a microemulsion cleaning
composition, the method comprising:
applying to a marking material on a substrate surface
a microemulsion cleaning composition comprising:
1% to 60% by weight of a terpene compound
comprising alpha-pinene and beta-pinene;
1% to 60% by weight of a pyrrolidone compound;
1% to 35% by weight of a surfactant effective to
form a microemulsion;
9.5% to 20% by weight of a solvent extender; and
at least 20% by weight water;
contacting the marking material with said
microemulsion composition for a period of time sufficient
to solubilize said marking material; and
removing from said surface said composition and said
marking material with water.
16. The method of claim 15, wherein the solvent
extender is selected from the group consisting of small
chain alcohols, alkylene carbonates, monoglycols, and
glycol ethers, with the proviso that the solvent extender
is not ethyleneglycolmonobutylether.
17. The method of claim 15, wherein the solvent
extender is selected form the group consisting of small
chain alcohols, alkylene carbonates, ethylene glycol,

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propylene glycol, butylene glycol, hexylene glycol,
diethyleneglycolmonobutylether,
diethyleneglycolmonoethylether,
diethyleneglycolmonohexylether,
diethyleneglycolmonomethylether,
diethyleneglycolmonopropylether,
dipropyleneglycolmonobutylether,
dipropyleneglycolmonomethylether,
dipropyleneglycolmonopropylether,
ethoxypropyleneglycolmonobutylether,
ethyleneglycolmonoethylether,
ethyleneglycolmonohexylether,
ethyleneglycolmonomethylether,
ethyleneglycolmonopropylether,
propyleneglycolmonobutylether,
propyleneglycolmonomethylether,
propyleneglycolmonopropylether, propyleneglycolmono-t-
butylether, triethyleneglycolmonoethylether,
triethyleneglycolmonomethylether,
triethyleneglycolmonopropylether, and
tripropyleneglycolmonomethylether.
18. The method of claim 15, wherein the terpene
compound ranges from 5% to 40% by weight, the pyrrolidone
compound ranges from 5% to 40% by weight, the surfactant
ranges from 5% to 20% by weight, the solvent extender
ranges from 9.5% to 15% by weight, and the water ranges
from 25% to 60% by weight.
19. The method of claim 15, wherein the terpene
compound ranges from 10% to 20% by weight, the pyrrolidone
compound ranges from 10% to 20% by weight, and the
surfactant ranges from 10% to 15% by weight.

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20. The method of claim 19, wherein the cleaning
composition comprises from 10% to 15% by weight of a
solvent extender.
21. The method of claim 20, wherein:
the surfactant effective to form a microemulsion
comprises at least one of a nonionic surfactant and a
cationic surfactant;
the pyrrolidone compound is N-methylpyrrolidone;
the solvent extender comprises propylene glycol
monomethyl ether and hexylene glycol;
the cleaning composition has a flash point of at
least 105°F; and
the cleaning composition has a pH of 6 to 8.

Description

Note: Descriptions are shown in the official language in which they were submitted.


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CLEANING COMPOSITIONS AND METHODS OF USING THE SAME
BACKGROUND OF THE INVENTION
This invention relates generally to cleaning compositions
and methods. More particularly, this invention relates to
microemulsion cleaning compositions that effectively and
economically remove markings from surfaces and to methods of
using the microemulsion compositions. The compositions and
methods are effective to remove a wide variety of marking
materials from many substrate surfaces without damage to or
alteration of the surfaces, their coatings, or adjacent areas.
While this invention is subject to a wide range of
applications, it is especially suited for removing graffiti
and will be described particularly in that connection.
The removal of markings from various surfaces has been of
interest for a long time. The restoration of the original
appearance of inadvertently or intentionally marked surfaces
can present considerable problems. More recently, there has
been increased concern in removing undesired markings known as
graffiti, which are defacements in the form of words or
figures on walls and other surfaces of public and private
places. In part due to proliferation and availability of
aerosol paint sprays, ink marking devices, and other marking
means, it has proven difficult to avoid defacement of surfaces
by graffiti.
Removing graffiti is difficult because of the great
variety of marking materials, many of which are inherently
difficult to remove. These marking materials include paints,
inks, marking pens, ballpoint pens, lipstick, shoe polish,
nail polish, permanent markers, chalk, and crayon.
Consistent removal of markings made by these materials is
complicated by the variety of substrate surfaces on which the
markings are made. These surfaces include acrylic, aluminum,
anodized aluminum, brick, ceramics, concrete, CorianT",
enameled surfaces, formica, glass, grout, marble, MarliteT",
metals, plastic, polycarbonate (Lexan'"), plexiglass,
polyethylene, polysulfone, quarry tile, stainless steel,
stone, tile, and wood. Some surfaces are porous, and the

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markings may penetrate the pores, making removal even more
difficult. In addition, metals and other substrate surfaces
may have a coating or other finish which has been defaced by
the markings.
Graffiti has become prevalent in many public and private
institutions, buildings, and places such as restaurants,
schools, school buses, automobiles, trucks, trains, libraries,
rest rooms, and other places accessible to the public at
large. Graffiti is also problematic in open areas and on
public works, such as support walls, piers, bridges, retaining
walls, sound barriers, exterior building walls, sculptures,
and other structures found in parks, highways, and open
spaces . -
Perhaps the most common way of removing graffiti is to
repaint or recoat the surface. This approach is perhaps the
least effective and least economical. Repainting a surface is
costly and labor intensive. It requires using a paint capable
of covering and masking the graffiti without the graffiti
bleeding through the overcoat. Often several coats are
required. Moreover, this method is often undesirable because
it destroys the desired original finish of many surfaces.
Other methods for removing graffiti have included
sandblasting, hydrosanding, or hydroblasting. These methods
also are costly and because of their abrasive nature often
damage the substrate surface or its coating, making it porous
and rough. This etching or scoring of the surfaces or their
coatings creates a degree of porosity that helps hold graffiti
applied later to.the surface, as well as to areas in close
proximity to the originally marked area. Like repainting,
these methods cannot be used for surfaces where maintaining an
original finish characteristic is desired. Further,
sandblasting emits potentially carcinogenic siliceous
particles into the air. ,
Still other methods and compositions for removing
graffiti involve the use of chemical removing agents, such as
acids orcaustics. These agents also frequently damage or

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destroy the defaced surfaces. For example, chemical agents
are known to etch, fog, or melt many common surfaces. Use of
these compositions often must be for limited periods.of time
or not over an extended period of time to avoid permanent
damage to the surface being cleaned. Highly acid and caustic
compositions also present an unreasonable health and safety
risk to the persons using or otherwise exposed to these
compositions.
Still other widely used cleaning compositions include a
volatile organic chemical solvent base, particularly
halogenated solvents such as methylene chloride. The high
volatility of these solvents leads to high evaporation losses,
risks ignition of the organic vapors, and causes contamination
of the environment. These compositions also are highly
objectionable due to their extreme toxicity, particularly from
inhalation or exposure. Many chlorinated hydrocarbons,
including methylene chloride, are suspected carcinogens. The
hazardous nature of these chemicals is well-documented in the
literature, and it is clear that a safe, non-toxic alternative
is required.
Accordingly, there is a great need for cleaning
compositions that are economical, that effectively remove a
wide variety of marking materials from many surfaces with
minimal damage to the substrate surfaces or their protective
coatings,-and that minimize safety-and environmental ha~ar~~
SUMMARY OF THE INVENTION
The present invention is directed to improved cleaning
compositions and methods that effectively and economically
remove a wide variety of marking materials from a wide variety
of uncoated and coated substrate surfaces with no or
negligible effect to the substrates or their coatings. The
present compositions are easily applied to substrate surfaces,
fast actin
g, and easily rinsed or otherwise removed from the
substrate surfaces with water or an aqueous solution, thus
avoiding the often difficult labor associated with prior

CA 02205585 2006-03-28
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compositions and methods. Further, the present
compositions are relatively non-toxic and present a
reduced health risk from exposure to the skin, eyes, and
mucous membranes. The compositions of this invention also
are relatively nonvolatile, reducing the safety hazards
associated with volatile vapors.
Additional features and advantages of the invention
will be set forth in the description that follows and, in
part, will be apparent from the description or may be
learned by practice of the invention. The objectives and
other advantages of this invention will be realized and
attained by the compositions and methods particularly
pointed out in the following written description,
examples, and claims.
To achieve these and other advantages, and in
accordance with the purpose of this invention as embodied
and described herein, the invention is a microemulsion
cleaning composition that includes a terpene compound, a
pyrrolidone compound, a surfactant effective to form a
microemulsion, and water.
According to another aspect, there is provided a
cleaning composition characterized as forming a
microemulsion, the microemulsion cleaning composition
comprising: to to 60o by weight of a terpene compound
comprising alpha-pinene and beta-pinene; to to 60% by
weight of a pyrrolidone compound; 1% to 35o by weight of a
surfactant effective to form a microemulsion; 9.5o to 20%
by weight of a solvent extender; and at least 20% by
weight water.
In a further aspect, there is provided a cleaning
composition characterized as forming a microemulsion, the

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microemulsion cleaning composition comprising: 10% to 200
by weight of a terpene compound comprising alpha-pinene
and beta-pinene; 10% to 20% by weight of N-
methylpyrrolidone; loo to 15% by weight of a surfactant
effective to form a microemulsion, said surfactant
comprising a nonionic surfactant and a cationic
surfactant; 40o to 50o by weight of water; and loo to 150
by weight of a solvent extender comprising at least one of
propylene glycol monomethyl ether and hexylene glycol;
said composition having a flash point of at least 105°F
and a pH of 6 to 8.
According to another aspect, there is provided a
method for removing markings from a surface, the method
characterized by using a microemulsion cleaning
composition, the method comprising: applying to a marking
material on a substrate surface a microemulsion cleaning
composition comprising: to to 60o by weight of a terpene
compound comprising alpha-pinene and beta-pinene; 1o to
60o by weight of a pyrrolidone compound; 1% to 35% by
weight of a surfactant effective to form a microemulsion;
9.5% to 20o by weight of a solvent extender; and at least
20o by weight water; contacting the marking material with
said microemulsion composition for a period of time
sufficient to solubilize said marking material; and
removing from said surface said composition and said
marking material with water.
It is to be understood that the foregoing general
description and the following detailed description are
exemplary, explanatory, and intended to provide further
explanations of the invention as claimed.

CA 02205585 2005-08-24
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DETAILED DESCRIPTION OF THE INVENTION
The compositions of the present invention contain a
terpene compound, preferably about 1% to about 60o by
weight, more preferably about 5o to about 40o by weight,
_..,a ____~ .r____

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preferably about 10% to about 20o by weight, of a terpene or
terpene compound. As used herein, the terms terpene and
~ terpene compound refer to a class of acyclic and cyclic
unsaturated compounds derived from the isoprene molecule and
having at least 10 carbon atoms. However, terpenes that find
use in the present invention also include terpene alcohols and
aldehydes as well as unsaturated terpene hydrocarbons. Any
number of compounds, including combinations of terpenes, can
be used in the present invention.
Terpene compounds for use in the present include alpha-
pinene, beta-pinene, citronellal, citronellol, 3,7-dimethyl-
octanol, d-limonene, delta 3-carine, gamma-terpinene,
hydroxycitronellal, linalool, p-menthane, terpinerol, and
tetrahydrolinalool, among others, with cyclic terpenes being
preferred. Other preferred terpenes for use in compositions
of the present invention include Solvenol'" 226 terpene by
Hercules, Inc. and Glidsol'" 190, LimoneneT" 125, LimoneneT" 135,
and LimoneneT" 145 terpenes by Glidco Organics Corp. Solvenol'"
226 terpene by Hercules, Inc. is a terpene solvent mixture
having as its major components by weight 34% to 40o trans-p-
menthane, 12% to 15% p-cymene, 10a to 15o dipentene, 8% to l00
alpha-pinene, 6% to loo beta-pinene, 3o to 4% camphene, and 20
to 5o alpha-terpinene. Glidsol'" 190, Limonene'" 125, LimoneneT"
135, and Limonene'" 145 terpenes sold by Glidco Organics
Corporation are mixtures of various isomers of terpene (C10)
hydrocarbons, primarily isomers of p-menthadiene. In addition
the Glidsol'" 190 terpene contains aromatic terpene
hydrocarbons.
Compositions of the present invention also contain a
pyrrolidone compound, preferably about 1% to about 60% by
i
weight, more preferably about 5% to about 400, and even more
preferably about loo to about 20% by weight, of a pyrrolidone
compound. As used herein, the term pyrrolidone compound
refers to a class of cyclic compounds including and derived
from 2-pyrrolidinone, 3-pyrrolidinone, or pyrrolidine,

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unsubstituted or substituted at the ring nitrogen or one or
more of the ring carbons.
As described and claimed herein, the nitrogen of. the
pyrrolidone ring may be unsubstituted or substituted with
alkyl groups. A preferred pyrrolidone compound for this
invention is N-methylpyrrolidone, a highly polar, water-
miscible solvent that is miscible with many conventional
organic solvents. Other solvents similar to N-
methylpyrrolidone in solubility and solvent power may be used
in the present invention, and may include structural analogues
of N-methylpyrrolidone, for example N-ethylpyrrolidone and N-
propylpyrrolidone, among other solvents. However, as the
number of carbon atoms within the N-substituted moiety
increases beyond 3 (propyl), water miscibility of the
pyrrolidone decreases. In addition, such substitution may
affect the solvent power of the pyrrolidone compound used.
In addition to nitrogen substitution, the carbon atoms of
the pyrrolidone ring may also be substituted. These
substituted compounds are less preferred for use in this
invention than N-methylpyrrolidone because of cost and the
reduced polarity caused by their substitutions. For example,
N,5-dimethyl-2-pyrrolidone and 3,3-dimethyl-2-pyrrolidone may
be used in the present invention, but are less preferred than
is N-methylpyrrolidone.
The 2-keto group of N-methylpyrrolidone is not a
requirement for the pyrrolidone compound of the present
invention and certain pyrrolidone analogs, for example, N,2-
dimethylpyrrolidine, 2,4-dimethylpyrrolidine, 2,5-
dimethylpyrrolidine, and N-methyl-pyrrolidine, among others,
may be used in this invention. Pyrrolidone and pyrrolidine
compounds that may be used in the present invention may be
less polarthan N-methylpyrrolidone, necessitating adjustment
to the amount and type of surfactant and/or terpene compound
used.
The compositions of the present invention also include a
surfactant effective to form a microemulsion, preferably about

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-
1% to about 35% by weight, more preferably about 5% to about
20% by weight, and even more preferably about 10% to about 15%
~ by weight, of a surfactant effective to form a microemulsion,
selected from nonionic, cationic, anionic, or amphoteric
surfactants. As used herein, the phrase "surfactant effective
to form a microemulsion" refers to at least one such nonionic,
cationic, anionic, or amphoteric surfactant.
Examples of nonionic surfactants that can be employed are
alkoxylated alkyl phenols, amides, amines, ethoxylated or
propoxylated higher aliphatic alcohols, and sulphonamides.
These well known surfactants include sorbitan esters of C10 to
C22 fatty acids, polyoxyethylene sorbitan esters of C10 to C22
fatty acids, polyoxyethylene sorbitol esters of C10 to C22
fatty acids, polyoxyethylene derivatives of C6 to C20 fatty
phenols, and polyoxyethylene condensates of C10 to C22 fatty
acids or fatty alcohols. Polyoxyethylene and polyoxypropylene
analogs of the above surfactants also can be used in the
present invention. Preferred nonionic surfactants for use in
this invention are Shell NeodolT" 91-6 and Shell Neodol'" 91-2.5
surfactants. Neodol'" 91-6 surfactant is a polyethylene glycol
ether of a mixture of synthetic C9-11 fatty alcohols with an
average of 6 moles of ethylene oxide. Neodol'" 91-2.5
surfactant is a polyethylene glycol ether of a mixture of
synthetic C9-11 fatty alcohols with an average of 3 moles of
ethylene oxide.
Other suitable nonionic surfactants include sorbitol
monolaurate propylene oxide condensates, sorbitol
monomyristate propylene oxide condensates, sorbitol
monostearate propylene oxide condensates, dodecyl phenol
propylene oxide condensates, myristyl phenol propylene oxide
condensates, octylphenyl propylene oxide condensates,
nonlyphenyl propylene oxide condensates, stearyl phenol
propylene oxide condensates, lauryl alcohol propylene oxide
condensates stearyl alcohol propylene oxide condensates,
secondary alcohol propylene oxide condensates such as C14-C15
secondary alcohols condensed with propylene oxide, sorbitan

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tristearate condensed with propylene oxide, sorbitan trioleate
condensed with propylene oxide, and sorbitan trioleate.
Cationic surfactants useful in this invention include,
e.g., the quaternary ammonium surfactants such as C10 to C22
fatty ammonium compounds having 10 to 22 carbon atoms, C10 to , '
C22 fatty morpholine oxides, propylene oxide condensates of
C10 to C22 fatty acid monoesters of glycerins, the mono- or
diethanol amides of C10 to C22 fatty acids, and alkoxylated
siloxane surfactants containing. propylene oxide units and/or
propylene oxide units. As is known in the surfactant art, the
counter ion for quaternary ammonium surfactants is usually a
halide, sulfate, or methylsulfate, the chlorides being the
most common industrially available compounds.
Other suitable cationic surfactants suitable for use in
the present invention include straight chain alkyl fatty
amines, quaternary ammonium salts, alkyl-substituted
quaternary ammonium salts, alkylaryl-substituted quaternary
ammonium salts, quaternary imidazolinium salts, amine oxides,
fatty amine oxides, tri-fatty amine oxides, tri-quaternary
phosphate esters, amphoglycinate phosphates, amine acetates,
long chain amines and their salts, diamines and their salts,
polyamines and their salts, polyoxyethylenated long chain
amines, and quaternized polyoxyethylenated long chain amines.
Specific cationic surfactants useful in the present
invention include decyl dimethyl amino oxide, coco amido
dimethyl amine oxide, trimethyl dodceyl ammonium chloride, and
trimethyl stearyl ammonium methylsulfate. Particularly
preferred cationic surfactants include the surfactant sold
under the trademark Q-17-2T" and the AO-3,8T" surfactant by the
Exxon Chemical Company, VarisoftT" 222 and ArosurfT" TA-100
surfactants by the Witco Chemical Company, and Ninox L=" ,
surfactant by the Stepan Chemical Company. Q-17-2'" surfactant
by the Exxon Chemical Company is a 75% by weight aqueous
solution of isotridecyloxypropyl dihydroxyethyl methyl
ammonium chloride. The Exxon AO-3,8T" surfactant is a
proprietary tertiary eight-carbon amine oxide. The Varisoft'"

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PCT/US95/15114
222 surfactant is a diamidoamine-based quaternary with a
formula of methyl bis (tallow amidoethyl) 2-hydroxyethyl
~ ammonium methyl sulfate. The Arosurf'" TA-100 surfactant is a
dialkyl dimethyl quaternary with the chemical composition of
distearyl dimethyl ammonium chloride. The Ninox-L'" surfactant
is a lauryl dimethylamine oxide.
Anionic surfactants useful in this invention generally
include alkali metal, ammonium and magnesium salts of alpha
olefin sulfonates, alkyl sulfonates, alkyl aryl sulfonates,
alkyl aryl ether sulfates, alkyl ether sulfates, sulfated
alcohol ethoxylates, taurates, petroleum sulfonates, alkyl
napthalene sulfonates, alkyl sarcosinates and the alkyl
sulfosuccinates.
Specific anionic surfactants useful in this invention
include sodium lauryl sulfonate, ammonium lauryl sulfonate,
dodecyl benzene sulfonate, sodium lauryl ether sulfate,
diethanolamine lauryl sulfate, ammonium salts of sulfated
alcohol ethoxylates, sodium cocoyl isethionate, sodium
N-methyl-N-oleoyl taurate, sodium N-methyl-N-cocyl taurate,
triethanolamine lauryl sulfate, disodium monooleamide PEG-2
sulfosuccinate, petroleum sulfonates sodium salt, alkyl
napthalene sodium sulfonates, sodium lauroyl sarcosinate, and
sodium alkyl sulfosuccinate. Other useful anionic surfactants
include sodium or potassium dodecyl sulfate, sodium trioleate,
sodium or potassium stearyl sulfate, sodium or potassium
dodecyl benzene sulfonate, sodium or potassium stearyl
sulfonate, triethanol amine salt of dodecyl sulfate, sodium
laurate, sodium or potassium myristate, and sodium or
potassium stearate.
Amphoteric surfactants useful in this invention generally
include betaines, sultaines, imidazoline derivatives and the
like. Specific amphoteric surfactants useful in this
invention include ricinoleamidopropyl betaine, cocamidopropyl
betaine, stearyl betaine, stearyl amphocarboxy glycinate,
sodium lauraminopro-pinnate, cocoamidopropyl hydroxy sultaine,
disodium lauryliminodipropionate, tallowiminodipropionate,

CA 02205585 1997-OS-16
R'O 96!16132 PCT/US95115114
- 10 -
cocoampho-carboxy glycinate, cocoimidazoline carboxylate,
lauric imidazoline mono-carboxylate, lauric imidazoline
dicarboxylate, lauric myristic betain, cocoamidosulfobetaine,
alkylamidophospho betain and the like. Other useful
amphoteric surfactants include decyl amino betaine; coco amido ''
sulfobetaine, oleyl amido betaine, coco imidazoline, coco
sulfoimidazoline, cetyl imidazoline, 1-hydroxyethyl-2-
heptadecenyl imidazoline, 1-hydroxyethyl-2 mixed heptadecenyl
heptadecadienyl imidazoline, and n-coco morpholine oxide.
Preferred amphoteric surfactants include Miranol'" FBS
surfactant by Rhone-Poulenc and MackaleneT" 316 surfactant by
the McIntyre Chemical Company. The Miranol"' FBS surfactant is
a 39% by weight aqueous solution of disodium cocoampho
dipropionate. The Mackalene'" 316 surfactant is a
stearamidopropyl dimethylamine lactate.
The foregoing compounds have been described with
particular reference to fatty derivatives. It is the fatty
moiety that usually forms the lipophilic moiety. A common
fatty group is an alkyl group of-natural or synthetic origin.
In most instances, the alkyl group may be replaced by the
corresponding ethylenically saturated group having one or more
ethylene linkages such as commonly occur in nature. Common
unsaturated groups are oleyl, linoleyl, decenyl, hexadecenyl,
dodecenyl, etc. In appropriate cases, as known in the art,
the alkyl group may be cyclic, i.e., cycloalkyls, or may be
straight or branched chain.
Any combination of nonionic, cationic, anionic, or
amphoteric surfactants can be used in the present invention.
It may be preferable in certain embodiments of the present
invention to include a mixture of surfactants. In all
embodiments, the surfactant selected is effective to form a
microemulsion in the final composition.
The compositions of this invention further include water,
preferably at least about 20%, more preferably about 25% to
about 60% by weight, and even more preferably about 40% to
about 50°s by weight, of water. Water is critical to the

CA 02205585 1997-OS-16
WO 96/16132 PCT/US95/15114
- 11 -
formation of the microemulsion compositions of this invention.
Further, water increases the solubility of the present
compositions and thus enhances their removal after application
to a marked substrate. It is to be understood by one of
ordinary skill in the art that the other components,
particularly the emulsifying surfactant, may require
adjustment to accommodate a given water concentration and to
result in formation of a microemulsion composition.
Compositions of the present invention may also include a
solvent extender or a combination of solvent extenders,
preferably about 5% to about 20a by weight, and more
preferably about 10% to 15o by weight, of a solvent extender
or combination of solvent extenders. The solvent extender in
the present invention functions either or both to enhance
solubility characteristics or to raise the flash point of the
compositions. In addition, the solvent extenders used in the
present invention may be useful for forming the microemulsions
of the present invention.
The microemulsion cleaning compositions of the present
invention have a flash point of at least about 105°F by virtue
of the amount and type of solvent extender added to the
compositions. Preferred solvent extenders for use in the
present invention have a flash point of at least about 150°F.
Typical solvent extenders for use in the present invention
include small chain alcohols, e.g.ethanol and isopropanol,
alkylene carbonates, e.g. ethylene carbonate, propylene
carbonate and butylene carbonate, and glycols and glycol
ethers.
Glycols useful as solvent extenders in the compositions
of the present invention include ethylene glycol, propylene
glycol and butylene glycol, among others. Useful glycol
ethers include diethyleneglycolmonobutylether,
diethyleneglycolmonoethylether, diethyleneglycolmono-
hexylether, diethyleneglycolmonomethylether, diethylene-
glycolmonopropylether, dipropyleneglycolmonobutylether,
dipropyleneglycolmonomethylether, dipropyleneglycolmono-

CA 02205585 1997-OS-16
WO 96!16132 PCT/US95/15114
- 12 -
propylether, ethoxylpropyleneglycolmonobutylether,
ethyleneglycolmonoethylether, ethyleneglycolmonohexylether,
ethyleneglycolmonomethylether, ethyleneglycolmonobutylether,
ethyleneglycolmonopropylether, propyleneglycolmonobutylether,
propyleneglycolmonomethylether, propyleneglycolmono-
propylether, propyleneglycolmono-t-butylether, triethylenegly-
colmonoethylether, triethyleneglycolmonomethylether,
triethyleneglycolmono-propylether, and tripropyleneglycol-
monomethylether, among others. Preferred solvent extenders
are propylene glycol, hexylene glycol, and propylene glycol
monomethyl ether because of their favorable flash points as
well as their general safety and lack of toxicity.
The pH of the cleaning compositions of the present
invention can vary from highly acidic to highly alkaline
within the range of about 2.0 to about 12Ø Preferred
embodiments of the cleaning compositions of the present
invention have a pH within the range of about 5.5 to about
8.0, preferably within the range of about 6.0 to about 8Ø
Adjustment of pH in the present compositions to desired levels
can be accomplished by methods well known to the art, such as,
for example, by addition of alkali earth carbonates or
hydroxides, or by addition of inorganic or organic acids.
The preparation of the microemulsion compositions of the
invention is not critical, and the compositions of the
invention are prepared easily by any one of numerous methods
known to those skilled in the art. All that is required is a
suitable vessel to hold the components and a simple mixing
means effective to bring the combined ingredients into a
microemulsion form-: A suitable apparatus for preparing the
compositions of this invention would be a stainless steel tank
furnished with a conventional, paddle-type mixer. Generally,
the ingredients can be added to the vessel in any order.
Mixing should continue until the product becomes a stable, ,
clear microemulsion. The microemulsion compositions of the
invention give rise to no separation, coalescence,
crystallization, or sedimentation on storage.

CA 02205585 1997-OS-16
WO 96!16132 PCT/US95/15114
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To remove unwanted markings on smooth, non-porous
surfaces, the present compositions are sprayed, brushed, or
wiped onto the affected area. A preferred method of.
application is a light spray. After application, the cleaning
composition is allowed to stand at least several seconds to
permit solubilization of the marking material. The
composition and marking material then are wiped or rinsed off
with a dry or damp paper towel, cloth, or sponge, or by a
stream or spray of water or other aqueous solution. As used
in describing and claiming the step of removing the
compositions and marking material according to the methods
herein, the term water refers to both water and aqueous
solutions. To remove unwanted markings from porous surfaces,
the present compositions are applied in the manners described
above, again, preferably by a light spray. The compositions
then preferably are brushed into the surface and allowed to
stand for several seconds, followed by rinsing with a stream
or spray of water or other aqueous solution.
EXAMPLES
GRAFFITI REMOVER FORMULAS
In the following Examples 1-17, the compositions were
prepared by adding the ingredients in the order listed to a
glass beaker equipped with a magnetic stirring bar. After
each ingredient was added, the beaker contents were mixed
thoroughly to form a uniform composition. In each example a
microemulsion was obtained that was clear, fluid, and stable
when tested under a temperature cycle of 25°F to 120°F.

CA 02205585 1997-OS-16
WO 96/16132 PCT/US95/15114
- 14 -
EXAMPLE 1
Ingredients Concentration w/wo
N-methylpyrrolidone - - .14.3
Solvenol 226 14.3
Propylene Glycol MonomethylEther 7.2 '
Hexylene Glycol 5.1
Q-17-2'" 1.6
Neodol'" 91-2.5 6.2
Neodol'" 91-6 - 6.2
H20 45.1
EXAMPLE 2
N-methylpyrrolidone 20.0
Solvenol 226 20.0
Propylene Glycol Monomethyl Ether 9.5
Neodol~" 91-6 0.5
Triethanolamine - 5.0
Oleic Acid 10.0
H20 - 35.0
EXAMPLE 3
N-methylpyrrolidone 19.0
Solvenol 226 19.0
Propylene Glycol Monomethyl Ether 9.5
Q-17-2'" 2.8
Neodol'" 91-2.5 8.1
NeodolT" 91-6 8.1
H20 33.5

CA 02205585 1997-OS-16
WO 96116132 PCT/US95/15114
- 15 -
EXAMPLES NO. 4 NO. 5 NO. 6 NO. 7
N-methylpyrrolidone 14.8 13 13
9 3
. . 13.4
Solvenol 226 14.8 13.9 13.3 . 13.4
Propylene Glycol 7.4 7 6
0 7
. . 6.8
Monomethyl Ether
Hexylene Glycol 5.3 4 4
9 7
. . 4.8
Q-17-2"' 0.5 0.5 1.5 ___
Neodol'" 91-2 . 5 5 . 3 4 4
1 6
. . 9 - 6
NeodolT" 91-6 5 . 3 12 . 1 13 . 9 9 , 6
H2~ 46.6 43.6 42.0 42.4
EXAMPLES NO. 8 NO. 9 NO. 10 NO. 11
N-methylpyrrolidone 13.7 14.0 11.5 12.5
Solvenol 226 13.7 14.0 11.5 12.5
Propylene Glycol 6.9 7.0 5.8 6.3
Monomethyl Ether
Hexylene Glycol . 4.9 5.0 4.1 4.4
Q-17-2T" ___
2.9 ___ ___
NeodolT" 91-2.5 4.5 6.5 23.1 --_
Neodol~' 91-6 13.3 6.5 7.7 25.0
H2~ 43.0 44.1 36.3 39.3

CA 02205585 1997-OS-16
WO 96/16132 PCT/US95/15114
- 16 -
EXAMPLE 12
N-methylpyrrolidone 14.1
Solvenol 226 . 14.1
Propylene Glycol Monomethyl Ether 7.1 '"
Hexylene Glycol 5.0
Arosurf'" TA-100 1.6
Neod01"' 91-2.5 ~ 6.7
Neodol'" 91-6 6.7
H20 44.7
EXAMPLE 13
N-methylpyrrolidone 14.3
Solvenol 226 14.3
Propylene Glycol Monomethyl Ether 7.2
Hexylene Glycol 5.1
Varisoft'" 222 1.6
Neodoll" 91-2.5 3.7
NeodolT" 91-6 3.7
H20 50.1

CA 02205585 1997-OS-16
WO 96!16132
- 17 -
PCT/US95/15114
EXAMPLE 14
N-methylpyrrolidone 14.3
Solvenol 226 ~ 14.3
" Propylene Glycol Monomethyl Ether 7.2
Hexylene Glycol 5.1
Mackalene~" 316 1.6
Neodol'" 91-2.5 4.6
Neodol'" 91-6 4.6
H2~ 48.3
EXAMPLE 15
N-methylpyrrolidone 14.3
Solvenol 226 14.3
Propylene Glycol Monomethyl Ether 7.2
Hexylene Glycol 5.1
Arosurf'" TA 100 0.5
NeodolT" 91-2.5 5.0
NeodolT" 91-6 5.0
H2~ 48.6

CA 02205585 1997-OS-16
WO 96/16132 PCT/US95/15114
- 18 -
EXAMPLE 16
N-methylpyrrolidone 14.3 ,,
Solvenol 226 14.3
Propylene Glycol Monomethyl Ether 7.2
Hexylene Glycol 5.1
N7.nOXT" L 1.6
Neodol'" 91-2.5 2.5
Neodol'" 91-6 2.5
H20 52.5
EXAMPLE 17
N-methylpyrrolidone 14.3
Solvenol 226 14.3
Propylene Glycol Monomethyl Ether 7.2
Hexylene Glycol 5.1
Miranol'" FBS 1.6
NeodolT" 91-2.5 2.8
NeodolT" 91-6 2.8
H20 51.9
EXAMPLE 18
GRAFFITI REMOVER TEST - PERFORMANCE AND EFFECT ON SURFACE
This table summarizes the performance and effect on
substrate surface of the composition of Example 1 tested on a
variety of marking materials and substrates. The composition
was used in accordance with the methods described above in the
specification for use of the present compositions to remove
markings from porous and non-porous surfaces.

CA 02205585 1997-OS-16
WO 96!16132
- 19 -
PCT/US95/15114
TABLE
Surface Graffiti Effect on
Description Type Performance Surface
Painted dumpste r Red spray paint Complete removal
Abrasion
Concrete wall White spray paint
Only shadow left
Dis-
colored
Brick wall White spray paint Only shadow left
Dis-
colored
Painted cement Gray spray paint Complete removal None
Wallpaper Blue pen Complete removal None
Grout lines Ballpoint pen Complete removal None
Ceramic tiles White marker Complete removal None
Quarry tile Glue Complete removal None
Ceramic tile Color markers Complete removal None
Marble store Black marker Complete removal None
front
Table tops Various markers Complete removal None
Painted gate Black spray paint Only shadow left None
Brick Spray paint Only shadow left None
Polished granite Various markers Complete removal None
White sink Black marker Complete removal None
White wall Marker Complete removal None
Ceramic tile Black marker Complete removal None
Table Blue pen Complete removal None
Grout lines Black marker Complete removal None
- Air freshener Marker Complete removal None
Painted door .= Grey spray paint Complete removal None
-
Glass Gold spray paint Complete removal None
Mirror Black marker Complete removal None

CA 02205585 1997-OS-16
WO 96/16132 PCT/US95/15114
- 20 -
Surface Graffiti Effect on
Description Type Performance Surface
Plastic seating Silver marker Complete removal None
Aluminum window Silver marker Complete removal None
frame -
Porcelain sink Blue marker Complete removal None
Pay phone Assortment Complete removal None
Polished marble Black spray paint No removal None
Brick wall Dark spray paint Only shadow None
left
Rest room wall Black marker Only shadow None
left
Glass door Black spray paint Complete removal None
Ceramic tiles Blue marker Complete removal None
Mirrors Black marker Complete removal None
Seating Black marker Complete removal None
Ceramic tile wallWhite marker Complete removal None
Stainless door Black marker Complete removal None
frame -
Plastic air Gold marker Complete removal None
freshener -
Brown painted Black marker Complete removal None -
surface
Chain link fence Silver spray paint Complete removal None
Bathroom doors Gold spray paint Complete removal None
Painted door Black spray paint Complete removal None
Seating - Ballpoint pen Complete removal None
Brick wall Black marker Complete removal None ..
Brick wall Black marker Only shadow None
left
Rest room wall White marker Complete removal None
Quarry tile Silver marker Complete removal None
baseboard
Brick wall - Various paints Complete removal None

CA 02205585 1997-OS-16
WO 96!16132 PCT/US95/15114
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Surface Graffiti Effect
on
Description Ty~ Performance Surface
Wallpaper Black marker Only shadow left None
.,
Entryway frame Marker Complete removal None
Baby changer Black/green marker Only shadow left None
table
Trash can, Spray paint Complete removal None
Brick wall Black spray paint Only shadow left None
Block wall Black spray paint No removal None
Dumpster =Gold spray paint Complete removal N
one
Natural wood Red spray paint Slight removal None
Pay phone booth Black marker Complete removal None
Garbage pail Red spray paint Complete removal None
Painted door Black marker Complete removal Removed
paint
Painted metal Brown spray paint Only shadow left R
d
door emove
paint
Wallpaper Black marker Complete removal Slight
abrasion
Painted door Black marker Complete removal Softened
paint
It will be apparent to those skilled in the art that
various modifications and variations can be made in the
composition and method of the present invention without
departing from the spirit or scope of the invention. Thus, it
is intended that the present invention cover the modifications
and variations of this invention provided they come within the
scope of the appended claims and their equivalents.

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Administrative Status

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Event History

Description Date
Inactive: Expired (new Act pat) 2015-11-17
Grant by Issuance 2007-01-23
Inactive: Cover page published 2007-01-22
Pre-grant 2006-11-10
Inactive: Final fee received 2006-11-10
Notice of Allowance is Issued 2006-09-01
Letter Sent 2006-09-01
4 2006-09-01
Notice of Allowance is Issued 2006-09-01
Inactive: Approved for allowance (AFA) 2006-05-02
Amendment Received - Voluntary Amendment 2006-03-28
Inactive: IPC from MCD 2006-03-12
Inactive: IPC from MCD 2006-03-12
Inactive: IPC from MCD 2006-03-12
Amendment Received - Voluntary Amendment 2005-08-24
Inactive: S.29 Rules - Examiner requisition 2005-03-09
Inactive: S.30(2) Rules - Examiner requisition 2005-03-09
Letter Sent 2002-08-21
Request for Examination Requirements Determined Compliant 2002-07-10
Request for Examination Received 2002-07-10
All Requirements for Examination Determined Compliant 2002-07-10
Inactive: Office letter 2001-12-19
Inactive: Delete abandonment 2001-12-19
Deemed Abandoned - Failure to Respond to Maintenance Fee Notice 2001-11-19
Letter Sent 1998-02-27
Letter Sent 1998-02-27
Inactive: Single transfer 1997-09-25
Inactive: IPC assigned 1997-08-05
Inactive: First IPC assigned 1997-08-05
Classification Modified 1997-08-05
Classification Modified 1997-08-05
Inactive: IPC assigned 1997-08-05
Inactive: IPC assigned 1997-08-05
Inactive: IPC assigned 1997-08-05
Inactive: Courtesy letter - Evidence 1997-07-22
Inactive: Notice - National entry - No RFE 1997-07-22
Application Received - PCT 1997-07-15
Application Published (Open to Public Inspection) 1996-05-30

Abandonment History

Abandonment Date Reason Reinstatement Date
2001-11-19

Maintenance Fee

The last payment was received on 2006-09-21

Note : If the full payment has not been received on or before the date indicated, a further fee may be required which may be one of the following

  • the reinstatement fee;
  • the late payment fee; or
  • additional fee to reverse deemed expiry.

Patent fees are adjusted on the 1st of January every year. The amounts above are the current amounts if received by December 31 of the current year.
Please refer to the CIPO Patent Fees web page to see all current fee amounts.

Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
KAY CHEMICAL COMPANY
Past Owners on Record
CHARLES L. HAWES
DAVID R., JR. HARRY
GERALD E. LA COSSE
KAREN PURCELL
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Abstract 1997-05-15 1 46
Description 1997-05-15 21 900
Claims 1997-05-15 4 150
Cover Page 1997-09-09 1 34
Claims 2005-08-23 6 171
Description 2005-08-23 23 931
Description 2006-03-27 23 931
Claims 2006-03-27 6 171
Cover Page 2006-12-18 1 32
Reminder of maintenance fee due 1997-07-19 1 111
Notice of National Entry 1997-07-21 1 193
Courtesy - Certificate of registration (related document(s)) 1998-02-26 1 118
Courtesy - Certificate of registration (related document(s)) 1998-02-26 1 118
Reminder - Request for Examination 2002-07-17 1 128
Acknowledgement of Request for Examination 2002-08-20 1 177
Commissioner's Notice - Application Found Allowable 2006-08-31 1 162
PCT 1997-05-15 8 259
Correspondence 1997-07-21 1 30
Correspondence 2006-11-09 1 37