USOO6465411B2

(12) United States Patent (10) Patent No.: US 6,465,411 B2

Manske et al. (45) Date of Patent: Oct. 15, 2002

(54) PINE OIL CLEANING COMPOSITION Primary Examiner-Gregory E. Webb

(74) Attorney, Agent, or Firm-Scott E. Hanf, Krishna
(75) Inventors: Scott D. Manske, Davidson; Martha Banerjee
Shea McPherson, Weddington, both of
NC (US) (57) ABSTRACT
(73) Assignee: Clariant International Ltd., Muttenz Disclosed is a liquid pine oil cleaning composition contain
(CH)
ing: A) water; B) about 5-20% by weight of pine oil; C)
(*) Notice: Subject to any disclaimer, the term of this about 2-10% by weight of an organic solubilizer distinct
patent is extended or adjusted under 35 from said pine oil; D) about 0.1-5% by weight of an
U.S.C. 154(b) by 89 days. alkalinity agent; E) about 0.1-15% by weight of an anionic
(21) Appl. No.: 09/742,821 surfactant; F) about 0.01 to about 2% by weight by weight
(22) Filed: Dec. 21, 2000 of a cationic Surfactant comprising a quaternary ammonium
(65) Prior Publication Data
Salt represented by the formula
US 2002/0123451A1 Sep. 5, 2002
(51) Int. Cl." .............................. C11D 1/86; C11D 3/44 R10-N-R12 X
(52) U.S. Cl. ....................... 510/417; 510/238; 510/357; R11
510/365; 510/405; 510/433; 510/435; 510/504;
510/505; 510/506
(58) Field of Search ................................. 510/238, 365, wherein R and R' are independently a hydrogen or a C
510/357, 405, 435, 433, 504,505, 506, alkyl group; R'' is a CsCls alkyl group; and R' is a C
417
alkyl group or an ethoxylate group represented by the
(56) References Cited formula -(CH2CH2O), H, wherein y is a number from 1 to
U.S. PATENT DOCUMENTS 3; and X is a halide ion or a methosulfate, and G) about 0.1
4.414,128 A 11/1983 Goffinet to 10% by weight of a nonionic Surfactant comprising an
4,597.887. A * 7/1986 Colodney et al. alcohol alkoxylate. Also disclosed is a method for cleaning
5,591,708 A 1/1997 Richter a hard Surface comprising contacting the hard Surface in
5,728,672 A 3/1998 Richter need of cleaning with the aforementioned pine oil cleaning
5,962,394 A 10/1999 Gry et al. composition.
5,985,819 A 11/1999 Lu et al.
6,066,606 A 5/2000 Lu et al.
* cited by examiner 17 Claims, No Drawings
 US 6,465,411 B2
1 2
PINE OL CLEANING COMPOSITION Solvent being Selected from the group consisting of benzyl
FIELD OF THE INVENTION
alcohol, polyethoxylated phenols containing from 2 to 6
ethoxy groups, phenylethyl alcohol, mono C-C alkyl
The present invention provides a blooming pine oil clean ethers of ethylene glycol, di-C-Co alkyl ethers of ethylene
ing composition. The present invention also provides a glycol, and mixtures thereof.
method of cleaning a Surface using the disclosed pine oil U.S. Pat. Nos. 5,591,708 and 5,728,672 disclose a liquid
cleaning composition. pine oil hard Surface cleaning composition comprising a
BACKGROUND OF THE INVENTION germicidally effective amount of a quaternary ammonium
Water-Soluble cleaning compositions are commercially
compound according to the formula N' R, R-R-R))X
important products and enjoy a wide field of utility in wherein at least one of R, R2, R and R is Selected from
hydrophobic, aliphatic, aryl aliphatic or aliphatic aryl radical
assisting in the removal of dirt and grime from Surfaces, of from 6 to 26 carbon atoms, and any remaining are
especially those characterized as useful with “hard Sur hydrocarbons of from 1 to 12 carbon atoms, wherein any of
faces'. One particular category of aqueous cleaning com 15
R, R2, R and R may be linear or branched and may
positions are those which provide a “blooming effect upon include one or more ester or amide linkages, and, X is a
being added to water. Such an effect may be described as the Salt-forming anionic radical.
change of the water's appearance from eSSentially colorleSS
and transparent to that of a milky white or milky yellowish SUMMARY OF THE INVENTION
white, cloudy appearance upon the addition of an amount of The present invention provides a liquid pine oil cleaning
the cleaning composition. This effect is also Sometimes composition comprising:
referred to as the “break”. Such blooming is highly desirable A) water;
in Such pine oil type water-Soluble cleaning compositions as B) about 5-20% by weight of pine oil;
consumer/end user associates cleaning effectiveness with 25
C) about 2-10% by weight of an organic solubilizer
the extent and degree of this blooming upon formation of a distinct from Said pine oil;
cleaning composition. Such an effect is particularly known D) about 0.1-5% by weight of an alkalinity agent;
and generally associated with pine oil type water-Soluble
cleaning compositions which typically include one or more E) about 0.1-15% by weight of an anionic surfactant;
of the following identifying characteristics: containing an F) about 0.01 to about 2% by weight by weight of a
amount of one or more resins or oils derived from coniferous cationic Surfactant comprising a quaternary ammonium
Species of trees, containing natural fragrances or Synthetic Salt represented by the formula
fragrance compositions which are intended to mimic the
Scent of one or more resins or oils derived from coniferous 35
Species of trees, a color ranging from colorleSS to a deep
amber, deep amber yellow or deep amber reddish color;
generation of a milky or cloudy appearance when diluted
with water in dilutions useful for cleaning applications. Such
pine oil type cleaning compositions are generally provided 40 wherein RandR'' are independently a hydrogen or a
in a concentrated composition which is Subsequently diluted Cs alkyl group; R' is a CsCls alkyl group; and R'
with water by an end user/consumer to form a cleaning is a C- alkyl group or an ethoxylate group represented
Solution therefrom. by the formula -CH2CH2O), H, whereiny is a number
from 1 to 3; and X is a halide ion or a methoSulfate ion,
Another important characteristic of pine oil cleaning 45 and
compositions is phase Stability. The composition should be G) about 0.1 to 10% by weight of a nonionic surfactant
clear and phase Stable at temperatures of normal use and comprising an alcohol alkoxylate.
storage, before being further diluted with water. There is The present invention also provides a method for cleaning
thus a need for a water-Soluble pine oil cleaning composition 50 a hard Surface comprising contacting the hard Surface in
that possesses the characteristics of phase Stability, need of cleaning with the aforementioned pine oil cleaning
blooming, and efficient cleaning properties. The present composition.
invention provides Such a cleaning composition. The present
cleaning composition further has the attribute of providing DETAILED DESCRIPTION OF THE
Synergistic detergency/cleaning effects resulting from the INVENTION
55
combined use of the cationic, anionic and nonionic Surfac In addition to A) water, the liquid pine oil cleaning
tants present in the claimed cleaning compositions. composition of the present invention comprises B) 5 to 20%
U.S. Pat. No. 4,414,128 discloses an aqueous liquid (of total composition weight), and in one embodiment
detergent composition comprising: (a) from 1% % to 20% of 60
5-10%, in one embodiment 10-15%, and in one embodi
Surfactant Selected from Synthetic anionic, nonionic, ampho ment 15-20% by weight of pine oil.
teric and Zwitterionic Surfactants and mixtures thereof; (b) Pine oil is an organic Solvent, and is a complex blend of
from 0.5% to 10% of terpene selected from mono- and oils, alcohols, acids, esters, aldehydes and other organic
Sesquiterpenes and mixtures thereof, the weight ratio of compounds. These include terpenes which include a large
Surfactant:terpene lying in the range from 5:1 to 1:3 and (c) 65 number of related terpene alcohols and terpene ketones. The
from 0.5 to 10% of a polar solvent having a solubility in terpenes include mono- and Sesquiterpenes or mixtures
water at 25 C. in the range from 0.2% to 10%, said polar thereof.
 US 6,465,411 B2
3 4
Preferred terpenes are mono- and bicyclic monoterpenes, an alkylene group of from 2 to 5 carbon atoms, and in one
especially those of the hydrocarbon class, which can be embodiment 2 to 3 carbon atoms; n is a number from 1 to
Selected from terpinenes, terpinolenes, limonenes and 10, and in one embodiment from 2 to 5; and R is a hydrogen
pinenes. Highly preferred materials of this type include or hydrocarbyl group of 1 to 10 carbon atoms, and in one
d-limonene, dipentene, C-pinene, B-pinene and the mixture embodiment from 2 to 6 carbon atoms, and mixtures of Said
of terpene hydrocarbons obtained from the essence of alcohols, glycols and glycol ethers.
oranges (e.g., cold-pressed orange terpenes and orange ter As used herein, the term “hydrocarbyl substituent” or
pene oil phase ex fruit juice). “hydrocarbyl group' is used in its ordinary Sense, which is
An important terpene alcohol is terpineol, which is one of well known to those skilled in the art. Specifically, it refers
three isomeric alcohols having the basic molecular formula to a group having a carbon atom directly attached to the
CoH7OH. One type of pine oil, Synthetic pine oil, will remainder of the molecule and having predominantly hydro
generally have a specific gravity at 15.5 C. of about 0.9300, carbon character. Examples of hydrocarbyl groups include:
which is lower than the two other grades of pine oil, namely (1) hydrocarbon Substituents, that is, aliphatic (e.g., alkyl
Steam distilled and Sulfate pine oils, and will generally 15 or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl)
contain a higher content of turpentine alcohols. Other impor Substituents, and aromatic-, aliphatic-, and alicyclic
tant compounds include abietic acid (rosin), and other iso Substituted aromatic Substituents, as well as cyclic
prene derivatives. Substituents wherein the ring is completed through
Particularly effective pine oils which are presently com another portion of the molecule (e.g., two Substituents
mercially available include Unipine(R) 60 (from Union together form an alicyclic radical);
Camp, which is believed to contain approximately 60% (2) substituted hydrocarbon Substituents, that is, substitu
ents containing non-hydrocarbon groups which, in the
terpene alcohols), Unipine(R) S-70 and Unipine(R) S-70 (from context of this invention, do not alter the predominantly
Union Camp, both are believed to contain approximately hydrocarbon Substituent (e.g., halo (especially chloro
70% terpene alcohols), Unipine(R) S and Unipine(R) 80 (from 25 and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto,
Union Camp, both are believed to contain approximately nitro, nitroso, and Sulfoxy);
80% terpene alcohols), Unipine(R) 80 (from Union Camp, (3) hetero substituents, that is, Substituents which, while
which is believed to contain approximately 80% terpene having a predominantly hydrocarbon character, in the
alcohols), Unipine(R 85 (from Union Camp, which is context of this invention, contain other than carbon in
believed to contain approximately 85% terpene alcohols), a ring or chain otherwise composed of carbon atoms.
Unipine(R) 90 (from Union Camp, which is believed to Heteroatoms include Sulfur, oxygen, nitrogen, and
contain approximately 90% terpene alcohols), as well as encompass Substituents as pyridyl, furyl, thienyl and
Alpha Terpineol 90 (from Union Camp, which is believed to imidazolyl. In general, no more than two, preferably no
contain approximately 100% terpene alcohols). Further 35
more than one, non-hydrocarbon Substituent will be
present for every ten carbon atoms in the hydrocarbyl
effective pine oils include Glidco(E) Pine Oil TM 60 (available group; typically, there will be no non-hydrocarbon
from Glidco Organics Corp., Jacksonville, Fla., believed to Substituents in the hydrocarbyl group.
contain approximately 60% terpene alcohols), Glidco(R) Pine Suitable examples of C-C alcohols include ethanol,
Oil 60 (available from Glidco Organics Corp., Jacksonville, 40
isopropanol, butanol, pentanol, hexanol, heptanol and
Fla., believed to contain approximately 60% terpene octanol. Suitable examples of glycols include ethylene and
alcohols); Glidco(R) Pine Oil 140 (available from Glidco propylene glycols. The glycol etherS falling within the Scope
Organics Corp., Jacksonville, Fla., believed to contain of the above formula include alkylene glycol monoalkyl
approximately 70% terpene alcohols); Glidco(R) Pine Oil 80 ethers and alkylene glycol dialkyl ethers. Examples of useful
(available from Glidco Organics Corp., Jacksonville, Fla., 45 glycol ethers include propylene glycol methyl ether, dipro
believed to contain approximately 80% terpene alcohols) pylene glycol methyl ether, tripropylene glycol methyl ether,
Glidco(R) Pine Oil 150 (available from Glidco Organics propylene glycol isobutyl ether, ethylene glycol methyl
Corp., Jacksonville, Fla., believed to contain approximately ether, ethylene glycol ethyl ether, ethylene glycol butyl
85% terpene alcohols); Glidco(R) Terpene SW (available 50
(including n-butyl) ether, diethylene glycol n-butyl ether,
from Glidco Organics Corp., Jacksonville, Fla., believed to diethylene glycol phenyl ether, propylene glycol phenol
contain approximately 75% terpene alcohols); as well as ether, and mixtures thereof. Such glycols are presently
Glidco(R Terpineol 350 (available from Glidco Organics commercially available from a number of Sources (such as
Corp., Jacksonville, Fla., believed to contain approximately Dow Chemical Company and Union Carbide). As used
100% terpene alcohols). A pine oil (only one type) is also 55 herein, the term “propylene' includes both Straight chain
available from Whitaker Oil Company, Spartansburg, S.C. (-CHCHCH-) and branched (-CHCH(CH)-)
Other products which can contain up to 100% pure alpha StructureS.
terpineol, may also be used in the present invention. The fourth component (D) of the present pine oil cleaning
The third component (C) of the present cleaning compo 60
composition is 0.1-5%, and in one embodiment 1-4% by
sition is 2-10%, and in one embodiment 4-8% by weight of weight of an alkalinity agent well known to those skilled in
an organic Solubilizer, distinct from the pine oil. Preferred the art. Preferred alkalinity agents include Sodium and
organic Solubilizers include C-C alcohols, glycols and potassium hydroxide and mixtures thereof.
glycol ethers represented by the formula R'O-R-O-R The fifth component (E) of the present pine oil cleaning
wherein R is a hydrogen or hydrocarbyl group of 1 to 10 65 composition is 0.1-15%, and in one embodiment 2-10% by
carbon atoms, and in one embodiment 1 to 8, and in one weight of an anionic Surfactant well known to those skilled
embodiment 2 to 6 carbon atoms; each R independently is in the art. Preferred anionic Surfactants include Sulfate and
 US 6,465,411 B2
S
Sulfonate metal Salts, Said Salts having a hydrocarbyl group
of from 5 to 20, and in one embodiment from 8-18 carbon
atoms. The metal ion in these metal Salts are preferably R HCH-OH
N C
Sodium and potassium with Sodium being more preferred. /V
Such Sulfate and Sulfonate metal Salts are available com HC CH
mercially from Clariant Corporation under the trademarks
GenapolTM and Hostapur.T.M. In one embodiment, the sulfate wherein R is a C-C alkyl group. This material is
Salt is a C/C-alkyldiglycoletherSulfate Sodium Salt rep available commercially under the trademark “PraepagenTM
resented by the formula HY” from Clariant Corporation.
The Seventh component (G) of the present cleaning com
RO-(CH2CH2O)-SO, Na' position is 0.1 to 10%, and in one embodiment, 2-8% by
wherein R" is a C2-alkyl group, and is available com weight of a nonionic Surfactant comprising at least one
mercially under the name GenapolTM LRO from Clariant alcohol alkoxylate.
Corporation. In one embodiment, the Sulfate Salt is a C/ 15 In one embodiment, the alcohol alkoxylate is represented
C-alkyltriglycoletherSulfate Sodium Salt represented by the by the formula RO-CHCH(R')O-H wherein R'
formula is a hydrocarbyl group of 1 to 20 carbon atoms, and in one
RO-(CH2CH2O)-SO, Na' embodiment 10 to 20 carbon atoms; each R' independently
is hydrogen or methyl, and m is a number from 3 to 15.
wherein R is a C-C, alkyl group, and is available In one embodiment, the alcohol alkoxylate is one where
commercially under the name GenapolTM ZRO from Clari R" is a C, alkyl group (i.e., undecyl), R'' is hydrogen, and
ant Corporation. m is 3, 5, 7, 8, or 11. These alcohol alkoxylates which are
In one embodiment, the Sulfonate Salt is a mixture of (i) ethoxylates (i.e., R' is hydrogen) are commercially avail
a C/C-C-olefin Sulfonate Sodium Salt represented by the 25 able under the name “Genapole) UD” from Clariant Corpo
formula RCH=CHCH-SONa" and (ii) the corre ration. In an especially preferred embodiment, the alcohol
sponding hydrolyzed product represented by the formula
RCH(OH)CHCH-SONa", wherein R is a C ethoxylate is one where R' is undecyl, R' is hydrogen, and
alkyl group, Said mixture available commercially under the m is 7 and is available under the name Genapole) UD 070
names HostapurTM OS and OSB from Clariant Corporation. and 079. In this nomenclature, the first two digits of the three
In an especially preferred embodiment, the Sulfonate Salt is digit number that follow the name indicate the number of
a Secondary alkane Sulfonate Sodium Salt represented by the moles of ethylene oxide on the alcohol. The last digit
formula represents the activity of the product. Thus both Genapole
UD 070 and UD 079 contain 7 ethylene oxide repeat units,
35 and while the former is 100% active, the latter is 90% active.
In one embodiment, the ethoxylate is one where R' is a
SO Nat linear C/C/C mixed alkyl group. These ethoxylates are
based on C/C/C mixed linear alcohols derived from
wherein R and R are alkyl groups, such that R and R' 40
coconut/palm kernel oil, and are available commercially
together contain 12 to 16 carbon atoms, and is available under the name “Genapole 26-L from Clariant Corpora
commercially under the name HostapurTM SAS from Clari tion. At low ethylene oxide content, the number following
ant Corporation. the “L” (for linear), is the number of ethylene oxide (EO)
The Sixth component (F) of the present cleaning compo repeat units in the molecule. For water Soluble ethoxylates
sition is 0.01-2%, and in one embodiment 0.05 to 1% by 45 in the same Series, the aqueous cloud point is used in the
weight of a cationic Surfactant comprising a quaternary nomenclature. Thus “Genapole 26-L indicates the hydro
ammonium Salt represented by the by the formula phoble is a C/C/C mixed oleochemical alcohol with 3
moles of ethylene oxide; Genapole 26-L-60 is the same
50
hydrophobe (i.e., C2/C/C mixed linear alcohol) with a
cloud point of 60° C.
In one embodiment, the ethoxylate is one where R' is
nonylphenyl. These ethoxylates are available under the
name “Hostapal(R)' available from Clariant Corporation.
wherein R and R'' are independently a hydrogen or a C 55 These nonylphenol based ethoxylates contain 4, 6, 9, 10, 13,
alkyl group, Such as a methyl, ethyl, isopropyl and n-propyl and 15 ethylene oxide repeat units. The same nomenclature
group; R' is a Csis alkyl group, and in one embodiment a as described hereinabove for the Genapole UD Series of
Cso alkyl group, and in one embodiment a Co- alkyl ethoxylates is also used for the Hostapale ethoxylates. Thus,
group, and in one embodiment a Cais alkyl group; and R' the name “Hostapal(R) N 090" that the ethoxylate is 100%
is a C- alkyl group, Such as a methyl, ethyl, isopropyl and 60
active nonylphenol and contains 9 ethylene oxide repeat
n-propyl, or an ethoxylate group represented by the formula units.
-CHCH.O),H, whereiny is a number from 1 to 3; and X The compositions of the present invention are clear and
is a halide ion, Such as fluoride, chloride, bromide, and
iodide, or a methoSulfate. In one especially preferred phase stable at room temperature and higher (e.g., 52 C.)
embodiment, both R and R'' are methyl, R' is a C-C, 65 for prolonged periods (e.g., after one month). The compo
alkyl group, R' is CHCH-OH, and X is chloride; i.e., the Sitions exhibit exceptional blooming properties upon dilu
quaternary ammonium Salt is represented by the formula tion with water.
 US 6,465,411 B2
7 8
The cleaning compositions of the present invention may The present invention also provides a method for cleaning
be used directly as a “concentrate', or used after dilution a hard Surface comprising contacting the hard Surface in
with water. The term “concentrate” refers to the pre need of cleaning with the foregoing pine oil composition in
consumer dilution and composition of the cleaning compo an a mount effective for providing cleaning treatment.
sition which essentially is the form of the product that may Suitable hard Surfaces include without limitation, painted
be used by the consumer or other end user, who then would woodwork and panels, tiled walls, wash bowls, bathtubs,
normally dilute the Same with water to form a cleaning
composition. It is to be understood however that nothing in linoleum or tile floors, and washable wallpaper. The method
the invention would bar its use as cleaning composition may comprise using the cleaning composition directly (neat)
without any further dilution. Dilutions may be prepared by or first diluting the composition in a Sufficient amount of
diluting the concentrate with water in the range of 1:0.1 to water or other carrier.
1:1000, preferably in the range of 1:1 to 1:500, and more
preferably in the range of 1:10 to 1:150. The actual dilution EXAMPLES
Selected is in part determined by the degree and amount of 15 The following specific examples will provide detailed
dirt and grime to be removed from a Surface(s), the amount illustrations of the methods of producing and utilizing
of mechanical force imparted to remove the same, as well as compositions of the present invention. These examples are
the observed efficacy of a particular dilution. Generally not intended, however, to limit or restrict the Scope of the
better results and faster removal is to be expected at lower invention in any way and should not be construed as
relative dilutions of the concentrate in the water.
Optional Ingredients providing conditions, parameters or values which must be
Compositions of the present invention may optionally utilized exclusively in order to practice the present inven
include one or more conventional additives known to be tion. Unless otherwise Specified, all parts and percents are by
useful in pine oil type cleaning compositions including weight, and all temperatures are in degrees Centigrade.
25
germicidal agents, Viscosity modification agents, fragrances The following liquid compositions (shown below in Table
(natural or synthetically produced), foaming agents, water 1 are prepared by mixing the ingredients in water:

TABLE 1.
Formulation #

Ingredients #1 #2 #3 #4 #5 #6 #7
Hostapur (R) SAS 5% 5% 5% 5% 5% 5% 5%
Genapol (R) UD070 2% 2% 2% 2% 2% 2% 2%
Praepagen (R) HY O% O.05% O.10% O.15% O.20% O.40% O.60%
Pine oil 15% 15% 15% 15% 15% 15% 15%
Dipropylene glycol 6% 6% 6% 6% 6% 6% 6%
monomethyl ether'
Sodium hydroxide 2.35% 2.35% 2.35% 2.35% 2.35% 2.35% 2.35%
Water to 100% to 100% to 100% to 100% to 100% to 100% to 100%

'obtained from Whitaker Oil Company, Spartanburg, South Carolina

45
Softening agent, additional co-Surfactants including anionic, Cleaning performance testing utilizing the above formu
cationic, nonionic, amphoteric and Zwitterionic Surface lations was conducted using a using a HunterLab Col
active agents, especially those useful in providing further orCuest(R) II reflectometer (available from HunterLab,
detersive effects, additional organic Solvents for physical Reston, Va.). The hard surface substrate was a white lino
Stability purposes, Sequestering agents (chelating agents), 50
Such as phosphonate chelating agents (e.g., the Dequest" leum tile and the Soil was an iron oxide based composition
line of phosphonates), amino carboxylate chelating agents comprising 51% Solvent comprising kerosene and Stoddard
(e.g., EDTA and metal Salts thereof), carboxylate chelating solvent, 43% iron oxide and 6% oil comprising Crisco TM,
agents, polyfunctionally-Substituted aromatic chelating mineral oil and motor oil. The Soil was applied over the
agents and mixtures thereof, and coloring agents. Chelating 55 whole Surface of the linoleum Substrate and the Soil coated
agents such as the above are disclosed in U.S. Pat. Nos. substrate was heated in an oven at 52 C. (125 F) for 1
6,048,836 and 4,414,128. hours, and then allowed to cool. Each composition was
Such optional constituents should be selected So as to tested in 4-8 replicate runs and the results shown below are
have little or no detrimental effect upon the blooming 60 determined by reflectance measurements prior to and after
behavior provided by the inventive compositions, and gen cleaning using the compositions below. The results, shown
erally the total weight of Such further conventional additives
may comprise up to 20%, and in one embodiment up to 10% below in Table 2, are reported as AR (Delta R) (reflectance
by weight of the pine oil cleaning composition. Such after cleaning minus reflectance before cleaning), which is
optional ingredients are well known to those of ordinary 65 indicative of Stain removal power of the cleaning
skill in the art and are disclosed in U.S. Pat. No. 5,591,708. composition, with the larger values being indicative of better
Method for Cleaning a Hard Surface cleaning performance.
 US 6,465,411 B2
9 10
TABLE 2 TABLE 4
Results from Iron Oxide based Soil System Bloom Performance

Formulation AR Error Formulation Bloom Bloom Stability

#1 30.284 1953 #1 Immediate Excellent
#2 29.190 1.211 Excellent Homogeneous
#3 30.32O O.363 #3 Immediate Excellent
#4 30.718 1.229 Excellent Homogeneous
#5 30.16S 4097 Pine Power TM Nearly immediate Good
#6 27.893 3.123 Good Homogeneous
#7 28.025 2.221 Lysol TM Delayed Poor
Pine Power TM (Commercial cleaner) 26.718 2.111 Poor Separated
Lysol TM Disinfectant Pine Cleaner (Commercial 4.026 1173 PineSOITM Delayed Poor
cleaner) Poor Separated
PineSol TM (Commercial cleaner) 11.012 O.805 15
Each of the documents referred to above is incorporated
A Second cleaning performance testing was also con herein by reference in its entirety, for all purposes. Except in
the Examples, or where otherwise explicitly indicated, all
ducted using an oily soil comprising 58% hexane, 34% oil numerical quantities in this description Specifying amounts
comprising WessonTM Cannola and Wesson TM vegetable of materials, reaction and process conditions (such as
oils, and 8% carbon black. The soil is pipetted onto the temperature, time, pressure), and the like are to be under
center of the white linoleum tile and allowed to remain in stood to be modified by the word “about'.
contact for 24 hours. The testing was done in 4-8 replicates What is claimed is:
25 1. A liquid pine oil cleaning composition comprising:
for each System, and the results determined by reflectance
measurements before and after cleaning. In this testing, AR A) water;
B) about 5-20% by weight of pine oil;
values reflect the residual stain on the white linoleum tile, C) about 2-10% by weight of an organic solubilizer
and a lower AR value is indicative of better cleaning power distinct from Said pine oil;
of the cleaning composition. The results are Summarized in D) about 0.1-5% by weight of an alkalinity agent;
Table 3 below. E) about 0.1-15% by weight of an anionic surfactant;
F) about 0.01 to about 2% by weight by weight of a
TABLE 3 cationic Surfactant comprising a quaternary ammonium
Salt represented by the formula
Results from Oily Soil System 35

Formulation AR Error

#1 9.43O 2.404
#2 8.712 3.570
#3 7.440 2.487 40
#4 10.926 2.214
#5 11.800 4.026
#6
#7
11.413
9.376
6.199
3.584
wherein R and R'' are independently a hydrogen or a
Pine Power TM (Commercial cleaner) 8.96S 1942 Cs alkyl group; R' is a CsCls alkyl group; and R'
Lysol TM Disinfectant Pine Cleaner 17.333 3.328 45
is a C- alkyl group or an ethoxylate group represented
(Commercial cleaner)
PineSol TM (Commercial cleaner) 40.093 11.573
by the formula -(CH2CH2O), H, wherein y is a num
ber from 1 to 3; and X is a halide ion or a methosulfate,
and
G) about 0.1 to 10% by weight of a nonionic surfactant
The blooming properties of Some of the compositions 50
comprising an alcohol alkoxylate.
were also evaluated against commercial products and there 2. The cleaning composition of claim 1, wherein the pine
are shown in Table 4 below. oil (B) is a terpene that comprises at least one member
Selected from the group consisting of mono and Sesquiter
The term “blooming” or “bloom” refers to the change of peneS.
water's appearance from essentially colorless and transpar 55 3. The cleaning composition of claim 2, wherein the
ent to that of a milky white, cloudy appearance upon the terpene is a mono- or bicyclic monoterpene Selected from
addition of a Sufficient amount of cleaning composition. The the group consisting of terpinenes, terpinolenes, limonenes,
bloom effect can be immediate and delayed. The bloom pinenes, and mixtures of at least two thereof.
effect can be more or less stable. The formulations used two 60
4. The cleaning composition of claim 3, wherein the
terpene is Selected from the group consisting of d-limonene,
ounces of test product (cleaning composition according to dipentene, C-pinene and B-pinene.
formulation numbers 1 and 3 or the listed commercial 5. The cleaning composition of claim 2 wherein the
products in concentrated form out of the bottle) per gallon of terpene is a terpene alcohol, terpene aldehyde or terpene
tap water at room temperature. Visual assessments of bloom 65 ketone.
and bloom Stability as well as the Speed of blooming and 6. The cleaning composition of claim 1, wherein the
bloom persistence were made. organic Solubilizer (C) is at least one member Selected from
 US 6,465,411 B2
11 12
the group consisting of Cls alcohols, glycols and glycol wherein R and R are alkyl groups such that R and R'
ethers, Said glycols and glycol ethers being represented by together contain about 12 to 16 carbon atoms.
the formula RO-RO), R wherein R is a hydrogen or 12. The cleaning composition of claim 1, wherein the
hydrocarbyl group of 1 to 10 carbon atoms; each R inde nonionic Surfactant (G) comprises at least one alcohol
pendently is an alkylene group of about 2 to about 6 carbon alkoxylate represented by the formula RO-CH-CH(R')
atoms; n is a number from 1 to about 10; and R is a O-H wherein R' is a hydrocarbyl group of 1 to about 20
hydrogen or a hydrocarbyl group of 1 to about 10 carbon carbon atoms; each R' independently is hydrogen or
atOmS. methyl, and m is a number from about 3 to about 15.
7. The cleaning composition of claim 1, wherein the 13. The cleaning composition of claim 12, wherein R' is
organic Solubilizer (C) is dipropylene glycol monomethyl a C alkyl group, R' is hydrogen, and m is 3,5,7,8, or 11.
ether.
8. The cleaning composition of claim 1, wherein the 14. The cleaning composition of claim 1, wherein in (F),
alkalinity agent (D) is Sodium or potassium hydroxide. both R and R'' are CH; R' is C-C alkyl; R' is
9. The cleaning composition of claim 1, wherein the 15 CHCH-OH; and X is Cl.
anionic Surfactant (E) comprises at least one Sulfate or 15. The cleaning composition of claim 1, further com
Sulfonate metal Salt, Said Salt having a hydrocarbyl group of prising at least one optional ingredient Selected from the
about 5 to about 20 carbon atoms. group consisting of germicidal agents, Viscosity modifica
10. The cleaning composition of claim 9, wherein the tion agents, fragrances, foaming agents, detersive agents,
metal Salt is a Sodium or potassium Salt. co-Surfactants, and coloring agents.
11. The cleaning composition of claim 9, wherein the 16. A method for cleaning a hard Surface comprising
Sulfonate metal Salt is a Secondary alkane Sulfonate Sodium contacting the hard Surface in need of cleaning with the
Salt represented by the formula composition of claim 1.
25
17. A method for cleaning a hard Surface comprising
contacting the hard Surface in need of cleaning with the
SONat composition of claim 15.