WO2001023515A1

WO2001023515A1 - Novel polymer based cleaning compositions for use in hard surface cleaning and laundry applications

Info

Publication number: WO2001023515A1
Application number: PCT/US2000/026799
Authority: WO
Inventors: Gladys S. Gabriel; Manilal S. Dahanayake
Original assignee: Rhodia Inc.
Priority date: 1999-09-29
Filing date: 2000-09-29
Publication date: 2001-04-05
Also published as: AU7622100A

Abstract

An improved cleaning composition for use in carpet cleaners, dryer activated fabric softener sheets, laundry additives such as pre-treatment spotter liquids, gel and solid stick and laundry bar soaps is comprised of a sulfonated copolyester soil release polymer, one ore more anionic nonionic, cationic and/or amphoteric surfactants, a solvent and water. Optionally, the compositions may comprise a second surfactant compound selected from the group consisting of gemini surfactants and excipients such as builders, deflocculating agents enzymes and the like.

Description

NOVEL POLYMER BASED CLEANING COMPOSITIONS

FOR USE IN HARD SURFACE CLEANING

AND LAUNDRY APPLICATIONS

FIELD OF THE INVENTION The present invention relates to cleaning compositions and more

specifically their use in hard surface cleaners and laundry applications More specifically,

the present invention relates to the use of novel soil release polymer compounds in carpet

cleaners, laundry bars, clothes dryer sheets, fabπc softener sheets, laundry additives such

as spot cleaners and other detergent formulations.

BACKGROUND OF THE INVENTION

Detergents and other cleaning compositions for use m laundry,

dishwashing, floor cleaning and carpet cleaning applications are numerous and well known

in the art. Generally these consist of one or more anionic. noniomc. or canonic

surfactants, builders, enzymes, emulsifϊers. stabilizers. pH modifiers and the like.

The present invention comprises a unique combination of surfactants and

other excipients with a soil release polymer for enhanced cleaning and subsequent resistance to soilation in laundry bar soaps, clothes dryer sheets, fabπc softener sheets and

carpet cleaners. Laundry bar soaps, although not common in the United States, are used

throughout the rest of the world, mostly in third world countnes where clothes are

manually washed by hand. Obviously, these systems are not as sophisticated and effective

as the presently available detergent compositions for use m elecmc washers, dryers and carpet cleaning machines. Nevertheless, there is a growing need in this area for detergent

systems that not only effectively clean the soiled mateπais but also protect the surface thus cleaned by resisting subsequent re-deposition of dirt, grease, oils and the like.

United States Patent No. 5,510,042 to Hartman et al. discloses and claims fabric softening bar compositions compπsed of from about 40 wt% to 90 wt.% of a

hvdrophobic fabric softener, 5.0 wt% to about 30 wt% of a nonionic surfactant and water.

The fabric softener is selected from the group comprising quaternary ammonium

compounds, carboxylic acid salts of tertiary amines, sorbitan esters of fatty alcohols and

the like. The compositions are asserted to be low sudsing, low lathering, non-detersive

fabric softening compositions.

United States Patent No. 5,813,086 to Ueno et al. discloses a carpet cleaner

device that cleans the carpets using a foam composition comprised of .005% lauryl alcohol

combined with 0.1 % sodium lauryl sulfate in water. It is further disclosed however, that

other suitable agents comprising anionic surfactants such as alkyl ester sulfates, nonionic

surfactants such as alkyl phenols, ampholytic surfactants such as alkyl dimethyl amine

oxides as well as higher order fatty alcohols may also be used.

United States Patent No. 5,728,669 to Tyerech teaches a carpet cleaning

composition comprising urethane perfluoroalkyl esters, oxidizing agents, anionic surfactants and nonionic surfactants. The compositions are asserted to be effective in the

removal of oxidizable carpet stains and for imparting oil repellancy to the carpet fibers.

Published International Application No. WO98/31776 Al to Tyerech

discloses carpet cleaning compositions consisting of a mixture of one or more anionic, nonionic and amphoteric surfactants in an amount of from about 0.1 wt.% to 11.0 wt%, an

amino-polycarboxylic acid salt that serves as a resoiling inhibition agent in an amount of from about 0.1 wt% to 6.0 wt%, an organic solvent in an amount of 0.1-5.0 wt.% and additives in an amount of about 0-20 \vt %

Usually most commercially available carpet cleaning compositions are

compπsed of pπmary anionic surfactants, one or more amphoteπc and/or nonionic

secondary surfactants, an acrylic soil release polymer as an antiredeposition agent, a stabilizer and a solvent None of the compositions known in the pπor art utilize a

copolyester soil release polymer in a cleaning system that provides the supeπor cleaning

and stam-removal capabilities as those disclosed herein

SUMMARY OF THE INVENTION

The present invention compπses novel cleaning compositions and their

incorporation in a vaπety of end use formulations such as laundry bar soaps, carpet

cleaners and laundry additives such as pre-wash spot removers and fabπc softener sheets

for use in the dryer. The compositions are compπsed of a unique blend of a novel sulfonated copolyester soil release polymer, a surfactant blend consisting of one or more surfactants and amphoteπc/zwitteπonic surfactants, a stabilizer, a builder, a co-solvent,

processing aids an aminocarboxylic or carbonate salt and water. A secondary surfactant

component compπsing one or more gemini type surfactants may also be added to the

composition. The cleaning compositions are particularly useful m carpet cleaning compositions, heat activated laundry dryer fabnc softener sheets and laundry bar soaps.

DETAILED DESCRIPTION OF THE INVENTION

The cleaning compositions of the present invention provide a surpπsingly

supeπor, efficacious cleaner that not only readily removes dirt, soil and stains from hard surfaces, but also prevents the re-deposition of these mateπais onto the surface of whatever

is being cleaned. The basic cleaning composition can be formulated into one of a number

of different applications and additional excipients may be added as desired to more

specifically tailor the formulation to its end use application. In particular, supeπor carpet cleaning, laundry bar soap compositions and dryer sheets and fabπc softener sheets are

realized.

Central to the novelty and efficacy of the cleaning compositions of the

present invention is the incorporation of a sulfonated co-polyester soil release copolymer

which is represented by the general formula:

-[C(O)-Ar-C(O)-O-(CH₂CH₂O)_a]_b-

wherein - C(O)-Ar-C(O)- is terephthalate, isophthalate or sulfoisophthalate, a is a whole

number of from 1-4 and b is an anion such as -SO₃, -PO , Cl etc.

There water dispersible or water soluble sulfonated polyesters are prepared

by the esterification and/or transesterification and polycondensation of a monomer

composition. These are based on an unsulphonated diacidic monomer (A), as opposed to a

sulfonated diacide monomer (SA), consisting of at least one dicarboxylic acid or anhydride chosen from terephthalic, isophthalic and 2,6-naphthalenedicarboxylic acids, anhydπdes or their diesters in a quantity corresponding to a molar ratio (A)/(A)+(SA) of the order of

95/100 to 60/100, preferably of the order of 93/100 to 65/100; a sulphonated diacidic

monomer (SA) consisting of at least one sulphonated aromatic or sulphonated aliphatic

dicarboxylic acid or anhydride, or their diesters, in a quantity corresponding to a molar ratio (SA)/(A)+(SA) of the order of 5/100 to 40/100, preferably of the order of 7/100 to 35/100, it being possible for up to 50 mol %, preferably up to 30 mol %, of the quantity of unsulphonated diacidic monomer (SA) to be replaced with a hydroxylated diacidic

monomer (HA) consisting of at least one hydroxylated aromatic or aliphatic dicarboxylic

acid or anhydπde or a diester of the said hydroxylated aromatic or aliphatic dicarboxylic

acid.

These polyesters are also compπsed of a polyoi monomer (P) consisting of

at least one polyoi chosen from ethylene glycol, propylene gylcol, diethv iene glycol,

dipropylene glycol, glycerol, 1,2.4-butanetπol and 1,2,3-butanetπol. in a quantity

corresponding to a ratio of number of OH functional groups of the polyoi monomer

(P)/number of COOH functional groups or functional group equivalents of the diacidic

monomers (A)-r(SA)+(HA) of the order of 1.05 to 4, preferably of the order of I 1 to 3.5

and very particularly of the order of 1.8 to 3 in that the sulphonated diacidic monomer

(SA) consists of at least one sulphonated aromatic dicarboxylic acids or anhydπdes and of

sulphonated aliphatic acids or anhydπdes or their diesters when the polyoi monomer (P)

does not contain any polyoi other than a glycol or when the hydroxylated diacidic

monomer (HA) is absent and in that the said sulphonated polyesters exhibit a number

molecular mass lower than 20,000, a sulfur weight content of the order of 0 5 to 10%,

preferably of the order of 1 2 to 8% and a hydroxyl functional group content, expressed as

OH equivalent/kg of polymer, higher than 0 2

The copolymers and their preparation are more specifically set forth in co- pending application U S S N 08/737,548, which corresponds to W095 32997 published Dec. 7, 1995, and PCT/FR/95/00658. filing date Vlay 19, 1995, all of which are incorporated herein by reference in their entirety

The liquid hard surface cleaner πnse compositions of the present invention - 5A

consist of the anionic surface active polymer, a primary anionic, nonionic or amphoteric

surfactant, water, and a number of other optional ingredients which can vary as desired by

the formulator depending on the particular application, strength necessary, etc Taken in

their broadest aspect, the anionic ester polymer surfactants of the present invention

compπse an oligomeπc ester backbone which preferably contains anionic hydrophiles

connected to the ester backbone by means of aryl groups or by an ester or ether linkage Preferably, the anion source is a sulfonated group.

Polymers of the subject invention encompass o gomeπc (low molecular

weight polymeπc), substantially linear esters. These esters compπse, in their backbone,

oxyalkyleneoxy, preferably oxy-l,2-propyleneoxy and polyoxyethylene units, and

hydrophobic aryldicarbonyl, preferably oxy-l,2-propyleneoxy and oxyethyleneoxy umts,

and hydrophobic aryldicarbonyl, preferably terephthaloyl units. Preferred esters

additionally compπse units of sulfonsophthalate and, optionally, poly(oxyethylene)oxy

units having a degree of polymeπzation from about 2 to about 4. Mixtures of such esters

with reaction by-products and the like retain their highly effective surface active properties

when such mixtures contain at least about 10%, preferably at least about 25%, more

preferably at least about 50%, by weight, of the subject esters. The esters useful herein are of relatively low molecular weight (i.e., generally below the range of fiber-forming

polyesters) typically ranging from about 500 to about about 20,000, preferably from about 550 to about 8,000, also preferably from about 650 to about 2500.

Preferred anionic hydrophiles connected to the ester backbone include

sulfoaroyl umts, especially sulfobenzoyl umts of the formula (MO-,S)(C₆H₄)C(O)- wherein M is a salt-forming cation such as sodium or tetraalkylammomum. Preferably M is

sodium. Preferably not more than 0 15 mole fraction of the sulfobenzoyl backbone units

are in para-form. More preferred are the sulfobenzoyl backbone umts being essentially in ortho- or meta-form.

Other preferred backbone units include those derived from sulfonated

polyethoxy/propoxy groups, which are connected to the backbone by an ester linkage.

Preferred are those of the formula (MO₃S)(CH₂)_m(RO)_n-, wherein M is a salt- forming

cation such as sodium or tetraalkylammonium; m is 0 or 1, preferably 0; R is ethylene,

propylene, or a mixture thereof, preferably ehtylene; and n is on average from I to about

20, preferably 1-5. More preferred are capping units derived from monomers selected

from the group comprising sodium 2-(2-hydroxyethoxy) ethanesulfonate, sodium.

2-(2(hydroxyethoxy)ethoxy)ethanesulfonate, and

2-(2-(2-hydroxyethoxyethoxy)ethoxy)ethanesulfonate.

Still other preferred backbone units include ethoxylated or propoxylated

phenolsulfonate units of the formula MO₃S(C₆H₄)(OR)_p- wherein M and R are as defined

above, and p is a number of from about 1 to about 20, preferably from about 2 to about 10.

Additionally suitable preferred backbone units include modified

poly(oxyethylene)oxy monoalkyl ether units of the formula R"O(CH₂CH₂O)_k- wherein R" is about C,.C₄, preferably about C,-C₂ saturated alkyl, and k is a number of from about 3 to

about 100, preferably from about 5 to about 50.

The ester "backbone" of the surfactant polymers, by definition, comprises

all the anionic hydrophiles that are incorporated into the esters and these are

interconnected by means of ester bonds. The essential oxyalkyleneoxy units of the backbone of the subject polymers are mixtures of symmetπcal (a) -OCH_:CH₂O- (oxvethyleneoxv) units with unsymmetπcal

(b) -OCH(R^a)CH(R^b)O- (oxy- 1,2-alkyleneoxy) units, wherein R^a and R^b are selected so

that in each of the units, on of R^a or R^b is H and the other is non-hydrogen R group (as

specified below), or R and R^b can be different non-hydrogen R groups. The (b) units are

believed to provide a sufficiently unsymmetπcal character required for stability of the desired viscosity of the anionic or nonionic surfactant polymers, whereas the (a) units are

believed to provide sufficient symmetry for supeπor surface active functionality A

convenient measure of the unsymmetπcal character required is given by the mole ratio of

(a) units to (b) units. For the subject invention processes, the ratio of (a) units to (b) umts

in the subject polymers preferably vanes from about 1 :2 to about 4: 1. At a ratio of greater

than about 4 1 , the polymers spontaeously change from an amorphous character to a

crystalline form quickly, and are not useful in commercial scale processes where

concentrated aqueous solutions are prepared and kept for more than a few minutes. At a

ratio less than about 1 :2, the polymer do not tend to change from amorphous to crystalline

form. As a result, more preferred ratios of (a) umts to (b) units in the subject polymers is

from about 1:1 to about 3:1 and more preferred still is from about 1.3:1 to about 2: 1.

In the above paragraph, R is preferably a non-hydrogen, non-charged group

with a low molecular weight (typically below about 500). R is chemically unreactive

(especially in that it is a non-esteπfiable group) and is compπsed of C and H, or of C, H

and O. The preferred R groups are selected from lower n-alkyl groups, such as methyl, ethyl, propyl and butyl, especially methyl. Thus, the preferred oxy- 1,2 alkyleneoxy and

oxy-l,2-hexyleneoxy units. Especially preferred are oxy-1.2-propyleneoxy as (b) units.

The backbones of the subject esters compπse, per mole of ester, from about - 9 - 0 5 to about 66 moles of the oxyalkyleneoxy units, preferably from about 1 to about 22

moles, more preferably from about 3 to about 16 moles.

Certain non-charged, hydrophobic aryl dicarbonyl units are also in the

backbone of the subject polymers. Preferably, these are exclusively terephthaloyl units

Other non-changed, hydrophobic dicarbonyl units, such as isophthaloyl. adipoyl. or the

like, can also be present if desired, provided that the soil release properties of esters

(especially polyester substantivity) are not significantly diminished. These other, non-

charged, hydrophobic dicarbonyl units can aid in providing sufficient lrregulaπty in the

subject esters to avoid a too great tendency to crystallize.

The backbones of the subject esters compπse, per mole of ester, from about

1 to about 40 moles of the hydrophobic aryl dicarbonyl units; preferably from about 2 to

about 24 moles, more preferably from about 3 to about 14 moles.

Generally, if it is desired to modify the umts of the esters, use of additional

hydrophillic units is preferred over the use of additional, non-charged, hydrophobic units. To this end. minor amounts, preferably compπsing less than about 5% of the molecular

weight of the ester, of additional umts such as di- or tπ- (oxyethylene) oxy units are

incorporated into the esters.

It is also possible to introduce charged, hydrophilic units into the backbone;

preferably such units compπse less than about 20%, more preferably less than ahout 14% of the backbone units. One example is to incorporate a charged moiety R^c in place of one

or more R^a or R^b moieties of the above oxy- 1 ,2alkyleneoxy umts. Such R^c moiety

preferably has the structure MO₃SL-, wherein M is a slat-formmg cation such as sodium or

tetraalkylammomum, and L is a side chain connecting moiety selected from alkylene, - 10 - oxyalkylene. alkyleneoxyalkylene. aryiene, oxyarylene, alkylomethoxyarylene,

polyoxyalkylene. alkyleneoxyarylene, poly (oxyalkylene), alkylene poly (oxyalkylene),

and mixtures thereof. As used in this paragraph, the alkylene moieties are about a C₂-C_b

chain, preferably ethylene or 1,2-propylene; aryiene is preferably phenylene

As another example, anionic hydrophil c units capable of forming two

ester bonds may be included in the backbone of the esters. Suitable anionic hydrophilhc

units of this specific type are well illustrated by sulfonated dicarbonyl units, such as

sulfosuccmyl, i.e., or more preferably, sulfoisophthaloyl, i.e., -(O)C(C₆H₃)(SO,M)C(O)-

wherein M is a salt-forming cation, such as an alkali metal or tetraalkylammonium ion.

The backbones of the subject esters compπse, per mole of ester, from 0

moles to about 20 moles of sulfonated dicarbonyl umts, preferably from about 0.5 moles to

about 9 moles, preferably from about 1 mole to about 4 moles.

The anionic and nomonic low molecular weight poly(oxyethylene)

oxy/aryldicarbonyl ester polymer surfactants are incorporated in the cleaner formulations in an amount of from about 0.01 wt% to about 5.0 wt% based upon the total weight of the

πnse formulation. Preferably, the ester polymer is in an amount of 0.5 wt.% to 3.0 wt. %.

A second element of the cleaning compositions of the present invention is a

surfactant component consisting of one or more and preferably a blend of surfactants selected from the group consisting of anionic surfactants, nonionic surfactants, catiomc

surfactants, amphoteπc surfactants and natural surfactants such as tallow which are

commonly found in third world countries. Examples of suitable nomonic surfactants

useful in the practice of the present invention include fatty acid glyceπne esters, polyglyceπne fatty acid esters, higher alcohol ethylene oxide adducts. single long chain polyoxyethylene lanolin alcohol, polyoxyethylene fatty acid esters, polyoxyethylene

glyceπne fatty acid esters, polyoxyethylene propylene glycol fatty acid esters,

polyoxyethylene sorbitol fatty acid esters, polyoxyethylene castor oil or hardened castor

oil deπvatives, polyoxyethylene lanolin deπvatives, polyoxyethylene fatty acid amides,

polyethylene alkyl amines, alkylpyrrolidones. glucamides. alkylpolyglucosides. mono- and dialkanol amides, polyoxyethylene alcohol mono- or diamides, alkylamine oxides and

mixtures thereof.

Examples of the anionic surfactants used herein include fatty acid soaps,

ether carboxylic acids and salts thereof, alkane sulfonate salts, α-olefin sulfonate salts,

sulfonate salts of higher fatty acid esters, higher alcohol sulfate ester salts, fatty alcohol

ether sulfate salts, higher alcohol phosphate ester salts, condensates of higher fatty acids

and ammo acids, and collagen hydrolysate deπvatives.

Examples of the amphoteπc surfactants used herein include ammo acids,

betame, sultaine, phosphobetaines, lmidazohne type amphoteπc surfactants, soybean

phospholipid, and yolk lecithin. The cleaner concentrate compositions may also optionally contain a secondary surfactant component composing a class of surface active cleaners known as gemini surfactants. Whereas the conventional surfactants discused earlier are generally linear chain molecules compπsed of one hydrophi c "head" portion attached to a

hydrophobic "tail" portion, gemini surfactants are compπsed of two of these

hydrophobic/hydrophi c chains attached by an alkylene bπdge. These are descπbed in the

literature (Chemtech, Mar. 1993 pp. 30-33) and exhibit unusually low cπtical micelle concentration values and higher pC-20 values together with supeπor surface active - 12 - characteπstics.

Examples of suitable anionic gemini surfactants useful in the compositions

of the present invention are disclosed in United States Patent No. 5.643.864 to Li et al.,

and United States Patent No. 5,710, 121 to Tracy et al., both of which are incorporated

herein by reference. Examples of suitable nonionic gemini surfactants useful in the

compositions of the present invention are disclosed in United States Patent Nos.

5,846,926; 5,81 1,384 and 5,863,886 all to Tracy et al. which are also incorporated herein

by reference. Examples of suitable catiomc gemini surfactants useful in the compositions

of the present invention are disclosed m United States Patent No. 5,643,498 to Li et al.

while examples of suitable amphoteπc gemini surfactants useful in the compositions of the

present invention may be found m United States Patent Nos. 5,656,586 to Li et al.,

5,789,371 to Tracy et al. and 5,846,923 to Riererson et al, all of which are incorporated

herein by reference.

The surfactant or surfactant blend component is incorporated into said

cleaning compositions in an amount of from about 5 0 wt. % - 80.0 wt. % and preferable

from about 20 wt. % to 50 wt. % based upon the total weight of the cleaning composition.

Any of the commonly used auxil ary additives such as inorganic salts such

as Glauber salt and common salt, builders such as tetrapotassium pyrophosphate.

humectants. solubilizing agents, deflocculating agents such as sodium tπpolyphasphate.

UV absorbers, softeners, whitening agents such as distyryl biphenyl deπvates (TruopaKS-

cyanuπc chloπde/diaminostilbene deπvatives. chelating agents such as tetrasodium

ethylene diamine tetracetic acid (NaEDTA), solvents, water and oils for pre-spotting stick

applicators and cellulosic substrates for fabπc softener dryer sheets. Viscosity modifiers - 13 - may also be added to the surfactants of the invention or blends thereof with other

surfactants as disclosed herein.

When prepared as carpet cleaner formulations, the cleaning compositions of the present invention also include a number of other components which can be tailored for

the specific application. Generally, the cleaner will compπse an additional salt such as

citπc acid salts, bone acid salts, alkali metal carbonates, aminopolycarboxylic acid salts,

an absorbent such as cellulose, zeolite or amorphous silica. All the components are

incorporated an amount of from about 5.0 wt. % to about 30 wt. % and preferably 4.0-

10 wt. % based on the total weight of the composition.

Laundry bar soaps are pπmaπly used in third-world countnes and those

poorer countnes where clothes washers and dryers are a luxury and a ranty. The laundry

bar soaps are used to scrub the clothes and physically beat and pull the dirt out of the

soiled fabπc. Apart from the sulfonated copolyester soil release copolymer, the surfactant

blend and excφients additives the laundry bar soaps may also contain fabπc softeners,

enzymes, color bπghteners, antimicrobial agent, dispersants, bleach or other oxidizing agents. Long chain fatty acid sulfonates may also be employed.

The compositions of the present invention may also be incorporated in automatic clothes dryer sheets to impact desireable tactile and anti-static properties to the clothes as well as giving additional soil release properties. See United States Patent No. 4,849.257 to

Barcher et. al. which is hereby incorporated by reference. The soil release polymer is

incorporated in the sheets in an amount of from about 0.5 wt. % to about 50 wt. % as well as from 0.5 wt. % to 50 wt. % of a catiomc fabnc softener. A deflocculant and viscosity

adjuster are also preferably added to the sheets compπsing a non-woven fabπc substrate, - 14 - see U S. Patent Nos. 4,237,155 to ardouche and 4.103.047 to Zaki et. al which are also

incorporated by reference

Fabπc conditioner sheets may also incorporate the soil release polymer

compositions of the present invention for imparting additional protection to the garments

while drying them. The fabπc soil release components are combined with a fabπc softener

and a dispersing aid to be released from the sheet when exposed to heat generated duπng a

clothes drying cycle. Suitable fabπc softening agents include disteryl dimethyl ammonium

methylsulfate, ditallowalkyl dimethyl ammonium methyl sulfate, dibehenyldimethyl

ammonium methyl sulfate and dipalmityl dimethylammonium methyl sulfate. More

specifically, the fabnc softening sheets are prepared from a non-woven absorbant fabπc

substrate in which the soil release polymer, dispersing aid, fabnc softener and viscosity

control agent are imbedded. Suitable heat activated laundry dryer fabnc softener sheets

for the incorporation of the cleaning compound in the present invention and methods for

their preparation are fully set forth m U.S. Patent No. 4,849,257 to Borcher et. al which is

hereby incorporated by reference. The following examples are provided to more specifically set forth and define

particular formulations of the present invention that exhibit supenor claiming and soil removing attributes. They are presented for illustrative purposes only, and it is recognized

that minor changes and modifications can be made with regards to the components or

amounts that are not contemplated herein. To the extent any such changes do not

matenally alter the final product or its properties it is to be understood that any such differences are encompassed within the spint and scope of the invention as recited in the

subsequent claims that follow 15

Example 1

A standard rug and upholstery shampoo composition was prepared using

the following ingredients in their respective weight percentage (wt %) amounts.

WEIGHT %

1 ) Sulphonated Copolyester Soil Release Polymer 2.0

2) Alkyl Sulfate Anionic Surfactant¹ 7 0

3) Disodium lauramide anionic surfactant² 15.0

4) Sodium Tπpolyphosphate (deflocculating agent) 2.0

5) Ethyl Carbitol (Solvent) 1.5

6) Cyanuπc Chloπde Diaminostilbene Disulfomc Acid³ 0.05

7) Water Q.S. to 100%

Mix all the ingredients and stir for approximately thirty (30) minutes until a clear,

homogenous solution is formed. The rug shampoo exhibited the following physical

properties.

PHYSICAL PROPERTIES

APPEARANCE CLEAR, WATER- WHITE LIQUID

pH 10.2

SOLIDS 9.5

SPECIFIC GRAVITY 1.0

VISCOSITY 100 CPS MAX. -16-

Example 2

A laundry bar soap was prepared from the following components in their respective weight percentage (wt%) amounts.

Weight % 1 Sulfonated Copolyester Polymer 0.4

2. Sodium Tπpolyphosphate 14.0

3. Dodecyl Benzene Sulfomc Acid 25.0

4. Sodium Sulfate 36.0

5. Sodium Carbonate 17.2

6. Water 7.4

The laundry bar soap compnsing the above listed ingredients was compared

in terms of cleaning efficacy performance to a known conventional bar soap that did not contain the soil release polymer. Specifically, they were tested in their ability to release oily stains from synthetic fabrics namely, dacron single knit (DSK), dacron double knit

(DDK) and a dacron /cotton blend (DCB). The fabπcs were first pre-washed,

stained and then washed with the laundry bar composition. Two stains were applied to the fabπc; one a melted lard and violet dye mix and the other being lipstick . Each stain was applied evenly within a 3.0 cm diameter circle. The stains were allowed to set overnight

for approximately sixteen hours in each instance. The reflectance (Rd) of each stain (1-3)

on the fabπcs was measured using a Gardner reflectometer and the soil release

performance was calculated using the formula : Soil release % = Rd3 - Rd2 \ 100 % Rdl - Rd2

The results obtained are recorded in the following Tables I - III

Table I

Detergent Bars: Test Method Development Initial screening

Washing Conditions:

Tap water

Temp; approx. 70° F

Hand washing, 15 sec. Scrub each side Stain: liquefied lard/violet dye

6 DSK cloth avg.

Table II

Detergent Bar Test Method Development Duplication of results

Washing Conditions:

Tap Water Temp; approx. 70 °F Hand washing, 15 sec. Scrub each side Stain: liquefied lard/violet dye 18-

6 DSK cloth avg.

Table III

Detergent Bars: Soil removal with lower soil release polymer concentration in bar (0.25% active) vs. control (no SRP)

Washing Conditions: Tap water Temp; 70° F Pre-wash: Scrub each side 15 sec. Final wash : 15 sec. each side for Soil Release Polymer treated and control set # l

A second control set had a 2 min. final wash in order to try and remove the soil.

Stain : liquefied lard/violet dye

6 DSK cloth avg.

Clearly, the bar soaps containing the soil release polymer exhibited superior results. -19- Example 3

A carpet extraction cleaner was prepared using the following components in their respective weight percentage (wt.%) amounts

WEIGHT %

1. Sulphonated Copolyester Polymer 2.0

2. Sodium Amphocarboxylate Amphoteπc Surfactant¹ 2.0 3 Linear Alcohol Ethyleneoxide/Proplylene Oxide Nomonic Surfactant² 2.0 4 Sodium Polymethylacrylate Anionic Polymer³ 2.0

5. Glycol Monoether 3.0

6. Tetrapotassium Pyrophosphate 4.0 7 Fragrance/Optical Whitener 1.0 8. Water Q.S. to 100

In order to prepare the cleaner, all the above ingredients were blended together in their respective amounts and mixed until uniformly dispersed for about forty-five (45) minutes The cleaner had the following physical properties

JEM Cone. (Rhodia Inc ) ²Antrarox BL-225 (Rhodia. Inc ) ^JColloιd 226/35 (Rhodia) -20-

Phvsical Properties

APPEARANCE CLEAR, WATER- WHITE LIQUID

pH 11.3

SPECIFIC GRAVITY 1.01

VISCOSITY <1000 CPS

Example 4

A liquid steam carpet cleaner was prepared using the following ingredients in their respective weight percentage (wt%) amounts.

Weight %

1. Sulphonated Copolyester Polymer 5.0 2. Linar Alcohol Ethoxlyate Anionic Surfactant⁴ 4.0

3. Nonyl Phenol Aromatic Ethoxylate Nononic Surfactant- 1.0

4. Sodium Polymethacrylate Anionic Polymer⁶ 2.0

5. Sodium Metasilicate Builder (anhydrous) 7.5

6. Tetrapotassium Pyrophosphate Detergent Base 12.5 7. Water (with, optionally, fragrance and colorant) Q.S. to 100

⁴Rhodafac RA-600 (Rhodia, Inc.) ⁵Igepal co-710 (Rhodia, Inc.) ⁶Colloid 226/35 (Rhodia. Inc.) -21- The ca et cleaner was prepared by first dissolving the anhydrous sodium metasilicate in water. The surfactants and polymers were individually added slowly thereafter wnh constant agitation followed by the addition of the detergent base. The mixture was stirred until a umform consistency was achieved m about 30 minutes.

PHYSICAL PROPERTIES

APPEARANCE CLEAR LIQUID pH (as is) 12.8 VISCOSITY 10.0 CPS SPECIFIC GRAVITY 1.04

Example 5

A caφet shampoo with additional grease cutting functionality was prepared using the following components in their respective weight percentage (wt%) amounts.

Weight %

Sulphonated Copolyester Soil Release Polymer 1.0 Sodium Lauryl Sulfate Anionic Surfactant 10.0 Disodium Lauramide Anionic Surfactant⁸ 3.0 Tetrasodium Ethylenediamme Tetraacetic Acid (EDTA 38% sol.) 5.0

⁷Rhodapon SB-8208/S (Rhodia, Inc.) ⁸Gerapon SBL-203 (Rhodia, Inc.) -22-

5. Glycol Monoether⁹ 5.0

6. Fragrance, Colorants, Preservatives 1.0

7. Water Q.S. to 100%

To prepare the cleaner composition, the sodium lauryl sulfate anionic surfactant was first mixed with the water until fully dispersed. This was then followed by the addition of the tetrasodium EDTA and the disodium lauramide anionic surfactant. After stirπng for approximately thirty (30) minutes, and the system was uniform, the fragrance, dyes and glycol monoether are added. The cleaner exhibited the following properties.

PHYSICAL PROPERTIES

APPEARANCE CLEAR, WATER- WHITE LIQUID pH, (as is) 12.0 specific gravity 1.00 viscosity <10 CPS

Example 6

A carpet cleaner composition similar to that prepared in example 2 was prepared with 0.5 wt.% and 1 0 wt.% of the soil release polymer incorporated therein These were tested against the control detergent containing no soil release polymer using the mateπais and apparatus listed below in the following procedure

Nylon fiber light color carpet (off-white)

'Dowanol EB (Dow Corp., Midland, Mich.) -23- Stain Sources:

Dirty Motor Oil Red Lipstick Spaghetti Sauce Black Shoe Polish

Tea Coffee Analytical Balance Micro Pipette Applicator Sponge

White Paper Towels Timer

Vacuum Cleaner Steam Cleaner Professional Strength Steam Cleaning Concentrate

A. Carpet Preparation

The caφet was cleaned side to side and back and forth with professional strength steam cleaning concentrate diluted according to label directions (2oz gal), using the steam cleaner After drying, the caφet was cut into 4"x4" squares and marked on the underside to ensure all nap was going m the same direction to yield similar viewing characteπstics (least reflection) Caφet swatches were coded to indicate replicate and product. -24-

B. Staining /Cleaning

Two replicates were used for each of the above listed stains. Rdl was measured before swatches were stained. Oil stains were delivered using the micro-pipette, whereas waxy stams were weighed first on the application sponge, then stamped onto the caφet swatches. Oils were applied at a rate of 0.12±0.05g to each caφet swatch within a 2"x2" square template using a spatula. Waxes were applied at 0.15±0.05g weight rate. The stains were allowed to dry overnight before cleaning. Rd2 was measured. Following the directions on the commercial caφet cleaner label, the caφet swatches were blotted, 4 times for 5 seconds each time, using white absorbent paper towels.

Caφets were then treated with 4.0±0. lg of the appropπate caφet cleaning product from a distance of 4-6 inches. The cleaner compositions were allowed to sit for the time indicated per label directions, to allow the foam to penetrate into the stain. Using an absorbent dry paper towel, stains were cleaned using 5 strokes working from top of the stain through the center. The paper towel was rotated to yield a clean surface and 5 more strokes were completed working from the bottom of the stam through the center. Steps 5 through 7 were repeated 4 more times for each swatch for a total of 5 cleaning cycle treatments Caφets were allowed to dry and then vacuumed. The reflectance for stam 3 (Rd3) was measured and soil release performance was calculated as in example 2.

% Soil release = Rd2-Rd3 x 100% Rd2-Rdl

The following data was obtained with respect to the lipstick and dirty motor oil to stains. Both stams were tested separately, differences of 10% soil release or greater are visibly -25- identified.

Example 7

A laundry dry fabric softener sheet was prepared using the following components in

their respective percentage amounts. -26-

Weight %

Sulfonated Copolyester Soil Release Polymer 40.0 Ditallow dimethylarnmonium methyl sulfate 50.5 Bentonite Clay (viscosity adjuster) 3.0

4. Xylene Sulfonate (diffacculant) 12.0 5. Water 5.0

The components are mixed in their respective amounts and the liquid solution is applied to a flexible, non-woven fabric material comprised of cellulosic fibers that are bounded together with a binder resin. The mixture is subjected to high shear for a uniform molten nears which then is heated to about 75°C. Other suitable absorbant materials can be substituted as is known in the art such as rayon fibers, nylon fibers, etc. When added to the drying cycle, fabrics did not cling together, possessed no static charge and had a softer sheen and feel.

1. Repel-O-Tex® (Rhodia Inc; Cranbury NJ.)

Claims

-27- What is claimed is:

1. A cleaning compound useful in the preparation of caφet cleaners, anti-static, dryer sheets, fabπc softener dryer sheets, laundry bar soap and laundry additives compπsmg: a. a sulfonated copolyester soil release polymer; b one or more surfactants selected from the group consisting of anionic surfactants, nonionic surfactants, catiomc surfactants, amphoteπc surfactants and mixtures thereof; c one or more organic solvents; and d. water.

2. The cleaning composition of claim 1 wherein said sulfonated copolyester soil release polymer is represented by the structure: -[C(O)-Ar-C(O)-(CH₂CH₂O)_a]_b- wherem a is a number of from about 1-4 and b is an anion.

3. The cleaning composition of claim 2 wherein said anion is selected from the group consisting essentially of -SO₃ ^~PO, , and CO,

4 The cleaning composition of claim 3 wherein said anionic surfactant is selected from the group consisting essentially of fatty acid soaps, ether carboxy c acids and salts thereof, alkane sulfonate salts, -olefin sulfonate salts, sulfonate salts of higher fatty acid esters, higher alcohol sulfate ester salts, fatty alcohol phosphate ester salts, fatty alcohol ether phosphate ester salts, condensates of higher fatty acids and ammo acids, collagen hydrolysate deπvatives and mixtures thereof

5 The cleaning composition of claim 4 wherein said nomonic surfactant is selected from the group consisting essentially of fatty acid glyceπne esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyglyceπne fatty acid esters, higher alcohol ethylene oxide -28- adducts, single long chain polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene lanolin alcohol, poiyoxyethylene fatty acid esters, polyoxyethylene glycerine fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene castor oil or hardened castor oil derivatives, polyoxyethylene lanolin derivatives, polyoxyethylene fatty acid amides, polyoxyethylene alkyl amines, alkylpyrrolidones, glucamides, alkylpolyglucosides, mono- and diamides, alkylamine oxides and mixtures thereof.

6. The blend of surfactants of claim 5, wherein said cationic surfactant is selected from the group consisting of alkyltrimethylammonium salts, dialkyl dimethylammonium salts, alkyldimethylbenzylammonium salts, benzethonium chlorides, acylamino acid-type cationic surfactants and mixtures thereof.

7. The cleaning composition of claim 6 wherein said amphoteric surfactant is selected from the group consisting essentially of amino acids, betaine, sultiane, phosphobetaines, imidazoline type amphoteric surfactants, soybean phospholipid, yolk lecithin and mixtures thereof.

8. The cleaning composition of claim 7 wherein said solvent is selected from the group consisting of ethanol, protic solvents, non-protic solvents and mixtures thereof.

9. The cleaning composition of claim 8 wherein said sulfonated copolyester soil release polymer is incoφorated into said cleaning composition in an amount of from about .01 wt% to about 20 wt% based on the total weight of the cleaning compositon.

10. The cleaning composition of claim 9 wherein said one or more surfactants are incoφorated in to said cleaning composition in an amount of from about 2.0 wt.% to about 80 wt.% based on the total weight of the cleaning composition. -29-

11. The cleaning composition of claim 10 wherein said one or more surfactants are incoφorated into said cleamng composition in an amount of from about 20 wt.% to about 50 wt.%) based on the total weight of the cleaning composition.

12. The cleaning composition of claim 11 further composing builders, deflocculating agents, whitening agents, anti-redeposition agents, perfumes and mixtures thereof.

13. A cleaning composition useful in the preparation of caφet cleaners, anti-static dryer sheets, fabnic softener dryer sheets and laundry bar soaps comprising: a. a sulfonated copolyester soil release polymer; b. one or more surfactants selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteπc surfactants and mixtures thereof; c. one or more secondary surfactants selected from the group consisting of gemini surfactants; d. one or more organic solvents; and e. water

14. The cleaning composition of claim 13 wherein said sulfonated copolyester soil release polymer is represented by the structure:

[C(O)-Ar-C(O)-(CH₂CH₂O)J_b wherein a is a number of from about 1-4 and b is an anion 15 The cleaning composition of claim 14 wherein said anion is selected from the group consisting essentially of -SO₃ ^~PO₃ , and CO₃

16. The cleaning composition of claim 15 wherein said anionic surfactant is selected from the group consisting essentially of fatty acid soaps, ether carboxylic acids and salts thereof, alkane sulfonate salts, α-olefin sulfonate salts, sulfonate salts of higher fatty -30- acid esters, higher alcohol sulfate ester salts, fatty alcohol phosphate ester salts, fatty alcohol ether phosphate ester salts, condensates of higher fatty acids and ammo acids, collagen hydrolysate denvatives and mixtures thereof.

17. The cleaning composition of claim 16 wherein said nonionic surfactant is selected from the group consisting essentially of fatty acid glyceπne esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyglyceπne fatty acid esters, higher alcohol ethylene oxide adducts, single long chain polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene lanolin alcohol, polyoxyethylene fatty acid esters, polyoxyethylene glyceπne fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene castor oil or hardened castor oil deπvatives, polyoxyethylene lanolin deπvatives, polyoxyethylene fatty acid amides, polyoxyethylene alkyl amines, alkylpyrrolidones, glucamides, alkylpolyglucosides, mono- and diamides, alkylamine oxides and mixtures thereof.

18. The blend of surfactants of claim 17, wherein said cationic surfactant is selected from the group consisting of alkyltπmethylammonium salts, diakyldimethylammonium salts, alkydimethylbenzylammonium salts, benzethonium chloπdes, acylammo acid-type catiomc surfactants and mixtures thereof

19 The cleaning composition of claim 18 wherein said amphoteπc surfactant is selected from the group consisting essentially of ammo acids, betaines, sultaines, phospho- betaines, lmidazohne-type amphoteπc surfactants, soybean phospho pid, yolk lecithin and mixtures thereof

20 The cleaning composition of claim 19 wherein said gemini surfactant is selected from the group consisting of nonionic gemini surfactants, anionic gemini surfactants, cationic gemini surfactants, amphoteπc gemini surfactants and mixtures thereof -31-

21. The cleaning composition of claim 20 wherein said solvent is selected from the group consisting of ethanol, protic solvents, non-protic solvents and mixtures thereof.

22. The cleaning composition of claim 21 wherein said gemini surfactant is selected from the group consisting of anionic gemini surfactants, nonionic gemini surfactants, cationic gemini surfactants, amphoteric gemini surfactants and mixtures thereof.

23. The cleaning composition of claim 22 wherein said sulfonated copolyester soil release polymer is incoφorated into said cleaning composition in an amount of from about 20 wt% to about 40 wt% based on the total weight of the cleaning compositon.

24. The cleaning composition of claim 23 wherein said one or more surfactants are incoφorated in to said cleaning composition in an amount of from about 20 wt.% to about

40 wt.% based on the total weight of the cleaning composition.

25. The cleaning composition of claim 24 wherein said one or more surfactants are incoφorated into said cleaning composition in an amount of from about 20 wt. % to about 40 wt. % based on the total weight of the cleaning composition.

26. The cleaning composition of claim 25 further comprising builders, deflocculating agents, whitening agents, anti-redeposition agents, perfumes and mixtures thereof.