CA1301584C - Isotropic laundry detergents containing polymeric quaternary ammoniumsalts - Google Patents

Abstract

D.N. 7-5302/3A

ISOTROPIC LAUNDRY DETERGENTS CONTAINING
POLYMERIC QUATERNARY AMMONIUM SALTS

***********************

ABSTRACT OF THE DISCLOSURE
Stable, isotropic liquid laundry detergent and sanitizer com-positions comprising a polymeric linear quaternary ammonium salt, one or more nonionic surfactants and water. The polymeric linear ammonium salt is of the formula:

IA
(where R1 is lower alkyl, a is 4 to 20 and X- is halide) or of the for-mula:

IB
(where R2 is lower hydroxyalkyl, b is 27 to 57). The nonionic surfact-ants are polyethylene glycol alkyl ether, polyethylene glycol alkyl-phenyl ether,N-alkyl-N,N-dilower-alkylamine-N-oxide and alkyl poly-glycoside.

Description

D.N~ 7-5302/3A
~3~S~

ISOTROPIC LAUNDRY DETERGENTS CONTAINING
POLYMERIC QUATERNARY~A~MONIUM_SALT_ ***********************
BACKGROVND OF THE INVENTION
This invention relates to isotropic liquld laundry detergents containing polymeric quaternary ammonium salts in combination with one or more nonionic surfactants.

INFOE~MATION DISCLOSURE STATEMENT
Pera et al. U.S. Patent 3,771,98~ discloses poly-meric polyelectrolytes, useful as algicides, having the formula:

7H3 Cl CH3 Cl 2 H2 N C~12C~2 - N - CH2CH2- _ ~ CH3 CH3 ~ n where n is an integer from 4 to 40, with molecular weights ranging from 1,000 to 10,000, which are chemically desig-nated poly[oxyethylene(dimethyliminio)ethylene(dimethyl-iminio)ethylene dichloride]. As far as is presently known~ compounds of this class are not known to have useful bactericidal. properties nor are they known to be useful for incorporation in laundry de~ergents.
Creen et al. U.S. Patents 3,931,319; 4,001,432 and 4,012,44~ disclose so-called "capped" polymers useful as "microbiocidal" agents, which have linear polymeric quaternary chains terminated by quaternary'ammonium moieties, having the formula: I

NR~IIRIVRvCH~CH=CHCH2 ~NR'R''ZNR'R''-CH2CH=CHCH2~nNRIIIRI~R~ 2nX

~h D N. 7-5302/3A
~3~

where X is halide and "n is an integer from about ~
to about 30; where R' and R" may be either (1~ a primary or secondary alkyl radical having from 1 to 20 carbon atoms, (2) hydroxy or dihydroxy derivatives of R' and R"; (3) benzyl, or (4) benzyl containing at least one alkyl group . . ~; where Z consists of from one to three aliphatic divalent radicals, each of whic~ has 2 to 10 carbon atoms, each aliphatic radical cont~ining 0 to 2 double bonds and 0 to 2 hydroxy substituents" and where ~RIII, RIV and RV rnay be either (1~ primary or secondary alkyl containing from 1 to 20 carbon atoms, or (2) hydroxy~
ethyl ...."
Green et al. U.S. Patent 4,027,020 discloses so-called "randomly terminated" capped linear quaternary ammonium polymers generally similar to those described in U.S. Patents 3,931,31g; 4,001,432 and 4,012,446 above prepared by reaction of a 1,4-dihalo-2-butene, XCH2OEI=
CHCH2X, where X is halogen, with a mixture of a difunc~
tional tertiary amine:

R~I / RII
V N - Z - N~ I

and a monofunctional tertiary amine:

RIII N _ ~IV
lV

The compounds are said to be effective ayainst bacteria and algae and to a lesser extent against fungiO They D.N. 7-5302/3A
S~

are also stated to be non-foaming, a property which is said to be impor~ant in anti-microbial agents used in products and processes where the generation of foam is undesirable.
Green et al. U.S. Patent 4,091,113 discloses "ran-domly terminated" capped linear quaternary ammonium poly-mers prepared in the same manner as described in U.S.
Patent 4,027,020 ~e_a. The gua~ernaries are said to be "uniquely excellent hair conditionin~ agents" which are "compatible in binary or tertiary systems with most of the lathering and cleansing surfactants used in hair conditioning consumer products". The patentee states that 40~ aqueous solu~ions are non-irritating to the skin and that 4~ aqueous solutions are non-irritating to the eyes. More specifically, the quaternaries are described as being compatible with surfactants and emulsi-fiers of the cationic, nonionic, amine oxide, alkylol-amide, amphoteric, aminoacetic or ~-aminopropionic acid and betaine or betaine salt classes. The compositions are exemplified in Examples 28~ 29 and 30 by formulations containing the polymeric ~uaternary which is prod~ced by reaction of 1,4-bis-dimethylamino-2-butene, triethan-olamine and 1,4-dichloro-2-butene in water in combination with surfactants of the cationic ~AMMONYX 4, i.e. stearal-konium chloride -Example 30), nonionic (TERGITOL~ 15-S-12, i.e. pareth-15-12 - Example 29~, alkylolamide (ONYXOL~
42, i.e. stearyl diethanolamide - Example 30 and SUP~R
AMIDE~ GR, i.e. cocoyldiethanolamide - Example 28), ampho-ter iG ~MIRANOL~ C~-2M-SF, i.eO cocoamphocarboxypropionate and S~NDOPAN~ TFL, i.e. oleoamphopropylsulfonate -D~N. 7-5302/3A
S~

both Example 28) and anionic (MAP~OFIX~ Ç0S, i~e. sodium laureth sulfate - Example 28) classes. As far as is presently known the compounds of the structural type disclosed in U.S. Patents 3,931,319; 4,001,432; 4,012,446;

4,027,020 and 4,091,113 above are not known to have been previously incorporated in laundry detergents.
Smith et al. U.S. Patent 4,333,862 discloses, as one possible cationic surfactant in liquid detergent compositions containing an anionic, a cationic and a nonionic surfactant, polyammonium salts of the formula:

R3-W ~ ~C~l2)n-N ~ R4.2 R4 ~4 m where R3 is C8-C20 alkyl, alkenyl or aralkyl; each R4 is Cl-C4 alkyl or hydroxyalkyl; n is from 1 to 6;
and m is from 1 to 3.
SUMMARY OF THE INVENTION
As noted above, polymeric linear quaternary ammonium salts of the structural types represented by those dis-closed in U,S. Patents 3,771,989; 3,931,319; 4,001,432;
4r012,446; 4,027,020 and 4,091,113 are not known to have been incorporated in laundry detergents. We have dis-covered that polymeric quaternary ammonium salts of those classes, when formulated in an aqueous medium with one or more nonionic surfactants, provide stable, isotropic liquid laundry detergents and sanitizer compositions having good detergency and bactericidal properties, which, in addition, are moderately irritating to the eyes and practically non irritating to the skin~

D.N. 7-5302/3 ~ 3 ~ f~

Accordingly9 the invention resides in stable, isotropic liqu.id laundry detergent and sanitizer composi-tions comprising: tA) a polymeric linear quaternary ammo-nium salt selected from the group consisting of a poly[oxy-ethylene(di-lower-alkyliminio)ethylene(di-lower-alkyliminio)-ethylene dihalide~ and a polymeric quaternary ammonium halide corresponding to formula IB hereinbelow; (B) one or more nonionic surfactants selected from the group consisting of the polyethylene glycol long chain alkyl ether, polyethylene glycol alkylphenyl ether, N-alkyl--N,N-di-lower-alkylamine-N-oxide and alkyl polyglycoside classes; and (C) water.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
More specifically the isotropic liquid laundry detergent and sanitizer compositions of the invention comprise: (A) a polymeric linear quaternary ammonium salt selected from the group consisting of a poly[oxy-ethylene(di-lower-alkyliminio)ethylene(di-lower alkyl-iminio)ethylene dihalide] having the formula:

D.N. 7-53O2/3A
~3~S~

rC 11 11 ~+
2CH2 1 _ CH2CH2--N--CH2CM~ - 2X
L ~ 1 Rl _ a IA
where Rl is lower-alkyl having from vne to four carbon - atoms, a is an integer from ~ to 40,preferably wi~ an average value of 19, and X is halide, and a polymeric yuaternary ammonium halide having the formula:

(R2)3N-CH2CH=CHCH2 ~ - CH2CH=CHCH ~ N -~R233 (b+2)X

IB
where R2 is hydroxy-lower-alkyl having from two to four carbon atoms, b is an integer from 27 to 57 and R
and X have the meanings given above; tB) one or more nonionic surfactants selected from the group consisting of a polyethylene qlycol long chain alkyl ether having LS th~ formula:

R4~0CH2CH~ ) C~
IIA
where R4 is Cll-C15 alkyl and c is an integer from 5 to 15l a polyethylene glycol alkylphenyl ether having the formula:

D N. 7-5302/~
~3~

R5 ~ ocH2cH2)doH

IIB
where R5 is C8-Cg alkyl and d is an integer. from 7 to 13; an N-alkyl-N,N-di-lower-alkylamine-N-oxide havin~
the formula:

Rl C12-C18 Alkyl -N-~a IIC

where Rl has' the meaning given above and an alkyl poly-. glycoside; and (C) water.
The polymeric quaternary ammonium salts of for-mulas IA and IB used to prepare the compositions of the invention are well known classes of compounds. The poly-~oxyethylene(di-lower-alkyliminio~ethylene(di-lower-alkyl-iminio)ethylene dihalide~ quaternaries of formula IA
include, for example, poly[oxyethylene~dimethyliminio)-~thylene(dimethyliminio~ethylene dichloride] sold under the trade mark BUSAN~ 77 by Buckman Laboratories, Memphis, Tennessee as a 60~ actives solution in water and which is ident.ified as WSCP (water soluble cationic polymer).
The polymeric quaternary ammonium halides of for-mula IB include, for example, poly(dimethylbutenyl ammo-nium chloride)~ bis triethanolammonium chloride (as named by the manufacturer) sold under the tradem~rks ONYXSP~RSE~ 12S and ONAMER~ M by the Onyx Chemical D.N. 7-5302/3A

Companyr Jersey City, New Jersey, now owned by The Stepan Company, Northfield, Illinois. ONYXSPERSE~ and ONAMER~
are aqueous solutions of the salt each containing, respec-tively, 28.5~ and- 29~5% actives and 12~ and 1~ sodium chloride respectively.
The nonionic surfactants of formulas IIA, IIB
and IIC and the nonionic alkyl polyglycoside surfactants used in the practice of the present invention àre well known in commerce. Examples of the polyethylene glycol long chain alkyl ethers of formula IIA are sold under theUnion Carbide (D~nbury, Connecticut) trademark TERGITOL~
or the Shell Chemical Company (Houston, Texas) trade mark NEODOL~ and are identified by the CTFA adopted name, pareth. Suitable members of the group for the practice of the present invention are pareth-15-5, pareth-15-7, pareth-15-9, pareth-15-12, pareth-23-7, pareth-25-5, pareth-25-7, pareth-25-9, pareth-25-12, pare~h-45-7, pareth-45-11 and pareth~45-13, where ',the first given numbers 15, 23, 25 and 45 indicate R4 alkyl chain lengths from 11 to 15, 12 to 13, 12 to 15 and 14 to 15 carbon atoms, respectively, and the second given numbers 5, 7, 3, 11, 12 and 13 indicate the average number (c) of ethyleneoxy yroups.
The polyethylene glycol alkyl phenyl ethers of formula IIB are available, for example, under the Rohm and Haas (Philadelphia, Pennsylvania) trademarks TRITON~
X and TRITON~ N or the GAF Corporation (Wayne, New Jersey) trade marks IGEPAL~ CA and ~GEPAL~ CO and are identified by the CTE'A adopted names of octoxynols and nonoxynols.

D.N. 7-5302/3~
3L3(~
_ 9 These include, for example, octoxynol-7, octoxynol-10 and octoxynol-13, where R5 in formula IIs i~ C8 alkyl and d has an average value of 7, ~0 and 13, respectively, and nonoxynol-7, nonoxynol-8, nonoxynol-9 and nonoxynol-13, etc. where R5 in formula IIB is Cg alkyl, and d hasan average value of 7, 8, 9 and 13, respectively.
The alkylamine oxides of formula IIC are sold under the trade mark AMMONYX~ by the Onyx Chemical Som-pany (Jersey City, New Jersey) and include, for example, lauramine oxide, myristylamine oxide, palmitamine oxide and stearamine oxicle which are the CTFA adopted names for the compounds oE formula ~IC where Rl in each in-stance is methyl and the alkyl group has 12, 14, 16 and 18 carbon atoms respectively.
The nonionic alkyl polyglycoside surfactants are sold by Staley Industrial Products of the A. E. Staley Manufacturing Company (Decatur, Illinois) and include, for example, APG~23-3 which is a surfactant of the alkyl polyglycoside class having an aIkyl chain derived from a C12-C13 straight chain alcohol and an average of 3 glucose units in the polyglycoside moiety.
Although it is preferred in the practice of the present invention to include either one or the other of the polymeric quaternary ammonium salts represented by formulas IA and IB, it is also contemplated that mix-tures of salts of those two structural types can, if desired, be used in the liquid laundry detergent formula-tions of the invention.
The compositions of the invention contain from about 5.5 to about 20 weight percent of the polymeric quat-ernary ammonium salt of formulas IA or IB and from about D N. 7-5302/3 ~3~
~ 10 -5 to about 50 weight percent of the nonionic surfactant, all amounts being based on total weight of the composi-tion. Preferred ranges are from about 5 to about 10 weight percent of tlle polymeric quaternary salt and from about 5 to about 17 weight percent of the nonionic surfactant, and particularly preferred amounts are about 5.5 to about 6.5 weight percent of the polymeric quaternary salt and from about 7 to abou~ 12 weight percent of the nonionic surfactant.

The compositions may, in order to provide addi-tional benefits, optionally contain nonessential ingred-ients such as fragrances, dyes, pEI adjusters such as triethylamine" brighteners, solvents such as eth-anol, and thickeners. Generally fragrances may be used in amounts up to about 0.7 weight percent, dyes in amounts lS up to about 0.02 weight percent, pH adjusters in amounts up to about 4 weight percent, brighteners in amounts up to about 0.5 weight percent, ethanol in amounts up to about 7 weight percent, and thickeners in amounts up to about 2.0 weight percent.
The compositions are prepared by addition to water, with stirring and heating as necessaxy, of the nonionic surfactant(s), followed by alcohol if desired, followed by the polymeric quaternary ammonium salt, followed by the dyes, fragrances, brighteners, pH adjusters or thickeners, stirring being continued at each stage to effect completa solution or homogeneous dispersion.
The compositions of the inven~lon poBBe~ very good detergency and bactericidal properties and further-more have very low eye and skin irritancy. They are30 therefore particularly valuahle in household sanitizing D.N. 7-5302/3 ~3~

and cleaning operations where such properties are desir-able, such as in laundry detergents and hard surface cleaners.
The manner and process of making and using the invention~ and the best mode contemplated by the inven-tors for carrying out the invention, will now be described so as to enable any person skilled in the art to which it pertains to make and to use the same.
EXAMPLES
A number of formulation6, composed a8 indiaated in Table 1, each containing a quaternary ammoniu~ salt and at least one nonionic surfactant were prepared using the procedure described above.
Formulations ~-K, each containin~ a polymeric quaternary of formulas IA or IB and one or more nonionic surfactants of formulas IIA, IIB or IIC or an alkyl poly-glycoside, are formulated in accordance with the inven-tion as described above and are within the ambit of the invention, whereas formulations L-O, each containing a monomeric quaternary halide, i.e. CYNCAL~ 80, and a nonionic surfactant, were prepared for comparative pur-poses and are outside the scope of the invention.

D.N. 7-5302/3 o Zl ~ ~

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a~ ~ r~ ~ ~ ,1 o ~ a 1~ W al ~ o o - ~ h ~; æ ~ o o O m c~

D.N. 7-5302/3 :~l3C} ~

The formulations of the invention and the compar-ative formulations were tested for cleaning efficacy using the standard EMPA and Krefeld detergency tests;
for germicidal activity against K. pneumoniae ATCC 4352 and S. aureus ATCC 6538 using the EPA-approved Petrocci-Clark test procedure ~Proposed Test Method for Antimicro-bial Laundry Additives, Petrocci and Clark, J. ~ss.
Offic. Anal. Chem. 52(43, 836-842 (1969)1 which is a simu-lated in-use test method (see EP~ Publication DIS/TSS-13, May 2, 1979); for eye irritation in rabbits using the standard FIFRA method (described at 40 C F.R. 163.81-4); and for skin irritation using the standard FIFRA
dermal irrita$ion test in rabbits (NAS 1138 modification described at 40 C.F.R. 163~81-5).
The EMPA and Krefeld detergency tests used in the present study are described in U.S. Patent 4,576,729 except that the temperature of the wash and rinse water was 1~5~F instead of 120-130F. In the EMPA test (a test by the Swiss Federal Testing Station in Switzerland), the standard soil is an India ink and olive oil emollient (an oily type soil~, and in the Krefeld test (a test by the Wascherei Forschungs Institute of Krefeld, West Germany), the soil is 84~ clay~ 8% lamp black, 4% black iron oxide and 2% yellow iron oxide oversprayed with a solution of 3.4~ lanolin dissolved in carbon tetra-chloride and salt solution (the salt ~o r~semble human perspiration). The cleaning efficacy, expressed as g Soil Removal, was calculated in each test,procedure for the test swatches as follows, the values obtained for 30 any given detergent formulation being the average of the individual values so determined:

D.N. 7-530~/3 ~L3~

% Soil Removal - w s x 100 R - R

where:
Rw ~ Average reflectance of washed soiled cloths Rs = Average reflectance of unwashed soiled cloths RQ = Averaye reflectance of unsoiled cloths before washing Thu~ the higher the value for % Soil Removal, the greater the detergency.
In the germicidal activity test, EPA protocols require a germ reduction of at least 99.90~ for laundry sanitizers against the two test organisms, R. E~eumoniae and S. aureu~.
Eye irritation results are expressed in terms of Draize scores in accordance with the standard FIFRA
method.
Skin irritation scores are expressed in terms of Primary Irritation Index (P.I.I.) also in accordance with the standard FIFRA method. The lower the score thus obtained, the less irritating is the formulation.
The results obtained are set forth,in Tables 2, 3 and 4 where ~MPA and Krefeld detergency results are expressed in terms of soil removal values, the antimicro-bial activity is expressed in terms of percent ~erm reduc-tlon and antimicrobial effectiveness based on the above-noted EPA protocols, eye irritation is expressed in terms of Draize scores; and skin irrita~ion is expressed as PoI~I~ values.

n~No 7-5302/3 ~l3~

Table 2 (EMPA/Krefeld Detergency) Formulation EMPA Krefeld C 36.4 4~.6 L 27.Q 9.2 M 22.8 7.9.

Table 3 (Antimicrobial Activlty vs. K. pneumoniae and S. aureus) ..
Formulation , % Germ Reduction Sanitization Result A 99.9 , Ef~ective B 99.9 ~~ Effective C 99.9 Effective .L 99.9 Effective M 99.9 Efective N 99.9 Effective O 99.7 Not Effective Table 4 (Irritanc~ Scores) Eye Irritancy ~Highest mean Skin Irritancy Formulation Draize Score) (P.I.I.?
A 16.3 ~unwashed) 0.71 7.7 (washed) N 73 ~unwashed~ 2.78 58 (washed) D.N. 7-5302/3 ~3~ S~
- 16 ~

These results show that formulations A, C and D prepared in accordance w.ith the invention are markedly superior in detergency properties, 3S determined in both EMPA and Krefeld detergency tests, to any of comparative formulations L, M and N~ Formulations A, B and C are also shown to be equally or more effective,.in antimicro-bial activity to comparative formulations L, M, N and O, and Formulation A i5 shown to have lower eye and skin irritancy than comparative formulation N.
1~ The li~uid laundry detergent formulations of the invention are formulated as concentrates. In use khe concentra~e is added to the wash waker in such amounts as to provide good cleaning and sanitization. It has been found that about 1/2 cup (about 4 ounces) of concen-trate per wash load (or about 4 ounces per 16 gallons), which provides a use dilution of around 1:500, is ade-quate to achieve such purposes.

Claims (27)

1. A liquid laundry detergent and sanitizing composition comprising: (A) a polymeric linear quaternary ammonium salt selected from the group consisting of a compound having the formula:

IA
where R1 is lower-alkyl having from one to four carbon atoms, a is an integer from 4 to 40 and X? is halide, and a compound having the formula:

IB
where R2 is hydroxy-lower-alkyl having from two to four carbon atoms, b is an integer from 27 to 57 and Rl and X? have the meanings given above; (B) one or more nonionic surfactants selected from the group consisting of a compound having the formula:
R4?OCH2CH2)COH
IIA
where R4 is C11-C15 alkyl and c is an integer from 5 to 15, a compound having the formula:

D,N. 7-5302/3 IIB
where R5 is C8-C9 alkyl and d is an integer from 7 to 13, a compound having the formula:

IIC
where R1 has the meaning given above, and an alkyl poly-glycoside; and (C) water.

2. A composition according to Claim 1 wherein the quaternary ammonium salt is a compound of formula IA.

3. A composition according to Claim 1 wherein the quaternary ammonium salt is a compound of formula IB.

4. A composition according to Claim 2 containing from about 5.5 to about 20 weight percent of the quaternary ammonium salt and from about 5 to about 50 weight per-cent of the nonionic surfactant.

5. A composition according to Claim 3 containing from about 5.5 to about 20 weight percent of the quarternary ammonium salt and from about 5 to about 50 weight per-cent of the nonionic surfactant.

6. A composition according to Claim 4 containing one or more nonionic surfactants of formulas IIA, IIB
and IIC.

D.N, 7-5302/3

7. A composition according to Claim 5 containing one or more nonionic surfactants of formulas IIA, IIB
and IIC.

8. A composition according to Claim 6 containing a nonionic surfactant of formula IIA.

9. A composition according to Claim 6 containing a mixture of nonionic surfactants of formulas IIA and IIC.

10. A composition according to Claim 7 containing a nonionic surfactant of formula IIA.

11. A composition according to Claim 7 containing a mixture of nonionic surfactants of formulas IIA and IIC.

12. A composition according to Claim 8 containing from about 5.5 to about 10 weight percent of the quaternary ammonium salt and from about 5 to about 17 weight per-cent of the nonionic surfactant.

13. A composition according to Claim 9 containing from about 5.5 to about 10 weight percent of the quaternary ammonium salt and from about 5 to about 17 weight per-cent of the mixture of nonionic surfactants.

14. A composition according to Claim 10 contain-ing from about 5.5 to about 10 weight percent of the quat-ernary ammonium salt and from about 5 to about 17 weight percent of the nonionic surfactant.

15. A composition according to Claim 11 contain-ing from about 5.5 to about 10 weight percent of the quat-ernary ammonium salt and from about 5 to about 17 weight percent of the mixture of nonionic surfactants.

D.N. 7-5302

16. A composition according to Claim 12 contain-ing about 6 weight percent of poly[oxyethylene(dimethyl-iminio)ethylene(dimethyliminio)ethylene dichloride}
and about 12 weight percent of pareth-45-7.

17. A composition according to Claim 14 contain-ing about 6 weight percent of poly (dimethyl butenyl ammonium chloride)-.alpha.,.omega. -bis-triethanolammonium chloride and about 12 weight percent of pareth-45-7.

18. A composition according to Claim 16 which includes up to about 7 weight percent of elthanol.

19. A composition according to Claim 17 which includes up to about 7 weight percent of ethanol.

20. A method of sanitizing or cleaning clothes or hard surfaces, in which method it is expected that unprotected hands are exposed to and that uprotected eyes are accidentally exposed to an operation liq-uid, said method comprising treating the clothes or the hard surfaces with, as the operation liquid, a water dilution of the liquid compos-ition defined in claim 1.

21. A method according to claim 20, wherein the liquid composit-ion is as defined in claim 2 or 3.

22. A method according to claim 20, wherein the liquid composit-ion is as defined in claim 4 or 5.

23. A method according to claim 20, wherein the liquid composit-ion is as defined in claim 6 or 7.

24. A method according to claim 20, wherein the liquid composit-ion is as defined in claim 8 or 9.

25. A method according to claim 20, wherein the liquid composit-ion is as defined in claim 10 or 11.

26. A method according to claim 20, wherein the liquid composit-on is as defined in claim 12 or 13.

27. A method according to claim 20, wherein the liquid composit-ion is as defined in claim 14 or 15.