WO1997034971A1

WO1997034971A1 - Surfactant blend for non-solvent hard surface cleaning

Info

Publication number: WO1997034971A1
Application number: PCT/US1997/002976
Authority: WO
Inventors: Stephen F. Gross
Original assignee: Henkel Corporation
Priority date: 1996-03-18
Filing date: 1997-03-05
Publication date: 1997-09-25
Also published as: AU2057197A; BR9708073A; US5770549A; CA2249424A1

Abstract

A cleaning composition containing: (a) from about 3 to about 67 % by weight of a sugar surfactant; and (b) from about 1 to about 3 % by weight of a C6-C12 linear alcohol ethoxylate, all weights being based on the weight of the concentrate.

Description

SURFACTANT BLEND FOR NON-SOLVENT HARD SURFACE CLEANING

Field of the Invention:

The present invention generally relates to a novel hard surface cleaner.

More particularly, the present invention relates to a non-solvent degreasing

composition use for removing oils and grease from hard surfaces.

Background of the Invention:

US-PS 3,663,445 relates to liquid, storable concentrates consisting of 6

to 45% by weight of a nonionic surfactant, for example a fatty alcohol ethoxylate,

4 to 33% by weight of an ethanolamine salt of a fatty acid, 2 to 90% by weight

of an ethanolamine and 0 to 50% by weight water and to cleaning and

degreasing preparations, more particularly for metallic surfaces, which are

obtained from the concentrates by dilution with water.

AT-PS 308 936 relates to liquid, storable concentrates consisting of at

least 5% by weight of a nonionic surfactant, for example a fatty alcohol ethoxylate, at least 3% by weight of a saturated or unsaturated fatty acid con¬

taining 8 to 22 carbon atoms in the molecule, at least 4.5% by weight of one or

more alkanolamines and typical additives, such as complexing agents, and water

and to cleaning and degreasing preparations obtainable from the concentrates

by dilution with water.

GB-PS 1,321,513 relates to a process for cleaning metal surfaces using

two cleaning baths applied one after the other, namely a precleaning bath and

a degreasing bath. The precleaning bath consists of at least 5% by weight of a

nonionic surfactant containing 3 to 5 mol ethylene oxide, at least 3% by weight

of a fatty acid and/or an alkyl polyethylene oxide carboxylic acid, at least 1.5%

by weight of an alkanolamine and/or oxazine and, for the rest, of water. The

degreasing bath consists of an inorganic or organic alkaline substance, for

example potassium hydroxide, potassium carbonate, potassium orthophosphate,

potassium pyrophosphate, potassium borate, alkanolamine, preferably mono-,

di- or triethanolamine, morpholine, and a complexing agent, a low-foaming

surfactant, for example a condensation product of fatty acids with 3 to 5 mol

ethylene oxide, and other additives and, for the rest, of water.

AT-PS 299421 relates to a water-based liquid detergent for dishwashing

machines containing 2 to 6% by weight of a nonionic surfactant, 15 to 25% by

weight of an organic sequestrant, 7 to 15% by weight of a hydrotropic substance,

3 to 15% by weight of an ethanolamine and 0.1 to 0.6% of a corrosion inhibitor.

DE-OS 25 05 252 relates to a process for the industrial cleaning and

degreasing of articles, more particularly of metals, by treatment of the articles with a solventless aqueous solution containing an organic sequestrant and a

hydrotropic substance, characterized in that the aqueous solution used contains

0.1 to 20% by weight of an organic hydrotropic electrolyte in the form of

benzenesulfonates, lower alkylbenzenesulfonat.es, di-(lower alkyl)-benzene-

sulfonates or mixtures thereof and 0.1 to 25% by weight of an organic

sequestrant in the form of aminopolycarboxylic acids or aminopolyphosphonic

acids or salts or mixtures thereof, the ratio by weight of the electrolyte to the

sequestrant being 2:1 to 1 :3 and the pH value ofthe solution being in the range

from 9 to 13.

US-PS 4,321 ,166 relates to liquid cleaning preparations containing 20 to

70% by weight of a surfactant, for example a fatty alcohol ethoxylate, 0.85 to 2%

by weight of a corrosion inhibitor system consisting essentially of a mixture of an

oligomeric olefinic fatty acid and an aromatic triazole and 1 to 75% by weight

water.

DE-OS 35 30 623 relates to emulsifying cleaning preparations with a

surface moisturizing effect which contain builders/complexing agents in a

quantity of 0.5 to 10% by weight, one or more alkanolamine(s) in a quantity of

20 to 60% by weight, one or more nonionic surfactant(s) in a quantity of 1 to 15%

by weight and, for the rest, water. These cleaning preparations and

corresponding cleaning compositions are suitable for the cleaning and

degreasing of painted and unpainted vehicle surfaces, engines, floors and walls

of workshops, etc., even at room temperature, with demulsification of the oily or greasy soil removed. However, the emulsifying effect of these known cleaning preparations

does not satisfy present-day requirements. In other words, their emulsification

of the oil-containing soil removed and the resulting, subsequent separation of oil

are not sufficient to reduce the residual oil contents in the wastewater to the low

levels required today.

By contrast, the problem addressed by the present invention was to

provide a degreasing composition for the cleaning of hard surfaces soiled with

oil (whether polar or nonpolar) which would have a better emulsifying effect and

also a better cleaning effect than known cleaning preparations. In addition, the

demulsifying effect of the cleaning preparations would result in improved oil

removal and hence in lower residual oil contents in the wastewater.

Moreover, known degreasing compositions typically employ solvents,

harmful to the environment, which act as carriers for the surfactants contained

therein. The surfactant blend of the present invention, on the other hand, does

not require the use of a solvent, thereby imparting a significantly enhanced

ecotoxicological profile onto its degreasing compositions.

Summary of the Invention:

The present invention is thus directed to a degreasing composition and

process for removing oils and grease from hard surfaces. The degreasing composition contains a mixture of (a) from about 3 to about 67% by weight of a

sugar surfactant selected from the group consisting of alkyl polyglycosides and

polyhydroxy fatty acid amides, (b) from about 1 to about 33% by weight of a C₆- C₁₂ linear alcohol ethoxylate, and (c) up to about 96% by weight of water, all

weights being based on the weight of the composition.

There is also provided a process for removing oils and grease from hard

surfaces involving contacting the hard surfaces with the above-disclosed

degreasing composition.

Description of the Invention:

Other than in the operating examples, or where otherwise indicated, all

numbers expressing quantities of ingredients or reaction conditions used herein

are to be understood as being modified in all instances by the term "about".

The sugar surfactants which may be employed in the degreasing

composition of the present invention include alkyl polyglycosides and

polyhydroxy fatty acid amides. The alkyl polyglycosides which can be used in

the compositions according to the invention have the formula I

R.O^OyZ)- I

wherein R is a monovalent organic radical having from about 6 to about 30

carbon atoms; R₂ is divalent alkylene radical having from 2 to 4 carbon atoms;

Z is a saccharide residue having 5 or 6 carbon atoms; b is a number having a

value from 0 to about 12; a is a number having a value from 1 to about 6.

Preferred alkyl polyglycosides which can be used in the compositions according

to the invention have the formula I wherein Z is a glucose residue and b is zero.

Such alkyl polyglycosides are commercially available, for example, as APG®,

GLUCOPON®, or PLANTAREN® surfactants from Henkel Corporation, Ambler, PA., 19002. Examples of such surfactants include but are not limited to:

1. APG® 225 Surfactant - an alkyl polyglycoside in which the alkyl group

contains 8 to 10 carbon atoms and having an average degree of polymerization

of 1.7.

5 2. GLUCOPON® 425 Surfactant - an alkyl polyglycoside in which the alkyl group

contains 8 to 16 carbon atoms and having an average degree of polymerization

of 1.48.

3. GLUCOPON® 625 Surfactant - an alkyl polyglycoside in which the alkyl

groups contains 12 to 16 carbon atoms and having an average degree of

o polymerization of 1.6.

4. APG® 325 Surfactant - an alkyl polyglycoside in which the alkyl groups

contains 9 to 11 carbon atoms and having an average degree of polymerization

of 1.5.

5. GLUCOPON® 600 Surfactant - an alkyl polyglycoside in which the alkyl

5 groups contains 12 to 16 carbon atoms and having an average degree of

polymerization of 1.4.

6. PLANTAREN® 2000 Surfactant - a C^e alkyl polyglycoside in which the alkyl

group contains 8 to 16 carbon atoms and having an average degree of

polymerization of 1.4. 0 7. PLANTAREN® 1300 Surfactant - a C₁₂.₁₆ alkyl polyglycoside in which the alkyl

groups contains 12 to 16 carbon atoms and having an average degree of

polymerization of 1.6.

Other examples include alkyl polyglycoside surfactant compositions which are comprised of mixtures of compounds of formula I wherein Z represents a

moiety derived from a reducing saccharide containing 5 or 6 carbon atoms; a is

a number having a value from 1 to about 6; b is zero; and R, is an alkyl radical

having from 8 to 20 carbon atoms. The compositions are characterized in that

they have increased surfactant properties and an HLB in the range of about -10

to about 16 and a non-Flory distribution of glycosides, which is comprised of a

mixture of an alkyl monoglycoside and a mixture of alkyl polyglycosides having

varying degrees of polymerization of 2 and higher in progressively decreasing

amounts, in which the amount by weight of polyglycoside having a degree of

polymerization of 2, or mixtures thereof with the polyglycoside having a degree

of polymerization of 3, predominate in relation to the amount of monoglycoside,

said composition having an average degree of polymerization of about 1.8 to about 3. Such compositions, also known as peaked alkyl polyglycosides, can be

prepared by separation of the monoglycoside from the original reaction mixture

of alkyl monoglycoside and alkyl polyglycosides after removal of the alcohol. This

separation may be carried out by molecular distillation and normally results in the removal of about 70-95% by weight of the alkyl monoglycosides. After removal

of the alkyl monoglycosides, the relative distribution of the various components,

mono- and poly-glycosides, in the resulting product changes and the

concentration in the product of the polyglycosides relative to the monoglycoside

increases as well as the concentration of individual polyglycosides to the total,

i.e. DP2 and DP3 fractions in relation to the sum of all DP fractions. Such

compositions are disclosed in U.S. patent 5,266,690, the entire contents of which are incorporated herein by reference.

Other alkyl polyglycosides which can be used in the compositions

according to the invention are those in which the alkyl moiety contains from 6 to

18 carbon atoms and the average carbon chain length ofthe composition is from

about 9 to about 14 comprising a mixture of two or more of at least binary

components of alkylpolyglycosides, wherein each binary component is present

in the mixture in relation to its average carbon chain length in an amount

effective to provide the surfactant composition with the average carbon chain

length of about 9 to about 14 and wherein at least one, or both binary

components, comprise a Flory distribution of polyglycosides derived from an

acid-catalyzed reaction of an alcohol containing 6-20 carbon atoms and a

suitable saccharide from which excess alcohol has been separated.

The polyhydroxy fatty acid amides which can be used in the compositions

and processes according to the invention are compounds of the formula II:

O R_

R,-C-N-Y ( I I )

wherein: R., is H, 0,-0₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a

mixture thereof, preferably 0,-0₄ a.kyl, more preferably C, or C₂ alkyl, most

preferably C, alkyl (i.e., methyl); and R₂ is a C₅-C₃₁ hydrocarbyl moiety,

preferably straight chain C₇-C₁₉ alkyl or alkenyl, more preferably straight chain C₉-C₁₇ alkyl or alkenyl, most preferably straight chain C_{ι r}C₁₉ alkyl or alkenyl, or

mixture thereof; and Y is a polyhydroxyhydrocarbyl moiety having a linear

hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an

alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Y

5 preferably will be derived from a reducing sugar in a reductive amination

reaction; more preferably Y is a glycityl moiety. Suitable reducing sugars include

glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw

materials, high dextrose corn syrup, high fructose corn syrup, and high maltose

corn syrup can be utilized as well as the individual sugars listed above. These

l o corn syrups may yield a mix of sugar components for Y. It should be understood

that it is by no means intended to exclude other suitable raw materials. Y preferably will be selected from the group consisting of -CH₂-(CHOH) _n -CH₂OH,

-CH(CH₂OH)-(CHOH) _n-1 -CH₂OH,

-CH₂-(CHOH)₂(CHOR')(CHOH)-CH₂OH, where n is an integer from 3 to 5,

15 inclusive, and R' is H or a cyclic mono- or poly- saccharide, and alkoxylated

derivatives thereof. Most preferred are glycityls wherein n is 4, particularly

-CH₂-(CHOH)₄-CH₂OH. Compounds of the formula I are also known as

glucamides. Therefore, when, for example, R, is methyl, R₂ dodecyl; and Y is

-CH₂-(CHOH)₄-CH₂OH, the compound in question is referred to as dodecyl N-

20 methylglucamide.

Methods for making polyhydroxy fatty acid amides are known in the art.

In general, polyhydroxy fatty acid amides can be made by reductively aminating

a reducing sugar reacting with an alkyl amine to form a corresponding N-alkyl 10

polyhydroxyamine and then reacting the N-alkyl polyhydroxyamine with a fatty

aliphatic ester or triglyceride to form the N-alkyl, polyhydroxy fatty acid amide.

Processes for making polyhydroxy fatty acid amides are disclosed in U.S. patent

numbers 1 ,985,424; 2,965,576; 5,194,639; and 5,334,764 the entire contents of

each of which is incorporated herein by reference.

In a particularly preferred embodiment of the present invention the sugar surfactant employed is an alkyl polyglycoside of formula I wherein R, is an alkyl

group having from 8 to 16 carbon atoms, b is zero, and a is a number having a

value of 1.48.

The linear alcohol ethoxylates which may be employed in the present

invention are generally the C₆-C₁₂ straight-chain alcohols which are ethoxylated

with from about 3 to about 6 moles of ethylene oxide. Their derivation is well

known in the art.

In a particularly preferred embodiment of the present invention, the linear

alcohol ethoxylate is preferably a straight-chain C₈-C₁₀ alcohol alkoxylated with

4.5 moles of ethylene oxide.

The cleaning composition is preferably formed by mixing from about 3 to

about 67% by weight, and most preferably from about 5 to about 30% by weight

of a sugar surfactant, with from about 1 to about 33% by weight, and most

preferably from about 2 to about 10% by weight of a linear alcohol ethoxylate,

all weights being based on the composition. The sugar surfactant thus

employed is preferably an alkyl polyglycoside of formula I wherein R is a C₈-C₁₆

alkyl group, b is zero, and a is 1.48. The linear alcohol ethoxylate is preferably a C₈-C₁₀ linear alcohol alkoxylated with about 4.5 moles of ethylene oxide.

It should be noted that the above-disclosed cleaning composition may, if

desired, be further diluted with up to about 96% by weight of water, based on the

weight of the cleaning composition. However, regardless of the amount of water

to dilute the cleaning composition of the invention, the critical formulation

parameter is that the cleaning composition contain the sugar surfactant and

linear alcohol ethoxylate in a percent active ratio of from 3:1 to 2:1 , respectively.

The cleaning composition may also include builders and auxilliaries

typically employed in such cleaning preparations. Examples of suitable builders

which may be used include, but are not limited to, TSPP, STPP, silicates and

citrates. Similarly, examples of suitable auxilliaries which may be used include,

but are not limited to, sodium hydroxide, potassium hydroxide, TEA and MEA.

The advantages associated with the use of cleaning compositions

according to the present invention are numerous, with the most obvious being

that it is a non-butyl cleaner. For example, the hydrotrope properties of the

sugar surfactant component enables more builders and surfactants to be

incorporated into the composition. Also, the present composition possesses

enhanced emulsification properties with respect to both polar and non-polar oils,

thereby imparting superior grease cutting properties to the composition, at

reduced formulation costs.

The present invention will be better understood from the examples which

follow, all of which are intended to be illustrative only and not meant to unduly

limit the scope ofthe invention. Unless otherwise indicated, percentages are on a weight-by-weight basis.

Example I

A cleaning composition in accordance with the present invention was

prepared having the following formulation.

Component %/wt

(a) GLUCOPON® 425-N (50% active) 4.0

(b) ALFONIC® 810-4.5 (100% active) 1.2

(c) water 94,8

100.0

^•GLUCOPON® 425-N is an alkyl polyglycoside having a monovalent

organic radical with from 8 to 16 carbon atoms, and an average degree of

polymerization of 1.48, commercially available from Henkel Corp., Ambler, PA.

*ALFONIC® 810-4.5 is C_8-10 linear alcohol alkoxylated with 4.5 moles of

ethylene oxide, commercially available from Vista Chemical.

Comparative Example I

Component %/wt.

(a) nonylphenol(9)EO (100% active) 2.0

(b) amine oxide¹ (50% active) 1.0

(c) quaternary² ammonium (75% active) 1.0

(d) water 96-0 100 100

¹=bishydroxyethylisodecyloxypropyl amine oxide

²=isodecyloxypropyl dihydroxyethyl methyl ammonium chloride

The cleaning compositions of Example I and Comparative Example I were

then tested to determine their cleaning efficiency per the following test method.

A test soil consisting of kerosene, mineral oil, motor oil, a 5:1 mixture of mineral

oil arbon black, and band black clay was applied onto the rough side of two

3"x3" vinyl tiles in equal amounts of 0.5ml. The tiles were then dried for 20

minutes at room temperature, for 20 minutes at 100°C, and then for an

additional 20 minutes at room temperature. The two tiles were then placed into

a Gardner Apparatus wash tray, with the grain parallel to the direction of sponge

travel. The two cleaning compositions were then individually added to the

separate trays in amount of 200ml and allowed to stand for 1 minute. The tiles

were then scrubbed with a synthetic sponge for 40 cycles, rotating the tiles 90°

after 20 cycles. The tiles were then rinsed with deionized water and dried at

room temperature for about 1 hour. The reflectance of the washed tiles was

measured and cleaning efficiency determined using the calculation % soil

removal = (R_w-R_s/R_u-R_s)x100, wherein R_w is reflectance of washed tile, R_s is

reflectance of soiled tile, and R_u is reflectance of unsoiled tile. The results are

found in Table I below. % SOIL REMOVAL

EXAMPLE 1 45.48

COMPARATIVE EXAMPLE 1 35.40

As can be seen from the data obtained, a cleaning composition utilizing

the cleaning concentrate of the present invention is significantly more effective at removing oils and greases from hard surfaces than other known concentrates.

Claims

What is claimed is:

1. A cleaning composition comprising:

(a) from about 3 to about 67% by weight of a sugar surfactant;

(b) from about 1 to about 33% by weight of a C₆-C₁₂ linear alcohol

ethoxylate; and

(c) up to about 96% by weight water, all weights being based on the

weight of the composition.

2. The composition of claim 1 wherein the sugar surfactant is selected from

the group consisting of alkyl polyglycosides having general formula I:

R₁O(R₂O)_b(Z)_a I wherein R, is a monovalent organic radical having from about 6 to about 30

Z is a saccharide residue having 5 or 6 carbon atoms; b is a number having a

value from 0 to about 12; a is a number having a value from 1 to about 6,

polyhydroxy fatty acid amides having general formula II:

O R,

II I

R₂-C-N-Y (II)

wherein R, is H, 0,-0₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, R₂ is a

C₅-C₃₁ hydrocarbyl moiety, and Y is a polyhydroxyhydrocarbyl moiety having a

linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain,

or an alkoxylated derivative, and mixtures thereof.

3. The composition of claim 2 wherein the sugar surfactant is an alkyl

polyglycoside of formula I and wherein R, is a monovalent organic radical having from 8 to 16 carbons, b is zero and a is a number having a value of 1.48.

4. The composition of claim 2 wherein the sugar surfactant is a polyhydroxy

fatty acid amide.

5. The composition of claim 4 wherein the polyhydroxy fatty acid amide is a

glucamide.

6. The composition of claim 1 wherein the linear alcohol ethoxylate is

alkoxylated with from about 3 to about 6 moles of ethylene oxide.

7. The composition of claim 1 wherein the linear alcohol ethoxylate is a C₈-

C₁₀ linear alcohol alkoxylated with 4.5 moles of ethylene oxide.

8. The composition of claim 1 wherein the sugar surfactant and linear

alcohol ethoxylate are present in the composition in a percent active ratio of from

about 3:1 to about 2:1 , respectively.

9. A process for removing oils and grease from a hard surface comprising

contacting the hard surface with a cleaning composition, the composition

containing:

(a) from about 3 to about 67% by weight of a sugar surfactant;

(b) from about 1 to about 33% by weight of a C₆-C₁₂ linear alcohol

ethoxylate; and

(c) up to about 96% by weight water, all weights being based on the

o weight of the composition.

10. The process of claim 9 wherein the sugar surfactant is selected from the

group consisting of alkyl polyglycosides having general formula I:

Z is a saccharide residue having 5 or 6 carbon atoms; b is a number having a

value from 0 to about 12; a is a number having a value from 1 to about 6,

polyhydroxy fatty acid amides having general formula II:

O R,

I I

R₂-C-N-Y (II)

wherein R, is H, C,-C₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, R₂ is a

or an alkoxylated derivative, and mixtures thereof.

11. The process of claim 10 wherein the sugar surfactant is an alkyl

polyglycoside of formula I and wherein R, is a monovalent organic radical having

from 8 to 16 carbons, b is zero and a is a number having a value of 1.48.

12. The process of claim 10 wherein the sugar surfactant is a polyhydroxy

fatty acid amide.

13. The process of claim 12 wherein the polyhydroxy fatty acid amide is a

glucamide.

14. The process of claim 9 wherein the linear alcohol ethoxylate is alkoxylated

with from about 3 to about 6 moles of ethylene oxide.

15. The process of claim 9 wherein the linear alcohol ethoxylate is a C₈-C₁₀

linear alcohol ethoxylated with 4.5 moles of ethylene oxide.

16. The process of claim 9 wherein the sugar surfactant and linear alcohol ethoxylate are present in the composition in a percent active ratio of from about

3:1 to about 2:1 , respectively.

17. A cleaning comprising:

(a) from about 5 to about 30% by weight of an alkyl polyglycoside of

formula I:

R,O(R₂O)_b(Z)_a I

wherein R, is a monovalent organic radical having from about 8 to about 16

carbon atoms; b is zero; a is a number having a value of 1.48;

(b) from about 2 to about 10% by weight of a C₈-C,₀ linear alcohol

ethoxylated with about 4.5 moles of ethylene oxide; and

(c) remainder water, all weights being based on the weight of the

composition.

18. The cleaning composition of claim 17 wherein the sugar surfactant and

linear alcohol ethoxylate are present in the composition in a percent active ratio

of from about 3: 1 to about 2:1 , respectively.