AU623852B2

AU623852B2 - Hard-surface cleaning compositions

Info

Publication number: AU623852B2
Application number: AU14193/88A
Authority: AU
Inventors: Stephen Culshaw; Eddy Vos
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1987-04-06
Filing date: 1988-04-06
Publication date: 1992-05-28
Anticipated expiration: 2008-04-06
Also published as: AU1419388A; EP0286167A2; MX170928B; EP0286167A3; CA1332217C; DK185888A; JPS6420295A; FI881587L; FI91539B; FI91539C; DK185888D0; FI881587A0

Description

Form COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 COMPLETE SPECIFIC I

(ORIGINAL)

Class Int. Class Application Number: Lodged: Con'plete Specification Lodged: Accepted: Published: ?:iority Related Art: 'I C I- Name of Applicant: THE PROCTER GAMBLE COMPANY Address of Applicant: Actual Inventor: Address for Service: One Procter Gamble Plaza, United States of America Cincinnati, Ohio 45202, STEPHEN CULSHAW and EDDY VOS.

EDWD. WATERS SONS, 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.

Jl~ Complete Specification for the invention entitled: HARD-SURFACE CLEANING COMPOSITIONS The fcllowing statement is a full description of this invention, including the best method of performing it known to

-D

I CM-246M2 41-, Z, la HARD-SURFACE CLEANING COMPOSITIONS 7 C C cc Stephen Culshaw Eddy Uos Technical .eld The present invention relates to hard-surface cleaning compositions containing a binary mixture of an organic solvent and a narrowly defined organic chelating agent.

Background of the Invention ~-f

M

It is well known to formulate hard-surface cleaning compositions, containing organic solvents and chelating agents.

European Patent Applications 0 040 882, 0 080 749, 0 126 545 describe the use of solvents represented by mixtures of terpenes with benzyl alcohol or butyl carbitol, together with builders which are mainly polyphosphates, or nitrogen containing strong sequestrants like NTA.

EP 0 105 863 and U.S. Patent 3,591,510 describe the use of certain glycol ether derivatives as solvents in liquid cleansers, together with polyphosphate builders.

The above solvent/builder combinations have proven very effective; however, in recent years phosphates have come S° under scrutiny for environmental reasons, and other non-phosphate strong sequestering agents are also facing acceptability problems related to toxicity/environmental safety.

There is therefore a need for hard-surface-cleaning compositions which are effective and at the same time are not likely to raise safety concerns with regard to toxicology and environment.

S The present invention is based on the discovery that certain known chelating agents, when combined with a specific class of organic solvents, provide very good results in terms of soil-removal from hard surfaces, because of unexpected and beneficial chelant/solvent interaction, said known chelating agents being safe compounds constituted solely of carbon, hydrogen, and oxygen.

Carboxymethyltartronic acid has been described as .i detergency builder in U.S. Patent 3,865,755, and in DE-OS-2 549 741.

Oxydisuccinic acid and carboxymethyloxysuccinic acid are known in the same functionality, from U.S. 3,635,830, and 3,692,685.

3 Tetrahydrofuran tetracarboxylic acid is known as phosphate replacement builder from U.S. 3,580,852.

Diglycolic acid is known as sequestering agent in detergent compositions, from DE-OS 2 150 325.

i All above materials have not found great success as phosphate builder replacement in laundry detergent compositions, since their sequestering power has been considered as too weak.

None of the above detergent compositions encompass hard-surface cleaning compositions, and there has been no I .disclosure of the chelating agents described herein, in i combination with organic solvents according to the present i t i. invention, It has now been surprisingly discovered that the combination of the chelating agents herein with certain organic solvent provide very good results in terms of soil j removal from hard surfaces.

It is therefore the object of the present invention to provide efficient hard surface cleaning compositions containing the combination of a safe chelating agent, and a suitable organic solvent.

Summary of the Invention The iniPntinn relates to hard-surface cleaning compositions containing a binary mixture of or g olvent Shaving a boiling point equal to or e 90 0 C, and an organic chelating aa ontaining neither phosphorous nor -n-i f:.r46 ra h rhpi at-ing ajpnf-c hping qp1pri-Pri From 3a According to the present invention there is provided a hard surface cleaning composition containing from 1% to 20% of organic solvent having a boiling point above 90 0 C, said solvent being selected from the group of glycol ethers and diols having 6 to 16 carbon atoms in their molecular structure or the group of C 6

-C

9 alkyl aromatics and from 1% to 20% of chelating agent selected from the group of carboxymethyloxysuccinic acid, carboxymethyltartronic acid, tetrahydrofurantetracarboxylic acid, combinations of tartrate monosuccinic acid and tartrate disuccinic acid, oxydisuccinic acid and mixtures 1 0 thereof or their alkali metal salts, the ratio of said organic solvent to said chelating agent being from 2:3 to 2:1.

A hard surface cleaning comp -ition according to claim 1 wherein the solvent is selected from the group of glycol ethers and diols having 6 to 16 carbon atoms in their molecular structure.

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i e c r(/hd 4 o 4 of pI COM~Cr~inr nIOMHS e -rr~mn Id~lU- tfI;~

I

i Vt ti 7ii h Detailed Description of the Invention to #t tt ada o 0 te

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The non-phosphorous chelating agent The chelating agents for use in the present invention are hydrocarbon compounds which do not contain phosphorous or nitrogen, and where the chelating ability is provided by carboxylate groups.

Although such chelating agents are not considered as strong builders by detergent manufacturers, especially in comparison with phosphate builders, it has been surprisingly discovered that their combination with certain organic solvents leads to excellent soil removal action from hard surfaces.

The cholating agenS Which can be used in the context of the present invention are selected from the group of: compounds of the form a (I) COOM Rr R.

R-.C -O D I i-V C R C -0 C C 0 R n m

R

2

R

6 R R 10

R

4 wherein R1 to R1 are selected independently rom the group of: H, COOM, CH 3

CHC

3

CH

2 COOM. CH 2

OH,

CH(OH)COOM, C 2 H C 3

H

7 OH; n is 0 or an integer *frl-m_ 31-nd-m-i n nr n 3inimpnpy Pm 1 4-n I.

L

f-PA-R 1 t 3-ap M j- 0 QP an i-I-eclr fl- M 1 -n A The mixture of tartrate monosuccinic acid and tartrate discussinic acid is preferably in a weight ratio of monosuccinic to disuccinic of 70:30 to 90:10.

The chelating agents of the invention are present at levels preferably of from 2% to 10% of the total composition.

The organic solvent It has been found that the organic solvents suitable for use in combination with the above-described chelating agents must have a boiling point equal to or above 90 0 C, in order to give the unexpected soil-release benefits derivable from the solvent-chelating agent combination.

For instance, C 1

-C

3 aliphatic alcohols like isopropanol 82°C) are not 1 0 suitable for use in the present invention.

Representatives of organic solvents which are effective in the present context are especially the C 6

-C

9 alkyl benzenes.

A type of solvent especially suitable for the compositions herein comprises diols having, preferably from 8 to 12 carbon atoms in their molecular structure. Preferred S1 5 diol solvents have a solubility in water of from about 0.1 to about 20 g/100 g of water at S" 20°C. The most preferred diol solvents are 2,2,4-trimethyl-1,3-pentanediol and 2-ethyl-1,3-hexanediol.

I The glycol ethers may be selected from water-soluble CARBITOL® solvents or S water-soluble CELLOSOLVE® solvents. Water-soluble CARBITOL® solvents are compounds of the 2-(2-alkoxyethoxy)ethanol class wherein the alkoxy group is derived from ethyl, propyl, butyl, pentyl hexyl; a preferred water-soluble carbitol is 2-(2butoxyethoxy)ethanol also known as butyl carbitol. Preferred are also hexyl carbitol and 2-methyl pentyl carbitol. Water-soluble CELLUSOLVE® solvents are compounds of the 2-alkoxyethoxy ethanol class, wherein the alkoxy group is preferably butyl or S 25 hexyl.

Still in the glycol ether category, certain propylene-glycol derivatrives have been found to be particularly efficient in the present context; these species include i -n-butoxypropane-2-ol, and 1(2-n-butoxy-1-methylethoxy)propane-2-ol(butyoxypropoxypropanol), with the latter being especially preferred.

3 0 Mixtures of the above solvents can also be used, like Butyl carbitol and/or Benzyl alcohol together with diols and/or glycol ethers.

The organic solvent is preferably at levels of from 1% to 10% by weight of the total composition.

41 6 Chelating agent/solvent combination The benefits of the present compositions are derived from the combination of the specific organic chelating agents and organic solvents described hereinabove.

They are particularly noticeable in terms of calcium soap-soil removal from surfaces such as bathtub surfaces.

I In order to obtain such an effect, the weight ratio of organic solvent to chelating agent is in the range from 2/3 to 2/1, preferably 1/1 to 2/1.

Optional ingredients In addition to the essential chelating agent/solvent binary mixture I described i e

I

1 r; 4 7 hereinabove, the compositions of the invention can contain additional ingredients, which are often highly desirable.

The compositions herein will usually contain a surface-active agent.

Water-soluble detersive surfactants useful herein include well-known synthetic anionic, nonionic, cationic, amphoteric and zwitterionic surfactants and mixtures thereof. Typical of these are the alkyl benzene sulfates and sulfonates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl 4, phenols, amine oxides, sulfonates of fatty acids and of fatty acid esters, and the like, which are well-known in the detergency art. In general, such detersive surfactants Scontain an alkyl group in the C -C 1 range, the anionic 10 18 S detersive surfactants are most conmonly used in the form of their sodium, potassium or triethanolammonium salts. The nonionics generally contain from 3 to 17 ethylene oxide 4, groups per mole of hydrophobic moiety. Cationic surfactants will generally be represented by quaternary ammonium compounds such as ditallow dimethyl ammonium chloride, and will be preferably used in combination with nonionic surfactants.

Especialiy preferred in the compositions of the present invention are: C12-C16 alkyl benzene sulfonates, C12-C18 paraffin-sulfonates and the ethoxylated alcohols of the formula RO(CH 2 CH20) with R being a C 12 -C 5 alkyl chain and n being a number from 6 to and C 12 -C18 ethoxylated alcohol sulfates of formula

RO-(CH

2

CH

2 0)n-SO 3

M.

Anionic surfactants are frequently present at levels from 0.3% to 8% of the composition. Nonionic surfactants, Sare used at levels between 0.1% to 6% by weight of the i composition. Mixtures of the like surfactants can also be i used.

Z

of th.oml OC H0),ljt en

-I-

Other optional ingredients are represented by conventional detergency builders, which may be used in addition to the chelating agent herein; compounds classifiable and well-known in the art as detergent builders include the nitrilotriacetates (NTA), polycarboxylates, citrates, water-soluble phosphates such as tri-polyphosphate and sodium ortho- and pyro--phosphates, silicates, ethylene diamine tetraacetate (EDTA), amino-polyphosphonates (DEQI'EST), phosphates and mixtures thereof.

Highly desirable ingredients for use herein are represented by conventional detergent hydrotropes. Eamples of suitable hydrotropes are urea, monoethanolamine, diethanolamine, triethanolamine and the sodium potassium, I ammonium and alkanol ammonium salts of xylene-, toluene-, I t f t. 1 ethylbenzene- and isopropyl-benzene sulfonates.

The hard-surface cleaning compositions of the invention may also contain an abrasive material.

S 'The abrasives suitable herein are selected from water-insoluble, non-gritty materials well-known in the literature for their relatively mild abrasive properties.

It is highly preferred that the abrasives used herein not be I undesirably "scratchy". Abrasive materials having a Mohs hardness in the range of about 7, or below, are typically used; abrasives having a Mohs hardness of 3, or below, can be used to avoid scratches on aluminum or stainless steel finishes. Suitable abrasives herein include inorganic materials, especially such materials as calcium carbonate and diatomaceous earth, as well as materials such as Fuller's earth, magnesium carbonate, China clay, attapulgite, calcium hydroxyapatite, calcium orthophosphate, dolomite and the like. The aforesaid inorganic materials can be qualified as "strong abrasives". Organic abrasives such as urea-formaldehyde, methyl methacrylate It melamine-formaldehyde resins, polyethylene spheres and i polyvinylchloride can be advantageously used in order to avoid scratching on certain surfaces, especially plastic surfaces.

j Typically, abrasives have a particle size range of 10-1000 microns and are used at concentrations of 5% to l in the compositions. Thickeners are frequently added to suspend the abrasives.

Thickeners will preferably be included in the compositions of the inventions, mainly in order to suspend j the abrasive; high levels of thickener are detrimental to the performance because they are difficult to rinse from the S 'cleaned surfaces. Accordingly, the level will be kept under Ij t preferably from 0.2% to Common thickeners such as i' the polyacrylates, xanthan gums, carboxymethyl celluloses, swellable smectite clays, and the like, can be used herein.

Soaps can be included in the compositions herein, the Ssoaps prepared from coconut oil fatty acids being preferred.

Optional components are also represented by ingredients typically used in commercial products to provide aesthetic or additional product performance benefits. Typical L C t ingredients include perfumes, dyes, optical brighteners, soil suspending agents, detersive enzymes, gel-control agents, thickeners, freeze-thaw stabilizers, bactericides, preservatives, and the like.

Preferred executions of the compositions The hard-surface cleaning compositions herein will advantageously be executed in the form of an aqueous liquid compositions, including concentrates, containing as essential ingredients a surface-active agent, and the solvent/chelating agent binary mixture according to the invention.

0 "i? Liquid executions at normal dilution usually contain 2-6% surfactant and 8-12% solvent/chelating agent binary mixture.

Concentrated liquid executions usually contain 6-10% surfactant and 16-24% solvent/chelating agent binary mixture.

Alternatively, the compositions herein will be in the form of a creamy scouring cleanser, containing an abrasive material, surface-active agent, and the solvent/chelating agent binary mixture of the invention.

00 00 0 0 In both executions, the pH of such compositions will be

E

p neutral or in the alkaline range, generally in the range of 0 4 pH 5-11.

o 0 i i 4 0 rl i -o 0 0 The following examples are given by way of illustrating the compositions herein, but are not intended to be limiting of the scope of the invention.

Abbreviations NaPS

'LAS

Lutensol ®AO7 Lutensol®AO 3 Neodol 25E3S HCnFA

ETHD

BPP

NaCS

CMTA

CMOS

THFTA

CPTA

OBHTA

TSA/TDSA

ODS

Sodium C13 to C 16 paraffin sulfonate Sodium salt of linear C 1 1

-C

8 alkyl benzene sulfonate Condensate of 1 mole C 12 -C14 fatty alcohol with 7 moles of ethylene oxide Condensate of 1 mole C12-C14 fatty alcohol with 3 moles of ethylene oxide Sulfated condensate of 1 mole C12-C15 fatty alcool with 3 moles of ethylene oxide Narrow cut, hardened, coconut fatty acid 2-Ethyl-1,3-hexanediol Butoxy Propoxy Propanol=1(2-n-butoxy-1methylethoxy)propane-2-ol Sodium cumene sulfonate Carboxymethyltartronic acid Carboxymethyloxysuccinic acid Tetrahydrofurantetracarboxylic acid Cyclopentanetetracarboxylic acid 2 Oxa-bicyclo heptane tricarboxylic acid tartrate monosuccinic acid/tartrate disuccinic acid blend, at 80:20 weight ratio Oxydisuccinic acid Crosslinked polyacrylate thickener i The following liquid hard surface cleaning compositions according to the invention are prepared.

Examples III and V are concentrates, in accordance with one execution of the present invention.

ti.

1 it a, 9 e u. 9 .1 4 a r a a a 04 C *4 percent by weight Ingredients Ex I Ex II Ex III Ex IV Ex U Ex VI Ex VII ExUIII Ex IX Ex X Ex XI Ex XII ExXIII Ex XIV

LAS

NaPS Lutensol

AO

7 Lutensol

AO

3 Neodol 25E3S Benzyl alcohol Butyl Carbitol

ETHD

BPP

Oxydiacetic acid

CMTA

CMOS

THFTA

CPTA

Tartaric acid

OBHTA

Mellitic acid

STSA/TDSA

ODS

Na2CO 3 NaCS 2.5 1.0 6.0 6.0 2.0 3.0 7.0 10.0

I

3.0 1.0 0.2 4.0 0.5 3.0 0.2 0.5 3.0 0.2 6.0 2.5 2.0 0.6 2.5 6.5 6.0 0.6 4~.0 10.0 3.5 8.0 .0 .0 3.5 4.0 3.5 3.0 .5 1.0 1.0 1.5 1.0 1.0 3.5 1.5 8.0 2.5 2.0 2.5 2.5 2.0 2.0 2.5 water minors UP TO

J

2 a4 f *t The following creamy scouring compositions according to the invention are also prepared eq 0 0 eec.

C

*c 0 @0000* 0 cc cc eec.

C

Lns NaPS Lutensol o07 HCnFA B8nzyl alcohol

BPP

CMTA

CMOS

THFT A TSn/TDSn

ODS

Na 2

CO

3

COCO

3 PolyuS nrichloride Ex XV it 0 4.0 2.0 1.0 3.0 3.0 3.0 30.0 0.4 EX XUI Ex XUII Ex XUI1I 0.6 3.0 0.3 0.6 1.3 2.0 3.0 30.0 0.6 4.0 1.5 4.0 3 .0 3.0 10.0 0.4 0.6 3.0 0.3 0.4 1.3 2.0 3.0 30.0 0.6 0.6 0.3 0.5 1.3 2.0 3.0 30.0 0.6 Ex XIX Ex XX 1 10.0 0.4 eq 0 0* cc e C

OU

*1 0 t *04 C .0 0 0 The compositions prepared in accordance with Examples I to XX show very good performance in terms of kitchen and bathroom soil removal from hard surfaces, especially calcium soap soil removal from bathtub surfaces, composition containing isopropanol as solvent and CMTA as builder, was found to be less efficient in terms of soil-removal properties, thus showing the criticality of the boiling point parameter used to select the solvents useful herein.

hat this and the preceding /rue d eact copy of pages Mja 1eiftion originally lodged.

LA pages are a of J (16

Claims

1. A hard surface cleaning composition containing from 1% to 20% of organic solvent 'aving a boiling point above 900C, said solvent being selected from the group of glycol ethers and diols having 6 to 16 carbon atoms in their molecular structure or the group of C6-C9 alkyl aromatics and from 1% to 20% of chelating agent selected from the group of carboxymethyloxysuccinic acid, carboxymethyltartronic acid, tetrahydrofurantetracarboxylic acid, combinations of tartrate monosuccinic acid and i tartrate disuccinic acid, oxydisuccinic acid and mixtures thereof or their alkali metal salts, the ratio of said organic solvent to said chelating agent being from 2:3 to 2:1.

2. A hard surface cleaning composition according to claim 1 wherein the solvent is selected from the group of glycol ethers and diols having 6 to 16 carbon atoms in their molecular structure. S* DATED this 10th day of March, 1992 THE PROCTER GAMBLE COMPANY S WATERMARK PATENT TRADEMARK ATTORNEYS THE ATRIUM 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIUA S tI AU1419388.WPC(DOC.010) LCG:EK