CA1332217C - Hard-surface cleaning compositions - Google Patents
Hard-surface cleaning compositionsInfo
- Publication number
- CA1332217C CA1332217C CA 563241 CA563241A CA1332217C CA 1332217 C CA1332217 C CA 1332217C CA 563241 CA563241 CA 563241 CA 563241 A CA563241 A CA 563241A CA 1332217 C CA1332217 C CA 1332217C
- Authority
- CA
- Canada
- Prior art keywords
- composition
- accordance
- coom
- chelating agent
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5022—Organic solvents containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0013—Liquid compositions with insoluble particles in suspension
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
ABSTRACT
The invention relates to hard-surface cleaning compositions containing a binary mixture of organic solvent having a boiling point equal to or above 90°C, and an organic chelating agent containing neither phosphorous nor nitrogen, such chelating agents being selected from compounds having the formulae (I) to (VII) hereinafter described, or mixtures of compounds (I) to (VII).
The invention relates to hard-surface cleaning compositions containing a binary mixture of organic solvent having a boiling point equal to or above 90°C, and an organic chelating agent containing neither phosphorous nor nitrogen, such chelating agents being selected from compounds having the formulae (I) to (VII) hereinafter described, or mixtures of compounds (I) to (VII).
Description
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-~ H~RD-SURFACE CLE~NING COMPOSITIONS
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~ Technical Field s -.~ The ~resent inuention relates to hard-surface cleaning .i compositions containing a binary mixture of an organic ~`` soluent and a narrowly defined organic chelating agent.
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i~ .Backqround of the Inuention . . .
,. ~ .
.~- It is well known to formulate hard-surface cleaning:~
compositions, containing organic sol~ents and chelating -~
~gents. : ~ :
.. - ~
,~ European Patent Application 0 126 545 ~:
(November 28, 1984) and Canadian Patents 1,174,551 and 1,202,858 describe the use of solvents represented by ~ -. mixtures of terpenes with benzyl alcohol or butyl :
^` 1332217 carbitol, together with builders which are mainlypolyphosphates, or nitrogen containing strong sequestrants like NT~.
EP O 105 863 and U.S. Patent 3,591,510 describe the use of certain glycol ether deri~atiues as soluents in liquid cleansers, together with polyphosphate builders.
The abo~e sol~ent/builder combinations haue pro~en uery effecti~e; howe~er, in recent years phosphates ha~e come under scrutiny for enuironmental reasons, and other non-phosphate strong sequestering agents are also facing acceptability problems related to toxicity/en~ironmental safety.
There is therefore a need for hard-surface-cleaning compositions which are effectiue and at the same time are not likely to raise safety concerns with regard to toxicology and en~ironment.
: .
The present in~ention is based on the discovery that certain known chelating agents, when combined with a specific class of organic sol~ents, pro~ide ~ery good results in terms of soil-remoual from hard surfaces, because of unexpected and beneficial chelant/sol~ent interaction, said known chelating agents being safe compounds constituted solely of carbon, hydrogen, and oxygen.
Carboxymethyltartronic acid has been described as 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.
.
,~ .
:$~:- ' : . , -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.
-. ~ll aboue materials haue 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 aboue detergent compositions encompass hard-surface cleaning compositions, and there has been no disclosure of the chelating agents described herein, in combination with organic soluents according to the present -~ inuention.
.-`' ~
~,~ It has now been surprisingly discouered that the . combination of the chelating agents herein with certain ~ organic soluent prouide uery good results in terms of soil .-- remoual from hard surfaces.
:, :
It is therefore the object of the present inuention to . prouide efficient hard surface cleaning compositions containing the combination of a safe chelating agent, and a suitable organic soluent.
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Summar~ of the Inuention The inuention relates to hard-surface cleaning compositions containing a binary mixture of organic soluent hauing a boiling point equal to or aboue 90C, and an ` organic chelating agent containing neither phosphorous nor nitrogen, such chelating agents being selected from .'`;~ ~'. ~
~ .:
' `: :
~ .
.
,:i. . :
.. ~
-~ H~RD-SURFACE CLE~NING COMPOSITIONS
. .
,.i ::
: ~ :
.. ..
~ Technical Field s -.~ The ~resent inuention relates to hard-surface cleaning .i compositions containing a binary mixture of an organic ~`` soluent and a narrowly defined organic chelating agent.
?I`
:~3 : :
i~ .Backqround of the Inuention . . .
,. ~ .
.~- It is well known to formulate hard-surface cleaning:~
compositions, containing organic sol~ents and chelating -~
~gents. : ~ :
.. - ~
,~ European Patent Application 0 126 545 ~:
(November 28, 1984) and Canadian Patents 1,174,551 and 1,202,858 describe the use of solvents represented by ~ -. mixtures of terpenes with benzyl alcohol or butyl :
^` 1332217 carbitol, together with builders which are mainlypolyphosphates, or nitrogen containing strong sequestrants like NT~.
EP O 105 863 and U.S. Patent 3,591,510 describe the use of certain glycol ether deri~atiues as soluents in liquid cleansers, together with polyphosphate builders.
The abo~e sol~ent/builder combinations haue pro~en uery effecti~e; howe~er, in recent years phosphates ha~e come under scrutiny for enuironmental reasons, and other non-phosphate strong sequestering agents are also facing acceptability problems related to toxicity/en~ironmental safety.
There is therefore a need for hard-surface-cleaning compositions which are effectiue and at the same time are not likely to raise safety concerns with regard to toxicology and en~ironment.
: .
The present in~ention is based on the discovery that certain known chelating agents, when combined with a specific class of organic sol~ents, pro~ide ~ery good results in terms of soil-remoual from hard surfaces, because of unexpected and beneficial chelant/sol~ent interaction, said known chelating agents being safe compounds constituted solely of carbon, hydrogen, and oxygen.
Carboxymethyltartronic acid has been described as 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.
.
,~ .
:$~:- ' : . , -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.
-. ~ll aboue materials haue 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 aboue detergent compositions encompass hard-surface cleaning compositions, and there has been no disclosure of the chelating agents described herein, in combination with organic soluents according to the present -~ inuention.
.-`' ~
~,~ It has now been surprisingly discouered that the . combination of the chelating agents herein with certain ~ organic soluent prouide uery good results in terms of soil .-- remoual from hard surfaces.
:, :
It is therefore the object of the present inuention to . prouide efficient hard surface cleaning compositions containing the combination of a safe chelating agent, and a suitable organic soluent.
~..
. .
r,, ~ .
Summar~ of the Inuention The inuention relates to hard-surface cleaning compositions containing a binary mixture of organic soluent hauing a boiling point equal to or aboue 90C, and an ` organic chelating agent containing neither phosphorous nor nitrogen, such chelating agents being selected from .'`;~ ~'. ~
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- 4 - ~332217 : compounds ha~ing the formulae (I) to (UII) hereinafter described, or mixtures of compounds (I) to (UII).
., _et _ d Description of the Inuention The _on-phosphorous chelatinq aqent - The chelating agents for use in the present in~ention are hydrocarbon compounds ` which do not contain phosphorous or nitrogen, and where the chelating ability is pro~ided by carboxylate groups.
~ ~lthough such chelating agents are not considered as - strong builders by detergent manufacturers, especially in comparison with phosphate builders, it has been surprisingly disco~ered that their combination with certain organic soluents leads to excellent soil remoual action from hard ` surfaces.
The chelating agents which can be used in the context of the present in~ention are selected from the group of:
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compounds of the formula (I) ,~ R~ - C ~ I )n~
. R2 R6 R8 R1o R4 , wherein Rl to R1 are selected independently from the r. group of: H, COOM, CH3, CH2CH3, CH2COOM~ CH20H~ ~:
CH~OH)COoM, C2H5, C3H7, OH; n is O or an int g ` from 1 to 3; and m is O or an integer from 1 to 4;
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'''; ' ' .: , compounds of the formula (II) ~., I ~ C ~ I
` T l ,,T6 -~ HOOC'' ~ X ~ ----- T7 :; ~
wherein X is - O - or - CH2 T1 to Tg are selected independently from the group of: H, COOM, CH3, CH2CH3, CH2COOM, CH20H, .' OH; and p is O, 1, or 2;
compounds of the formula (III) :: Y2 ;-: / X Y3 ~;' Y7 ,C ~ C C y4 C/~~ y ~i COOM
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wherein X is - O - or -CH2 ~:
Yl to Y7 are selected independently from the group of: H, COOM, CH3, CH2COOM, CH20H, OH;
.~ compounds of formula (I~
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L L L ~ ~:
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L1 C ; t 6 ~ t :: L3 L8 L5 .~ . .
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- 6 _ 1332217 wherein Ll to L8 are selected independently from th~
group of: H, COOM, CH3, CH2COOM, CH20H, OH, OCH2COOM, OCHz(COOM)2; t is O or an integer from 1 to ~ 8;
`: with the pro~iso that when t is 1, L6 and L7 are selected from H, OH, CH3, CH2COOM, CH20H, OCH2COOM, . OCH2(COOM)2;
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~ - compound of formula (U) ':
B3 ~ B5 ( ~ l , B~ ~ - B6 B
~ 1 wherein B1 to B6 are selected from the group of H, COOM, CH3, CH2CH3, CH2COOM, CH20H, OH, CH20CH2COOM
CH20CH(COOM)2, CH20CH3, CH2CH(OH)CM, CH = CH-C-O-CH(COOM)2 ,~ O
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' - compounds of formula UI -: COOM
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: HO - CH
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COOM
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.` or formula UII
HO ~ COOM
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HO/ \COOM
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In formulas I to ~II, M is H or an alkalimetal ion such as Na or K.
. The compounds of formula (I) preferably contain at least ~ two carboxylate groups. m and n are preferably O or 1.
:. Most preferably, n and m are zero in formula (I), and such . category includes oxydiacetic acid (Rl to R4 are . hydrogen, R11 is -COOH), carboxymethyltartronic acid ~i~ (Rl, R2, R3 are H, R4 and Rll are -COOH), :
~ oxydimalonic acid (R1 to R4 and Rll are COOH), .~ carboxymethyloxysuccinic acid (Rl, R2, R3 are .
hydrogen, R4 is CH2COOH, Rll is -COOH)~ tartrate . monosuccinic acid (Rl is H, R2 is CH(OH)COOH, R4 is CH2COOM, Rll is -COOH, R3 is H),oxydisuccinic acid :~
- (Rl and R3 are H and R2 and R4 are CH2COOH R~
- is -COOH). When n=1 and m=O, tartrate disuccinic acid :~n~.
(Rl, R3, R5, R7 are H, R2 and R3 are -CH2COOH, ~ ~:
R6, R8 and R11 are -COOH) and Ethylene glycol dimalonate (Rl, R3~ Rs~ R6~ R7~ R8 are H~ R2 and R3 are -CH2COOH, Rll is -COOH) are suitable ~: compounds.
:; ~lso preferred is a mixture of tartrate monosuccinic acid and tartrate disuccinic acid, preferably in a weight ratio of monosuccinic to disuccinic of 70:30 to 90:10.
.~ In compounds of formula (II), p is preferably O and T7 ~: preferably -COOM; such compounds include deriuatiues of ;~ tetrahydrofuran, when X is oxygen, and substituted . .
cyclopentane, when X is -CH2.
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~ eriuatiues of tetrahydrofuran are particularly represented by tetrahydrofurandicarboxylic acid (T1 to T6 are H), tetrahydrofurantetracarboxylic acid (T2 and T4 are -COOM, T1, T3, T5, T6 are H). ~nother :`~ alternatiue is represented by tetrahydrofurantetracarboxylic acids wherein T1 and T6 are -COOM, and T2 to T5 are H.
-~ Suitable substituted cyclopentanes include cyclopentane tetracarboxylic acid (T2 and T4 are -COOM, T1, T3, T5, T6 are H) The compounds of formula (III) - Such chelating agents include 2-oxa-bicyclo(2.2.1) heptane (1,4,5) tricarboxylic acid, 2-oxa-bicyclo(2.2.1)heptane(4,5,6)tricarboxylic acid.
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The compounds of formula (I~) - When t is zero, suitable species include tartaric acid, (Ll and L6 are OH, L2 and L4 are H, L3 and L5 are -COOM); when t = 1, deriuatiues of glycerol with L3, L8, L5 selected from O-CH2COOM ancl O-CH(COOM)2 are suitable.
- The compounds of formula (~) contain at least a carboxy group, either directly attached to the benzene ring, or comprised in an alkyl substituent of said benzene ring.
preferred species is represented by mellitic acid, wherein B1to B6 are COOM
The chelating agents of the inuention are present at leuels of from 1% to 20% of the total composition, ~ preferably 2% to 10%.
.' :
~- The compounds of formula (UI) and (UII) are hydroxypropanedioic acid and dihydroxypropanedioic acid.
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The orqanic soluent - It has been found that the organic soluents suitable for use in combination with the aboue-describe'd chelating agents must haue a boiling point equal to or aboue 90C, in order to giue the unexpected soil-release benefits deriuable from the soluent-chelating agent combination.
For instance, C1-C3 aliphatic alcohols like isopropanol (B.P. 82C) are not suitable for use in the present inuention.
. ., ~ epresentatiues of organic soluents which are effectiue ~i in the present context are: C6-Cg alkyl arornatic .' solùents, especially the C6-Cg alkyl benzenes, ~- alpha-olefins, like 1-decene or 1-dodecene, benzyl alcohol, n-hexanol, phthalic acid esters.
type of soluent especially suitable for the . compositions herein comprises diols hauing from 6 to 16, '` preferably a to 12, carbon atoms in their molecular structure. Preferred diol soluents haue a solubility in ~; water of from about 0.1 to about 20 9/100 9 of water at 20C. The most preferred diol soluents are ~.` 2,2,4-trimethyl-1,3-pentanediol, and 2-ethyl-1,3-hexanediol.
:
Glycol ethers are another class of particularly ~
preferred soluents. ;
In this category, are: water-soluble C~RBITOL~
soluents or water-soluble CELLOSOLUE~ soluents.
Water-soluble C~RBITO ~ soluents are compounds of the 2-(2-alkoxyethoxy)ethanol class wherein the alkoxy group is ~ deriued from ethyl, propyl, butyl pentyl hexyl; a preferred i~ water-soluble carbitol is 2-(2-butoxyethoxy)ethanol also .~ known as butyl carbitol. Preferred are also hexyl carbitol and 2-methyl pentyl carbitol. Water-soluble C~LLOSOLU ~
soluents are compounds of the 2-alkoxyethoxy ethanol class, wherein the alkoxy group is preferably butyl or hexyl.
~.-. .
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- lo- 1332217 Still in the glycol ether category, certain propylene-glycol deriuatiues haue been found to be particularly e~ficient in the present context; these species include 1-n-butoxypropane-2-ol, and 1(2-n-butoxy-1-methylethoxy)propane-2-ol (butoxypropoxypropanol), with the latter being especially preferred.
.
Mixtures of the aboue soluents can also be used, like , Butyl carbitol and/or Ben~yl alcohol together with diols `~ and/or glycol ethers.
!
The organic soluent is present at leuel of from 1% to 20% by weight of the total composition, preferably from 1%
to 10%~
_ elatinq agent/s luent combination - The benefits of the present compositions are deriued from the combination of the ::
specific organic chelating agents and organic sol~ents described hereinaboue.
, .
They are particularly noticeable in terms of calcium m soap-soil remoual from surfaces such as bathtub surfaces.
:-~ In order to obtain such an effect, the weight ratio or `: organic soluent to chelating agent is in the rang~ from 2~3 to 2/1, preferably 1/1 to 2/1.
`. Combinations of e.g. the preferred chelating agen~s of formula (I) with 2-(2-butoxy-1-methylethoxy)propanol, or ~ with 2,2,4-trimethyl-1,3-pentane diol in a ratio in the : preferred 1/1 to 2/1 range haue been found to be : particularly effectiue.
:
- O~tional inqredients - In addition to the essential chelating agent~soluent binary mixture described ~.~ .:, : `
:, hereinaboue, the compositions of the inuention can contain additional ingredients, which are often highly desirable.
. ., :
The compositions herein will usually contain a . ~ .
surface-actlue agent.
Water-soluble detersiue 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 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 detersiue surfactants contain an alkyl group in the C10-Cl8 range; the anionic detersiue surfactants are most commonly used in the form of their sodium, potassium or triethanolammonium salts. The nonionics generally contain from 3 to 17 ethylene oxide 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.
Especially preferred in the compositions of the present in~ention are: C12-C16 alkyl benzene sulfonates, C12-C18 paraffin-sulfonates and the ethoxylated alcohols of the formula RO(CH2CH20)n, with R being a C12-C15 alkyl chain and n being a number from 6 to 10 and C12-C18 ethoxylated alcohol sulfates of formula Ro-(cH2cH2o) n-S03M.
~ nionic surfactants are frequently present at leuels from 0.3% to 8% of the composition. Nonionic surfactants, are used at leuels between 0.1% to 6~ by weight of the composition. Mixtures of the like surfactants can also be used.
:
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- 12 - 1 33~217 Other optional ingredients are represented by conuentional detergency builders, which may be used in addition to ~be chelating agent herein; compounds classifiable and well-known in the art as detergent builders include the nitrilotriacetates (NT~)~ polycarboxylates, citrates, water-soluble phosphates such as tri-polyphosphate and sodium ortho- and pyro-phosphates, silicates, ethylene diamine tetraacetate (EDT~), amino-polyphosphonates (DEQUEST), phosphates and mixtures thereof.
Highly desirable ingredients for use herein are represented by conuentional detergent hydrotropes. Examples of suitable hydrotropes are urea, monoethanolamine, diethanolamine, triethanolamine and the sodium potassium, ammoniu~ and alkanol am~onium salts of xylene-, toluene-, ..
ethylbenzene- and isopropyl-benzene sulfonates.
The hard-surface cleaning compositions of the inuention may also contain an abrasiue material.
The abrasiues suitable herein are selected from water-insoluble, non-gritty materials well-known in the literature for their relatiuely mild abrasiue properties.
It is highly preferred that the abrasiues used herein not be undesirably "scratchy". ~brasiue materials hauing a Mohs hardness in the range of about 7, or below, are typically used; abrasiues hauing a Mohs hardness of 3, or below, can be used to auoid scratches on aluminum or stainless steel finishes. Suitable abrasiues 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 abrasiues". Organic abrasiues such as urea-formaldehyde, methyl methacrylate ' ~' : ~
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. _ 13 l 3~22 1 7 .
~-melamine-formaldehyde resins, polyethylene spheres and polyuinylchloride can be aduantageously used in order to auoid scratch~ng on certain surfaces, especially plastic :. surfaces.
~`' I Typically, abrasiues haue a particle size range of 10-1000 microns and are used at concentrations of 5% to 30%
.. in the compositions. Thickeners are frequently added to suspend the abrasiues.
..
Thickeners will preferably be included in the compositions of the inuentions, mainly in order to suspena ~` the abrasiue; high leuels of thickener are detrimental to the performance because they are difficult to rinse from the ` cleaned surfaces. ~ccordingly, the leuel will be kept under .
2%, preferably from 0.2% to 1.5%. Common thickeners such as ; the polyacrylates, xanthan gums, carboxymethyl celluloses, :
swellable smectite clays, and the like, can be used herein.
.l Soaps can be included in the compositions herein, the ~-~ soaps prepared from coconut oil fatty acids being preferred.
~ Optional components are also represented by ingredients 3 typically used in commercial products to prouide aesthetic ~; or additional product performance benefits. Typical -~ ingredients include perfumes, dyes, optical brighteners, -~
l soil suspending agents, detersiue e~nzymes, gel-control -~ agents, thickeners, freeze-thaw stabilizers, bactericides, `~ preservatiues, and the like.
Preferred executions of the compositions - ~he hard-surface .
cleaning compositions herein will aduantageously be executed ~; in the form of an aqueous liquid compositions, including - concentrates, containing as essential ingredients a surface-actiue agent, and the soluent/chelating agent binary -.- mixture according to the inuention.
~:.3 ~ ~3 - ~ ~
~. . . .
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Liquid executions at normal dilution usually contain 2-6% surfactant and 8-12% soluent/chelating agent binary mixture. ,, :
:~ Concentrated liquid executions usually contain 6-10%
surfactant and 16-24% soluent/chelating agent binary mixture.
Qlternatiuely, the compositions herein will be in the form of a creamy scouring cleanser, containing an abrasiue material, surface-actiue agent, and the soluent/chelating agent binary mixture of the inuention.
In both executions, the pH of such compositions will be neutral or in the alkaline range, generally in the range of ~ pH 5-11.
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~ - 15 - l 3322 1 7 The following examples are giuen by way of illustrating the compositions herein, but are not intended to be limiting :~ -of the scop~,of the in~ention.
~bbre~iations NaPS Sodium C13 to C16 paraffin sulfonate L~S Sodium salt of linear C11-C8 alkyl benzene sulfonate Lutensol~ 07 Condensate of 1 mole C12-C14 fatty alcohol with 7 moles of ethylene oxide Lutenso~ ~ 03 Condensate of 1 mole C12-C14 fatty alcohol with 3 moles of ethylene oxide Neodol 25E3S Sulfated condensate of 1 mole C12-C15 fatty alcool with 3 moles of ethylene ! `, oxide HCnF~ Narrow cut, hardened, coconut fatty acid ETHD 2-Ethyl-1,3-hexanediol :~
BPP Butoxy Propoxy Propanol=1(2-n-butoxy-1-.~ methylethoxy)propane-2-ol . NaCS Sodium cumene sulfonate '~ CMT~ Carboxymethyltartronic acid . CMOS Carboxymethyloxysuccinic acid THFTP, Tetrahydrofurantetracarboxylic acid CP~P Cyclopentanetetracarboxylic acid OBHTP 2 Oxa-bicyclo (2.2.1) heptane . (1.4.5.) tricarboxylic acid -1, TSP/TDS~ tartrate monosuccinic acid/tartrate .. , disuccinic acid blend, at 80:20 weight ratio :~
~ ODS Oxydisuccinic acid --~ Sokolan~ HC25 Crosslinked polyacrylate thickener .,: :~
The following liquid hard surface cleaning compositions .~. according to the inuention are prepared. ~-~
. . : ~
.. Examples III and U are concentrates, in accordance with ~.
~:~ one execution of the present in~ention.
':
:~: :
~ ! ' ~:`
.'~`' ~.: ' x I ' I ' ' ' ' ' ' ' ' ' ' ' ~ ~ ~ 1 33221 7 ~ ~o~,, , ~ ~ ~ ~ I ~
w ;. ~c , o,, I,, o~ o o o x ~ I I I O I O o :~ ~
~:
~ X , o ~,,, o o . ~ X ~ o~ ~
.~ W
X ~ o ~ o o o . - X o ~ o W
: , o ~ oI o o ~ o o - ,~, W
. ~ ~ ~
-~ 3~ 1O 1 11 ~1lll Il~.n !
.-`- ,, W
~ O, ~ ~ _ o~ ~ I I I
. . , ~ , o o, , o, o ,, o,,,, ,, ~ o o ~c I I I I ~o I 1 1,~ 1 1 1 1 1 1 .,;,` X o o,,,,, ,.`. W
.~ , X o ~ - ~
'."'~ W :~:' ~ ~ ~ ~ O ~ O O O
...
.
~ O O ~ ~ ~ O
: JJ G ~ D n~ ~15 E
r~ ~ L ~ r~ ~ 0~ L
c ~ ~ ~ a. O :c ~ 11 o .~ ~ Cl z z 3 : ~ :~ .:
~: i~. : : . .
'~ `
~-:
The following creamy scouring compositions according to the invention are also prepared :
:, :
~ Ex X~Ex XUI Ex XUII Ex XUIII Ex XIX Ex XX
- L~S _ 0.6 4.0 0.6 0.6 4.0 NaPS 4.0 3.0 _ 3.0 3.0 . Lutensol ~07 _ 0.3 _ 0.3 0.3 . HCnF~ 2.0 0.6 1.5 0.4 0.5 1.5 Benzyl alcohol1.0 1.3 _ 1.3 1.3 8PP 3.0 2.0 4.0 2.0 2.0 4.0 . CMT~ 3.0 3.0 _ _ _ CMOS _ _ 3.0 _ _ THFT~ _ _ _ 3.0 _ TS~/TDS~ _ _ _ _ 3.0 . ODS _ _ _ _ _ 3.0 2 3 3.0 3.0 3.0 3.0 3.0 3.0 CaC03 30.0 30.0 _ 30.0 30.0 :~ Polyvin~lchloride _ _ 10.0 _ _ 10.0 Sokolan~ HC25 0.4 0.6 0.4 0.6 0.6 0 4 The compositions prepared in accordance with Examples I to XX show uery 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 -~
CMT~ as builder, was found to be less efficient in terms of soil-remoual properties, thus showing the criticality~:
. of the boiling point parameter used to select the solvents useful herein.
;t~
~-.
.: ~.
: ~.. - : : . .
- .~,- , . . :
., _et _ d Description of the Inuention The _on-phosphorous chelatinq aqent - The chelating agents for use in the present in~ention are hydrocarbon compounds ` which do not contain phosphorous or nitrogen, and where the chelating ability is pro~ided by carboxylate groups.
~ ~lthough such chelating agents are not considered as - strong builders by detergent manufacturers, especially in comparison with phosphate builders, it has been surprisingly disco~ered that their combination with certain organic soluents leads to excellent soil remoual action from hard ` surfaces.
The chelating agents which can be used in the context of the present in~ention are selected from the group of:
~'.
compounds of the formula (I) ,~ R~ - C ~ I )n~
. R2 R6 R8 R1o R4 , wherein Rl to R1 are selected independently from the r. group of: H, COOM, CH3, CH2CH3, CH2COOM~ CH20H~ ~:
CH~OH)COoM, C2H5, C3H7, OH; n is O or an int g ` from 1 to 3; and m is O or an integer from 1 to 4;
., . ,~
`.'' `` ~
'''; ' ' .: , compounds of the formula (II) ~., I ~ C ~ I
` T l ,,T6 -~ HOOC'' ~ X ~ ----- T7 :; ~
wherein X is - O - or - CH2 T1 to Tg are selected independently from the group of: H, COOM, CH3, CH2CH3, CH2COOM, CH20H, .' OH; and p is O, 1, or 2;
compounds of the formula (III) :: Y2 ;-: / X Y3 ~;' Y7 ,C ~ C C y4 C/~~ y ~i COOM
.~ ~
wherein X is - O - or -CH2 ~:
Yl to Y7 are selected independently from the group of: H, COOM, CH3, CH2COOM, CH20H, OH;
.~ compounds of formula (I~
~;
L L L ~ ~:
~ I I\
L1 C ; t 6 ~ t :: L3 L8 L5 .~ . .
t' :
? '~
- 6 _ 1332217 wherein Ll to L8 are selected independently from th~
group of: H, COOM, CH3, CH2COOM, CH20H, OH, OCH2COOM, OCHz(COOM)2; t is O or an integer from 1 to ~ 8;
`: with the pro~iso that when t is 1, L6 and L7 are selected from H, OH, CH3, CH2COOM, CH20H, OCH2COOM, . OCH2(COOM)2;
:~
. ~ .
~ - compound of formula (U) ':
B3 ~ B5 ( ~ l , B~ ~ - B6 B
~ 1 wherein B1 to B6 are selected from the group of H, COOM, CH3, CH2CH3, CH2COOM, CH20H, OH, CH20CH2COOM
CH20CH(COOM)2, CH20CH3, CH2CH(OH)CM, CH = CH-C-O-CH(COOM)2 ,~ O
~ .
' - compounds of formula UI -: COOM
. I . .
: HO - CH
\
COOM
.' :
,'.:
.
.
:
' .
~a ~
.` or formula UII
HO ~ COOM
\C / ~
HO/ \COOM
.~
In formulas I to ~II, M is H or an alkalimetal ion such as Na or K.
. The compounds of formula (I) preferably contain at least ~ two carboxylate groups. m and n are preferably O or 1.
:. Most preferably, n and m are zero in formula (I), and such . category includes oxydiacetic acid (Rl to R4 are . hydrogen, R11 is -COOH), carboxymethyltartronic acid ~i~ (Rl, R2, R3 are H, R4 and Rll are -COOH), :
~ oxydimalonic acid (R1 to R4 and Rll are COOH), .~ carboxymethyloxysuccinic acid (Rl, R2, R3 are .
hydrogen, R4 is CH2COOH, Rll is -COOH)~ tartrate . monosuccinic acid (Rl is H, R2 is CH(OH)COOH, R4 is CH2COOM, Rll is -COOH, R3 is H),oxydisuccinic acid :~
- (Rl and R3 are H and R2 and R4 are CH2COOH R~
- is -COOH). When n=1 and m=O, tartrate disuccinic acid :~n~.
(Rl, R3, R5, R7 are H, R2 and R3 are -CH2COOH, ~ ~:
R6, R8 and R11 are -COOH) and Ethylene glycol dimalonate (Rl, R3~ Rs~ R6~ R7~ R8 are H~ R2 and R3 are -CH2COOH, Rll is -COOH) are suitable ~: compounds.
:; ~lso preferred is a mixture of tartrate monosuccinic acid and tartrate disuccinic acid, preferably in a weight ratio of monosuccinic to disuccinic of 70:30 to 90:10.
.~ In compounds of formula (II), p is preferably O and T7 ~: preferably -COOM; such compounds include deriuatiues of ;~ tetrahydrofuran, when X is oxygen, and substituted . .
cyclopentane, when X is -CH2.
,, ~
', ::
. .
~ eriuatiues of tetrahydrofuran are particularly represented by tetrahydrofurandicarboxylic acid (T1 to T6 are H), tetrahydrofurantetracarboxylic acid (T2 and T4 are -COOM, T1, T3, T5, T6 are H). ~nother :`~ alternatiue is represented by tetrahydrofurantetracarboxylic acids wherein T1 and T6 are -COOM, and T2 to T5 are H.
-~ Suitable substituted cyclopentanes include cyclopentane tetracarboxylic acid (T2 and T4 are -COOM, T1, T3, T5, T6 are H) The compounds of formula (III) - Such chelating agents include 2-oxa-bicyclo(2.2.1) heptane (1,4,5) tricarboxylic acid, 2-oxa-bicyclo(2.2.1)heptane(4,5,6)tricarboxylic acid.
,`,;
The compounds of formula (I~) - When t is zero, suitable species include tartaric acid, (Ll and L6 are OH, L2 and L4 are H, L3 and L5 are -COOM); when t = 1, deriuatiues of glycerol with L3, L8, L5 selected from O-CH2COOM ancl O-CH(COOM)2 are suitable.
- The compounds of formula (~) contain at least a carboxy group, either directly attached to the benzene ring, or comprised in an alkyl substituent of said benzene ring.
preferred species is represented by mellitic acid, wherein B1to B6 are COOM
The chelating agents of the inuention are present at leuels of from 1% to 20% of the total composition, ~ preferably 2% to 10%.
.' :
~- The compounds of formula (UI) and (UII) are hydroxypropanedioic acid and dihydroxypropanedioic acid.
''~' `' :'.
,, ~ - - - . , - - . -. ~ . . .~ , .
The orqanic soluent - It has been found that the organic soluents suitable for use in combination with the aboue-describe'd chelating agents must haue a boiling point equal to or aboue 90C, in order to giue the unexpected soil-release benefits deriuable from the soluent-chelating agent combination.
For instance, C1-C3 aliphatic alcohols like isopropanol (B.P. 82C) are not suitable for use in the present inuention.
. ., ~ epresentatiues of organic soluents which are effectiue ~i in the present context are: C6-Cg alkyl arornatic .' solùents, especially the C6-Cg alkyl benzenes, ~- alpha-olefins, like 1-decene or 1-dodecene, benzyl alcohol, n-hexanol, phthalic acid esters.
type of soluent especially suitable for the . compositions herein comprises diols hauing from 6 to 16, '` preferably a to 12, carbon atoms in their molecular structure. Preferred diol soluents haue a solubility in ~; water of from about 0.1 to about 20 9/100 9 of water at 20C. The most preferred diol soluents are ~.` 2,2,4-trimethyl-1,3-pentanediol, and 2-ethyl-1,3-hexanediol.
:
Glycol ethers are another class of particularly ~
preferred soluents. ;
In this category, are: water-soluble C~RBITOL~
soluents or water-soluble CELLOSOLUE~ soluents.
Water-soluble C~RBITO ~ soluents are compounds of the 2-(2-alkoxyethoxy)ethanol class wherein the alkoxy group is ~ deriued from ethyl, propyl, butyl pentyl hexyl; a preferred i~ water-soluble carbitol is 2-(2-butoxyethoxy)ethanol also .~ known as butyl carbitol. Preferred are also hexyl carbitol and 2-methyl pentyl carbitol. Water-soluble C~LLOSOLU ~
soluents are compounds of the 2-alkoxyethoxy ethanol class, wherein the alkoxy group is preferably butyl or hexyl.
~.-. .
:. , :
.:
- lo- 1332217 Still in the glycol ether category, certain propylene-glycol deriuatiues haue been found to be particularly e~ficient in the present context; these species include 1-n-butoxypropane-2-ol, and 1(2-n-butoxy-1-methylethoxy)propane-2-ol (butoxypropoxypropanol), with the latter being especially preferred.
.
Mixtures of the aboue soluents can also be used, like , Butyl carbitol and/or Ben~yl alcohol together with diols `~ and/or glycol ethers.
!
The organic soluent is present at leuel of from 1% to 20% by weight of the total composition, preferably from 1%
to 10%~
_ elatinq agent/s luent combination - The benefits of the present compositions are deriued from the combination of the ::
specific organic chelating agents and organic sol~ents described hereinaboue.
, .
They are particularly noticeable in terms of calcium m soap-soil remoual from surfaces such as bathtub surfaces.
:-~ In order to obtain such an effect, the weight ratio or `: organic soluent to chelating agent is in the rang~ from 2~3 to 2/1, preferably 1/1 to 2/1.
`. Combinations of e.g. the preferred chelating agen~s of formula (I) with 2-(2-butoxy-1-methylethoxy)propanol, or ~ with 2,2,4-trimethyl-1,3-pentane diol in a ratio in the : preferred 1/1 to 2/1 range haue been found to be : particularly effectiue.
:
- O~tional inqredients - In addition to the essential chelating agent~soluent binary mixture described ~.~ .:, : `
:, hereinaboue, the compositions of the inuention can contain additional ingredients, which are often highly desirable.
. ., :
The compositions herein will usually contain a . ~ .
surface-actlue agent.
Water-soluble detersiue 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 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 detersiue surfactants contain an alkyl group in the C10-Cl8 range; the anionic detersiue surfactants are most commonly used in the form of their sodium, potassium or triethanolammonium salts. The nonionics generally contain from 3 to 17 ethylene oxide 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.
Especially preferred in the compositions of the present in~ention are: C12-C16 alkyl benzene sulfonates, C12-C18 paraffin-sulfonates and the ethoxylated alcohols of the formula RO(CH2CH20)n, with R being a C12-C15 alkyl chain and n being a number from 6 to 10 and C12-C18 ethoxylated alcohol sulfates of formula Ro-(cH2cH2o) n-S03M.
~ nionic surfactants are frequently present at leuels from 0.3% to 8% of the composition. Nonionic surfactants, are used at leuels between 0.1% to 6~ by weight of the composition. Mixtures of the like surfactants can also be used.
:
~
- 12 - 1 33~217 Other optional ingredients are represented by conuentional detergency builders, which may be used in addition to ~be chelating agent herein; compounds classifiable and well-known in the art as detergent builders include the nitrilotriacetates (NT~)~ polycarboxylates, citrates, water-soluble phosphates such as tri-polyphosphate and sodium ortho- and pyro-phosphates, silicates, ethylene diamine tetraacetate (EDT~), amino-polyphosphonates (DEQUEST), phosphates and mixtures thereof.
Highly desirable ingredients for use herein are represented by conuentional detergent hydrotropes. Examples of suitable hydrotropes are urea, monoethanolamine, diethanolamine, triethanolamine and the sodium potassium, ammoniu~ and alkanol am~onium salts of xylene-, toluene-, ..
ethylbenzene- and isopropyl-benzene sulfonates.
The hard-surface cleaning compositions of the inuention may also contain an abrasiue material.
The abrasiues suitable herein are selected from water-insoluble, non-gritty materials well-known in the literature for their relatiuely mild abrasiue properties.
It is highly preferred that the abrasiues used herein not be undesirably "scratchy". ~brasiue materials hauing a Mohs hardness in the range of about 7, or below, are typically used; abrasiues hauing a Mohs hardness of 3, or below, can be used to auoid scratches on aluminum or stainless steel finishes. Suitable abrasiues 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 abrasiues". Organic abrasiues such as urea-formaldehyde, methyl methacrylate ' ~' : ~
~ - ~
, .:
' :
. _ 13 l 3~22 1 7 .
~-melamine-formaldehyde resins, polyethylene spheres and polyuinylchloride can be aduantageously used in order to auoid scratch~ng on certain surfaces, especially plastic :. surfaces.
~`' I Typically, abrasiues haue a particle size range of 10-1000 microns and are used at concentrations of 5% to 30%
.. in the compositions. Thickeners are frequently added to suspend the abrasiues.
..
Thickeners will preferably be included in the compositions of the inuentions, mainly in order to suspena ~` the abrasiue; high leuels of thickener are detrimental to the performance because they are difficult to rinse from the ` cleaned surfaces. ~ccordingly, the leuel will be kept under .
2%, preferably from 0.2% to 1.5%. Common thickeners such as ; the polyacrylates, xanthan gums, carboxymethyl celluloses, :
swellable smectite clays, and the like, can be used herein.
.l Soaps can be included in the compositions herein, the ~-~ soaps prepared from coconut oil fatty acids being preferred.
~ Optional components are also represented by ingredients 3 typically used in commercial products to prouide aesthetic ~; or additional product performance benefits. Typical -~ ingredients include perfumes, dyes, optical brighteners, -~
l soil suspending agents, detersiue e~nzymes, gel-control -~ agents, thickeners, freeze-thaw stabilizers, bactericides, `~ preservatiues, and the like.
Preferred executions of the compositions - ~he hard-surface .
cleaning compositions herein will aduantageously be executed ~; in the form of an aqueous liquid compositions, including - concentrates, containing as essential ingredients a surface-actiue agent, and the soluent/chelating agent binary -.- mixture according to the inuention.
~:.3 ~ ~3 - ~ ~
~. . . .
.~ , .
: - 14 -~`
Liquid executions at normal dilution usually contain 2-6% surfactant and 8-12% soluent/chelating agent binary mixture. ,, :
:~ Concentrated liquid executions usually contain 6-10%
surfactant and 16-24% soluent/chelating agent binary mixture.
Qlternatiuely, the compositions herein will be in the form of a creamy scouring cleanser, containing an abrasiue material, surface-actiue agent, and the soluent/chelating agent binary mixture of the inuention.
In both executions, the pH of such compositions will be neutral or in the alkaline range, generally in the range of ~ pH 5-11.
: .
. . , ',, ~, :~
: '~
,~
" :~
. .
.-- , . .
.. ,, ~ -, . i :-; .::
':
'.~. ' ~
::
'` :` . : ':
:- .
~ - 15 - l 3322 1 7 The following examples are giuen by way of illustrating the compositions herein, but are not intended to be limiting :~ -of the scop~,of the in~ention.
~bbre~iations NaPS Sodium C13 to C16 paraffin sulfonate L~S Sodium salt of linear C11-C8 alkyl benzene sulfonate Lutensol~ 07 Condensate of 1 mole C12-C14 fatty alcohol with 7 moles of ethylene oxide Lutenso~ ~ 03 Condensate of 1 mole C12-C14 fatty alcohol with 3 moles of ethylene oxide Neodol 25E3S Sulfated condensate of 1 mole C12-C15 fatty alcool with 3 moles of ethylene ! `, oxide HCnF~ Narrow cut, hardened, coconut fatty acid ETHD 2-Ethyl-1,3-hexanediol :~
BPP Butoxy Propoxy Propanol=1(2-n-butoxy-1-.~ methylethoxy)propane-2-ol . NaCS Sodium cumene sulfonate '~ CMT~ Carboxymethyltartronic acid . CMOS Carboxymethyloxysuccinic acid THFTP, Tetrahydrofurantetracarboxylic acid CP~P Cyclopentanetetracarboxylic acid OBHTP 2 Oxa-bicyclo (2.2.1) heptane . (1.4.5.) tricarboxylic acid -1, TSP/TDS~ tartrate monosuccinic acid/tartrate .. , disuccinic acid blend, at 80:20 weight ratio :~
~ ODS Oxydisuccinic acid --~ Sokolan~ HC25 Crosslinked polyacrylate thickener .,: :~
The following liquid hard surface cleaning compositions .~. according to the inuention are prepared. ~-~
. . : ~
.. Examples III and U are concentrates, in accordance with ~.
~:~ one execution of the present in~ention.
':
:~: :
~ ! ' ~:`
.'~`' ~.: ' x I ' I ' ' ' ' ' ' ' ' ' ' ' ~ ~ ~ 1 33221 7 ~ ~o~,, , ~ ~ ~ ~ I ~
w ;. ~c , o,, I,, o~ o o o x ~ I I I O I O o :~ ~
~:
~ X , o ~,,, o o . ~ X ~ o~ ~
.~ W
X ~ o ~ o o o . - X o ~ o W
: , o ~ oI o o ~ o o - ,~, W
. ~ ~ ~
-~ 3~ 1O 1 11 ~1lll Il~.n !
.-`- ,, W
~ O, ~ ~ _ o~ ~ I I I
. . , ~ , o o, , o, o ,, o,,,, ,, ~ o o ~c I I I I ~o I 1 1,~ 1 1 1 1 1 1 .,;,` X o o,,,,, ,.`. W
.~ , X o ~ - ~
'."'~ W :~:' ~ ~ ~ ~ O ~ O O O
...
.
~ O O ~ ~ ~ O
: JJ G ~ D n~ ~15 E
r~ ~ L ~ r~ ~ 0~ L
c ~ ~ ~ a. O :c ~ 11 o .~ ~ Cl z z 3 : ~ :~ .:
~: i~. : : . .
'~ `
~-:
The following creamy scouring compositions according to the invention are also prepared :
:, :
~ Ex X~Ex XUI Ex XUII Ex XUIII Ex XIX Ex XX
- L~S _ 0.6 4.0 0.6 0.6 4.0 NaPS 4.0 3.0 _ 3.0 3.0 . Lutensol ~07 _ 0.3 _ 0.3 0.3 . HCnF~ 2.0 0.6 1.5 0.4 0.5 1.5 Benzyl alcohol1.0 1.3 _ 1.3 1.3 8PP 3.0 2.0 4.0 2.0 2.0 4.0 . CMT~ 3.0 3.0 _ _ _ CMOS _ _ 3.0 _ _ THFT~ _ _ _ 3.0 _ TS~/TDS~ _ _ _ _ 3.0 . ODS _ _ _ _ _ 3.0 2 3 3.0 3.0 3.0 3.0 3.0 3.0 CaC03 30.0 30.0 _ 30.0 30.0 :~ Polyvin~lchloride _ _ 10.0 _ _ 10.0 Sokolan~ HC25 0.4 0.6 0.4 0.6 0.6 0 4 The compositions prepared in accordance with Examples I to XX show uery 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 -~
CMT~ as builder, was found to be less efficient in terms of soil-remoual properties, thus showing the criticality~:
. of the boiling point parameter used to select the solvents useful herein.
;t~
~-.
.: ~.
: ~.. - : : . .
- .~,- , . . :
Claims (18)
1. A hard surface cleaning composition containing an organic solvent having a boiling point above 90°C and a chelating agent selected from the group of:
- compounds of the formula (I) wherein R1 to R11 are selected independently from the group of: H, COOM, CH3, CH2CH3, CH2COOM, CH2OH, OH, CH(OH)COOM, C2H5, C3H7; n is 0 or an integer from 1 to 3; m is 0 or an integer from 1 to 4;
- compounds of the formula (II) wherein X is - O - or - CH2 T1 to T9 are selected independently from the group of: H, COOM, CH3, CH2CH3, CH2COOM, CH2OH, OH; and p is 0, 1, or 2;
- compounds of the formula (III) wherein X is - O - or -CH2 Y1 to Y7 are selected independently from the group of: H, COOM, CH3, CH2COOM, CH2OH, OH;
- compounds of formula (IV) wherein L1 to L8 are selected independently from the group of: H, COOM, CH3, CH2COOM, CH2OH, OH, OCH2COOM, OCH2(COOM)2; t is 0 or an integer from 1 to 8;
with the proviso that when t is 1, L6 and L7 are selected from H, OH, CH3, CH2COOM, CH2OH, OCH2COOM, OCH2(COOM)2;
- compounds of formula (V) wherein B1 to B6 are selected from the group of H, COOM, CH3, CH2CH3, CH2COOM, CH2OH, OH, CH2OCH2COOM, CH2OCH(COOM)2, CH2OCH(OH)COOM , ;
- compounds of formula VI
or formula VII
;
- mixtures of above compounds;
wherein M is H or an alkalimetal ion.
- compounds of the formula (I) wherein R1 to R11 are selected independently from the group of: H, COOM, CH3, CH2CH3, CH2COOM, CH2OH, OH, CH(OH)COOM, C2H5, C3H7; n is 0 or an integer from 1 to 3; m is 0 or an integer from 1 to 4;
- compounds of the formula (II) wherein X is - O - or - CH2 T1 to T9 are selected independently from the group of: H, COOM, CH3, CH2CH3, CH2COOM, CH2OH, OH; and p is 0, 1, or 2;
- compounds of the formula (III) wherein X is - O - or -CH2 Y1 to Y7 are selected independently from the group of: H, COOM, CH3, CH2COOM, CH2OH, OH;
- compounds of formula (IV) wherein L1 to L8 are selected independently from the group of: H, COOM, CH3, CH2COOM, CH2OH, OH, OCH2COOM, OCH2(COOM)2; t is 0 or an integer from 1 to 8;
with the proviso that when t is 1, L6 and L7 are selected from H, OH, CH3, CH2COOM, CH2OH, OCH2COOM, OCH2(COOM)2;
- compounds of formula (V) wherein B1 to B6 are selected from the group of H, COOM, CH3, CH2CH3, CH2COOM, CH2OH, OH, CH2OCH2COOM, CH2OCH(COOM)2, CH2OCH(OH)COOM , ;
- compounds of formula VI
or formula VII
;
- mixtures of above compounds;
wherein M is H or an alkalimetal ion.
2. A composition in accordance with Claim 1 wherein the organic solvent is present at levels of from 1% to 20% of the total composition and the chelating agent is present at levels of from 1% to 20% of the total composition.
3. A composition in accordance with Claim 2 wherein the weight ratio of organic solvent to chelating agent is from 2/3 to 2/1, preferably 1/1 to 2/1.
4. A composition in accordance with any one of claims 1, 2 or 3 wherein the chelating agent has the formula (I).
5. A composition in accordance with Claim 4 wherein in formula (I) n = 0, and m = 0.
6. A composition in accordance with Claim 5 wherein the chelating agent is carboxymethyltartronic acid or its alkali metal salt.
7. A composition in accordance with Claim 5 wherein the chelating agent is carboxymethyloxysuccinic acid or its alkali metal salt.
8. A composition in accordance with claim 5 wherein the chelating agent is oxydisuccinic acid or its alkali metal salt.
9. A composition in accordance with claim 4 wherein the chelating agent is a combination of tartrate monosuccinic acid and tartrate disuccinic acid or their alkali metal salts.
10. A composition in accordance with claim 9 where the weight ratio of tartrate monosuccinic acid to tartrate disuccinic acid is 70:30 to 90:10.
11. A composition in accordance with Claim 1 wherein the chelating agent has the formula (II) with n = 0 and X is oxygen.
12. A composition in accordance with Claim 11 wherein the chelating agent is tetrahydrofurantetracarboxylic acid or its alkali metal salt.
13. A composition in accordance with Claim 1 wherein the chelating agent has the formula (II) with n = 0 and X is -CH2.
14. A composition in accordance with Claim 13 wherein the chelating agent is cyclopentanetetracarboxylic acid or its alkali metal salt.
15. A composition in accordance with any one of claims 1, 2, 3, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 wherein the organic solvent is selected from the group of benzyl alcohol, glycol ethers, and diols having 6 to 16 carbon atoms in their molecular structure.
16. A composition in accordance with Claim 15 wherein the organic solvent is selected from the group of butoxypropanol, 1(2-butoxy-1-methylethoxy)propanol, 2-(2-butoxyethoxy-ethanol, benzyl alcohol, 2,2,4-trimethyl-1,3-pentanediol.
17. A composition in accordance with claim 16 wherein the organic solvent is 1-(2-butoxy-1-methylethoxy)propanol.
18. A composition in accordance with Claim 1 which in addition contains an abrasive.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB878708151A GB8708151D0 (en) | 1987-04-06 | 1987-04-06 | Hard surface cleaning compositions |
| GB87-08151 | 1987-04-06 | ||
| GB87-09621 | 1987-04-23 | ||
| GB878709621A GB8709621D0 (en) | 1987-04-23 | 1987-04-23 | Hard-surface cleaning compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1332217C true CA1332217C (en) | 1994-10-04 |
Family
ID=26292102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 563241 Expired - Fee Related CA1332217C (en) | 1987-04-06 | 1988-04-05 | Hard-surface cleaning compositions |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0286167A3 (en) |
| JP (1) | JPS6420295A (en) |
| AU (1) | AU623852B2 (en) |
| CA (1) | CA1332217C (en) |
| DK (1) | DK185888A (en) |
| FI (1) | FI91539C (en) |
| MX (1) | MX170928B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8802086D0 (en) * | 1988-01-30 | 1988-02-24 | Procter & Gamble | Creamy scouring compositions |
| US5254290A (en) * | 1991-04-25 | 1993-10-19 | Genevieve Blandiaux | Hard surface cleaner |
| DE4243477A1 (en) * | 1992-12-22 | 1994-06-23 | Henkel Ecolab Gmbh & Co Ohg | Neutral liquid detergent (II) |
| DE4243468A1 (en) * | 1992-12-22 | 1994-06-23 | Henkel Ecolab Gmbh & Co Ohg | Neutral liquid detergent (I) |
| US5632780A (en) * | 1995-03-30 | 1997-05-27 | The Procter & Gamble Company | Dry cleaning and spot removal proces |
| EP0817877A1 (en) * | 1995-03-30 | 1998-01-14 | The Procter & Gamble Company | Dry cleaning article |
| US5547476A (en) * | 1995-03-30 | 1996-08-20 | The Procter & Gamble Company | Dry cleaning process |
| US5630847A (en) * | 1995-03-30 | 1997-05-20 | The Procter & Gamble Company | Perfumable dry cleaning and spot removal process |
| US5591236A (en) * | 1995-03-30 | 1997-01-07 | The Procter & Gamble Company | Polyacrylate emulsified water/solvent fabric cleaning compositions and methods of using same |
| US5630848A (en) * | 1995-05-25 | 1997-05-20 | The Procter & Gamble Company | Dry cleaning process with hydroentangled carrier substrate |
| US5687591A (en) * | 1995-06-20 | 1997-11-18 | The Procter & Gamble Company | Spherical or polyhedral dry cleaning articles |
| US5885362A (en) | 1995-07-27 | 1999-03-23 | Mitsubishi Chemical Corporation | Method for treating surface of substrate |
| CA2238194A1 (en) * | 1995-11-21 | 1997-05-29 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing specific concentration of tartaric acid detergent builder |
| DE19935083A1 (en) | 1999-07-29 | 2001-02-08 | Benckiser Nv | Detergent for glass ceramic surfaces |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1338966A (en) * | 1970-12-14 | 1973-11-28 | Procter & Gamble | Detergent builder compositions |
| DE3002789A1 (en) * | 1980-01-26 | 1981-07-30 | Henkel KGaA, 4000 Düsseldorf | LIQUID CLEANING AND CARE PRODUCT |
| US4507219A (en) * | 1983-08-12 | 1985-03-26 | The Proctor & Gamble Company | Stable liquid detergent compositions |
| US4581161A (en) * | 1984-01-17 | 1986-04-08 | Lever Brothers Company | Aqueous liquid detergent composition with dicarboxylic acids and organic solvent |
| GB8409055D0 (en) * | 1984-04-07 | 1984-05-16 | Procter & Gamble | Cleaning compositions |
| US4566984A (en) * | 1984-11-16 | 1986-01-28 | The Procter & Gamble Company | Ether polycarboxylates |
| JPS61157593A (en) * | 1984-12-28 | 1986-07-17 | ライオン株式会社 | Detergent composition for bathroom |
| US4663071A (en) * | 1986-01-30 | 1987-05-05 | The Procter & Gamble Company | Ether carboxylate detergent builders and process for their preparation |
| US4749509A (en) * | 1986-11-24 | 1988-06-07 | The Proctor & Gamble Company | Aqueous detergent compositions containing diethyleneglycol monohexyl ether solvent |
-
1988
- 1988-03-30 EP EP88200593A patent/EP0286167A3/en not_active Withdrawn
- 1988-04-05 CA CA 563241 patent/CA1332217C/en not_active Expired - Fee Related
- 1988-04-06 AU AU14193/88A patent/AU623852B2/en not_active Ceased
- 1988-04-06 MX MX1100288A patent/MX170928B/en unknown
- 1988-04-06 FI FI881587A patent/FI91539C/en not_active IP Right Cessation
- 1988-04-06 DK DK185888A patent/DK185888A/en not_active Application Discontinuation
- 1988-04-06 JP JP8496088A patent/JPS6420295A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| MX170928B (en) | 1993-09-22 |
| FI881587A (en) | 1988-10-07 |
| AU1419388A (en) | 1988-10-06 |
| EP0286167A3 (en) | 1989-08-30 |
| FI91539B (en) | 1994-03-31 |
| FI91539C (en) | 1994-07-11 |
| EP0286167A2 (en) | 1988-10-12 |
| FI881587A0 (en) | 1988-04-06 |
| JPS6420295A (en) | 1989-01-24 |
| DK185888A (en) | 1988-10-07 |
| AU623852B2 (en) | 1992-05-28 |
| DK185888D0 (en) | 1988-04-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |