Note: Descriptions are shown in the official language in which they were submitted.
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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
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.~- It is well known to formulate hard-surface cleaning:~
compositions, containing organic sol~ents and chelating -~
~gents. : ~ :
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,~ 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
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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.
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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.
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Tetrahydrofuran tetracarboxylic acid is known as
phosphate replacement builder from U.S. 3,580,852.
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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.
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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
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: compounds ha~ing the formulae (I) to (UII) hereinafter
described, or mixtures of compounds (I) to (UII).
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_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)
COOM 7 5 7 7 19
,~ 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
.~ ~
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
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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)
':
B4
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
11
,~ O
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' - compounds of formula UI -
: COOM
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: HO - CH
\
COOM
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.` 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.
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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.
,`,;
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%.
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~- 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.
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~ 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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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.
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They are particularly noticeable in terms of calcium
m soap-soil remoual from surfaces such as bathtub surfaces.
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~ 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.
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- O~tional inqredients - In addition to the essential
chelating agent~soluent binary mixture described
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hereinaboue, the compositions of the inuention can contain
additional ingredients, which are often highly desirable.
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The compositions herein will usually contain a
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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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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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melamine-formaldehyde resins, polyethylene spheres and
polyuinylchloride can be aduantageously used in order to
auoid scratch~ng on certain surfaces, especially plastic
:. surfaces.
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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.
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Liquid executions at normal dilution usually contain
2-6% surfactant and 8-12% soluent/chelating agent binary
mixture. ,,
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:~ 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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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. ~-~
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.. Examples III and U are concentrates, in accordance with ~.
~:~ one execution of the present in~ention.
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;. ~c , o,, I,, o~ o o o
x ~ I I I O I O o
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~:
~ 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,,,,,
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.~ , X o ~ - ~
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~ ~ ~ ~ O ~ O O O
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~ O O ~ ~ ~ O
: JJ G ~ D n~ ~15 E
r~ ~ L ~ r~ ~ 0~ L
c ~ ~ ~ a. O :c ~ 11 o .~ ~ Cl z z 3
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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.
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