Note: Descriptions are shown in the official language in which they were submitted.
LAUNDRY MATERIAL
The present invention relates to a new laundry
material, especially adapted for washing fabrics, the said
laundry material presenting a phosphate content reduced to
less than 5% by weight and even equal to zero and compris-
ing at least one zeolite.
For a long time phosphates played a predominant
role in laundry materials, especially as sequestrants of
cations which form salts insoluble in water, in particular
the calcium and magnesium ions; the excellent performance
that they enable to be achieved resides in their
particular structure.
However, one of the acute problems which the
laundry materials industry must face, is the very pollut-
ing character of said phosphates. In fact, thelr presence
in waste water causes the well-known phenomenon of the
eutrophisation; and for this reason the use of phosphates
in laundry materials must comply with restrictions parti-
cularly ecolog:Lcal which are more and more severe.
This ecological aspect is all the more pronounced
as the powerful detergents currently employed and, in
particular, the products used in industrial laundries,
contain large amounts of phosphates which can exceed 30%.
Many attempts have therefore been made to elimi-
nate entirely or at least partly the phosphates in laundry
materials.
It has especially been proposed to use, as total
or partial replacement agent for the phosphates, zeolites
of natural or synthetic origin ; these products are well-
known for their cation exchange power, particularly of
calcium and magnesium, which are the source of the
hardness of water and of mineral incrustation problems in
the laundry or linen.
20~4a
However, while zeolites contribute to the elimi-
nation of these cations, their total substitution for
phosphates does not permit a degree of washing compatible
with the exigencies of practice to be achieved.
5Also, to improve the washing quality of laundry
material based on zeolite and containing few or no phos-
phates, it has been proposed to combine the said zeolites
with various other agents such as notably nitrilotriacetic
acid (NTA) and its salts, especially sodium nitrilotriace-
10tate (European patents EP-A-0 070 079 and EP-A-0 319 053).
However, besides their imperfect biodegradability,
the said products are surmised to fix heavy metals, which
possibly could pass into drinking water. Consequently, it
is generally recommended and even rendered compulsory
today in certain countries, to limit to 5~ their propor-
tion in detergent materials.
This 5~ proportion appears to be the optimum
proportion of nitrilotriacetate of alkaline metal in the
phosphates free compositions disclosed in the European
Patent EP 0 319 053, which compositions contain from 20 to
35% by weight of zeolites.
It has also been proposed, as far as laundry mate-
rials containing few or no phosphates are concerned, to
associate the zeolites with special polycarboxylic poly-
mers based on well-defined mixtures of mono- and dicarbo-
xylic monoolefinic acids and of non-ionic esters of the
said acids (European Patent EP 193 360). Among the
monoolefinic derivatives of mono- and dicarboxylic acids,
the derivatives of acrylic and/or methacrylic acid as well
as the derivatives of maleic and/or itaconic acid, are
especially mentioned.
It appears that such compositions may be free of
phosphates and contain less than 20~ by weight of
zeolites. However, in that case, the said zeolites are
associated not only with the said polycarboxylic polymers
but also with clays and with NTA.
~ ~3~ ri i~ ~
Among the polycarboxylic agents the most commonly
recommended to improve the qua]ity of the laundry mate-
rials based on zeolites and containing few or no phos-
phates, there may be mentioned the acrylic polymers, and
especially the homopolymers of acrylic and of methacrylic
~cids or of their salts, especially polyacrylic acid (PA)
and sodium polyacrylates (NaP).
Compositions containing for example from 2 to 7~
by weight of polyacrylates and from 25 to 60% by weight of
zeolites are disclosed in the German Patent DE 37 07 806.
Laundry materials associating zeolites and poly-
acrylates are also disclosed in the German Patent DE
38 3~ 478.
It must however been recalled that acrylic poly-
mers, especially polyacrylic acid and its salts, present
the major drawback of not being biodegradable.
Consequently, it seems at present preferable to
use these products at rates which do not exceed 4% by
weight o~ the laundry material.
From the preceeding explanations, it appears that,
generally speaking, there is a need for laundry materials
presenting a reduced content of phosphates or which are
even free of phosphates and which, while playing with
efficiency the:Lr role without necess~ty of an overdosage
in zeolites and without the use of ecologically unaccep-
table additives, enable to reach global rates of polymers
and/or polycarboxylic monomers non or weakly biodegradable
and compatible with the present requirements of the
environment protection and, especially, specific rates of
nitrilotriacetic acid (NTA), polyacrylic acid (PA) or
their salts which do not e~ceed 4~ by weight.
And Applicants have had the merit of finding that
the said object is reached as soon as the laundry mate-
rials of the kind in question comprise at least one oxi-
dized polysaccharide selected from the group comprising:
~38~
a) the products resulting from the oxidation of disaccha-
rides presenting a terminal function of the aldonic
type,
b) the products resulting from the oxidation of trisaccha-
rides and of oligosaccharides presenting a terminal
function of the aldonic type,
c) the products resulting from the oxidation of starch
hydrolysates, of cellulose and hemicelluloses present-
ing a terminal function of the aldonic type,
d) any mixtures of at least two of the above-identified
oxidation products.
Advantageously, the oxidized polysaccharides which
can be used within the scope of the present invention are
those which are obtained startin~ from di-, tri- and
oli~osaccharides, from starch hydrolysates, from cellulose
and hemicellulose and of which only the terminal unction
of the aldehyde type before oxidation (among their poten-
tially oxidable functions) is substantiall~ oxidized into
a function of the aldonic type.
Such oxidized polysaccharides can be obtained,
especially if the intended oxidation is actually "selec-
tive" at the level of the terminal function of the aldonic
type by way of the catalytic oxidation process disclosed
by the Applicants in their European Patent EP 232 202.
The polysaccharides whose process, disclosed in
the above-mentioned European Patent EP 232 202, makes the
selective oxidation possible comprise especially:
- disaccharides such as lactose, maltose, isomaltose,
cellobiose, xylobiose and mannobiose, having a terminal
function of the aldehydic type,
- the starch hydrolysates obtained by acid and/or enzy-
matic route,
- the hydrolysis products of hemicelluloses such as the
D-galacto-D-mannanes, the D-gluco-D-mannanes, the
L-arabino-D-xylanes, the D-xylo-L-arabinanes.
2~38~
According to another advantageous embodiment of the
laundry material according to the invention, the oxidized
polysaccharide used within the said product appears in the
form of an oxidation product of starch hydrolysate having a
DE (Dextrose Equivalent) from about 5 to about 90 and
presents preferably an acid index I comprised between about
1 and about 20, the said acid index being expressed in
number of grams of carboxylic function per 100 g of
oxidized polysaccharide, and given by the formula:
DE x 45
I = 100 x 180
100 + DElx8o218 _ DE
According to the present invention, very particu-
larly preferred are oxidized polysaccharides which have an
acid index comprised between about 5 and about 14 and
which are obtained by oxidation of starch hydrolysates
having a DE comprised between a~out 20 and about 65.
Very particularly advantageous are oxidized
polysaccharides which have an acid index comprised between
about 8 and about 14 and which are obtained by oxidation
of starch hydrolysates having a DE comprised between about
35 and about 650
According to another advantageous embodiment, the
oxidized polysaccharide is an oxidized product having,
especially due to its reducing sugars content, a good
stability, especially from the point of view of its
colour, when the said oxidized product is used (when
preparing or using the laundry material according to the
invention) at any moment and for example at the moment of
3 atomization or spraying, within an environment presenting
an alkaline pH and/or a high temperature, environment
which is adapted to colour (more or less pronounced
yellowing) any composition containing lt.
In that connection, Applicants have elaborated new
products consisting of "stabilized" oxidized polysaccha-
rides which present low contents, generally lower than
2 ~
0.6%, preferably lower than about 0.1~ and still more
preferably lower than 0.05% by weight, in reducing sugars.
In particular, Applicants have found that, when
subiecting oxidized polysaccharides, in particular of the
type constituted of oxidized starch hydrolysates to hydro-
genation techniques, one obtains the intended products
especially oxidized products which have a content in
reducing sugars practically equal to zero and which are
"stabilized" as far as a possible yellowing in the
presence of a particular environment which favours such a
yellowing (alkaline pH, high temperature) is concerned.
The abovesaid hydrogenation techniques comprise in
particular catalytic hydrogenation techniques carried out
continuously or not and using at least one catalyst
selected from the groups IB, IIIB, IVB, VI, VII and VIII
of the periodical table and especially selected from the
group comprising nickel, platine, palladium, cobalt,
molybdenum and mixtures of the said metals.
Hydrogenation techniques using Raney nickel as a
catalyser fixed or not on an inert carrier in the presence
or not of an additional hydrogene source are particularly
preferred.
Other hydrogenation techniques using, in the
absence of any hydrogenation catalyst, hydrogen sources
other than hydrogene gas, for example borohydrides of
alkaline metals, especially sodium borohydride, may also
be contemplated.
The oxidized polysaccharides, especially of the
type of the oxidized starch hydrolysates, which are
"stabilized" after such a hydrogenation treatment, in
particular those having a D~ comprised between 5 and 90,
an acid index I comprised between 1 and 20 and which are
"stabilized" by catalytic hydrogenation, when used in
laundry compositions and laundry materials furthermore
provide the latter with performances which are comparable
with the performances of the same oxidized products which
st-~
are not "stabilized" and even performances improved in
connection with certain parameters.
Moreover, it ~ust be recalled, at that precise
state of the specification, that the characteristic use of
at least one oxidized polysaccharide, especially of a
polysaccharide, for instance a starch hydrolysate, "selec-
tively" oxidized at the level of its aldehydic terminal
function, within the laundry materials according to the
invention, not only enables to substitute efficiently
within the said materials at least part of the polycarbo-
xylic compounds non-biodegradable or weakly biodegradable
of the type NTA, PA or their salts, by products, i.e.
oxidized polysaccharides, with which no problems of
biodegradability occur, but also does not necessitate in
no case the concomitant increase of the rate of zeolite(s)
contained within the said materials with respect to the
rates at present used within laundry materials available
in the trade, which are generally of about 21 to 25% by
weight.
And it is remarkable to notice that, in an all the
more surprising and unexpected manner, the characteristic
presence of at least one oxidized polysaccharide, espe-
cially a polysaccharide, notably a starch hydrolysate,
"selectively" oxidized at the level of its aldehydic
terminal function, enables the said materials which
contain the said oxidized polysaccharide to be efficient:
- for constitutive zeolite(s) rates lower than 20% by
weight and/or
- for constitutive rates of polycarboxylic compounds of
the type NTA, PA or their sal~s, not higher than 2%
by weight and even in the substantial absence of the
said polycarboxylic compounds.
In addition to the advantages which have just been
disclosed in connection with the laundry materials
according to the invention, it must be noticed that the
said materials, on the contrary to certain materials of
~ $~
the prior art, do not produce any substantial desactiva-
ti~n of the bleaching agents, between which especially
perborate, currently used in laundry materials for the
elimination of oxidable stains and produce high levels of
whiteness.
Without wishing to be bound by theory, Applicants
attribute the excellence of these performances to the
stabilizing effect played by the oxidized polysaccharides
with respect to the oxidizing agents.
This result is particularly pronounced when the
oxidising agent is a perborate, especially of sodium, and
when the composition according to the invention comprises,
as oxidized polysaccharide, an oxidized starch hydro-
lysate.
According to an advantageous embodiment of the
laundry material according to the invention, the latter
comprises :
- a proportion from about 5 to about 35% by weight, pre-
ferably from 10 to 25% and, still more preferably, from
15 to 20% by weight of at least one zeolite,
- a proportion from about 3 to about 20~ by weight, pre-
ferably from 5 to 20~ and, still more preferably, from
7 to 20% by weight of at least one oxidized polysaccha-
ride, in particular of a polysaccharide "selectively"
o~idized in respect with its terminal function of the
aldehydic type.
According to another advantageous embodiment of
the above-mentioned material, the ratio by weight between,
on the one hand, the zeolite and, on the other hand, the
oxidized polysaccharide is comprised between about 0.5/1
and about 4/1, preferably between 1/1 and 2/1.
In connection with the present invention, the term
"zeolite" comprises any ion exchanging material of the
aluminosilicate type, of crystalline or amorphous nature
and of natural or synthetic origin, such as disclosed for
example in the above-mentioned European patents EP 70 079
and EP 193 360. Such products are for example available in
the trade under the commercial names "zeolite A", "zeolite
B", "zeolite X" or "zeolite HS".
In particular, a crystalline sodium silicoalumi-
nate of the "zeolite A" type can be used.
In practice, the laundry materlal according to the
invention, which constitutes a new industrial product,
comprises also one or several other constituents which are
selected in particular from the group comprislng the
detergent agents, the surfactive agents, the antiredeposi-
tion agents, the oxidizing agents, the structural agents,
the anticorrosion agents, the antifoaming agents, the
enzymes, the perfumes, the dyes, the solubilizing agents,
etc., for example such as disclosed in the above-mentioned
European patents EP 70 079 and EP 319 0530
The detergent agents may be, for example, selected
among synthetic anionic detergent agents, such as hydro-
soluble alkaline metal salts of organic sulphates and
sulphonates comprising alkyl radicals having from about 8
to 22 carbon atoms, such as for example sodium or potas-
sium dodecylbenzene sulphonates.
It is also possible to select the said agents
among the non-ionic detergent agents, such as especially
the alkylpolyg]ucosides or the ethoxylated fatty alcohols.
The oxidizing agents, i.e. the products which are
adapted to set free peroxide ions in an amount sufficient
to permit the bleaching of wine stains, of tea stains, of
coffee stains, etc., may be in particular perborates,
percarbonates, persilicates or perphosphates of alkaline
metals and especially the sodium perborate.
The structural agents may in particular be select-
ed, as recommended in the European patent EP 215 637, from
the susars, the hydrogenated sugars and the mixtures of
the above-mentioned products and especially those which
consist of or which at least contain a monosaccharide such
as glucose or fructose and/or a disaccharide such as
2 ~ 3 8 6 ~ ~
maltose or saccharose and/or their hydrogenation products.
The structural agents may especially consist of or
contain, at least partially, sorbitol and especially
consist of hydrogenated products obtained by hydrogenation
of starch hydrolysates or glucose syrups.
Furthermore, the laundry material according to the
invention may contain detergency additives normally used
such as polyacrylic acid (PA), nitrilotriacetic acid (NTA)
and/or their respective salts, especially their sodium
salts.
However, as already indicated above, the charac-
teristic presence of at least one oxidized polysaccharide
wlthin the laundry materials according to the invention
enables the said products to be, in a remarkable manner,
while having a zeolite rate not higher and even lower than
those of the materials of the prior art, efficient or
constitutive rates of NTA, of PA or of their salts, lower
than those currently encountered in the said materials of
the prior art, especially for rates which are not higher
than 2% by weight and which are even substantially equal
to 0.
The laundry materials according to the invention,
which are adapted in particular for the washing of tex-
tiles as well in a machine or "hand-washed", are prefera-
bly in the form of free-flowing particles, especially in
the form of a powder or of granulates.
No special process and no special installation
other than those normally used by those skilled in the art
is necessary for the preparation of the above-mentioned
materials; those skilled in the art may for example resort
to classic techniques of drying of aqueous suspensions by
spraying.
The mixture of the at least one zeolite and the at
least one oxidized polysaccharide to be comprised by the
laundry materials according to the invention can be
carried out in various manners, the said products being in
the form of powders, of liquids, or of mi~tures of
powders/liquids, in the presence or not of all or part of
the other constituents of the said materials.
For example, it is possible to mix the oxidized
polysaccharide with a laundry "precomposition" already in
the powder form and containing the ma~ority or even the
totality of the other constituents of the final material.
The association of at least one zeolite and of at
least one oxidized polysaccharide may also be realized
within the laundry materials, the said materials being
then in another form than that of free-flowing particles,
in particular in the form of liquids, gels or pastes.
These products, which generally will present a dry
matter content from about 15% to about 80%, and especially
from 30 to 50~, can be obtained, for example, by
increasing, by any possible manner and especially by mere
dissolution or suspension in water or in another liquid,
the water content of the laundry materials according to
the invention previously prepared in the form of powders
or of granulates.
They can also, in other cases, present a formula-
tion substantially different of that used for the powders
or granulates, especially as far as their content in
tensio-active or surfactive additives is concerned.
The invention will be still better understood by
means of the following examples relating to particularly
advantageous embodiments of the products according to the
invention.
To demonstrate the effectiveness of the laundry
materials according to the invention, comparative trials
were carried out using, on the one hand, a laundry mate-
rial according to the prior art denoted by the letter "T"
whose constitution is given in the following Table I and,
on the other hand, four laundry materials according to the
invention, denoted respec~ively by the letters A, B, C and
D, whose respective contents in zeolite(s), in o~idized
polysaccharide(s) and possibly in sodium polyacrylates
(PNa) are given in Table II.
In this first series vf trials, an oxidation
product of a starch hydrolysate having a DE of about 61.5
and an acid index I of about 13.6 is ussd in the laundry
materials according to the invention as ox~dized poly-
saccharide.
TABLE I
Manufacturing Producing .
Constituentsbrand or formula Company by weight
AntifoamingUKANIL 2136 ICI 0.2
dodecylbenzene
sulphonate FLUKA 6
15 ethoxylated fatty
alcohol KC 7/L
ethoxylated ceto-
stearylic alcohol EMPILAN KM 11MARCHON 5
Sodium sulphate Na2 SO4PANREAC 21
Sodium metasilicate anhydrous SiO2Na2O PROLABO 3
20 Sodium carbonate Na2 CO3PANREAC 5
Sodium perborate Na BO3 4H2OFLUKA 18
Tetraacetylethylene
diamine LEVER 2
Carboxymethyl-
25 celluloseBLANOSE 7M65 AQUALON
Zeolite ANa2O Al2O~ 2SiO~
x H2O (x= 4 to 5) MONTEDISON 25
Sodium Polyacrylate SOKALAN C 245 BASF 4
EnzymeESPERASE NOVO 0.6
Water _ _ qsp 100
3o _
'~3~
TABLE II
_
Constituents Composition (% by weight~
T A B C D
Zeolite A 25 18 18 19 19
_
Polyacrylates 4 2 ~ _
Oxidized polysaccharide _ I0 18 14 10
The said comparative trials consist of washing
trials which were performed by means of a washing machine
of the VEDETTE 8596 SYSTEME CHOIX brand with top loading.
The trials were carried out at the two following
temperatures: 40C and 60C.
For the trial at 40C, a rise of temperature of 13
minutes, then a plateau at 40C of 22 minutes was selected.
The complete cycle, that is to say including the fillings,
rincings and spin-drying, lasts 80 minutes.
For the trial at 60C, there was provided a rise in
temperature of 21 minutes, then a plateau at 60~C of 22
minutes. The complete cycle lasts 90 minutes.
In the two trials, the volume of washing water was
11 liters.
Two washings were carried out per temperature.
The hardness of the water was 30 TH.
The washing load was composed of 2.2 kg of pieces
of white fabric (cotton) of which the sizes were 55 cm x 70
cm.
On each washing, there was included with a load of
2.2 kg of pieces of white fabric, a group of "soiled
fabrics" of different natures and which include soilings
predetermined and predeposited on these fabrics.
In practice, these "presoiled" fabrics which are
pinned to the washing load, are as follows:
- 2 strips of grey polyest(er/cotton (64/35) of the KREFELD
brand ~ref. WFK 20 C), soiled by a mixture of an animal
14
oil and carbon black,
- 2 strips of cotton of the brand EMPA 103 constituted by
eight pieces sewn together, namely:
- a piece of white cotton (of the EMPA 221 type),
- a piece of grey cotton (of the EMPA 101 type soiled
by a mixture of vegetable oil and carbon black),
- a piece of cotton soiled with blood (of the EMPA 111
type),
- a piece of cotton soiled with cocoa (of the EMPA 112
type),
- a piece of COttOII soiled by a mixed stain of milk,
blood, carbon blac~ (of the EMPA 116 type),
- a piece of unbleached cotton (of the EMPA 222 type),
- a piece of cotton soiled with wine (of the EMPA 114
type),
- a piece of cotton soiled with sulphur black (not
used in the present measurements),
- 2 strips of polyester/cotton (65/35) soiled with tea, of
the KREFELD brand (ref. WFK 20G),
20 - 2 strips of polyester/cotton (65/35) soiled with cocoa,
of the KREFELD brand (ref. WFK 20F),
- 2 strips of white polyester/cotton (65/35) of the EMPA
brand (ref. EMPA 213).
The dosle of laundry material was 8 g/l of water.
To evaluate the quality of the washing, on the one
hand the removal of the soiling and o$ the stains and, on
the other hand, the effect of the washings on the degree
of bleaching were measured.
To evaluate the removal of the soiling and of the
stains, procedure was by photometry (measurements of the
amount of light reflected by the fabric); it was thus
possible to calculate the percentages of removal of the
soiling. A device for measuring the reflection of light,
marketed under the brand ACS 1400 SPECTR0 was used.
The removal of the soiling is expressed by the
formula
Removal in ~ _ C - B x 100 (1)
in which:
A = reflectance of the control white sample,
B = reflectance of the control soiled sample,
C = reflectance of the soiled sample after testing.
The reflectances were determined by means of the
blue trichromatic component.
The number of measurements carried out per fabric
was 4, which means 4 measurements (that is to say at four
different places on the same piece of fabric) x 2 washings
x 2 strips of fabric = 16 measurements per soiling, per
formulation and per temperature.
Regarding the degree of bleaching, the effect of
the washings was measured on two cuttings of EMPA 221
unsoiled white cotton and on two cuttings of EMPA 213
unsoiled white polyester/cotton, which were incorporated
in the washing bath. On each cutting, 4 measurements were
carried out, which therefore gave 16 measurements per
formulation and per temperature studied.
If there are denoted :
- by Rbo, the blue trichromatic component obtained
before washing,
- by Rb, the blue trichromatic component obtained
25after washing,
the degree of b]eaching is given by the formula
BL = Rb - Rbo.
In the trials proper which will now be described,
the effectiveness of the laundry materials according to
the invention was studied successively on soilings based
on oil and on carbon black, then on proteinic stains and
oxidizable stains and finally the "degree of whiteness"
conferred by said materials on the treated fabrics was
determined.
2~3~
EXAMPLE 1
Stains produced by mixtures of mineral, vegetable and/or
animal oil with carbon black.
Washing trials were carried out, on the one hand,
on grey cotton and, on the other hand, on synthetic
fabrics (polye~ter/cotton~.
1) Trials on grey cotton
By washing, there were treated successively each
time two strips of grey cotton of the brand EMPA 101
soiled by a mixture of vegetable oil and carbon black.
This type of soiled cotton is representative of
insoluble pigmentary soilings bound to the fabric by
greasy film, as for example the collars of shirts and of
coats, the rags and the greasy stains.
The two groups of tests carried out respectively
at 40C and 60C gave for the products according to the
invention A, B, C and D, on the one hand, and for the
product T according to the prior art, on the other hand,
from the point of view of removal of soiling represented
by the abovesaid formula (1), the results collected
respectlvely in Tables III and IV.
TABLE III
(Trial at 40C)
-
~rype Removal of soiling (in %)
of fabric T A B C D
_
EMPA 101 17.4 17.5 16.3 16.7 16.1
TABLE IV
3 (Trial at 60C)
I
Type Removal of soiling (in %)
of fabric T A B C D
EMPA 101 17.7 18.8 23.1 16.9 17.1
_
~8~
2) Trials on grey synthetic materials
The synthetic fabric used here was a fabric of the
polyester/cotton (dacron/cotton) type of the brand
KREFELD; it was soiled with a mixture of animal oil with
carbon black (ref. WFK 20C).
The two groups of the trials carried out respecti-
vely at 40C and 60C gave for the compositions A, B, C
and D, on the one hand, and for the control product T, on
the other hand, from the point of view of the removal of
soiling represented by the abovesaid formula (l), the
results which are collected respectively in Tables V and
VI.
TABLE V
(Trial at 40~C)
Type of ¦ Removal of soiling (in %)
synthetic fabric 1 T A B D
Polyester/cotton 20.2 20.0 18.1 19.0 18.8
WFK 20C _ _
TABLE VI
(Trial at 60C)
Type of Removal of soiling (in ~)
25 synthetic fabric T ~ _ _ C I D
Polyester/cotton l9.9 20.1 24.7 19.2 19.5
WFK 20C _ _
From Tables III to VI, it appears that the charac-
teristic presence of at least one oxidized polysaccharide,
especially of at least one polysaccharide "selectively"
oxidized at the level of its terminal function of the
aldehydic type, in the laundry materials according to the
invention, enables and that, for washing performances
similar or even higher than those noticed with the prior
art laundry material:
2038~
18
- to decrease the rate of incorporation of zeolite(s~
and/or
- to decrease the rate of incorporation of a non-biode-
gradable detergence additive currently used, such as
polyacrylates, and even to suppress completely the
incorporation of such an agent.
EXAMPL~ 2
Proteinic stains
The action of the laundry materials according to
the invention on proteinic stains is studied by using
fabrics of the cotton type of EMPA b~and, namely: EMPA lll
fabric soiled with blood, EMPA 112 fabric soiled with
cocoa and EMPA 116 fabric soiled with a mixture of blood,
milk and carbon black, and of the polyester/cotton type of
the KREFELD type, namely: WFK 20F fabric soiled with
cocoa.
These soilings are representative of stains of the
blood, milk, egg, meat juice, mayonnaise, sauce type and
the like.
Two groups of trials performed at 40~C and 60C
gave for the compositions A, B, C and D according to the
invention and for the control product T, from the point of
view of the removal of soiling represented by the above-
said formula (l), the results collected in following
Tables VII and VIII.
TABLE VII
(Trial at 40C)
Type of Removal of soiling (in ~) ¦
fabric T A B C D
3o _ .
EMPA 111 (blood) 54.3 55.9 51.1 53.5 58.8
EMPA 112 (cocoa) 22.8 22.9 24.4 24.3 20.7
EMPA 116 (mixed) 20.3 19.9 16.6 16.0 22.0
Average cotton 32.5 32.9 30.7 31.3 33.8
35 WFK 20F (cocoa) 75.3 76.2 68.3 69.0 68.0
19
TABLE V _
(Trial at 60C)
Type of Removal of soiling (in %)
fabric T A B C D
EMPA 111 (blood) 65.4 75.3 64.8 57.5 66.0
EMPA 112 (cocoa) 25.8 24.5 30.3 21.3 20.6
EMPA 116 (mixed) 31.3 38.0 33.0 36.1 32.2
Average cotton 40.8 45.9 42.7 41.6 39.6
10 WFK 20F (cocoa) 76.3 76.5 80.0 73.3 77.2
From Tables VII and VIII, it appears that, in the
case of the proteinic stains, the same conclusions as
those previously made in connect~on with stains produced
by mixtures of oil and carbon black, may be drawn as far
as the efficiency of the laundry materials according to
the invention is concerned as well as their interest
comparatively with a material of the prior art which,
while containing simultaneously more zeolite(s) and more
polyacrylates, appears not to be more performant, espe-
cially for a test temperature of 60C.
EXAMPLE 3
Oxidizable stains
The effect of ~he laundry materials according to
the invention on oxidizable stains was studied by using
the following fabrics:
- polyester/cotton of the brand KREFELD soiled with tea
(ref. WFK 20G)
- cotton of the brand EMPA 222, that is to say unsoiled
3 unbleached cotton
- cotton of the brand EMPA 114 soiled with wine.
The abovesaid fabrics are sensitive to chemical
oxidation; the stains caused are those which the bleaching
attenuates or causes to disappear (other stains of this
type are those caused by fruits, coffee, vegetables and
the like).
2 ~
A group of trials performed at 60C gave for the
composition A, B, C and D and for the control product T,
from the point of view of the removal of soil~ng repre-
sented by the abovesaid formula (1), the results collected
in Tables IX.
TABLE IX
Type of Removal of soiling (in %)
fabric T A B C D
10 EMPA 222 (unbleached) 14.7 13.1 12.5 12.7 13.1
EMPA 114 (cocoa) 76.8 78.6 68.0 75.7 75.0
~verage cotton 45.7 45.8 40.2 44.2 44
WFK 20G (tea) 85.9 85.4 65.6 82.0 83.5
15 The average of the results obtained on the stains
of tea and wine and on unbleached cotton reflects the
behaviour of the products tested on all stains of this
family.
From Table IX, it appears that, in the specific
case of oxidizable stains, the laundry materials according
to the invention enable to reach a level of efficiency
equal to that of the prior art laundry material. The
laundry materials according to the invention fully respond
to the criterium generally required as far as the elimina-
tion of that type of stain is concerned.EXAMPLE 4
Degree of bleaching
Unblued white cotton of the brand EMPA 221 and
unblued polyester/cotton of the brand EMPA 213 were used
3 to determine whether a given laundry material was suitable
for preserving, for increasing or for diminishing the
initial degree of whiteness of the fabric.
The two groups of trials performed respectively at
40C and 60C gave for the compositions A, B, C and D, on
the one hand, and for the control product T, on the other
hand, from the point of view of degree of whiteness, the
20~8~0
results collected in Table X.
TABLE X
Variation (in ~) of the degree
of whiteness
Trial~ _______ ______. ______ ______ D
Cotton at 40C + 3.1 + 3.1 + 2.6 + 2.5 + ~.
________________________ ______ ,______. ____ __. ______ ____ I
Cotton at 60C + 4.5 + 4.3 + 5.7 + 4.3 + 4. l
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ . _ _ _ _ _ _ . _ _ _ _ _ _ _ _ _ _ _
Polyester/cotton at 40C + 0.7 + 0.1 + 0.3 + 0.5 ~ 0. l
__ _ _ __ _ _ _ _ _ _ _ _____ __ __ _ _ _ _ _ _ _ _ ___ _ __ . __ _ _ _ _. _ ___ _ _ _ _ _ _ I
Polyester/cotton at 60C + 1.2 + 0.~ + 1.6 + t.3 + 1.~
From Table X, it appears that, as far as the
criterium under examination is concerned, the laundry
materials according to the invention are globally as good
as the prlor art laundry material, the said materials
according to the invention enabling to obtain, after
washing, a fabric whose degree of whiteness is higher than
that which it had before washing.
EXAMPLE 5
In connection with a second group of trials, there
were compared, according to tests identical to those
previously disclosed, the efficiency of four laundry
materials according to the invention referred to by E, F,
G and H, and with respect to that of a prior art product
containing 20% of zeolite and 10% of tripolyphosphates.
In order to prepare the said products E to ~, the
10% of tripolyphosphates of the composition of the control
were substituted by the same weight respectively:
- of the product of oxidation of a starch hydrolysate
having a DE close to 37, and presenting an acid index I
close to 8.6 as far as product E is concerned,
- of the product of oxidation of a starch hydrolysate
having a ~E close to 37, presenting an acid index I
close to 8.6 and "stabilized" by catalytic hydrogena-
tion with nickel ~residual rate in reducing sugars SR
~$~0
22
lower than 0.1%) as far as product F is concerned,
- of the product of oxidation of a starch hydrolysate
having a DE close to 61.5, presenting an acid index I
close to 13.6 and "stabilized" by the action of sodium
borohydrate (residual rate in SR lower than 1%) as far
as product G is concerned,
- of the product of oxidation of a starch hydrolysate
having a DE close to 61.5 ~I close to 13.6) and "stabi-
lized" by catalytic hydrogenation with nic~el (residual
rate in SR lower than 0.~1%) as far as product H is
concerned.
It appears from the said trials that, in a general
manner, all of the laundry materials E to H according to
the invention present performances which are similar and
even higher in some cases with respect to those of a
laundry material of the prior art in which zeolites and
phosphates are associated.
EXAMPLE 6
In connection with a third group of trials, there
is shown the interest of the laundry materials according
to the invention by way of other trials than those
disclosed previously and which will be disclosed in detail
hereinafter.
In connection with these trials, the prior art
control product was a laundry materlal denoted by the
letter T whose constitution has been given in the above-
mentioned Table I.
Three further laundry materials according to the
invention, respectively denoted by the letters I, J and K,
were tested, the respective rates in zeolite(s), in oxi-
dized polysaccharide(s) and, if any, in sodium poly-
acrylates (NaP) or in nitrllotriacetates (NTA), being
indicated in the following Table XI.
~3~
TABLE XI
Constituents Composition ~% by weight)
T I J K
Zeolite A 25 20 20 20
Polyacrylates 2
Nitrilotriacetates _ 2 _
10 Oxidized Polysaccharide 10
In connection with these trials, there is used, as
an oxidized polysaccharide contained within the laundry
materials according to the invention, an oxidation product
of a starch hydrolysate having a DE of about 37, and pre-
senting an acid index I of about 8.6, the said oxidation
product having moreover being subjected to catalytic
hydrogenation with Raney nic~el (residual rate in reducing
sugars lower than 0.05%).
The trials were carried out at 60C on a washing
machine commercialized under the brand WASCATOR FOM 71,
the amount of laundry material being 7 g/l, i.e. 154 g for
every washing.
2.5 kg of fabrics containing two wear strips on
the basis of pure cotton and a ballast of terry towels and
dish towels of determined sizes or basis weight were
washed (Standard NF T 73-600).
The tests which were carried out, were intended to
measure, for every studied product (4 measures for each
product), the chemical wear and the rate of organic
incrustation obtained at the level of the fabrics being
washed and that after 25 successive and cumulative washing
cycles.
The chemical wear consists in measuring the ave-
rage polymer$zation degree or DP of the cotton cellulosebeEore and after the 25 washings in order to evaluate the
2a3~o
24
action on the macromolecular chain of cellulose of pro-
ducts such as perborate and alkaline agents.
The determination of the DP of the cellulose is
carried out by measuring the viscosity of a solution of a
cotton sample subjected to the test within a convenient
solvent (diamine cupriethylene) with respect to the
viscosity of the solvent as such, said determination being
carried out accordingly to the standard NF T 73-601,
paragraph 3.6 or NF G 06-037.
The object sought for is that the detergent action
does not cause a substantial decrease of the DP thus that
the tear of the fabric thus washed is not facilitated.
In connection with the present tests, it is to be
noticed that the cotton under test presents, before
washing, a DP of 1925.
The organic incrustation permits to know the
deposit of residual tensio-active(s) or soap(s) complexed
by the calcium in the case of a sequestration of bad
quality.
The test is carried out according to the standard
NF T 73-601, paragraph 3.3 and ISO 4312, paragraph 6.
Generally speaking, one estimates that the rate of
organic incrustation should not exceed about 1%.
In Table XII hereafter, the average degree of
polymerization DP and the organic incrustation rate IO
obtained after 25 washings carried out at 60C are given
in connection with the control laundry material T and with
each one of the laundry materials I, J and K according to
the invention.
TABLE XII
Laundry material
T I J K
Degree of polymerization DP 1924 1865 1914 1892
_____________________________ ______ _______ ______. ._______
Organic incrustation
rate IO (in ~) 1.05 0.59 0.64 0.41
2~38~4~1
The results recorded in Table XII globally show
that the laundry materials according to the invention
enable to obtain results which are similar with (from the
standpoint of view of DP), and even higher (from the
standpoint of view of I0) than those recorded with the
prior art laundry material.
EXAMP$E 7
Using standard methods (Standards NF T 73-601,
paragraph 3.4 et IS0 4312, paragraph 7), there is measured
the rate of ashes of cotton strips which were subjected to
a cycle of 25 successive washings at 60C using respecti-
vely one or the other of the above-identified products T
(control), J and K (laundry materials according to the
invention).
The measuring of the ash rate enables to know the
importance of the deposit of mineral salts, especially of
the calcium or magnesium carbonate, bicarbonate and
sulphate, on the fabric at the end of the washing cycle.
In connection with laundry materials containing
zeolites, it is generally agreed that an ash rate lower or
equal to 1~ provides total satisfaction.
The results recorded in the following Table XIII
show, once again, that the laundry materials according to
the invention enable to satisfy totally the requirements
of the technique.
TABLE XIII
Laundry material
T I J I K
3o Ashes rate (in %~ 0-74 ¦ 0-93 0.89
