U.S. patent application number 10/658577 was filed with the patent office on 2005-02-10 for rinsing formulation for textiles.
Invention is credited to Geffroy, Cedric.
Application Number | 20050028293 10/658577 |
Document ID | / |
Family ID | 31978723 |
Filed Date | 2005-02-10 |
United States Patent
Application |
20050028293 |
Kind Code |
A1 |
Geffroy, Cedric |
February 10, 2005 |
Rinsing formulation for textiles
Abstract
Formulation for rinsing textile fiber articles in an aqueous or
aqueous-alcoholic medium, comprising an active substance comprising
a liquid or solid, hydrophobic organic or organosilicon material in
particulate form, a surfactant and a vehicle comprising a
water-soluble organic polymer, the vehicle being capable of
bringing said active substance to the surface of said textile fiber
articles in the rinsing operation.
Inventors: |
Geffroy, Cedric; (Poitiers,
FR) |
Correspondence
Address: |
Jean-Louis SEUGNET
RHODIA INC.
259 Prospect Plains Road, Bldg. N-2
CRANBURY
NJ
08512-7500
US
|
Family ID: |
31978723 |
Appl. No.: |
10/658577 |
Filed: |
September 9, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60409164 |
Sep 9, 2002 |
|
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|
Current U.S.
Class: |
8/115.51 |
Current CPC
Class: |
C11D 3/373 20130101;
C11D 3/162 20130101; C11D 3/3742 20130101; C11D 3/0015 20130101;
C11D 17/0013 20130101; C11D 3/3734 20130101; C11D 3/222 20130101;
C11D 3/001 20130101 |
Class at
Publication: |
008/115.51 |
International
Class: |
D06M 010/00 |
Claims
1. Formulation (F) intended for use in an operation of rinsing (R)
textile fiber articles (S) by means of an aqueous or
aqueous-alcoholic medium (MR), said formulation (F) comprising at
least one active substance (A) comprising at least one solid or
liquid organic or organosilicon material in particulate form and a
vehicle (V) comprising at least one organic polymer, capable of
taking said active substance (A) to the surface of said textile
fiber articles (S) in the rinsing operation (R), in the form: of a
stable dispersion, with a pH of from 2 to 5, of said active
substance (A) in an aqueous or aqueous-alcoholic medium (MAV)
comprising said vehicle (V), or in a solid form obtained by drying
said dispersion, the nature of the active substance (A), of the
aqueous or aqueous-alcoholic medium (MAV), and of the vehicle (V)
being such that the active substance (A) is insoluble in the medium
(MAV), has an overall zero or cationic charge in the medium (MAV),
is stabilized in the medium (MAV) by means of a cationic surfactant
(TAC), it being possible for said cationic surfactant (TAC) to be
wholly or partly replaced by a nonionic surfactant when the
material constituting the active substance (A) is intrinsically
cationic or intrinsically potentially cationic in the medium (MAV),
remains insoluble in the rinsing medium (MR); the vehicle (V) is
soluble or dispersible in the medium (MAV) and in the rinsing
medium (MR) has an overall cationic or zero ionic charge in the
medium (MAV), at the pH of the rinsing operation in the rinsing
medium (MR) is capable of developing anionic charges in sufficient
quantity to destabilize the active substance (A) in the rinsing
medium (MR).
2. Formulation according to claim 1), characterized in that the
rinsing medium (MR) has a pH of from 5.5 to 8.
3. Formulation according to claim 1) or 2), characterized in that
the material constituting the active substance (A) is an oil or a
meltable solid.
4. Formulation according to any one of claims 1) to 3),
characterized in that the particles of active substance (A) have an
average diameter ranging from 10 nm to 200 .mu.m, preferably from
10 nm to 5 .mu.m and more preferably from 10 nm to 2 000 nm.
5. Formulation according to any one of claims 1) to 4),
characterized in that the active substance (A) comprises material
having lubricating properties with regard to textile fiber
articles.
6. Formulation according to any one of claims 1) to 5),
characterized in that the material constituting the active
substance (A) is a polyorganosiloxane selected from nonionic
polyorganosiloxanes polyorganosiloxanes having at least one
cationic or potentially cationic function in the medium (MAV)
amphoteric polyorganosiloxanes having at least one cationic or
potentially cationic function in the medium (MAV) and at least one
function which is neutral in the medium (MAV) and potentially
anionic in the rinsing medium (MR) polyorganosiloxanes having at
least one function which is neutral in the medium (MAV) and
potentially anionic in the rinsing medium (MR).
7. Formulation according to any one of claims 1) to 6),
characterized in that the material constituting the active
substance (A) is an
.alpha.-.omega.-bis(hydroxy)polydimethylsiloxane, an
.alpha.-.omega.-bis(trimethyl)polydimethylsiloxane, a
polymethylphenylsiloxane or a cyclic polydimethylsiloxane,
preferably in oil form.
8. Formulation according to any one of claims 1) to 6),
characterized in that the material constituting the active
substance (A) is an amino polyorganosiloxane.
9. Formulation according to claim 8), characterized in that the
amino polyorganosiloxane is a polyorganosiloxane which has hindered
piperidyl groups.
10. Formulation according to any one of claims 6) to 9),
characterized in that said polyorganosiloxane is linear.
11. Formulation according to any one of claims 1) to 5),
characterized in that the active substance (A) comprises a material
selected from mono-, di- or triglycerides of C.sub.1-C.sub.30
carboxylic acids or mixtures thereof, such as vegetable oils sugar
esters, sucroglycerides --C.sub.1-C.sub.30 alcohol esters of
C.sub.1-C.sub.30 carboxylic or C.sub.2-C.sub.30 dicarboxylic acids
ethylene or propylene glycol monoesters or diesters of
C.sub.1-C.sub.30 carboxylic acids propylene glycol C.sub.4-C.sub.20
alkyl ethers di(C.sub.8-C.sub.30 alkyl) ethers organic waxes
comprising alkyl chains containing 4 to 40 carbon atoms.
12. Formulation according to any one of claims 1) to 11),
characterized in that the ratio of the mass of polymer constituting
the active substance (A) to the mass of surfactant (TAC) is from
0.01 to 10, preferably from 0.01 to 1.
13. Formulation according to any one of claims 1) to 12),
characterized in that the cationic charges generated by the
optional cationic or potentially cationic units of the material
constituting the active substance (A) and by the cationic
surfactant or surfactants at the surface of the material
constituting the active active substance (A) in dispersion in the
medium (MAV) are such that the zeta potential of said polymer or
copolymer in dispersion in (MAV) is from 0 to +50 mV, preferably
from +10 to +40 mV.
14. Formulation according to any one of claims 1) to 13),
characterized in that the dispersion medium (MAV) for the active
substance (A) is water or an aqueous-alcoholic polar medium.
15. Formulation according to claim 14), characterized in that the
alcohol or alcohols present in the aqueous-alcoholic polar medium
represent up to 70% of the volume of the medium (MAV).
16. Formulation according to any one of claims 1) to 15),
characterized in that the polymer constituting the vehicle (V) is
any polymer which is soluble or dispersible in aqueous or
aqueous-alcoholic medium with a pH of between 2 and 8 and which
comprises at least one unit which is neutral in the medium (MAV)
and potentially anionic (HA) in the rinsing medium (MR).
17. Formulation according to claim 16), characterized in that the
vehicle (V) polymer further comprises at least one unit which is
cationic or potentially cationic (HC) in the medium (MAV) and/or at
least one hydrophilic or hydrophobic nonionic unit.
18. Formulation according to any one of claims 1) to 17),
characterized in that the relative amounts of the various units of
the polymer constituting the vehicle (V) are such that in the
medium (MAV) the overall charge of the polymer or copolymer is zero
or cationic.
19. Formulation according to any one of claims 1) to 18),
characterized in that the relative amounts of vehicle (V) polymer,
surfactant (TAC), and material constituting the active substance
(A) are such that in the course of the rinsing operation the number
of anionic charges developed in the rinsing medium (MR) by the
vehicle polymer (V) is sufficient to destabilize the active
substance (A) in the rinsing medium (MR), in particular by
electrostatic attraction with the surface charges of the active
substance (A) in the medium (MR).
20. Formulation according to claim 19), characterized in that the
number of anionic charges developed in the rinsing medium (MR) by
the vehicle (V) polymer to destabilize the active substance is at
least 1% relative to the number of cationic surface charges of the
active substance (A) in the medium (MR), and not more than 200%
relative to the number of cationic surface charges of the active
substance (A) in the medium (MR).
21. Formulation according to any one of claims 1) to 20),
characterized in that the polymer constituting the vehicle (V) is a
polymer selected from polymers derived from ethylenically
unsaturated monomers, potentially anionic natural polysaccharides,
potentially anionic or amphoteric substituted or modified
polysaccharides, or mixtures thereof.
22. Formulation according to any one of claims 1) to 21),
characterized in that the polymer constituting the vehicle (V) is a
polymer derived: from at least one .alpha.-.beta. monoethylenically
unsaturated monomer which is neutral in the medium (MAV) and
potentially anionic (HA) in the rinsing medium (MR) and optionally
at least one .alpha.-.beta. monoethylenically unsaturated monomer
which is cationic or potentially cationic (HC) in the medium (MAV),
and optionally at least one nonionic .alpha.-.beta.
monoethylenically unsaturated monomer which is hydrophilic or
hydrophobic, preferably hydrophilic.
23. Formulation according to any one of claims 1) to 22),
characterized in that the polymer constituting the vehicle (V) is a
random, block or graft copolymer derived: from at least one
.alpha.-.beta. monoethylenically unsaturated hydrophilic monomer
which is neutral in the medium (MAV) and potentially anionic (HA)
in the rinsing medium (MR) and from at least one .alpha.-.beta.
monoethylenically unsaturated hydrophilic monomer which is cationic
or potentially cationic (HC) in the medium (MAV), and optionally
from at least one nonionic .alpha.-.beta. monoethylenically
unsaturated monomer which is hydrophilic or hydrophobic, preferably
hydrophilic.
24. Formulation according to any one of claims 1) to 23),
characterized in that the polymer constituting the vehicle (V)
derives from one or more .alpha.-.beta. monoethylenically
unsaturated monomers and has an average molar mass of greater than
5 000 g/mol, preferably from 20 000 to 500 000 g/mol.
25. Formulation according to any one of claims 1) to 24),
characterized in that the polymer constituting the vehicle (V) is
selected from polyacrylic or polymethacrylic acids, alkali metal
polyacrylates or polymethacrylates, preferably with a molar mass by
weight of from 100 000 to 1 000 000 g/mol acrylic acid/DADMAC
copolymers, with a molar ratio of 50/50 to 30/70, preferably with a
molar mass by weight of from 70 000 to 350 000 g/mol acrylic
acid/MAPTAC copolymers, with a molar ratio of 60/40 to 30/70,
preferably with a molar mass by weight of from 90 000 to 300 000
g/mol acrylic acid/MAPTAC/linear C.sub.4-C.sub.18 alkyl
methacrylate terpolymers comprising 0.005 to 10% by mass of alkyl
methacrylate, with an acrylic acid/MAPTAC molar ratio ranging from
60/40 to 30/70, and preferably having a molar mass by weight of
from 50 000 to 250 000 g/mol acrylic acid/dimethylaminoethyl
methacrylate (DMAEMA) copolymers, with a molar ratio of 60/40 to
30/70, preferably with a molar mass by weight of from 50 000 to 300
000 g/mol.
26. Formulation according to any one of claims 1) to 21),
characterized in that the polymer constituting the vehicle (V) is a
potentially anionic natural polysaccharide formed of nonionic
monosaccharide units and of monosaccharide units which are neutral
in the medium (MAV) and potentially anionic in the rinsing medium
(MR), and are alike or different.
27. Formulation according to claim 26), characterized in that said
potentially anionic natural polysaccharide is a branched
polysaccharide formed of a main chain comprising alike or different
anhydrohexose units and of branches comprising at least one
anhydropentose and/or anhydrohexose unit which is neutral in the
medium (MAV) and optionally potentially anionic in the rinsing
medium (MR).
28. Formulation according to claim 26) or 27), characterized in
that said potentially anionic natural polysaccharide is a xanthan
gum, a succinoglycan, a rhamsan, a gellan gum or a welan gum.
29. Formulation according to any one of claims 26) to 28),
characterized in that said potentially anionic natural
polysaccharide has a molar mass by weight of from 2 000 to 5 000
000, preferably from 10 000 to 5 000 000, more particularly from 10
000 to 4 000 000 g/mol.
30. Formulation according to any one of claims 1) to 21),
characterized in that the polymer constituting the vehicle (V) is a
substituted or modified polysaccharide whose native skeleton is
formed of nonionic monosaccharide units and/or of monosaccharide
units which are neutral in the medium (MAV) and potentially anionic
in the rinsing medium (MR), said monosaccharide units being alike
or different and being substituted or modified by one or more
groups which carry at least one charge which is neutral in the
medium (MAV) and potentially anionic in the medium (MR) and
optionally by one or more groups which carry at least one charge
which is cationic or potentially cationic in the medium (MAV), the
degree of substitution or modification of the monosaccharide units
by the entirety of the groups which carry charges which are
potentially anionic and of optional groups which carry cationic
charges being such that said substituted or modified polysaccharide
is soluble or dispersible in aqueous or aqueous-alcoholic medium
and has an overall cationic or zero charge in the medium (MAV).
31. Formulation according to claim 30), characterized in that said
substituted or modified polysaccharide further comprises at least
one nonionic modifying or substituent group.
32. Formulation according to claim 30) or 31), characterized in
that said substituted or modified polysaccharide is a substituted
or modified branched polysaccharide whose native skeleton is formed
of a main chain comprising alike or different anhydrohexose units
and of branches comprising at least one anhydropentose and/or
anhydrohexose unit which is neutral in the medium (MAV) and
optionally potentially anionic in the rinsing medium (MR), the
anhydrohexose and/or anhydropentose units of said polysaccharide
being substituted or modified by one or more groups which carry at
least one charge which is neutral in the medium (MAV) and
potentially anionic in the medium (MR) and optionally at least one
charge which is cationic or potentially cationic in the medium
(MAV), the degree of substitution or modification DSi of the
anhydrohexose and/or anhydropentose units by the entirety of said
groups which carry charges which are ionic or potentially ionic
ranging from 0.01 to less than 3, preferably from 0.01 to 2.5, with
a ratio of the number of potentially anionic charges in the medium
(MR) to the number of cationic or potentially cationic charges in
the medium (MAV) ranging from 100/0 to 30/70, preferably from 100/0
to 50/50.
33. Formulation according to any one of claims 29) to 32),
characterized in that said substituted or modified polysaccharide
has a molar mass by weight of from 2 000 to 5 000 000, preferably
from 10 000 to 5 000 000 g/mol.
34. Formulation according to any one of claims 29) to 33),
characterized in that the native skeleton of said substituted or
modified polysaccharide is a galactomannan.
35. Formulation according to any one of claims 29) to 34),
characterized in that the native skeleton of said substituted or
modified polysaccharide is selected from
carboxymethylgalactomannans, especially carboxymethylguars,
carboxymethylhydroxypropylgalactomannans, especially
carboxymethylhydroxypropylguars,
carboxymethyl-hydroxypropyltrimethylammo- nium chloride
galactomannans, especially carboxymethylhydroxypropyltrimeth-
ylammonium chloride guars,
carboxymethylhydroxypropyl-hydroxypropyltrimeth- ylammonium
chloride galactomannans, especially carboxymethyl-hydroxypropyl-
hydroxypropyltrimethylammonium chloride guars.
36. Formulation according to any one of claims 1) to 35),
characterized in that the amount of vehicle (V) present in said
formulation is from 0.01 to 5 parts by weight, preferably from
0.001 to 4 parts by weight, and more particularly from 0.05 to 2
parts by weight per 100 parts by weight of active substance
(A).
37. Formulation according to any one of claims 1) to 36),
characterized in that it is in the form of an aqueous or
aqueous-alcoholic dispersion comprising per 100 parts of its
weight: from 0.01 to 40, preferably from 0.05 to 30 parts by dry
weight of active substance (A) from 0.01 to 50, preferably from
0.01 to 35 parts by dry weight of surfactant (TAC) from 0.001 to 4,
preferably from 0.01 to 1 part by dry weight of vehicle (V)
polymer.
38. Formulation according to any one of claims 1) to 37),
characterized in that it further comprises one or more customary
constituents of cationic rinsing formulations, selected from
cationic softeners, optical brighteners, color transfer inhibitors,
water-soluble monovalent mineral salts, dyes, fragrances, foam
suppressants, enzymes and bleaches.
39. Process for treating textile fiber articles by contacting said
articles in the course of a rinsing operation in aqueous or
aqueous-alcoholic medium with the rinsing formulation (F) of any
one of claims 1) to 38), and recovering said rinsed articles.
40. Process intended to enhance the antiwrinkle and/or easy-iron
and/or soil release and/or abrasion resistance properties of
textile fiber articles, which consists in contacting said articles
in the course of a rinsing operation in aqueous or
aqueous-alcoholic medium with the rinsing formulation (F) of any
one of claims 1) to 38), and in recovering said rinsed
articles.
41. Use in a formulation (F) intended for use in an operation of
rinsing (R) textile fiber articles (S) by means of an aqueous or
aqueous-alcoholic medium (MR), formulation (F) comprising at least
one active substance (A) comprising at least one liquid or solid
organic or organosilicon material in particulate form and being in
the form of a stable dispersion with a pH of from 2 to 5 of said
active substance (A) in an aqueous or aqueous-alcoholic medium
(MAV) or in a solid form obtained by drying said dispersion, the
nature of the active substance (A) and of the aqueous or
aqueous-alcoholic medium (MAV) being such that the active substance
(A) is insoluble in the medium (MAV) has an overall zero or
cationic charge in the medium (MAV), is stabilized in the medium
(MAV) by means of a cationic surfactant (TAC), it being possible
for said cationic surfactant (TAC) to be wholly or partly replaced
by a nonionic surfactant when the material constituting the active
substance (A) is intrinsically cationic or intrinsically
potentially cationic in the medium (MAV) remains insoluble in the
rinsing medium (MR); of at least one organic polymer which is
soluble or dispersible in the medium (MAV) and in the rinsing
medium (MR) has an overall cationic or zero ionic charge in the
medium (MAV) and is capable, at the pH of the rinsing operation in
the rinsing medium (MR), of developing anionic charges in
sufficient quantity to destabilize the active substance (A) in the
rinsing medium (MR); as a vehicle (V) capable of bringing said
active substance (A) toward the surface of said textile fiber
articles (S) in the rinsing operation (R).
42. Process for enhancing the deposition of an active substance (A)
comprising at least one solid or liquid organic or organosilicon
material in particulate form on the surface of textile fiber
articles (S), during an operation of rinsing of said articles by
means of an aqueous or aqueous-alcoholic medium (MR) obtained from
a formulation (F) comprising said active substance (A), the
formulation (F) being in the form of a stable dispersion with a pH
of from 2 to 5 of said active substance (A) in an aqueous or
aqueous-alcoholic medium (MAV) or in a solid form obtained by
drying said dispersion, the nature of the active substance (A) and
of the aqueous or aqueous-alcoholic medium (MAV) being such that
the active substance (A) is insoluble in the medium (MAV) has an
overall zero or cationic charge in the medium (MAV), is stabilized
in the medium (MAV) by means of a cationic surfactant (TAC), it
being possible for said cationic surfactant (TAC) to be wholly or
partly replaced by a nonionic surfactant when the material
constituting the active substance (A) is intrinsically cationic or
intrinsically potentially cationic in the medium (MAV) remains
insoluble in the rinsing medium (MR); by adding to said formulation
(F) a vehicle (V) comprising at least one organic polymer which is
soluble or dispersible in the medium (MAV) and in the rinsing
medium (MR) has an overall cationic or zero ionic charge in the
medium (MAV) and is capable, at the pH of the rinsing operation in
the rinsing medium (MR), of developing anionic charges in
sufficient quantity to destabilize the active substance (A) in the
rinsing medium (MR).
43. Processes according to any one of claims 40), 41) or 43), or
use according to claim 42), characterized in that the amount of
formulation employed, expressed in terms of dry matter, is from
0.001 to 5 g/l, preferably from 0.05 to 2 g/l in the rinsing bath.
Description
[0001] The present invention relates to an improved formulation
intended for the rinsing of textile fiber articles, comprising a
hydrophobic active substance comprising a solid or liquid,
particulate organic or organosilicon material.
[0002] It is known to use hydrophobic organic or organosilicon
materials in textile rinsing compositions.
[0003] Patent U.S. Pat. No. 4,818,242 describes an aqueous rinsing
formulation which facilitates ironing, comprising a silicone oil
cationically dispersed in water, a fatty acid-polyamine condensate,
and a cationic film-forming agent.
[0004] Patent U.S. Pat. No. 4,923,622 proposes rinse compositions
comprising an emulsifiable concentrate which comprises cationic
surfactants and an oil capable of exhibiting lubricating properties
with regard to textiles to be treated, such as mineral oils and
vegetable oils containing 8 to 22 carbon atoms, and fatty acid
esters.
[0005] The Applicant has found that the addition, to a formulation
comprising particles of insoluble organic or organosilicon
hydrophobic active substance and intended for the rinsing of
textile fiber articles, of a small amount of an appropriately
selected soluble vehicle for said active substance makes it
possible to improve significantly the deposition of particles on
the surface of said articles and hence to confer notable benefits
on said articles, such as benefits of lubrication, of softness to
the touch, of antiwrinkle properties and/or easy-iron properties
and/or soil release properties, and of abrasion resistance.
[0006] The invention first provides a formulation (F) intended for
use in an operation of rinsing (R) textile fiber articles (S) by
means of an aqueous or aqueous-alcoholic medium (MR), said
formulation (F)
[0007] comprising at least one active substance (A) comprising at
least one solid or liquid organic or organosilicon material in
particulate form and a vehicle (V) comprising at least one organic
polymer, capable of taking said active substance (A) to the surface
of said textile fiber articles (S) in the rinsing operation
(R),
[0008] in the form:
[0009] of a stable dispersion, with a pH of from 2 to 5, of said
active substance (A) in an aqueous or aqueous-alcoholic medium
(MAV) comprising said vehicle (V), or
[0010] in a solid form obtained by drying said dispersion,
[0011] the nature of the active substance (A), of the aqueous or
aqueous-alcoholic medium (MAV), and of the vehicle (V) being such
that
[0012] the active substance (A)
[0013] is insoluble in the medium (MAV),
[0014] has an overall zero or cationic charge in the medium
(MAV),
[0015] is stabilized in the medium (MAV) by means of a cationic
surfactant (TAC), it being possible for said cationic surfactant
(TAC) to be wholly or partly replaced by a nonionic surfactant when
the material constituting the active substance (A) is intrinsically
cationic or intrinsically potentially cationic in the medium
(MAV),
[0016] remains insoluble in the rinsing medium (MR);
[0017] the vehicle (V)
[0018] is soluble or dispersible in the medium (MAV) and in the
rinsing medium (MR)
[0019] has an overall cationic or zero ionic charge in the medium
(MAV),
[0020] at the pH of the rinsing operation in the rinsing medium
(MR) is capable of developing anionic charges in sufficient
quantity to destabilize the active substance (A) in the rinsing
medium (MR).
[0021] The formulation according to the invention is intended for
use equally for implementing a washing machine rinsing operation as
a hand rinsing operation. This operation is commonly carried out at
a pH which can range from 5.5 to 8 (pH of the supply circuit
water); it usually takes place at ambient temperature. In a
conventional laundry washing operation, the rinsing formulation is
employed in the final rinse.
[0022] A particle dispersion is considered as being stable if no
sedimentation, phase separation or development of turbidity is
observed over time. This dispersion is destabilized when the
particles undergo aggregation with one another.
[0023] According to the invention the active substance (A) is
considered as being destabilized in the rinsing medium (MR)
comprising the vehicle (V) when the size of the objects in the
dispersion is at least twice that of the same objects in the
absence of vehicle (V).
[0024] According to the invention the active substance (A) is in a
solid or liquid organic or organosilicon material in particulate
form which is insoluble in the medium (MAV), has an overall zero or
cationic charge in the medium (MAV), and remains insoluble in the
rinsing medium (MR).
[0025] According to the invention the material constituting the
active substance (A) is considered as being insoluble when less
than 15%, preferably less than 10%, of its weight is soluble in the
medium (MAV) and the rinsing medium (MR).
[0026] Said material constituting the active substance (A) is in
particulate soluble or liquid form. Preferentially it is in the
form of an oil or a meltable solid (a wave for example).
[0027] Said particles may have an average diameter ranging from 10
nm to 200 .mu.m, preferably from 10 nm to 5 .mu.m and more
preferably from 10 nm to 2 000 nm.
[0028] The diameter of said particles may be determined in
well-known fashion by light scattering, by laser diffraction or by
microscopy.
[0029] Among the materials which may constitute the active
substance (A) mention may be made in particular of those having a
lubricating action which are capable of conferring on the textile
fiber articles properties of lubrication, which may be manifested
in the provision of benefits such as softness, wrinkle resistance,
ease of ironing, abrasion resistance, soil release, etc.
[0030] According to a first embodiment of the invention said
material constituting the active substance (A) is an organosilicon
material.
[0031] It is in particular a linear, cyclic, branched or
crosslinked polyorganosiloxane resin, wax or oil. Said
polyorganosiloxane preferably has a dynamic viscosity, measured at
25.degree. C. and at a shear rate of 0.01 Hz for a stress of 1 500
Pa (carried out on a Carrimed.RTM. of type CSL2-500), of between
10.sup.4 and 10.sup.9 cP. According to the invention it is:
[0032] a nonionic polyorganosiloxane
[0033] a polyorganosiloxane having at least one cationic or
potentially cationic function in the medium (MAV)
[0034] an amphoteric polyorganosiloxane having at least one
cationic or potentially cationic function in the medium (MAV) and
at least one function which is neutral in the medium (MAV) and
potentially anionic in the rinsing medium (MR)
[0035] a polyorganosiloxane having at least one function which is
neutral in the medium (MAV) and potentially anionic in the rinsing
medium (MR).
[0036] Examples of polyorganosiloxanes that may be mentioned
include
[0037] linear, cyclic or crosslinked polyorganosiloxanes formed of
nonionic organosiloxane units of general formula
(R).sub.a(X).sub.bSi(O).sub.[4-(a+b)]/2 (I)
[0038] in which formula
[0039] the symbols R are identical or different and represent a
linear or branched alkyl hydrocarbon radical having 1 to 4 carbon
atoms or an aryl radical, phenyl in particular;
[0040] the symbols X are identical or different and represent a
hydroxyl group, a linear or branched alkoxy radical having 1 to 12
carbon atoms, or a functional group OCOR', where R' represents an
alkyl group containing 1 to 12 carbon atoms, preferably 1 carbon
atom;
[0041] a is 0, 1, 2 or 3
[0042] b is 0, 1, 2 or 3
[0043] a+b is 0, 1, 2 or 3
[0044] Preferentially said polyorganosiloxane is at least
substantially linear, and very preferably is linear. By way of
example mention may be made in particular of
.alpha.-.omega.-bis(hydroxy)polydimethylsiloxane oils,
.alpha.-.omega.-bis(trimethyl)polydimethylsiloxane oils, cyclic
polydimethylsiloxanes, and polymethylphenylsiloxanes.
[0045] linear, cyclic or crosslinked polyorganosiloxanes comprising
per mole at least one ionic or nonionic organosiloxane unit of
general formula
(R).sub.a(X).sub.b(B).sub.cSi(O).sub.[4-(a+b+c)]/2 (II)
[0046] in which formula
[0047] the symbols R are identical or different and represent a
linear or branched monovalent alkyl hydrocarbon radical having 1 to
4 carbon atoms or an aryl radical, phenyl in particular;
[0048] the symbols X are identical or different and represent a
hydroxyl group, a linear or branched alkoxy radical having 1 to 12
carbon atoms or a functional group OCOR', where R' represents an
alkyl group containing 1 to 12 carbon atoms, preferably 1 carbon
atom;
[0049] the symbols B are identical or different and represent an
aliphatic and/or aromatic and/or cyclic hydrocarbon radical
containing up to 30 carbon atoms, optionally interrupted by one or
more oxygen and/or nitrogen and/or sulfur heteroatoms, optionally
carrying one or more ether, ester, thiol, hydroxyl, optionally
quaternized amine or carboxylate functions, the symbol B being
linked to the silicon preferably by way of an Si--C-- bond;
[0050] a is 0, 1 or 2
[0051] b is 0, 1 or 2
[0052] c is 1 or 2
[0053] a+b+c is 1, 2 or 3
[0054] The other organosiloxane units present besides those of
formula (II) are preferably nonionic and of formula (I) above.
[0055] Organosiloxane units having one or more strong anionic
functions of sulfonate and/or phosphonate type may also be present
when the units of formula (II) are cationic or potentially cationic
in the medium (MAV). They are present, however, in limited
quantity, in order that said polyorganosiloxane has an overall zero
or cationic charge in the medium (MAV).
[0056] By way of example of substituents corresponding to the
symbol (B) in the formula (II) above, mention may be made of
[0057] polyether groups of formula
--(CH.sub.2).sub.n--(OC.sub.2H.sub.4).sub.m--(OC.sub.3H.sub.6).sub.p--OR'
[0058] where n is 2 or 3, m and p are each from 0 to 30, and R'
represents an alkyl radical containing 1 to 12 carbon atoms,
preferably 1 to 4 carbon atoms.
[0059] primary, secondary, tertiary or quaternized amino groups,
such as those of formula
--R.sup.1--N(R.sup.2)(R.sup.3)
[0060] where
[0061] the symbol R.sup.1 represents an alkylene group containing 2
to 6 carbon atoms, optionally substituted or interrupted by one or
more nitrogen or oxygen atoms,
[0062] the symbols R.sup.2 and R.sup.3, identical or different,
represent
[0063] H,
[0064] an alkyl or hydroxyalkyl group containing 1 to 12 carbon
atoms, preferably 1 to 6 carbon atoms,
[0065] an aminoalkyl group, preferably primary, whose alkyl group
contains 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms,
optionally substituted and/or interrupted by at least one nitrogen
and/or oxygen atom,
[0066] said amino group being optionally quaternized, for example,
by a hydrohalic acid or an alkyl or aryl halide.
[0067] Mention may be made in particular of those of formulae
--(CH.sub.2).sub.3NH.sub.2
--(CH.sub.2).sub.3NH.sub.3.sup.+X.sup.---(CH.s-
ub.2).sub.3N(CH.sub.3).sub.2
--(CH.sub.2).sub.3N.sup.+(CH.sub.3).sub.2(C.s-
ub.18H.sub.37)X.sup.---(CH.sub.2).sub.3NHCH.sub.2CH.sub.2NH.sub.2
--(CH.sub.2).sub.3N(CH.sub.2CH.sub.2OH).sub.2
--(CH.sub.2).sub.3N(CH.sub.- 2CH.sub.2NH.sub.2).sub.2
[0068] Preferentially the polyorganosiloxanes which carry amino
functions have in their chain, per 100 total silicon atoms, from
0.1 to 50, preferably from 0.3 to 10, and very particularly from
0.5 to 5 amino-functionalized silicon atoms.
[0069] sterically hindered piperidyl groups of formula III 1
[0070] where
[0071] R.sup.4 is a divalent hydrocarbon radical selected from:
[0072] linear or branched alkylene radicals having 2 to 18 carbon
atoms;
[0073] alkylene-carbonyl radicals whose alkylene moiety is linear
or branched and contains 2 to 20 carbon atoms;
[0074] alkylene-cyclohexylene radicals whose alkylene moiety is
linear or branched and contains 2 to 12 carbon atoms and whose
cyclohexylene moiety contains an OH group and optionally 1 or 2
alkyl radicals having 1 to 4 carbon atoms;
[0075] radicals of formula --R.sup.7--O--R.sup.7 in which the
radicals R.sup.7 are identical or different and represent alkylene
radicals having 1 to 12 carbon atoms;
[0076] radicals of formula --R.sup.7--O--R.sup.7 in which the
radicals R.sup.7 have the meanings indicated above and one of them
or both are substituted by one or two --OH group(s);
[0077] radicals of formula --R.sup.7--COO--R.sup.7 in which the
radicals R.sup.7 have the meanings indicated above;
[0078] radicals of formula --R.sup.8--O--R.sup.9--O--CO--R.sup.8 in
which the radicals R.sup.8 and R.sup.9 are identical or different
and represent alkylene radicals having 2 to 12 carbon atoms and the
radical R.sup.9 is optionally substituted by a hydroxyl
radical;
[0079] U represents --O-- or --NR.sup.10--, R.sup.10 being a
radical selected from a hydrogen atom, a linear or branched alkyl
radical containing 1 to 6 carbon atoms, and a divalent radical of
formula: 2
[0080] in which R.sup.4 has the meaning indicated above, R.sup.5
and R.sup.6 have the meanings indicated below, and R.sup.11
represents a linear or branched divalent alkylene radical having 1
to 12 carbon atoms, one of the valence bonds (that of R.sup.11)
being connected to the atom of --NR.sup.10--, the other (that of
R.sup.4) being connected to a silicon atom;
[0081] the radicals R.sup.5 are identical or different and are
selected from linear or branched alkyl radicals having 1 to 3
carbon atoms and the phenyl radical;
[0082] the radical R.sup.6 represents a hydrogen radical or the
radical R.sup.5 or O..
[0083] or sterically hindered piperidyl groups of formula IV 3
[0084] where
[0085] R'.sup.4 is selected from a trivalent radical of formula:
4
[0086] where m represents a number from 2 to 20,
[0087] and a trivalent radical of formula: 5
[0088] where p represents a number from 2 to 20;
[0089] U' represents --O-- or NR.sup.12--, R.sup.12 being a radical
selected from a hydrogen atom and a linear or branched alkyl
radical containing 1 to 6 carbon atoms;
[0090] R.sup.5 and R.sup.6 have the same meanings as those given
above in relation to the formula III.
[0091] Preferentially said amino-functional polyorganosiloxanes are
polyorganosiloxanes containing a sterically hindered piperidyl
function, especially those which can be prepared by the process
described in EP-A-659930.
[0092] Very preferably said polyorganosiloxane containing a
sterically hindered amino function is a linear, cyclic or
three-dimensional polyorganosiloxane of formula (V): 6
[0093] in which:
[0094] (1) the symbols Z, identical or different, represent R.sup.1
below and/or B;
[0095] (2) the symbols R.sup.1, R.sup.2 and R.sup.3, identical
and/or different, represent a monovalent hydrocarbon radical
selected from linear or branched alkyl radicals having 1 to 4
carbon atoms, linear or branched alkoxy radicals having 1 to 4
carbon atoms, a phenyl radical and, preferably, a hydroxyl radical,
an ethoxy radical, a methoxy radical or a methyl radical;
[0096] (3) the symbols B, functional groups which are identical
and/or different, represent a group containing sterically hindered
piperidyl function(s), selected from those mentioned above; and
[0097] (4) the number of units .eta.Si without a group B is from 10
to 450, preferably from 50 to 250;
[0098] the number of units .eta.Si with a group B is from 1 to 5,
preferably from 1 to 3;
[0099] 0.ltoreq.w.ltoreq.10 and 8<y<448.
[0100] Very preferably said polyorganosiloxane is linear.
[0101] According to a second embodiment of the invention, said
material constituting the active substance (A) is an organic
material.
[0102] By way of example mention may be made of
[0103] mono-, di- or triglycerides of C.sub.1-C.sub.30 carboxylic
acids or mixtures thereof, such as vegetable oils (colza oil,
castor oil, sunflower oil, erucic rapeseed oil, linseed oil,
etc.)
[0104] sugar esters, sucroglycerides
[0105] --C.sub.1-C.sub.30 alcohol esters of C.sub.1-C.sub.30
carboxylic or C.sub.2-C.sub.30 dicarboxylic acids
[0106] ethylene or propylene glycol monoesters or diesters of
C.sub.1-C.sub.30 carboxylic acids
[0107] propylene glycol C.sub.4-C.sub.20 alkyl ethers
[0108] di(C.sub.8-C.sub.30 alkyl) ethers
[0109] organic waxes comprising alkyl chains containing 4 to 40
carbon atoms. Among waxes mention may be made in particular of:
[0110] animal waxes (beeswax, lanolin, whale oil)
[0111] plant waxes (carnauba wax, candelilla wax, sugar cane wax,
jojoba)
[0112] mineral waxes (montan, ozokerite, Utah wax)
[0113] hydrocarbon waxes containing 4 to 35 carbon atoms (mineral
oils, paraffins, microcrystalline waxes)
[0114] synthetic waxes such as polyolefins (polyethylene and
polypropylene), sterone, and carbowax.
[0115] According to the invention the active substance (A) is
dispersed stably in the medium (MAV) by means of a surfactant
(TAC).
[0116] Said surfactant (TAC) may be a nonionic surfactant and/or a
cationic surfactant when the material constituting the active
substance (A) is intrinsically cationic or intrinsically
potentially cationic in the medium (MAV).
[0117] Said surfactant (TAC) is a cationic surfactant or a mixture
of cationic surfactant and nonionic surfactant when said material
constituting the active substance (A) is uncharged or has a zero
charge; the amount of nonionic surfactant represents less than 70%
of the weight of all of the surfactants (TAC).
[0118] For effective realization of the invention the ratio of the
mass of polymer constituting the active substance (A) to the mass
of surfactant (TAC) is from 0.01 to 10, preferably from 0.01 to
1.
[0119] The cationic charges generated by the optional cationic or
potentially cationic functions of the active substance (A) and by
the cationic surfactant or surfactants at the surface of the active
active substance (A) in dispersion in the medium (MAV) are such
that the zeta potential of the active substance in dispersion in
(MAV) is from 0 to +50 mV, preferably from +10 to +40 mV.
[0120] Among cationic surfactants mention may be made in particular
of the quaternary ammonium salts of formula
R.sup.1R.sup.2R.sup.3R.sup.4N.sup.+X.sup.-
[0121] where
[0122] R.sup.1, R.sup.2 and R.sup.3, alike or different, represent
H or an alkyl group containing less than 4 carbon atoms, preferably
1 or 2 carbon atom(s), which is optionally substituted by one or
more hydroxyl function(s), or may form, together with the nitrogen
atom N.sup.+, at least one aromatic or heterocyclic ring,
[0123] R.sup.4 represents a C.sub.8-C.sub.22, preferably
C.sub.12-C.sub.22, alkyl or alkenyl group, an aryl group or benzyl,
and
[0124] X.sup.- is a solubilizing anion such as halide (for example,
chloride, bromide or iodide), sulfate or alkyl sulfate (methyl
sulfate), carboxylate (acetate, propionate or benzoate) or alkyl-
or arylsulfonate. Mention may be made in particular of
dodecyltrimethylammonium bromide, tetradecyltrimethylammonium
bromide, and cetyltrimethylammonium bromide, stearylpyridinium
chloride, Rhodaquat.RTM. TFR and Rhodamine.RTM. C15, sold by
Rhodia, cetyltrimethylammonium chloride (Dehyquart ACA and/or AOR
from Cognis), and cocobis(2-hydroxyethyl)ethylammonium chloride
(Ethoquad C12 from Akso Nobel).
[0125] Mention may also be made of other cationic surfactants
having softening properties, such as:
[0126] the quaternary ammonium salts of formula
R.sup.1'R.sup.2'R.sup.3'R.sup.4'N.sup.+X.sup.-
[0127] where
[0128] R.sup.1' and R.sup.2', alike or different, represent H or an
alkyl group containing less than 4 carbon atoms, preferably 1 or 2
carbon atom(s), which is optionally substituted by one or more
hydroxyl function(s), or may form, together with the nitrogen atom
N.sup.+, a heterocyclic ring,
[0129] R.sup.3' and R.sup.4' represent a C.sub.8-C.sub.22,
preferably C.sub.10-C.sub.22, alkyl or alkenyl group, an aryl group
or benzyl, and
[0130] X.sup.- is an anion such as halide (for example, chloride,
bromide or iodide), sulfate or alkyl sulfate (methyl sulfate),
carboxylate (acetate, propionate or benzoate) or alkyl- or
arylsulfonate.
[0131] The following may be mentioned in particular:
dialkyldimethylammonium chlorides such as ditallow dimethylammonium
chloride or methyl sulfate, etc., and alkylbenzyldimethylammonium
chlorides.
[0132] C.sub.10-C.sub.2-5alkylimidazolium salts such as
C.sub.10-C.sub.25alkylimidazolinium methyl sulfates
[0133] substituted polyamine salts such as
N-tallow-N,N',N'-triethanol-1,3- -propylenediamine dichloride or
dimethyl sulfate and
N-tallow-N,N,N',N',N'-pentamethyl-1,3-propylenediamine
dichloride
[0134] Among nonionic surfactants mention may be made of
polyoxyalkenylated derivatives such as
[0135] ethoxylated or ethoxy-propoxylated fatty alcohols
[0136] ethoxylated or ethoxy-propoxylated triglycerides
[0137] ethoxylated or ethoxy-propoxylated fatty acids
[0138] ethoxylated or ethoxy-propoxylated sorbitan esters
[0139] ethoxylated or ethoxy-propoxylated fatty amines
[0140] ethoxylated or ethoxy-propoxylated
di(1-phenylethyl)phenols
[0141] ethoxylated or ethoxy-propoxylated
tri(1-phenylethyl)phenols
[0142] ethoxylated or ethoxy-propoxylated alkyl phenols
[0143] The dispersion medium (MAV) for the active substance (A) is
an aqueous or aqueous-alcoholic polar medium.
[0144] Alcohols which may be present include ethanol, isopropanol,
propylene glycol, butoxy ethanol, etc. These alcohols may represent
up to 70% of the volume of medium (MAV)
[0145] Preferentially the medium (MAV) is water.
[0146] The medium may be brought to the desired pH of from 2 to 5
by addition of an acid, such as hydrochloric acid, citric acid,
phosphoric acid, benzoic acid, etc.
[0147] The rinsing formulation (F) forming the subject of the
invention comprises a vehicle (V) which is capable of bringing the
active substance (A) onto the surface of the textile fiber articles
in the rinsing operation.
[0148] According to the invention said vehicle (V)
[0149] comprises an organic polymer which is soluble or dispersible
in the medium (MAV) and in the rinsing medium (MR)
[0150] has an overall cationic or zero ionic charge in the medium
(MAV)
[0151] is capable, at the pH of the rinsing operation in the
rinsing medium (MR), of developing anionic charges in sufficient
quantity to destabilize the active substance (A) in the rinsing
medium (MR).
[0152] Said organic polymer constituting the vehicle (V) may be any
polymer which is soluble or dispersible in aqueous or
aqueous-alcoholic medium with a pH of between 2 and 8 and which
comprises at least one unit which is neutral in the medium (MAV)
and potentially anionic (HA) in the rinsing medium (MR).
[0153] They may further comprise at least one unit which is
cationic or potentially cationic (HC) in the medium (MAV) and/or at
least one hydrophilic or hydrophobic nonionic unit.
[0154] The term "dispersible" signifies that the vehicle (V) does
not form a macroscopic precipitate in aqueous or aqueous-alcoholic
medium.
[0155] Preferentially the polymer constituting the vehicle (V) is a
copolymer comprising:
[0156] at least one hydrophilic unit which is neutral in the medium
(MAV) and potentially anionic (HA) in the rinsing medium (MR)
and
[0157] at least one hydrophilic unit which is cationic or
potentially cationic (HC) in the medium (MAV)
[0158] and optionally at least one hydrophobic or hydrophilic
nonionic unit.
[0159] The polymer constituting the vehicle (V) may optionally
contain anionic units (whose first pKa is less than 3), but in a
very small amount, for example in an amount much less than 5% by
weight relative to the entirety of the units.
[0160] The relative amounts of the various units of the polymer
constituting the vehicle (V) are such that in the medium (MAV) the
overall charge of the polymer or copolymer is zero or cationic.
[0161] The relative amounts of vehicle (V) polymer, cationic
surfactant (TAC), and material constituting the active substance
(A) are such that in the course of the rinsing operation the number
of anionic charges developed in the rinsing medium (MR) by the
vehicle polymer (V) is sufficient to destabilize the active
substance (A) in the rinsing medium (MR), in particular by
electrostatic attraction with the surface charges of the active
substance (A) in the medium (MR).
[0162] According to the invention the active substance (A) is
considered as being destabilized in the rinsing medium (MR)
comprising the vehicle (V) when the turbidity of said medium
reaches in less than 5 minutes a value at least 5 times greater
than the turbidity that the same medium would have in the absence
of vehicle (V).
[0163] The number of anionic charges developed in the rinsing
medium (MR) by the vehicle (V) polymer to destabilize the active
substance is preferably at least 1% relative to the number of
cationic surface charges of the active substance (A) in the medium
(MR).
[0164] This number of anionic charges may range up to 200% relative
to the number of cationic surface charges of the active substance
(A) in the medium (MR).
[0165] Possible examples that may be mentioned of polymers which
may constitute the vehicle (V) include in particular the polymers
derived from ethylenically unsaturated monomers, and also natural
polysaccharides and substituted or modified polysaccharides, and
also mixtures of said polymers derived from ethylenically
unsaturated monomers and said polysaccharides.
[0166] The term "polymer" is used here to denote both a homopolymer
and a copolymer. The term copolymer will be used when the polymer
in question is derived from at least least two monomers of
different type.
[0167] A first example of polymers which may constitute the vehicle
(V) are the polymers derived:
[0168] 0 from at least one .alpha.-.beta. monoethylenically
unsaturated monomer which is neutral in the medium (MAV) and
potentially anionic (HA) in the rinsing medium (MR) and
[0169] optionally at least one .alpha.-.beta. monoethylenically
unsaturated monomer which is cationic or potentially cationic (HC)
in the medium (MAV), and
[0170] optionally at least one nonionic .alpha.-.beta.
monoethylenically unsaturated monomer which is hydrophilic or
hydrophobic, preferably hydrophilic.
[0171] Preferentially the (V) is a random, block or graft copolymer
derived
[0172] from at least one .alpha.-.beta. monoethylenically
unsaturated hydrophilic monomer which is neutral in the medium
(MAV) and potentially anionic (HA) in the rinsing medium (MR)
and
[0173] from at least one .alpha.-.beta. monoethylenically
unsaturated hydrophilic monomer which is cationic or potentially
cationic (HC) in the medium (MAV),
[0174] and optionally from at least one nonionic .alpha.-.beta.
monoethylenically unsaturated monomer which is hydrophilic or
hydrophobic, preferably hydrophilic.
[0175] The relative amounts of monomers from which (V) is derived
are such that in the medium (MAV) the overall charge of the
copolymer (V) is zero or cationic.
[0176] The average molar mass of said polymer or copolymer (V)
derived from one or more .alpha.-.beta. monoethylenically
unsaturated monomers (measured by aqueous gel permeation
chromatography (GPC) and expressed in polyoxyethylene equivalents)
is greater than 5 000 g/mol, generally of the order of from 20 000
to 500 000 g/mol.
[0177] As examples of hydrophilic .alpha.-.beta. monoethylenically
unsaturated monomer which is neutral in the medium (MAV) and
potentially anionic (HA) in the rinsing medium (MR) mention may be
made of
[0178] monomers possessing at least one carboxyl function, such as
.alpha.-.beta. ethylenically unsaturated carboxylic acids or the
corresponding anhydrides, such as acrylic, methacrylic, and maleic
acid or anhydride, fumaric acid, itaconic acid,
N-methacryloylalanine, N-acryloylglycine and their water-soluble
salts
[0179] monomers which are precursors of carboxylic functions, such
as tert-butyl acrylate, which give rise, after polymerization, to
carboxylic functions by hydrolysis.
[0180] As examples of hydrophilic .alpha.-.beta. monoethylenically
unsaturated monomer which is cationic or potentially cationic (HC)
in the medium (MAV) mention may be made of
[0181] acryloyl- or acryloyloxyammonium monomers such as
trimethylammonium propyl methacrylate chloride,
trimethylammoniumethylacrylamide or -methacrylamide chloride or
bromide, trimethylammoniumbutylacrylamide or -methacrylamide methyl
sulfate, trimethylammoniumpropylmethacrylamide methyl sulfate
(MES), (3-methacrylamidopropyl)trimethylammonium chloride (MAPTAC),
(3-acrylamidopropyl)trimethylammonium chloride (APTAC),
methacryloyloxyethyltrimethylammonium chloride or methyl sulfate,
and acryloyloxyethyltrimethylammonium chloride;
[0182] 1-ethyl-2-vinylpyridinium or 1-ethyl-4-vinylpyridinium
bromide, chloride or methyl sulfate;
[0183] N,N-dialkyldiallylamine monomers such as
N,N-dimethyldiallylammoniu- m chloride (DADMAC);
[0184] polyquaternary monomers such as
dimethylaminopropylmethacrylamide chloride and
N-(3-chloro-2-hydroxypropyl)trimethylammonium (DIQUAT), etc.
[0185] carboxybetaine monomers
[0186] N,N-(dialkylamino-co-alkyl)amides of .alpha.-.beta.
monoethylenically unsaturated carboxylic acids such as
N,N-dimethylaminomethylacrylamide or -methacrylamide,
2-(N,N-dimethylamino)ethylacrylamide or -methacrylamide,
3-(N,N-dimethylamino)propyl-acrylamide or -methacrylamide, and
4-(N,N-dimethylamino)butyl-acrylamide or -methacrylamide
[0187] .alpha.-.beta. monoethylenically unsaturated amino esters
such as 2-(dimethylamino)ethyl methacrylate (DMAM),
3-(dimethylamino)propyl methacrylate, 2-(tert-butylamino)ethyl
methacrylate, 2-(dipentylamino)ethyl methacrylate, and
2-(diethylamino)ethyl methacrylate
[0188] monomers which are precursors of amine functions, such as
N-vinylformamide, N-vinylacetamide, etc., which give rise to
primary amine functions by simple acid or base hydrolysis.
[0189] As examples of hydrophilic .alpha.-.beta. monoethylenically
unsaturated monomers which are uncharged or unionizable mention may
be made of
[0190] hydroxyalkyl esters of .alpha.-.beta. ethylenically
unsaturated acids, such as hydroxyethyl and hydroxypropyl acrylate
and methacrylate, glyceryl monomethacrylate, etc.
[0191] .alpha.-.beta. ethylenically unsaturated amides such as
acrylamide, N,N-dimethylmethacrylamide, N-methylolacrylamide,
etc.
[0192] .alpha.-.beta. ethylenically unsaturated monomers bearing a
water-soluble polyoxyalkylene segment of the polyethylene oxide
type, such as polyethylene oxide .alpha.-methacrylates (Bisomer
S20W, SLOW, etc., from Laporte) or .alpha.,.omega.-dimethacrylates,
Sipomer BEM from Rhodia (.omega.-behenyl polyoxyethylene
methacrylate), and Sipomer SEM-25 from Rhodia
(.omega.-tristyrylphenyl polyoxyethylene methacrylate), etc.
[0193] .alpha.-.beta. ethylenically unsaturated monomers which are
precursors of hydrophilic units or blocks, such as vinyl acetate,
which, once polymerized, can be hydrolyzed in order to give rise to
vinyl alcohol units or polyvinyl alcohol blocks
[0194] .alpha.-.beta. ethylenically unsaturated monomers of ureido
type, and in particular 2-imidazolidinone-ethyl methacrylamide
(Sipomer WAM II from Rhodia).
[0195] By way of examples of hydrophobic nonionic .alpha.-.beta.
monoethylenically unsaturated monomers mention may be made of
[0196] vinylaromatic monomers such as styrene, vinyltoluene,
etc.
[0197] alkyl esters of .alpha.-.beta. monoethylenically unsaturated
acids, such as methyl and ethyl acrylate and methacrylate, etc.
[0198] vinyl or allyl esters of saturated carboxylic acids, such as
vinyl or allyl acetates, propionates, and versatates
[0199] .alpha.-.beta. monoethylenically unsaturated nitriles such
as acrylonitrile, etc.
[0200] As examples of hydrophilic anionic .alpha.-.beta.
monoethylenically unsaturated monomer (whose first pKa is less than
3) mention may be made of
[0201] monomers possessing at least one sulfate or sulfonate
function, such as 2-sulfooxyethyl methacrylate, vinylbenzene
sulfonic acid, allyl sulfonic acid, 2-acrylamido-2-methylpropane
sulfonic acid, sulfoethyl acrylate or methacrylate, sulfopropyl
acrylate or methacrylate and their water-soluble salts
[0202] monomers possessing at least one phosphonate or phosphate
function, such as vinylphosphonic acid, etc., the esters of
ethylenically unsaturated phosphates, such as the phosphates
derived from hydroxyethyl methacrylate (Empicryl 6835 from Rhodia)
and those derived from polyoxyalkylene methacrylates, and their
water-soluble salts.
[0203] By way of examples of polymers derived from ethylenically
unsaturated monomers constituting the vehicle (V) mention may be
made of:
[0204] polyacrylic or polymethacrylic acids, alkali metal
polyacrylates or polymethacrylates, preferably with a molar mass by
weight of from 100 000 to 1 000 000 g/mol
[0205] acrylic acid/DADMAC copolymers, with a molar ratio of 50/50
to 30/70, preferably with a molar mass by weight of from 70 000 to
350 000 g/mol
[0206] acrylic acid/MAPTAC copolymers, with a molar ratio of 60/40
to 30/70, preferably with a molar mass by weight of from 90 000 to
300 000 g/mol
[0207] acrylic acid/MAPTAC/linear C.sub.4-C.sub.18 alkyl
methacrylate terpolymers comprising 0.005 to 10% by mass of alkyl
methacrylate, with an acrylic acid/MAPTAC molar ratio ranging from
60/40 to 30/70, and preferably having a molar mass by weight of
from 50 000 to 250 000 g/mol
[0208] acrylic acid/dimethylaminoethyl methacrylate (DMAEMA)
copolymers, with a molar ratio of 60/40 to 30/70, preferably with a
molar mass by weight of from 50 000 to 300 000 g/mol.
[0209] A second example of polymers which can constitute the
vehicle (V) are potentially anionic natural polysaccharides and
potentially anionic or amphoteric substituted or modified
polysaccharides.
[0210] The potentially anionic natural polysaccharides are formed
of nonionic monosaccharide units and of monosaccharide units which
are neutral in the medium (MAV) and potentially anionic in the
rinsing medium (MR), these units being alike or different. They may
be linear or branched.
[0211] More particularly said potentially anionic natural
polysaccharides are branched polysaccharides formed
[0212] of a main chain comprising alike or different anhydrohexose
units
[0213] and of branches comprising at least one anhydropentose
and/or anhydrohexose unit which is neutral in the medium (MAV) and
optionally potentially anionic in the rinsing medium (MR).
[0214] The hexose units (alike or different) of the main chain may
be units of D-glucose, D- or L-galactose, D-mannose, D- or
L-fucose, L-rhamnose, etc.
[0215] The pentose and/or hexose units (alike or different) which
are nonionic or neutral in the medium (MAV) and potentially anionic
in the medium (MR) of the branches may be units of D-xylose etc.,
L- or D-arabinose, D-glucose, D- or L-galactose, D-mannose, D- or
L-fucose, L-rhamnose, D-glucuronic acid, D-galacturonic acid,
D-mannuronic acid, D-mannose substituted by a pyruvic group,
etc.
[0216] By way of examples of natural polysaccharides which are
neutral in the medium (MAV) and potentially anionic in the rinsing
medium (MR) mention may be made of xanthan gum (such as the
Rhodopol.RTM. products from Rhodia), succinoglycans, rhamsans,
gellan gums, welan gums, etc.
[0217] Their molar mass by weight may range from 2 000 to 5 000
000, preferably from 10 000 to 5 000 000, more particularly from 10
000 to 4 000 000 g/mol.
[0218] The molar mass by weight Mw of said polysaccharides may be
measured by size exclusion chromatography.
[0219] When the polysaccharides in question are substituted or
modified, their native skeleton is formed of nonionic
monosaccharide units and/or of monosaccharide units which are
neutral in the medium (MAV) and potentially anionic in the rinsing
medium (MR), said monosaccharide units being alike or different and
being substituted or modified:
[0220] by one or more groups which carry at least one charge which
is neutral in the medium (MAV) and potentially anionic in the
medium (MR)
[0221] and optionally by one or more groups which carry at least
one charge which is cationic or potentially cationic in the medium
(MAV),
[0222] the degree of substitution or modification of the
monosaccharide units by the entirety of the groups which carry
charges which are potentially anionic and of optional groups which
carry cationic charges being such that said substituted or modified
polysaccharide is soluble or dispersible in aqueous or
aqueous-alcoholic medium and has an overall cationic or zero charge
in the medium (MAV).
[0223] Said substituted or modified polysaccharides may further
comprise at least one nonionic modifying or substituent group.
[0224] Among the native skeletons which can be employed mention may
be made of linear or branched polysaccharides.
[0225] More particularly said polysaccharide is a substituted or
modified branched polysaccharide whose native skeleton is
formed
[0226] of a main chain comprising alike or different anhydrohexose
units
[0227] and of branches comprising at least one anhydropentose
and/or anhydrohexose unit which is neutral in the medium (MAV) and
optionally potentially anionic in the rinsing medium (MR),
[0228] the anhydrohexose and/or anhydropentose units of said
polysaccharide being substituted or modified by one or more groups
which carry at least one charge which is neutral in the medium
(MAV) and potentially anionic in the medium (MR) and optionally at
least one charge which is cationic or potentially cationic in the
medium (MAV),
[0229] the degree of substitution or modification DSi of the
anhydrohexose and/or anhydropentose units by the entirety of said
groups which carry charges which are ionic or potentially ionic
ranging from 0.01 to less than 3, preferably from 0.01 to 2.5,
[0230] with a ratio of the number of potentially anionic charges in
the medium (MR) to the number of cationic or potentially cationic
charges in the medium (MAV) ranging from 100/0 to 30/70, preferably
from 100/0 to 50/50.
[0231] When the polysaccharide in question is amphoteric the ratio
of the number of charges which are potentially anionic in the
medium (MR) to the number of charges which are cationic or
potentially cationic in the medium (MAV) is from 99.5/0.5 to 30/70,
preferably from 99.5/0.5 to 50/50.
[0232] Said substituted or modified branched polysaccharide may
further comprise at least one nonionic modifying or substituent
group.
[0233] The molar mass by weight of said substituted or modified
polysaccharides may range from 2 000 to 5 000 000, preferably from
10 000 to 5 000 000 g/mol. The molar mass by weight, Mw, of said
polysaccharides may be measured by size exclusion
chromatography.
[0234] When the polysaccharide in question carries substituent
groups which are potentially anionic in the medium (MR) the
measurement is made in water at a pH of 9-10 containing 0.1 M LiCl
and 2/10 000 of sodium nitrate.
[0235] When the polysaccharide in question is amphoteric, i.e.,
carries substituent groups which are potentially anionic in the
medium (MR) and groups which are cationic or potentially cationic
in the medium (MAV), the measurement is made in a 0.1 M aqueous
formic acid solution containing 0.05 M sodium nitrate and 10 ppm of
high molar mass polyallyldimethylamine chloride (PDADMA) in the
case of polysaccharides whose DSi in terms of ionic or potentially
ionic function is less than 0.5. For those whose DSi is greater
than 0.5 a 0.025 M aqueous hydrochloric acid solution is used. The
molar mass by weight, Mw, is established directly in a known manner
by means of the light scattering values.
[0236] The degree of substitution or of modification, DSi,
corresponds to the average number of hydroxyl functions of the
anhydrohexose and/or anhydropentose units which are substituted or
modified by said ionic or potentially ionic group or groups per
anhydrohexose and/or anhydropentose unit.
[0237] Said ionic or potentially ionic groups are linked to the
carbon atoms of the sugar skeleton either directly or by way of
--O-- bonds.
[0238] In the case of amphoteric polysaccharides the potentially
anionic charges may be provided by modifying groups or substituent
groups which are different from those which carry cationic or
potentially cationic charges; in that case said polymer is an
ampholyte polysaccharide.
[0239] When a modifying group or substituent group at the same time
carries a potentially anionic charge and a cationic or potentially
cationic charge, said polysaccharide is in that case of betaine
type.
[0240] Said substituted or modified polysaccharide may further
exhibit at least one nonionic modifying group or substituent group.
Said nonionic groups are attached to the carbon atoms of the sugar
skeleton either directly or by way of --O-- bonds. The presence of
such groups is expressed in number of moles of substitution MS,
i.e., in average number of moles of precursor of said nonionic
substituent which have reacted per anhydrohexose and/or
anhydropentose unit. If said precursor is not appropriate for
forming new, reactive hydroxyl groups (alkylation precursor, for
example), the degree of substitution or of modification by the
entirety of the ionic or ionizable groups and nonionic groups is
less than 3 by definition. If said precursor is capable of forming
new, reactive hydroxyl groups (hydroxyl alkylation precursor, for
example), there is theoretically no limit on the number of moles of
substitution, MS; it may, for example, be up to 6, preferably up to
2.
[0241] Among the groups which are potentially anionic in the medium
(MR) mention may be made of those containing one or more
carboxylate (carboxylic) functions.
[0242] Mention may be made in particular of those of formula
--[--CH.sub.2--CH(R)--O].sub.x--(CH.sub.2).sub.y--COOH or
--[--CH.sub.2--CH(R)--O].sub.x--(CH.sub.2).sub.y--COOM
[0243] where
[0244] R is a hydrogen atom or an alkyl radical containing 1 to 4
carbon atoms
[0245] x is an integer ranging from 0 to 5
[0246] y is an integer ranging from 0 to 5
[0247] M represents an alkaline metal.
[0248] Very particular mention may be made of the carboxy groups
--COO.sup.-Na.sup.+ attached directly to a carbon atom of the sugar
skeleton and of carboxy methyl (sodium salt) groups
--CH.sub.2--COO.sup.-Na.sup.+ attached to a carbon atom of the
sugar skeleton via an --O-- bond.
[0249] Among cationic or potentially cationic groups mention may be
made of those which contain one or more amino, ammonium,
phosphonium, pyridinium, etc., functions.
[0250] Mention may be made in particular of the cationic or
potentially cationic groups of formula
[0251] --NH.sub.2
[0252]
--[--CH.sub.2--CH(R)--O].sub.x--(CH.sub.2).sub.y--COA-R'--N(R").sub-
.2
[0253]
--[--CH.sub.2--CH(R)--O].sub.x--(CH.sub.2).sub.y--COA-R'--N.sup.+(R-
'").sub.3X.sup.-
[0254]
--[--CH.sub.2--CH(R)--O].sub.x--(CH.sub.2).sub.y--COA-R'--NH--R""---
N(R").sub.2
[0255] --[--CH.sub.2--CH(R)--O].sub.x--R'--N(R").sub.2
[0256]
--[--CH.sub.2--CH(R)--O].sub.x--R'--N.sup.+(R'").sub.3X.sup.-
[0257] --[--CH.sub.2--CH(R)--O].sub.x--R'--NH--R""--N(R").sub.2
[0258] --[--CH.sub.2--CH(R)--O].sub.x--Y--R"
[0259] where
[0260] R is a hydrogen atom or an alkyl radical containing 1 to 4
carbon atoms
[0261] x is an integer ranging from 0 to 5
[0262] y is a integer ranging from 0 to 5
[0263] R' is an alkylene radical containing 1 to 12 carbon atoms,
optionally carrying one or more OH substituents
[0264] the radicals R", which are alike or different, represent a
hydrogen atom or an alkyl radical containing from 1 to 18 carbon
atoms
[0265] the radicals R'", which are alike or different, represent an
alkyl radical containing 1 to 18 carbon atoms
[0266] R"" is a linear, branched or cyclic alkylene radical
containing 1 to 6 carbon atoms
[0267] A represents O or NH
[0268] Y is a heterocyclic aliphatic group containing 5 to 20
carbon atoms and one nitrogen heteroatom
[0269] X.sup.- is a counterion, preferably halide (chloride,
bromide and iodide in particular),
[0270] and N-alkylpyridinium-yl groups whose alkyl radical contains
1 to 18 carbon atoms, with a counterion, preferably halide
(chloride, bromide and iodide in particular).
[0271] Among cationic or potentially cationic groups mention may be
made very particularly of:
[0272] those of formula
[0273] --NH.sub.2
[0274] --CH.sub.2--CONH--(CH.sub.2).sub.2--N(CH.sub.3).sub.2
[0275] --CH.sub.2--COO--(CH.sub.2).sub.2--NH--
(CH.sub.2).sub.2--N(CH.sub.- 3).sub.2
[0276]
--CH.sub.2--CONH--(CH.sub.2).sub.3--NH--(CH.sub.2).sub.2--N(CH.sub.-
3).sub.2
[0277]
--CH.sub.2--CONH--(CH.sub.2).sub.2--NH--(CH.sub.2).sub.2--N(CH.sub.-
3).sub.2
[0278] --CH.sub.2--CONH--(CH.sub.2).sub.2--N.sup.+(CH.sub.3).sub.3
Cl.sup.-
[0279] --CH.sub.2--CONH--(CH.sub.2).sub.3--N.sup.+(CH.sub.3).sub.3
Cl.sup.-
[0280] --(CH.sub.2).sub.2--N(CH.sub.3).sub.2
[0281]
--(CH.sub.2).sub.2--NH--(CH.sub.2).sub.2--N(CH.sub.3).sub.2
[0282] --(CH.sub.2).sub.2--N.sup.+(CH.sub.3).sub.3 Cl.sup.-
[0283] 2-hydroxypropyltrimethyl ammonium chloride
--CH.sub.2--CH(OH)--CH.s- ub.2--N.sup.+(CH.sub.3).sub.3
Cl.sup.-
[0284] pyridinium-yl groups such as N-methylpyridinium-yl groups,
of formula 7
[0285] with a chloride counterion
[0286] hindered amino groups such as those derived from HALS amines
of general formula 8
[0287] where R represents CH3 or H.
[0288] Among betaine groups mention may be made more particularly
of the function of formula:
--(CH.sub.2).sub.2--N.sup.+(CH.sub.3).sub.2--
(CH.sub.2).sub.2--COO.sup.-, an ethyldimethylammonium betaine
function.
[0289] Among nonionic groups mention may be made of those of
formula:
--[--CH.sub.2--CH(R)--O].sub.x--R.sup.1 where
[0290] R is a hydrogen atom or an alkyl radical containing 1 to 4
carbon atoms
[0291] x is an integer ranging from 0 to 5
[0292] R.sup.1 represents
[0293] a hydrogen atom
[0294] an alkyl radical containing 1 to 22 carbon atoms which is
optionally interrupted by one or more oxygen and/or nitrogen
heteroatoms, cycloalkyl, aryl or arylalkyl, containing 6 to 12
carbon atoms
[0295] a radical --(CH.sub.2).sub.y--COOR.sup.2
[0296] a radical --(CH.sub.2).sub.y--CN
[0297] a radical --(CH.sub.2).sub.y--CONHR.sup.2
[0298] where R represents an alkyl, aryl or arylalkyl radical
containing 1 to 22 carbon atoms,
[0299] and y is an integer ranging from 0 to 5
--CO--NH--R.sup.1,
[0300] where R.sup.1 is as defined above,
[0301] attached to a carbon atom of the sugar skeleton via an --O--
bond.
[0302] Very particular mention may be made of the following
groups:
[0303] methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl,
dodecyl, octadecyl, phenyl and benzyl, which are attached to a
carbon atom of the sugar skeleton by way of ether, ester, amide or
urethane linkage,
[0304] cyanoethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl,
which are attached to a carbon atom of the sugar skeleton by way of
an --O-- bond.
[0305] The hexose units (alike or different) of the main chain of
the native skeleton may be units of D-glucose, D- or L-galactose,
D-mannose, D- or L-fucose, L-rhamnose, etc.
[0306] The pentose and/or hexose units (alike or different) which
are nonionic or neutral in the medium (MAV) and potentially anionic
in the medium (MR) of the branches of the native skeleton may be
units of D-xylose, etc., L- or D-arabinose, D-glucose, D- or
L-galactose, D-mannose, D- or L-fucose, L-rhamnose, D-glucuronic
acid, D-galacturonic acid, and D-mannuronic acid.
[0307] Examples of native skeleton that may be mentioned include
galactomannanes, galactoglucomannanes, xyloglucans, xanthan gums,
scleroglucans, succinoglycans, rhamsans, welan gums, etc.
[0308] Preferentially the native skeleton is a galactomannan.
[0309] The galactomannanes are macromolecules containing a main
chain of D-mannopyranose units attached in .beta.(1-4) position
which is substituted by D-galactopyranose units in .alpha.(1-6)
position. Among these mention may be made of guar gum, carob gum,
and tara gum.
[0310] Very preferentially the native skeleton is a guar gum. Guar
gums have a mannose/galactose ratio of 2.
[0311] The substituted or modified polysaccharides used according
to the invention may be obtained by functionalizing the native
skeleton by means of precursors of the ionic or potentially ionic
groups and optionally nonionic groups.
[0312] These operations of functionalization may be carried out in
a known way by oxidation, substitution, condensation, and/or
addition.
[0313] Examples of substituted or modified polysaccharides which
can be used according to the invention include
[0314] carboxymethylgalactomannans, especially
carboxymethylguars,
[0315] carboxymethylhydroxypropylgalactomannans, especially
carboxymethylhydroxypropylguars,
[0316] carboxymethyl-hydroxypropyltrimethylammonium chloride
galactomannans, especially
carboxymethylhydroxypropyltrimethylammonium chloride guars,
[0317] carboxymethylhydroxypropyl-hydroxypropyltrimethylammonium
chloride galactomannans, especially
carboxymethyl-hydroxypropyl-hydroxypropyltrime- thylammonium
chloride guars.
[0318] When the vehicle (V) is a polysaccharide it is preferable
for the dispersion of the active substance (A) in the medium (MAV)
comprising the vehicle (V) to have a pH ranging from 3.5 and in
particular from 4.5 to 5 when said polysaccharide is a substituted
or modified guar.
[0319] For effective realization of the invention the amount of
vehicle (V) present in the formulation according to the invention
is from 0.001 to 5 parts by weight, preferably from 0.01 to 4
parts, and more particularly from 0.05 to 2 parts by weight per 100
parts by weight of active substance (A).
[0320] The formulation (F) according to the invention may be in the
form
[0321] of a stable dispersion (liquid, cream, paste, gel, etc)
[0322] or in solid form (powder, granules, block, tablet, etc).
[0323] The formula (F) in the form of a stable dispersion may be
obtained by
[0324] 1) preparing an aqueous dispersion (emulsion, microemulsion,
suspension) of the material constituting the active substance (A)
with the aid of a surfactant (TAC) as stabilizer;
[0325] 2) optionally diluting with water or a water/alcohol mixture
(depending on the desired proportion of active substance A in the
formulation F) and adjusting the pH to a value of 2.5-5 using an
acid (hydrochloric acid, citric acid, phosphoric acid, benzoic
acid, etc);
[0326] 3) adding the vehicle (V) to the resulting dispersion;
[0327] 4) optionally adding an additional amount of surfactant
(TAC) before or after adding said vehicle, and
[0328] 5) if necessary readjusting the pH to a value of from 2.5-5
using an acid.
[0329] For effective realization of the invention the aqueous or
aqueous-alcoholic formulation (F) comprises per 100 parts of its
weight:
[0330] from 0.01 to 40, preferably from 0.05 to 30 parts by dry
weight of active substance (A)
[0331] from 0.01 to 50, preferably from 0.01 to 35 parts by dry
weight of cationic surfactant (TAC)
[0332] from 0.001 to 4, preferably from 0.01 to 1 part by dry
weight of vehicle (V) polymer.
[0333] Said dispersion may have a solids content of from 0.021 to
90%, preferably from 0.07 to 51% by weight.
[0334] The formulation (F) in the form of a solid may be obtained
by
[0335] 1) preparing an aqueous dispersion of polymer constituting
the active substance (A) with the aid of a surfactant (TAC) as
stabilizer;
[0336] 2) adjusting the pH to a value of 2.5-5 using an acid
(hydrochloric acid, citric acid, phosphoric acid, benzoic acid,
etc);
[0337] 3) adding the vehicle (V) to the resulting dispersion;
[0338] 4) optionally adding an additional amount of surfactant
(TAC) before or after adding said vehicle, and
[0339] 5) if necessary readjusting the pH to a value of from 2.5-5
using an acid;
[0340] evaporating/drying.
[0341] The evaporating/drying step may be carried out in accordance
with any means known to the skilled worker, in particular by
lyophilization (i.e., freezing, then sublimation) or, preferably,
by spray drying.
[0342] Spray drying may be carried out in any known apparatus, such
as a spraying tower in combination with a spraying operation
carried out by a nozzle or a turbine with a stream of hot air. The
implementation conditions are dependant on the type of atomizer
used; these conditions are generally such that the temperature of
the entirety of the product in the course of drying is at least
30.degree. C. and does not exceed 150.degree. C.
[0343] The evaporating/drying step may be facilitated by the
presence within the dispersion which is subjected to said step of a
protectant, in particular by the presence of at least one sugar,
saccharide or polysaccharide which is water-soluble or
water-dispersible, preferably a sugar. The amount of protectant may
represent of the order of from 10 to 50 parts by weight per 100
parts by weight of active substance (A).
[0344] Among sugars mention may be made of aldoses such as glucose,
mannose, galactose, and ribose and of ketoses such as fructose.
[0345] The granules obtained may be ground to give a powder or
compacted conventionally to give tablets, for example.
[0346] The formulation (F) may further comprise other, customary
constituents of cationic rinsing formulations.
[0347] It may in particular comprise at least one cationic and/or
nonionic softener, such as acyclic quaternary ammonium compounds,
alkoxylated polyamines, quaternary diamido ammonium salts,
quaternary ammonium esters, quaternary imidazolium salts, primary,
secondary or tertiary amines, alkoxylated amines, cyclic amines,
nonionic sugar derivatives, etc., which are mentioned in particular
in WO 00/68352. Examples of some of these cationic softeners have
already been mentioned earlier on as surfactant (TAC).
[0348] The softeners may be present in a proportion of from 0.5 to
90%, preferably from 0.5 to 40%, depending on the concentration of
said formulation (F).
[0349] Also present may be:
[0350] optical brighteners (0.1 to 0.2%)
[0351] color transfer inhibitors (polyvinylpyrrolidone,
polyvinyloxazolidone, polymethacrylamide, etc. 0.03 to 25%,
preferably 0.1 to 15%)
[0352] water-soluble monovalent mineral salts, such as sodium,
potassium or ammonium chlorides, nitrates or sulfates (especially
when the vehicle (V) is a polysaccharide), in a proportion, for
example, of from 0.01 to 2 mol per liter
[0353] dyes,
[0354] fragrances,
[0355] foam suppressants
[0356] enzymes
[0357] bleaches.
[0358] The formulation (F) of the invention may be employed to
carry out a rinsing operation which follows an operation of
washing--by hand or in a washing machine--textile fiber articles.
Said articles may consist of natural and/or artificial and/or
synthetic fibers.
[0359] Said formulation is especially advantageous for rinsing
cotton or cotton-based articles.
[0360] It may be employed in the rinsing bath in a proportion of
from 0.001 to 5 g/l, preferably from 0.005 to 2 g/l, the proportion
of formulation being expressed in terms of dry matter. This rinsing
operation may be carried out at ambient temperature.
[0361] This rinsing operation makes it possible to impart to said
articles, in addition to the conventional benefits of softness
which are provided by the nonionic and/or cationic softener or
softeners, properties of wrinkle resistance (antiwrinkle
properties) and/or of ease of ironing, of abrasion resistance, and
soil release properties, which are provided by the deposition of
the active substance (A) on the surface of said articles, this
deposition being promoted by the presence of the vehicle (V).
Advantageous soil release properties are provided in particular
through the use as active substance (A) in the formulation (F) of a
silicone oil, in particular of a silicone oil containing a hindered
piperidyl function.
[0362] The invention secondly provides a process for treating
textile fiber articles by contacting said articles in the course of
a rinsing operation in aqueous or aqueous-alcoholic medium with the
rinsing formulation (F) as described above, then recovering said
rinsed articles.
[0363] The operating conditions of such a treatment have already
been mentioned above.
[0364] The invention thirdly provides a process for enhancing the
antiwrinkle and/or easy-iron and/or soil release and/or abrasion
resistance properties of textile fiber articles which consists in
contacting said articles in the course of a rinsing operation in
aqueous or aqueous-alcoholic medium with the rinsing formulation
(F) as described above, then in recovering said rinsed
articles.
[0365] The operating conditions for carrying out such a process
have already been mentioned above.
[0366] The invention fourthly provides for the use in a formulation
(F) intended for use in an operation of rinsing (R) textile fiber
articles (S) by means of an aqueous or aqueous-alcoholic medium
(MR), formulation (F) comprising at least one active substance (A)
comprising at least one liquid or solid organic or organosilicon
material in particulate form and being
[0367] in the form of a stable dispersion with a pH of from 2 to 5
of said active substance (A) in an aqueous or aqueous-alcoholic
medium (MAV) or
[0368] in a solid form obtained by drying said dispersion,
[0369] the nature of the active substance (A) and of the aqueous or
aqueous-alcoholic medium (MAV) being such that the active substance
(A)
[0370] is insoluble in the medium (MAV)
[0371] has an overall zero or cationic charge in the medium
(MAV),
[0372] is stabilized in the medium (MAV) by means of a cationic
surfactant (TAC), it being possible for said cationic surfactant
(TAC) to be wholly or partly replaced by a nonionic surfactant when
the material constituting the active substance (A) is intrinsically
cationic or intrinsically potentially cationic in the medium
(MAV)
[0373] remains insoluble in the rinsing medium (MR);
[0374] of at least one organic polymer which
[0375] is soluble or dispersible in the medium (MAV) and in the
rinsing medium (MR)
[0376] has an overall cationic or zero ionic charge in the medium
(MAV)
[0377] and is capable, at the pH of the rinsing operation in the
rinsing medium (MR), of developing anionic charges in sufficient
quantity to destabilize the active substance (A) in the rinsing
medium (MR);
[0378] as a vehicle (V) capable of bringing said active substance
(A) toward the surface of said textile fiber articles (S) in the
rinsing operation (R).
[0379] The nature and the relative amounts of the various
constituents, their conditions of use, and the operating conditions
to be employed have already been set out above.
[0380] The object fifthly provides a process for enhancing the
deposition of an active substance (A) comprising at least one solid
or liquid organic or organosilicon material in particulate form on
the surface of textile fiber articles (S), during an operation of
rinsing of said articles by means of an aqueous or
aqueous-alcoholic medium (MR) obtained from a formulation (F)
comprising said active substance (A), the formulation (F) being
[0381] in the form of a stable dispersion with a pH of from 2 to 5
of said active substance (A) in an aqueous or aqueous-alcoholic
medium (MAV) or
[0382] in a solid form obtained by drying said dispersion,
[0383] the nature of the active substance (A) and of the aqueous or
aqueous-alcoholic medium (MAV) being such that the active substance
(A)
[0384] is insoluble in the medium (MAV)
[0385] has an overall zero or cationic charge in the medium
(MAV),
[0386] is stabilized in the medium (MAV) by means of a cationic
surfactant (TAC), it being possible for said cationic surfactant
(TAC) to be wholly or partly replaced by a nonionic surfactant when
the material constituting the active substance (A) is intrinsically
cationic or intrinsically potentially cationic in the medium
(MAV)
[0387] remains insoluble in the rinsing medium (MR);
[0388] by adding to said formulation (F) a vehicle (V) comprising
at least one organic polymer which
[0389] is soluble or dispersible in the medium (MAV) and in the
rinsing medium (MR)
[0390] has an overall cationic or zero ionic charge in the medium
(MAV)
[0391] and is capable, at the pH of the rinsing operation in the
rinsing medium (MR), of developing anionic charges in sufficient
quantity to destabilize the active substance (A) in the rinsing
medium (MR).
[0392] The nature and the relative amounts of the various
constituents, their conditions of use and the operating conditions
to be employed have already been set out above.
[0393] The examples which follow are given by way of
illustration.
EXAMPLE 1
Antiwrinkle and Easy-Iron Effect
[0394] 30% of a sunflower oil of type Lubrirob.RTM. TOD18.80 (from
Rhodia/Novance) is emulsified in water in a microfluidizer (4 bar,
3 cycles) with heating (50.degree. C.) in the presence of 3% by
weight of cationic surfactants (cetyltrimethylammonium bromide
type).
[0395] This gives an emulsion (E) having a dry extract of 30% by
weight of active substance, whose size, measured by laser
diffraction (Horiba granulometer), is 250 nm. This size is a
mass-average size of the size distribution of the emulsion.
[0396] This emulsion (E) is used to produce various
formulations.
[0397] Formulation I1
[0398] The pH of the emulsion (E) is adjusted to 4.0 with 1 N
hydrochloric acid solution. The resulting dispersion is milky.
[0399] Under mechanical stirring 20 ml of the dispersion are poured
into 1 ml of water whose pH has been adjusted to 4. This gives a
mixture, pH=4, whose appearance is not significantly different from
that of the original dispersion. This mixture is stable for a
number of days, does not form any precipitate and does not change
in turbidity over time.
[0400] Formulation II1
[0401] The pH of the emulsion (E) is adjusted to 4.0 with 1 N
hydrochloric acid solution. The resulting dispersion is milky.
[0402] Also prepared is a 2.2% by weight aqueous solution of a 1:1
molar acrylic acid-DADMAC copolymer (with a molar mass of 100 000
g/mol) (vehicle V), the solution having been adjusted to a pH of
4.0 with 10% by weight hydrochloric acid solution.
[0403] 20 ml of the dispersion of active substance (A) are poured
into 1 ml of the vehicle (V) copolymer solution under mechanical
stirring. This gives a mixture with a pH of 4 whose appearance is
not significantly different from that of the original dispersion.
This mixture is stable for a number of days, does not form any
precipitate and does not change in turbidity over time.
[0404] Dilute Formulations I1(a) and II1(a) Obtained by Diluting
Formulations I1 and II1 in Water at a pH of 4
[0405] A Horiba granulometer vessel is introduced with water whose
pH has been adjusted to 4 (approximately 100 ml). 0.1 ml of the
formulation II is added to the vessel under mechanical stirring and
the change in size of the emulsion over time is monitored.
[0406] The same operation is repeated with 0.1 ml of formulation
II1.
[0407] The results are given in table 1.
1TABLE 1 Size of the Size of the emulsion in nm emulsion in nm Time
(min) Formulation I1(a) Formulation II1(a) 1 525 525 5 525 525 10
525 525 This size does not change over time.
[0408] Dilute Formulations I1(b) and II11(b) Obtained by Diluting
Formulations I1 and II1 in Water at a pH of 7.2
[0409] The granulometer vessel is charged with water at its natural
pH of 7.2 (approximately 100 ml).
[0410] 0.1 ml of the formulation I1 is added therein under
mechanical stirring and the change in size of the emulsion over
time is monitored.
[0411] The same operation is repeated with 0.1 ml of formulation
II1.
[0412] The results are given in table 2.
2TABLE 2 Size of the Size of the emulsion in nm emulsion in nm Time
(min) Formulation I1(b) Formulation II1(b) 1 525 750 5 525 1230 10
525 1800
[0413] Effect of the (V)/(A) Weight Ratio: Amount of Vehicle
(V)/Amount of Active Substance (A)
[0414] The pH of the emulsion (E), containing 30% by weight of
active substance, is adjusted to 4.0 with 1 N hydrochloric acid
solution. The dispersion obtained is milky.
[0415] Also prepared is an 11% by weight aqueous solution of a 1:1
molar acrylic acid-DADMAC copolymer (with a molar mass of 100 000
g/mol) (vehicle V), the pH of the solution having been adjusted to
4.0 with 10% by weight hydrochloric acid solution.
[0416] 20 ml of the dispersion of active substance (A) are poured
respectively into 4 ml (formulation 1), 0.1 ml (formulation 2) and
0.05 ml (formulation 3) of the solution of vehicle (V) copolymer
under mechanical stirring.
[0417] Formulations 2 and 3 are made up respectively with 3.9 ml of
3.95 ml of water, so as to keep the active substance (A)
concentration constant.
[0418] This gives three formulations with a pH of 4 whose
appearance is not significantly different from that of the original
dispersion and in which the (V)/(A) weight ratios are 7.2/100,
0.18/100 and 0.09/100 respectively. Three beakers are prepared each
containing 200 ml of water at its natural pH of 7.2.
[0419] 0.1 ml of formulation is added to each beaker under
mechanical stirring, and the change in appearance of the
dispersions is monitored.
3 (V)/(A) (V)/(A) (V)/(A) 7.2/100 0.18/100 0.09/100 Appearance
Stable, milky Flocculation Flocculation
[0420] These results show that the ratio (V)/(A) has an effect on
the capacity of the vehicle (V) to cause flocculation of the active
substance (V).
[0421] Washing Machine Test
[0422] The following three rinsing formulations are prepared or
employed:
[0423] 50 ml of a commercial softener formulation FR, containing
only cationic surfactants (15% solids)
[0424] a softener formulation FRI1 obtained by adding 10 ml of the
formulation I1 above, of pH=4, to 50 ml of the formulation FR,
corresponding to 196 mg of active substance (A) per liter of water
in the machine
[0425] a softener formulation FRII1 obtained by adding 10 ml of the
formulation II1 above, of pH=4, to 50 ml of the formulation FR,
corresponding to 190 mg of active substance (A) per liter of water
in the machine.
[0426] 1.5 kg of flat cotton fabric samples measuring 50
cm.times.50 cm (their finish having been removed beforehand by
three successive washes with demineralized water at 90.degree. C.)
are washed at 30.degree. C. using a commercial powder detergent
formulation in a Miele.RTM. washing machine (from Miele).
[0427] At the end of the wash cycle one of the samples is placed in
reserve and rinsed with 15 liters of mains water at 23.degree. C.,
then wrung; the rinse cycle lasts 5 minutes. The other samples are
divided into three batches.
[0428] The first batch is rinsed for 5 minutes with 15 liters of
mains water at 23.degree. C., to which 50 ml of formulation FR have
been added, then is wrung under the same conditions as the reserved
sample.
[0429] The second batch is rinsed for 5 minutes with 15 liters of
mains water at 23.degree. C., to which 60 ml of formulation FRI1
have been added, then is wrung under the same conditions as the
reserved sample.
[0430] The third batch is rinsed for 5 minutes with 15 liters of
mains water at 23.degree. C., to which 60 ml of formulation FRII1
have been added, then is wrung under the same conditions as the
reserved sample.
[0431] During the rinse cycle the pH of the medium reaches 7.
[0432] After wringing, the articles are placed on a rack to
dry.
[0433] After drying, a digital color photograph is taken of an area
of the dry samples, which is subsequently converted into 256 levels
of grey (grey scale from 0 to 255).
[0434] The number of pixels corresponding to each level of grey is
counted.
[0435] For each resulting histogram the standard deviation a of the
distribution of the level of grey is measured. If wrinkling is
substantial, the distribution of the level of grey is large.
[0436] .sigma.1 corresponds to the standard deviation corresponding
to the reserved sample (rinsed without a rinsing formulation).
[0437] .sigma.2 corresponds to the standard deviation obtained with
the rinsing formulation in question.
[0438] .sigma.3 corresponds to the standard deviation obtained on
flat starting samples which have not undergone an operation of
washing, rinsing or wringing.
[0439] The performance value WR (wrinkle recovery) is given by the
following equation
WR(%)=[(.sigma.1-.sigma.2)/.sigma.1]f.times.100
[0440] where f is a standardization factor, equal to
1/[(.sigma.1-.sigma.3)/.sigma.1]
[0441] A value of:
[0442] 0% corresponds to zero benefit
[0443] 100% corresponds to a flat surface
[0444] The results of the wrinkle test are as follows:
4 Rinsing formulation FR FRI1(a) FRII1(a) WR 30% 38% 52%
[0445] The above results show that the addition of the vehicle (V)
enhances the deposition of the active substance (A) on the fabric,
which manifested in an improvement in the antiwrinkle effect of the
active substance (A).
EXAMPLE 2
Soil Release Effect
[0446] Formulation I2
[0447] An emulsion is used which comprises 30% by weight of
silicone containing hindered piperidyl functions (Rhodorsil.RTM.
21645 from Rhodia) and 3% of a nonionic surfactant of ethoxylated
fatty alcohol type (Symperonic A7).
[0448] Under mechanical stirring, 20 ml of the dispersion are
poured into 1 ml of water whose pH has been adjusted to 4.5.
[0449] 0.1 g of sodium chloride is added (for better comparison
with formula II2 below).
[0450] Formulation II2
[0451] An emulsion is used which comprises 30% by weight of
silicone containing hindered piperidyl functions (Rhodorsil.RTM.
21645 from Rhodia) and 3% of a nonionic surfactant of ethoxylated
fatty alcohol type (Symperonic A7).
[0452] Also prepared is a 1% by weight solution of xanthan gum
(Rhodopol.RTM. from Rhodia) with a molar mass by weight of 4 000
000 g/mol in water with a pH of 4.5.
[0453] Under mechanical stirring, 20 ml of the dispersion are
poured into 1 ml of the xanthan gum solution. The final dispersion
has a pH of 4.5.
[0454] 0.1 g of sodium chloride is added to stabilize the
dispersion over time.
[0455] Test
[0456] The test is carried out in a Tergotometer laboratory
apparatus which is well known to the formulators of detergent
compositions. The apparatus simulates the mechanical and thermal
effects of the American-type washing machines with a pulsing
action; by virtue of the presence of 3 washing pots, it allows
series of simultaneous tests to be carried out with a considerable
time saving.
[0457] The composition of the laundry detergent employed is as
follows:
5 Parts by Composition of the laundry detergent weight Zeolite 4A
25 Light carbonate 15 Disilicate R2A 5 Acrylic/maleic copolymer
Sokalan CP5 (BASF) 5 Na sulfate 9.5 Carboxymethylcellulose 1
Perborate monohydrate 15 Tetraacetylethylenediamine 5 Linear
dodecylbenzenesulfonate 6 Synperonic A3 (C12-C15 fatty alcohol 3
ethoxylated with 3 EO) Synperonic A9 (C12-C15 fatty alcohol 9
ethoxylated with 9 EO) Enzyme esperase 4.0 T 0.5 Fragrances 1
[0458] The following three rinsing formulations are tested:
[0459] 7 ml of a commercial softener formulation FR containing only
cationic surfactants (15% solids)
[0460] a softener formulation FRI2 obtained by adding 0.3 ml of the
formulation I2 above to 7 ml of the formulation FR,
[0461] a softener formulation FRII2 obtained by adding 0.3 ml of
the formulation II2 above to 7 ml of the formulation FR.
[0462] (a) Prewash/Rinsing/Drying:
[0463] 6 test specimens measuring 10.times.10 cm and made of flat
woven cotton are prewashed in a Tergotometer for 20 minutes at
23.degree. C. with the above laundering formula; the water used has
a hardness of 30.degree.HT (diluted Contrexville.RTM. mineral
water); the amount of laundry detergent employed is 5 g per liter
of water; the number of test specimens per pot is 6.
[0464] The squares of fabric are subsequently rinsed 3 times for 5
minutes (each time), twice with cold water and the third time with
cold water to which either 7 ml of commercial rinsing formula FR or
7.3 ml of the rinsing formulas FRI2 or FRII2 have been added.
[0465] The squares of fabric are subsequently wrung out and then
dried on clotheshorses.
[0466] (b) Staining:
[0467] 4 drops of dirty motor oil (DMO) are deposited on the test
specimens prewashed as above.
[0468] To ensure good fixing of the stains, the soiled fabrics are
placed in an oven at 60.degree. C. for 1 hour.
[0469] To allow effective reproducibility of the results, the
fabrics are washed within 24 hours.
[0470] (c) Washing/Rinsing/Drying:
[0471] The soiled tests specimens are washed, rinsed, wrung and
dried under the same conditions as those described in (a).
[0472] Evaluation
[0473] The reflectance of the fabrics before and after washing is
measured using a Dr. Lange/Luci 100 colorimeter. The efficacy of
the test polymer as a soil release agent is evaluated by the
percentage elimination of the stains, calculated by the formula
E in %=100.times.(R3-R2)/(R1-R2)
[0474] where
[0475] R1 represents the reflectance before washing of the unsoiled
fabric (step (a))
[0476] R2 represents the reflectance before washing of the soiled
fabric (steps (a) and (b))
[0477] R3 represents the reflectance after washing of the soiled
fabric (steps (a), (b) and (c))
[0478] For each test product the mean percentage stain elimination
is calculated.
[0479] The results obtained are as follows:
6 Rinsing formulation Cotton E in % FR 55 FRI2 61 FRII2 68
[0480] A significant enhancement of the removal of stains of the
dirty motor oil type is observed when xanthan gum is employed as
vehicle.
* * * * *