Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – Specific organic component
Reexamination Certificate
2000-03-08
2001-10-09
Hardee, John (Department: 1751)
Cleaning compositions for solid surfaces, auxiliary compositions
Cleaning compositions or processes of preparing
Specific organic component
Reexamination Certificate
active
06300306
ABSTRACT:
The present invention relates to a novel sulfonated copolymer comprising polyether and polyamide units, to a process for its preparation and to its use as a detergent for hard or textile surfaces, in particular formed from synthetic polymer, most particularly polyamide textile surfaces, and/or as an agent which can endow said surfaces with stain-resistance properties and/or which can facilitate soil release from said surfaces. It also relates to a method using said sulfonated copolymer, to clean and/or treat said surfaces to endow them with stain-resistance properties and/or to facilitate soil release. It also relates to detergent compositions comprising said copolymer.
French patent application FR-A-2 192 167 has proposed the use, in detergent compositions for washing polyamide fabrics, of copolymers obtained by condensation a) of an aliphatic dicarboxylic acid, b) of a hydroxypolyoxyalkylene compound and c) of a compound selected from amino acids or lactams, diamines or salts thereof with the dicarboxylic acid a), in combination with a detergent agent selected from ethoxylated alkylphenols, alkoxylated primary or secondary alcohols and alkoxylated monoethanolamides.
Patent application WO92/02570 describes dyed polyamide articles (fibers, carpets) which are resistant to acid stains, said polyamide being a polyhexamethylene adipamide, a poly-&egr;-caprolactam or a hexamethylenediamine/adipic acid/&egr;-caprolactam copolymer, containing 1% to 4% by weight of sulfonated aromatic carboxylic groups (for example 5-isophthalic acid) and containing 20 to 40 milliequivalents of amine end groups per 10
6
g, said polyamide being dyed using an acid dye.
French patent application FR-A-2 722 804 describes water-soluble and/or water-dispersible copolyamides with a number-average molecular mass of 2000 to 30,000, comprising aromatic and/or aliphatic dicarbonyl, sulfoaryldicarbonyl and polyoxyalkylenediamine units, alone or with aliphatic diamine units, and their use to size synthetic polyamide yarns or synthetic polyamide fibers which may be mixed with natural, artificial or other synthetic fibers.
A first subject of the invention is thus a water-soluble or water-dispersible copolymer (C) comprising
at least one polyoxyalkylene (POA) unit; and
at least one sulfonated polyamide (PAS) unit;
said copolymer (C) being characterized in that:
said polyoxyalkylene (POA) unit comprises 2 to 200, preferably 5 to 150, similar or different oxyalkylene elementary units, wherein the linear or branched alkylene residue contains 2 to 12, preferably 2 to 6, carbon atoms, most particularly 2 or 3 carbon atoms;
said sulfonated polyamide (PAS) unit comprises:
(i) non-sulfonated polyfunctional units elementary (mNS) which may be similar or different, with formula (mNS
1
) and/or (mNS
2
)
—C(O)—A—C(O)—N(R)—D—N(R)— (mNS
1
)
(dicarbonyl/diimino)
and/or —C(O)—K—N(R)— (mNS
2
)
(“lactam”)
and/or —C(O)—K—N(R) —C(O)—A—C(O)— (mNS
3
)
(“lactam”/dicarbonyl)
and/or —N(R)—D—N(R)—C(O)—K—N(R)— (mNS
4
)
(diimino/“lactam”)
in which formulae
A represents an aliphatic, cycloaliphatic or aromatic hydrocarbon group;
D represents an aliphatic, cycloaliphatic or aromatic hydrocarbon group which may be interrupted by one or more oxygen or tertiary nitrogen hetero atoms;
A K represents an aliphatic, cycloaliphatic or aromatic group;
the symbols R are identical or different and represent a hydrogen atom or a C
1
-C
4
alkyl group;
(ii) sulfonated polyfunctional elementary units (mS) which are similar or different, with formula:
—V—Q (L—SO
3
M)
n
—W—
where:
the symbols V and W, which are identical or different, represent:
a carbonyl
—C(O)— group;
an oxy
—O— group;
an imino
—NH— group; or
an (R)imino
—N(R)— group where R represents a
C
1
-C
4
alkyl group;
the symbol Q represents an aromatic, aliphatic or cycloaliphatic hydrocarbon group;
L is a valence bond or an alkylene, alkoxyalkylene, oxyalkylene, arylene, alkylarylene or alkoxyarylene group;
M represents a hydrogen atom or an alkaline cation;
n is 1 or more;
(iii) and binding groups (glPAS) of the elementary units of (PAS)
—C(O)—O— and/or —O—C(O)— and/or —C(O)—N(R)— and/or —N(R)—C(O)—, where R represents a hydrogen atom or a C
1
-C
4
alkyl group;
the quantity of SO
3
M functions, expressed as the mass of SO
3
function, in said (PAS) unit or units is such that it represents at least 0.1%, preferably at least 0.2%, most particularly at least 0.4%, in particular 0.4% to 15%, of the total copolymer (C) mass;
the mass ratio of the total (POA) units/total (PAS) units is 95/5 to 30/70, preferably 90/10 to 40/60, most particularly 85/15 to 50/50;
the number of amine functions —NH
2
present in said copolymer (C) is at most 80 milliequivalents per kilogram of copolymer (C);
the number of carboxyl functions —COOH present in said copolymer (C) is at least 80 milliequivalents, preferably at least 100 milliequivalents per kilogram of copolymer (C).
Copolymer (C) can have a number-average molecular mass of 100,000 or less, preferably 70,000 or less, most particularly 5000 to 60,000, measured at 100° C. by gel exclusion chromatography (SEC) in solution in dimethylacetamide (DMAC) with 10
−2
mol of added LiBr; this mass is measured in polystyrene equivalents.
Said copolymer (C) can also comprise monovalent functions other than —COOH and —NH
2
.
Examples which can be cited are hydroxyl, alcohol, (R)amino, urea, imide, ester, alkyl, aryl, and quaternary ammonium functions.
Said copolymers (C) can be of any type—linear, branched, crosslinked, etc.
Preferably, said copolymer is a linear block polymer; the ratio of the number of (POA) units
umber of (PAS) units is 1/2 to 2/1.
The optional monovalent —NH
2
functions and —COOH functions are generally at the ends of the chains of copolymer (C).
Said copolymers can also comprise, in their polyamide (PAS) unit(s), other polyfunctional units such as:
non-sulfonated dicarbonyl elementary units (mD) with formula —C(O)—A—C(O)—, where A represents an aliphatic, cycloaliphatic or aromatic hydrocarbon group, similar or not similar to the dicarbonyl sub-elementary unit of the (mNS
1
) (mNS3) elementary unit, not bonded to a diimino sub-elementary unit —N(R)—D—N(R)— or to a “lactam” elementary unit —C(O)—K—N(R)—;
non-sulfonated polyfunctional elementary units (mP) with formula:
(i) —X—E—Y— where
the symbols X and Y, which may be identical or different, represent:
an oxy
—O— group;
an imino
—NH— group; or
an (R)imino
—N(R)— group where R
represents a C
1
-C
4
alkyl group;
the symbol E represents a polyvalent aliphatic, cycloaliphatic or aromatic hydrocarbon group which may be interrupted by one or more oxygen or tertiary nitrogen heteroatom(s), said polyvalent group being bonded to at least one group X and to at least one group Y; or
(ii) —C(O)—E′—C(o)—, where
the symbol E′ represents an aliphatic, cycloaliphatic or aromatic hydrocarbon group substituted with at least one hydroxyl or carboxyl group.
Non-sulfonated polyfunctional elementary units (mNS
1
) (dicarbonyl/diimino) which can be mentioned include those in which:
the dicarbonyl sub-elementary unit is an aliphatic or cycloaliphatic elementary unit the aliphatic or cycloaliphatic residue of which contains 2 to 10 carbon atoms, such as adipoyl, glutaroyl, succinoyl, trimethyladipoyl, pimeloyl, azeloyl, sebacoyl, suberoyl, itaconoyl, maleoyl, fumaroyl, dicarbonyl cyclopentanes, dicarbonyl cyclohexanes, 2-oxymethylsuccinoyl, oxymethylglutaroyl or oxyglutaroyl elementary units;
the dicarbonyl sub-elementary unit is an aromatic elementary unit, such as terephthaloyl, isophthaloyl, orthophthaloyl, dicarbonyl naphthalenes, dicarbonyl anthracenes, dicarbonyl biphenyl, dicarbonyl oxyisophthalics or dicarbonyl 4-oxyphthalic elementary units;
the diimino sub-elementary unit is an aliphatic elementary unit wherein the aliphatic residue is a linear, branched or cyclic alkylene group containing 2 to 50, preferably 2 to 20, carbon atoms and can be interrupted by one or more oxygen or tertiary nitrogen heteroatoms, su
Firkins Simon
Gabriel Gladys Saliba
Perier Marie-Eve
Rochat Sandrine
Vovelle Louis
Hardee John
Rhodia Chimie
Seugnet Jean-Louis
Wood John Daniel
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