Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Nitrogen-containing reactant
Reexamination Certificate
2000-10-02
2004-08-17
Hardee, John R. (Department: 1751)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Nitrogen-containing reactant
C510S475000
Reexamination Certificate
active
06777530
ABSTRACT:
The invention relates to the use of crosslinked nitrogenous compounds which are soluble or dispersible in water in detergents and cleaners. The invention particularly relates to the use of crosslinked oligo- and polyamines as soil release agents and enzyme stabilizers in detergents and cleaners.
The use of nitrogenous polymers in detergents is known.
DE-A1-31 24 210 describes liquid detergents with additives to prevent dye transfer. The detergent additionally contains nonionic or zwitterionic surfactants in combination with polyethyleneimines, polyamines, polyamineamides or polyacrylamides, by which transfer of dyes from colored textiles to white or pale-colored textiles on washing together is counteracted. The polyamineamides can be obtained by condensing polybasic acids such as dibasic, saturated, aliphatic C
3-8
-acids and polyamines. The polymers are described as soluble in water but are not identified more exactly.
DE-A-1 922 450 describes detergents and cleaners which contain antiredeposition agents to prevent reabsorption of detached soil on the cleaned surfaces. Polyamides which can be prepared from polyethyleneimines with an average molecular weight of from 300 to 6000 and di- and tricarboxylic acids are used as antiredeposition agents. Products of reactions with diglycolic acid, thiodiglycolic acid, iminodiacetic acid and nitrilotriacetic acid are also mentioned.
DE-A-2 165 900 describes detergents Smith a content of antiredeposition additives The product of the reaction of a polyethyleneimine with a molecular weight of from 430 to 10,000 with C
8-18
-alkyl glycidyl ethers, which may additionally be reacted with ethylene oxide is used as antiredeposition agent.
It is furthermore known to use soil release agents, which are reversibly adsorbed from the wash liquor on the textile or the fibers of the textile during the washing process, in detergents. When a textile treated with such a soil release agent is soiled, in the next wash the adsorbed soil release agent improves detachment of the soil. This soil release effect is thus a reversible antisoil finish on the textile during the washing. Various soil release agents are known such as polyesters from polyethylene oxides with ethylene glycol and/or propylene glycol and aromatic and/or aliphatic dicarboxylic adds. For example, DE-A-43 44 357 describes a soil release polymer which has ethylene glycol terephthalic groups and polyethylene glycol terephthalic groups.
In addition, modified celluloses, such as methylcellulose, hydroxypropylcellulose or carboxymethylcellulose, have been employed. U.S. Pat. No. 4,138,352 describes the combination of a nonionic reactant and a hydroxybutylated methylcellulose with low molecular weight as soil release agent.
EP-A1-0 042 187 describes detergent compositions which contain small amounts of substituted polyamines. The polyamines are in this case substituted by a longchain alkyl or alkenyl radical. They may additionally be substituted by at least two alkylene oxide residues on different nitrogen atoms. The compositions show in particular improved soil release properties.
It is an object of the present invention to provide soil release agents for detergents and cleaners which preferably also act as enzyme stabilizers and have an advantageous property profile.
We have found that this object is achieved by the use of crosslinked nitrogenous compounds which are soluble or dispersible in water and are obtainable by crosslinking of
(a) compounds containing at least three NH groups with
(b) at least bifunctional crosslinkers which react with NH groups,
in detergents and cleaners.
The NH groups can be present in primary (NH
2
) and/or (NH) amino groups.
The nirogenous compounds according to the invention are preferably used as soil release agents and/or enzyme stabilizers.
The soil release effect presumably derives from the adsorption, described above, of the agent from the wash liquor onto the textile. The soil release effect thus emerges on washing several times. It must be distinguished from the single wash cycle or soil removal effect. The soil removal effect relates to detachment of soil directly on the first wash of a stained, non-pretreated fabric. Polyamines ethoxylated with ethylene oxide often show a single wash cycle or soil removal effect. It has been found, surprisingly, that oligo- and polyamines crosslinked in particular by polyether chains show soil release properties. The additional enzyme-stabilizing effect was unexpected because the stabilizing additives employed to date have been mainly boric acid derivatives with polyols and alkyl- or arylboronic acids.
The compounds employed according to the invention moreover show the advantageous properties in a large number of detergent formulations, such as heavy duty detergents, colored textile detergents, which can be in liquid or solid form.
Compounds (a)
The crosslinked nitrogenous compounds used according to the invention can be obtained by crosslinking of (a) compounds containing at least three NH groups. Compounds (a) are preferably selected from oligo- and polyamines, polyalkylenepolyamines, polyamidoamines, polyamidoamines grafted with (poly)ethyleneimine, and mixtures thereof Polyallylenepolyamines are suitable as component (a). Polyalkylenepolyamines mean in the present connection compounds which contain at least three NH groups, eg. diethylene triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, diaminopropylethylenediamine, trisaminopropylamine and polyethyleneimines. The polyethyleneimines preferably have an average molecular weight (Mw) of at least 300. The average molecular weight of the polyethyleneimines may be up to 1,000,000. Of particular interest industrially is the use of polyethyleneimines with average molecular weights of from 600 to 25,000.
Also preferred are polyethyleneimine homopolymers with a degree of polymerization n of 5, 6, 10, 20, 35 and 100. These polyethyleneiminehomopolymers may be prepared either water-containing or anhydrous, or be dehydrated. Synthesis of appropriate polyethyleneimines is described in the examples.
The polyethyleneimines ray also be partly modified, for example in one embodiment of the invention rendered hydrophobic with benzoic acid.
In one embodiment of the Invention, the polyalkylenepolyamine is selected from amines of the formula (I)
RR′N—[—(CR
1
R
2
)
x
—NR
3
—]
a
—[—(CR
4
R
6
—]
b
—R″ (I)
where the radicals R, R′ and R″, R
1
, R
2
, R
4
and R
5
are, independently of one another, hydrogen atoms, linear or branched-chain C
1-20
-alkyl -alkoxy, -hydroxyalkyl, -(alkyl)-carboxyl, -alcylamino radicals, C
2-20
-alkenyl radicals or C
6-20
-aryl, -aryloxy, -hydroxyaryl, -arylcarboxyl or -arylaino radicals, which may be further substituted, the radicals R
3
and R
6
are, independently of one another, hydrogen atoms, linear or branched-chain C
1-20
-alkyl radicals, C
6-20
-aryl radicals, which are unsubstituted or substituted, or radicals [(CR
7
R
8
)
2
—NR
9
]
c
—R
10
, where the radicals R
7
, R
8
, R
9
and R
10
are defined, independently of one another, as above for R, R′, R″, R
1
, R
2
, R
4
, R
5
, or are carboxymethyl, carboxyethyl, phosphonomethyl or carbamoylethyl radicals, x, y and z are, independently of one another, 2, 3 or 4, and a, b and c are, independently of one another, integers from 0-300, there being at least three NH groups in the molecule.
5 to 100%, in particular 10 to 95%, of the nitrogen atoms in the above amines are preferably present in primary or secondary amino groups.
In one embodiment of the invention, the above amines have a number average molecular weight of from 80 to 150,000, preferably 100 to 50,000, particularly preferably 110 to 10,000, especially 129 to 5000.
The amine or polyalkylenepolyamine of the formula (I) may be a block copolymer or, in one embodiment of the invention, a polymer with randomly distributed blocks or a polymer with an overall random distribution.
Further suitable compounds (a) are polyamidoamines. They are obtained, for
Boeckh Dieter
Decker Jürgen
Ehle Beate
Lux Jürgen Alfred
Meixner Hubert
BASF - Aktiengesellschaft
Hardee John R.
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
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