[0001] The present invention is directed to detergent formulations containing certain fluorescent
whitening agents or mixtures of fluorescent whitening agents, as well as to mixtures
of fluorescent whitening agents.
[0002] It is commonly known to use fluorescent whitening agents in detergent formulations.
They exhaust during the treatment on to the material to be washed and, by virtue of
their special light absorption/emission properly, result in elimination of the yellowish
shades.
[0003] EP-A-O 728 749 discloses triazine derivatives as ultraviolet adsorbing agents and as fluorescent
whitening agents.
EP-A-0 682 145 describes a composition containing at least one fluorescent triazine whitening agent
US-A-4 460 485 depits a polyester fabric conditioning and brightening composition comprising (i)
a cationic fabric softening compound and ii) a cotton- or nylon-substantive fluorescent
whitening agent.
WO 95/13354 describes compositions comprising bis-triazinylamino-stilbene and enzymes.
[0004] However there is still a need to find improved fluorescent whitening agents for this
application. It has now been found that mixtures of the following compounds of formulae
(1), (2), (3) or (4), and (5) possess superior properties with regard to, for example,
solubility, build-up properties, light-fastness degree of whiteness, and also possess
excellent white aspects in the solid state. The whiteness properties, like whiteness
maintenance, can even be enhanced by the use of mixtures of compounds of formulae
(1), (2), (3) or (4), and (5) in detergents containing cellulose, protease, amylase
or lipase enzymes. Favourable results are even obtained at low washing temperatures.
[0005] Accordingly, the present invention provides, as a first aspect, a detergent composition
comprising
at least one compound of formula
or
wherein M is hydrogen or cation,
together with at least one compound of formula
wherein
R
6 and R
7, independently of each other, are hydrogen, C
1-C
8alkyl, C
1-C
6alkoxy or halogen, and M is as defined above under formulae (1) to (4).
[0006] Within the scope of the above definitions, C
1-C
8alkyl may be methyl, ethyl, n- or isopropyl, n-, sec.- or t-butyl, or linear or branched
pentyl, hexyl, heptyl or octyl. Preferred are C
1-C
4alkyl groups. In case the alkyl groups are substituted examples of possible substituents
are hydroxyl, halogen, like fluorine, chlorine or bromine, sulfo, sulfato, carboxy
and C
1-C
4alkoxy, like methoxy and ethoxy. Other substituents of such alkyl groups are, for
example, cyano, -CONH
2 and phenyl. Preferred substituents are hydroxy, carboxy, cyano, -CONH
2 and phenyl, especially hydroxy and carboxy. Furthermore, highly preferred substituents
are hydroxy and C
1-C
4alkoxy, especially hydroxy. The alkyl groups can also be uninterrupted or interrupted
by -O- (in case of alkyl groups containing two or more carbon atoms).
[0007] Within the scope of the above definitions, C
1-C
8alkoxy may be methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec.-butoxy,
tert.-butoxy, or linear or branched higher alkoxy groups. Preferred are C
1-C
4alkoxy groups, especially methoxy or ethoxy. Highly preferred is methoxy.
[0008] Halogen may be fluorine, chlorine, bromine or iodine, preferably chlorine.
[0009] The cation M is preferably an alkali metal atom, an alkaline earth metal atom, ammonium
or a cation formed from an amine. Preferred are Na, K, Ca, Mg, ammonium, mono-, di-,
tri- or tetra-C
1-C
4alkylammonium, mono-, di- or tri-C
2-C
4-hydroxyalkylammonium or ammonium that is di- or tri-substituted with a mixture of
C
1-C
4-alkyl and C
2-C
4-hydroxyalkyl groups. Highly preferred is sodium.
[0010] M is preferably hydrogen, an alkaline- or alkaline earth-metal, or ammonium, especially
sodium.
R
6 and R
7 are preferably hydrogen. Each of the sulfo groups indicated in formula (5) are preferably
bonded in ortho position. Interesting compounds of formula (5) are those wherein R
6 and R
7 are hydrogen and each of the sulfo groups indicated in formula (5) are bonded in
ortho position.
[0011] In the mixtures of compounds of formulae (1), (2), (3) or (4), and (5) the molar
ratio of compound (1), (2), (3) or (4) to compound (5) is usually in the range of
from 0.1:99.9 to 99.9:0.1, preferably from 1:99 to 99:1 and more preferably from 5:95
to 95:5. Highly preferred is a molar ratio of from 10:90 to 90:10, especially 20:80
to 80:20. Most important is a molar ratio of from 30:70 to 70:30, especially 40:60
to 60:40.
[0012] The compounds of formulae (1), (2), (3), (4), and (5) are known or can be prepared
in analogy to known processes.
[0013] Compounds of formulae (1), (2), (3) and (4) can for example be prepared by first
reacting cyanuric chloride with methanol, reacting the product obtained with 4,4'-diaminostilbene-2,2'-disulfonic
acid and then reacting the intermediate with the corresponding amines.
[0014] Furthermore, the present invention is directed to mixtures of compounds of formulae
(1), (2), (3) or (4), and (5). As to compounds of formulae (1), (2), (3), (4) and
(6) the preferences given above apply. Compounds of formula (5) wherein R
6 and R
7 are hydrogen and each of the sulfo groups indicated in formula (5) are bounded in
ortho position are preferred. In such mixtures, the molar ratio of compound (1), (2),
(3) or (4) to compound (5) is usually in the range of from 0.1:99.9 to 99.9:0.1, preferably
from 1:99 to 99:1 and more preferably from 5:95 to 95:5. Highly preferred is a molar
ratio of from 10:90 to 90:10, especially 20:80 to 80:20. Most important is a molar
ratio of from 30:70 to 70:30, especially 40:60 to 60:40.
[0015] The detergent compositions used preferably comprise
- i) 1-70% of an anionic surfactant and/or a nonionic surfactant:
- ii) 0-75% of a builder;
- iii) 0-30% of a peroxide;
- iv) 0-10% of a peroxide activator; and
- v) 0.001-5% of a mixture of compounds of formulae (1), (2), (3) or (4), and (5),
each by weight, based on the total weight of the detergent.
[0016] More preferably the detergent compositions used comprise
- i) 5-70% of an anionic surfactant and/or a nonionic surfactant;
- ii) 5-70% of a builder;
- iii) 0.5-30% of a peroxide;
- iv) 0.5-10% of a peroxide activator and/or 0.1-2% of a bleaching catalyst; and
- v) 0.01-5% of a mixture of compounds of formulae (1), (2), (3) or (4), and (5),
each by weight, based on the total weight of the detergent.
[0017] In general, an amount of a mixture of compounds of formulae (1), (2), (3) or (4),
and (5) of 0.001-6%, especially an amount of 0.01-5% is used. Highly preferred is
an amount of 0.05-5%, especially 0.05 to 2%. In general, amounts given in percent
are to be understood as being percent by weight, based on the total weight, unless
otherwise stated.
[0018] The detergent may be formulated as a solid, as an aqueous liquid comprising, e.g.,
5-50, preferably 10-35% water or as a non-aqueous liquid detergent, containing not
more than 5, preferably 0-1 wt.% of water, and based on a suspension of a builder
in a non-ionic surfactant, as described, e.g., in
GB-A-2158454.
[0019] The anionic surfactant component may be, e.g., an alkylbenzenesulfonate, an alkylsulfate,
an alkylethersulfate, an olefinsulfonate, an alkanesulfonate, a fatty acid salt, an
alkyl or alkenyl ether carboxylate or an α-sulfofatty acid salt or an ester thereof.
Preferred are alkylbenzenesulfonates having 10 to 20 carbon atoms In the alkyl group,
alkylsulfates having 8 to 18 carbon atoms, alkylethersulfates having 8 to 18 carbon
atoms, and fatty acid salts being derived from palm oil or tallow and having 8 to
18 carbon atoms. The average molar number of ethylene oxide added in the alkylethersulfate
is preferably 1 to 20, preferably 1 to 10. The salts are preferably derived from an
alkaline metal like sodium and potassium, especially sodium. Highly preferred carboxylates
are alkali metal sarcosinates of formula R-CO(R
1)CH
2COOM
1 in which R is alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical,
R
1 is C
1-C
4 alkyl and M
1 is alkali metal, especially sodium.
[0020] The nonionic surfactant component may be, e.g., primary and secondary alcohol ethoxylates.
especially the C
6-C
20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene
oxide per mole of alcohol, and more especially the C
10-C
15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to
10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants
include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
[0021] The total amount of anionic surfactant and nonionic surfactant is preferably 5-50%
by weight, preferably 5-40% by weight and more preferably 5-30% by weight. As to these
surfactants it is preferred that the lower limit is 10% by weight.
[0022] The builder component may be an alkali metal phosphate, especially a tripolyphosphate;
a carbonate or bicarbonate, especially the sodium salts thereof; a silicate or disilicate;
an aluminosilicate; a polycarboxylate; a polycarboxylic acid; an organic phosphonate;
or an amlnoalkylene poly (alkylene phosphonate); or a mixture of these.
Preferred silicates are crystalline layered sodium silicates of the formula NaHSi
mO
2m+1pH
2O or Na
2Si
mO
2m+1·pH
2O in which m is a number from 1.9 to 4 and p Is 0 to 20.
Preferred aluminosilicates are the commercially-available synthetic materials designated
as Zeolites A, B, X, and HS, or mixtures of these. Zeolite A is preferred.
Preferred polycarboxylates include hydroxypolycarboxylates, in particular citrates,
polyacrylates and their copolymers with maleic anhydride.
Preferred polycarboxylic acids include nitrilotriacetic acid and ethylene diamine
tetra-acetic acid.
Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) are alkali
metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene
diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.
[0023] The amount of builders Is preferably 5-70% by weight, preferably 5-60% by weight
and more preferably 10-60% by weight. As to the builders it is preferred that the
lower limit is 15% by weight, especially 20% by weight.
[0024] Suitable peroxide components include, for example, the organic and inorganic peroxides
(like sodium peroxides) known in the literature and available commercially that bleach
textile materials at conventional washing temperatures, for example at from 5 to 95°C.
In particular, the organic peroxides are, for example, monoperoxides or polyperoxides
having alkyl chains of at least 3, preferably 6 to 20, carbon atoms; in particular
diperoxydicarboxylates having 6 to 12 C atoms, such as diperoxyperazelates, diperoxypersebacates,
diperoxyphthalates and/or diperoxydodecanedioates, especially their corresponding
free acids, are of interest. It is preferred, however, to employ very active inorganic
peroxides, such as persulphate, perborate and/or percarbonate. It is, of course, also
possible to employ mixtures of organic and/or inorganic peroxides.
[0025] The amount of peroxide is preferably 0.5-30% by weight, preferably 1-20% by weight
and more preferably 1-15% by weight. In case a peroxide is used, the lower limit is
preferably 2% by weight, especially 5% by weight.
[0026] The peroxides, especially the inorganic peroxides, are preferably activated by the
inclusion of a bleach activator. Preferred are such compounds that, under perhydrolysis
conditions, yield unsubstituted or substituted perbenzo- and/or peroxo-carboxylic
acids having from 1 to 10 carbon atoms, especially from 2 to 4 carbon atoms. Suitable
compounds include those that carry O- and/or N-acyl groups having the said number
of carbon atoms and/or unsubstituted or substituted benzoyl groups. Preference is
given to polyacylated alkylenediamines, especially tatraacetylethylenediamine (TAED),
acylated glycolurils, especially tetraacetylglycoluril (TAGU), N,N-diacetyl-N,N-dimethyl-urea
(DDU), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
(DADHT), compounds of formula
wherein R is a sulfonate group, a carboxylic acid group or a carboxylate group, and
wherein R' is linear or branched (C
7-C
15)alkyl; also activators that are known under the names SNOBS, SLOBS, NOBS and DOBA,
acylated polyhydrio alcohols, especially triacetin, ethylene glycol dlacetate and
2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol and acylated sugar
derivatives, especially pentaacetylglucose (PAG), sucrose polyacetate (SUPA), pentaacetylfructose,
tetraacetylxylose and octaacetyllactose, and acetylated, optionally N-alkylated, glucamine
and gluconolactone. The combinations of conventional bleach activators disclosed in
German Patent Application
DE-A-44 43 177 may also be used. Nitrile compounds that form peroxyimidic acids with peroxides are
also suitable as bleach activators, Preferred are tetraacetyl ethylenediamine and
nonoyloxybenzene sulfonate.
[0027] The amount of bleach activator is preferably 0-10% by weight, preferably 0-8% by
weight. In case a bleach activator is used, the lower limit Is preferably 0.5% by
weight, especially 1% by weight.
[0028] Bleaching catalysts, which may be added, include, e.g., enzymatic peroxide precursors
and/or metal complexes. Preferred metal complexes are manganese, cobalt or iron complexes
such as manganese or iron phthalocyanines or the complexes described in
EP-A-0509787. In case a bleaching catalyst is used the amount is preferably 0.005 to 2% by weight,
more preferably 0.01 to 2% by weight, especially 0.05 to 2% by weight. Highly preferred
is an amount of 0.1-2% by weight.
[0029] As examples for bleaching catalysts the following are mentioned:
- WO-A-95/30661 (see i.e. formula (I) and the following definition on page 1, lines 7 to 30: especially
formula (I) and the following definitions given on page 2, lines 29 to page 11, line
11). Preferred ligands are those given on page 13, line 12 to page 28, line 11.
- WO-A-01/09276 (see i.e. formulae (1), (2) and (3) and the following definitions given on pages
2 and 3).
- WO-A-01/05925 (see i.e, formula (1) and the following definition on page 1, last paragraph to page
2, first paragraph. The preferences given for the metal complexes apply, see especially
those of formula (2) on page 3 and those of formula (3) on page 4).
- WO-A-02/088289 (see i.e. formula (1) and the following definition on page 2. The preferences given
for the metal complexes apply, see especially the ligands of formula (3) and also
the preferences given on page 3, fourth paragraph to page 4. paragraph 7).
[0030] Furthermore, the detergent can optionally contain enzymes. Enzymes can be added to
detergents for stain removal. The enzymes usually improve the performance on stains
that are either protein- or starch-based, such as those caused by blood, milk, grass
or fruit juices. Preferred enzymes are cellulases, proteases, amylases and lipases.
Preferred enzymes are cellulases and proteases, especially proteases. Cellulases are
enzymes which act on cellulose and its derivatives and hydrolyze them into glucose,
cellobiose, cellooligosaccharide. Cellulases remove dirt and have the effect of mitigating
the roughness to the touch. Examples of enzymes to be used include, but are by no
means limited to, the following:
proteases as given in US-B-6,242,405, column 14, lines 21 to 32;
lipases as given in US-B-6,242,405, column 14, lines 33 to 46;
amylases as given in US-B-6,242,405, column 14, lines 47 to 56; and
cellulases as given in US-B-6,242,405, column 14, lines 57 to 64.
[0031] The enzymes can optionally be present in the detergent. When used, the enzymes are
usually present in an amount of 0.01-5% by weight, preferably 0.05-5% and more preferably
0.1-4% by weight, based on the total weight of the detergent.
[0032] Further preferred additives for the detergents according to the invention are polymers
that, during the washing of textiles, inhibit staining caused by dyes in the washing
liquor that have been released from the textiles under the washing conditions (dye
fixing agents, dye transfer inhibitors). Such polymers are preferably polyvinylpyrrolidones,
polyvinylimidazoles or polyvinylpyridine N-oxides which may have been modified by
the incorporation of anionic or cationic substituents, especially those having a molecular
weight in the range from 5000 to 60 000, more especially from 10 000 to 50 000. Such
polymers are usually used in an amount of from 0.01 to 5 %, preferably 0.05 to 5 %
by weight, especially 0.1 to 2 % by weight, based on the total weight of the detergent.
Preferred polymers are those given in
WO-A-02/02865 (see especially page 1, last paragraph and page 2, first paragraph).
[0033] The detergents used will usually contain one or more auxiliaries such as soil suspending
agents, for example sodium carboxymethylcellulose; salts for adjusting the pH, for
example alkali or alkaline earth metal silicates; foam regulators, for example soap;
salts for adjusting the spray drying and granulating properties, for example sodium
sulphate; perfumes; and also, if appropriate, antistatic and softening agents; such
as smectite clays; photobleaching agents; pigments; and/or shading agents. These constituents
should, of course, be stable to any bleaching system employed. Such auxiliaries can
be present in an amount of, for example, 0.1 to 20% by weight, preferably 0.5 to 10
% by weight, especially 0.5 to 5 % by weight, based on the total weight of the detergent.
[0034] The detergent compositions can take a variety of physical forms including powder
granular, tablet and liquid forms. Examples thereof are conventional powder heavy-duty
detergents, compact and supercompact heavy-duty detergents and tablets, like heavy-duty
detergent tablets, One important physical form is the so-called concentrated granular
form adapted to be added to a washing machine.
[0035] Of importance are also the so-called compact (or supercompact) detergents. In the
field of detergent manufacture, a trend has developed recently towards the production
of compact detergents, which contain increased amounts of active substance. In order
to minimize energy expenditure during the washing process, the compact detergents
are required to operate efficiently at temperatures as low as 40°C, or even at room
temperatures, e.g. at 25°C, Such detergents usually contain only low amounts of fillers
or processing aids, like sodium sulfate or sodium chloride. The amount of such fillers
is usually 0-10% by weight, preferably 0-5 % by weight, especially 0-1 % by weight,
based on the total weight of the detergent. Such detergents usually have a bulk density
of 650-1000 g/l, preferably 700-1000 g/l and especially 750-1000 g/l.
[0036] The detergents can also be present in the form of tablets. Relevant characteristics
of tablets are ease of dispensing and convenience in handling. Tablets are the most
compact delivery of solid detergents and have a bulk density of, for example, 0.9
to 1.3 kg/litre. To enable fast disintegration laundry detergent tablets generally
contain special disintegrants:
- Effervescents such as carbonate/hydrogencarbonate/citric acid;
- swelling agents like cellulose, carboxymethyl cellulose, cross-linked poly(N-vinylpyrrollidone);
- quickly dissolving materials such as Na (K) acetate, or Na (K) citrate;
- rapidly dissolving water-soluble rigid coating such as dicarboxy acids.
The tablets can also contain combinations of any of the above disintegrants.
[0037] The detergent may also be formulated as an aqueous liquid comprising 5-50, preferably
10-35% water or as a non-aqueous liquid detergent, containing not more than 5, preferably
0-1 wt.% of water. Non-aqueous liquid detergent compositions can contain other solvents
as carriers, Low molecular weight primary or secondary alcohols exemplified by methanol,
ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred
for solubilizing surfactant, but polyols such as those containing from 2 to about
6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene
glycol, glycerine, and 1,2-propanediol) can also be used. The compositions may contain
from 5% to 90%, typically 10% to 50% of such carriers. The detergents can also be
present as the so-called "unit liquid dose" form.
[0038] This detergent treatment of textiles can be conducted as a domestic treatment in
normal washing machines.
[0039] The textile fibres treated may be natural or synthetic fibres or mixtures thereof.
Examples of natural fibres include vegetable fibres such as cotton, viscose, flax,
rayon or linen, preferably cotton and animal fibres such as wool, mohair, cashmere,
angora and silk. preferably wool. Synthetic fibres include polyester, polyamide and
polycarylonitrile fibres. Preferred textile fibres are cotton, polyamide and wool
fibres, especially cotton fibres. Preferably, textile fibres treated according to
the method of the present invention have a density of less than 200 g/m
2.
[0040] According to this process usually an amount of 0.01 to 3.0% by weight, especially
0.05 to 3.0% by weight, based on the weight of the textile fibre material, of a mixture
of compounds of formulae (1), (2), (3) or (4), and (5) is used.
[0041] The process is usually conducted in the temperature range of from 5 to 100°C, especially
5 to 60°C. Preferred is a temperature range of 5 to 40°C, especially 5 to 35°C and
more preferably 5 to 30°C,
[0042] The detergent compositions herein will preferably be formulated such that, during
use In aqueous cleaning operations, the wash water will have a pH of between about
6.5 and about 11, preferably between about 7.5 and 11. Laundry products are typically
at pH 9-11. Techniques for controlling pH at recommended usage levels include the
use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
[0043] Machine laundry methods herein typically comprise treating soiled laundry with an
aqueous wash solution in a washing machine having dissolved or dispensed therein an
effective amount of a machine laundry detergent composition in accordance with the
Invention. By an effective amount of the detergent composition it is meant, e.g.,
from 20 g to 300 g of product dissolved or dispersed in a wash solution of volume
from 5 to 85 litres, as are typical product dosages and wash solution volumes commonly
employed in conventional machine laundry methods. Examples are
- top-loading, vertical axis U.S.-type automatic washing machines using about 45 to
63 liters of water in the wash bath, a wash cycle of about 10 to about 14 minutes
and a wash water temperature of about 10 to about 50°C;
- front-loading, horizontal-axis European-type automatic washing machine using about
8 to 15 liters of water in the wash bath, a wash cycle of about 10 to about 60 minutes
and a wash water temperature of about 30 to about 95°C;
- top-loading, vertical-axis Japanese-type automatic washing machine using about 26
to 52 liters of water in the wash bath, a wash cycle of about 8 to about 15 minutes
and a wash water temperature of about 5 to about 25°C.
[0044] The liquor ratio is preferably 1:4 to 1:40, especially 1:4 to 1:15. Highly preferred
is a liquor ratio of 1:4 to 1:10, especially 1:5 to 1:9.
[0045] A further object of the present invention is to provide a process for the domestic
washing treatment of a textile fibre material wherein the textile fibre material Is
contacted with an aqueous solution of a detergent comprising a compound of formulae
(1), (2), (3) or (4) as defined above,
and wherein the detergent contains at least one enzyme selected from the group consisting
of cellulase, protease, amylase and lipase,
and wherein the temperature of the solution is between 5°C and 40°C, preferably between
5°C and 30°C, throughout the process.
[0046] As to the compounds of formulae (1), (2), (3) or (4) as well as for the detergents
and the washing process the definitions and preferences given above apply.
[0047] The above washing treatment of textile fibers can also be conducted with the mixture
of compounds of formulae (1), (2), (3) or (4) and (5).
[0048] The compounds and mixtures used according to the present invention are particularly
advantageous in that they exhibit not only extremely high whitening ability, but,
in addiction, in many cases highly desirable water solubilities and also possess excellent
white aspects in the solid state. A further advantage of the present invention Is
that the detergent composition delivers improved whiteness performance and fabric
feel. Furthermore the compounds and especially the mixtures show very good results
with respect to exhaustion properties.
[0049] The compounds have the advantage that they are also effective in the presence of
active chlorine donors, such as, for example, hypochlorite and can be used without
substantial loss of the effects in washing baths with non-ionic washing agents, for
example alkylphenol polyglycol ethers. Also in the presence of perborate or peracids
and activators, for example tetraacetylglycoluril or ethylenediamine-tetraacetic acid
are the compounds and mixtures of compounds stable both In pulverulent washing agent
and in washing baths. In addition, they impart a brilliant appearance in daylight.
[0050] Compounds of the formulae (1), (2), (3) or (4) and mixtures of compounds of formulae
(1), (2), (3) or (4) and (6) have also been found to be useful for the fluorescent
whitening of textile materials, in which connection polyamides, wool and cotton should
be singled out particularly. The textile fibres treated according to this embodiment
of the present invention may be natural or synthetic fibres or mixtures thereof. Examples
of natural fibres include vegetable fibres such as cotton, viscose, flax, rayon or
linen, preferably cotton and animal fibres such as wool, mohair, cashmere, angora
and silk, preferably wool. Synthetic fibres include polyester, polyamide and polyacrylonitrile
fibres. Preferred textile fibres are cotton, polyamide and wool fibres. Preferably,
textile fibres treated according to the present invention have a density of less than
1000 g/m
2, especially less than 500 g/m
2 and most preferred less than 250 g/m
2.
[0051] The following Examples serve to illustrate the invention: parts and percentages are
by weight, unless otherwise stated.
Preparation Example 1:
[0052]
In a 1 litre flask 0.05 mole of the compound of formula
[0053]
are mixed with 600ml of water and heated to a temperature of 60°C. Then 9.5g of morpholine
are added and the reaction mixture is heated to a temperature of 98°C; during heating
the pH is maintained at a value between 8.5 and 9 by addition of a 4-molar aqueous
solution of sodium hydroxide. The reaction mixture is cooled to 40°C and the precipitate
is filtered off, washed with 100ml of a 10% aqueous sodium chloride solution and dried
in vacuum. In this way, there are obtained 30g of a yellow product.
Preparation Examples 2 to 4:
[0054] The following compounds of formula
can be prepared in analogy to the process given in Preparation Example 1, by replacing
9.5 g of morpholine with an equimolar amount of the corresponding amine. X is as defined
in the following Table 2. Compounds having high solubility are treated with a 6-molar
aqueous solution of hydrochloric acid in order to adjusted the pH to a value of 4.5
before cooling to 50°C.
Table 2
Example |
X |
2 |
-N(CH2CH3)CH2CH2OH |
3 |
|
4 |
-N(CH2CH2OH)2 |
Application Example 1:
[0055] General procedure:
A wash liquor is prepared by dissolving 0.8 g of a washing powder in 200 ml of tap
water. 10 g of bleached cotton fabric is added to the bath and washed at 40°C over
15 minutes and then rinsed, spin-dried and ironed at 160°C.
[0056] The following washing powders A and B are used (amounts given in the following Tables
3a and 3b are in g):
Table 3a (Ingredients of washing powders A and B)
|
A |
B |
Sodium laurylbenzene-sulfonate (LAS) |
10g |
10g |
Sodium lauryl ether sulfate (AES) |
3g |
3g |
Dobanol 23-6.5 (nonionic alcoholethoxylate) |
4g |
4g |
Sodium tripolyphosphate |
30g |
----- |
Zeolite A |
----- |
20g |
Sodium carbonate |
15g |
15g |
Sodium silicate |
5g |
5g |
Sodium sulfate |
11g |
17g |
Cellulase |
1.5g |
----- |
Protease |
----- |
1.5g |
Polycarboxylate (co-builder) |
----- |
4g |
Carboxymethylcellulose |
2g |
2g |
Perfume |
0.1g |
0.1g |
Water |
5g |
5g |
Fluorescent whitener or mixture of fluorescent whitener used |
Xg |
Xg |
Table 3b (Washing powders used)
|
Amount of fluorescent whitener or mixture of fluorescent whitener used |
Washing powder |
Compound of Prep. Ex. 1 |
0.3g |
B |
Mixture of compound of Prep. Ex. 2 and compound of formula (8) [1:1 weight ratio] |
0.2g |
B |
Mixture of compound of Prep. Ex. 3 and compound of formula (8) [1:2 weight ratio] |
0.5g |
B |
Constitution of compound of formula (8):
[0057]
[0058] The cotton fabrics washed with the detergents given in Table 3b according to the
general procedure show good whiteness properties.
Application Example 2:
[0059] General procedure:
A wash liquor is prepared by dissolving 0.8 g of a washing powder in 200 ml of tap
water. 10 g of bleached cotton fabric is added to the bath and washed at 30°C over
15 minutes and then rinsed, spin-dried and ironed at 160°C.
The following washing powders are used (amounts given in the following Tables 4a and
4b are percent by weight, based on the total weight of the detergent):
Table 4a (Ingredients of washing powders C and D)
|
C |
D |
Sodium laurylbenzene-sulfonate (LAS) |
8% |
8% |
Sodium lauryl ether sulfate (AES) |
3% |
3% |
Dobanol 23-6.5 (nonionic alcoholethoxylate) |
5% |
5% |
Zeolite A |
20% |
20% |
Polycarboxylate (co-builder) |
5% |
5% |
Soda ash |
18% |
18% |
Sodium silicate |
4% |
4% |
Sodium sulfate |
5% |
5% |
Hydroxyethanediphosphonic acid (complexing agent) |
0.5% |
0.5% |
Cellulase |
1.5% |
----- |
Protease |
----- |
1.5% |
Carboxymethylcellulose |
1% |
1% |
Sodium perborate monohydrate |
15% |
15% |
TAED |
5% |
5% |
Soap |
2% |
2% |
Fluorescent whitener or mixture of fluorescent whitener used |
X% |
X% |
In each of the above detergents a sufficient amount of water is used to give 100%. |
Table 4b (Washing powders used)
|
Amount of fluorescent whitener or mixture of fluorescent whitener used |
Washing powder |
Compound of Prep. Ex. 2 |
0.4% |
C |
Mixture of compound of Prep. Ex. 1 and compound of formula (8) [9:1 weight ratio] |
0.3% |
D |
Mixture of compound of Prep. Ex. 4 and compound of formula (8) [1:5 weight ratio] |
0.2% |
D |
[0060] As to the constitution of compounds of formulae (8) see Application Example 1.
[0061] The cotton fabrices washed with the detergents given in Table 4b according to the
general procedure show good whiteness properties.
1. A detergent composition comprising
at least one compound of formula
or
wherein M is hydrogen or cation
together with at least one compound of formula
wherein
R
6 and R
7, independently of each other, are hydrogen, C
1-C
8alkyl, C
1-C
8alkoxy or halogen, and M is is as defined above under formulae (1) to (4).
2. A composition according to claim 1, wherein
R6 and R7 are hydrogen and each of the sulfo groups indicated in formula (5) are bonded in
ortho position.
3. A composition according to claim 1 or 2, wherein
M is hydrogen, an alkaline- or alkaline earth-metal, or ammonium, preferably sodium.
4. A composition according to any of claims 1 to 3, comprising
i) 1-70% of an anionic surfactant and/or a nonionic surfactant;
ii) 0-75% of a builder;
iii) 0-30% of a peroxide;
iv) 0-10% of a peroxide activator; and
v) 0.001-5% of a mixture of compounds of formulae (1), (2), (3) or (4), and (5).
5. A composition according to claim 4, comprising
i) 5-70% of an anionic surfactant and/or a nonionic surfactant;
ii) 5-70% of a builder;
iii) 0.5-30% of a peroxide;
iv) 0.5-10% of a peroxide activator and/or 0.1-2% of a bleaching catalyst; and
v) 0.01-5% of a mixture of compounds of formulae (1), (2), (3) or (4), and (5).
6. A composition according to any of claims 1 to 5 in which the detergent composition
comprises at least one enzyme selected from the group consisting of cellulase, protease,
amylase and lipase, preferably protease.
7. A mixture of compounds comprising at least one compound of formula
or
wherein M is hydrogen or cation,
together with at least one compound of formula
wherein
R
6 and R
7, independently of each other, are hydrogen, C
1-C
8alkyl, C
1-C
8alkoxy or halogen, and M is as defined above under formulae (1) to (4).
8. A mixture of compounds according to claim 7, wherein
R6 and R7 are hydrogen and each of the sulfo groups indicated in formula (5) are bonded in
ortho position.
9. A mixture of compounds according to claim 7 or 8, wherein
M is hydrogen, an alkaline- or alkaline earth-metal, or ammonium, preferably sodium.
10. A process for the fluorescent whitening of textile materials comprising contacting
the textile materials with a mixture of compounds of formulae (1), (2), (3) or (4),
and (5) as defined in claim 1.
11. A process according to claim 10 in which the textile materials are polyamides, wool
or cotton.
1. Detergenszusammensetzung umfassend
wenigstens eine Verbindung der Formel
oder
wobei M Wasserstoff oder Kation ist,
zusammen mit wenigstens einer Verbindung der Formel
wobei
R
6 und R
7 unabhängig voneinander Wasserstoff, C
1-C
8Alkyl, C
1-C
8Alkoxy oder Halogen sind und M wie vorstehend für die Formeln (1) bis (4) definiert
ist.
2. Zusammensetzung gemäß Anspruch 1, wobei
R6 und R7 Wasserstoff sind und jede der in Formel (5) gezeigten Sulfogruppen in ortho-Position
gebunden ist.
3. Zusammensetzung gemäß Anspruch 1 oder 2, wobei
M Wasserstoff, ein Alkali- oder Erdalkalimetall oder Ammonium ist, vorzugsweise Natrium.
4. Zusammensetzung gemäß einem der Ansprüche 1 bis 3, umfassend
i) 1-70 % an einem anionischen grenzflächenaktiven Mittel und/oder einem nichtionischen
grenzflächenaktiven Mittel;
ii) 0-75 % an einem Builder;
iii) 0-30 % an einem Peroxid;
iv) 0-10 % an einem Peroxid-Aktivator; und
v) 0,001-5 % an einem Gemisch von Verbindungen der Formeln (1), (2), (3) oder (4)
und (5).
5. Zusammensetzung gemäß Anspruch 4, umfassend
i) 5-70 % an einem anionischen grenzflächenaktiven Mittel und/oder einem nichtionischen
grenzflächenaktiven Mittel;
ii) 5-70 % an einem Builder;
iii) 0,5-30 % an einem Peroxid;
iv) 0,5-10 % an einem Peroxid-Aktivator und/oder 0,1-2 % an einem Bleichkatalysator;
und
v) 0,01-5 % an einem Gemisch von Verbindungen der Formeln (1), (2), (3) oder (4) und
(5).
6. Zusammensetzung gemäß einem der Ansprüche 1 bis 5, wobei die Detergenszusammensetzung
wenigstens ein Enzym ausgewählt aus der Gruppe bestehend aus Cellulase, Protease,
Amylase und Lipase, vorzugsweise Protease, umfasst.
7. Gemisch von Verbindungen, umfassend wenigstens eine Verbindung der Formel
oder
wobei M Wasserstoff oder Kation ist,
zusammen mit wenigstens einer Verbindung der Formel
wobei
R
6 und R
7 unabhängig voneinander Wasserstoff, C
1-C
8Alkyl, C
1-C
8Alkoxy oder Halogen sind und M wie vorstehend für die Formeln (1) bis (4) definiert
ist.
8. Gemisch von Verbindungen gemäß Anspruch 7, wobei
R6 und R7 Wasserstoff sind und jede der in Formel (5) gezeigten Sulfogruppen in ortho-Position
gebunden ist.
9. Gemisch von Verbindungen gemäß Anspruch 7 oder 8, wobei
M Wasserstoff, ein Alkali- oder Erdalkalimetall oder Ammonium ist, vorzugsweise Natrium.
10. Verfahren zum Fluoreszenz-Weißmachen von Textilmaterialien, umfassend Inkontaktbringen
der Textilmaterialien mit einem Gemisch von Verbindungen der Formeln (1), (2), (3)
oder (4) und (5) gemäß Anspruch 1.
11. Verfahren gemäß Anspruch 10, wobei die Textilmaterialien Polyamide, Wolle oder Baumwolle
sind.
1. Composition de détergent comprenant au moins un composé de formule
ou
où M est hydrogène ou un cation
conjointement avec au moins un composé de formule
où
R
6 et R
7, indépendamment l'un de l'autre, sont hydrogène, alkyle en C
1-C
8, alcoxy en C
1-C
8 ou halogène, et M est tel que défini ci-dessus dans les formules (1) à (4).
2. Composition selon la revendication 1, dans laquelle
R6 et R7 sont hydrogène et chacun des groupes sulfo indiqués dans la formule (5) sont liés
en position ortho.
3. Composition selon la revendication 1 ou 2, dans laquelle
M est hydrogène, un métal alcalin ou alcalino-terreux, ou ammonium, de préférence
le sodium.
4. Composition selon l'une quelconque des revendications 1 à 3, comprenant
i) 1 à 70 % d'un tensioactif anionique et/ou un tensioactif non ionique ;
ii) 0 à 75 % d'un adjuvant ;
iii) 0 à 30 % d'un peroxyde ;
iv) 0 à 10 % d'un activateur de peroxyde ; et
v) 0,001 à 5 % d'un mélange de composés de formules (1) , (2), (3) ou (4), et (5)
.
5. Composition selon la revendication 4, comprenant
i) 5 à 70 % d'un tensioactif anionique et/ou un tensioactif non ionique ;
ii) 5 à 70 % d'un adjuvant ;
iii) 0,5 à 30 % d'un peroxyde ;
iv) 0,5 à 10 % d'un activateur de peroxyde et/ou 0,1 à 2 % d'un catalyseur de blanchiment
; et
v) 0,01 à 5 % d'un mélange de composés de formules (1), (2), (3) ou (4), et (5).
6. Composition selon l'une quelconque des revendications 1 to 5 caractérisée en ce que la composition de détergent comprend au moins une enzyme choisie dans le groupe constitué
d'une cellulase, une protéase, une amylase et une lipase, de préférence une protéase.
7. Mélange de composés comprenant au moins un composé de formule
ou
où M est hydrogène ou un cation,
conjointement avec au moins un composé de formule
où
R
6 et R
7, indépendamment l'un de l'autre, sont hydrogène, alkyle en C
1-C
8, alcoxy en C
1-C
8 ou halogène, et M est tel que défini ci-dessus dans les formules (1) à (4).
8. Mélange de composés selon la revendication 7, dans lequel
R6 et R7 sont hydrogène et chacun des groupes sulfo indiqués dans la formule (5) sont liés
en position ortho.
9. Mélange de composés selon la revendication 7 ou 8, dans lequel
M est hydrogène, un métal alcalin ou alcalino-terreux, ou ammonium, de préférence
le sodium.
10. Procédé pour le blanchiment fluorescent de matériaux textiles comprenant la mise en
contact des matériaux textiles avec un mélange de composés de formules (1), (2), (3)
ou (4), et (5) tels que défini dans la revendication 1.
11. Procédé selon la revendication 10 dans lequel les matériaux textiles sont des polyamides,
de la laine ou du coton.