U.S. patent application number 09/091238 was filed with the patent office on 2002-01-31 for solid composition consisting of heterocyclic compounds and/ or oxime esters and inert porous carrier materials and the use thereof as stable bleach activator component in detergents, bleaches and cleaners.
Invention is credited to BOECKH, DIETER, KAPPES, ELISABETH, MUELLER, REINHARD, OETTER, GUENTER, SCHOENHERR, MICHAEL, WEHLAGE, THOMAS.
Application Number | 20020013245 09/091238 |
Document ID | / |
Family ID | 7788218 |
Filed Date | 2002-01-31 |
United States Patent
Application |
20020013245 |
Kind Code |
A1 |
OETTER, GUENTER ; et
al. |
January 31, 2002 |
SOLID COMPOSITION CONSISTING OF HETEROCYCLIC COMPOUNDS AND/ OR
OXIME ESTERS AND INERT POROUS CARRIER MATERIALS AND THE USE THEREOF
AS STABLE BLEACH ACTIVATOR COMPONENT IN DETERGENTS, BLEACHES AND
CLEANERS
Abstract
1The invention concerns a solid composition substantially
comprising between 5 and 98 parts by weight of heterocyclic
compounds (I) R.sup.1--X--L.sup.1, wherein L.sup.1 stands for
groups with a cyclic carbamate, a lactoneoxy or a lactam structure,
X means a carbonyl, a double carbonyl or a heterocarbonyl group,
and R.sup.1 designates an organic group or a second L.sup.1 group,
and/or oxime esters (II), wherein L.sup.2 stands for an oxime group
(a) or (b), R.sup.2, R.sup.3 and Z.sup.4 designating organic groups
or bridge members, L.sup.3 stands for the R.sup.1 group, a second
L.sup.2 oxime group or a carbon ester group, carbon amide group,
phenolate group, vinyloxy group, sulphoneamide group, imidazole
group, amidolactam group, cyclic carbamate group, lactoneoxy group
or lactam group, and m means 0 or 1. The composition further
comprises between 2 and 95 parts by weight of inert porous carrier
materials with an internal area of between 10 and 500 m.sup.2/g.
The solid composition described is suitable as a stable
bleach-activator component in washing, bleaching and cleaning
agents.
Inventors: |
OETTER, GUENTER;
(FRANKENTHAL, DE) ; WEHLAGE, THOMAS; (SPEYER,
DE) ; KAPPES, ELISABETH; (LIMBURGERHOF, DE) ;
MUELLER, REINHARD; (FRIEDELSHEIM, DE) ; BOECKH,
DIETER; (LIMBURGERHOF, DE) ; SCHOENHERR, MICHAEL;
(FRANKENTHAL, DE) |
Correspondence
Address: |
OBLON SPIVAK MCCLELLAND MAIER & NEUSTADT
1755 JEFFERSON DAVIS HIGHWAY
FOURTH FLOOR
ARLINGTON
VA
22202
|
Family ID: |
7788218 |
Appl. No.: |
09/091238 |
Filed: |
June 16, 1998 |
PCT Filed: |
March 6, 1997 |
PCT NO: |
PCT/EP97/01125 |
Current U.S.
Class: |
510/302 ;
510/311; 510/312; 510/376 |
Current CPC
Class: |
C11D 3/392 20130101;
C11D 3/3907 20130101; C11D 17/0034 20130101; C11D 3/3935 20130101;
C07D 223/10 20130101 |
Class at
Publication: |
510/302 ;
510/311; 510/312; 510/376 |
International
Class: |
C11D 009/42; C11D
007/18; C11D 003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 14, 1996 |
DE |
19609953.6 |
Claims
We claim
1. A solid composition consisting essentially of 5-98 parts by 5
weight of heterocyclic compounds of the general formula I
R.sup.1--X--L.sup.1 (I) where L.sup.1 is (a) a cyclic carbamate
residue of the formula 71(b) a lactonoxy residue of the formula
72or (c) a lactam residue of the formula 73where Z.sup.1 to Z.sup.3
are 1,2-, 1,3-, 1,4- or 1,5-alkylene groups which have 2 to 20
carbon atoms, and which can additionally be functionalized by one
to three hydroxyl groups, C.sub.1-C.sub.4-alkoxy groups, amino
groups, C.sub.1-C.sub.4-alkyl amino groups,
di-C.sub.1-C.sub.4-alkylamino groups, chlorine atoms, bromine
atoms, nitro groups, cyano groups, carboxyl groups, sulfo groups,
carboxy-C.sub.1-C.sub.4-alkyl groups, carboxamide groups or phenyl,
tolyl or benzyl radicals, it likewise being possible for aromatic
nuclei in turn to be substituted by said radicals, or interrupted
by one or two non-adjacent oxygen atoms, amino groups,
C.sub.1-C.sub.4-alkylamino groups or carbonyl groups, and T is
hydrogen or C.sub.1-C.sub.4-alkyl, X is an oxygen-containing group
of the formula 74where Y is hydrogen, ammonium which can be
unsubstituted or substituted by organic radicals, or
C.sub.1-C.sub.4-alkyl, and A is a chemical bond or a
C.sub.1-C.sub.18-alkylene group, a C.sub.2-C.sub.16-alkenylene
group, a C.sub.5-C.sub.32-cycloalkylene group, a
C.sub.7-C.sub.30-aralkylene group, a C.sub.6-C.sub.18-arylene group
or a C.sub.3-C.sub.18-hetarylene group, it additionally being
possible for aliphatic structural units to be functionalized by one
to five hydroxyl groups, C.sub.1-C.sub.4-alkoxy groups, amino
groups, C.sub.1-C.sub.4-alkylamino groups,
di-C.sub.1-C.sub.4-alkylamino groups, chlorine atoms, bromine
atoms, nitro groups, cyano groups, carboxyl groups, sulfo groups,
carboxy-C.sub.1-C.sub.4-alkyl groups, carboxamide groups or phenyl,
tolyl or benzyl radicals, it likewise being possible for aromatic,
cycloaliphatic and heteroaromatic structural units to be
substituted by said radicals, or interrupted by one to eight
non-adjacent oxygen atoms, amino groups, C.sub.1-C.sub.4-alkylamino
groups or carbonyl groups, and R.sup.1 has the following meaning:
C.sub.1-C.sub.30-alkyl, C.sub.2-C.sub.30-alkenyl,
C.sub.5-ClB-cycloalkyl, C.sub.7-C.sub.18-aralky- l,
C.sub.6-C.sub.18-aryl or C.sub.3-C.sub.18-hetaryl, it being
additionally possible for aliphatic radicals to be functionalized
by one to five hydroxyl groups, C.sub.1-C.sub.4-alkoxy groups,
amino groups, C.sub.1-C.sub.4-alkylamino groups,
di-C.sub.1-C.sub.4-alkylamino groups, chlorine atoms, bromine
atoms, nitro groups, cyano groups, carboxyl groups, sulfo groups,
carboxy-C.sub.1-C.sub.4-alkyl groups, carboxamide groups or phenyl,
tolyl or benzyl radicals, it likewise being possible for aromatic,
cycloaliphatic and heteroaromatic structural units to be
substituted by said radicals, or interrupted by one to eight
non-adjacent oxygen atoms, amino groups, C.sub.1-C.sub.4-alkylamino
groups or carbonyl groups, or a heterocyclic radical L.sup.1,
and/or oxime esters of the general formula II 75where L.sup.2 is an
oxime moiety of the formula 76where R.sup.2 and R.sup.3 are
hydrogen, C.sub.1-C.sub.30-alkyl, C.sub.2-C.sub.30-alkenyl,
C.sub.5-C.sub.18-cycloalkyl, C.sub.7-C.sub.18-aralkyl,
C.sub.6-C.sub.18-aryl or C.sub.3-C.sub.18-hetaryl, it being
additionally possible for aliphatic radicals to be functionalized
by one to five hydroxyl groups, C.sub.1-C.sub.4-alkoxy groups,
amino groups, C.sub.1-C.sub.4-alkylamino groups,
di-C.sub.1-C.sub.4-alkyl-amino groups, chlorine atoms, bromine
atoms, nitro groups, cyano groups, carboxyl groups, sulfo groups,
carboxy-C.sub.1-C.sub.4-alkyl groups, carboxamide groups or phenyl,
tolyl or benzyl radicals, it likewise being possible for aromatic,
cycloaliphatic and heteroaromatic structural units to be
substituted by said radicals, or interrupted by one to eight
non-adjacent oxygen atoms, amino groups, C.sub.1-C.sub.4-alkylamino
groups or carbonyl groups, and Z.sup.4 is 1,3-, 1,4-, 1,5-, 1,6-,
1,7- or 1,8-alkylene groups which have 3 to 30 carbon atoms and
which can additionally be functionalized by one to five hydroxyl
groups, C.sub.1-C.sub.4-alkylamino groups,
di-C.sub.1-C.sub.4-alkylamino groups, chlorine atoms, bromine
atoms, nitro groups, cyano groups, carboxyl groups, sulfo groups,
carboxy-C.sub.1-C.sub.4-alkyl groups, carboxamide groups or phenyl,
tolyl or benzyl radicals, it likewise being possible for aromatic
nuclei in turn to be substituted by said radicals, or interrupted
by one or two non-adjacent oxygen atoms, amino groups,
C.sub.1-C.sub.4-alkylamino groups or carbonyl groups, L.sup.3 is
the radical R.sup.1, a second oxime moiety L.sup.2 or (a) a
carboxylic ester residue of the formula 77(b) a carboxamide residue
of the formula 78(c) a phenolate residue of the formula 79(d) a
vinyloxy-radical of the formula --O--CR.sup.2.dbd.CHR.su- p.3 (e) a
sulfonamide residue of the formula 80(f) an imidazole residue of
the formula 81(g) an amidolactam residue of the formula 82(h) a
cyclic carbamate residue of the formula 83(j) a lactonoxy residue
of the formula 84or (k) a lactam residue of the formula 85where
R.sup.1, R.sup.2, R.sup.3, T, Z.sup.1 to Z.sup.3 and A have the
abovementioned meanings, R.sup.4 is hydrogen, a carboxyl group, a
sulfo group, a phosphono group or the alkali metal or ammonium salt
thereof, and m is the number 0 or 1, and 2-95 parts by weight of
inert porous carrier materials with an internal surface area of
from 10 to 500 m.sup.2/g.
2. A solid composition as claimed in claim 1, wherein the inert
porous carrier materials have an average particle size of from 3 nm
to 2 mm.
3. A solid composition as claimed in claim 1 or 2, wherein silica
gels, silicas, aluminum oxide, kaolins and/or aluminum silicates
are employed as inert porous carrier materials.
4. A solid composition as claimed in any of claims 1 to 3, wherein
the oxygen-containing group X in the heterocyclic compounds I is
86
5. A solid composition as claimed in any of claims 1 to 4, wherein
the radical R.sup.1 in the heterocyclic compounds I is
C.sub.6-C.sub.18-alkyl, C.sub.6-C.sub.18-alkenyl,
C.sub.7-C.sub.12-aralky- l, phenyl or alkyl-substituted phenyl with
a total of up to 14 carbon atoms or a second heterocyclic radical
L.sup.1 which has the same structure as the first heterocyclic
radical L.sup.1.
6. A solid composition as claimed in any of claims 1 to 3, wherein
the radical L.sup.2 in the oxime esters II is an oxime moiety of
the formula 87where R.sup.5 and R.sup.6 are hydrogen,
C.sub.1-C.sub.4-alkyl, phenyl or benzyl, and Z.sup.5 is
1,4-butylene, 1,5-pentylene or 1,6-hexylene.
7. A solid composition as claimed in any of claims 1 to 3 or 6,
wherein the radical L.sup.3 in the oxime esters II is a second
oxime moiety L.sup.2 or a C.sub.1-C.sub.18-alkyl radical, a
C.sub.2-C.sub.18-alkenyl radical, a C.sub.7-C.sub.12-aralkyl
radical or phenyl or alkyl-substituted phenyl with a total of up to
14 carbon atoms.
8. A process for preparing a solid composition as claimed in any of
claims 1 to 7, which comprises mixing together 5-98 parts by weight
of heterocyclic compounds I and/or oxime esters II with 2-95 parts
by weight of inert porous carrier materials in a conventional way
and converting this mixture where appropriate by conventional
methods into a formulated form suitable for the particular
application.
9. A process for preparing a solid composition as claimed in claim
8, wherein a solution or a melt of the heterocyclic compounds I
and/or of the oxime esters II is mixed with the inert porous
carrier materials by stirring in, spraying on or impregnating, the
solvent, where present, is substantially removed by distillation or
drying and, if necessary, the resulting mixture is converted, where
appropriate after mixing with other auxiliaries, by conventional
methods into a formulated form suitable for the particular
application.
10. A detergent, bleach or cleaner comprising 0.1-30% by weight,
based on the total amount of the formulation, of the solid
composition as claimed in any of claims 1 to 7.
11. The use of a solid composition as claimed in any of claims 1 to
7 as stable bleach activator component in detergents, bleaches and
cleaners. Solid composition consisting of heterocyclic compounds
and/or oxime esters and inert porous carrier materials and the use
thereof as stable bleach activator component in detergents,
bleaches and cleaners Abstract A solid composition consisting
essentially of 5-98 parts by weight of heterocyclic compounds I
R.sup.1--X--L.sup.1 (I) where L.sup.1 is groups with a cyclic
carbamate, a lactonoxy or a lactam structure, X is a carbonyl, a
doubled carbonyl or a heterocarbonyl group, and R.sup.1 is an
organic radical or a second moiety L.sup.1, and/or oxime esters II
88where L.sup.2 is an oxime moiety 89where R.sup.2, R.sup.3 and
Z.sup.4 are organic radicals or linkers, L.sup.3 is the radical
R.sup.1, a second oxime moiety L.sup.2 or a carboxylic ester
residue, carboxamide residue, phenolate residue, vinyloxy radical,
sulfonamide residue, imidazole residue, amidolactam residue, cyclic
carbamate residue, lactonoxy residue or lactam residue, and m is 0
or 1, and 2-95 parts by weight of inert porous carrier materials
with an internal surface area of from 10 to 500 m.sup.2/g. The
solid composition described is suitable as stable bleach activator
component in detergents, bleaches and cleaners.
Description
[0001] Solid composition consisting of heterocyclic compounds
and/or oxime esters and inert porous carrier materials and the use
thereof as stable bleach activator component in detergents,
bleaches and cleaners
[0002] The present invention relates to a solid composition
consisting of heterocyclic compounds with cyclic carbamate,
lactonoxy or lactam structure and/or oxime esters and inert porous
carrier materials whose internal surface area has a particular
value. The invention furthermore relates to a process for preparing
this solid composition and to its use in detergents, bleaches and
cleaners, especially as stable bleach activator component.
[0003] A number of cold bleach activators, including some of the
compounds I and II defined hereinafter, are liquid or plastic in
the pure form and, accordingly, can be converted only with great
difficulty into free-flowing granules or powders using conventional
auxiliaries and formulation methods. Free-flowing formulations with
no tendency to agglomerate are, however, required for use in
detergent and some cleaner formulations.
[0004] Conventional drying processes for producing solids from
solutions, such as spray drying, frequently give unsatisfactory
results for cold bleach activators which are solid in pure form,
because these substances are, as a rule, very hygroscopic and
mostly have relatively low melting points. The applicability of
crystallization processes is just as low because these substances
are often prone to form supersaturated solutions, i.e.
crystallization is greatly inhibited and thus uncontrollable.
[0005] It is an object of the present invention to provide a
storage-stable solid, free-flowing form for cold bleach activators
with a heterocyclic structure, in particular using auxiliaries
which are described in large numbers in the prior art for such
purposes. It was moreover intended that these compositions also be
improved in their formulated form with regard to the dissolving
rate and the activity in the wash liquor.
[0006] Thus, for example, DE-A 27 33 849 (1) discloses solid cold
bleach activator formulations for detergents and cleaners, the only
cold bleach activators mentioned are acyl compounds such as
diacetyl-methylamine or diacetylbutylamine. These cold bleach
activators are mixed with adsorbents such as kieselguhr, silicates,
silicas or aluminum oxide. However, (1) contains no information on
the internal surface area and average particle size of these
adsorbents.
[0007] DE-A 34 44 960 (2) relates to a coarse-particle adsorbent
for liquid and pasty detergent and cleaner formulations which may,
inter alia, contain bleach activators. The granules of adsorbent
and detergent or cleaner formulation produced in this way can also
be dusted or surface-coated with fine-particle powders. Examples of
such dusting powders are zeolites or silica aerogel with a particle
size of from 0.001 to 0.1 mm, but no information is given on their
internal surface area.
[0008] EP-A 170 386 (3) discloses bleach systems which contain as
bleaching agent inter alia N-acyl- or
N-benzoyl-6-aminoperoxy-caproic acid. These bleach systems are
employed in detergent formulations which contain sodium aluminum
silicates, eg. zeolite A, as builder which is present separate from
the bleach system.
[0009] EP-A 382 464 (4) discloses a coating or encapsulation
process for solid particles or liquid drops, for example bleaches,
with polyethylene glycols, polyethylene oxides,
polyvinylpyrrolidone, oxidized polyethylene or similar substances.
In this case, fine-particle substances such as Aerosil.RTM. 380 or
Aerosil R 972 are added as formulation aids ("crumbling
agents").
[0010] We have now found a solid composition consisting essentially
of 5-98 parts by weight of heterocyclic compounds of the general
formula I
R.sup.1--X--L.sup.1 (I)
[0011] where
[0012] L.sup.1 is (a) a cyclic carbamate residue of the formula
2
[0013] (b) a lactonoxy residue of the formula 3
[0014] or
[0015] (c) a lactam residue of the formula 4
[0016] where
[0017] Z.sup.1 to Z.sup.3 are 1,2-, 1,3-, 1,4- or 1,5-alkylene
groups which have 2 to 20 carbon atoms, and which can additionally
be functionalized by one to three hydroxyl groups,
C.sub.1-C.sub.4-alkoxy groups, amino groups,
C.sub.1-C.sub.4-alkylamino groups, di-C.sub.1-C.sub.4-alkylamino
groups, chlorine atoms, bromine atoms, nitro groups, cyano groups,
carboxyl groups, sulfo groups, carboxy-C.sub.1-C.sub.4-alkyl
groups, carboxamide groups or phenyl, tolyl or benzyl radicals, it
likewise being possible for aromatic nuclei in turn to be
substituted by said radicals, or interrupted by one or two
non-adjacent oxygen atoms, amino groups, C.sub.1-C.sub.4-alkylamino
groups or carbonyl groups, and
[0018] T is hydrogen or C.sub.1-C.sub.4-alkyl,
[0019] X is an oxygen-containing group of the formula 5
[0020] where
[0021] Y is hydrogen, ammonium which can be unsubstituted or
substituted by organic radicals, or C.sub.1-C.sub.4-alkyl, and
[0022] A is a chemical bond or a C.sub.1-C.sub.18-alkylene group, a
C.sub.2-C.sub.18-alkenylene group, a C.sub.5-C.sub.32-cycloalkylene
group, a C.sub.7-C.sub.30-aralkylene group, a
C.sub.6-C.sub.18-arylene group or a C.sub.3-C.sub.18-hetarylene
group, it additionally being possible for aliphatic structural
units to be functionalized by one to five hydroxyl groups,
C.sub.1-C.sub.4-alkoxy groups, amino groups,
C.sub.1-C.sub.4-alkylamino groups, di-C.sub.1-C.sub.4-alkylamino
groups, chlorine atoms, bromine atoms, nitro groups, cyano groups,
carboxyl groups, sulfo groups, carboxy-C.sub.1-C.sub.4-alkyl
groups, carboxamide groups or phenyl, tolyl or benzyl radicals, it
likewise being possible for aromatic, cycloaliphatic and
hetero-aromatic structural units to be substituted by said
radicals, or interrupted by one to eight non-adjacent oxygen atoms,
amino groups, C.sub.1-C.sub.4-alkylamino groups or carbonyl groups,
and
[0023] R.sup.1 has the following meaning: C.sub.1-C.sub.30-alkyl,
C.sub.2-C.sub.30-alkenyl, C.sub.5-C.sub.18-cycloalkyl,
C.sub.7-C.sub.18-aralkyl, C.sub.6-C.sub.18-aryl or
C.sub.3-C.sub.18-hetaryl, it being additionally possible for
aliphatic radicals to be functionalized by one to five hydroxyl
groups, C.sub.1-C.sub.4-alkoxy groups, amino groups,
C.sub.1-C.sub.4-alkylamino groups, di-C.sub.1-C.sub.4-alkylamino
groups, chlorine atoms, bromine atoms, nitro groups, cyano groups,
carboxyl groups, sulfo groups, carboxy-C.sub.1-C.sub.4-alkyl
groups, carboxamide groups or phenyl, tolyl or benzyl radicals, it
likewise being possible for aromatic, cycloaliphatic and
heteroaromatic structural units to be substituted by said radicals,
or interrupted by one to eight non-adjacent oxygen atoms, amino
groups, C.sub.1-C.sub.4-alkylamino groups or carbonyl groups, or a
heterocyclic radical L.sup.1,
[0024] and/or oxime esters of the general formula II 6
[0025] where
[0026] L.sup.2 is an oxime moiety of the formula 7
[0027] where
[0028] R.sup.2 and R.sup.3 are hydrogen, C.sub.1-C.sub.30-alkyl,
C.sub.2-C.sub.30-alkenyl, C.sub.5-C.sub.18-cycloalkyl,
C.sub.7-C.sub.18-aralkyl, C.sub.6-C.sub.18-aryl or
C.sub.3-C.sub.18-hetaryl, it being additionally possible for
aliphatic radicals to be functionalized by one to five hydroxyl
groups, C.sub.1-C.sub.4-alkoxy groups, amino groups,
C.sub.1-C.sub.4-alkylamino groups, di-C.sub.1-C.sub.4-alkylamino
groups, chlorine atoms, bromine atoms, nitro groups, cyano groups,
carboxyl groups, sulfo groups, carboxy-C.sub.1-C.sub.4-alkyl
groups, carboxamide groups or phenyl, tolyl or benzyl radicals, it
likewise being possible for aromatic, cycloaliphatic and
heteroaromatic structural units to be substituted by said radicals,
or interrupted by one to eight non-adjacent oxygen atoms, amino
groups, C.sub.1-C.sub.4-alkylamino groups or carbonyl groups,
and
[0029] Z.sup.4 is 1,3-, 1,4-, 1,5-, 1,6-, 1,7- or 1,8-alkylene
groups which have 3 to 30 carbon atoms and which can additionally
be functionalized by one to five hydroxyl groups,
C.sub.1-C.sub.4-alkylamino groups, di-C.sub.1-C.sub.4-alkylamino
groups, chlorine atoms, bromine atoms, nitro groups, cyano groups,
carboxyl groups, sulfo groups, carboxy-C.sub.1-C.sub.4-alkyl
groups, carboxamide groups or phenyl, tolyl or benzyl radicals, it
likewise being possible for aromatic nuclei in turn to be
substituted by said radicals, or interrupted by one or two
non-adjacent oxygen atoms, amino groups, C.sub.1-C.sub.4-alkylamino
groups or carbonyl groups,
[0030] L.sup.3 is the radical R.sup.1, a second oxime moiety
L.sup.2 or
[0031] (a) a carboxylic ester residue of the formula 8
[0032] (b) a carboxamide residue of the formula 9
[0033] (c) a phenolate residue of the formula 10
[0034] (d) a vinyloxy radical of the formula
--O--CR.sup.2.dbd.CHR.sup.3
[0035] (e) a sulfonamide residue of the formula 11
[0036] (f) an imidazole residue of the formula 12
[0037] (g) an amidolactam residue of the formula 13
[0038] (h) a cyclic carbamate residue of the formula 14
[0039] (j) a lactonoxy residue of the formula 15
[0040] or
[0041] (k) a lactam residue of the formula 16
[0042] where
[0043] R.sup.1, R.sup.2, R.sup.3, T, Z.sup.1 to Z.sup.3 and A have
the abovementioned meanings,
[0044] R.sup.4 is hydrogen, a carboxyl group, a sulfo group, a
phosphono group or the alkali metal or ammonium salt thereof,
and
[0045] m is the number 0 or 1
[0046] and 2-95 parts by weight of inert porous carrier materials
with an internal surface area of from 10 to 500 m.sup.2/g.
[0047] The variables Z.sup.1 bis Z.sup.3 in the heterocyclic
systems (a) to (c) can be, in particular, C.sub.2-C.sub.10-alkylene
groups of the following structure: 17
[0048] where, in the case of non-symmetrical alkylene groups, in
principle both ways of incorporation into the rings are possible.
The variables Z.sup.1 to Z.sup.3 can be functionalized or
interrupted as stated.
[0049] Typical examples of the linker A are the following:
[0050] as linear or branched C.sub.1-C.sub.18-alkylene group, in
particular C.sub.6-C.sub.12-alkylene group, it is possible for
methylene, 1,2-ethylene, 1,1-ethylene, 1,3-propylene,
1,2-propylene, 1,1-propylene, 2,2-propylene, 1,4-butylene,
1,2-butylene, 2,3-butylene, pentamethylene, 3-methyl-1,5-pentylene,
hexamethylene, heptamethylene, octamethylene, nonamethylene,
decamethylene, undecamethylene, dodecamethylene,
tetradeca-methylene, hexadecamethylene or octadecamethylene to
occur;
[0051] as linear or branched C.sub.2-C.sub.18-alkenylene group, in
particular C.sub.6-C.sub.12-alkenylene group, it is possible for
linkers with one, two or three olefinic double bonds to occur, eg.
1,2-ethenylene, 1,3-propenylene, 1,4-but-2-enylene,
1,6-hex-3-enylene, 1,8-oct-4-enylene or 1,12-dodec-6-enylene;
[0052] suitable as C.sub.5-C.sub.32-cycloalkylene groups, in
particular C.sub.5-C.sub.10-cycloalkylene groups, are 1,2- or
1,3-cyclopentylene, 1,2-, 1,3- or 1,4-cyclohexylene, 1,2-, 1,3- or
1,4-cyclo-heptylene, 1,2-, 1,3-, 1,4- or 1,5-cyclooctylene or
groups of the formula 18
[0053] suitable as C.sub.7-C.sub.30-aralkylene groups, in
particular unsubstituted or alkyl-substituted
C.sub.7-C.sub.22-phenylalkylene and -diphenyl-alkylene groups, are
groups of the formula 19
[0054] particularly suitable as C.sub.6-C.sub.18-arylene groups, in
particular unsubstituted or alkyl-substituted phenylene,
biphenylylene or naphthylene groups, are 1,4-, 1,3- and
1,2-phenylene, but also groups of the formula 20
[0055] suitable as C.sub.3-C.sub.18-hetarylene groups, in
particular five- or six-membered C.sub.3-C.sub.12-hetarylene groups
with one or two hetero-atoms from the group of nitrogen, oxygen and
sulfur, are groups of the formula 21
[0056] examples of suitable structures interrupted by oxygen or
amino groups, in particular NH or N(CH.sub.3) groups, are the
following structures: 22
[0057] with n=2 to 8 and m=2 to 5.
[0058] Suitable meanings for the radical R.sup.1 are the
following:
[0059] suitable as C.sub.1-C.sub.30-alkyl group are, for example,
methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl,
tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, tert-pentyl,
neo-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl,
iso-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, iso-tridecyl,
n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl,
n-nonadecyl or n-eicosyl; C.sub.6-C.sub.18-alkyl groups are
preferred, especially C.sub.8-C.sub.12-alkyl groups;
[0060] suitable as C.sub.2-C.sub.30-alkenyl group are, for example,
vinyl, allyl, 2-methyl-2-propenyl or the corresponding radical
derived from oleic acid, linoleic acid or linolenic acid;
C.sub.16-C.sub.22-alkenyl groups are preferred;
[0061] particularly suitable as C.sub.5-C.sub.18-cycloalkyl group
are C.sub.5-C.sub.10-cycloalkyl groups, eg. cyclopentyl,
cyclohexyl, 2-, 3- or 4-methylcyclohexyl, 2,3-, 2,4-, 2,5- or
2,6-dimethylcyclohexyl, cycloheptyl or cyclooctyl;
[0062] particularly suitable as C.sub.7-C.sub.18-aralkyl, in
particular C.sub.7-C.sub.12-aralkyl, group are alkyl-substituted
phenylalkyl groups, eg. benzyl, 2-, 3- or 4-methylbenzyl,
2-phenylethyl, 3-phenyl-propyl, 4-phenylbutyl, 2-, 3- or
4-ethylbenzyl, 3- or 4-isopropylbenzyl or 3- or 4-butylbenzyl;
[0063] suitable as C.sub.6-C.sub.18-aryl group are, for example,
phenyl, 2-, 3-or 4-biphenylyl, .alpha.- or .beta.-naphthyl, 2-, 3-
or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 3- or
4-isopropylphenyl, 3- or 4-butylphenyl or 3- or
4-(2-ethylhexyl)phenyl; C.sub.6-C.sub.14-aryl groups are preferred,
especially phenyl and alkyl-substituted phenyl;
[0064] particularly suitable as C.sub.3-C.sub.18-hetaryl group are
five- or six-membered C.sub.3-C.sub.12-hetaryl groups with one or
two heteroatoms from the group of nitrogen, oxygen and sulphur;
examples thereof are: 23
[0065] examples of suitable aliphatic radicals interrupted by
oxygen or amino groups, in particular NH or N(CH.sub.3) groups, are
the following structures: 24
[0066] with n=2 to 8 and m=2 to 5.
[0067] The variables Z.sup.1 to Z.sup.3, A and R.sup.1 defined
above can additionally be functionalized by the stated groups. In
this connection C.sub.1-C.sub.4-alkoxy groups are in particular
methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy,
sec-butoxy or tert-butoxy. Preferred amino groups are --NH.sub.2,
--NH (CH.sub.3), --NH (CH.sub.2CH.sub.3), --N(CH.sub.3).sub.2 and
--N(CH.sub.2CH.sub.3).sub.2. Examples of
carboxy-C.sub.1-C.sub.4-alkyl groups are carboxymethyl,
carboxyethyl, carboxypropyl, carboxybutyl or
carboxy-tert-butyl.
[0068] The oxygen-containing group X in which one or two oxygen
atoms are linked by a double bond on carbon, sulfur or phosphorus
atoms, ie. are carbonyl or heterocarbonyl functionalities, is
preferably 25
[0069] In the case where R.sup.1=L.sup.1, the two heterocyclic
radicals L.sup.1 bonded to the group X are preferably the same.
[0070] A particularly preferred solid composition is one in which
the radical R.sup.1 in the heterocyclic compounds I is
C.sub.6-C.sub.18-alkyl, C.sub.6-C.sub.18-alkenyl,
C.sub.7-C.sub.12-aralky- l, phenyl or alkyl-substituted phenyl with
a total of up to 14 carbon atoms or a second heterocyclic radical
L.sup.1 which has the same structure as the first heterocyclic
radical L.sup.1. With a view to the preferred use of the
heterocyclic compounds I as cold bleach activators in detergents,
bleaches and cleaners, it has proven beneficial for R.sup.1 to be a
long-chain or bulky radical with corresponding hydrophobicity.
[0071] The following types of structures of the heterocyclic
compounds I are preferably employed:
[0072] (1) N-Acyloxazolidones of the formula 26
[0073] (2) N-Acyl-1,3-tetrahydrooxazinones of the formula 27
[0074] (3) Acyloxy-.gamma.-butyrolactone der Formel 28
[0075] (4) Acyloxy-.gamma.-valerolactones of the formula 29
[0076] (5) O-Acylpantolactones of the formula 30
[0077] (6) Acyloxy-.delta.-valerolactones of the formula 31
[0078] (7) Acyloxy-.epsilon.-caprolactones of the formula 32
[0079] (8) Acyl-.gamma.-butyrolactams of the formula 33
[0080] (9) N-Acyl-.delta.-valerolactams of the formula 34
[0081] (10)N-Acyl-.epsilon.-caprolactams of the formula 35
[0082] (11)N,N'-Carbonylbisoxazolidones of the formula 36
[0083] (12) N,N'-Carbonylbis-1,3-tetrahydrooxazinones of the
formula 37
[0084] (13)Carbonic acid bis-.gamma.-butyrolactones of the formula
38
[0085] (14) Carbonic acid bis-.gamma.-valerolactones of the formula
39
[0086] (15) O,O'-Carbonylbispantolactones of the formula 40
[0087] (16)Carbonic acid bis-.delta.-valerolactones of the formula
41
[0088] (17)Carbonic acid bis-.epsilon.-caprolactones of the formula
42
[0089] (18)N,N'-Carbonylbis-.gamma.-butyrolactams of the formula
43
[0090] (19)N,N'-Carbonylbis-.delta.-valerolactams of the formula
44
[0091] (20) N,N'-Carbonylbis-.epsilon.-caprolactams of the formula
45
[0092] (21)doubled N-acyloxazolidones of the formula 46
[0093] (22)doubled N-acyl-1,3-tetrahydrooxazinones of the formula
47
[0094] (23) doubled acyloxy-.gamma.-butyrolactones of the formula
48
[0095] (24) doubled acyloxy-.gamma.-valerolactones of the formula
49
[0096] (25) doubled O-acylpantolactones of the formula 50
[0097] (26) doubled acyloxy-.delta.-valerolactones of the formula
51
[0098] (27) doubled acyloxy-.epsilon.-caprolactones of the formula
52
[0099] (28)doubled acyl-.gamma.-butyrolactams of the formula 53
[0100] (29) doubled acyl-.delta.-valerolactams of the formula
54
[0101] (30) doubled N-acyl-.epsilon.-caprolactams of the formula
55
[0102] The radical R.sup.1 in types (1) to (10) of structure is, in
particular, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl,
n-undecyl, n-dodecyl, cyclohexyl, benzyl, phenyl or 2-, 3- or
4-methyl-phenyl.
[0103] The linker A in types (21) to (30) of structure is, in
particular, hexamethylene, octamethylene, decamethylene,
dodeca-methylene, 1,3- or 1,4-cyclohexylene or 1,4-, 1,3- or
1,2-phenylene; of particular interest for A is 1,4-phenylene
(derived from terephthalic acid).
[0104] The following meanings, besides hydrogen, are suitable for
the radicals R.sup.2 and R.sup.3 in the oxime esters II, which can
be identical or different:
[0105] examples of suitable linear or branched
C.sub.1-C.sub.30-alkyl groups are methyl, ethyl, n-propyl,
iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl,
iso-pentyl, sec-pentyl, tert-pentyl, neo-pentyl, n-hexyl, n-heptyl,
n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,
n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl,
n-nonadecyl or n-eicosyl; C.sub.1-C.sub.12-alkyl groups are
preferred, especially C.sub.1-C.sub.4-alkyl groups;
[0106] examples of suitable linear or branched
C.sub.2-C.sub.30-alkenyl groups are vinyl, allyl,
2-methyl-2-propenyl or the corresponding radical derived from oleic
acid, linoleic acid or linolenic acid; C.sub.2-C.sub.6-alkenyl and
C.sub.16-C.sub.22-alkenyl groups are preferred;
[0107] particularly suitable C.sub.5-C.sub.18-cycloalkyl groups are
C.sub.5-C.sub.10-cycloalkyl groups, eg. cyclopentyl, cyclohexyl,
2-, 3- or 4-methylcyclohexyl, 2,3-, 2,4-, 2,5- or
2,6-dimethylcyclohexyl, cycloheptyl or cyclooctyl;
[0108] particularly suitable C.sub.7-C.sub.18-aralkyl, especially
C.sub.7-C.sub.12-aralkyl, groups are alkyl-substituted phenylalkyl
groups, eg. benzyl, 2-, 3- or 4-methylbenzyl, 2-phenylethyl,
3-phenylpropyl, 4-phenylbutyl, 2-, 3- or 4-ethylbenzyl, 3- or
4-isopropylbenzyl or 3- or 4-butylbenzyl;
[0109] examples of suitable C.sub.6-C.sub.18-aryl groups are
phenyl, 2-, 3- or 4-biphenylyl, .alpha.- or .beta.-naphthyl, 2-, 3-
or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 3- or
4-isopropylphenyl, 3- or 4-butyl-phenyl or 3- or
4-(2-ethylhexyl)phenyl; C.sub.6-C.sub.14-aryl groups are preferred,
especially phenyl and alkyl-substituted phenyl;
[0110] particularly suitable C.sub.3-C.sub.18-hetaryl groups are
five- or six-membered C.sub.3-C.sub.12-hetaryl groups with one or
two heteroatoms from the group of nitrogen, oxygen and sulfur;
examples thereof are: 56
[0111] examples of suitable aliphatic radicals interrupted by
oxygen or amino groups, especially NH or N(CH.sub.3) groups, are
the following structures: 57
[0112] with p=2 to 8 and q=2 to 5.
[0113] The variable Z.sup.4 in the cyclic oxime moieties L.sup.2
can mean, in particular, C.sub.3-C.sub.12-alkylene groups of the
following structure: 58
[0114] where the variable Z.sup.4 can be functionalized or
interrupted as stated.
[0115] The variables Z.sup.1 to Z.sup.3 in the heterocyclic systems
(h), (j) and (k) can be, in particular, C.sub.2-C.sub.10-alkylene
groups of the following structure: 59
[0116] where, in the case of non-symmetrical alkylene groups, in
principle both ways of incorporation into the rings are possible.
The variables Z.sup.1 to Z.sup.3 can be functionalized or
interrupted as stated.
[0117] Particularly suitable unsubstituted or substituted
hydrocarbon radicals R.sup.1 for the variable L.sup.3 in the oxime
esters II are C.sub.1-C.sub.18-alkyl radicals,
C.sub.2-C.sub.18-alkenyl radicals, C.sub.7-C.sub.12-aralkyl
radicals or phenyl or alkyl-substituted phenyl with a total of up
to 14 carbon atoms. Typical examples thereof are:
[0118] methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,
n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl,
n-hexadecyl, n-octadecyl, benzyl, 2-phenylethyl, 4-phenylbutyl,
phenyl and o-, m- or p-tolyl.
[0119] Particularly suitable carboxylic ester residues (a) for
L.sup.3 are: 60
[0120] Particularly suitable carboxamide residues (b) for L.sup.3
are: 61
[0121] Particularly suitable phenolate residues (c) for L.sup.3
are: 62
[0122] and the relevant sodium or potassium salts.
[0123] Particularly suitable vinyloxy radicals (d) for L.sup.3 are:
63
[0124] Particularly suitable sulfonamide residues (e) for L.sup.3
are: 64
[0125] Particularly suitable imidazole residues (f) for L.sup.3
are: 65
[0126] Particularly suitable amidolactam residues (g) for L.sup.3
are: 66
[0127] Particularly suitable cyclic carbamate residues (h) for
L.sup.3 are: 67
[0128] Particularly suitable lactonoxy residues (j) for L.sup.3
are: 68
[0129] T in the general formula for the lactonoxy residue (j) is
preferably hydrogen or methyl.
[0130] Particularly suitable lactam residues (k) for L.sup.3 are:
69
[0131] Typical examples of the linker A in the oxime esters II are
like-wise those stated above for the oxygen-containing group X in
the heterocyclic compounds I.
[0132] The linker A in the oxime esters II is, in particular, a
chemical bond (formally derived from oxalic acid) or 1,2-ethylene
(derived from succinic acid), 1,4-butylene (derived from adipic
acid), hexamethylene (derived from suberic acid), octamethylene
(derived from sebacic acid), 1,3- or 1,4-cyclohexylene or 1,2-,
1,3- or 1,4-phenylene (derived from phthalic acid, isophthalic acid
or terephthalic acid).
[0133] The variables R.sup.1, R.sup.2, R.sup.3, Z.sup.1 to Z.sup.4
and A defined above may additionally be functionalized by the
stated groups. In this connection, C.sub.1-C.sub.4-alkoxy groups
are, in particular, methoxy, ethoxy, n-propoxy, isopropoxy,
n-butoxy, isobutoxy, sec-butoxy or tert-butoxy. Preferred amino
groups are --NH.sub.2, --NH(CH.sub.3), --NH(CH.sub.2CH.sub.3),
--N(CH.sub.3).sub.2 and --N(CH.sub.2CH.sub.3).sub- .2. Examples of
carboxy-C.sub.1-C.sub.4-alkyl groups are carboxymethyl,
carboxyethyl, carboxypropyl, carboxybutyl or
carboxy-tert-butyl.
[0134] In a preferred embodiment there is use of oxime esters II in
which L.sup.2 is an oxime moiety of the formula 70
[0135] where
[0136] R.sup.5 and R.sup.6 are hydrogen, C.sub.1-C.sub.4-alkyl,
especially methyl or ethyl, phenyl or benzyl, and
[0137] Z.sup.5 is 1,4-butylene, 1,5-pentylene or 1,6-hexylene.
[0138] Aldoxime or ketoxime moieties of this type are derived from
conventional aldehydes or ketones, for example from formaldehyde,
acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde,
acetone, ethyl methyl ketone, diethyl ketone, acetophenone,
henylacetone, benzophenone, cyclopentanone, cyclohexanone or
cycloheptanone.
[0139] Furthermore, preferred oxime esters II are those where
L.sup.3 is a second oxime moiety L.sup.2; particularly preferred in
this connection are those oxime esters II where L.sup.2 and L.sup.3
are the same oxime moiety.
[0140] Of particular interest are bisoxime esters II derived from
oxalic acid, succinic acid, adipic acid, phthalic acid, isophthalic
acid or terephthalic acid and aliphatic ketones with 3 to 6 carbon
atoms or from C.sub.5-C.sub.7-cycloalkanones. Systems of this type
can be prepared in a simple manner, for example by reacting the
corresponding dicarbonyl chlorides or bromides with appropriate
aliphatic or cycloaliphatic ketoximes in the presence of bases.
[0141] Also of particular interest as bisoxime esters II are
furthermore bisiminocarbonates which are formally derived from
carbonic acid and aliphatic ketones with 3 to 6 carbon atoms or
from C.sub.5-C.sub.7-cycloalkanones. Systems of this type can be
prepared in a simple manner for example by reacting phosgene with
the appropriate aliphatic or cycloaliphatic ketoximes in the
presence of bases.
[0142] The oxime esters II described, methods for preparing them
and their use as bleach activators in detergents, bleaches and
cleaners are known in principle, for example from JP-A 06/336 468
(5), WO-A 93/04037 (6), the article by A. Jumar, P. Held and W.
Schulze in Z. Chem. 7 (1967), 344-345 (7) or German Patent
Application 1 95 41 012.2 (8). According to (7), non-symmetrical
bisoxime esters II and monooxime esters II can be prepared in the
case where m=0 (carbonic acid derivatives) via the intermediate
stage of the corresponding chloroformyloxime.
[0143] It is, of course, also possible to employ mixtures of the
hetero-cyclic compounds I with the oxime esters II in the solid
compositions according to the invention.
[0144] A high internal surface area of the inert porous carrier
materials is crucially important for the required properties of the
resulting solid composition. The internal surface area is
preferably in the range from 50 to 480 m.sup.2/g, in particular 100
to 460 m.sup.2/g, especially 180 to 450 m.sup.2/g.
[0145] The average particle size of the inert porous carrier
materials is also important but it can vary within a wider range
than the internal surface area. The best results are obtained with
an average particle size of from 10 nm to 100 .mu.m, in particular
20 nm to 50 .mu.m, especially 1 .mu.m to 20 .mu.m, but the average
particle sizes can, depending on the nature of the carrier material
and the application of the solid composition according to the
invention, also be smaller, for example down to 3 nm, or larger,
for example up to 2 mm, especially up to 500 .mu.m.
[0146] Inert porous carrier materials which can be used are in
principle all conventional types of such chemically inert
materials. However, particularly suitable are silica gels, silicas,
aluminum oxides, kaolins or aluminum silicates or mixtures
thereof.
[0147] Silica gels are colloidal shaped or unshaped silicas with an
elastic or a solid consistency and with a loose to compact pore
structure and high adsorption capacity. Silica gel surfaces have
acidic properties. Silica gel is usually prepared from water glass
by reaction with mineral acids.
[0148] Silicas which can be employed are, besides the silicas
prepared in a wet process, particularly advantageously the highly
disperse pyrogenic SiO.sub.2 types which are obtained thermally,
ie. normally prepared by flash hydrolysis of SiCl.sub.4 (eg.
Aerosils.RTM. or Sipernats.RTM.). In a particularly preferred
embodiment of the present invention, silica with an average
(agglomerate) particle size of from 100 nm to 30 .mu.m, in
particular 1 .mu.m to 20 .mu.m, and an SiO.sub.2 content of 95-100,
preferably 98-100, % by weight is used.
[0149] Aluminum oxides occur in nature as, for example, aluminas or
corundum. The aluminum oxide is in the a modification in these
cases. Industrially, a-Al.sub.2O.sub.3 is obtained from bauxite by
the Bayer process. "Active" aluminum oxides with a high specific
surface area which are particularly suitable as adsorbents are
prepared by precipitation processes from aluminum salt solutions or
by calcination from a-aluminum hydroxide.
[0150] Kaolins are hydrated aluminum silicates (clays) which occur
naturally in soil and which are also called china clays because of
their former principal use. The main constituents are the triclinic
kaolinite and the monoclinic dickite and nacrite together with
montmorillonite and aluminum silicates in gel form
(allophanes).
[0151] Aluminum silicates are compounds with various proportions of
Al.sub.2O.sub.3 and SiO.sub.2, which occur in nature as andalusite,
disthene, mullite, sillimanite, etc. Aluminum silicate minerals in
which Al occupies sites in the crystal lattice in place of Si are
the alumosilicates (eg. ultramarines, zeolites, feldspars).
[0152] Freshly precipitated aluminum silicates are finely dispersed
and have a large surface area and high adsorption capacity.
[0153] The ratio of heterocyclic compounds I or oxime esters II and
inert porous carrier materials in the solid composition according
to the invention can vary within certain limits depending on the
method for preparing the solid composition and the material
properties of the components employed. A preferred ratio is 10-95
parts by weight of I or II to 5-90 parts by weight of carrier, in
particular 30-90 parts by weight of I or II to 10-70 parts by
weight of carrier. The stated parts by weight of I or II are always
based on anhydrous or solvent-free compound I or II. For economic
reasons, it is desirable to maximize the proportion of heterocyclic
compounds I or oxime esters II.
[0154] The solid composition according to the invention is, as a
rule, homogeneously composed of the components employed. The
hetero-cyclic compounds I and the oxime esters II and, where
appropriate, other auxiliaries are uniformly drawn into the
interior of the carrier material particles and are uniformly
distributed therein, because they have a relatively large internal
surface area. There is normally no noticeable gradient of
concentration of the substances which are drawn in between the
inner and outer surface of the particles or particle aggregates, so
that it is not possible to speak of "coating".
[0155] It may be advantageous for the properties of the solid
composition according to the invention if it contains, in addition
to the stated parts by weight of I and II and carrier material,
0.5-70 parts by weight, in particular 2-40 parts by weight,
especially 5-25 parts by weight, of anionic, nonionic or
zwitterionic surfactants, carboxyl-containing polymers,
polysaccharides, polyalkylene glycols, acidic alkali metal or
alkaline earth metal salts of inorganic acids, neutral alkali metal
salts, aliphatic C.sub.8-C.sub.18-monocarboxylic acids, aliphatic
di-or tricarboxylic acids, aromatic mono- or dicarboxylic acids, it
being possible for the abovementioned carboxylic acids additionally
to contain hydroxyl and amino groups in the molecule, aliphatic
C.sub.3-C.sub.7-monohydroxycarboxylic acids or mixtures
thereof.
[0156] Examples of suitable anionic surfactants in this case are
alkali metal salts of fatty acids (soaps), alkylbenzenesulfonates,
alkanesulfonates, .alpha.-olefinsulfonates, hydroxyalkanesulfonate,
.alpha.-sulfo fatty acid esters, alkyl sulfates, alkyl ether
sulfates or fatty alcohol ether sulfates. Of these,
alkylbenzene-sulfonates, especially the alkali metal and ammonium
salts of linear C.sub.11-C.sub.13-alkylbenzenesulfonates, eg.
sodium dodecylbenzenesulfonate, are preferred.
[0157] Examples of nonionic surfactants used in this case are
alcohol alkoxylates, especially fatty alcohol alkoxylates, and
alkylphenol alkoxylates, fatty acid alkylolamides and alkyl
glycosides, especially C.sub.8-C.sub.16-monoalkyl glucosides. Of
these, ethoxylates and propoxylates of saturated or unsaturated
C.sub.12-C.sub.20 fatty alcohols, eg. coconut fatty and tallow
fatty alcohol ethoxylates, are preferred.
[0158] Examples of suitable zwitterionic surfactants in this case
are secondary and tertiary amine oxides.
[0159] Suitable carboxyl-containing polymers are, in particular,
homopolymers of acrylic acid and methacrylic acid, and copolymers
containing acrylic acid and/or methacrylic acid, and the relevant
alkali metal or ammonium salts. Acrylic acid/maleic acid copolymers
are particularly preferred, especially in partially neutralized
form, eg. acrylic acid/maleic acid copolymer which is about 50% in
the form of the sodium salt (acrylic acid:maleic acid ratio=70:30
by weight).
[0160] The most advantageous polysaccharides are starch, amylose
and derivatives of these naturally occurring polysaccharides such
as carboxymethylcellulose, cellulose acetate hydrogen phthalate,
ethylcellulose or sulfated cellulose ethers. Of these, it is
possible to employ starch itself most favorably.
[0161] Particularly suitable polyalkylene glycols are polyethylene
glycols and ethylene oxide/propylene oxide copolymers.
[0162] Particularly suitable acidic alkali metal and alkaline earth
metal salts of inorganic acids are sodium bicarbonate and sodium
bisulfate, but also potassium bicarbonate, potassium bisulfate,
sodium dihydrogen phosphate, potassium dihydrogen phosphate,
disodium hydrogen phosphate, dipotassium hydrogen phosphate,
calcium hydrogen phosphate or magnesium hydrogen phosphate.
[0163] Particularly suitable neutral alkali metal salts are sodium
sulfate and sodium chloride.
[0164] Examples of suitable aliphatic
C.sub.8-C.sub.18-monocarboxylic acids, aliphatic di- or
tricarboxylic acids, aromatic mono- or dicarboxylic acids, it being
possible for the abovementioned carboxylic acids additionally to
contain hydroxyl and amino groups in the molecule, and aliphatic
C.sub.3-C.sub.7-monohydroxy carboxylic acids are fatty acids such
as lauric acid, myristic acid, palmitic acid and stearic acid,
oxalic acid, malonic acid, succinic acid, glutaric acid, adipic
acid, pimelic acid, suberic acid, maleic acid, fumaric acid,
tartaric acid, malic acid, citric acid, benzoic acid, salicylic
acid, anthranilic acid, sulfanilic acid, phthalic acid, .alpha.-
and .beta.-naphthoic acid, naphthalic acid and lactic acid. Of
these, palmitic acid, stearic acid, oxalic acid, malonic acid,
succinic acid, glutaric acid, adipic acid, pimelic acid, tartaric
acid, citric acid and benzoic acid are preferred. Said carboxylic
acids mainly improve the color stability on storage in detergent
powders.
[0165] It is also possible to employ mixtures of several of said
additives from one of the listed groups or from different
groups.
[0166] The invention also relates to a process for preparing the
described solid composition, which comprises mixing together 5-98
parts by weight of heterocyclic compounds I and/or oxime esters II
with 2-95 parts by weight of inert porous carrier materials in a
conventional way and converting this mixture where appropriate by
conventional methods into a formulated form suitable for the
particular application.
[0167] In a preferred embodiment, this preparation process is
carried out in such a way that a solution or a melt of the
heterocyclic compounds I and/or of the oxime esters II is mixed
with the inert porous carrier materials by stirring in, spraying on
or impregnating, the solvent, where present, is substantially
removed by distillation or drying and, if necessary, the resulting
mixture is converted, where appropriate after mixing with other
auxiliaries, by conventional methods into a formulated form
suitable for the particular application. Solvents suitable for this
purpose are, in particular, conventional organic solvents such as
alcohols, eg. methanol, ethanol or isopropanol, ketones, eg.
acetone, carboxylic esters, eg. methyl or ethyl acetate, or
unhalogenated or halogenated hydrocarbons, eg. n-hexane,
cyclohexane, toluene, xylene or chlorobenzene.
[0168] A typical preparation process of this type entails the inert
porous carrier materials being introduced into the solution of the
compounds I or II in an organic solvent and, where appropriate,
admixing other auxiliaries, in particular surfactants. The solvent
is subsequently removed virtually completely, which is
advantageously carried out by distillation at low temperature under
reduced pressure, especially when a relatively high-boiling solvent
has been employed. Then, if necessary, the product, which results
in the form of a free-flowing powder, is subjected to conventional
methods of compaction, where appropriate size reduction and
screening to a size fraction in the range from, for example, 200
.mu.m to 3 mm -depending on the application.
[0169] If necessary, the storage stability of the solid composition
according to the invention can be improved by other subsequent
treatments, for example by coating with fats, oils, melts or
solutions.
[0170] In place of the introduction and admixing (stirring in) of
the carrier materials, the solution of the compounds I or II can
also be sprayed onto the carrier materials by conventional
techniques. Impregnation processes can also be used. If the
mixtures after the spraying or impregnation process are already in
powder form, they can also be agglomerated directly without further
drying in a conventional mixer, it being necessary where
appropriate to add other auxiliaries, especially surfactants, for
example in molten form or as highly concentrated aqueous solution,
and this is followed, where appropriate, by the processing to the
required size fraction described above.
[0171] The solid composition according to the invention is mainly
suitable as a solid additive for detergents, bleaches and cleaners,
in particular as stable bleach activator component in such
compositions.
[0172] It is thus possible to formulate detergents, bleaches and
cleaners which contain 0.1-30% by weight, based on the total amount
of the formulation, of the solid composition according to the
invention. The present invention likewise relates to these
detergents, bleaches and cleaners. Other conventional components in
detergents, bleaches and cleaners are explained in detail
below:
[0173] The cold bleach activators I and II described form the
bleach system together with bleaches, as a rule peroxy compounds,
which are likewise present in the formulation, normally separately.
It is moreover possible for the pH of the washing or bleaching or
cleaning liquors to vary within wide limits, from the weakly acidic
region (pH 4) to the highly alkaline region (pH 13) depending on
the application. The alkaline range from pH 8 to pH 11 is preferred
because it is particularly advantageous for the activation reaction
and the stability of the peroxy compound formed.
[0174] For this reason, the bleach activators described are also
preferably used together with a sodium perborate or a sodium
carbonate perhydrate, the solutions of which already have pH values
in this range. Examples of other suitable peroxy compounds are
phosphate perhydrates and urea perhydrate. It may also occasionally
be expedient to change the pH of the medium again, especially into
the acidic region, by suitable additives after the activation
reaction has taken place.
[0175] The amounts of bleaches (peroxy compounds) employed are
generally chosen so that the liquors contain from 10 to 10,000 ppm
active oxygen, preferably from 50 to 5,000 ppm active oxygen. The
amount of bleach activator used also depends on the application.
From 0.03 to 1.0 mol, preferably 0.1 to 0.5 mol, of activator is
used per mole of inorganic peroxy compound, depending on the
required degree of activation, but amounts above or below these
limits are also possible in special cases.
[0176] Particularly suitable additional bleach activators which can
be employed in combination with the heterocyclic compounds I or the
oxime esters II (in the solid composition according to the
invention or as possibly formulated separate component) are:
[0177] polyacylated sugars, eg. pentaacetylglucose;
[0178] acyloxybenzenesulfonic acids and their alkali metal and
alkaline earth metal salts, eg. sodium
p-isononanoyloxybenzene-sulfonate or sodium
p-benzoyloxybenzenesulfonate;
[0179] N,N-diacylated and N,N,N',N'-tetraacylated amines, eg.
N,N,N',N'-tetraacetylmethylenediamine and -ethylenediamine,
N,N-diacetylaniline, N,N-diacetyl-p-toluidine or 1,3-diacylated
hydantoins such as 1,3-diacetyl-5,5-dimethylhydantoin;
[0180] N-alkyl-N-sulfonylcarbonamides, eg.
N-methyl-N-mesylacetamide or N-methyl-N-mesylbenzamide;
[0181] N-acylated cyclic hydrazides, acylated triazoles or
urazoles, eg. monoacetylated maleic hydrazide;
[0182] O,N,N-trisubstituted hydroxylamines, eg.
O-benzoyl-N,N-succinylhydr- oxylamine,
O-acetyl-N,N-succinylhydroxylamine or O,N,N-triacetylhydroxylam-
ine;
[0183] N,N'-diacylsulfamides, eg.
N,N'-dimethyl-N,N'-diacetylsulfamide or
N,N'-diethyl-N,N'-dipropionylsulfamide;
[0184] triacylcyanurates, eg. triacetylcyanurate or
tribenzoyl-cyanurate;
[0185] carboxylic anhydrides, eg. benzoic anhydride,
m-chlorobenzoic anhydride or phthalic anhydride;
[0186] 1,3-diacyl-4,5-diacyloxyimidazolines, eg.
1,3-diacetyl-4,5-diacetox- yimidazoline;
[0187] tetraacetylglycoluril and tetrapropionylglycoluril;
[0188] diacylated 2,5-diketopiperazines, eg.
1,4-diacetyl-2,5-diketopipera- zine;
[0189] acylation products of propylenediurea and
2,2-dimethyl-propylenediu- rea, eg. tetraacetylpropylenediurea;
[0190] .alpha.-acyloxypolyacylmalonamides, eg.
.alpha.-acetoxy-N,N'-diacet- ylmalonamide;
[0191] diacyldioxohexahydro-1,3,5-triazines, eg.
1,5-diacetyl-2,4-dioxohex- ahydro-1,3,5-triazine;
[0192] benzo-(4H)1,3-oxazin-4-one with alkyl radicals, eg. methyl,
or aromatic radicals, eg. phenyl, in position 2.
[0193] For textile laundering, the bleach activators described can
be combined with virtually all conventional ingredients of
detergent formulations. It is possible in this way to design
formulations suitable specifically for textile treatment at low
temperatures, and those suitable in several temperature ranges up
to the traditional boiling wash range.
[0194] The principal ingredients of such detergent formulations
are, besides bleaches (peroxy compounds) and bleach activators,
builders and surfactants. These compositions may also contain other
conventional auxiliaries and additives such as antiredeposition
agents, peroxide stabilizers, electrolytes, optical brighteners,
enzymes, perfume oils, foam regulators and activating substances if
expedient. The components of bleach and cleaner formulations are in
principle the same.
[0195] Examples of conventional builders are condensed phosphates,
alkali metal silicates, alkali metal carbonates, salts of amino
carboxylic acids such as nitrilotriacetic acid, salts of
polyphosphonic acids such as hydroxyethanediphosphonic acid, salts
of polycarboxylic acids such as citric acid or polyacrylic acid and
insoluble sodium aluminum silicates of the zeolite NaA and NaX
types.
[0196] Particularly suitable surfactants are those of the nonionic
and synthetic anionic surfactant types. Examples of nonionic
surfactants are the polyethylene glycol monoalkyl and monophenyl
ethers prepared from long-chain alcohols or alkylphenols and
ethylene oxide, and the long-chain alkyl glycosides.
[0197] The anionic surfactants are primarily sulfates and
sulfonates of long-chain compounds, for example
alkylbenzenesulfonates, fatty acid ester sulfonates,
alkanesulfonates, olefin sulfonates, fatty alcohol sulfates and
sulfates of polyethylene glycol monoethers. It is furthermore
possible to use soaps and salts of long-chain acylcyanamides, and
long-chain succinates and sulfosuccinates.
[0198] Typical textile detergents and bleaches of these types have
approximately the following composition:
[0199] 0.5-30% by weight, preferably 5-25% by weight, of anionic
and/or nonionic surfactants,
[0200] 0.5-60% by weight, preferably 5-50% by weight, of builders
from the group of condensed phosphates, alkali metal silicates,
alkali metal carbonates, sodium aluminum silicates and mixtures
thereof,
[0201] 0-20% by weight, preferably 0.5-8% by weight, of builders
from the group of salts of amino carboxylic acids, salts of
polyphosphonic acids, salts of polycarboxylic acids and mixtures
thereof,
[0202] 2-35% by weight, preferably 5-30% by weight, of inorganic
peroxy compounds,
[0203] 0.1-30% by weight, preferably 0.5-20% by weight, of the
solid composition according to the invention,
[0204] ad 100% conventional auxiliaries and additives and
water.
[0205] The solid composition according to the invention has the
advantage that it has a sufficiently long shelf life, ie. remains
free-flowing without forming lumps or agglomerates. During this
storage time there are negligible losses of activity, for example
in respect of the bleaching action. Detergents, bleaches and
cleaners which contain the solid composition according to the
invention are usually more effective than those containing
conventional bleach activators such as
N,N,N',N'-tetraacetyl-ethylenediamine (TAED) in the same
amounts.
PREPARATION EXAMPLES
Example 1
[0206] 10 g of N-(n-octanoyl)-.epsilon.-caprolactam were dissolved
in 20 g of acetone, and 10 g of highly disperse silica with an
internal surface area of about 190 m.sup.2/g and an average
particle size of about 7 .mu.m (Sipernat.RTM.22S from Degussa) were
added. After thorough mixing of the suspension, the solvent was
removed by distillation to leave a dry, free-flowing powder which
contained the cold bleach activator uniformly dispersed.
Example 2
[0207] 10 g of N-(n-octanoyl)-.epsilon.-caprolactam were dissolved
in 20 g of acetone, and 10 g of the same highly disperse silica as
in Example 1, 2 g of sodium sulfate, 2 g of citric acid and 1 g of
corn starch were added. After thorough mixing of the suspension,
the solvent was removed by distillation to leave a dry,
free-flowing powder which contained the cold bleach activator
uniformly dispersed.
[0208] Technical Investigations of Use
[0209] Washing tests were carried out with hydrophilic and
hydrophobic test soilings using the product from Example 2, and,
for comparison, using unformulated
N-(n-octanoyl)-.epsilon.-caprolactam and
N,N,N',N'-tetraacetylethylenediamine (TAED). It emerged from this
that the bleach activator formulated according to the invention has
a distinctly greater bleaching action, especially with hydrophobic
soilings such as grass on cotton, than the bleach activator TAED
which represents the prior art (see Table 1). The test was carried
out in a launder-o-meter, Atlas standard type, using a heavy duty
detergent of the following composition (% by weight):
1 linear alkylbenzenesulfonate (50% by weight) 0.8 conventional
soap 0.4 conventional fatty alcohol sulfate 12.0
C.sub.13/C.sub.15-Oxo alcohol reacted with 7 mol 4.7 of ethylene
oxide Magnesium silicate 0.8 Sodium bicarbonate 9.0 Sodium
percarbonate 18.0 Sodium sulfate 3.2 Sodium citrate dihydrate 5.0
Conventional sheet silicate 14.0 Zeolite A 15.0
Carboxymethylcellulose 0.6 Water Remainder to 100
[0210] The concentration of bleach activator employed in Table 1 or
2 was in each case 5% by weight of active substance based on the
amount of detergent.
[0211] The tests were carried out under the following
conditions:
2 Amount of liquor: 250 g Water hardness: 3.0 mmol/l
Ca/Mg/HCO.sub.3 molar ratio: 4:1:8 Detergent dose: 4.5 g/l
Temperature: 22.degree. C./38.degree. C./60.degree. C. Washing
time: 30 min Soiled fabric 1: 2.5 g of bleached cotton (WFK
Krefeld) soiled with chlorophyll Soiled fabric 2: 2.5 g of bleached
cotton soiled with red wine Soiled fabric 3: 2.5 g of unbleached
cotton cheesecloth Rinsing: 3 .times. 30 sec with tapwater
(14.degree. German hardness)
[0212] The tests were evaluated by measurements of the reflectance
on the dried fabrics. The color strength of each of the test
soilings before and after the washing were determined by the method
described by A. Kud, Seifen, ole, Fette, Wachse 119 (1993) 590-594
from the measurements of the reflectance at 18 wavelengths in the
range from 400 to 700 nm at intervals of 20 nm on the individual
test fabrics, and the absolute bleaching action A.sub.abs in % was
calculated therefrom. The bleaching action in % is indicated in the
following tables.
3TABLE 1 Test fabric soiled with grass Temperature Bleach activator
22.degree. C. 38.degree. C. 60.degree. C. TAED 27.2 32.0 41.7
Example 2 30.8 37.6 46.2 (formulated)
[0213]
4 TABLE 2 Temperature Bleach activator 22.degree. C. 38.degree. C.
60.degree. C. a) Soiling with chlorophyll Octanoylcaprolactam 31.1
39.5 45.6 Example 2 30.8 37.6 46.2 (formulated) b) Soiling with red
wine Octanoylcaprolactam 60.3 64.0 70.6 Example 2 63.8 67.6 73.9
(formulated) c) Unbleached cotton cheesecloth Octanoylcaprolactam
7.1 14.1 14.2 Example 2 9.1 13.9 19.6 (formulated)
[0214] The results of measurements from the washing tests in Table
2 show that the formulation, represented by the example of
octanoylcaprolactam, does not necessarily entail a loss of
effect.
* * * * *