U.S. patent application number 10/512636 was filed with the patent office on 2005-10-27 for method for brightening textile materials.
This patent application is currently assigned to BASF AKTIENGESSELLSCHAFT. Invention is credited to Reichelt, Helmut, Wagenblast, Gerhard, Weber, Dieter.
Application Number | 20050235429 10/512636 |
Document ID | / |
Family ID | 29265083 |
Filed Date | 2005-10-27 |
United States Patent
Application |
20050235429 |
Kind Code |
A1 |
Weber, Dieter ; et
al. |
October 27, 2005 |
Method for brightening textile materials
Abstract
A process for brightening textile materials by treatment with
optical brighteners in an aqueous liquor, which comprises using
from 20 to 80% by weight, each percentage being based on the sum
total of all brightening compounds, of the compound I 1 of which up
to 40 mol % can be present as cis isomer, and also from 80 to 20%
by weight of at least one compound II selected from 2 and also from
0 to 30% by weight of at least one compound of the general formula
III
Inventors: |
Weber, Dieter; (Hassloch,
DE) ; Reichelt, Helmut; (Neustadt, DE) ;
Wagenblast, Gerhard; (Wachenheim, DE) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
BASF AKTIENGESSELLSCHAFT
LUDWIGSHAFEN
DE
|
Family ID: |
29265083 |
Appl. No.: |
10/512636 |
Filed: |
October 27, 2004 |
PCT Filed: |
April 30, 2003 |
PCT NO: |
PCT/EP03/04497 |
Current U.S.
Class: |
8/115.51 |
Current CPC
Class: |
D06P 1/18 20130101; D06L
4/657 20170101; D06L 4/636 20170101; D06P 1/13 20130101; C11D 3/42
20130101; D06P 1/08 20130101; D06P 1/20 20130101 |
Class at
Publication: |
008/115.51 |
International
Class: |
D06M 010/00 |
Foreign Application Data
Date |
Code |
Application Number |
May 3, 2002 |
DE |
102 19 993.0 |
Claims
1. A process for brightening textile materials by treatment with
optical brighteners in an aqueous liquor, which comprises using
from 20 to 80% by weight, each percentage being based on the sum
total of all brightening compounds, of the compound I 38of which up
to 40 mol % can be present as cis isomer, and also from 80 to 20%
by weight of at least one compound II selected from the group
consisting of 39 40and also from 0 to 30% by weight of at least one
compound of the general formula III 41where R is selected from
C.sub.4-C.sub.10-alkyl, in the optional presence of one or more
blue or violet shading dyes from the class of the anthraquinones,
azo dyes or methine dyes.
2. The process as claimed in claim 1, wherein from 20 to 70% by
weight of the compound II p,o' is used as well as from 20 to 80% by
weight of the compound I and from 0 to 30% by weight of a compound
of the general formula III.
3. The process as claimed in claim 1, wherein from 20 to 70% by
weight of the compound II m,p' is used as well as from 20 to 80% by
weight of the compound I and from 0 to 30% by weight of a compound
of the general formula III.
4. The process as claimed in claim 1, wherein from 20 to 70% by
weight of the compound II p,o' and from 10 to 50% by weight of the
compound II m,p' are used as well as from 20 to 70% by weight of
the compound I and from 0 to 30% by weight of a compound of the
general formula III.
5. The process as claimed in claim 1, wherein from 30 to 60% by
weight of the compound II p,o' and from 10 to 30% by weight of the
compound II o,o' are used as well as from 30 to 60% by weight of
the compound I and from 0 to 30% by weight of a compound of the
general formula III.
6. The process as claimed in claim 1, wherein from 20 to 60% by
weight of the compound II p,o', from 10 to 50% by weight of the
compound II m,p' and from 10 to 30% by weight of the compound II
o,o' are used as well as from 20 to 50% by weight of the compound I
and from 0 to 30% by weight of a compound of the general formula
III.
7. The process as claimed in claim 1, wherein R is 2-ethylhexyl in
the compound III.
8. The process as claimed in claim 1, wherein from 0.5 to 200% by
weight, based on the sum total of all brightening compounds, is
additionally used of one or more dispersants.
9. The process as claimed in claim 1, wherein the textile material
is polyester.
10. The process as claimed in claim 1, wherein the textile material
is a blend containing from 45 to 90% by weight of polyester.
11. A formulation comprising from 20 to 80% by weight, each
percentage being based on the sum total of all brightening
compounds, of the compound I, 42from 20 to 70% by weight of at
least one compound II selected from the group consisting of, 43from
0 to 30% by weight of at least one compound of the formula III
44and also in each case optionally one or more blue or violet
shading dyes from the class of the anthraquinones, azo dyes,
methine dyes, violanthrones or indanthrones, one or more
dispersants, water and further additives.
12. (canceled)
13. A method of brightening at least one textile material, said
method comprising applying said formulation as claimed in claim 11
to said at least one textile material.
Description
[0001] The present invention relates to a process for brightening
textile materials by treatment with optical brighteners in an
aqueous liquor, which comprises using from 20 to 80% by weight,
each percentage being based on the sum total of all brightening
compounds, of the compound I 3
[0002] of which up to 40 mol % can be present as cis isomer, and
also from 80 to 20% by weight of at least one compound II selected
from 4
[0003] and also from 0 to 30% by weight of at least one compound of
the general formula III 5
[0004] where R is selected from C.sub.4-C.sub.10-alkyl, in the
optional presence of one or more blue or violet shading dyes from
the class of the anthraquinones, azo dyes or methine dyes.
[0005] Optical brighteners are of immense economic immportance as
assistants for the textile industry and for the plastics industry.
Numerous compounds are known for their ability to confer a white
color on textiles or plastics. However, most of these known
compounds also have disadvantages. For instance, compounds of the
general formula 1 6
[0006] where for example R.sup.1 and R.sup.2 may each be for
example hydrogen, fluorine, chlorine, phenyl, trifluoromethyl,
alkyl or numerous other radicals and where V is selected from 7
[0007] are known from EP 0 023 026 and can be applied at low
temperature, but their efficiency is limited in that a lot of
product is needed to achieve the desired white effect.
[0008] Also known is a process for brightening textiles by treating
the textiles with distyrylbenzene compounds which are known for
example from CH-A 366 512, CH-A 382 709, CH-A 388 294, CH-A 389
585, CH-A 411 329, CH-A 416 078 and CH-A 465 548. EP-A 0 023 027
and EP-B2 0 030 917 and also the references cited in EP-B2 0 030
917 demonstrate the use of mixtures of two or more
dicyanostyrylbenzene compounds for the optical brightening of
polyesters.
[0009] EP 0 023 026 discloses mixtures of optical brighteners that
contain from 0.05 to 0.95 part by weight of one or more compounds
of the formula 2 p 8
[0010] where A is a phenyl group substituted by an ortho- or
para-cyano group, and also from 0.95 to 0.05 part by weight of one
or more other compounds selected from a large multiplicity of other
compounds. Preference is given to mixtures of 2 p,o' 9
[0011] with compounds of the general formula 1 10
[0012] where R.sup.1 and R.sup.2 may each be: hydrogen, fluorine,
chlorine, phenyl, trifluoromethyl, C.sub.1-C.sub.9-alkyl, alkoxy,
alkylamino and numerous further radicals which are recited at page
2 lines 14-21 and V is as defined above,
[0013] or with compounds of the formula 3b-4b 11
[0014] where B is a functional group, R.sup.1 and R.sup.2 are each
as defined above, n is an integer, R.sup.3 is selected from
hydrogen and C.sub.1-C.sub.4-alkoxy, R.sup.4 is selected from
C.sub.1-C.sub.4-alkoxy groups and R.sup.5 is selected from for
example C.sub.1-C.sub.6-alkyl and B is preferably a functional
group, or further with compounds of the formulae 5b to 6b 12
[0015] where R.sup.6 to R.sup.10 are each selected from various
groups and V is as defined above.
[0016] From this multiplicity of embodiments, Table 2 demonstrates
by way of example what are essentially mixtures of 2 p,o' or other
isomers with 3c 13
[0017] and with the following derivatives of 4 b.1 and 4 b.2:
14
[0018] The brighteners thus defined are applied by various methods
and provide good CIE whiteness.
[0019] EP-A 0 023 028 claims mixtures containing from 0.05 to 0.95
part by weight of a mixture consisting of from 20 to 100% by weight
of 2 p,o' 15
[0020] and from 0 to 80% by weight each of the compounds 2 p,p' and
2 o,o' 16
[0021] and also from 0.05 to 0.95 part by weight of one or more
derivatives of the formulae 1a and 3a to 6a, useful as optical
brighteners, 1a and 3a to 6a being defined essentially similarly to
EP-A 0 023 026.
[0022] DE-A 197 32 109 demonstrates the optical brightening of
polyamide or polyurethane by mixtures of derivatives of compounds
of type 1a 17
[0023] where R.sup.1 and R.sup.2 are independently H or
C.sub.1-C.sub.6-alkyl, A is selected from N and CH and X is
selected from 18
[0024] and also from stilbenyl, styryl or imidazolyl, with one or
more isomers of 2 or one of the numerous derivatives of 4 19
[0025] or numerous further derivatives, for example with 5 b (see
above). By way of example, mixtures are demonstrated inter alia
(Examples 19-21) of 1 a.1 with 4 b.1 20
[0026] The mixtures exhibit a synergistic effect with regard to CIE
whiteness and also good lightfastness.
[0027] EP-A 0 321 393 describes the use of compounds of type 1 b,
21
[0028] where D is a C.sub.1-C.sub.4-alkyl group, and compounds of
the formula 2 in brightener dispersions. The compounds of type 1 b
or 2 are disclosed either by themselves or as specific mixtures,
referred to in the cited reference as mixtures 1 to 6 (pages 6-8).
In EP-A 0 321 393 it is stated at page 9 line 18 that it is
essential to the invention that the mixture contain a copolymer of
2-vinylpyrrolidone with 3-vinylpropionic acid.
[0029] In EP-A 0 682 145 the lightfastness of textiles is improved
by treating them with formulations containing a fluorescent UV
absorber which absorbs at a wavelength of from 280 to 400 nm and is
selected from 4,4'-bistriazinylaminostilbene-2,2'-disulfonic acids,
4,4'-diphenylstilbenes, 4,4'-distyrylbiphenyls,
4-phenyl-4'-benzoxazylsti- lbenes, stilbenylnaphthotriazoles,
4-styrylstilbenes, coumarins, pyrazolines, naphthalimides,
triazinylpyrenes, 2-styrylbenzoxazole or 2-styrylnaphthoxazole
derivatives, benzimidazolebenzofurans, oxanilide derivatives and
bisbenzoxazol-2-yl and bisbenzimidazol-2-yl derivatives, for
example of the formulae 1 c or 1 d (claim 8), 22
[0030] where
[0031] each R.sup.14 is independently hydrogen or
C.sub.1-C.sub.4-alkyl or tert-butyl or --C(CH.sub.3).sub.2-phenyl
or COO--C.sub.1-C.sub.4-alkyl
[0032] R.sup.15 and R.sup.16 are the same or different and selected
from H, C.sub.1-C.sub.4-alkyl and CH.sub.2--CH.sub.2--OH,
[0033] each R.sup.17 is the same or different and selected from H
and SO.sub.3.sup.-
[0034] X is selected from 23
[0035] and X.sup.1 is selected from 24
[0036] However, lightfastness improvement is usually governed by
other factors than play a part in the optical brightening of
textiles.
[0037] A bright white is of immense economic importance in relation
to a very wide variety of products, for example in relation to
textiles and in relation to shaped plastics articles. The
above-demonstrated numerous mixtures, especially the mixtures
demonstrated in the examples of EP-A 0 023 026 and EP-A 0 023 028
and also EP-A 0 682 145, exhibit a white which is frequently not
sufficiently bright for demanding customers. Moreover, further
performance characteristics have room for improvement. Finally, it
is desirable for economic reasons for brighteners to be more
efficient in that less brightener is needed to achieve the same or
a greater effect.
[0038] It is an object of the present invention to provide
[0039] a process for brightening textile materials which provides a
particularly bright white coupled with improved efficiency and
otherwise likewise improved performance characteristics;
formulations for a process for brightening textile materials
and
[0040] uses for the new formulations.
[0041] We have found that this object is achieved by the process
defined at the beginning.
[0042] Textile materials for the purposes of the present invention
include fibers, slivers, yarns, threads, wovens, knits, nonwovens
and garments composed for example of polyester or polyester blends.
The textile materials are preferably composed of synthetic
polyesters or of blends containing from 45 to 90% by weight of
polyester.
[0043] Brightening or optically brightening compounds for the
purposes of the present invention are fluorescent compounds which
are capable of absorbing in the range from 280 to 400 nm and of
emitting at a higher wavelength. Examples include compounds from
the class of the stilbenes, distyrylbenzenes, diphenyldistyryls,
triazinyls, benzoxazoles, bisbenzoxazoles,
bisbenzoxazolylthiophenes, bisbenzoxazolylnaphthalenes, pyrenes,
coumarins and naphthaleneperidicarboximides. Brightening or
optically brightening compounds shall refer especially to
brightening or optically brightening compounds of the formulae I,
II and III. Weight percentages shall hereinafter be based on the
sum total of the brightening compounds, unless expressly stated
otherwise.
[0044] The term "aqueous liquors" as used herein also comprehends
liquors which, as well as water as main constituent, contain up to
40% by volume of one or more further solvents, for example alcohols
such as ethanol. The pH of the liquors used according to the
present invention is preferably in the range from 3 to 12 and more
preferably in the range from 3 to 8.
[0045] The processed defined at the beginning is embodied by
treating textile materials with from 20 to 80% and preferably from
20 to 70% by weight and more preferably from 30 to 50% by weight of
the compound of the formula I 25
[0046] of which up to 40 mol % may be in the form of the
corresponding cis isomer, and also from 80 to 20% by weight of at
least one of the compounds II 26
[0047] and also from 0 to 30% by weight of a compound of the
general formula III 27
[0048] where R is selected from C.sub.4-C.sub.10-alkyl, for example
n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl,
sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,
isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl,
n-nonyl and n-decyl; preference is given to n-butyl and
2-ethylhexyl.
[0049] It is preferable, as well as from 20 to 80% by weight of the
compound I, to use:
[0050] from 0 to 30% by weight of a compound of the general formula
III and from 20 to 70% by weight each of at least one of the
compounds II p,o' or m,p'.
[0051] Particular preference is given to using from 20 to 70% by
weight of the compound II p,o' and from 10 to 50% by weight of the
compound m,p'
[0052] as well as from 20 to 70% by weight of the compound I and
from 0 to 30% by weight of a compound of the general formula
III.
[0053] Another particularly preferred embodiment, as well as from
30 to 50% by weight of compound I and from 0 to 30% by weight of a
compound of the general formula III, utilizes
[0054] from 30 to 60% by weight of the compound II p,o',
[0055] from 10 to 30% by weight of the compound II o,o' and
optionally
[0056] from 10 to 50% by weight of the compound m,p'.
[0057] The compound I is synthesized for example as described in
U.S. Pat. No. 2,842,545, U.S. Pat. No. 2,875,089 or U.S. Pat. No.
3,147,253. For the purposes of the present invention, the
definition of I also comprehends such isomer mixtures as contain
from 0.2 to 40 mol % and preferably fromn 0.7 to 20 mol % of cis
isomer. The fraction of cis isomer is determined by spectroscopic
or chromatographic methods familiar to one skilled in the art, see
for example J. Chromat. 1967, 27 (2), 413-22.
[0058] The dicyanostyryl compounds II p,o', II m,p', II p,p' and II
o,o' are used in the form of their trans isomers. They customarily
contain from 0.01 to 10 and preferably from 0.1 to 5 mol % of
isomers having at least one cis double bond, the fraction of cis
isomers being determined by spectroscopic methods known to one
skilled in the art. They are readily obtainable from
terephthaldicarboxaldehyde and the corresponding cyanobenzyl
phosphorylides by a twofold Wittig reaction.
[0059] In the practice of the process according to the present
invention, it may be advantageous to add one or more blue or violet
shading dyes. Useful shading dyes generally belong to the class of
disperse dyes and vat dyes. These are customary designations. The
Colour Index lists such dyes for example as Disperse Blue or
Disperse Violet or Vat Blue or Vat Violet.
[0060] Blue dyes from the class of the anthraquinones, azo dyes or
methine dyes are particularly suitable.
[0061] Dyes from the class of the anthraquinones conform for
example to the formulae A 1 to A 4 28
[0062] where
[0063] Z.sup.1 is C.sub.1-C.sub.10-alkyl with or without
interruption by 1 or 2 oxygen atoms in ether function and with or
without C.sub.1-C.sub.4-alkoxycarbonyl or cyano substitution or
phenl with or without C.sub.1-C.sub.4-alkoxy, phenyl,
substitution,
[0064] Z.sup.2 is C.sub.1-C.sub.10-alkyl with or without
interruption by 1 or 2 oxygen atoms in ether function and with or
without hydroxyl, phenyl or C.sub.1-C.sub.8-alkoxycarbonyl
substitution,
[0065] Z.sup.3 is oxygen or N--H,
[0066] Z.sup.4 is hydrogen, C.sub.1-C.sub.10-alkyl with or without
interruption by 1 or 2 oxygen atoms in ether function and with or
without C.sub.1-C.sub.4-alkoxycarbonyl or cyano substitution or
unsubstituted or C.sub.1-C.sub.4-alkoxy-substituted phenyl,
[0067] Z.sup.5 is hydrogen or halogen or CN,
[0068] Z.sup.6 is hydrogen or nitro, and
[0069] Z.sup.7 is C.sub.2-C.sub.6-alkylene or phenylene.
[0070] The abovementioned dyes are generally known dyes. Dyes of
the formula A2 are described for example in U.S. Pat. No.
2,628,963, U.S. Pat. No. 3,835,154, DE-A 12 66 425 or DE-A 20 16
794. Dyes conforming to the formulae A1, A3 and A4 are known for
example from K. Venkataraman, "The Chemistry of Synthetic Dyes",
Volume 3, pages 391 to 423, 1970.
[0071] Suitable azo dyes are in particular monoazo dyes having a
diazo component of the aniline or heterocyclic series and a
coupling component of the aniline or heterocyclic series.
[0072] Suitable heterocycles from which the diazo components are
derived come for example from the class of the aminothiophenes,
aminothiazoles, aminoisothiazoles, aminothiadiazoles or
aminobenzisothiazoles.
[0073] Suitable heterocycles from which the coupling components are
derived come for example from the class of the thiazoles or
diaminopyridines.
[0074] More particularly, such azo dyes conform to one of the
formulae B 1 to B 7 2930
[0075] where
[0076] Z.sup.8 is formyl, cyano, C.sub.1-C.sub.4-alkoxycarbonyl or
phenylsulfonyl,
[0077] Z.sup.9 is hydrogen, halogen, C.sub.1-C.sub.8-alkoxy,
phenoxy, C.sub.1-C.sub.6-alkylthio, phenylthio,
C.sub.1-C.sub.4-alkylsulfonyl, phenylsulfonyl, methyl or
unsubstituted or chlorine-, methoxy-, ethoxy- or methyl-substituted
phenyl,
[0078] Z.sup.10 is cyano, C.sub.1-C.sub.6-alkoxycarbonyl with or
without interruption by one or two oxygen atoms in ether function
in the alkyl chain, carbamoyl or mono- or
di-C.sub.1-C.sub.4-alkylcarbamoyl,
[0079] Z.sup.11 and Z.sup.12 are independently
C.sub.1-C.sub.8-alkyl with or without interruption by from 1 to 3
oxygen atoms in ether function and with or without hydroxyl, cyano,
chlorine, phenyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkoxycarbonyl, C.sub.1-C.sub.6-alkoxycarbonyloxy
or mono- or di-C.sub.1-C.sub.6-alkylami- nocarbonyloxy substitution
or C.sub.3-C.sub.4-alkenyl or else in the case of Z.sup.11 but not
in the case of Z.sup.12 hydrogen,
[0080] Y.sup.1 is hydrogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy, chlorine, bromine or a radical of the
formula --NH--CO--R.sup.11, where R.sup.11 is C.sub.1-C.sub.4-alkyl
with or without C.sub.1-C.sub.4-alkoxy, cyano, hydroxyl, chlorine
or C.sub.1-C.sub.4-alkanoyloxy substitution or
C.sub.2-C.sub.3-alkenyl,
[0081] Y.sup.2 is hydrogen, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-alkoxy,
[0082] Z.sup.13 is unsubstituted or
C.sub.1-C.sub.4-alkoxy-substituted C.sub.1-C.sub.4-alkyl,
unsubstituted or C.sub.1-C.sub.4-alkoxy-substitute- d benzyl,
unsubstituted or chlorine-, methyl-, methoxy- or ethoxy-substituted
phenyl, 2-pyridyl or 3-pyridyl,
[0083] Z.sup.14 is cyano, chlorine or bromine,
[0084] Z.sup.15 is unsubstituted or C.sub.1-C.sub.4-alkoxy- or
acetylamino-substituted thienyl or pyridyl, and
[0085] Z.sup.16 is cyano, chlorine or bromine.
[0086] The abovementioned azo dyes are known per se. Dyes of the
formulae B1 and B2 are described for example in U.S. Pat. No.
5,283,326 or U.S. Pat. No. 5,145,952. EP-A 0 087 616, EP-A 0 087
677, EP-A 0 121 875, EP-A 0 151 287 and U.S. Pat. No. 4,960,873
disclose dyes of the formula B3. U.S. Pat. No. 5,216,139 discloses
dyes of the formula B4. U.S. Pat. No. 5,132,412 discloses dyes of
the type of the formula B5. Dyes of the formulae B6 and B7 are
described for example in U.S. Pat. No. 3,981,883, DE-A 31 12 427,
EP-A 0 064 221 or in Venkataraman "The Chemistry of Synthetic
Dyes", Volume 3, pages 444 to 447, or are obtainable by the methods
mentioned therein.
[0087] Suitable methine dyes conform for example to the formula C
31
[0088] where
[0089] Y.sup.3 is nitrogen or CH,
[0090] Z.sup.18 is C.sub.1-C.sub.20-alkyl with or without
substitution and with or without interruption by one or more oxygen
atoms in ether function, substituted or unsubstituted phenyl or
hydroxyl,
[0091] Z.sup.19 is a 5-membered aromatic heterocyclic radical,
[0092] Z.sup.20 is hydrogen, cyano, carbamoyl, carboxyl or
C.sub.1-C.sub.4-alkoxycarbonyl,
[0093] Z.sup.21 is oxygen or a radical of the formula C(CN).sub.2,
C(CN)COOZ.sup.23 or C(COOZ.sup.23).sub.2, where Z.sup.23 is in each
case C.sub.1-C.sub.8-alkyl with or without interruption by 1 or 2
oxygen atoms in ether function,
[0094] Z.sup.22 is hydrogen or C.sub.1-C.sub.4-alkyl.
[0095] Substituted alkyl in the formula C may have as substituents
for example, unless otherwise stated, phenyl,
C.sub.1-C.sub.4-alkylphenyl, C.sub.1-C.sub.4-alkoxyphenyl,
halophenyl, C.sub.1-C.sub.8-alkanoyloxy,
C.sub.1-C.sub.8-alkylaminocarbonyloxy,
C.sub.1-C.sub.20-alkoxycarbonyl, C.sub.1-C.sub.20-alkoxycarbonyloxy
(the alkyl chain in the last two radicals mentioned being
optionally interrupted by from 1 to 4 oxygen atoms in ether
function and/or substituted by phenyl or phenoxy), halogen,
hydroxyl or cyano. The number of substituents in substituted alkyl
is generally 1 or 2.
[0096] Alkyl radicals appearing in the formula C which are
interrupted by oxygen atoms in ether function are preferably,
unless otherwise stated, alkyl radicals which are interrupted by
from 1 to 4 oxygen atoms and especially by 1 or 2 oxygen atoms in
ether function.
[0097] Substituted phenyl or pyridyl appearing in the formula C may
have as substituents for example C.sub.1-C.sub.8-alkyl,
C.sub.1-C.sub.8-alkoxy, halogen, especially chlorine or bromine, or
carboxyl. The number of substituents in substituted phenyl or
pyridyl is generally from 1 to 3.
[0098] Z.sup.19 radicals can be derived for example from components
of the pyrrole, thiazole, thiophene or indole series.
[0099] Important Z.sup.19 radicals include for example those of the
formulae C 1 to C 4 32
[0100] where
[0101] m is 0 or 1,
[0102] Z.sup.24 and Z.sup.25 are the same or different and are each
independently hydrogen or C.sub.1-C.sub.20-alkyl with or without
substitution and with or without interruption by one or more oxygen
atoms in ether function, substituted or unsubstituted phenyl or
combined with the interjacent nitrogen atom to form a 5- or
6-membered saturated heterocyclic radical with or without further
heteroatoms,
[0103] Z.sup.26 is hydrogen, halogen, C.sub.1-C.sub.8-alkyl,
unsubstituted or C.sub.1-C.sub.4-alkyl- or
C.sub.1-C.sub.4-alkoxy-substituted phenyl, unsubstituted or
C.sub.1-C.sub.4-alkyl- or C.sub.1-C.sub.4-alkoxy-substit- uted
benzyl, cyclohexyl, thienyl, hydroxyl or
C.sub.1-C.sub.8-monoalkylami- no,
[0104] each Z.sup.27 is the same or different and independently
represents hydrogen, hydroxyl, unsubstituted or phenyl- or
C.sub.1-C.sub.4-alkylphen- yl-substituted C.sub.1-C.sub.8-alkyl,
unsubstituted or phenyl- or C.sub.1-C.sub.4-alkylphenyl-substituted
C.sub.1-C.sub.8-alkoxy, C.sub.1-C.sub.8-alkanoylamino,
C.sub.1-C.sub.8-alkylsulfonylamino or mono- or
di-C.sub.1-C.sub.8-alkylaminosulfonylamino,
[0105] Z.sup.28 is cyano, carbamoyl, mono- or
di-C.sub.1-C.sub.8-alkylcarb- amoyl, C.sub.1-C.sub.8-alkoxycarbonyl
or substituted or unsubstituted phenyl, and
[0106] Z.sup.29 is halogen, hydrogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio, unsubstituted or
C.sub.1-C.sub.4-alkyl- or C.sub.1-C.sub.4-alkoxy-substituted phenyl
or thienyl.
[0107] Such methine dyes are described for example in prior German
patent application DE-A 44 03 083.
[0108] Of particular importance is a process wherein the polyester
or polyester blends are treated in the presence of one or more blue
or violet shading dyes from the class of the anthraquinones,
especially those of the formula A.
[0109] The process works technically particularly well when
practised in the presence of the dye of the formula A 3.1 33
[0110] which is also known under the name C.I. Disperse Violet 28
(61102).
[0111] The brightening compounds are used according to the present
invention in an amount of from 0.005 to 0.07% and preferably from
0.02 to 0.05% by weight, based on the weight of the textile
material to be brightened, and provide a white effect which is the
same as or superior to that provided by prior art optically
brightening materials.
[0112] The amount of blue or violet shading dye used is generally
in the range from 0.00005 to 0.02% by weight and preferably in the
range from 0.005 to 0.002% by weight, based on the weight of the
textile material to be brightened. But the use of the shading dye
is not obligatory.
[0113] The textile materials are generally brightened by the
exhaust process or by the thermosol process.
[0114] The exhaust process is carried out from an aqueous liquor
mostly at from 90 to 135.degree. C. and usually at around
130.degree. C. In the case of application at above 100.degree. C.,
an autoclave, a high pressure apparatus or a high pressure machine
has to be used. The thermosol process is carried out at atmospheric
pressure.
[0115] The exhaust process is generally carried out by introducing
the textile material to be brightened into an aqueous liquor
containing the optically brightening compounds, optionally a blue
or violet shading dye or a mixture thereof and optionally
additives, for example dispersants, carboxylic acids or alkali
donors and whose pH is usually in the range from 3 to 12 and
preferably in the range from 3 to 8, at from 10 to 35.degree. C.
The liquor ratio (weight ratio of liquor to textile material) is in
the range from 3:1 to 40:1 and preferably in the range from 5:1 to
20:1. The bath is then heated over 15-30 minutes to 90-130.degree.
C., preferably 95-100.degree. C., and maintained at that
temperature for 15-60 minutes. Thereafter, the brightened textile
material is rinsed and dried.
[0116] In the thermosol process, the textile material to be
brightened is customarily pad-mangled with an aqueous liquor
containing the optically brightening substances, optionally a blue
or violet shading dye or mixtures thereof and optionally additives
(see above). The wet pickup is generally in the range from 50 to
100%. Thereafter, the textile material is dried and fixed at from
150 to 200.degree. C. for from 5 to 60 seconds.
[0117] The dispersants used are preferably dispersants which are
colorless and stable to yellowing at up to 210.degree. C. at
least.
[0118] Examples of particularly suitable dispersants are anionic or
nonionic dispersants, especially anionic or nonionic dispersants
from the class of the ethylene oxide adducts with fatty alcohols,
higher fatty acids or alkylphenols or ethylenediamine-ethylene
oxide-propylene oxide adducts.
[0119] Particularly preferred dispersants are alkoxylation products
which, based on aliphatic or alkylaromatic hydroxy, amino or
aminohydroxy compounds, are commercially available under the brand
names Synperonic.RTM. and Ukanil.RTM., Dehypon.RTM., Neopol.RTM.
ethoxylates, Emulan.RTM., Lutensol.RTM., Plurafac.RTM. and
Pluronic.RTM. or Elfapur.RTM.. Particular preference is given to
alkoxylated phenols. Dispersants which are very particularly
preferred are alkoxylated phenols of the general formulae IV and V
34
[0120] where
[0121] a and b are integers such that
[0122] a is in the range from 0 to 180 and preferably from 0 to
125,
[0123] b is in the range from 20 to 180 and especially from 35 to
125, with the proviso that b.gtoreq.a;
[0124] M is an alkali metal, preferably Na or K and more preferably
Na;
[0125] d is 0 or 1;
[0126] or mixtures thereof.
[0127] The preparation of the compounds IV and V is known and is
advantageously effected by reacting the phenols VI and VII
respectively 35
[0128] with propylene oxide and subsequent reaction of the adduct
with ethylene oxide or by reacting VI and VII respectively with
ethylene oxide. It is then possible to completely or partially
convert the adducts with chlorosulfonic acid or sulfur trioxide
into acid sulfuric esters and for the acid esters obtained to be
neutralized with alkalis.
[0129] The phenols of the formula VI or VII can be obtained by
reacting bisphenol A (2,2-(p,p'-bishydroxydiphenyl)propane) or
phenol with respectively 4 or 2 mol of styrene in the presence of
an acid as a catalyst. The phenols VI and VII are converted by
known methods first with propylene oxide and then with ethylene
oxide or only with ethylene oxide in the presence of acidic or
alkaline catalysts, for example with NaOCH.sub.3 or with
SbCl.sub.5, into the corresponding alkoxylation products IV and V
respectively where d=0. The alkoxylation can be effected for
example by the process described in U.S. Pat. No. 2,979,528.
[0130] The acid sulfuric esters are prepared by reacting the
alkoxylation products with chlorosulfonic acid or sulfur trioxide,
the amount of chlorosulfonic acid or sulfur trioxide being chosen
so as to sulfate all the free hydroxyl groups or only a certain
percentage thereof. The latter case gives rise to mixtures of
compounds of the formula IV or V which contain free and sulfated
hydroxyl groups. For use as surfactants, the as-synthesized acid
esters of sulfuric acid are converted into water-soluble salts.
Water-soluble salts which are advantageous include the alkali metal
salts, for example the sodium or potassium salts. Chlorosulfonic
acid requires two equivalents and sulfur trioxide one equivalent of
alkaline compound. The alkaline compound used is advantageously
aqueous alkali metal hydroxide. A temperature of 70.degree. C.
should not be exceeded in the neutralization. The salts obtained
can be used in the form of aqueous solutions or else isolated as
such and used in solid form.
[0131] Preference is given to dispersants IV and V where a is from
0 to on average 2.5, b is on average from 25 to 250 and d is from 0
to on average 0.5. Particular preference is given to dispersants IV
and V where a is from 0 to on average 2.5, b is on average from 50
to 100 and d is on average 0.5.
[0132] Compounds of the formulae IV and V are known and numerous
representatives are described in U.S. Pat. No. 4,218,218 for
example.
[0133] Additives optionally to be added further include for example
the biocides or water retention aids customarily used in the
textile industry. Additives optionally to be added further include
the copolymers of N-vinylpyrrolidone with 3-vinylpropionic acid
which are described in EP-A 0 321 393.
[0134] A preferred embodiment of the process utilizes a formulation
which, as well as water, contains (each percentage being based on
the weight of the formulation) from 1 to 40% by weight and
preferably from 3 to 10% by weight of the above-particularized
mixture of brightener and shading dye, from 3 to 12% by weight of
anionic or nonionic dispersant, from 1 to 15% by weight of
copolymers of N-vinylpyrrolidone with vinyl acetate or vinyl
propionate or mixtures thereof and from 1 to 25% by weight of
further additives (e.g. water retention aids or biocides).
[0135] The process of the present invention provides excellent
white effects on textile materials not only in the exhaust process
but also in the thermosol process. The brightened materials have
excellent service fastnesses.
[0136] The above-described aqueous liquor may be prepared by
separate metering of the individual predispersed optically
brightening substances and also of each or every optionally
employed shading dye, dispersant and/or other additive.
[0137] However, the process of the present invention is preferably
carried out by applying optically brightening compounds and
optionally one or more of the above-described shading dyes,
dispersants and other additives as a formulation. The present
invention accordingly further provides formulations comprising from
20 to 80% by weight, each percentage being based on the sum total
of all brightening compounds, of the compound I,
[0138] from 20 to 80% by weight of at least one compound II,
[0139] from 0 to 30% by weight of at least one compound of the
formula III
[0140] and also in each case optionally
[0141] one or more blue or violet shading dyes from the class of
the anthraquinones, azo dyes, methine dyes, violanthrones or
indanthrones,
[0142] one or more dispersants, water and further additives.
[0143] Formulations according to the present invention generally
contain water and (each percentage being based on the weight of the
formulation) from 1 to 40% by weight and preferably from 3 to 25%
by weight of the above-particularized mixtures of brightened
compounds, optionally from 0.001 to 0.1% by weight of shading dye,
optionally from 0.5 to 40% by weight of dispersant and also from 5
to 60% by weight and preferably from 5 to 52% by weight of
additives.
[0144] The present invention further provides for the use of the
formulation according to the present invention for brightening
textile materials, especially polyester or polyester blends.
[0145] The examples hereinbelow illustrate the invention.
GENERAL DESCRIPTION
[0146] The isomer distribution was as follows: I trans-cis, 95:5
mol %; II p,o', II mp', II o,o', each above 95 mol % of trans, each
determined by .sup.1H NMR spectroscopy.
[0147] 1. High-Temperature Exhaust Process
[0148] 100 liters of a dyebath in an autoclave containing the total
concentration of brightening compounds reported in Table 1, which
were individually dispersed ("finished") in water and then added,
were entered at 25.degree. C. with 10 kg of polyester fabric. The
bath was then heated to 130.degree. C. over 30 minutes and
maintained at 130.degree. C. for a further 30 minutes. The fabric
was then removed from the bath, rinsed and dried. The optical CIE
whiteness was determined for analysis in each case.
[0149] Comparative (V) tests each utilized a mixture of 50% by
weight of II o,p' and 50% by weight of 4 b.1 36
[0150] from Table 2 of EP 0 023 026.
1TABLE 1 Brightening of polyester fabric with various mixtures of
optical brightening compounds by the exhaust process Total concen-
Brightening compounds tration CIE [% by weight] in white- No. I II
p, o' II m, p' 4 b.I liquor ness 1.1 45 55 -- -- 0.02 147 1.2 45 55
-- -- 0.03 155 1.3 45 55 -- -- 0.057 166 1.4 45 55 -- -- 0.077 167
1.5 45 55 -- -- 0.095 167 1.6 40 40 20 -- 0.02 150 1.7 40 40 20 --
0.03 158 1.8 40 40 20 -- 0.057 164 1.9 40 40 20 -- 0.077 169 1.10
40 40 20 -- 0.095 169 V 1.11 -- 50 -- 50 0.02 145 V 1.12 -- 50 --
50 0.03 153 V 1.13 -- 50 -- 50 0.057 163 V 1.14 -- 50 -- 50 0.077
163 V 1.15 -- 50 -- 50 0.095 163
[0151] The process of the present invention provides in each case a
stronger effect than prior art processes while using a smaller
amount of brightening compound. Similarly, the process of the
invention achieves a peak brightening effect at lower
concentrations of optically brightening substances.
[0152] 2. Thermosol Process
[0153] Inventive examples 2.1 to 2.8 were carried out by
pad-mangling polyester fabric at room temperature with an aqueous
liquor containing a total of 0.8 g/l of optically brightening
compounds of the hereinbelow reported composition. The pH was
adjusted to 5.5 with acetic acid. The wet pickup was 60%. The
fabric was then dried at 110.degree. C. for 20 s and thereafter
fixed for 30 seconds at the temperature shown in Table 2.
[0154] The comparative examples V 2.9 to V 2.12 were carried out in
a similar fashion, except that 0.8 g/l of liquor was used of a
mixture of 50% by weight II o,p' and 50% by weight of 37
[0155] from Table 2 of EP 0 023 026.
[0156] The comparative examples V 2.13 to V 2.16 were carried out
similarly to the inventive examples, except that 1.5 g/l of a
mixture of 70% by weight of II o,p' and 30% by weight of II o,o'
was used.
2TABLE 2 Brightening of polyester fabric with various mixtures of
optically brightening compounds by the thermosol process; fixing at
different temperatures. Fixing Brightening compounds temp- CIE [%
by weight] erature white- No. I II p, o' II m, p' II o, o' 4 b.l
[.degree. C.] ness 2.1 45 55 -- -- -- 140 133 2.2 45 55 -- -- --
150 139 2.3 45 55 -- -- -- 160 142 2.4 45 55 -- -- -- 170 144 2.5
40 40 20 -- -- 140 135 2.6 40 40 20 -- -- 150 139 2.7 40 40 20 --
-- 160 142 2.8 40 40 20 -- -- 170 143 V 2.9 -- 50 -- -- 50 140 128
V 2.10 -- 50 -- -- 50 150 132 v 2.l1 -- 50 -- -- 50 160 136 v 2.12
-- 50 -- -- 50 170 137 v 2.13 -- 70 -- 30 -- 140 130 V 2.14 -- 70
-- 30 -- 150 135 V 2.15 -- 70 -- 30 -- 160 136 v 2.16 -- 70 -- 30
-- 170 140
[0157] The process of the present invention provides a stronger
effect at the same fixing temperature using a smaller or the same
amount of optically brightening compound.
* * * * *