U.S. patent application number 10/470265 was filed with the patent office on 2004-04-22 for method for providing textile material with uv protection.
Invention is credited to Detering, Jurgen, Heidenfelder, Thomas, Wagenblast, Gerhard.
Application Number | 20040074012 10/470265 |
Document ID | / |
Family ID | 7672904 |
Filed Date | 2004-04-22 |
United States Patent
Application |
20040074012 |
Kind Code |
A1 |
Heidenfelder, Thomas ; et
al. |
April 22, 2004 |
Method for providing textile material with uv protection
Abstract
A method for UV protecting a textile material which comprises
applying (a) zinc oxide and/or titanium oxide as a component A and
(b) one or more organic UV absorbers as a component B to said
textile material. Component B preferably comprises one or more
compounds selected from the group consisting of
phenylbenzotriazoles, dibenzoylmethanes, esters of p-aminobenzoic
acid, esters of cinnamic acid, esters of salicylic acid,
nonnitrogenous 2-hydroxybenzophenones, phenylbenzimidazoles,
acrylates, diarylbutadienes, amino-substituted
hydroxybenzophenones, triazines.+
Inventors: |
Heidenfelder, Thomas;
(Romerberg-Mechtersheim, DE) ; Detering, Jurgen;
(Limburgerhof, DE) ; Wagenblast, Gerhard;
(Wachenheim, DE) |
Correspondence
Address: |
Oblon Spivak McClelland Maier & Neustadt
Fourth Floor
1755 Jefferson Davis Highway
Arlington
VA
22202
US
|
Family ID: |
7672904 |
Appl. No.: |
10/470265 |
Filed: |
August 6, 2003 |
PCT Filed: |
February 5, 2002 |
PCT NO: |
PCT/EP02/01179 |
Current U.S.
Class: |
8/115.51 |
Current CPC
Class: |
C11D 3/001 20130101;
D06M 13/2035 20130101; D06M 13/358 20130101; C11D 3/1213 20130101;
D06M 2200/25 20130101; D06M 13/335 20130101; C11D 3/42 20130101;
D06M 13/352 20130101; D06M 13/1845 20130101; D06M 11/44 20130101;
D06M 13/12 20130101; D06M 13/184 20130101; C11D 1/62 20130101; D06M
13/224 20130101; D06M 11/46 20130101; C11D 3/0015 20130101 |
Class at
Publication: |
008/115.51 |
International
Class: |
D06M 010/00 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 6, 2001 |
DE |
10105143.3 |
Claims
We claim:
1. A method for UV protecting a textile material, which comprises
applying (a) zinc oxide and/or titanium oxide as a component A and
(b) one or more organic UV absorbers as a component B to said
textile material.
2. A method as claimed in claim 1, wherein said component A
comprises UV absorbers having an absorption maximum in the range
from 280 to 450 nm.
3. A method as claimed in claim 1 or 2, wherein said component B
comprises one or more compounds selected from the group consisting
of phenylbenzotriazoles, dibenzoylmethanes, esters of
p-aminobenzoic acid, esters of cinnamic acid, esters of salicylic
acid, nonnitrogenous 2-hydroxybenzophenones, phenylbenzimidazoles,
acrylates, diarylbutadienes, amino-substituted
hydroxybenzophenones, triazines.
4. A method as claimed in any of claims 1 to 3, wherein the weight
ratio of said component A to said component B is in the range from
20:1 to 1:10.
5. A method as claimed in any of claims 1 to 4, wherein said
components A and B are applied to said textile material in the form
of an aqueous liquor containing said components A and B alongside
further ingredients.
6. A method as claimed in any of claims 1 to 5, wherein said
components A and B are applied to said textile material in the
course of textile finishing during the manufacture of said textile
material, in the course of laundering and/or in the course of
laundry aftertreatment.
7. A laundry detergent formulation comprising from 0.01 to 20% by
weight, based on their total, of said components A and B as defined
in any of claims 1 to 4 as well as further customary
constituents.
8. A laundry aftertreatment and laundry conditioning formulation
comprising from 0.01 to 20% by weight, based on their total, of
said components A and B as defined in any of claims 1 to 4 as well
as further customary constituents.
9. A laundry aftertreatment and laundry conditioning formulation as
claimed in claim 8, comprising from 1 to 50% by weight of one or
more cationic surfactants selected from the group consisting of
quaternary diesterammonium salts, quaternary tetraalkylammonium
salts, quaternary diamidoammonium salts, amidoamino esters and
imidazolines.
10. A finishing composition for UV protecting a textile material,
comprising a mixture of said components A and B as defined in any
of claims 1 to 4.
11. Textile material comprising a mixture of said components A and
B as defined in any of claims 1 to 4.
12. The use of zinc oxide and/or titanium dioxide together with
organic UV absorbers on textile material to protect the human skin
against harmful UV radiation and/or to protect dyed textile
material against fading.
Description
[0001] This invention relates to a method for UV protecting textile
material, laundry detergent, laundry aftertreatment, and fabric
conditioning formulations, finish compositions for UV protecting
textile material, the thus finished textile material itself and the
use of zinc oxide and/or titanium dioxide together with organic UV
absorbers.
[0002] The harmful effects of the UV content of sunlight on human
skin are not restricted to premature skin aging and the formation
of erythemas (skin reddening, sunburn). Excessively long and
intensive exposure of the skin to UV radiation also raises the risk
of developing skin cancer. The chief culprit responsible for skin
reddening and the increased risk of skin cancer is the UV-B-range
of UV radiation, i.e., the range from about 280 to about 315 nm.
The peak of the erythema action spectrum is located at 308 nm.
[0003] Textiles scatter or absorb UV radiation and so act as a
physical barrier to protect the skin against the harmful effects of
sunlight ("textile skin protection"). However, the skin-protecting
effect of textiles is dependent on many factors such as fiber type,
fabric construction, fabric weight, color, moisture content or
nature of finish. Summer clothing in the form of lightweight and
light-colored cotton textiles offers only slight and hence
inadequate protection against UV radiation.
[0004] An excessive dose of UV radiation may not only cause skin
damage, but is also crucially responsible for sunlight-induced
fading of colored textiles. There is therefore considerable
interest in protecting colored textiles as well as human skin
against the harmful effects of UV radiation.
[0005] It is mainly customary optical brighteners which have
hitherto been used to finish and to protect the textiles themselves
and also for textile skin protection, especially stilbene- and
triazine-based optical brighteners as described for example in EP-A
682 145, GB-A 2 313 375 or EP-A 728 749. But the agents are still
in need of improvement with regard to their efficacy and possess a
number of disadvantages. Significant disadvantages are their poor
formulatability and their inadequate solubility in the respective
application medium.
[0006] WO 97/44422 discloses that sunscreens especially from the
group consisting of phenylbenzotriazoles, dibenzoylmethanes,
p-aminobenzoic esters, cinnamic esters, salicylic esters,
nonnitrogenous 2-hydroxybenzophenones, phenylbenzimidazoles and
2-cyano-3,3-diphenylacry- lic esters and also mixtures
thereof--without the respective mixing ratios being specified,
however--are able to protect dyed textile material against fading.
WO 96/03486 describes essentially the same sunscreens as mentioned
in WO 97/44422 as agents for protecting dyed textile material
against fading. But these agents are likewise still in need of
improvement with regard to their efficacy and possess a number of
disadvantages. An essential disadvantage is the frequently
inadequate UV stability of the abovementioned agents.
[0007] The incorporation of pigments such as titanium dioxide or
zinc oxide in fibers is a tried and tested way of conferring UV
protection on textiles comprising these fibers. Especially
manufactured fibers comprising polyamide, polyester or
polyacrylonitrile are useful for this kind of UV protection.
Cellulose fibers less so.
[0008] JP 03/277699 describes solid detergents, specifically soaps,
containing from 0.1 to 15% by weight of zinc oxide. The soaps
exhibit good UV absorption and possess a deodorizing effect.
[0009] WO 98/42909 describes UV protecting textile fabric by
treatment with inorganic particles in combination with a binder
that are capable of absorbing, reflecting or scattering UV
radiation. These particles may be applied during the washing or
laundering of clothing as well as by other methods.
[0010] It is an object of the present invention to provide UV
absorber systems which are improved in their efficacy and
photostability.
[0011] We have found that this object is achieved by a method for
UV protecting a textile material, which comprises applying
[0012] (a) zinc oxide and/or titanium oxide as a component A
and
[0013] (b) one or more organic UV absorbers as a component B to
said textile material.
[0014] Surprisingly, the combined use of organic UV absorbers and
inorganic pigments comprising zinc oxide and/or titanium dioxide in
textile finishes, laundry detergents or fabric conditioner
compositions leads to a more effective UV protection of the
textiles treated with these compositions than the sole use of the
organic UV absorbers or inorganic pigments. Not only is skin better
and more consistently protected against harmful UV radiation, but
colored fabric is provided with improved protection against UV
induced color fading.
[0015] Component A comprises zinc oxide and/or titanium dioxide as
UV absorbing inorganic pigments. Component A can consist of zinc
oxide or titanium dioxide each on their own or of mixtures of the
two pigments.
[0016] Titanium dioxide can be used in its three crystal forms
rutile, anatase or brookite, with rutile being preferred. The
particle size is generally in the range from 0.01 to 100 .mu.m and
preferably in the range from 0.02 to 0.25 .mu.m.
[0017] Zinc oxide is generally used in a particle size of from 0.01
to 100 .mu.m. The particle size is preferably in the range from
0.02 to 2 .mu.m and more preferably in the range from 0.08 to 0.25
.mu.m.
[0018] The titanium dioxide and zinc oxide pigment particles may be
passivated with a layer of inorganic oxides, especially silicon
dioxide or aluminum oxide. The pigment surface may further be
specifically hydrophilicized or hydrophobicized by treatment with
organic compounds or silicones. Useful surface modifiers include
for example amines, cationic polymers such as amino-containing
polymers, polyols, organophosphates, alkyl phthalates, stearic
acid, lauric acid or silicone oils.
[0019] Examples of very useful surface modifiers are:
[0020] Uvinul.RTM. TiO.sub.2 (from BASF AG),
[0021] Z-COTE.RTM. (from BASF AG) and
[0022] Z-COTE HP1.RTM. (from BASF AG).
[0023] Component B may be commercially available sunscreen having
at least one UV absorption maximum in the range from 280 to 450
nm.
[0024] In a preferred embodiment, component B comprises such
compounds as have at least one UV absorption maximum in the range
from 290 to 375 nm.
[0025] In a further preferred embodiment, component (B) comprises
compounds having at least one UV absorption maximum in the range
from 280 to 315 nm (UV-B range) with an E.sup.1.sub.1 value of at
least 200, especially at least 250, and at least one UV absorption
maximum in the range from 315 to 400 nm (UV-A range) with an
E.sup.1.sub.1 value of at least 200, especially at least 250.
[0026] Organic UV absorbers B have one or more bands in the UV
absorption spectrum. UV absorption maxima for the purposes of the
present invention are the bands belonging to the corresponding
local or absolute maxima in the UV spectrum of the particular
compound, measured in customary organic solvents such as
dichloromethane or methanol at room temperature.
[0027] The E.sup.1.sub.1 value designates the extinction of the
organic UV absorbers B which is measured in solution at a
concentration of 1% by weight and a path length of 1 cm. The
solvent used for this solution is customarily dichloromethane,
although the use of other solvents customary for such UV
measurements does not give fundamentally different values.
[0028] In a further preferred embodiment, the organic UV absorbers
present as component B in the mixture of the invention have an
n-octanol/water partition coefficient log P of at least 1.9,
especially of at least 2.5, in particular of at least 3.3. Log P
can be determined experimentally or arithmetically. Both techniques
are described in Chemical Reviews Volume 71, No. 5, pages 52-5-616
(1971).
[0029] Preference is given to using organic UV absorbers B selected
from the group consisting of
[0030] (I) phenylbenzotriazoles,
[0031] (II) dibenzoylmethanes,
[0032] (III) esters of p-aminobenzoic acid,
[0033] (IV) esters of cinnamic acid,
[0034] (V) esters of salicylic acid,
[0035] (VI) nonnitrogenous 2-hydroxybenzophenones,
[0036] (VII) phenylbenzimidazoles,
[0037] (VIII)acrylates,
[0038] (IX) diarylbutadienes,
[0039] (X) amino-substituted hydroxybenzophenones and
[0040] (XI) triazines.
[0041] Typical UV-absorbing phenylbenzotriazoles (I) are:
[0042] 2,2'-hydroxy-5-methylphenylbenzotriazole,
[0043] 2,2'-hydroxy-5-tert-octylphenylbenzotriazole,
[0044] 2-hydroxy-3-sec-butyl-5-tert-butylbenzotriazole
(Tinuvin.RTM. 350),
[0045] 2-hydroxy-3-dodecyl-5-methylphenylbenzotriazole
(Tinuvin.RTM. 571),
[0046] 2-(2H-benzotriazol-2-yl)-4-methylphenol (Tinuvin.RTM.
P),
[0047] 2-(2H-benzotriazol-2-yl)-4-n-octylphenyl (Tinuvin.RTM.
329),
[0048] 2-(2H-benzotriazol-2-yl)-4,6-di(2'-phenylisopropyl)phenol
(Tinuvin.RTM. 234),
[0049] 2-(2H-benzotriazol-2-yl)-4,6-di(tert-butyl)phenol
(Tinuvin.RTM. 320),
[0050]
2-(6-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol
(Tinuvin.RTM. 326),
[0051] 2-(6-chloro-2H-benzotriazol-2-yl)-2,6-di-tert-butylphenol
(Tinuvin.RTM. 327),
[0052] 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)-2H-benzotriazole
(Tinuvin.RTM. 328),
[0053] mixture of polyoxyethylene glycol
.alpha.-[3-(2H-benzotriazol-2-yl)- -5-tert-butyl-4-hydroxyphenyl]
propionate and polyoxyethylene glycol
bis.beta.-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]
propionate having an average molecular weight>600 (Tinuvin.RTM.
1130),
[0054] cocoyl-2-[2'-hydroxy-3'-(cocoyl
dimethylbutanoate)-5'-methylphenyl]- benzotriazole,
[0055] cocoyl
3-[3'-(2H-benzotriazol-2'-yl)-5-tert-butyl-4'-hydroxyphenyl]-
propionate,
[0056]
2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbu-
tyl)]phenol (Tinuvin.RTM. 360),
[0057]
2-(2H-1,2,3-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3-{1,3,3,3-tetr-
amethyl-1-[(trimethylsilyl)oxy]disiloxanyl}propyl)phenol.
[0058] Typical UV-absorbing dibenzoylmethanes (II) are:
[0059] 3-(4-isopropylphenyl)-3-phenylpropane-1,3-dione
(Eusolex.RTM. 8020),
[0060] 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione
(Uvinul.RTM. BMBM),
[0061] 1,3-bis(4-methoxyphenyl)propane-1,3-dione.
[0062] Typical UV-absorbing esters of p-aminobenzoic acid (II)
are:
[0063] ethyl 4-bis(hydroxypropyl)aminobenzoate
(Amerscheen.RTM.P),
[0064] 2,3-dihydroxypropyl 4-aminobenzoate (Nipa.RTM. GMPA),
[0065] menthyl 2-aminobenzoate (Sunarome.RTM. UVA),
[0066] 2-ethylhexyl 4-dimethylaminobenzoate (Escalol.RTM. 507),
[0067] amyl 4-dimethylaminobenzoate,
[0068] ethyl 4-dimethylaminobenzoate,
[0069] butyl 4-dimethylaminobenzoate,
[0070] octyl 4-dimethylaminobenzoate,
[0071] lauryl 4-dimethylaminobenzoate,
[0072] oleyl 4-dimethylaminobenzoate,
[0073] polyethoxyethyl 4-bis(polyethoxy)-4-aminobenzoate
(Uvinul.RTM. P-25),
[0074] N-propoxylated ethyl 4-aminobenzoate.
[0075] Typical UV-absorbing esters of cinnamic acid (IV) are:
[0076] 2-ethylhexyl 4-methoxycinnamate (Uvinul.RTM. MC80,
Parsol.RTM. MCX),
[0077] 2-ethoxyethyl 4-methoxycinnamate,
[0078] propyl 4-methoxycinnamate,
[0079] isoamyl 4-methoxycinnamate,
[0080] cyclohexyl 4-methoxycinnamate,
[0081] isopropyl 4-methoxycinnamate,
[0082] octyl cinnamate,
[0083] ethyl 4-isopropylcinnamate,
[0084] ethyl .alpha.-cyano-.beta.-phenylcinnamate,
[0085] 2-ethylhexyl .alpha.-cyano-.beta.-phenylcinnamate.
[0086] Typical UV-absorbing esters of salicylic acid (V) are:
[0087] 2-ethylhexyl salicylate (Sunarome.RTM. WMO),
[0088] 3,3,5-trimethylcyclohexyl 2-hydroxybenzoate,
[0089] 3,3,5-trimethylcyclohexyl 2-acetamidobenzoate,
[0090] 2-ethylhexyl 2-(4-phenylbenzoyl)benzoate,
[0091] 4-isopropylbenzyl salicylate,
[0092] amyl salicylate,
[0093] menthyl salicylate,
[0094] homomethyl salicylate,
[0095] phenyl salicylate,
[0096] benzyl salicylate,
[0097] isodecyl salicylate.
[0098] Typical UV-absorbing nonnitrogenous 2-hydroxybenzophenones
(VI) are:
[0099] 2-hydroxy-4-methoxybenzophenone (Uvinul.RTM. M40),
[0100] 2,2'-dihydroxy4-methoxybenzophenone (Spectra-Sorb.RTM.
UV-24),
[0101] 2,4-dihydroxybenzophenone (Uvinul.RTM. 3000),
[0102] 2,2',4,4'-tetrahydroxybenzophenone (Uvinul.RTM. D-50),
[0103] 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (Uvinul.RTM.
D-49),
[0104] 2,2-dihydroxy-4,4-dimethoxybenzophenone (Uvinul.RTM.
3049),
[0105] 2-hydroxy-4-(2-ethylhexyloxy)benzophenone,
[0106] 2-hydroxy-4-(n-octyloxy)benzophenone (Uvinul.RTM. 3008),
[0107] 2-hydroxy-4-methoxy-4'-methylbenzophenone
(Mexenone.RTM.),
[0108] 2-ethylhexyl 4'-phenylbenzophenone-2-carboxylate,
[0109] 2-hydroxy-3-carboxybenzophenone,
[0110] benzophenone-3 cocoyl acetate ether,
[0111] 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (Uvinul.RTM.
MS 40) and its sodium salt,
[0112] 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-bissulfonic
acid and its sodium salt (Uvinul.RTM. DS 49).
[0113] Typical UV-absorbing phenylbenzimidazoles (VII) are:
[0114] 2-phenylbenzimidazole-5-sulfonic acid (Eusolex.RTM. 232) and
its potassium, sodium and triethanolamine salts,
[0115]
2-[5,6-disulfo-(1H-benzimidazol-2-yl)phenyl]-1H-benzimidazole5,6-di-
sulfonic acid.
[0116] Typical UV-absorbing acrylates (VIII) are:
[0117] 3-imidazol-4-ylacrylic acid,
[0118] ethyl 3-imidazol-4-ylacrylate,
[0119] 2-cyano-3-(4-methoxyphenyl)acrylic acid,
[0120] hexyl 2-cyano-3-(4-methoxyphenyl)acrylate.
[0121] Preferred acrylates include C.sub.6- to C.sub.18-alkyl
esters or C.sub.5- to C.sub.8-cycloalkylesters of
2-cyano-3,3-diphenylacrylic acid. The C.sub.6- to C.sub.1-8-alcohol
radical in the cyano-3,3-diphenylacryli- c esters can be linear or
singly or multiply branched, and it can be of natural or synthetic
origin. Such alcohols can be for example fatty alcohols, oxo
alcohols, Ziegler alcohols or Guerbet alcohols. Typical examples of
such compounds are n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl,
n-nonyl, isononyl, n-decyl, n-dodecyl, n-tridecyl, isotridecyl,
n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl
or eicosyl ester. It is also possible for unsaturated alcohol
radicals such as the oleyl, linolyl or linolenyl radical to occur.
Mixtures of such esters can also be present.
[0122] As C.sub.5- to C.sub.8-cycloalkanol radicals in the
cyano-3,3-diphenylacrylic esters there may be mentioned for example
cyclopentyl, 2- or 3-methylcyclopentyl, cyclohexyl, 2-, 3- or
4-methylcyclohexyl, dimethylcyclohexyl, cycloheptyl or cyclooctyl
radicals.
[0123] Preference is given to linear or singly or multiply branched
C.sub.8- to C.sub.13-alkyl esters of 2-cyano-3,3-diphenylacrylic
acid. The corresponding 2-ethylhexyl ester is commercially
available as Uvinul.RTM. N-539 T from BASF Aktiengesellschaft.
[0124] Typical UV-absorbing diarylbutadienes (IX) are especially
4,4-diarylbutadienes of the formula (1) as are described in DE-A
198 28 463 for cosmetic and pharmaceutical preparations: 1
[0125] where the diene system has the Z,Z; Z,E; E,Z or E,E
configuration or a mixture thereof, and where the variables
independently of one another have the following meanings:
[0126] R.sup.1 and R.sup.2
[0127] hydrogen, C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.10-alkenyl,
C.sub.3-C.sub.10-cycloalkyl, C.sub.3-C.sub.10-cycloalkenyl,
C.sub.1-C.sub.12-alkoxy, C.sub.1-C.sub.20-alkoxycarbonyl,
C.sub.1-C.sub.12-alkylamino, C.sub.1-C.sub.12-dialkylamino, aryl,
hetaryl, unsubstituted or substituted, and
[0128] substituents which confer solubility in water and are
selected from the group consisting of carboxylate, sulfonate or
ammonium radicals;
[0129] R.sup.3 hydrogen, COOR.sup.5, COR.sup.5, CONR.sup.5R.sup.6,
CN;
[0130] R.sup.4 COOR.sup.6, COR.sup.6, CONR.sup.5R.sup.6;
[0131] R.sup.5 hydrogen, [X].sub.o-R.sup.7,
C.sub.1-C.sub.6-alkylene-SO.su- b.3Y,
C.sub.1-C.sub.6-alkylene-PO.sub.3Y,
C.sub.1-C.sub.6-alkylene-N(R.sup- .8).sub.3.sup.+A.sup.-;
[0132] R.sup.6 [X].sub.o-R.sup.7,
C.sub.1-C.sub.6-alkylene-SO.sub.3Y,
C.sub.1-C.sub.6-alkylene-PO.sub.3Y,
C.sub.1-C.sub.6-alkylene-N(R.sup.8).s- ub.3.sup.+A.sup.-;
[0133] x --CH.sub.2--CH.sub.2-Z-,
--CH.sub.2--CH.sub.2--CH.sub.2-Z-, --CH(CH.sub.3)--CH.sub.2-Z-,
--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2-Z-,
--CH.sub.2CH(CH.sub.2--CH.sub.3)-Z-;
[0134] A Cl, Br, I, SO.sub.4R.sup.9;
[0135] Y hydrogen, Na.sup.+, K.sup.+, Mg.sup.2+, Ca.sup.2+,
Li.sup.+, A+, N(R.sup.8).sub.4+;
[0136] Z O, NH;
[0137] R.sup.7 and R.sup.8
[0138] hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-acyl;
[0139] R.sup.9 hydrogen, C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl;
[0140] n 1 to 3;
[0141] o 1 to 150.
[0142] With regard to a more particular specification of the
structures of the 4,4-diarylbutadienes of the formula (1) and
examples of such compounds (1), the disclosure in DE-A 198 28 463
is expressly incorporated herein by reference. A typical example of
a representative of such a compound (IX) is
1,1-bis(neopentyloxycarbonyl)-4,4-diphenyl-1,3- -butadiene.
[0143] Typical UV-absorbing amino-substituted hydroxybenzophenones
(X) are in particular those of the formula (2) as are described in
German patent application 199 17 906.9 for cosmetic and
pharmaceutical preparations: 2
[0144] in which the variables independently of one another have the
following meanings:
[0145] R.sup.1 and R.sup.2 are hydrogen, C.sub.1-C.sub.20-alkyl,
C.sub.2-C.sub.10-alkenyl, C.sub.3-C.sub.10-cycloalkyl,
C.sub.3-C.sub.10-cycloalkenyl, where the substituents R.sup.1 and
R.sup.2 together with the nitrogen atom to which they are bonded
can form a 5- or 6-membered ring;
[0146] R.sup.3 and R.sup.4 are C.sub.1-C.sub.20-alkyl,
C.sub.2-C.sub.10-alkenyl, C.sub.3-C.sub.10-cycloalkyl,
C.sub.3-C.sub.10-cycloalkenyl, C.sub.1-C.sub.12-alkoxy,
C.sub.1-C.sub.20-alkoxycarbonyl, C.sub.1-C.sub.1-2-alkylamino,
C.sub.1-C.sub.12-dialkylamino, aryl, heteroaryl, optionally
substituted, and
[0147] substituents which confer solubility in water and are
selected from the group consisting of a nitrile group, carboxylate,
sulfonate or ammonium radicals;
[0148] X is hydrogen, COOR.sup.5, CONR.sup.6R.sup.7;
[0149] R.sup.5 to R.sup.7 are hydrogen, C.sub.1-C.sub.20-alkyl,
C.sub.2-C.sub.10-alkenyl, C.sub.3-C.sub.10-cycloalkyl,
C.sub.3-C.sub.10-cycloalkenyl, --(Y--O).sub.o-Z, aryl;
[0150] Y is --(CH.sub.2).sub.2--, --CH.sub.2).sub.3--,
--(CH.sub.2).sub.4--, --CH(CH.sub.3)--CH.sub.2--;
[0151] Z is --CH.sub.2--CH.sub.3, --CH.sub.2--CH.sub.2--CH.sub.3,
--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.3,
--CH(CH.sub.3)--CH.sub.3;
[0152] m is from 0 to 3;
[0153] n is from 0 to 4;
[0154] o is from 1 to 20.
[0155] With regard to a more particular specification of the
structures of the amino-substituted hydroxybenzophenones of the
formula II and examples of such compounds II, the disclosure in
German patent application 199 17 906.9 is expressly incorporated
herein by reference. A typical example of a representative of such
a compound (X) is n-hexyl 2-(4'-diethylamino-2'-hydroxybenzoyl)
benzoate.
[0156] Typical UV-absorbing triazines (XI) are:
[0157]
2,4,6-trianilino-4-(carbo-2'-ethylhexyl-1'-oxy)-1,3,5-triazine
(Uvinul.RTM. T-150),
[0158] 2-ethylhexyl
4-{[4-{4-[tert-butylamino)carbonyl]anilino}-6(4-{[2-et-
hylhexyl)oxy]carbonyl}
anilino)-1,3,5-triazin-2-yl]amino}benzoate,
[0159]
2-(4-methoxyphenyl)-4,6-di[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-1,3-
,5-triazine.
[0160] Representatives of the compounds (B) of the type (I) to
(VIII) and (XI) are incidentally described in WO 97/44422 and WO
96/03486.
[0161] As well as compounds of type (I) to (XI), useful organic UV
absorbers B further include for example the following:
[0162] 3-(4-methylbenzylidene)boman-2-one (Eusolex.RTM. 6300),
[0163] 5-(3,3-dimethyl-2-norbornylidene)-3-penten-2-one,
[0164] 3-benzylideneboman-2-one,
[0165] digalloyl trioleate,
[0166] 2-hydroxy-1,4-naphthalenedione,
[0167] 5-methyl-2-phenylbenzoxazole, dibenzaldehydeamine,
[0168] dianisoylmethane,
[0169] methyleugenol,
[0170] 2-amino-6-hydroxypurine,
[0171] N-(4-ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine
(Givosorb.RTM. UV 1),
[0172] N-(4-ethoxycarbonylphenyl)-N'-ethyl-N'-phenylformamidine
(Givosorb.RTM. UV2),
[0173] 3-(4'-methylbenzylidene)camphor (Uvinul.RTM. MBC95),
[0174] N.sup.1-(2-ethoxyphenyl)-N
2(2-ethylphenyl)ethanediamide,
[0175]
N.sup.1-(2-ethoxyphenyl)-N-(4-dodectphenyl)ethanediamide,
[0176] 2-ethylhexyl
2-cyano-(3-oxo-2,3-dihydro-1H-isoindol-1-ylidene)ethan- oate,
[0177] 1,1-dicyano-2-(4-butyloxy)phenyl-2-phenylethene.
[0178] Particularly preferred organic UV absorbers B, which are
used together with zinc oxide and/or titanium dioxide, include the
compounds:
[0179] 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione
(Uvinul.RTM. BMBM),
[0180] polyethoxyethyl 4-bis(polyethoxy)-4-aminobenzoate
(Uvinul.RTM. P-25),
[0181] 2-ethylhexyl 4-methoxycinnamate (Uvinul.RTM. MC80),
[0182] 2-hydroxy-4-methoxybenzophenone (Uvinul.RTM. M40),
[0183] 2,4-dihydroxybenzophenone (Uvinul.RTM. 3000),
[0184] 2,2',4,4'-tetrahydroxybenzophenone (Uvinul.RTM. D-50),
[0185] 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (Uvinul.RTM.
D-49),
[0186] 2,2-dihydroxy-4,4-dimethoxybenzophenone (Uvinul.RTM.
3049),
[0187] 2-hydroxy-4-(2-ethylhexyloxy)benzophenone,
[0188] 2-hydroxy-4-(n-octyloxy)benzophenone (Uvinul.RTM. 3008),
[0189] 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid
(Uvinul.RTM.) MS 40) and salts thereof,
[0190] 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-bissulfonic
acid and salts thereof (Uvinul.RTM. DS49),
[0191] 2'-ethylhexyl 2-cyano-3,3-diphenylacrylate (Uvinul.RTM. N
539 T),
[0192] ethyl 2-cyano-3,3-diphenylacrylate (Uvinul.RTM. 3035),
[0193]
1,1-bis(neopentyloxycarbonyl)-4,4-diphenyl-1,3-butadiene,
[0194] n-hexyl 2-(4'-diethylamino-2'-hydroxybenzoyl)benzoate,
[0195]
2,4,6-trianilino-4-(carbo-2'-ethylhexyl-1'-oxy)-1,3,5-triazine
(Uvinul.RTM. T-150),
[0196] 3-(4'-methylbenzylidene)camphor (Uvinul.RTM.) MBC95).
[0197] It may occasionally be of advantage for components A and B
to be used together with antioxidants and/or free-radical traps.
Antioxidants and free-radical traps which may be used here include
all compounds customarily used for stabilizing food and feed but
also for stabilizing plastics or lubricants. A list of such
compounds may be found for example in Kirk-Othmer, Encyclopedia of
Chemical Technology, fourth edition, volume 3, p. 424-447 or in
Ullmann's Encyclopedia of Industrial Chemistry, sixth edition, 2000
Electronic Release, chapters antioxidants and food additives.
[0198] However, they include in particular:
[0199] substituted phenols, hydroquinones, pyrocatechols and
gallates such as 2,6-di-tert-butylphenol,
2,4,6-tri-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol,
2,6-di-tert-butyl-4-methylphenol,
2,6-di-tert-butyl-4-methoxyphenol, 3-tert-butyl-4-methoxyphenol,
2,2'-methylenebis(4-methyl-6-tert-butylphenol), propyl, octyl and
dodecyl gallate or tert-butylhydroquinone (TBHQ), butylated
hydroxyanisoles (BHA) and butylated hydroxytoluene (BHT),
[0200] Irganox.RTM. antioxidants (from Ciba-Geigy) such as
Irganox.RTM. 1010 (tetrakis(methylene
3,5-di-tert-butyl-4-hydroxycinnamate)-methane), Irganox.RTM. 1035
(thiodiethylene bis(3,5-di-tert-butyl-4-hydroxycinnamat- e)) and
Irganox.RTM. 1076 (octadecyl propane(3-benzene-3',5'-di-tert-butyl-
-4'-hydroxybenzyl)phosphonate),
[0201] trihydroxybutyrophenone (THBP),
[0202] .alpha.-tocopherol and its natural or synthetic derivatives
such as acetyl-.alpha.-tocopherol,
[0203] ascorbic acid and ascorbic acid derivatives, especially
esterification products with long-chain fatty acids such as
ascorbyl palmitate,
[0204] diazabicyclooctane (DABCO),
[0205] chroman derivatives such as long-chain esters of
2,5,7,8-tetramethyl-6-hydroxychroman-2 acid,
[0206] aromatic amines such as ethoxyquin,
[0207] organic sulfides such as 3,3'-thiodipropionic acid and
dilauryl thiodipropionate,
[0208] sterically hindered amines, for example of the
tetramethylpiperidine type such as Uvinul.RTM.4049H, Uvinul.RTM.
4050H and Uvinul.RTM. 5050H from BASF AG,
[0209] free radicals of the N-oxyl type such as
4-hydroxytetramethylpiperi- dine N-oxide, esterification products
thereof with carboxylic acids and further derivatives,
[0210] hydroxylamines such as those of dialkylamines and
hydroxylamine ether derivatives of tetramethylpiperidine
compounds,
[0211] ascorbic, lactic, citric and tartaric acids and salts
thereof.
[0212] The inorganic pigments A and organic UV absorbers B
cooperate very well as UV absorbers possessing textile fiber
affinity and mutually reinforce their effect. First, they protect,
when applied to a textile material, the human skin against harmful
UV radiation. Secondly, they protect dyed textile material against
fading. The two protective effects preferably occur
simultaneously.
[0213] Textile materials with which the components A and B have
affinity and where they develop their protective effect include in
particular apparel articles, i.e., articles which are worn on the
human skin, but also house and garden articles comprising dyed
textiles such as awnings and sunshades which are exposed to
intensive solar irradiation. This textile material to be protected
preferably comprises cellulose (cotton), for example apparel
textiles comprising cotton or cotton-polyester blends.
[0214] The present invention also provides for the use of zinc
oxide and/or titanium dioxide together with organic UV absorbers on
textile material to protect human skin against harmful UV radiation
and/or to protect dyed textile material against fading.
[0215] The mixture containing the components A and B is customarily
applied to the textile material in the form of an aqueous liquor
containing the components A and B alongside further ingredients,
for example by spraying or dipping and squeezing off. The
components A and B can be applied to the textile material in the
course of textile finishing during the manufacture of the textile
material, in the course of laundering, in the course of laundry
pretreatment and/or laundry aftertreatment.
[0216] The UV protection factor UPF of the textile material is
increased as a result.
[0217] The UV protection factor or Ultraviolet Radiation Protection
Factor UPF of textiles is determined in accordance with the
Australian/New Zealand standard AS/NZS 4399:1996 using an in vitro
method. It measures the UV transmission of the textile object. The
spectral transmission can be used to determine the protection
factor directly using the following equation: 1 UPF = = 280 n m 400
n m S .times. E .times. = 280 n m 400 n m S .times. E .times. T
[0218] where:
[0219] S.sub..lambda. is the spectral irradiation of the sun in the
UV region at the wavelength .lambda.,
[0220] E.sub..lambda. is the spectral erythema action of the UV
radiation at the wavelength .lambda., and
[0221] T.sub..lambda. is the spectral transmissivity of the textile
object at the wavelength .lambda..
[0222] The present invention also provides a laundry detergent
formulation comprising from 0.01% to 20% by weight, preferably from
0.1% to 10% by weight, particularly preferably from 0.1 to 5% by
weight of the components A and B alongside further customary
ingredients. The weight ratio of component A to component B is
preferably in the range from 20:1 to 1:10, particularly preferably
in the range from 8:1 to 1:5 and specifically preferably in the
range from 3:1 to 1:1. In this connection, the components A and B
can be added separately to the formulation or a ready-prepared
mixture of A and B can be incorporated into the formulation.
[0223] Laundry detergent formulations according to the invention
can be solid or liquid formulations.
[0224] Solid laundry detergent formulations according to the
invention generally include as further customary ingredients
[0225] (c) from 0.1 to 40% by weight of at least one nonionic
and/or anionic surfactant as component C,
[0226] (d) from 0 to 50% by weight of one or more inorganic
builders as component D,
[0227] (e) from 0 to 20% by weight of one or more organic
cobuilders E,
[0228] (f) from 0 to 60% by weight of other customary ingredients
such as cationic surfactants, standardizing agents, enzymes,
perfume, complexing agents, corrosion inhibitors, bleaching agents,
bleach activators, bleach catalysts, dye transfer inhibitors, soil
antiredeposition agents, soil release polyesters, colorants,
dissolution improvers and/or disintegrants as component F,
[0229] components A to F adding up to 100% by weight.
[0230] The solid laundry detergent formulations of the invention
are customarily present in powder, granule, extrudate or tablet
form.
[0231] Liquid laundry detergent formulations according to the
invention generally include as further customary constituents
[0232] (c) from 0.1 to 40% by weight of at least one nonionic
and/or anionic surfactant as component C,
[0233] (d) from 0 to 20% by weight of one or more inorganic
builders as component D,
[0234] (e) from 0 to 10% by weight of one or more organic
cobuilders as component E,
[0235] (f) from 0 to 40% by weight of other customary ingredients
such as cationic surfactants, sodium carbonate, enzymes, perfume,
complexing agents, corrosion inhibitors, bleaching agents, bleach
activators, bleach catalysts, dye transfer inhibitors, soil
antiredeposition agents, soil release polyesters, colorants,
nonaqueous solvents, hydrotropes, thickeners and/or alkanolamines
as component F, and
[0236] (g) from 0 to 99.85% by weight of water as component G,
[0237] components A to G adding up to 100% by weight.
[0238] Useful anionic surfactants are in particular:
[0239] fatty alcohol sulfates of fatty alcohols having from 8 to 22
and preferably from 10 to 18 carbon atoms, for example C.sub.9- to
C.sub.11-alcohol sulfates, C.sub.12- to C.sub.14-alcohol sulfates,
C.sub.12- to C.sub.18-alcohol sulfates, lauryl sulfate, cetyl
sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and
tallow fatty alcohol sulfate;
[0240] sulfated alkoxylated C.sub.8- to C.sub.22-alcohols (alkyl
ether sulfates). Compounds of this kind are prepared for example by
first alkoxylating a C.sub.8- to C.sub.22-alcohol, preferably a
C.sub.10- to C.sub.18-alcohol, for example a fatty alcohol, and
then sulfating the alkoxylation product. The alkoxylation is
preferably carried out using ethylene oxide;
[0241] linear C.sub.8- to C.sub.20-alkylbenzenesulfonates (LAS),
preferably linear C.sub.9- to C.sub.13-alkylbenzenesulfonates and
-alkyltoluenesulfonates,
[0242] alkanesulfonates such as C.sub.8- to C.sub.24- and
preferably C.sub.10- to C.sub.18-alkanesulfonates,
[0243] soaps such as for example the sodium and potassium salts of
C.sub.8- to C.sub.24-carboxylic acids.
[0244] The anionic surfactants mentioned are preferably included in
the laundry detergent in the form of salts. Suitable cations in
these salts are alkali metal ions such as sodium, potassium and
lithium and ammonium ions such as hydroxyethylammonium,
di(hydroxyethyl)ammonium and tri(hydroxyethyl)ammonium.
[0245] Useful nonionic surfactants are in particular:
[0246] alkoxylated C.sub.8- to C.sub.22-alcohols such as fatty
alcohol alkoxylates or oxo alcohol alkoxylates. These may have been
alkoxylated with ethylene oxide, propylene oxide and/or butylene
oxide. Useful surfactants here include all alkoxylated alcohols
which contain at least two molecules of one of the aforementioned
alkylene oxides. Here it is possible to use block polymers of
ethylene oxide, propylene oxide and/or butylene oxide or addition
products which contain the aforementioned alkylene oxides in random
distribution. Nonionic surfactants generally contain from 2 to 50
and preferably from 3 to 20 mol of at least one alkylene oxide per
mole of alcohol. The alkylene oxide component is preferably
ethylene oxide. The alcohols preferably have from 10 to 18 carbon
atoms. Depending on the nature of the alkoxylation catalyst used to
make them, alkoxylates have a broad or narrow alkylene oxide
homologue distribution;
[0247] alkylphenol alkoxylates such as alkylphenol ethoxylates
having C.sub.6- to C.sub.14-alkyl chains and from 5 to 30 alkylene
oxide units;
[0248] alkylpolyglucosides having from 8 to 22 and preferably from
10 to 18 carbon atoms in the alkyl chain and generally from 1 to 20
and preferably from 1.1 to 5 glucoside units;
[0249] N-alkylglucamides, fatty acid amide alkoxylates, fatty acid
alkanolamide alkoxylates and also block copolymers of ethylene
oxide, propylene oxide and/or butylene oxide.
[0250] Useful inorganic builders are in particular:
[0251] crystalline or amorphous aluminosilicates having
ion-exchanging properties such as zeolites in particular. Useful
zeolites include in particular zeolites A, X, B, P, MAP and HS in
their sodium form or in forms in which sodium has been partly
replaced by other cations such as lithium, potassium, calcium,
magnesium or ammonium;
[0252] crystalline silicates such as in particular disilicates or
sheet-silicates, for example .delta.-Na.sub.2Si.sub.2O.sub.5 or
.beta.-Na.sub.2Si.sub.2O.sub.5 The silicates can be used in the
form of their alkali metal, alkaline earth metal or ammonium salts,
preferably as sodium, lithium and magnesium silicates;
[0253] amorphous silicates such as sodium metasilicate or amorphous
disilicate;
[0254] carbonates and bicarbonates. These can be used in the form
of their alkali metal, alkaline earth metal or ammonium salts.
Preference is given to sodium, lithium and magnesium carbonates or
bicarbonates, especially sodium carbonate and/or sodium
bicarbonate;
[0255] polyphosphates such as pentasodium triphosphate.
[0256] Useful organic cobuilders include in particular low
molecular weight, oligomeric or polymeric carboxylic acids.
[0257] Useful low molecular weight carboxylic acids include for
example citric acid, hydrophobically modified citric acid such as
for example agaric acid, malic acid, tartaric acid, gluconic acid,
glutaric acid, succinic acid, imidodisuccinic acid, oxydisuccinic
acid, propanetricarboxylic acid, butanetetracarboxylic acid,
cyclopentanetetracarboxylic acid, alkyl- and alkenylsuccinic acids
and aminopolycarboxylic acids such as for example nitrilotriacetic
acid, .beta.-alaninediacetic acid, ethylenediaminetetraacetic acid,
serinediacetic acid, isoserinediacetic acid,
N-(2-hydroxyethyl)iminodiace- tic acid, ethylenediaminedisuccinic
acid and methyl- and ethylglycinediacetic acid;
[0258] useful oligomeric or polymeric carboxylic acids include for
example homopolymers of acrylic acid, oligomaleic acids, copolymers
of maleic acid with acrylic acid, methacrylic acid,
C.sub.2-C.sub.22-olefins such as for example isobutene or
long-chain .alpha.-olefins, vinyl alkyl ethers having
C.sub.1-C.sub.8-alkyl groups, vinyl acetate, vinyl propionate,
methacrylic esters of C.sub.1-C.sub.8-alcohols and styrene.
Preference is given to using the homopolymers of acrylic acid and
also copolymers of acrylic acid with maleic acid. Polyaspartic
acids are also useful as organic cobuilders. Oligomeric and
polymeric carboxylic acids are used in acid form or as sodium
salt.
[0259] Useful bleaching agents include for example adducts of
hydrogen peroxide with inorganic salts such as for example sodium
perborate monohydrate, sodium perborate tetrahydrate or sodium
carbonate perhydrate or percarboxylic acids such as
phthalimidopercaproic acid.
[0260] Suitable bleaching activators are e.g. N,N,N',N'-tetraacetyl
ethylendiamine (TAED), sodium p-nonanoyloxybenzenesulfonate or
N-methylmorpholiniumacetonitrilmethylsulfate.
[0261] Enzymes preferably used in laundry detergents are proteases,
lipases, amylases, cellulases, oxidases or peroxidases.
[0262] Suitable dye transfer inhibitors are e.g. homopolymers and
copolymers of 1-vinylpyrrolidone, 1-vinylimidazole or
4-vinylpyridine-N-oxide. Homopolymers and copolymers of
4-vinylpyridine reacted with chloroacetic acid are also suitable
dye transfer inhibitors.
[0263] The present invention further provides laundry
aftertreatment and laundry conditioning compositions comprising
from 0.01% to 20% by weight, preferably from 0.1 to 10% by weight
and particularly preferably from 0.1% to 5% by weight of components
A and B as well as other customary constituents. The weight ratio
of component A to component B is preferably in the range from 20:1
to 1:10, more preferably in the range from 8:1 to 1:5 and
especially in the range from 3:1 to 1:1. In this connection, the
components A and B can be added separately to the formulation or a
ready-prepared mixture of A and B can be incorporated into the
formulation.
[0264] The laundry aftertreatment and laundry conditioning
compositions of the invention generally include as further
customary constituents c) from 0.1 to 40% by weight of at least one
cationic surfactant as component C,
[0265] d) from 0 to 30% by weight of one or more nonionic
surfactants as component D,
[0266] e) from 0 to 30% by weight of further customary ingredients
such as scents, colorants, stabilizers, fiber and color protection
additives, viscosity modifiers, soil release additives, soil
antiredeposition agents, dye transfer inhibitors, complexing
agents, corrosion control additives, bactericides, preservatives,
nonaqueous solvents, hydrotropes and/or alkanolamines as component
E,
[0267] f) from 0 to 25% by weight of cationic polymers as binders
as component F, and
[0268] g) water to 100% by weight as component G.
[0269] Useful cationic polymers (component F) include all natural
or synthetic cationic polymers containing amino and/or ammonium
groups and being soluble or dispersible in water. Examples of such
cationic polymers are polyethyleneimines, amidated, alkoxylated
and/or alkylated polyethyleneimines, crosslinked
polyethyleneimines, polyamidoamines, alkoxylated and/or alkylated
polyamidoamines, crosslinked polyamidoamines, ethyleneimine-grafted
crosslinked polyamidoamines, amine-epichlorohydrin polycondensates,
polyvinylamines, alkoxylated polyvinylamines, partially hydrolyzed
polyvinylformamides, polyallylamines, polydimethyldiallylammonium
chlorides, polymers containing 1-vinylimidazole units such as
poly-1-vinylimidazole or
poly-(1-vinylimidazole-co-1-vinylpyrrolidone), polymers containing
quaternary vinylimidazole units, condensates of imidazole and
epichlorohydrin, polymers containing basic methacrylamide or
methacrylic ester units, polymers containing basic quaternary
methacrylamide or methacrylic ester units and/or lysine
condensates.
[0270] The term "cationic polymers" also comprehends amphoteric
addition polymers which have a net cationic charge, i.e., the
polymers contain both anionic and cationic monomers in
copolymerized form, but the molar fraction of the cationic units
present in the polymers is greater than that of the anionic
units.
[0271] Preferred cationic surfactants (component C) are selected
from the group consisting of the quaternary diesterammonium salts,
the quaternary tetraalkylammonium salts, the quaternary
diamidoammonium salts, the amidoamine esters and imidazolium salts.
These are preferably present in the fabric conditioners in an
amount of from 3 to 30% by weight. Examples are quaternary
diesterammonium salts having two C.sub.11- to
C.sub.22-alk(en)ylcarbonyloxy(mono- to pentamethylene) radicals and
two C.sub.1- to C.sub.3-alkyl- or hydroxyalkyl radicals on the
quaternary nitrogen atom and, for example, chloride, bromide,
methosulfate or sulfate as counterion.
[0272] Quaternary diesterammonium salts are further in particular
those which have a C.sub.11- to
C.sub.2-2-alk(en)ylcarbonyloxytrimethyleneradic- al bearing a
C.sub.11- to C.sub.22-alk(en)ylcarbonyloxy radical on the central
carbon atom of the trimethylene group and three C.sub.1- to
C.sub.3-alkyl- or hydroxyalkyl radicals on the quaternary nitrogen
atom and, for example, chloride, bromide, methosulfate or sulfate
as counterion.
[0273] Quaternary tetraalkylammonium salts are in particular those
which have two C.sub.1- to C.sub.6-alkylradicals and two C.sub.8-
to C.sub.24-alk(en)yl radicals on the quaternary nitrogen atom and,
for example, chloride, bromide, methosulfate or sulfate as
counterion.
[0274] Quaternary diamidoammonium salts are in particular those
which have two C.sub.8- to
C.sub.24-alk(en)ylcarbonylaminoethyleneradicals, a substituent
selected from hydrogen, methyl, ethyl and polyoxyethylene having up
to 5 oxyethylene units and as fourth radical a methyl group on the
quaternary nitrogen atom and, for example, chloride, bromide,
methosulfate or sulfate as counterion.
[0275] Amidoamino esters are in particular tertiary amines bearing
a C.sub.11- to C.sub.22-alk(en)ylcarbonylamino(mono- to
trimethylene) radical, a C.sub.11- to
C.sub.22-alk(en)ylcarbonyloxy(mono- to trimethylene) radical and a
methyl group as substituents on the nitrogen atom.
[0276] Imidazolinium salts are in particular those which bear a
C.sub.14- to C.sub.18-alk(en)yl radical in position 2 of the
heterocycle, a C.sub.14- to C.sub.18-alk(en)ylcarbonyl(oxy or
amino)ethylene radical on the neutral nitrogen atom and hydrogen,
methyl or ethyl on the nitrogen atom carrying the positive charge,
while counterions here are for example chloride, bromide,
methosulfate or sulfate.
[0277] The present invention also provides for the use of zinc
oxide and/or titanium dioxide together with organic UV absorbers in
laundry detergent, laundry aftertreatment and laundry conditioning
compositions.
[0278] The present invention also provides a finishing composition
for UV protection of textile materials comprising the components A
and B.
[0279] The finishing compositions according to the invention are
present for example as finishes in the narrower sense in the course
of the manufacture of the textiles or in the form of an aqueous
wash liquor or as a liquid textile treatment composition. It is
accordingly possible for example to treat the textiles with the
finishing composition in connection with the manufacture of the
textiles. Textiles never treated or only inadequately treated with
a finish may be treated for example in the home before or after
washing with a textile treatment composition containing the
inorganic pigments A and the organic UV absorbers B. But it is also
possible to treat the textiles with the components (A) and (B) in
the main wash cycle or after the main wash cycle in the
conditioning rinse cycle of the washing machine, partly using the
above-described formulations.
[0280] The examples hereinbelow illustrate the present
invention.
Example 1
Application of the UV Protectant as a Laundry Aftertreatment in the
Conditioning Rinse Bath and Determination of the UV Protection
Factor UPF
[0281] White woven cotton fabric having a basis weight of 100
g/m.sup.2 and a UV protection factor (UPF) of 4.1 was washed at a
water hardness of 3 mmol/l. The laundering process was a main wash
cycle at 40.degree. C. with a commercially available laundry
detergent (Ariel.RTM. Color) and a subsequent conditioning rinse.
The conditioner used was a commercially available formulation
(Downy from Lenor.RTM.) in a dosage of 1000 ppm, based on the
liquor. The fabric conditioner formulation included either no UV
absorber or in each case 100 or 200 ppm, based on the liquor, of an
inventive UV absorber combination, added before the conditioning
rinse. The liquor ratio was 12.5:1. After the conditioning rinse
cycle, the fabric was removed and its UV protection factor was
determined in the dried state. Subsequently the fabric was tested
for photostability. The fabric sample was exposed in a SUNTEST.RTM.
CPS tabletop accelerated lighting unit from Heraeus, Hanau, for 4
and 24 hours under outdoor conditions using a WG 295 filter at the
maximum radiative power output of the instrument. The UV protection
factor was redetermined after 4 and 24 hours of exposure.
[0282] The inorganic pigments used were as follows:
[0283] Z-COTE.RTM., an amphiphilic zinc oxide from BASF AG
[0284] Uvinul.RTM. TiO.sub.2 from BASF AG
[0285] The organic UV absorbers were used as follows:
[0286] A=2-ethylhexyl 2-cyano-3,3-diphenylacrylate (Uvinul.RTM.
N-539 T)
[0287] B=2-hydroxy-4-(n-octyloxy)benzophenone (Uvinul.RTM.
3008)
[0288] The results are summarized in table 1.
1 TABLE 1 UPF UPF after 4 h after 24 h UPF .DELTA. exposure .DELTA.
exposure .DELTA. no additive 4.3 4.2 4.2 50 ppm of ZnO 4.7 0.4 4.5
0.3 4.6 0.4 100 ppm of ZnO 5.5 1.2 5.5 1.3 5.4 1.2 50 ppm of A 8.5
4.2 7.2 3.0 5.5 1.2 100 ppm of A 13.4 9.1 11.4 7.2 8.5 4.3 50 ppm
of A + 50 12.3 8.0 11.8 7.6 10.3 6.1 ppm of ZnO 100 ppm of A + 100
19.2 14.9 18.4 14.2 16.5 12.3 ppm of ZnO 100 ppm of TiO2 5.0 0.7
4.9 0.7 4.8 0.6 100 ppm of A + 100 17.6 13.3 17.5 13.3 14.5 10.3
ppm of TiO.sub.2 100 ppm of B 10.1 5.8 9.0 4.8 7.4 3.2 100 ppm of B
+ 100 14.8 10.5 14.5 10.3 12.4 8.2 ppm of TiO.sub.2 .DELTA. = UPF
(with additive) - UPF (without additive)
[0289] The results clearly show the synergistic effect on the
combined use of UV absorbers A and B with zinc oxide and titanium
dioxide respectively. It is similarly clear that the pigment oxides
have a positive effect on the photostability of the organic UV
absorbers A and B.
[0290] Zinc oxide and titanium dioxide increase the UV protection
factor of the cotton fabric only insignificantly when used alone in
either case.
EXAMPLE 2
Application as a Laundry Aftertreatment in the Conditioning Rinse
Bath and Determination of the Photostability of Dyed Cotton Fabric
Used
[0291] A woven cotton fabric dyed with Reactive Black 5 to 1/3
standard depth was treated in the conditioning rinse cycle with a
commercially available formulation (Downy from Lenor.RTM., 1000
ppm, based on the liquor) in the presence of an inventive UV
absorber combination (in each case 200 ppm, based on the liquor) in
a liquor ratio of 12.5:1. After the conditioning rinse cycle, the
dyed fabrics were removed and tested for photostability in the
dried state.
[0292] Photostability was measured as follows:
[0293] The samples were exposed in a SUNTEST.RTM. tabletop
accelerated lighting unit from Heraeus, Hanau for 8 or 24 hours
under outdoor conditions using a WG 295 filter at the maximum
radiative power output of the instrument. A spectrophotometer with
an integration sphere Lambda 900 from Perkin Elmer was used to
measure the reflectance spectra of the dyes before and after
exposure. These reflectance spectra were converted in line with the
Kubelka-Munk theory into K/S spectra (K=absorption coefficient,
S=scattering coefficient). The photostabilities were evaluated with
reference to the K/S values after 8 or 24 hour exposure relative to
the K/S values prior to exposure (K/S in each case at the maximum
of the K/S spectra). The higher the value in % reported in table 2,
the higher the photostability.
[0294] The inorganic pigment used was Z-COTE.RTM. from BASF AG.
[0295] The organic UV absorbers used were as follows:
[0296] C=n-hexyl 2-(4'-diethylamino-2'-hydroxybenzoyl)benzoate
[0297]
D=1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione
(Uvinul.RTM. BMBM)
2 TABLE 2 K/S (24 h)/K/S (0 h) .times. K/S (8 h)/K/S (0 h) .times.
100% 100% no additive 77.2% 57.7% 400 ppm of ZnO 82.0% 63.7% 400
ppm of C 81.3% 62.0% 200 ppm of C + 85.5% 68.8% 200 ppm of ZnO 400
ppm of D 80.8% 61.0% 200 ppm of D + 84.9% 67.0% 200 ppm of ZnO
[0298] The results clearly show the synergistic effect on the
combined use of C or D with zinc oxide.
* * * * *