CH318461A - Process for making coated paper and apparatus for carrying out this process - Google Patents

Description

  

  



  Use of organic compounds to protect textile fibers against UV rays
Numerous organic compounds have been proposed as absorbents for the 2900 to 3700 Å range, which is referred to as the ultraviolet range. The ultraviolet radiation contained in sunlight with wavelengths between 250 and 400 millimicrons is by far the most important.



   It is known that dyed textiles fade under the action of sunlight. The present invention is intended to enable improved protection of textile fibers against UV radiation, in particular against the UV component of sunlight.



   A UV protection filter compound or layer is known from German patent specification No. 1087902 which contains compounds as UV absorbers which correspond to the following formula:
EMI1.1

In this formula: Ar = a benzene ring which is substituted by one or more hydroxyl or alkoxy groups and optionally by further substituents, R '= CN, COOH, COX, (CH2) ns COOH, (CH COOR, R ″ = H , R, CN, COX, COOH, where X = for alkyl, aryl, substituted alkyl, subst.



  Aryl, OR, R N. R, NH R, NH2, R = for H, alkyl, aryl, subst. Alkyl, subst. Aryl, cycloalkyl and n = for an integer, such as. B. 1 or 2, is.



   It was found that compounds of the formula
EMI1.2
 where (AR) and (AR) mean aromatic carbocyclic cores without nitro substituents and without amino or free core-bound oxy groups bonded to the core, offer improved protection of textile fibers against UV radiation, in particular in the UV range of 250400 mM.



   Although the compounds used according to the invention show a very high absorption close to the visible range of the electromagnetic field, they are nevertheless essentially colorless, so that when used in normally colorless textile materials they do not lead to discoloration and do not impair the color in dyed textile fibers. Some of the compounds used in the invention also absorb some visible light at the violet end of the spectrum, which makes them particularly valuable for use in textile materials that are sensitive to visible light. As is well known, this applies to B. for polyester and polyethylene. The protection of textiles made from these materials with the aid of the compounds used according to the invention is therefore particularly effective.



   In the above formula (I) (AR) 1 and (AR) 2 are advantageously phenyl rings which, for. B. can be substituted by the following radicals: alkyl, alkenyl, aryl, aralkyl, alkaryl, alkoxy, aryloxy, acyloxy, halogen, carboxy, cyano, carbalkoxy, alkoxyalkyl, carboxyamide and sulfonamide. Alkyl substituents preferably have 1-18 carbon atoms. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, amyl, hexyl, octyl, decyl, lauryl and stearyl.



   The suitable alkoxy radicals also usually have 1 to 18 carbon atoms. Examples are: methoxy, ethoxy, hexoxy, lauroxy and stearoxy. Suitable aryl radicals are, for. B. phenyl, tolyl, xenyl, a-naphthyl, fi-naphthyl, substituted phenyl radicals, such as chloro- or bromophenyl,
Methoxyphenyl, athoxyphenyl, aryloxy, e.g. B. phenoxy,
Toloxy and xyloxy.



   Suitable acyloxy radicals are, for. E.g .: acetoxy, propoxy, butyroxy, valeroxy, caproxy, lauroxy and stearoxy. The halogens fluorine, chlorine, bromine and iodine are also suitable as substituents. Further examples of suitable substituents on the carbocyclic rings are the following: carbomethoxy, carbethoxy, carbopropoxy and carbobutoxy, methoxyethyl, methoxypropyl, methoxybutyl and methoxylauryl, ethoxyethyl, ethoxybutyl and ethoxylauryl.



   The compounds of the formula (I) can be obtained in a manner known per se by condensation of benzophenone or substituted benzophenone with malononitrile in a solvent under conditions which lead to condensation. With benzophenones, which have positive substituents and in particular -CH: s, -OCH. and the like, it is advantageous to use cyanoacetamide instead of malononitrile. This gives a cyanamide whose amido groups are dehydrated to nitrile groups by treatment with a 5- to 10-fold excess of phosphorus oxychloride (POCI: 1) and thus yield the dinitrile. Heating with POCI: can e.g.

   B. in 2 to 4 hours at 55 to 65 C, whereupon the reaction product is poured into water, filtered and washed to remove the excess of POCld.



   It can e.g. B. the following benzophenones are implemented: 2-, 3- or 4-methylbenzophenone, 2-, 3- or 4-chlorobenzophenone or the corresponding bromine or iodine compound, 4-fluoro or 4-cyanobenzophenone, benzophenonecarboxylic acid (2), Benzophenonecarboxylic acid (3), benzophenonocarboxylic acid (4), 2-benzoylbenzoic acid methyl or ethyl ester, 2-benzoylbenzoic acid amide, 2-benzoylbenzoic acid monoethylamide, 3-benzoylbenzoic acid, methyl or ethyl ester, 4-sulfonylbenzoic acid, 2- or 4-benzoic acid methyl ester, 2- or 4-benzoylbenzoic acid methyl ester 4-ethylbenzophenone, 2,4-, 2,5-, 3,4-, 2,4'-, 3,4'- or 4,4'-dimethylbenzophenone, 4-propyl- or 4-isopropylbenzophenone, 2, 4,5-, 2,4,6-, 2,4,2 or 2,4,3'-trimethylbenzo phenone, 2-methyl-5-isopropylbenzophenone, 2,3,4,6-, 2,3,5 , 6-, 2,4,2, 4-,

   2,5,2 ', 5 - or 2,4,3', 4'-
Tetramethylbenzophenone, 2, 4,6,3 ', 5'-pentamethylbenzophenone, 2,2'-dimethyl-5,5'-diisopropylbenzophenone, 4-n-octyl-, 4-cyclohexyl-, 2-benzoyl-, 4,4 '-Dicyclo hexyl- or 4,4-di-p-toluylbenzophenone, 2-, 3- or 4-phenylbenzophenone, 2-prophenyl- or 2-allylbenzophenone, N, N-dimethyl-2-sulfonamidobenzophenone, 4-phenethylbenzophenone, 2 -Carboxyamidobenzophenone, 2-, 3- or 4-methoxybenzophenone, 2-, 3- or 4-ethoxybenzophenone, 2-, 3- or 4-phenoxybenzophenone, 4-xylyloxybenzophenone,
4- (m- or p-tolyloxy) -benzophenone,
4-isopentyloxybenzophenone,
2-, 3- or 4-acetoxybenzophenone,
4-cyclohexyloxy- or 4-benzyloxybenzophenone,
2,4'- or 4,4-difluorobenzophenone,
2,4-, 2,6-, 2,2'-, 2,4'-, 3,

  3'- or 4,4-dibromobenzophenone, or 3,4-dichlorobenzophenone, 4,4> -, 2,4-, 2,4 '4,4 or 3,5-diiodobenzophenone,
4-chloro-4'-bromobenzophenone, 2,2'-diiodobenzophenone 2,4-dichloro-2 ', 4'-dibromobenzophenone, 2,4,6-tribromo- or 2,4,6-trichlorobenzophenone, 2,5, 2 ', 5'- or 2,4,2', 4'-tetrachlorobenzophenone, 2-bromo- or 2-chloro-4-phenylbenzophenone, 2-bromo-2 ', 4,4', 6,6'-pentamethylbenzophenone , 4-chloro-3 ', 4'-dimethylbenzophenone, 4-chloro-3,4'-dimethylbenzophenone, 2-chloro-2', 4'-dimethylbenzophenone, 2-bromo-4-methylbenzophenone, 4'-methoxy-2 -methylbenzophenone, 4-methoxy-3-methylbenzophenone, 6-methoxy-3-methylbenzophenone,

   4-methoxy-2-methylbenzophenone, 4,4'-dimethoxy, 4,4-diethoxy- or 4,4'-diisopropoxybenzophenone, 2,2'-, 2,3- or 2,4'-dimethoxybenzophenone, 4- Methoxy-2,5-dimethylbenzophenone, 5-methoxy-2,4-dimethyl- or 5-ethoxy-2,4-dimethylbenzophenone, 4-methoxy-3-methyl-6-isopropylbenzophenone, 4-acetoxy-2-methyl or 4-acetoxy-3-methyl-5-iso propylbenzophenone,
3-ethoxy-3 ', 4,4'-trimethoxybenzophenone, 3-Xthoxy-3', 4,4'-trimethoxybenzophenone, 4-ethoxy-3,3 ', 4'-trimethoxybenzophenone, 4- (p-methoxyphenyl) - 4'-phenylbenzophenone, 4,4'-bis (p-methoxyphenoxy) -benzophenone, 4- (p-methoxyphenyl) -benzophenone, 4-methoxy-3, S-dimethyl- or 6-ethoxy-3-methylbenzophenone , 3-chloro-4- (2-hydroxyethyl) -,

   2'-chloro-4-methoxy- or
4'-chloro-4-methoxybenzophenone, 3-fluoro-4-methoxy- or 5-fluoro-2-methoxybenzophenone, 4-fluoro-2-methylbenzophenone, 4'-bromo-4-ethoxybenzophenone, 3-iodo-4- methoxybenzophenone, 4'-iodo-4-ethoxybenzophenone, 3'-chloro-4-methoxy-3- or 5-Clh; or-2-methoxy-
3-methylbenzophenone, 3'-iodo-4'-methoxy-2-methylbenzophenone, 5'-iodo-2'-methoxy-2-methylbenzophenone, 2'-bromo-6-methoxy-3-methylbenzophenone, 3,5-dibromo -4-ethoxybenzophenone, 3,5-dichloro-2,2 ', 4,6'-tetramethoxy-4'-methylbenzo phenone, 3, 3'-difluoro-4,4'-dimethoxybenzophenone, 3,3'-difluoro 4,4'-diethoxybenzophenone, 4'-tert-butyl-2'-isopropenyl-2,3,5,6-tetramethylbenzophenone, 2,5-dimethoxy-3,4- or 4,4-dimethoxy-3, 3-dimethylbenzophenone, 2,6-dimethoxy-2 'or 2,

  6-dimethoxy-3-methylbenzophenone, 3,3'-diethoxy-4,4'-dimethoxybenzophenone, 3,3 ', 4,4', 5,5'-hexamethoxybenzophenone, 3,3'-dimethoxy-4, 4'-bis (benzyloxy) benzophenone.



   (A) Preparation of 3,4-dimethyldiphenylmethylene malononitrile a) 0.5 mol of malononitrile and 0.5 mol of 3,4-benzophenone were mixed with 6.5 g of ammonium acetate, 20 cm of glacial acetic acid and 200 cm of benzene. The mixture was refluxed with stirring for 10 hours. The benzene was distilled off, the residue was diluted with 250 cm3 of water and filtered. The solid residue was taken up in 250 cm3 of water and filtered again.

   The target product thus obtained was recrystallized from dilute ethanol. b) The same compound can also be prepared as follows: 100 g of 3,4-benzophenone, 45 g of cyanoacetamide, 250 cm of benzene, 6 g of ammonium acetate and 25 cm of glacial acetic acid were refluxed for 6 hours. The benzene was distilled off and the residue was diluted with 300 cm3 of water and filtered. The crude product was washed with 1 liter of water and then recrystallized from dilute ethanol.



   (B)
The 3,4-dimethyldiphenylmethylene malononitrile can be reacted with 6 moles of ethylene oxide in the presence of some potassium hydroxide in an autoclave at 800 ° C. to produce the polyalkoxylated derivative.



  The product thus obtained can easily be dispersed in water and can thus be used for the treatment of hydrophilic materials, for example cellulose products such as cotton, jute and the like.



   The polyoxyalkylation can also be carried out with 30 moles of ethylene oxide per mole of malononitrile. The product obtained in this way has extraordinarily strong surface-active properties.



   (C) Preparation of 4,4'-dichlorodiphenyl methylenemalononitrile
A mixture of 16.5 g malononitrile (0.25 mol), 62.75 g 4,4'-dichlorobenzophenone (0.25 mol), 3.85 g ammonium acetate, 12 cm 3 glacial acetic acid and 75 cm 3 benzene was stirred for 12 hours kept at reflux temperature. The benzene was distilled off, the residue was diluted with 150 cm of water and filtered.



  The crushed residue was made into a paste in 100 cm3 of water and filtered. The cake is washed on the funnel with 200 cms of water and the product is air dried. It is then distilled at 185 to 2000 ° C./0.5 mm Hg. The target product (18.5 g) is recrystallized from 150 cm of ethanol and 300 cm3 of water after treatment with activated charcoal.



     (D) Preparation of phenyl-4-n-dodecyloxy phenylmethylene malononitrile
4-n-dodecyloxybenzophenone was condensed with malononitrile according to procedure (C) with malononitrile. The 4-n-dodecyloxybenzophenone was obtained by alkylating 4-hydroxybenzophenone with n-dodecyl iodide.



   (E) Preparation of 4-chlorophenyl4'-methoxyphenylmethylene malononitrile 4-chloro-4'-methoxybenzophenone is condensed with malononitrile according to procedure (C).



   (F) 4,4'-Ditolylmethylene malononitrile was obtained from 4,4'-dimethylbenzophenone and malononitrile according to procedure (C).



   (G) Phenyl- (4-biphenyl) -methylene malononitrile is obtained from 4-phenylbenzophenone and malononitrile according to procedure (C).



   (H) Benzosu4onyl-bis-ester of di- (4-hydroxyphenyl) -methylene malononitrile
1 mole of di- (4-hydroxyphenyl) methylene malononitrile is dissolved in 4 moles of pyridine. 1.1 mol of benzenesulfonyl chloride is slowly added to the mixture at about 100 ° C. in the course of 15 minutes. The mixture is heated to 50 ° C. for 35 minutes, allowed to cool to room temperature and then poured into ice water, which contains enough hydrochloric acid to neutralize the pyridine. The precipitate obtained in this way is the target product and can be purified by recrystallization from aqueous methanol.



      (1) 4,4'-Dibromodiphenylmethylene malononitrile is obtained from 4,4'-dibromobenzophenone according to procedure (C).



   (K) polyalkoxylated derivatives
To prepare the polyalkoxylated derivatives, a compound of the formula (I) which contains at least one reactive hydrogen atom can be reacted directly with an alkylene oxide or a compound which, like an alkylene oxide, can be attached to reactive hydrogen atoms to form polyether chains. Examples of suitable alkylene oxides and compounds reacting similarly are: ethylene oxide, propylene oxide, butylene oxide, butylene dioxide, cyclohexane oxide, glycidol, epichlorohydrin, butadiene dioxide, isobutylene oxide, styrene oxide and mixtures of these compounds. The polyalkoxylated compounds thus obtainable, usable according to the invention, for. B. have the formula
EMI3.1
 wherein X is the hydrocarbon radical of the alkoxylating agent, e.g.

   B. ethylene (from ethylene oxide and epichlorohydrin), propylene (from propylene oxide), etc. means, n and m are zero or integers from zero to about 100, with the proviso that at least one of these numbers is not zero.



   The compounds used according to the invention as UV-absorbing agents for textile materials are generally soluble in many solvents, plastics, resins, waxes and the like. The non-alkoxylated compounds are insoluble in water.



   The compounds with lower proportions of alkoxy groups, i.e. H. up to about 4 or 6 per molecule, are mostly soluble in polar organic solvents and fairly dispersible in water. The compounds with higher proportions of alkoxy groups, i. more than about 6 moles per mole of the base compound show an increasing water solubility with increasing alkoxy content.



   The treatment concentration of the compounds used according to the invention is not particularly critical as long as the desired degree of stabilization is ensured. In general, proportions of 0.1 and 10%, based on the solids content of the liquor, preferably between 0.5 and 2%, are suitable. The present UV absorbers can be used to protect textile fabrics and translucent or opaque textile fibers.



   example
It became the compound of the formula
EMI4.1
 according to German Patent No. 1,087,902, hereinafter referred to as compound (A), with the compound of the formula
EMI4.2
 hereinafter referred to as compound (B), compared: First two staining solutions were prepared as follows: 0.25 g of the dye Genacryl Red 4B> on the one hand and 0.25 g of the dye Genacryl Blue 6Gs on the other hand were each dissolved in 100 ml of water and each of these Solutions are then made up to 350 ml with water. Then in each case 0.3 g of the absorber compound (A) or



  (B) dissolved in 60 ml of acetone and added 5 or 10 ml of this solution to the respective color bath.



   Analogue color baths were also produced without the addition of absorbers. A Dacron-64 sample of 5 g each was dyed in one of these baths at 1000 ° C. for 1 hour. The color samples were then rinsed and dried and exposed for 9 hours in a ° xenon fadeometer.



   A comparison of the samples shows that the colorations without the addition of an absorber show a very strong color change between the exposed and the unexposed parts. The samples with the comparative absorber (A) show a weaker color change than the samples without added absorber, but in all cases the color change is considerably greater than in the samples with absorber (B). The comparison shows that the absorbers used according to the invention provide better protection of the textile against UV rays than the known absorber compounds.

 

Claims (1)

PATENT CLAIM Use of compounds of the formula EMI4.3 where (AR) 1 and (AR) are aromatic carbocyclic radicals without nitro substituents and without amino or free core-bonded oxy groups, for protecting textile fibers against UV rays. SUBCLAIMS 1. Use according to patent claim, characterized in that 0.1-10% of these compounds, based on the weight of the textile material, are applied to the textile material. 2. Use according to claim of compounds in which (AR) 1 and (AR) 3 are benzene rings. 3. Use according to dependent claim 1 of compounds in which (AR) I and (AR) 2 are phenyl. 4. Use according to claim or one of the dependent claims 1-3, characterized in that a polyalkoxylated derivative of a compound of formula (I) is used. Cited sebrift and pictorial works German interpretative document No. 1 087 902