3,529,982 United States Patent Office Patented Sept. 22, 1970 2 tecting polycondensates, polyadducts and polyvinylchloride 3,529,982 PROCESS FOR PROTECTING ORGANIC MATE from the action of ultraviolet rays. RIAL FROM THE ACTION OF ULTRAVOLET Depending on the practical importance for certain types RAYS of Substrates, on the chemical relationship on the other Christian Luethi, Munchenstein, Max Duennenberger, hand or finally on the novelty of the substances these Frankendorf, and Hans Rudolf Biland, Basel, Switzer compounds may be classified according to different stand land, assignors to Ciba Limited, Basel, Switzerland, a points or Subdivided into subgroups. company of Switzerland No Drawing. Filed Feb. 6, 1967, Ser. No. 614,039 A group that is important from the standpoint of ap Claims priority, application Switzerland, Feb. 7, 1966, plication comprises asymmetrical compounds of the gen 1,679/66, 1,680/66 O eral formula Int. CI. C08f 45/60; C08g 51/60, B44d 1/00 U.S. C. 106-178 4 Claims (2) Y Yi Yr Y' ABSTRACT OF THE DISCLOSURE 5 Y3- > -NH-C O-C os- >-r This invention refers to a process for protecting organic Ya Ys y k materials that can be damaged by ultraviolet rays, from the action of ultraviolet rays, wherein asymmetrical oxalic acid diarylamides of the general formula in which Y1 and Ys as well as Y', and Y's each stands 20 for a hydrogen or halogen atom, or a substituent with up A-NH-CO-CO-NH-B to 20 carbon atoms from the series alkyl, substituted alkyl, where A and B are different from each other and each benzene radical, benzyl group, a group -CO-NHE or represents a benzene or naphthalene residue, these res -SO2-NH-El (where E1 is hydrogen, alkyl or aryl), a idues A and B (a) being free from hydroxyl groups in group -COOE or -SO3E2 (where E is hydrogen, alkyl, the ortho-positions to the amide nitrogen atom and (b) 25 aryl or a Salt-forming cation), a nitro group, a primary, containing if desired substituents that contain no more Secondary or tertiary amino group or an acylamino group, than 20 carbon atoms and do not displace the absorp and Y2, Ys and Y4 as well as Y'a, Y's and Y each rep tion maximum of the compound towards values above resents the same kind of group as Y and Ys or Y', and Y's 400 mu, are applied to said materials, as well as composi- : or a hydroxyl group, and tions containing said oxalic acid diarylamides. (a) each benzene nucleus contains at most two substi -ass. Lam tuents -CO-NH-E, -SO-NH-El, -COOE, -SO3E2 or hydroxyl, The present invention provides asymmetrical oxalic acid (b) each benzene nucleus contains at most three of the diarylamides and processes for their manufacture and use 35 other substituents different from hydrogen, and as light filters, especially ultraviolet absorbers, for organic (c) the Substituents in the two benzene nuclei differ from materials that are damaged by the action of ultraviolet each other in at least one point as to type, number or TayS. positions. It has already been described that oxalic acid bis hydroxyl arylamides are suitable for use as ultraviolet 40 Within the scope of the above definition halogen is, absorbers, but in the past it had been held that the light for example, chlorine or bromine; an alkyl is either one stability of such compounds depends on the presence of having a low number of carbon atoms (C, to C) and two free hydroxyl groups in ortho-position relatively to being branched or linear, or a higher alkyl group with 5 the amide nitrogen atom. In contradistinction to this as to 18 carbon atoms (for example octyl, dodecyl and the sumption it has now been found that a large class of oxalic 45 like). A substituted alkyl group is chloralkyl, bromalkyl, acid diarylamides that do not satisfy the requirement re hydroxyalkyl, alkoxyalkyl, carboxyalkyl or carbalkoxy ferred to are not only excellent ultraviolet absorbers suit alkyl. Acylamino groups are acetylamino or benzoyl able for industrial use but surprisingly even display a amino, and amino groups are above all methylamino and greater stability to light. ethylamino and anilino groups. Accordingly, the present invention provides a process Of value within the scope of Formula 1 are also those for protecting organic material that can be damaged by asymmetrical compounds which correspond to the formula the action of light-preferably non-textile organic mate rials-from the action of light and especially ultraviolet rays, characterized in that asymmetrical oxalic acid di (3) Yi Y Y's Y, arylamides of the formula (1) A-NH-CO-CO-NH-B Ys-{ >-NH-C O-C out- >-r are used, in which Formula A and B are different from Yo Yo Yo Y’ each other and each represents a benzene or naphthalene residue, these residues A and B 60 in which Ye and Y10, and Y's and Yo, are identical or (a) being free from hydroxyl groups in the ortho-posi different and each represents a hydrogen or halogen atom, tions relatively to the amide nitrogen atom and an alkyl group with 1 to 12 carbon atoms or a phenyl (b) possibly containing further substituents that contain group, and Y to Yg, as well as Y' to Y', represents the at most 20 carbon atoms and do not displace the ab Same groups as Ys and Y10, or Y's and Y' respectively, sorption maximum of the compound towards values or represent a hydroxyl group and above 400 mu; (a) each benzene nucleus contains at most two hydroxyl these arylamides are homogeneously distributed in the groups, organic material to be protected or applied to the surface (b) each benzene nucleus contains at most three of the of said material or the material to be protected is coated 70 other substituents different from hydrogen, and with a filter layer that contains the compounds described. (c) the Substituents in the two benzene nuclei differ in at These new compounds are particularly valuable for pro least one point as to kind, number or positions. 3,529,982 3. 4. According to one variant there are used compounds of in which Y and Y, and Y and Y'22 respectively, are the formula identical or different substituents from the series chlorine, Y1 Yi Y bromine, alkyl with 1 to 4 carbon atoms, a nitro group, (4) Ya or one of the two substituents Y1, Y22 or Y'21, Y22, Stands NH-CO-CO-NE for a hydrogen atom, a carboxylic acid group, a carboxylic acid alkyl ester group with 1 to 8 carbon atoms in the Yi Y15 Y1, Y14 alkyl residue, a sulphonic acid group or a sulphonic acid in which Y to Ys and Y11 to Y'15, are identical or dif amide group, or Y or Y' represents a hydroxyl group. ferent and each represents a hydrogen atom, a group (e) Compounds of the formula -CO-NH-E or -SO-NH-E-1 (where E1 is hy O (9) Y2 drogen, alkyl with 1 to 4 carbon atoms or phenyl), a group -COOE or SOE2 (where E2 is hydrogen, alkyl with 1 to 4 carbon atoms, phenyl, an alkali salt ion, Y25 ammonium salt ion or amine salt ion) and each benzene in which Y23 represents hydrogen, an alkyl group with 1 nucleus contains at most 1 or 2 of the indicated Sub 5 to 4 carbon atoms or a fluorine, chlorine, or bromine stituents different from hydrogen, and also in this case the atom, and Y24 and Y25 each stand for an alkyl group substituents in the two benzene nuclei differing from each with 1 to 4 carbon atoms, a chloralkyl or fluoralkyl group other in at least one point as to type, number or posi or a fluorine, chlorine or bromine atom. tions. (f) Compounds of the formula Of special practical value within the scope of the 20 (10) CH3 Y24 Formula 1 are those compounds which correspond to the following group formulae: X >-NH-co-co-NH-( x (a) Compounds of the formula CE3 Y25 in which Y2 and Yas have the above meanings and the (5) 25 methyl groups are preferably in positions 3 and 4. (g) Compounds of the formula where Y16 is a hydrogen or halogen atom or an alkyl (11) group with 1 to 4 carbon atoms; Y1, represents hydrogen or an alkyl group with 1 to 4 carbon atoms; Yi stands for 30 hydrogen, halogen, an alkyl group with 1 to 18 carbon atoms which may be substituted by hydroxyl groups, halogen atoms or carboxyl groups, for a nitro group, an amino group, an acylamino group or a carboxylic acid group or its functional derivatives (carboxylic acid amide, 35 where Y has the above meaning. carboxylic acid ester, carboxylic acid halide), and Y19 re (h) Compounds of the formula presents a hydrogen or halogen atom, and where at least 12) Y Yas one substituent Y is different from hydrogen. (b) Compounds of the formula 40 (6) where Y26 and Ya differ from each other as to position and/or meaning and each represents a hydrogen or chlo v-(D-si- O-CO-N- rine atom or a methyl group. In addition to the main group of compounds defined by the above Formula 2 there should be specially mentioned where Ys stands for a hydrogen or halogen atom or an as the second important main group of compounds the alkyl group with 1 to 4 carbon atoms, and Y1 for hy new asymmetrical oxalic acid diarylamides of the for drogen or an alkyl group with 1 to 4 carbon atoms. mula (c) Compounds of the formula (13) (R3)p-1 (7) Y NH-CO-CO-HN (1.

- N - in which R1 and R2 each represents an alkyl group with 1 to 18 carbon atoms which may be substituted by chlo (Y20) in (Yao) in rine, hydroxyl groups, alkoxy groups with 1 to 4 carbon atoms, carboxyl groups, nitrile groups, carboxylic acid in which the brackets indicate that both ox-naphthylamine amide groups or carboxylic acid alkyl ester groups with and (3-naphthylamine derivatives are possible. Compounds 60 1 to 12 carbon atoms; an alkenyl group containing 3 or of this Formula 7 must likewise be free from hydroxyl 4 carbon atoms; a benzyl group which may be substituted groups in ortho-position relatively to the amide nitrogen by chlorine or alkyl; an aliphatic acyl group with up to atom; in this formula Yao and Y'20 respectively stands for 18 carbon atoms a benzoyl group which may be substi a hydrogen atom, a lower alkyl group with 1 to 4 carbon tuted by chlorine or an alkyl group with 1 to 4 carbon atoms, a sulphonic acid group or a possibly etherified hy atoms; R3 and R4 each represents an alkyl group with 1 droxyl group (C. to C6 ethers), and, in the case of the to 12 carbon atoms, a halogen atom, a halogenalkyl sulphonic acid group, m = 1 or 2, and otherwise n=1. group, a Sulphonic acid group, a phenyl group or a phenyl In this formula, too, it suffices for the substituents in the alkyl group whose alkyl residue contains 1 to 4 carbon two aromatic rings to differ from each other in one point atoms, or two ortho-positioned residues R and/or R as to type, number or positions. 70 together form a fused-on six-membered aromatic carbon (d) Compounds of the formula ring, and where in and n=1 or 2 and p and q= 1, 2 or 3, (8) each of the two ring systems containing in addition to Ya Y' the bond via the -NH- group at most 3 substituents and the Sum in-- (n-1) being 1 or 2, and in other re Spects the Substituents R10-, R20-, R and R being 3,529,982 5 6 of a type, number and in positions such that the molecule a phenyl group, and alkyl group with 1 to 12 carbon is asymmetrical. In this formula and in the following for atoms or a phenylalkyl group. mulae the index symbols m, n, p and q (and r, s, t and u (b) compounds of the formula respectively) are to be interpreted so that, if the symbol stands for 0, a hydrogen atom in each case takes the place (17) R5 of the indicated residue. The term "aliphatic acyl group 5 containing up to 18 carbon atoms” refers both to Satu rated and unsaturated acyl groups, thus, for example, the acryl group. Ryo Of great value within the scope of the above formula in which R's stands for hydrogen, halogen or an alkyl O group with 1 to 4 carbon atoms, and R'2, R', and R's have are the compounds of the formula the same meanings as in Formula 16. (i.4) (R3) a (R4) (c) Compounds of the formula (18) Rs' NH-CO-CO-NH 5 (R1O) (OR2)s in which R1 and R2 each represents an alkyl group with 1 to 18 carbon atoms which may be substituted by chlorine, OR1 R2'O hydroxyl groups, alkoxy groups with 1 to 4 carbon atoms, in which R" represents an alkyl group with 1 to 4 carbon carboxyl groups, carboxylic acid amide groups or car 20 atoms, R'2 an alkyl group with 1 to 8 carbon atoms, an boxylic acid alkyl ester groups with 1 to 12 carbon atoms; alkyl group with 1 to 4 carbon atoms which contains an alkenyl group with 3 to 4 carbon atoms; a benzyl halogen atoms or carbalkoxy groups, a benzyl group or group which may be substituted by chlorine and methyl an aliphatic acyl group with 1 to 6 carbon atoms; and groups; an aliphatic acyl group containing up to 18 car R's stands for hydrogen, halogen or an alkyl group with bon atoms; a benzoyl group which may be substituted 25 1 to 4 carbon atoms. by chlorine or an alkyl group with 1 to 4 carbon atoms; (d) Compounds of the formula R3 and R4 each represents an alkyl group with 1 to 12 (19) R’ carbon atoms, a halogen atom, a halogenalkyl group, a sulphonic acid group, a phenyl group or a phenylalkyl group whose alkyl residue contains 1 to 4 carbon atoms 30 or two ortho-positioned residues R3 and/or R together 2 k O form a fused-on six-membered aromatic carbon ring and r", s, t and u each = 0 or 1, and the sum (r--s)=1 or 2. where R'2 and R's have the same meanings as in For Of special value are new asymmetrical oxalic acid di mula 18. arylamides of the formula 35 (e) Compounds of the formula (15) (20)

(R5O) (ORs) 40 where R1 stands for an alkyl radical with 1 to 4 carbon in which R5 and Rs each represents an alkyl group with atoms and R' for an alkyl group with 1 to 12 carbon 1 to 18 carbon atoms which may be substituted by chlo atoms, an alkenyl group with up to 4 carbon atoms, a rine atoms, hydroxyl groups or alkoxy groups with 1 to benzyl group or an aliphatic or aromatic acyl group with 4 carbon atoms, an alkyl group, a benzyl group which up to 12 carbon atoms. may be substituted by chlorine or methyl groups, a carbo 45 Specifically interesting variants of the compounds of methoxy- or carbethoxy-alkyl group with 1 to 6 carbons this invention correspond to the following formulae: in the alkyl grouping, an aliphatic acyl group with 1 to 12 Asymmetrical oxalic acid diarylamides of the formula carbon atoms, or a benzoyl group which may be substituted (21) Rg by chlorine or an alkyl group with 1 to 4 carbon atoms; R represents an alkyl group with 1 to 18 carbon atoms, 50 chlorine or a phenyl group, and r, s and t=0 or 1 and the sum (r--s) = 1 or 2, and in other respects the Sub R10 O ORs stituents R50-, R60- and R differ from each other in which Rs represents an alkyl group with 1 to 18 carbon as to type, number and positions so that the molecule is atoms, an alkenyl group with 3 or 4 carbon atoms, an acyl asymmetrical. 55 group with 2 to 12 carbon atoms or a benzyl group, R As further types of compounds of outstanding practi may stand for -O-Rs or may stand for a hydrogen or cal value there may be mentioned the following: chloroine atom, an alkyl group with up to 12 carbon (a) Compounds of the formula atoms or a phenyl group, and Rio represents an alkyl group with 1 to 4 carbon atoms. (i6) R5 60 Asymmetrical oxalic acid diarylamides of the formula (22)

R-5 OR8 in which R', represents an alkyl group with 1 to 4 car 65 in which R8 stands for an alkyl group with 1 to 18 bon atoms, R2 an alkyl group with 1 to 18 carbon atoms, carbon atoms, an alkenyl group with 3 or 4 carbon atoms, an alkyl group with 1 to 8 carbon atoms which may be an aryl group with 2 to 12 carbon atoms or a benzyl substituted by halogen, an alkoxy group with 1 to 4 car group. bon atoms, a nitrile, carboxyl, carboxylic acid amide or Asymmetrical oxalic acid diarylamides of the formula carboxylic acid ester group containing 1 to 18 carbon atoms, an allyl group, a benzyl group, an aliphatic acyl (23) R11 group with 1 to 12 carbon atoms or a benzoyl radical; R4 represents hydrogen, an alkyl group with 1 to 6 car bon atoms, an alkoxy group with 1 to 4 carbon atoms, in which R11 represents an alkyl group with 1 to 12 carbon a phenyl group or halogen; and R's represents hydrogen, atoms, a hydrogen or chlorine atom or a phenyl group. 3,529,982 7 8 From the large number of compounds of the above ond condensation it is in general advantageous to use formulae the following compounds may be specially a temperature higher by about 50 to 100 C., that is to mentioned: say a temperature from about 100 to 250 C. In this second condensation approximately equimolecular propor 24 3C tions are normally used as well. (24) 3 CH3 Suitable inert organic solvents, as referred to above, are especially those which boil above about 160 C., for example higher benzene-hydrocarbons or halogenated benzenes such as dichlorobenzenes or trichlorobenzenes. O Alternatively, the second amide grouping may be intro (25) duced by semi-hydrolysis of the amide-ester obtained in -NH-CO-CO-N C the first stage to form the amide-acid which is converted into the amide-acid halide, and this is followed by amida CHO HC8O tion of the acid halide group. In such primarily obtained oxalic acid diarylamides, which still contain free hydroxy groups, these groups may (26) o=-c H3 or must be etherfied or esterified in known manner to O satisfy the above general formulae. According to a preferred process for the manufacture CHO -NH-CO-CO-NH CH3 CH3 20 of asymmetrical oxalic acid diarylamides of the Formula / 13 the carboxyl groups or carboxylate groups of the (-CH.--CH. oxalic acid or of its semi-esters or diesters are reacted CH3 CH3 with primary aromatic amines in the presence of anhy drous boric acid (in the melt or in the presence of an (27) O C2Es 25 inert solvent) in an amount of 0.1 to 5% of the Weight of the oxalic acid or of its ester. CH,0-{X-NH-c O-CO-NH Thus, in the case of compounds of the Formula 13, the yoH. H. second stage consists in the condensation of an oxalic -C-C-CF3 acid derivative of the formula &H, &H, 30 (30) (R3)p-1 (28) g C8H17 -NE-CO-CO-A (R1O)in CHO-( >-NH-c O-C "O 35 with an amine of the formula (31) (RA) g-1 40

(29) One-C-C-cCE where R1, R3, R4, m, n, p and g have the above mean ings; A1 is a hydroxyl group, a halogen atom or an alkoxy group with 1 to 12 carbon atoms, or a group -O-benzyl or -O-phenyl, and Z stands for a hydrogen atom or equals R2 as defined above-at a temperature from 50 to 250 C., and then free hydroxyl groups are blocked by Subsequent etherification or acylation. Thus, taking into consideration the above statements, the preferred variant of the process for the manufacture of compounds of the general Formula 1 consists in con The oxalic acid bis-arylamides of the general For densing an oxalic acid derivative of the formula mula 1 to be used in this invention are accessibly by known 5 5 (32) (R3)p-1 methods. They are obtained when oxalic acid or an oxalic acid ester is semi-amidated in known manner in the first stage by reacting oxalic acid or an oxalic acid ester, -NH-CO-CO-A especially an alkyl ester, with an approximately equimo (R1O).m. lecular quantity of a suitable primary amine A-NH2 or 60 B-NH2 (where A and B have the above meanings). Ac with an amine of the formula cording to a preferred method, for example, oxalic acid, (33) (RA) g-1 an oxalic acid semi-ester or oxalic acid diester containing identical or different ester residues, is condensed with 2N- N approximately equimolecular quantities of one of the aforementioned amines in the melt or in an organic solvent (OZ)-1 that is inert towards the reactants, in the presence of (Where R1, R3, R4, Z, m, n, p and q have the above anhydrous boric acid, at a temperature ranging from about meanings and A2 represents an alkoxy group with 1 to 50 to 200 C. 12 carbon atoms) in the melt or in a solvent that is The resulting amide-ester or amide-acid is isolated and 70 inert towards the reactants, in the presence of anhydrous then in a second stage the remaining carboxyl group or boric acid, at a temperature from 100 to 250° C., where carboxylate group respectively of the oxalic acid semi upon free hydroxyl groups are blocked by etherification amide is condensed under analogous conditions with a or acylation. second amine A-NH2 or B-NH. (which is different In this condensation it is advantageous to use 0.1 to from the amine used in the first stage), for which sec 75 5% of anhydrous boric acid referred to the weight of 3,529,982 0. oxalic acid derivative, and to use a reaction temperature abrasion resistance, elasticity, ageing), triggering off of from 150 to 200 C. undesired chemical reactions (decomposition of delicate Within the scope of the requirements of Formula 1 chemical substances, for example medicaments), photo there may be used in the present process, for example, chemically induced rearrangements, oxidation and the the following amines to form in each case one of the like (for example of oils containing unsaturated fatty two amide groupings: 5 acids), causing of burns and irritations (for example on Aniline, 2-, 3- and 4-chloraniline, human skin) and the like. Of special importance is the 2,4- and 3,4-dichloraniline, use of the asymmetrical oxalic acid diarylamides defined 2,4,6-trichloraniline and the corresponding bromanilines, above for protecting polycondensates and polyadducts 2-, 3- and 4-fluoraniline, 10 from the action of ultraviolet rays. 2- and 4-iodaniline, The organic materials to be protected may be widely 3,5-diiodaniline, differing processing stages and physical states, their com 2-, 3- and 4-methylaniline, mon characteristic being their sensitivity towards ultra 2,4- and 2,5-dimethylaniline, violet rays. 2,6-diethylaniline, 5 As high-molecular and low-molecular substances that 2-methyl-5-isopropylaniline, can be protected or stabilized by the present process there 2-, 3- and 4-methoxyaniline, may be mentioned, for example, without any limitation 2,4- and 2,5-dimethoxyaniline, thereto: Organic natural substances such as are used for 2,5-diethoxyaniline, pharmaceutical purposes (medicaments), dyestuffs sensi 4-butoxyaniline, 20 tive to ultraviolet rays, compounds which as victuals or 3-trifluoromethylaniline, in victuals are decomposed by the action of light (un 3,5-bis-trifluoromethylaniline, saturated fatty acids in oils) and the like. 2-, 3- and 4-nitraniline, As examples of high-molecular organic substances 3- and 4-hydroxyaniline, there may be mentioned: 2-aminodiphenyl, 25 (I) Synthetic organic materials of high or higher molec meta- and para-aminoacetanilide, lular weight such as: 3- and 4-aminobenzoic acids and their amides, (a) Polymerization products based on organic com anthranilic acid and its methyl and ethyl esters, pounds containing at least one polymerizable carbon para-amino-N,N-dimethylaniline, to-carbon double bond, that is to say their homopolymers 4-amino-methylbenzoate and -ethylbenzoate, or copolymers as well as their after-treating products, metanilic acid, sulphanilic acid, metanilamide, for example cross-linking, grafting or decomposition prod sulphanilamide, ucts; diluted polymers modification products obtained by 4-hydroxy-3,5-di-tertiary butylaniline, modifying reactive groupings in the polymer molecule 4-hydroxy-3,5-dichloraniline, and the like, for example polymers based on cy,6-un 4,5-dichlorosulphanilic acid, saturated carboxylic acids (for example acrylates, acryl 2-methoxy-5-methylaniline, amides, acrylonitrile), of olefinic hydrocarbons, for 4-methyl-3-chloraniline, example c-olefines, ethylene, propylene or dienes, that 2-chloro-4-trifluoromethylaniline, is to say also rubbers and rubber-like polymers (also 2,4-dimethoxy-5-chloraniline and so-called ABS polymers), polymers based on vinyl and 2,4-dimethyl-6-nitraniline. 40 vinylidene compounds (for example styrene, vinyl esters, vinylchloride, vinyl alcohol), of halogenated hydrocar From among suitable naphthylamines there may be bons, of unsaturated aldehydes and ketones, allyl com mentioned: cy- and 3-naphthylamine, Sulphonic acids of pounds and the like; the naphthylamines such as (b) Other polymerization products obtainable, for 1-naphthylamine-4-, -5- and -8-sulphonic acid, example, by ring opening, for instance polyamides of 2-naphthylamine-1- and -5-sulphonic acid, the polycaprolactam type, also formaldehyde polymers, 2-naphthylamine-4,8- and -6,8-disulphonic acid, or polymers accessible by polyaddition or polyconden 8-hydroxy-1-naphthylamine-4-sulphonic acid, sation, such as polyethers, polythioethers, polyacetals, 8-hydroxy-2-naphthylamine-6-sulphonic acid, thioplasts; 8-hydroxy-1-naphthylamine-4,6- and 3,6-disulphonic acid (c) Polycondensation products or precondensates and based on bifunctional or polyfunctional compounds con 8-hydroxy-2-naphthylamine-3,6-disulphonic acid. taining condensable groups, their homocondensates and cocondensates as well as their after-treatment products, Hydroxyamines in which a hydroxyl group in ortho Such, for example, as polyesters, Isaturated (e.g., poly position to the amide nitrogen atom must subsequently 5 5 ethylene terephthalate) or unsaturated (e.g. maleic acid be etherified: dialcohol polycondensates and their crosslinked products 2-hydroxyaniline, with copolymerizable vinyl monomers), linear or 2-hydroxy-4- and -5-phenylamine, branched (also those based on polyhydric alcohols, e.g. 2-hydroxy-5-methylaniline, alkyd resins), polyamides (e.g. hexamethylenediamine 2-hydroxy-5-chloraniline, 60 adipate), maleinate resins, melamine resins, phenolic 2-hydroxy-5-isooctylaniline, resins (e.g. novolaks), aniline resins, furan resins, car 2-hydroxy-5-dodecylaniline, bamide resins and their precondensates and similarly 2-hydroxy-4-methoxyaniline, constituted products; polycarbonates, silicone resins and 2,4-dihydroxyaniline, the like; 1-hydroxy-2-naphthylamine and (d) Polyadducts, such as polyurethanes (crosslinked 2-hydroxy-1-naphthylamine. and not crosslinked); epoxy resins. (II) Semisynthetic organic materials, for example, Protection by stabilization can be given with the aid cellulose esters and mixed esters (cellulose acetate or of the oxalic acid diamides described above, in principle, propionate), nitrocellulose, cellulose ethers, regener to all those organic materials that are in any form ated cellulose (vicose rayon, cuprammonium cellulose) damaged or destroyed by the action of ultraviolet rays. or their after-treatment products; casein synthetics. Such damages by the action of the same agency, namely (III) Natural organic materials of animal or vegetable ultraviolet rays, may have very different effects, for ex origin, for example those based on cellulose or proteins ample colour shifts, changes in mechanical properties Such as Wool, cotton, silk, bast, jute, hemp, pelts and hairs, (brittleness, fissuring, tear strength, flexural strength, 75 leathers, finely divided wood pulp, natural resins (such 3,529,982 11 12 as colophony, especially lacquer resins), gelatin, glues, ials, that is to say also before or during the chemical re also rubber, gutta percha, balata and their after-treat action, for example in polycondensation (including pre ment and modification products, degradation products, condensates), in a polymerization (including pre products accessible by modification of reactive groups. polymers) or in a polyaddition. The organic materials concerned, especially Synthetic An important sphere of application of the stabilizers materials such as polymers of vinychloride, Saturated 5 to be used in the invention consists in incorporating these and unsaturated polyesters, celluloses and polyamides, substances in a protective layer used to protect material may be at widely differing stages of their processing placed underneath it. This application may take the form (raw materials, semi-finished products or finished prod of applying the ultraviolet absorber to the surface layer ucts) and physical states. They may be in the form of O (of a film of a fibre or of a multidimensional shaped products shaped in a wide variety of ways, that is to object). This can be done for example similar to a dyeing say, for example, as prediominantly three-dimensional process, or the active substance may be embedded in a objects such as sections, vessels or components of a polymer (polycondensate or polyadduct) film by one of great variety, chips or granules, foamed products; pre the known surface coating methods with polymeric sub dominantly two-dimensional materials such as films, foils, 5 stances, or the active substance may be dissolved in a lacquers, impregnations or coatings, or predominantly suitable solvent and caused to diffuse or swell into the unidimensional materials such as filaments, fibres, flocks, surface layer. According to another important variant bristles or wires. The said materials may also be in the ultraviolet absorber is embedded in a self-support unshaped states in a wide variety of homogeneous or ing, substantially two-dimensional carrier material, for inhomogeneous forms of distribution and physical states, 20 example a foil or the wall of a vessel, in order to keep for example in the form of powders, solutions, normal ultraviolet rays away from the substance located behind and reversed emulsions (creams), dispersions, latices, it (relevant examples; shop windows, films, transparent sols, gels, putties, waxes, adhesives or pore fillers, and packages, bottles). the like. From the foregoing it is self-evident that in addition to Fibrous materials may be used in a wide variety of 25 the protection of the substrate or carrier material contain processing forms of non-textile materials, for example ing the ultraviolet absorber also other substances con as threads, yarns, fibre fleeces, padding, felts, flocculated tained in the substrate are protected, for example dye materials or as textile fabrics or textile laminates, knit stuffs antioxidants, disinfectants, antistatics and other wear, papers, cardboards and the like. dressing agents, plasticizers and fillers. The new stabilizers may also be used, for example, as 30 Depending on the type of substance to be protected or follows: stabilized, on its sensitivity or on the form in which the (a) In cosmetics, such as perfumes, dyed or undyed protection and stabilization is to be imparted, the re soaps and bath salts, skin and face creams, powders quisite amount of stabilizer may vary within wide limits, repellants and especially sunburn oils and creams; for example from about 0.01 to 10% by weight, referred (b) In admixture with dyestuffs or pigments or as to the amount of substrate to be protected. For most additives to dyebaths, printing, discharge or reserve pastes, practical purposes, however, a quantity from about 0.05 also for after-treating dyeings, prints or discharge prints; to 2% will suffice. (c) In admixture with so-called carriers, antioxidants, Accordingly, as results from the foregoing, the process other light filters, heat stablizers or chemical bleaches; for protecting organic materials from the effects of ultra (d) In admixture with crosslinking agents or dressing 40 violet radiation and heat consists in homogeneously dis agents such as starch or synthetically produced dressings; tributing the oxalic acid diamides described in the organic (e) In combination with detergents (the detergents material to be protected, or applying it to the surface of and stabilizers may, if desired, be added separately to said material or coating the material to be protected with the washing liquors); a filter layer containing one of the compounds men (f) In gelatin layers used in photography; tioned. (g) In combination with polymeric vehicles (products In particular, this is advantageously done by homogen of polymerization, polycondensation or polyaddition) in eously incorporating the oxalic acid diarylamides de which the stabilizers, if desired in addition to other sub stances, are incorporated in the dissolved or dispersed scribed in substance or in the dissolved or dispersed form form, for example in coating, impregnating or binding 50 in an amount of 0.1 to 10%, preferably 0.2 to 2.0% by agents (solutions, dispersions, emulsions) for textiles, Weight (referred to the weight of the material to be pro fleeces, papers, leathers; tected) in the organic material to be protected before the (h) As additives to a wide variety of industrial prod latter undergoes its final shaping. lucts to reduce the speed of their ageing, for example as If the Substance to be used according to this invention additives to glues, adhesives, paints or the like. is to be applied to the surface of the substrate to be pro If the protective compounds of this invention are to tected, thus for instance a fibrous material (fabric), this be used for the treatment of textile organic materials of is advantageously done by immersing the substrate to be natural or synthetic origin, for example textile fabrics, protected in a liquor in which the ultraviolet absorber is they may be applied to the substrate to be protected at dissolved or dispersed. Suitable relevant solvents are, for any desired phase of the final processing of the latter, such 60 example, methanol, ethanol, acetone, ethyl acetate, as during a dressing or anticrease finishing or dyeing methylethylketone, cyclohexanol and above all water. The process or during any other finishing operation, by way Substrate to be treated is left in the liquor for some time, of a fixing operation similar to a dyeing process. similar to the way that dyeing processes are carried out; Furthermore, the new stabilizers to be used according as a rule, 10 minutes to 24 hours at 10 to 120° C. suffice, to this invention are preferably added to or incorporated during which, if desired, the liquor may be agitated. with the materials prior to or during their shaping. Thus, Finally, the material is rinsed, if necessary washed, and for example, they may be added to the moulding or injec dried. tion moulding compositions used in the manufacture of In many cases it is advantageous to use the light filters films, foils, tapes or mouldings, or they may be dissolved described above in combination with sterically hindered or dispersed or in any other way finely distributed in the 70 phenols, esters of thiodipropionic acid or organic phos spinning mass before it is spun. The protecting com phorus compounds. pounds may also be added to the starting substances, re Unless otherwise indicated, parts and percentages in action mixtures or intermediates used in thhe manu the following Manufacturing Instructions and Examples facture of fully synthetic or semisynthetic organic mater 75 are by weight. 3,529,982 13 14 MANUFACTURING INSTRUCTION A1 settles out in the form of almost colourless crystals. Yield: about 12 parts. A mixture of 9.1 parts of the compound of the formula An analytically pure product obtained by 3 recrystal (34) lizations from benezene-1-methanol melts at 234 to 235 NH-C-C-O C2Hs 5 C. and reveals the following data: - Ca1d. for CHONCH (percent): C, 48.94; H, 2.64; Cl N, 8.15. Found (percent): C, 49.09; H, 2.48; N, 8.17. In a similar or different manner the compounds listed 6.5 parts of 3,4-dichloraniline and 0.5 part of boric acid in the following table were obtained. In this table is stirred for 2 hours at 175 to 180°C. while continu- 10 column I-formula number ously distilling off the alcohol formed. The melt is then columns II--III-definition of the compound dissolved in dimethylformamide and at 20° C. water is column IV-melting point in C. (uncorrected) added to the solution. column V=analytical data CHN The product of the formula 1stline: calculated (35) O O. 2nd line: found NH-6-5-NH Cl Concerning Compounds 45 in Table D1 it should be stated that the C12H25-residue is a mixture of different Cl branched isomers (from a tetramerization of 4 propylene 20 molecules). TABLE D1 (36) -NH-CO-CO-NH -W

1. II (Vis) III (W=) IV w 37....--H -NO2 252-253 E3, S 63 38--- a-H -NH 211-212 SS 3:3: 39------NH-CO-CEis 295-297 ( : E 3: 40..... --H -COOH >330 ( 38 : SS 41------B -COC 229-281 ES S 3:33 42.--- -CONE >330 3 43-----H -CO-N-CH2CH-CH2CH 267-269 10.63 - &H)-CH, 69.87 7.28 10.72 44.-----H -COONa) >330 E. S. 8: 45------H -COOCH 202-203 8:3, 3 SS 46.-----H -Cushas 75-90 ( : SS 8:S 4.-coo-{Xol -H 222-223 ( : 383 :8 48------CH2CH-OH 217-21s ( : , SS 49------H -CHCOOH 254-256 E: 3:3: 50-----H -CH2CHCH2CH3 178-180 3 & 83

TABLE D2 W-NE-CO-CO-NE-Wa I IICV=) III(W2=) W w 6. C-( >- -{ X-CH, 2n-22 { ai: ; ; 3. CF 53---- C-{X- -K) 189-190 ( :46.79 32:2.21 3:6.82 CFs Cl 54- so- B-{X- 249-250 ( 33 3: ; is... Br-( >- -{X-ch, as oo ( : 33: 2. CF 56.---- B-(>- - > 203-204-- { 42.73. 2.15. 6.. 64

3,529,982 17 TABLE D2-Continued (71) V-NH-CO-CO-NH-W2 II(V=) (III)Wa=) V w CF3 7. KC- - ) 88-89 { 47.7747.93 2,2.56 41 7.577.34 &l GH, 78. { X- -( >-CH, 240-242 { 72.327.2.02 6.436.46 9.769.92 CH3 74. N=C-( >- >330 { 60.1160.9 3.363.39 14,024.16 75----- H.C.0-{ X 277,279 { 63.9963.95 5.375.34 9.339.06 O 302-304 { 67.0.66,98 4,4.24 29 7.7.49 44

EXAMPLES OF USE 25 EXAMPLE 4 In the following examples of use there were used in A mixture of 100 parts of polypropylene and 0.2 part each case typical representatives of every subgroup of of the compound of the Formula 50, 53, 56, 66 or 71 is compounds of this invention. In principle, all compounds rolled to and fro on a calender at 170° C. to form a sheet mentioned in the foregoing description and their equiva which is then pressed at 230 to 240° C. under a maximum lents are equally suitable, except that it is only necessary 30 pressure of 40 kg./cm. to form a panel 1 mm. thick. to take into consideration the solubility of the compound The panels obtained in this manner are substantitally concerned in the individual substrate, or to determine it by impermeable to ultraviolet light within the region from means of a small-scale test. Finally, it may also be neces 280 to 350 mu. Other compounds listed in the table dis sary to bear in mind the fact that the absorption maxi play a similar behaviour. mum of the compound to be incorporated is affected by 35 EXAMPLE 5 the substituents in the aromatic residue. A solution of 0.2 part of the compound of the Formula EXAMPLE 1. 26 in 1.8 parts of monostyrene is mixed with 0.2 part of a solution of cobalt naphthenate in monostyrene (contain An acetylcellulose film of about 50p, thickness is pro ing 1% of cobalt). Then 40 parts of an unsaturated poly duced by pouring a 10% acetonic solution of acetylcellu 40 ester resin based on phthalic acid/maleic acid/ethylenegly lose containing 1% (referred to the acetylcellulose) of the col in monostyrene are added and the whole is stirred for compound of the Formula 72. After drying, the film re 10 minutes. Then 1.7 parts of a catalyst solution (methyl veals the following light transmission values in percent: ethylketone peroxide in dimethylphthalate) are dropped Light transmission in and the well-stirred, air-free mass is poured in between in percent 45 two panes of glass. After 20 minutes the polyester panel Wavelength of 1 mm. thickness has sufficiently solidified to be taken in mp. Unexposed Exposed out of the mould. The panel is impermeable to ultraviolet 260-310------O 0 320 - 5 5 light within the region from 280 to 350 mu. 330 - 20 20 Instead of the compound 26 it is possible to use, for 340 -- 50 50 50 350- 75 75 example, the compound of the Formula 52 or 53. EXAMPLE 6 1100 hours in a fadeometer. 25 grams of distilled monostyrene are prepolymerized An analogous behaviour is observed, for example, with in a stoppered bottle in a heating cabinet for 2 days at 90° compounds 29, 48, 66, 68 and 74. C., and then 0.25 g. of the compound of the Formula 66, EXAMPLE 2 67, 69 or 72 and 0.025 g. of benzoyl peroxide are slowly A paste from 100 parts of polyvinylchloride, 59 parts stirred in. The mixture is poured into a cubic mould of aluminium foil and heated for 1 day at 70° C. When the by volume of dioctylphthalate and 0.2 part of the com mass has completely cooled and solidified, the mould is pound of the Formula 66 is rolled to and fro on a calender broken apart. The resulting block is then pressed in a hy at 145 to 150° C. to form a foil about 0.5 mm. thick. The 60 draulic press at a temperature of 138 C. under a pressure resulting polyvinylchloride foil absorbs in the ultraviolet of 150 kg/cm. to form a panel 1 mm, thick. region from 280 to 350 mu. The polystyrene panels manufactured in this manner are Instead of the compound 66 there may be used, for impermeable to ultraviolet light within the region from example, the compound 45, 50, 54, 58 or 62. 280 to 350 mu; they are completely colourless. On ex EXAMPLE 3 65 posure in a fadeometer a distinct improvement in the sta A mixture of 100 parts of polyethylene and 0.2 part of bility to light is observed since polystyrene panels that the compound of the Formula 63 is rolled to and fro on a contain the above compounds of the above formulae do calender at 130 to 140 C. to form a foil which is then not show any sign of yellowing after 200 hours, while pressed at 150° C. panels that do not contain them have already turned yel The polyethylene foil obtained in this manner is sub low. A similar behaviour is displayed by other compounds stantially impermeable to ultraviolet light within the range listed in the table. from 280 to 350 mu, EXAMPLE 7 Instead of the compound 63 there may be used, for ex 8 grams of a mixture of toluylene-2,4-diisocyanate and ample, the compound 24, 55, 67 or 68. 75 toluylene-2,6-diisocyanate (65:35) and 20 g. of a slightly 3,529,982 19 20 branched polyester from adipic acid, diethyleneglycol and settles out in the form of almost colourless crystals. triol (hydroxyl number: 60) are stirred together for about Yield: about 26 parts. An analytically pure product ob 15 seconds. Then 2 ml. of a catalyst mixture (consisting tained by three recrystallizations from chlorobenzene of 6 ml. of a tertiary amine, 3 ml. of a dispersant, 3 ml. melts at 213-214 C. and reveals the following data: of a stabilizer and 2 ml. of water) and 0.28 g. of the com Calculated for C15H4ON (percent): C, 62.93; H, pound 53, 56, 66 or 72 are added and the whole is stirred 4.93; N, 9.79. Found (percent): C, 63.09; H, 5.04; N, for a short time. A foam fleece forms which is immersed 9.86. in water after 30 minutes. After another 30 minutes it is 2.9 parts of the compound of the Formula 78 are dis thoroughly washed with water and dried at room tempera solved in a mixture of 10 parts of acetone and 0.4 part ture. O of Sodium hydroxide in 10 parts of water. 0.1 part of The addition of one of the afore-mentioned ultraviolet sodium carbonate is added and at 20° C. within 5 minutes absorbers improves the stability during the exposure in 1.4 parts of dimethylsulphate are dropped in. The batch the Xeno test apparatus. The above absorbers also lend is stirred for another 4 hours at 45° C., mixed with themselves well to incorporation with numerous other methanol, cooled to 0° C., and the product of the for polyurethanes obtained by the isocyanate polyaddition 5 mula process. (79) O CH3 A similar behaviour is observed also with other com pounds listed in the table. Y-NH-CO-Co-HN EXAMPLE 8 20 0.2 gram of the compound of the Formula 26 is dis H3CO solved in 10 g. of pure olive oil. The compound dissolves is suctioned off. Yield: about 2.5 parts. rapidly and without heating. A 50a-thick layer of this An analytically pure specimen of the product obtained solution absorbs ultraviolet light up to 340 mu. after two crystallizations from benzene melts at 160-161 In the same manner other fatty oils and creams, or 25 C. and reveals the following data: emulsions used for cosmetic purposes may be used for Calculated for C18H16ON (percent): C, 63.99; H, dissolving the above compound and others, for example 5.37; N, 9.33. Found (percent): C, 63.98; H, 5.43; N, the compound 53, 60 or 72. 9.31. EXAMPLE 9 MANUFACTURING INSTRUCTION B 12 grams of polyacrylonitrile are sprinkled with stir 30 A solution of 5.8 parts of the compound of the For ring into 88 g. of dimethylformamide until all has dis mula 78 in 20 parts of dimethylsulphoxide and 0.8 solved, and then 0.1 g. of the compound of, for example, part of sodium hydroxide is mixed at 20° C. with 6.7 Formula 67 is added which dissolves immediately. The parts of n-octadecylbromide, the temperature is raised viscous mass is then applied to a cleaned pane of glass within 30 minutes to 45° C. and the whole is stirred on and spread out with a film drawing rod. The coated pane for 4 hours at the same temperature. The crystalline is then dried for 20 minutes in a vacuum drying cabinet magma is then mixed with methanol and the product at 120° C. and under a vacuum of 150 mm. Hg. A foil of the formula about 0.05 mm. thick is obtained which is easy to de tach from the glass support. The foil obtained in this 40 V/ manner is completely colourless and absorbs ultraviolet lights up to a wavelength of 350 mu, almost completely, NEH-CO-CO-HN while a foil not containing the absorber of the Formula 67 passes at least 80% of the ultraviolet light. Incidental H3CO ly, the compounds mentioned in connection with poly 45 obtained in the form of colourless crystals is suctioned styrene are also suitable for incorporation with poly off. Yield: about 10 parts. acrylonitrile. An analytically pure specimen obtained after two crystal MANUFACTURING INSTRUCTION A2 lizations from hexane melts at 90.5 to 91.5° C. and reveals the following data: A mixture of 22.3 parts of the compound of the for Calculated for CH500N, (percent): C, 73.56; H, mula 9.35; N, 5.20. Found (percent): C, 73.81; H, 9.46; N, (77) 5.25. -NH-CO-C O-O CH MANUFACTURING INSTRUCTION C A mixture of 9 parts of the compound of the For 5 5 mula (prepared by condensing the oxalic acid diester (81) H5COCO-COOCH 60 (prepared as described for Compound 78 in Manufactur With para-anisidine in an anhydrous medium containing ing Instruction A) in 40 parts of dichlorobenzene and 5.4 a catalytic amount of anhydrous boric acid at a tempera parts of capryloylchloride is heated for 2 hours at 120° ture from 110 to 115° C.), 10.9 parts of 2-amino-1- C. and then for /2 hour at 140° C., during which the phenol and 0.5 part of boric acid is stirred for 2 hours at mixture dissolves. It is then cooled to 80° C., 50 parts of 175 to 180 C., while continuously distilling off the al hot ethanol are added, the whole is cooled and the pre cohol formed. The melt is dissolved in dimethylformamide cipitate suctioned off. The product (11.5 parts) is washed and the Solution is mixed with water at 20° C. The prod With alcohol and dried at 60° C. in vacuo; it corresponds uct of the formula to the formula (82)

(78) -EN-CO-CO-HN and melts at 219 to 221 C. after recrystallization from chlorobenzene--alcohol. 3CO EO 5 Analytical data-Calculated for CHON, (per. 3,529,982 cent): C, 67.58; H, 7.09; N, 6.57. Found (percent): C, TABLE X1-Continued 67.65; H, 6.98; N, 6.64. . . - I II (X=) II IV The compounds listed in the following tables were 87 CF 590 3, 48 7.50 obtained in an identical or a similar manner. In these - - - - 198-1998 51.gi 3.26 35 tables: r Column I-formula number ) Column II-definition of the compound C Column III= melting point in C. (uncorrected) Column IV=analytical data CHN (1st line: calculated, 88---- CF 182-188 523 29 6.90 2nd line:o found) O 50.82 2.79 7.04 Concerning Compound No. 104 in Table X it should - > be mentioned that the C12H25-residue is a mixture of CF3 differently branched isomers (from tetramerization of 4 propylene molecules). 89.---- 198-1998 3: 3 SG Remark: In Tables X5 to X18, X21, X23 to X25 there l5 are shown on the right of the general basic formula the melting point and the analytical data of the starting Compound X-FH used as intermediate. p X-H used as intermediate - 90---- 166-167 { 60.29 4.74 8.79 TABLE X 60.14 4.48 8.88 (83) 20 CH3O -NH-CO-CO-NH-X1

------Cl I II (X1=) III IV 91---- 67.59 5.67 9.85 - 3 - 196-197 { - 68.3 - 6.06 - is 25 -> 194-1954 GS 8. CH3 CBs (241) TABLE X 85-...-- CH 191-1928 68.44. . . , 6.08 9,39 68.56 5.94 9.48 t30 CHO -NH-CO-CO-NE -X

I I (X2=) III W CE3 92 -CF 230-231. 67.59 5, 6 9.85 86---- Cl 233-234 { 53.09..., 8:3,3.47 8.263. 35 93-----BrCF8 280–281231 SAES 3.52 7.98S. 94----Cl 267–268 { 59.2859,12 4,4.28 30 9.9.1 19 95----, -N (C3)2 243-244 ESS is 35

TABLE X I II III IV OC2H5 O C2H5 96----- {)-in-co- o-sik D 122-123 (EE 8:59 253 O C2H5

...... (H, 97----- HC,0-{ X-NH-c O-C o–NH-( >-ch, 237-239 (8:8; 8.3 s. &H,

...... och, GH, os. CH,0-{ X-NH-co-co-NH-{ } 157-158 {:8; 8: ; CH3 (CH, C (CH3)3 99.---- ch,0-{ X-NH-c o-oo-su-k) 110-111 (8:38 : : - O C8H17 QCH, C (CH3)3 100.... CHO-K X-NH-c O-C o-K) 184-185 (8 O CH3 101.--- H.C.0-{ X-NH-c O-CO-NH- E. 147-148 (; ; ; ; 3.

3,529,982 30 TABLE X23 A similar behaviour is observed, for example, with the (221) ox. compound of the Formula 93, 138, 149, 152, 171, 201 or 208. NH-co-co -NH-{ X EXAMPLE 11 A paste from 100 parts of polyvinylchloride, 59 parts by volume of dioctylphthalate and 0.2 part of the com 72.28 4.85 8.43 pound of the Formula 79 is rolled to and fro on a cal X23-E.------203-204 {: ; S: ender at 145 to 150° C. to form a foil about 0.5 mm. II (X23=) III. IV thick. The polyvinylchloride foil obtained in this manner 222---, -CH 72.82 5. 24 8.09 IO absorbs ultraviolet light within the region from 280 to 3 145-146 (3. ;3 S. 360 mu. 223----C8H8. 105-106 {::75.65 SS7.26 8.3:6. instead of the compound of the Formula 79 there may 224 -CECH2CH2Cl2.2.2 148-149 (ES67.56 5.8E 6.6: be used, for example, the compound of the Formula 96, 5 97, 110, 117, 136, 152, 168, 176, 208, 222 or 233. TABLE X24 EXAMPLE 12 (225) ox. A mixture of 100 parts of polyethylene and 0.2 part of the compound of the Formula 107 is rolled to and fro on a calender at 130 to 140 C. to form a foil which NH-co-c o-suk ) 20 is then pressed at 150° C. The polyethylene foil obtained in this manner is sub { X-Ki > (CH), stantially impermeable to ultraviolet light within the re X24-H:------227–2288:2874.20 6.2733 7.213:3: gion from 280 to 350 mu. I I (X24=) III W Instead of the compound of the Formula 107 there may 25 be used, for example, the compound of the Formula 100, 226-- -CH3 190-191 { ;3874.60 SSS6.51 6.96is 110, 146, 161, 172, 189, 209 or 223. 227- - -Cs.H17 149-150 {33 5.8 i. 63 EXAMPLE 1.3 228 -CH2-CH-C-Cl 168-169 (8: 83 G A mixture of 100 parts of polypropylene and 0.2 part 229----CO-CEI3 166-167 2:35 & 8.3: 30 of the compound of the Formula 99, 121, 138, 168, 180, 70.86 6.37 5.90 189, 199, 204, 209, 210 or 224 is turned on a calender 230 -C-COOCs 157-158 23: 3:3: 3:38 at 170° C. into a sheet which is then pressed at 230 to 240° C. under a maximum pressure of 40 kg./cm.2 to TABLE X25 form a panel 1 mm. thick. (231) The panels obtained in this manner are substantially impermeable to ultraviolet light within the region from H.C.0-{ >-NH-c O-C o–NH-( >-ox. 280 to 360 mp. Other compounds listed in the table re veal a similar behaviour. 63. 99 5.37 9.83 X-25-Hi------280–282 3:32:3: 33 40 EXAMPLE 1.4 II (X=) III IV A solution of 0.2 part of the compound of the Formula 79 in 1.8 parts of monostyrene is mixed with 0.5 part 232--- –co-( > 270-272 { 68.30SY 4.99S 6.983.3 of a solution of cobalt naphthenate in monostyrene (con taining 1% of cobait). Then 40 parts of an unsaturated 70, 42 6.13 6,08 polyester resin based on phthalic acid/maleic acid/ethyl 233.--- –co-( >-CCH). 281-282 ( 28 S. S. eneglycol in monostyrene are added and the whole is stirred for 10 minutes. 1.7 parts of a catalyst solution 234. -CO-NH-CHCH-CH, CH, 272-275 : 3 & 8:3 (methylethyl ketone peroxide in dimethylphthalate) are 235 -CH3 229–230 ( 3.33 E. S.S. dropped in and the well-stirred, air-free mass is poured 50 in between two panes of glass. After about 20 minutes 236----C4Hg 228-229 E3 E3 : the polyester panel of about 1 mm. thickness has suffi 237----C8H17 205-206 ( : ; ; 8:3 ciently solidified to be taken out of the mould; it is im 238-- -C12H25 202-203 :23 ES 3.3 permeable to ultraviolet light within the region from 280 70, 75 5, 68 7.18 to 350 mu, and reveals no sign of yellowing after 1000 239--- -CH-( > 245–246 283 : 3 hours' exposure in the xeno test. Instead of the compound of the Formula 79 there may 240 -CH-CH=CH f 67.04 5.92 8.23 be used, for example, the compound of the Formula 84, 2 2 243-244 863; S3; Si3 122, 141, 159, 165, 176, 187, 211 or 227. EXAMPLE 10 60 EXAMPLE 15 An acetylcellulose film about 50 u, thick is produced by 25 grams of distilled monostyrene are prepolymerized pouring out a 10% acetonic solution of acetylcellulose in a stoppered flask in a heating cabinet for 2 days at containing 1% (calculated from acetylcellulose) of the 90° C. Then 0.25 g. of the compound of the Formula compound of the Formula 106. The dried film reveals the 107, 114, 117, 126, 157, 178, 220 or 227 and 0.025 g. of following light transmission values in percent: 65 benzoyl peroxide are slowly stirred into the viscous mass. The mixture is poured into a cubic mould made from Light transmission aluminium foil and heated for 1 day at 70° C. After the in percent Wavelength mass has completely cooled and solidified, the mould is in mp. Unexposed Exposed 1 broken apart. The resulting block is then pressed in a O hydraulic press at 138 C. under a pressure of 150 kg./ 260-340- O 0 350- 3. 3 cm. to form a panel 1 mm. thick. 360 10 O 370 30 30 The polystyrene panels manufactured in this manner 380. 55 55 are impermeable to ultraviolet light within the region from 280 to 350 mu; they are completely colourless. On 1 100 hours in a fadeometer. 75 exposure in a fadeometer a distinct improvement in the 3,529,982 3. q9 stability towards light is observed since polystyrene panels EXAMPLE 2.0 containing a compound of the above formulae display 12 grams of polyacrylonitrile are sprinkled with stir no sign of yellowing after 200 hours' exposure, while ring into 88 g. of dimethylformamide until all has dis panels that do not contain such an absorber have already solved, and then 0.1 g. of the compound of, for example, become yellow. Similar results are obtained with other Farmula. 79 is added which dissolves immediately. The compounds listed in the table. viscous mass is then applied to a cleaned pane of glass EXAMPLE 16 and spread out with a film drawing rod. The coated pane is then dried for 20 minutes in a vacuum 0.1 gram of the compound of the Formula 78, 123, drying cabinet at 120° C. and under a vacuum of 130, 141, 156, 181, 192, 209, 224 or 233 is dissolved O 150 mm. Hg. A foil about 0.05 mm. thick is obtained in 40 g. of clear nitrocellulose lacquer of 25% strength. which is easy to detach from the glass support. The foil The lacquer is then evenly spread over maple boards with obtained in this manner is completely colourless and a coating doctor and is completely dry after a short time. absorbs ultraviolet light up to a wavelength of 350 mp. The addition of the above-mentioned ultraViolet absor almost completely, while a foil not containing the absor bers does not change the shade of the wood. The light ber of the Formula. 79 passes at least 80% of the ultra colour of the lacquered wood is not changed either after violet light. Incidentally, the compounds mentioned in several days exposure to the light of an ultraviolet lamp, connection with polystyrene are also suitable for incor provided the lacquer contains one of the above-men pcration with polyacrylonitrile. tioned compounds in a concentration of about 1%. Un We claim: treated wood darkens after only a few days' exposure 20 1. Process for protecting an organic material selected as described. from the group consisting of acetylcelluose, polyvinyl Similar results are obtained by using acrylic resin chloride, synthetic polyamides and copolymers of un lacquers of alkyd-melamine resin lacquers and other satured polyesters from the action of ultraviolet rays, compounds listed in the table. wherein an asymmetrical compound is applied to the EXAMPLE 17 25 organic material, said compound being free from hy 8 grams of a mixture of tolaylene-2,4-diisocyanate and droxyl groups in the ortho-positions to the amide nitrogen toluylene-2,6-diisocyanate (65:35) and 20 g. of a slight atom and corresponds to the formula ly branched polyester from adipic acid, diethyleneglycol Y Y. Y, Y and triol (hydroxyl number: 60) are stirred together 30 for about 15 seconds. Then 2 mi. of a catalyst mixture -NFI-CO-CO-NE (consisting of 6 ml. of a tertiary amine, 3 ml of a dis persant, 3 ml. of a stabilizer and 2 ml. of water) and Y Ys Y y 0.28 g. the compound (100), (107), (132), (150), (154), wherein Y1, Ys, Y and Ys' each represents a member (187), (208) or (223) are added and the whole is stirred 3 5 selected from the group consisting of hydrogen, halogen, for a short time. A foam fleece forms which is immersed a substituent containing up to 20 carbon atoms selected in Water after 30 minutes. After another 30 minutes it is from the group consisting of alkyl, substituted alkyl, thoroughly washed with water and dried at room tem -CO-NH-E, wherein E is hydrogen or alkyl, perature. -COOE2, where E2 is hydrogen or alkyl, and Y, Ya, The addition of one of the afore-mentioned ultra 40 Y4, Y, Ya' and Y, each represents the same group as violet absorbers improves the stability during the ex Y1, Ys, Y and Y and where (a) each benzene nucleus posure in the xeno test apparatus. The above absorbers contains at most two residues selected from the group also lend themselves well to incorporation with numerous consisting of -CO-NH-E and -COOE2, and (b) other polyurethanes obtained by the isocyanate polyaddi each benzene nucleus contains at most three of the other tion process. Substituents different from hydrogen, and the substituents A similar behaviour is observed also with other com 45 in the two benzene nuclei differ from each other in at pounds listed in the table. least one point insofar as kind, number or positions are concerned. EXAMPLE 1.8 2. Process according to claim i, wherein there are ap 10,000 parts of a polyamide in chip form, prepared in plied asymmetrical compounds, free from hydroxyl flnown manner from caprolactam, are mixed for 12 groups in the ortho-positions, of the formula hours with 30 parts of the compound of the Formula 107, 165, 184 or 208 in a tumbler. The chips treated in Yi Yo this manner are then melted in a boiler heated at 300 C., from which the atmospheric oxygen has been dis 5 5 placed with superheated steam, and the melt is stirred in which Y16 represents a member selected from the for 2 hour, then expressed through a spinneret under a group consisting of hydrogen, halogen and an alkyl group nitrogen pressure of 5 atmospheres (gauge), and the re with 1 to 4 carbon atoms, Y1, a hydrogen atom or an sulting, cooled filament is wound on a spinning top, alkyl group with 1 to 4 carbon atoms, Y18 a member whereby it is at the same time stretched. Selected from the group consisting of hydrogen, halo The addition of the above-mentioned compounds sub 60 gen, an alkyl group with up to 18 carbon atoms which stantially inhibits the degradation of the macromolecules may be substituted by hydroxyl groups or halogen atoms, - caused during the exposure in the fadeometer and deter a carboxylic acid group, a carboxylic acid amide or mined by measuring the relative viscosity in concentrated carboxylic acid ester, and Y19 represents a hydrogen or sulphuric acid. Other compounds of the table behave 65 halogen atom, with the proviso that at least one Y-sub similarly. stituent is different from hydrogen. EXAMPLE 1.9 3. Process according to claim 1, wherein there are ap 0.3 gram of the compounds of the Formula 80 is dis plied asymmetrical compounds of the formula solved in 10 g. of pure olive oil. The compound dissolves Y rapidly and without heating. A 50tu-thick layer of this 70 solution absorbs ultraviolet light up to 340 mu. In the same manner other fatty oils and creams, or emulsions used for cosmetic purposes may be used for in which Y21 and Yaa and Yai and Y, respectively, rep dissolving the above compound and others, for example resent a member selected from the group consisting of the compound (107), (138), (155), (178) or (189). 75 chlorine, bromine and an alkyl group with 1 to 4 carbon 3,529,982 33 34 atoms, and one of the two substituents Y21, Y22 and Yai, sisting of an alkyl group with 1 to 4 carbon atoms, a Y22 represents a member selected from the group consist fluor-alkyl group, fluorine, chlorine and bromine. ing of hydrogen, a carboxylic acid group and a carboxylic acid alkyl ester group with 1 to 8 carbon atoms in the alkyl grouping. References Cited 4. Process according to claim 1, wherein there are ap UNITED STATES PATENTS plied compounds of the general formula 3,211,562 10/1965 Biland et al. ----- 260-45.9 Y24 3,239,484 3/1966 Stark ------260-45.9 3,296,163 1/1967 Manaresi et al. ----- 260-45.9 l Y25 O HOSEA. E. TAYLOR, JR., Primary Examiner in which Y23 represents a member selected from the group consisting of hydrogen, an alkyl group with 1 to 4 carbon U.S. C. X.R. atoms, fluorine, chlorine and bromine, and Y24 and Y25 106-186; 117-138.5, 138.8, 144; 252-300; 260-45.85, each stands for a member selected from the group con lö 45.9, 595