DE1618196C - Use of asymmetric oxalic acid diarylamides as ultraviolet protection agents - Google Patents

Description

The present invention relates to the protection of organic materials by Ultraviolet radiation can be damaged in various ways against exposure to it this radiation with the help of asymmetric oxalic acid diarylamides, which are free of hydroxyl groups in the o-position for bonding the aryl radicals to the amide nitrogen atoms are.

It has already been described that oxalic acid-bis-oxyarylamide as a protective agent against Ultraviolet radiation is suitable, but it was previously believed that the light stability of such compounds bound to the presence of two free hydroxyl groups o to the amide nitrogen may be. Compounds of this type are e.g. B. in the German Auslegeschrift 1 188 080 described. This However, compounds give different substrates

discoloration when exposed to light, which in many cases makes the substrates unusable.

Contrary to the above view, it has now been found that there is an extensive class of oxalic acid diaralyamides without the mentioned

sometimes not only prove to be technically excellently usable ultraviolet absorbers, but surprisingly show a higher light stability. There is no discoloration of the substrates.

The present invention relates to
amides of the general formula

hereafter the use of asymmetric oxalic acid diaryl

(R ₁ O) _n

CO-NH

wherein R _{1 is} the methyl or ethyl group, R _{2 is} an alkyl group containing 1 to 18 carbon atoms, which can be substituted with a chlorine atom, a / 3-cyanoethyl, carboxyl, carboxamide or carboxy alkyl ester group with 1 to 12 carbon atoms, the allyl group, a benzyl group optionally substituted with a chlorine atom or an alkyl group containing 1 to 4 carbon atoms, a fatty aliphatic acyl group containing up to 12 carbon atoms, a benzoyl group optionally substituted with a chlorine atom or an alkyl group containing 1 to 4 carbon atoms, R _{3 represents} the chlorine atom, the methyl , Nitrile or phenyl group and R _{4 is} an alkyl group containing 1 to 12 carbon atoms, the chlorine atom, the trifluoromethyl group, the phenyl group or a phenylalkyl group with 1 to 4 carbon atoms in the alkyl part, or two o-position radicals R ₄ together form a fused benzene ring and where m = 0, 1 or 2, η = 1, 2 or 3, P = 1 or 2 and q = 1, 2, 3 or 4, each of the two ring systems containing at most three substituents in addition to the bond via the --NH - group and the sum m + (n - 1 ) has the values 1, 2 or 3 and, moreover, the substituents R ₁ O-, R ₂ O-, R ₃ and R ₄ are such as to type, number or position that an asymmetric molecule is present as an ultraviolet protective agent for organic materials that are damaged by ultraviolet radiation.

From the large number of compounds according to the above formulas, z. B. the following compounds singled out

CH ₃ O

H ₃ C CH ₃

NH - CO - CO - NH- / VC

/ V ^ CH
H ₃ CO ^Utl3

(12)

CH, O

NH - CO - CO - NH

H ₁₇ QO

Cl

(13)

CH, 0

NH-CO - CO-NH

(14)

CH ₃ CH ₃

C CH ₂ C CH ₃

CH ₃ CH ₃

CH ₁ O

NH- CO - CO -

CH ₃ CH ₃

C - CH ₂ - C - CH ₃

CH ₃ CH ₃

CH, O

NH-CO-CO -NH

OC ₈ H _n

(16)

O - CH ₂ - CH = CH ₂

CH, O

NH-CO-CO -NH

The asymmetric oxalic acid diarylamides described above are accessible in analogy to processes known per se. They can be prepared by analogously to methods known per se, by amidating oxalic acid, its half-esters or symmetrical and asymmetrical diesters with primary aromatic amines in an equimolecular amount in the first stage on one side. The amic acid or amide ester obtained primarily is then converted into the diamide by reaction with a further amine different from the primary aromatic amine used first. Both reaction stages can be carried out in the melt or in the presence of organic solvents which are inert towards the reactants, the temperatures depending on the nature of the reaction medium. Normally, is condensed in a first stage between 50 and 200 ⁰ C, while higher in the second stage by 50 to 100 ° C temperatures, ie, temperatures between 150 and 250 ⁰ C, suitably are. When working in the presence of inert solvents, condensation at the boiling point of the reaction mixture with azeotropic removal of the alcohol or water to be split off is recommended. Free hydroxyl groups are then etherified or esterified according to methods known per se. Suitable inert solvents are for example benzene, toluene, chlorobenzene, and also in particular those with a lying above about 140 ⁰ C boiling point, such as di- and trichlorobenzene, polyhydric alcohols or their ethers such as ethylene glycol, diethylene glycol, triethylene glycol, glycerol, Diäthylenglykoldiäthyläther, high-boiling hydrocarbons such as p-cymene, etc. A preferred process for the preparation of asymmetric oxalic acid diarylamides according to formula (1)

(17)

consists in that the carboxyl groups or carboxylate groups of oxalic acid or its half-ester or diesters with primary aromatic amines in the presence of anhydrous boric acid (in the Melt or in the presence of inert solvents) in amounts of 0.1 to 5 percent by weight, based to oxalic acid or ester.

The second reaction stage of the present process thus exists in the case of the compounds according to formula (1) in that one oxalic acid derivatives of the formula

(RiO)
with amines of the formula

(OZ) _n _,

(19)

wherein R ₁ , R ₃ , R ₄ m, n, p, q have the meaning given above, A _{1 represents} a hydroxyl group, a halogen atom or an alkoxy group having 1 to 12 carbon atoms, a group —O-benzyl or —O-phenyl , and Z represents a hydrogen atom or as defined above for R _2, are condensed at temperatures of 50 to 250 ⁰ C and closes free hydroxyl groups by subsequent etherification or acylation.

The preferred embodiment of the preparation process for compounds of the general formula

(1) then, according to the above statements, consists in using oxalic acid derivatives of the formula

NH

(R ₁ O) _n ,

with amines of the formula

-CO-CO-A ₂

(20)

H ₉ N

\ _A

(21)

wherein R ₁ , R ₃ , R ₄ , Z, m, η, ρ and q have the meaning given above and A _{2 is} an alkoxy group containing 1 to carbon atoms, in the melt or in a solvent inert to the reactants in the presence of anhydrous boric acid at temperatures of up to 250 ⁰ C condensed and free hydroxyl groups and then closes by etherification or acylation.

It is advisable to use 0.1 to 5 percent by weight of anhydrous boric acid, calculated on the oxalic acid derivative, used and maintained reaction temperatures between 150 and 200 ° C.

For the present procedure - always within the framework of the requirements according to formula (1) - For example, the following amines are used to form one of the two amide groups will:

Aniline,

2-chloroaniline,

4-chloroaniline,

3-chloroaniline,

2,4-dichloroaniline,

3,4-dichloroaniline,

2,4,6-trichloroaniline and the corresponding bromine

aniline,
2-fluoroaniline,
3-fluoroaniline,
4-fluoroaniline,
2-iodoaniline,
4-iodoaniline,
3,5-diiodaniline,

2-methyl-, 3-methyl- or 4-methylaniline,
2,4-dimethylaniline,
2,5-dimethylaniline,
2,6-diethylaniline,
2-methyl-5-isopropylaniline,
2-methoxy-, 3-methoxy- or 4-methoxyaniline, 2,4-dimethoxy- and 2,5-dimethoxyaniline,
2,5-diethoxyaniline,
4-butoxyaniline,
3-trinuomethylaniline,
3,5-bis-trifluoromethylaniline,
4-nitro-, 2-nitro- and 3-nitroaniline,
3-hydroxy- or 4-hydroxy-aniline,
2-aminodiphenyl,
m-aminoacetanilide,
p-aminoacetanilide,
3-aminobenzoic acid,
4-aminobenzoic acid and its amides,
Anthranilic acid and its methyl and ethyl esters

p-amino-NN-dimethylaniline,
4-aminomethyl benzoate and ethyl benzoate,
Methanilic acid,
Sulfanilic acid,
Metanilamide,
Sulfanilamide,

4-hydroxy-3,5-di-tert-butylaniline,
4-hydroxy-3,5-dichloroaniline,
4,5-dichlorosulfanilic acid,
2-methoxy-5-methylaniline,
4-methyl-3-chloroaniline,
2-chloro-4-trifluoromethylaniline,
2,4-dimethoxy-5-chloroaniline,
2,4-dimethyl-6-nitroaniline.

Possible naphthylamines are:

ct-naphthylamine,
(S-naphthylamine,

Sulfonic acids of naphthylamines such as

1-naphthylamine-4-sulfonic acid,
1-naphthylamine-5-sulfonic acid,
1-naphthylamine-8-sulfonic acid,
2-naphthylamine-1-sulfonic acid,

2-naphthylamine-5-sulfonic acid,

2-naphthylamine-4,8-disulfonic acid,
2-naphthylamine-6,8-disulfonic acid,
8-hydroxy-1-naphthylamine-4-sulfonic acid,
8-hydroxy-2-naphthylamine-6-sulfonic acid,

8-hydroxy-1-naphthylamine ^ o-disulfonic acid,

8-hydroxy-1-naphthylamine ^ o-disulfonic acid,
8-hydroxy-2-naphthylamine-3,6-disulfonic acid.

Hydroxyamines in which a hydroxyl group appearing in ortho position to the amide nitrogen is attached still has to be etherified:

2-hydroxyaniline,

2-hydroxy-5-phenylaniline,

2-hydroxy-4-phenylaniline,

2-hydroxy-5-methylaniline,

2-hydroxy-5-chloroaniline,

2-hydroxy-5-isooctylaniline,

2-hydroxy-5-dodecylaniline,

2-hydroxy-4-methoxyaniline,

2,4-dihydroxyaniline,

l-hydroxy-2-naphthylamine,

2-hydroxy-1-naphthylamine.

With the help of the oxalic acid diamides described above In principle, all such organic materials can be stabilized and protected, which are damaged or destroyed in any way by the influence of ultraviolet rays. Such Damage from exposure to the same cause, namely ultraviolet radiation, can be very severe have various effects, for example color change, change in mechanical properties (Fragility, cracking, tear strength, flexural strength, abrasion resistance, elasticity, aging), introduction unwanted chemical reactions (decomposition of sensitive chemical substances by photochemically induced rearrangements, oxidation, etc. (for example of unsaturated fatty acids containing oils), triggering of burns or irritations (e.g. in human Skin). The use of the asymmetric ones defined above is of preferred importance Oxalic acid diarylamides to protect polycondensation

sation products and polyaddition products against the effects of ultraviolet.

The organic materials to be protected can be in a wide variety of processing states and States of matter exist, while their common characteristic is a sensitivity to There is ultraviolet radiation.

As low-molecular or higher-molecular substances, for which the method according to the invention for protecting or stabilizing comes into consideration, are for example named: organic natural substances, such as those used for pharmaceutical purposes, UV sensitive dyes, compounds used as food or in food by exposure to light are decomposed (unsaturated fatty acids in oils).

Examples of high molecular weight organic substances are:

I. Synthetic organic high molecular or higher molecular materials such as:

a) Polymerization products based on organic compounds containing at least one polymerizable carbon-carbon double bond, ie their homopolymers or copolymers and their aftertreatment products such as crosslinking, grafting or degradation products, polymer blends, modification products by modifying reactive groups in the polymer molecule, etc., such as B. polymers based on α, β-unsaturated carboxylic acids (z. B. acrylates, acrylamides, acrylonitrile), olefin hydrocarbons such. B. α-olefins, ethylene, propylene or dienes, so that also rubbers and rubber-like polymers (so-called ^{ABS-Polymeri:} sate), polymers based on vinyl and vinylidene compounds (such as styrene, Vinylester, vinyl chloride. Vinyl alcohol), halogenated hydrocarbons, unsaturated aldehydes and ketones, allyl compounds, etc .;

b) other polymerization products such. B. obtainable by ring opening, e.g. B. polyamides from Polycaprolactam type, also formaldehyde polymers or polymers that are available both via polyaddition and polycondensation are, such as polyethers, polythioethers, polyacetals, thioplasts.

c) Polycondensation products or precondensates based on bifunctional or polyfunctional compounds with condensable groups, their homo- and mixed condensation products and Post-treatment products, for which examples include: polyester (saturated [e.g. Polyethylene terephthalate] or unsaturated [e.g. B. maleic acid - dialcohol - polycondensates as well their crosslinking products with polymerizable vinyl monomers], unbranched and branched ones [also based on higher alcohols, such as B. alkyd resins]), polyamides (e.g. hexamethylenediamine - adipate), maleinate resins, melamine resins, phenolic resins (e.g. novolaks), aniline resins, Furan resins, carbamide resins, or their precondensates and similarly built products, Polycarbonates, silicone resins and others.

d) Polyaddition products such as polyurethanes (crosslinked and uncrosslinked), epoxy resins.

II. Semi-synthetic organic materials such as. B. cellulose esters or mixed esters (acetate, propionate), Nitrocellulose, cellulose ether, regenerated cellulose (viscose, copper ammonia cellulose) or their Aftertreatment Products, Casein Plastics.

III. Natural organic materials of animal or vegetable origin, for example Base of cellulose or proteins such as wool, cotton, silk, raffia, jute, hemp, fur and hair, leather,

ίο Finely divided wood masses, natural resins (such as Colophony, especially varnish resins), gelatine, glues, also rubber, gutta-percha, balata, and their aftertreatment and modification products, degradation products, more reactive through modification Products available to groups.

The organic materials in question, in particular plastics from the polymer class des vinyl chloride, saturated and unsaturated polyesters, celluloses and polyamides can be found in the Various processing states (raw materials, semi-finished products or finished products) and aggregate states are present. They can even be in the form of the most varied of shaped structures, i. H. so z. B. predominantly three-dimensionally extended bodies such as profiles, containers or a wide variety of Workpieces, chips or granulates, foams; predominantly two-dimensional bodies like Films, foils, lacquers, impregnations and coatings or predominantly one-dimensional ones Bodies such as threads, fibers, bristles, wires. On the other hand, said materials can also be in unformed States in the most varied of homogeneous and inhomogeneous distribution forms and Physical states exist, e.g. B. as powder, solutions, normal and reverse emulsions (creams), Dispersions, latices, sols, gels, putties, waxes, adhesives and fillers, etc.

Fiber materials. can be available in a wide variety of predominantly non-textile processing forms, z. B. as threads, yarns, nonwovens, felts, wadding, flocking structures or as textile fabrics or textile composites, knitted fabrics, paper, cardboard, etc.

The new stabilizers can also be used, for example, as follows:

a) in cosmetic preparations such as perfumes, colored and uncolored soaps and bath additives, Skin and face creams, powders, repellants and especially sun protection oils and creams,

b) as a mixture with dyes or pigments or as an additive to dye baths, printing, etching or Reserve pastes. Also for post-treatment of dyeings, prints or etching prints,

c) in mixtures with so-called "carriers", antioxidants, other light stabilizers, heat stabilizers or chemical bleaches,

d) mixed with crosslinkers, finishing agents such as starch or synthetically accessible finishes,

e) in combination with detergents. The detergents and stabilizers can be the ones to be used Washing baths can also be added separately,

f) in gelatine layers for photographic purposes,

g) in combination with polymeric carrier materials (polymerization, polycondensation or poly

209 633/199

addition products), in which the stabilizers are incorporated, optionally in addition to other substances in dissolved or dispersed form, e.g. B. for coating, impregnating or binding agents (solutions, dispersions, emulsions) for textiles, nonwovens, paper, leather,
h) as additives to a wide variety of industrial products to reduce their aging rate, e.g. B. as an additive to glues, adhesives or paints.

If the protective agents to be used according to the invention are for the treatment of organic textiles Materials of natural or synthetic origin, e.g. B. textile fabrics are to be used, they can be used in every phase of the final processing, such as finishing, anti-crease finishing, dyeing processes, other finishing by fixation process similar to dyeing processes on the to be protected Substrate are applied.

The new stabilizing agents to be used according to the invention are preferably added to the materials added or incorporated before or during their deformation. For example, you can use it at the production of films, foils, tapes or moldings of the molding compound or injection molding compound or dissolve, disperse or otherwise finely distribute in the spinning mass before spinning. the Protective agents can also be added to the starting substances, reaction mixtures or intermediates Production of fully or semi-synthetic organic materials, i.e. also before or during the chemical Implementation, for example in the case of a polycondensation (including precondensates), in the case of a polymerization (also prepolymers) or a polyaddition can be added.

An important application variant for the stabilizers to be used according to the invention consists in the fact that these substances are incorporated into a protective layer, which is the one behind them Protect material. This can be done in such a way that the ultraviolet absorber acts on the Surface layer (a film, a fiber of a multi-dimensional molded body) are applied.

This can be achieved, for example, by a kind of dyeing process or the active substance known surface coating methods with polymeric substances in a polymer (polycondensate, Polyadduct) film, or you can mediate the active ingredient in dissolved form a suitable solvent diffuse into the surface layer or allow it to swell. Another important variant is that the ultraviolet absorber is essentially two-dimensional Carrier material, ζ. B. a film or a vessel wall, is embedded in order to do so Keep ultraviolet radiation in front of the substance behind it (examples: shop windows, films, transparent packaging, Bottles).

It goes without saying from the above that in addition to protecting the substrate or the carrier substance, which contains the ultraviolet absorber, at the same time also the protection from other accompanying substances of the substrate, for example dyes, antioxidants, disinfectant additives, antistatic agents and others Finishes, plasticizers and fillers.

Depending on the type of substance to be protected or stabilized, on its sensitivity or the application form of protection and stabilization can determine the required amount of stabilizer vary within wide limits, for example between about 0.01 and 10 percent by weight, based on on the amount of substrate to be protected. For most practical purposes, however, quantities are sufficient from about 0.05 to 2%.

The following procedure for protecting organic materials from exposure from ultraviolet radiation and heat thus consists in using the oxalic acid diamides described homogeneously distributed in the organic materials to be protected, superficially on these materials applies or covers the materials to be protected with a filter layer, which the designated Contains connections.

In particular, it is expedient to proceed in such a way that the asymmetric oxalic acid diarylamides described are used in substance, in dissolved or dispersed form in the organic materials to be protected in amounts of 0.1 to 10, preferably 0.2 to 2.0 percent by weight, based on the amount of materials to be protected are incorporated in a homogeneous distribution before the final deformation.

If the substance to be used according to the invention is to be applied superficially to the substrate to be protected, e.g. If, for example, a fiber material (fabric) is applied, this can advantageously be seen in such a way that the substrate to be protected is introduced into a liquor which contains the UV absorber in dissolved or dispersed form. Suitable solvents can e.g. B. methanol, ethanol, acetone, ethyl acetate, methyl ethyl ketone, cyclohexanol or especially water. As in dyeing processes, the substrate to be treated is left in the liquor for a certain time - usually 10 minutes to 24 hours - at 10 to 120 ^° C., it being possible for the liquor to be moved if necessary. The material is then rinsed, optionally washed and dried.

It is often expedient to use the light stabilizers described above in combination with sterically hindered ones Use phenols, esters of thiodipropionic acid or organic phosphorus compounds.

The parts and percentages given in the following production instructions and examples always represent parts by weight and percentages by weight, unless otherwise stated.
50

Manufacturing instruction A

22.3 parts of the compound of formula

NH-

H ₃ CO

CO- ¹ CO OC ₂ H ₅

(22)

(produced by condensation of the oxalic acid _{diester H 5} C ₂ OCO - COOC ₂ H ₅

anhydrous with p-anisidine in anhydrous medium in the presence of catalytic amounts of boric acid at temperatures of 110 and 115 ° C) are mixed with 10.9 parts of 2-amino-l-phenol and 0.5 parts of boric acid for 2 hours at 175 to 180 ⁰ C. stirred, the alcohol formed continuously distilling off

will. The melt is then dissolved in dimethylformamide, and water is ^{added to the solution at 20 ° C.} The product of the formula

H ₃ CO

NH-CO-CO-HN

HO

(23)

It separates out in the form of almost colorless crystals. Yield about 26 parts. One three times from chlorobenzene recrystallized analysis product melts at 213 to 214 ° C and shows the following data:

C ₁₅ H ₁₄ O ₄ N ₂ : . C. 62.93, H 4.93, N 9.79%; Calculated .. . C. 63.09, H 5.04, N 9.86%. found ...

2.9 parts of the compound of formula (23) are dissolved in a mixture of 10 parts of acetone and 0.4 part of sodium hydroxide in 10 parts of water. 0.1 part of soda is added and 1.4 parts of dimethyl sulfate are then added dropwise at 20 ° C. over 5 minutes. Followed by 4 hours at 45 ° C is stirred, treated with methanol, cooled to 0 ⁰ C and the product of formula

NH-CO-CO-HN

H ₃ CO

OCH ₃

(24)

sucked. Yield: about 2.5 parts.

An analysis product recrystallized twice from benzene melts at 160 to 161 ^° C. and shows the following data:

C ₁₆ H ₁₆ O ₄ N ₂ :

Calculated ... C 63.99, H 5.37, N 9.33%;
found .... C 63.98, H 5.43, N 9.31%.

trium hydroxide dissolved. Thereto is added to the solution at 2O ⁰ C and 6.7 parts n-octadecyl, increasing the temperature for a half hour at 45 ° C and stirred for 4 hours at the same temperature further. Now methanol is added to the crystal slurry and the product of the formula is sucked off

NH-CO -CO ^

H, C0

HN

O - CH ₂ - (CH ₂ ) ^ - CH ₃

(25)

which is in the form of colorless crystals. Yield: about 10 parts.

An analysis product recrystallized twice from hexane melts at 90.5 to 91.5 ° C and shows the following data:
C ₃₃ H ₅₀ O ₄ N ₂ :

Calculated ... C 73.56, H 9.35, N 5.20%;
found .... C 73.81, H 9.46, N 5.25%.

Manufacturing instruction C
9 parts of the compound of formula

H, C, O

NH-CO-CO-HN

Manufacturing specification B

5.8 parts of the compound of formula (23) are in 20 parts of dimethyl sulfoxide and 0.8 parts of Na-

OH

(26)

(prepared in an analogous manner to the compound (23) in the preparation procedure A) are lifted in 40 parts of dichlorobenzene together with 5.4 parts of capryloyl chloride for 2 hours at 120 ⁰ C and for _V2 hour at 140 ⁰ C. The mixture goes into solution. It is then cooled to 80 ⁰ C, is 50 parts hot ethyl alcohol to cool and suction filtered the precipitate. The product (11.5 parts) of the formula, washed with alcohol and ^{dried in vacuo at 60 ° C.}

H ₅ C ₂ O

NH

(27)

melts after recrystallization from chlorobenzene-alcohol at 219 to 221 ° C and has the following analytical data:

C ₂₄ H ₃₀ O ₅ N ₂ :

Calculated .
found ..

C 67.58, H 7.09, N 6.57%;
C 67.65, H 6.98, N 6.64%.

The compounds listed in the tables below were prepared in the same or an analogous manner manufactured. In these tables:

Column I = formula number
Column II = definition of the connection
Column III = melting point in ⁰ C (uncorrected)

Column IV = analysis data C, H, N

(first line calculated; second line found)

Regarding compound no. 50 in Table X ₃ , it should be noted that the C ₁₂ H ₂₅ radical represents a mixture of differently branched isomers (from tetramerization of four propylene molecules).

annotation

Tables X ₅ to X ₁₈ , X ₂₁ , X ₂₃ , X ₂₄ and X _{25 show} the melting point and analytical data of the starting compound (X = H) used as an intermediate to the right of the general basic formula.

NH - CO - CO - NH -X ₁

I. H (X ₁ =) III 68.44
68.31 f 50.26
50.82 IV 9.39
9.53 CH ₃ 29 196 to 197 68.44
68.56 71.24
71.32 6.08
6.06 9.39
9.43 CH ₃ 60.29
60.14 30th I. 191 to 192 6.08
5.94 CH ₃ 53.12
53.09 67.59
67.56 8.26
8.26 Cl
I. 31 -4 233 to 234 51.90
51.91 3.57
3.47 7.50
7.39 Cl 32 198 to 199 3.48
3.26 6.90
7.04 Cl 33 (
- 182 to 183 2.98
2.79 8.75
8.67 ^> 8.79
8.88 34 CF ₃ 198 to 199 5.03
4.92 35 "8th 166 to 167 4.74
4.48 9.85
9.84 < 36 194 to 195 5.67
5.70 Cl CH ₃

NH - CO - CO - NH

I. H (X ₂ =) III 67.59
67.40 IV 9.85
9.83 38 CH ₃ 230 to 231 51.60
51.69 5.67
5.42 8.02
7.98 39 - Br 280 to 281 59.12
59.28 3.75
3.86 9.19
9.11 40 -Cl 267 to 268 65.16
64.90 4.30
4.28 13.41
12.82 41 - N (CH ₃ J ₂ 243 to 244 6.11
6.03

I. H ₅ QO- OQH ₅ II OQH ₅ - < - j 122 III 123 64.50
64.50 IV 7.52
7.72 C ^ NH <I> CH ₃ 42 - co- OQH ₅ CH ₃ 237 until 239 69.92
69.65 6.50
6.37 8.58
8.46 CH ₃ O- -C ^ ^NH 43 —Co- CH ₃ until 6.79
6.74 OCH ₃ C (CH ₃ ) ₃ 157 158 65.84
66.09 8.53
8.72 CH ₃ O- <Ϊ> NH . — L 44 - co- OQH ₁₇ until 6.14
6.24 OCH ₃ QCH ₃ ) ₃ 110 111 69.39
69.49 5.78
5.87 CH ₃ O- <I> - ^NH Y ^ 45 —Co- OCH ₃ until 8.32
8.20 H ₅ QO- OCH ₃ 184 185 65.27
65.16 7.25
7.33 <I> - ^N H J 46 - co- 3 147 until 148 73.31
73.16 6.78
6.88 7.77
7.94 <I ^ NH 47 - co - until 5.59
5.51 -CO —NH- -CO-NH- CO-NH- CO-NH- CO-NH- CO-NH-

17th

continuation

18th

III

IV

H ₅ C ₂ O

H ₅ C ₂ O

NH-CO-CO -NH

NH-CO-CO -NH

NH - CO - CO - NH

CH ₂
CH ₂
CH ₂
CH ₃

to 223

C ₁₇ H.

12 ^ 25

to 268

to 138

69.92 7.09 8.14 70.12 7.12 8.33

63.15 5.30 8.18 62.90 5.33 8.27

74.30 8.91 6.19 74.36 8.69 6.25

CH ₃ O

> —NH-CO —CO —NH-X ₄

I. II OCH ₃ III 61.81
62.09 IV 8.48
8.48 ^^^ - OCH ₃ 52 O - CH ₂ CH ₂ Cl • 174 to 175 59.59
59.28 5.49
5.34 7.72
7.71 - <> 53 OCH ₃ 190 to 191 67.39
67.17 5.28
5.01 7.86
7.94 12th C (CH ₃ ) ₃ 173 to 174 6.79
6.90 OC ₈ H ₁₇ 71.33
71.59 6.16
6.25 54 C (CH ₃ ), 93 to 94 8.43
8.44 OC ₈ H ₁₇ 69.32
69.43 7.03
7.13 55 92 to 93 7.59
7.72

19th

continuation

20th

I. II OCH ₃ III 55.98
56.03 IV 7.68
7.73 - ^ V-OCH ₃ 56 Cl 189 to 190 4.70
4.77 OCH ₃ 70.20
70.43 7.44
7.44 57 J V 187 to 188 5.36
5.49 OC ₈ H ₁₇ 73.39
73.79 5.90
5.90 16 J V 144 to 146 7.22
7.25 O - CO - CH ₂ CHXH ₃ 69.43
69.49 6.48
6.55 58 J V 135 to 137 5.59
5.58

CH, O

NH-CO-CO -NH

(59)

II -CH ₃ "Y IJ.
Λ.5 - rl. 236 to 237 56.17
56.17 57.41
.57.34 4.09
4.02 8.73
8.67 I. -CH ₂ CH ₂ CH ₂ Cl III IV 54.42
54.52 60 (CH ₂ J ₁₆ CH ₃ 169 to 170 69.15
69.20 4.52
4.38 8.37
8.43 61 130 to 131 4.57
4.48 7.05
7.04 62 92 to 93 8.62
8.67 4.89
5.01

22nd

CH ₃ O

NH-CO-CO -NH

I. π Ph =) III 70.20
70.04 IV 5.36
5.11 7.44
7.63 64 ^, ΓΙ3 188 to 189 73.39
73.45 7.22
7.29 5.90
5.81 65 C ₈ H ₁₇ 145 to 146 66.90
66.91 5.39
5.35 6.24
6.23 66 - CH ₂ - COOC ₂ H ₅ 193 to 194 65.68
65.26 5.28
5.42 6.38
6.47 67 CH ₂ CH ₂ CH ₂ Cl 160 to 161

CH ₃ O

NH-CO —CO —NH- </ -CH ₃

II PC ₇ =) X ₇ = H: 226 to 227 64.95
65.07 5.77
5.80 8.91
8.82 I. CH ₃ III IV 69 C ₈ H ₁₇ 163 to 164 65.84
65.79 6.14
6.24 8.53
8.61 70 CH ₂ CH ₂ CH ₂ Cl 116 to 117 70.39
70.69 8.03
7.97 6.57
6.69 71 131 to 132 61.46
61.20 5.93
5.97 7.17
7.13

NH-CO —CO —NH- <k>

C (CH ₃ ) ₂ -CH ₂ -C (CH ₃ ),

π pc ₈ =) X ₈ = H: 226 to 228 69.32
69.15 7.59
7.36 7.03
7.16 I. - CO - CH ₃ III IV 14th 154 to 155 68.16
68.23 7.32
7.20 6.36
6.43

continuation

24

[ II (X ₈ =) III 72.13
72.55 IV 4.81
4.92 73 - co- ~ (CH ₂ ) ₁₀ CH ₃ 56 to 57 69.88
70.02 9.34
9.05 6.79
6.74 74 -CH ₃ 152 to 154 72.90
72.54 7.82
7.76 5.49
5.70 75 - (CH ₂ h - CH ₃ 86 to 88 71.20
71.44 9.08
8.86 6.39
6.46 76 -CH ₂ - - CH = CH ₂ 116 to 118 73.69
73.48 7.82
7.80 5.73
5.70 77 -CH ₂ O 104 to 106 7.43
7.55

Xc

H ₅ C ₂ O- ^ ^ -NH- CO - CO - NH

OX ₉

(78)

II (X ₉ =) -CH ₃ X ₉ = H: I ₂ - CN 229 to 230 63.99
64.05 5.37
5.51 9.30
9.19 I. CO CH - CH ₂ III IV 79 C ₈ H ₁₇ 155 to 156 64.95
64.97 5.77
5.82 8.91
9.01 80 - CH ₂ CH ₂ CH ₂ Cl 150 to 151 64.40
64.06 5.10
5.12 7.90
7.87 81 -CH ₂ - <^ y 94 to 95 69.88
69.83 7.82
7.55 6.79
6.76 82 - CH ₂ - COOC ₂ H ₅ 139 to 140 60.56
60.70 5.62
5.56 7.43
7.61 83 -CO-CH ₃ 166 to 167 70.75
70.81 5.68
5.71 7.18
7.39 84 152 to 153 62.16
62.28 5.74
5.72 7.25
7.51 85 - CH ₂ - COOH 147 to 148 63.15
63.89 5.30
5.84 8.18
8.10 86 131 to 132 63.46
63.89 5.83
5.84 10.58
10.13 87 193 to 194 60.33
60.37 5.06
5.11 7.82
7.77

209 633/199

continuation

I. -CH ₂ ii (X, =) III 65.54
65.62 IV 9.97
9.66 88 -CH ₂ - CONH- <r ~ y> 252 to 253 68.41
68.19 5.50
5.31 5.32
5.33 89 -CO- -COOC ₁₂ H ₂₅ 115 to 116 68.30
68.21 8.04
7.79 6.93
6.96 90 -CO- 167 to 168 62.95
62.92 4.99
5.13 6.38
6.53 91 -CO- 205 to 206 70.42
70.06 4.36
4.41 6.08
6.36 92 - CO- ^^ - C (CH ₃ ) 3 182 to 183 63.14
63.19 6.13
6.45 10.52
10.36 93 - NH - C ₄ H ₉ 161 to 162 6.31
6.21

NH-CO-CO-NH

C (CH ₃ ),

II PC ₁₀ =) Y τι.
■ * M0 - * "1 · 226 to 227 67.39
67.19 6.79
6.74 7.86
7.91 I. -CH ₃ III IV 95 C ₄ H ₉ 161 to 162 68.09
68.03 7.07
6.94 7.56
7.82 96 C ₈ H ₁₇ 124 to 125 69.88
70.07 7.82
7.93 6.79
6.62 97 C ₁₂ H ₂₅ 90 to 91 71.76
71.71 8.60
8.71 5.98
6.05 98 C ₁₈ H ₃₇ 94 to 95 73.24
73.29 9.22
9.18 5.34
5.54 99 - CO - CH = CH ₂ 98 to 99 74.95
75.25 9.93
10.10 4.60
4.87 100 151 to 152 67.30
67.47 6.39
6.43 6.83
6.97

H, QO

28

NH-CO-CO -NH

(101)

nothing ,, =) X ₁₁ = H: 267 to 268 70.20
70.12 5.36
5.47 7.44
7.32 I. -CH ₃ III IV 102 186 to 187 70.75
71.00 5.68
5.82 7.18
7.11 103 QH ₁₇ 181 to 182 72.20
72.23 6.53
6.70 6.48
6.66 104 C ₁₂ H ₂₅ 158 to 159 73.74
73.96 7.43
7.44 5.73
5.77 105 C ₁₈ H ₃₇ 150 to 151 74.96
75.33 8.14
8.21 5.14
5.02 106 -CH ₂ - ^ y 135 to 136 76.39
76.55 8.98
9.02 4.46
4.46 107 - CH ₂ - COOC ₂ H ₅ 185 to 186 74.66
74.46 5.62
5.59 6.01
6.05 108 - CO - CH ₃ 198 to 199 67.52
67.43 5.67
5.61 6.06
6.13 109 201 to 202 68.89
68.86 5.30
5.53 6.70
6.96

X,

H ₅ QO - <i V - NH - CO - CO - NH

X ₁₂ O

CH ₃
CH,

(110)

II (X ₁₂ =) X ₁₂ = H: 211 to 213 71.75
71.54 6.26
6.09 6.69
6.89 I. -C ₂ H ₅
C ₈ H ₁₇ III IV 111
112 155 to 156
88 to 89 72.62
72.53
74.68
74.49 6.77
6.65
7.98
7.94 6.27
6.35
5.28
5.40

χ,

M 3

NH-CO-CO -NH

. Π PC ₁₃ =) X ₁₃ = H: 261 to 262 65.62
65.64 4.72
4.82 10.93
11.13 I. -CH ₃ III IV 114 CH2CH2CH2CI 170 to 171 66.65
66.69 5.22
5.33 10.37
10.16 115 QH ₁₇ 91 to 92 61.36
61.30 5.15
5.24 8.42
8.64 116 -CH ₂ - (3 86 to 87 71.71
71.95 7.66
7.64 7.60
7.58 117 167 to 168 72.82
73.15 5.24
5.25 8.09
7.91

14th

NH-CO-CO -NH

π CJi ₁₄ =) X ₁₄ = H: 201 to 202 69.21
68.99 6.45
6.36 8.97
9.00 I. / -ITT III IV 119 - CH ₂ CH ₂ CH ₂ Cl 132 to 133 69.92
69.94 6.79
6.86 8.58
8.85 120 C ₈ H ₁₇ 96 to 97 64.86
64.98 6.48
6.24 7.20
7.21 121 -CH ₂ - <(~]> 99 to 100 73.55
73.79 8.55
8.69 6.60
6.36 122 QzH ₂₅ 182 to 183 74.60
74.75 6.51
6.58 6.96
7.03 123 - CO - CH ₃ 76 to 77 74.96
75.15 9.23
9.40 5.83
5.92 124 181 to 182 67.78
67.98 6.26
6.25 7.91
7.95

32

NH-CO-CO -NH

(125)

I. II Pi ₁₅ =) III IV 126 -CH ₃ 189 to 190 72.82 5.24 8.09
72.35 5.26 8.02 127 - CH ₂ - COOC ₂ H ₅ 182 to 183 68.89 5.30 6.70
68.93 5.34 6.76 128 C ₁₈ H ₃₇ 114 to 115 78.04 8.96 4.79
78.29 8.93 4.74

χ.

OX,

CH, - <^ -NH- CO - CO-NH- ^ ^>

C (CH ₃ ),

(129)

π (X ₁₆ =) X ₁₆ = H: 228 to 229 69.92
69.71 6.79
6.49 8.58
8.58 I. -CH ₃ III IV 130 CH ₂ CH ₂ CH ₂ Cl 169 to 170 70.56
70.81 7.11
7.32 8.23
8.12 131 QH ₁₇ 114 to 115 65.58
65.69 6.75
6.73 6.95
7.23 132 -Ch ₂ - ^ y 92 to 93 73.94
73.98 8.73
8.96 6.35
6.38 133 171 to 172 74.97
75.04 6.78
7.00 6.73
6.50

209 633/199

X.7

NH-CO-CO-NH ^ k ν

18th

OX ₁

18th

NH-CO-CO -NH

19th

NH-CO-CO-NH-X

19th

(134)

II PC ₁₇ =) Xn = H: 221 to 222 66.65
66.70 5.22
5.27 10.37
10.26 I. -CH ₃ III IV 135 C ₄ H ₉ 165 to 166 67.59
67.89 5.67
5.87 9.85
9.81 136 QH ₁₇ 103 to 104 69.92
69.78 6.79
6.79 8.57
8.32 .137 95 to 96 72.22
72.52 7.91
7.89 7.32
7.55

(138)

II PC ₁₈ =) X ₁₈ - H: 246 to 247 57.84
58.00 3.81
3.84 9.64
9.67 I. -CH ₃ III IV 139 -C ₂ H ₅ 212 to 213 59.12
59.31 4.30
4.33 9.19
9.22 140 C ₄ H ₉ 187 to 189 60.29
60.04 4.74
4.97 8.79
8.99 141 C ₈ H ₁₇ 116 to 117 62.34
62.42 5.52
5.51 8.08
8.02 142 94 to 95 65.58
65.61 6.75
6.63 6.95
7.09

(143)

I. II PC ₁₉ =) III 57.41
57.42 IV 8.37
8.33 OCH ₃ 144 - \ ^ "OCH ₃ 189 to 190 4.52
4.29

continuation

I. H (X ₁₉ =) III IV OC ₃ H ₁₇ 145 147 to 148 70.21 6.52 5.85
69.90 6.48 5.98 ( 146 DCH ₃ 172 to 173 63.24 5.87 7.76
62.69 5.80 7.71 C (CH ₃ ) ₃ 147 OC ₈ H ₁₇ 116 to 117 68.03 7.69 6.10
68.17 7.70 5.89 C (CH ₃ ) ₃

■ 20

I. NC- ^ II - CO —NH- OC ₂ H ₅ 217 III 218 66.01
65.98 IV 13.59
13.65 O, 148 <x - CO - CO —NH- OCH ₃ 188 until 189 74.60
74.55 4.89
4.91 6.96
6.97 149 - CO C (CH ₃ ), until 6.51
6.65 zy ^nh _Vnh

■ 21

OCH ₃ OX ₂₁

-CO -CO-NH- ^ x

Cl

I. II (X ₂₁ =) -CH ₃ III 57.41
57.39 IV 8.37
8.44 151 QH ₁ ? 209 to 210 63.81
64.10 4.52
4.49 6.47
6.49 152 - CH ₂ CH ₂ CH ₂ - Cl 91 to 92 54.42
54.32 6.75
6.76 7.05
7.00 153 146 to 147 64.31
64.68 4.57
4.76 6.82
6.79 154 - CH ₂ - COOC ₂ H ₅ 176 to 177 56.10
56.28 4.66
4.51 6.89
6.87 . 155 - CO - CH ₃ 161 to 162 56.29
56.33 4.71
4.65 7.72
7.81 156 167 to 168 4.17
4.13

37

OCH ₁

NH-CO —CO —NH-X

■ 22

(157)

I. π CK ₂₂ =) > III 71.33
71.21 IV 6.16
6.42 OQH ₁₇ 158 C (CH ₃ ), 119 to 120 69.32
69.59 8.43
8.39 7.03
7.18 OQH ₁₇ 159 117 to 118 59.59
59.94 7.59
7.31 7.72
7.81 (
J 70.20
70.25 7.44
7.37 160 DCH ₂ CH ₂ CH ₂ - Cl 146 to 147 61.28
61.06 5.28
5.17 7.52
7.66 161 189 to 190 62.19
61.93 5.36
5.46 8.53
8.76 162 O - CH ₂ - COOQH ₅ 155 to 156 5.41
5.39 163 ^ D
O - CO - CH ₃ 139 to 140 4.91
5.01 ι

₂₃

NH-CO-CO -NH

OX

₂₃

(164)

π CK ₂₃ =) X ₂₃ - H: 203 to 204 72.28
72.08 4.85
4.69 8.43
8.27 I. -CH ₃ III IV 165 QH ₁₇ 145 to 146 72.82
72.58 5.24
5.32 8.09
8.04 166 - CH ₂ CH ₂ CH ₂ Cl 105 to 106 75.65
75.58 7.26
7.40 6.30
6.41 167 148 to 149 67.56
67.89 5.18
5.32 6.85
6.65

40

χ.

■ 24

OX

■ 24

NH - CO - CO - NH

C (CH ₃

A ₂₄ - M. I. H (X ₂₄ =) -CH ₃ 227 to 228 74.20
73.63 6.27
6.34 7.21
7.24 169 QH ₁₇ III IV 170 CH ₂ CH ₂ CH ₂ Cl 190 to 191 74.60
74.70 6.51
6.56 6.96
7.16 171 - CO - CH ₃ 149 to 150 76.76
76.48 8.05
8.09 5.60
5.75 172 CH ₂ COOC ₂ H ₅ 168 to 169 69.74
69.65 6.29
6.04 6.02
6.16 173 166 to 167 72.54
72.35 6.09
6.16 6.51
6.35 157 to 158 70.86
70.77 6.37
6.38 5.90
6.20

X ₂₅
NH-CO-CO -NH

X.-H = I. II (X ₂ =) 280 to 282 63.99
63.95 5.37
5.34 9.33
9.06 175 III IV 176 - CO - ^^> - C (CH ₃ J ₃ 270 to 272 68.30
68.21 4.99
4.88 6.93
6.94 177 - CO - NH - CH ₂ CH ₂ CH ₂ CH ₃ 281 to 282 70.42
70.60 6.13
6.10 6.08
6.25 178 CH ₃ 272 to 275 63.14
63.40 6.31
6.03 10.52
10.31 179 C ₄ H ₉ 229 to 230 64.95
64.72 5.77
5.54 8.91
9.04 180 QH ₁₇ 228 to 229 67.79
67.54 6.79
6.63 7.86
7.94 205 to 206 69.88
69.71 7.82
7.52 6.79
6.84

continuation

1 . -Q ₂ H H (X ₂ =) 25th 111 71.76
71.70 IV 5.98
6.05 181 -CH ₂ - 202 to 203 70.75
70.62 8.60
8.50 7.18
7.26 182 -CH ₂ - CH = CH ₂ 245 to 246 67.04
66.91 5.68
5.59 8.23
8.12 183 243 to 244 5.92
5.67

Application examples

In the following application examples, typical UV protection agent representatives were given for each Subgroups of substances to be protected according to the invention are used. In principle, all of them are in the the previous description mentioned compounds and their equivalents in the same way suitable, with only the solubility of the compounds in question in the to be protected Connection to be taken into account or to be determined in a manual test. Finally, it should be noted if necessary nor the fact that the absorption maximum of the compound to be incorporated by the Substituents in the aromatic radical is influenced.

B e i s ρ i e 1 1

It is an acetyl cellulose film of about 50 μ thickness by pouring out a 10% acetone Acetyl cellulose solution which contains 1% (calculated on acetyl cellulose) of the compound according to formula (52), manufactured. After drying, the following values are obtained for the percentage of light transmission:

Light transmission in% exposed Wavelength in Γημ (100 hours unexposed Fadeometer) 0 260 to 340 0 3 350 3 10 360 10 30th 370 30th 55 380 55

40

45

Similarly behave z. B. the compounds of the formulas (39), (79), (92), (95), (114), (144) or (151).

Example 2

A paste of 100 parts of polyvinyl chloride, 59 parts by volume of dioctyl phthalate and 0.2 parts of the compound of the formula (24) is ^{rolled out on the calender at 145 to 150 °} C. to form a film of about 0.5 mm. The polyvinyl chloride film obtained in this way absorbs in the ultraviolet range from 280 to 360 ηΐμ.

Instead of the compound of the formula (24), it is also possible, for example, to use one of the compounds of the formulas (42), (43), (55), (61), (79), (95), (111), (119), (151), (165) and (176) can be used.

Example 3

A mixture of 100 parts of polyethylene and 0.2 parts of the compound of formula (53) is rolled on the calender at 130 to 140 ⁰ C into a sheet and pressed at 150 ⁰ C.

The polyethylene film thus obtained is practically impermeable to ultraviolet light in the range of 280 to 350 ΐημ.

Instead of the compound of the formula (53), it is also possible, for example, to use one of the compounds of the formulas (46), (55), (89), (104), (115), (132), (152) or (166) can be used.

Example 4

A mixture of 100 parts of polypropylene and 0.2 part of one of the compounds of the formulas (12), (65), (81), (111), (123), (132), (142), (147), (152 ) or (167) is processed on the calender at 17O ⁰ C for a coat. This is pressed at 230 to 240 ⁰ C and a maximum pressure of 40 kg / cm ² to form a plate of 1 mm.

The plates obtained in this way are practically impermeable to ultraviolet light in the range from 280 to 360 ηΐμ. Other connections listed in the table behave similarly.

Example 5

0.2 parts of the compound of formula (24) are dissolved in 1.8 parts of monosteryl and 0.5 parts a cobalt naphthenate monostyrene solution (containing 1% cobalt). There are 40 parts on it an unsaturated polyester resin based on phthalic acid-maleic acid-ethylene glycol in monostyrene added and the whole stirred for 10 minutes. After 1.7 parts of a catalyst solution (methyl ethyl ketone peroxide in dimethyl phthalate) are added dropwise the well mixed, air-free mass is poured out between two glass plates. After about 20 minutes it is the 1 mm thick polyester plate has solidified so far that it can be removed from the mold. She is for UV light in the range from 280 to 350 πΐμ impermeable and shows no yellowing in the Xenotest after 1000 hours of exposure.

Instead of the compound of the formula (24), it is also possible, for example, to use one of the compounds of the formulas (14), (66), (84), (102), (108), (119), (130), (154) or (169) can be used.

Example 6

25 g of distilled monostyrene are in a closed Bottle prepolymerized in a warming cabinet at 90 ° C for 2 days. Into the viscous mass then 0.25 g of a compound of the formulas (50), (58), (61), (70), (100), (121), (163) or (170) and 0.025 g of benzoyl peroxide slowly added. The mixture is then put into a cuboid shape Cast from aluminum foil and kept at 70 ° C for 1 day. After complete solidification and When the mass cools, the shape is broken apart. The block obtained in this way is then in

a hydraulic press at a temperature of 138 ° C and a pressure of 150 kg / cm ² to form a plate 1 mm thick.

The polystyrene plates produced in this way are impermeable to UV light in the range from 286 to 360 ηΐμ. They are completely colorless. When exposing in the fadeometer, you can see a significant improvement in light stability observe by placing polystyrene plates, which contain compounds of the above formulas, ίο show no yellowing after exposure for 200 hours, while plates without these additives are already yellowed. Other connections listed in the table behave similarly.

B e i s ρ i e 1 7

In 40 g of nitro clear lacquer (25%) 0.1 g of a Compound of formulas (23), (67), (73), (84), (99), (124), (135), (152), (167) or (176) resolved. The paint is then evenly applied to maple wood panels with a coating squeegee and is after a short time Time completely dry. By adding the aforementioned ultraviolet absorber to the paint does not change the color nuance of the wood. The light color nuance of the lacquered wood is also used in the Exposure under a UV lamp does not change after several days, provided the varnish has the above compounds contains in a concentration of about 10%. Untreated wood darkens under the given Exposure conditions after a few days.

Similar results are obtained when using acrylic resin or alkyd melamine resin varnishes, and other compounds listed in the table.

Examples

8 g of toluene - 2,4 - diisocyanate / toluene - 2,6 - di - isocyanate mixture (65:35) and 20 g of a slightly branched polyester made from adipic acid, diethylene glycol and triol (hydroxyl number = 60) become about 15 seconds stirred together for a long time. Then 2 ml of a catalyst mixture (consisting of 6 ml of a tertiary amine, 3 ml of dispersant, 3 ml of a stabilizer and 2 ml of water), and 0.28 g of a Combine the formulas (46), (53), (75), (85), (93), (97), (130), (151) or (166) and stir briefly. It educates a foam fleece that is placed in a water bath after 30 minutes. After another 30 minutes it is washed thoroughly with water and dried at room temperature.

The addition of one of the above-mentioned UV absorbers increases the resistance during exposure in the xenotest apparatus. The above absorbers are also found in numerous other polyurethanes based on the isocyanate polyaddition process are based, easy to incorporate.

Other connections listed in the table behave similarly.

Example 9

10 000 parts of a polyamide produced in a known manner from caprolactam will be in chip form with 30 parts of the compounds of the formulas (50), (108), (127) or (151) in a roller jar during Mixed for 12 hours. The chips treated in this way are in a kettle heated to 300 ° C Displacement of atmospheric oxygen by superheated steam, melted and during a half Hour stirred. The melt is then pressed out through a spinneret under nitrogen at 5 atmospheres and the cooled filament thus spun is wound onto a spinning bobbin, thereby simultaneously a stretching takes place.

By adding the above compounds, the and by measuring the relative viscosity in conc. Sulfuric acid certain breakdown of macomolecules significantly reduced.

Other connections listed in the table behave similarly.

Example 10

0.3 g of the compound of the formula (25) are dissolved in 10 g of pure olive oil. The solution is quick and without heating. A 50 μ thick layer of this solution completely absorbs the UV light up to 340 ηΐμ.

Likewise, other fatty oils and creams or emulsions that are cosmetic Find purposes use to solve the above or other compounds such. B. (50), (81), (98), Use (121) or (132).

Example 11

12 g of polyacrylonitrile are sprinkled into 88 g of dimethylformamide with stirring until they are completely dissolved. Then 0.1 g of the instantly dissolving compound, for example of the formula (24), is added. The viscous mass is then applied to a cleaned glass plate and drawn with a film rod crossed out. For 20 minutes is now in a vacuum drying cabinet at 120 ° C and a vacuum dried by 150 mm Hg. A film about 0.05 mm thick is created from the glass substrate can be easily detached. The film obtained in this way is completely colorless and absorbs UV light up to a wavelength of 350 ηΐμ practically completely, while a film without the above connection of the formula (24) allows at least 80% of the UV light to pass through. In addition, the at are also suitable Polystyrene mentioned compounds for incorporation into polyacrylonitrile.

Claims (1)

Claim:
Use of asymmetrical oxalic acid diarylamides of the general formula (Rs) P-! V / - ^NH - CO - CO - NH wherein R _{1 is} the methyl or ethyl group, R _{2 is} an alkyl group containing 1 to 18 carbon atoms, which with a chlorine atom, a / 3-cyanoethyl, carboxyl, carboxamide or car bonsäurealkylestergruppe with 1 to 12 carbon atoms, the allyl group, a benzyl group optionally substituted with a chlorine atom or an alkyl group containing 1 to 4 carbon atoms, a fatty aliphatic acyl group containing up to 12 carbon atoms, one optionally containing a chlorine atom or one containing 1 to 4 carbon atoms Alkyl group is substituted benzoyl group, R _{3 is} the chlorine atom, the methyl, nitrile or phenyl group and R _{4 is} an alkyl group containing 1 to 12 carbon atoms, the chlorine atom, the trifluoromethyl group, the phenyl group or a phenylalkyl group with 1 to 4 carbons represents material atoms in the alkyl part or two o-position radicals R ₄ together form a fused-on benzene ring and in which m = 0, 1 or 2, η = 1, 2 or 3, ρ = 1 or 2 and q = 1, 2, 3 or 4 are, each of the two ring systems in addition to the bond via the —NH— group contains a maximum of three substituents and the sum m + (n - Y) has the values 1, 2 or 3 and the rest of the substituents R ₁ 0 ^ 17R ₂ O -> R3 and R ₄ according to type, number or ^ PositiQri, are such that an asymmetrical '* molecule is present as an ultraviolet protective agent for organic materials which are damaged by ultraviolet radiation.