DE1188080B - Use of oxalic acid-bis-oxyarylamides as protective agents against ultraviolet radiation - Google Patents

Description

Use of oxalic acid-bis-oxyarylamides as protective agents against ultraviolet radiation The present invention relates to the use of oxalic acid-bis-oxyarylamides, which of the formula correspond. in which X is a hydrogen or chlorine atom, an alkyl radical having 1 to 12 carbon atoms. preferably a tertiary butyl radical. denotes a phenyl or a cyclohexyl radical or an alkoxy radical with 1 to 4 carbon atoms for protecting higher molecular weight organic substances against decomposition by ultraviolet radiation.

According to the invention too. using oxalic acid-bis-oxyarylamides the formula (1) can be obtained by methods known per se. by taking oxalic acid or their functional derivatives on both sides with corresponding arylamines of the benzene series condensed, which have an oxy group adjacent to the amino group.

The following list shows some typical compounds which can be used according to the invention; the melting points given are uncorrected.

Analysis: C14H12NO4. Melting point: 290 to 291 ° C.

Calculated ... C 61.76, H 4.44; found . . C 61.72, H H 4.55.

#max = 312 mµ (# = 17 700).

Analysis: C14HloN204Cl2. Melting point: 314 to 316 ° C.

Calculated ... C 49.29, H 2.95; found . . C 49.52, H 2.97.

Amax = 274 mµ (e = 10 600).

#max = 320 mµ (# = 16 500).

Analysis: C16H16N2O5. Melting point: 290 to 294 C.

Calculated ... C 63.99, H 5.37; found . . C 63.83, H 5.40.

#max = 285 mµ (# = 10 200).

#max = 320 mµ (# = 16 100).

Analysis: C22H28N2O4. Melting point: 297 to 298 ° C.

Calculated ... C 68.72, H 7.34; found . . C68.83, H7.13.

#max = 318 mµ (# = 15 800).

Analysis: C18H20N2O4. Melting point: 3220C (with decomposition).

Calculated ... C 65.84, H 6.14; found . C 65.76, H 6.07.

#max = 288 mµ (# = 10 350).

#max = 324 mµ (# = 17 550).

Analysis: C38H60N2O4. Melting point: 239 to 240 ° C.

Calculated ... C 74.95, H 9.93; found . . C 74.03, H 9.73.

#max = 319 mF (e = 16 500).

Analysis: C26H32N2O4. Melting point: 310 ° C (with decomposition).

Calculated ... C 71.53, H 7.39; found . . C 71.85, H 7.35.

#max = 283 mµ (# = 9950).

#max = 319 mµ (# = 15 400).

Analysis: C20H24N2O4. Melting point: 268 ° C (with decomposition).

Calculated ... C 67.39, H 6.79; found . . C 67.24, H 6.75.

#max = 285 mµ (# = 10 250).

#max = 320 mµ (# = 15 750).

Analysis: C22H28N2O4. Melting point: 257 to 260 ° C.

Calculated ... C 68.72, H 7.34; found . . C 68.11, H 7.08.

#max = 319 mµ (# = 14 600).

Analysis: C30H46N2O4. Melting point: 302 ° C (with decomposition).

Calculated ... C 72.25. H 9.30; found ... C 72.05. H 8.88.

Amax = 316 with (E = 11 450).

Analysis: C26HaoNa04. Melting point: 304 ° C (with decomposition).

Calculated ... C 73.57. H 4.75; found . . C 73.84, H 4.65.

Amax = 327 m (E = 14 600).

Analysis: C16H16N206. Melting point: 263 to 265 C (with decomposition).

Calculated ... C 57.83, H 4.85; found ... C 57.71, H 4.80.

Amax = 227 mµ (E = 16,500).

Amax = 253 m (e = 13 400).

Amax = 333 mP (e = 14,200).

There are basically three different types of application for the above UV protection agents can be distinguished. which are carried out separately or in combination can reach: A. The light stabilizer is incorporated into a substrate. with the Purpose. to protect this substrate from light attack by ultraviolet rays, wherein a change in one or more physical properties, such as e.g. B. a discoloration. Change in tear strength. Becoming brittle, etc. and / or chemical reactions excited by ultraviolet rays. such as B. Oxidation processes, should be prevented. The incorporation can take place before or during manufacture of the substrate or subsequently by a suitable process. z. B. by a Fixation process, carried out similar to a dyeing process.

B. The light stabilizer is incorporated into a substrate to provide a or several other substances incorporated into the substrate, such as e.g. B. Dyes.

Aids, etc. to protect. where the substrate protection mentioned under A. can occur at the same time.

C. The light protection agent is incorporated into a »filter layer«, with the purpose of creating a directly underneath or at some distance (e. B. in a shop window) located substrate before the attack of the ultraviolet To protect rays, the filter layer is solid (film, foil, finish) or semi-solid (cream, Dl. wax) can be.

As materials. that can be protected. may be mentioned: a) Textile materials in general. in any form, e.g. B. as fibers. Threads. Yarns.

Woven or knitted goods or as felt can be present. and all of it manufactured articles: such textile materials can consist of natural ones Materials of animal origin. like wool and silk, or of vegetable origin. such as cotton cellulosic materials. Hemp. Flax, linen, jute and ramie. further made of semi-synthetic materials such as regenerated cellulose. z. B. Artificial silk, Viscose. including rayon or synthetic materials made by polymerisation or mix polymerization, e.g. B. polyacrylonitrile, polyvinyl chloride or polyolefins or such. which are available by polycondensation, such as polyester and above especially polyamides. It is advisable to use the light stabilizer in the case of semi-synthetic materials already a spinning mass. z. B.

Viscose textile pulp, acetyl cellulose textile pulp (including cellulose triacetate) add and in the masses intended for the production of fully synthetic fibers. such as polyamide melts or polyacrylonitrile spinning masses this before. during or after to use the polycondensation or polymerization. b) fibrous materials of a different kind, which are not textiles. which can be of animal origin. like feathers, Hair, furs and Hides and from the latter by natural ones leather obtained or chemically tanned, as well as products made therefrom, furthermore those of vegetable origin, such as straw, wood, wood pulp or compacted Fibers consisting of fiber materials, such as paper, cardboard or compressed wood, as well as the latter manufactured materials. Furthermore, paper pulps used for the production of paper (e.g. Dutch masses). c) Coating and finishing agents for textiles and Paper, e.g. B. those based on starch or casein or those based on synthetic resin, for example from vinyl acetate or derivatives of acrylic acid. d) varnishes and films different composition, e.g. B. those made from acetyl cellulose, cellulose propionate, Cellulose butyrate and cellulose mixtures, such as. B. cellulose acetate butyrate and cellulose acetate propionate, also nitrocellulose, vinyl acetate, polyvinyl chloride, copolymers of vinyl chloride and vinylidene chloride, alkyd varnishes.

Polyethylene, polypropylene, polyamides, polyacrylonitrile, polyester etc. Another use for the oxalic acid bis-oxyarylamides is for incorporation in packaging materials, especially the known, transparent films regenerated cellulose (viscose) or acetyl cellulose. This is usually where it is expedient to add the light stabilizer to the mass from which these films getting produced. e) natural or synthetic resins, e.g. B. epoxy resins.

Polyester resins, vinyl resins, polystyrene resins.

Alkyd resins, aldehyde resins, such as phenol, urea or melamine-formaldehyde condensation products, and emulsions made from synthetic resins (e.g. oil-in-water or water-in-UL emulsions). Here, the light stabilizer can expediently before or during the polymerization or polycondensation can be used. Furthermore, they are reinforced with glass fibers Synthetic resins and laminates made from them called. f) Hydrophobic, oil, grease or waxy substances. such as candles, floor wax, floor stain or other wood stains, Furniture polishes, especially those that are lighter for treatment. possibly bleached wooden surfaces are intended. g) Natural, rubber-like materials such as rubber, balata, gutta-percha or synthetic vulcanizable materials, like polychloroprene. olefinic polysulphides, polybutadiene or copolymers of butadiene-styrene (e.g. Buna S) or butadiene acrylonitrile (e.g.

Buna N), which also contains fillers, pigments, vulcanization accelerators etc. and in which the addition of the oxalic acid-bis-oxyarylamide delay aging and thus the change in plasticity properties and prevent embrittlement. h) Cosmetic preparations such as perfumes. colored and undyed soaps and bath products, skin and face creams, powders, and repellants in particular sun protection oils and creams. i) For the production of filter sheets for photographic purposes, in particular for color photography.

It goes without saying. that the oxalic acid bis-oxyarylamide not only as a light stabilizer for uncolored, but also for colored or pigmented Materials are suitable. The light protection also affects the dyes, whereby in some cases a very considerable improvement in light fastness is achieved will. If necessary, the treatment with the light stabilizer and the dye or pigmentation process can be combined.

Depending on the type of material to be treated, requirements for effectiveness and durability and other factors may affect the amounts of the particular Materials to be incorporated light stabilizers within fairly wide limits vary, for example about 0.01 to 100/0, preferably 0.1 to 20in, of the material be. which should be protected directly against ultraviolet radiation.

Example 1 From a 100% acetonic acetyl cellulose solution. Which. calculated on acetyl cellulose containing 1 of the compound of the formulas (2), (3), (4) or (5), a film about 40 seconds thick is produced. After drying, the following values are obtained for the percentage of light transmission: Wavelength in mF Light transmission in ° iiO (2) (3) (4) (5) 280 to 320 0 0 0 0 330 8 0 0 0 340 35 2.5 1 5 350 70 11 5 13 360 80 31 18 24 370 84 57 40 50 380 86 76 65 67 390 88 84 80 79 EXAMPLE 2 10,000 parts of a polyamide in chip form prepared in a known manner from hexamethylenediamine adipate are mixed with 30 parts of titanium dioxide (rutile modification) and 50 parts of the compound of formula (3) or (5) in a roller jar for 12 hours. The chips treated in this way are melted in a boiler heated to 300-310 "C with DI, after the atmospheric oxygen has been displaced by superheated steam, and stirred for half an hour. The melt is then pressed out through a spinneret under a nitrogen pressure of 5 atmospheres spun, cooled filament wound on a spinning bobbin.

The tensile strength of the threads obtained in this way after stretching goes down under the influence of light much less than that of otherwise in the same way Way. but threads produced without the addition of the compound of formula (3) or (5).

Example 3 A paste made from 100 parts of polyvinyl chloride.

3 3 parts stabilizer. 59 parts by volume of dioctyl phthalate and 0.2 parts the compound of formula (5) becomes a film on the calender at 150 to 155 "C rolled out. The polyvinyl chloride film thus obtained absorbed in Ultraviolet range from 280 to 360 ms completely.

Instead of the compound of the formula (5), one of the compounds can also be used of formulas (6), (7).

(9), (10) or (11) can be used.

Example 4 1.0 part of the compound of formula (5) is in 100 parts by volume 30 0 / above sodium hydroxide solution and 100 parts by volume of ethanol dissolved. Be on it 3000 parts of water and 3 parts of an aqueous solution of the adduct of 35 moles of ethylene oxide added to 1 mole of stearyl alcohol. The solution thus obtained is now neutralized with 100% sulfuric acid under control on the potentiometer, until the pH is 7, a fine dispersion forming. In the so distributed Bath is now done with 100 parts of fabric made of polyamide fibers made from hexamethylenediamine and adipic acid are produced. at room temperature. slowly warms up to boiling temperature and then treated for 1 hour at this temperature. Then that will Tissues removed from the bath, rinsed with cold water and dried.

The fabric treated in this way shows after 100 hours of exposure to a Xenon lamp has a much smaller loss of tensile strength than when the connection of the formula (5) is not added.

You get similarly good results if you take the place of the connection of the formula (5) the compound of the formula (3) is used.

Example 5 A paper pulp is produced in a Hollander. Consists of 150 parts of bleached sulphite or sulphate cellulose. 60 parts of zinc sulfide. 3 parts of a finely dispersed aqueous paste containing 30 ° lo of the azo pigment of the formula contains. and 5000 parts of water.

The decorative paper made from this mass is treated with untreated Tissue or overlay paper brought into a bath, made from 100 parts of a powdery, hardenable, water-soluble condensation product from 1 mol of melamine and about 2 moles of formaldehyde and 100 parts of a mixture that comes from a solution of 0.5 part of the compound of formula (5) in 19.5 parts of dimethylformamide Diluting with 80 parts of water was obtained.

After removing the excess resin solution, the papers are dried.

The decorative paper treated in this way is used together with the treated tissue paper, which is used as a cover sheet, on a base, Consists of a layer of phenolic paper and barrier sheets impregnated with melamine resin as an intermediate layer for 10 minutes at 140 to 1500C and 100 kg per square centimeter Pressed pressure.

The laminate obtained shows a after exposure on the fadeometer much better lightfastness than one that uses the compound of the formula (5) does not contain.

Claims (1)

Claim: Use of oxalic acid bis-oxyarylamides of the general formula in which X is a hydrogen or chlorine atom, an alkyl radical with 1 to 12 carbon atoms, preferably a tertiary butyl radical, a phenyl or a cyclohexyl radical or an alkoxy radical with 1 to 12 carbon atoms, for protecting higher molecular weight organic substances against decomposition by ultraviolet radiation. Publications considered: Ust: rreichische Patentschrift No. 210 406.