DE1618198C - Oxalic acid ester amides as ultraviolet protection agents - Google Patents

Description

The present invention relates to the protection of organic materials by action be damaged by ultraviolet radiation, compared to this radiation, through the use of special Oxalic acid ester amides.

So far, the presence of a hydroxyl group has been a prerequisite for the UV absorber effect of a molecule in a benzene ring in the ortho position to the bond of this benzene ring with a> C = O, -ΟξΝ-, or -N = N bond. links of this type are e.g. B. in the German Auslegeschrift 1 188 080 described. These well-known However, compounds give various organic materials discoloration when exposed to light, which in many cases make the substrates commercially unusable.

According to the invention, such oxalic ester amides are used for the ultraviolet protection of organic materials used that of the formula

approx

H ₁ C

N - C - C - OC ₄ H ₁ ,

NCC-OC ₁₂ H

12 ⁿ 25

CH, 0

OCH,

NH-CO-COOR

(XO) ₁₁

CH, O

and where X is an alkyl group containing 1 to 18 carbon atoms, optionally containing a carboxylic acid alkyl ester group, an allyl group, a benzyl group, a fatty acyl group or a benzoyl group optionally substituted by a chlorine atom or a lower alkyl group, Y is an alkyl group containing 1 to 12 carbon atoms, a halogen atom , represents a halomethyl group, the phenyl group, the nitrile group, the nitro group, an alkylamino group or the sulfonic acid amide group or where two radicals Y together form a fused benzene ring and R an alkyl group containing 1 to 18 carbon atoms, an alkoxyalkyl group containing 1 to 6 carbon atoms, denotes the benzyl group or the cyclohexyl group, and u and υ denote the numbers 0, 1 or 2 with a sum for u + ν from 1 to 3 and the value 0 denotes an index number u or υ denotes a hydrogen atom.

From the large number of oxalic acid ester amides that can be used, some compounds are listed below as Examples given:

O O

N-C-C-O-CH

O O

CH, 0

NCCO-CH ₂ -CH-CH ₂ -CH ₃

O O

H Il Il

N - C - C - OC ₂ H ₅

The oxalic ester amides to be used according to the invention can be prepared by methods known per se the amidation of oxalic acid or its esters by reaction of oxalic acid, oxalic acid half-esters or oxalic acid diesters with identical or different ester residues with the corresponding primary Amines are produced. A new, particularly advantageous method for the production of oxalic acid ester amides of the formula (1) consists in that oxalic acid diesters of the formula

(1)

ROOC-COOR

with aromatic primary amines of the formula

55

OCH,

NCC-OC ₈ H ₁₇

H Il Il. ο ο

(2)

(X0) "

NH,

O O

C ₈ H ₁₇ O

C - OCH ₁

(3)

- with the meanings for X, Y, R, u and ν as given under formula (1) - reacted with one another in the melt or in inert organic solvents in the presence of anhydrous boric acid. The amount of boric acid to be used corresponds to 0.1 to 5 percent by weight, based on the. Oxalester. The reaction temperatures here are generally from 50 to 250 ° C., preferably between 100 and 150 ° C. Inert solvents here are to be understood as meaning those which are opposite to the

Reaction partners are chemically indifferent under the specified reaction conditions. Examples are: benzene, toluene, chlorobenzene, particularly those having a lying approximately above 140 ⁰ C boiling point, such as di- and trichlorobenzene, polyhydric alcohol such as Diäthylenglykoldiäthyläther, high-boiling hydrocarbons, such as p-cymene.

In the case of the use of such solvents, condensation is carried out with removal of the split off Alcohol.

The condensation in the presence of boric acid is not only very economical, it also makes it possible a significant shortening of the reaction times or, in interaction, lowering of the reaction temperatures. As a result, not only are known compounds in significantly more favorable yields accessible, but there can also be compounds that were previously inaccessible due to thermal instability can be obtained in a smooth manner.

A variation of the ester radical R in the oxalic acid ester amides described can also be achieved by transesterification - Preferably the methyl or ethyl ester - in the presence of catalytic amounts Alkali metal or alkali alcoholate and in solution of the alcohol required for the transesterification (in Excess) can be obtained.

Another possible variation for the ester residue is that the oxalic acid half-amide (prepared from oxalic acid and primary amine or by saponification of the methyl or ethyl ester of the oxalic acid ester amide) is converted into the acid chloride (e.g. with thionyl chloride or phosphorus pentachloride according to methods known per se) and this at temperatures of 0 to 100 ⁰ C in an inert solvent allows the corresponding alcohol or the alkali metal salt of a phenol to act.

All compounds with modified hydroxyl groups (e.g. alkoxy or alkenyloxy groups) can is known by primary condensation of the aromatic containing free hydroxyl groups Amines with oxalic acid esters and subsequent modification of these hydroxyl groups per se known etherification and esterification methods are obtained.

The above-described oxalic acid amide esters can in principle be used to protect all such organic Materials are used by the influence of ultraviolet radiation in any Shape can be damaged or destroyed, since the said oxalic acid derivatives have a pronounced absorption specifically in the range of the normally damaging spectral range. Such damage exposure to ultraviolet radiation can have very different effects, e.g. color change, change in mechanical properties (brittleness, cracks, tear resistance, Flexural strength, abrasion resistance, elasticity, aging), initiation of undesired chemical reactions (e.g. decomposition of sensitive chemical substances), photochemically induced rearrangements or oxidation (for example of oils containing unsaturated fatty acids), triggering of burns and irritation (e.g. to human skin).

The organic materials to be protected can therefore be of the most varied of substance classes belong and exist in various processing states and aggregate states while their common feature is sensitivity to ultraviolet radiation.

Organic materials of this type can be both high molecular and low molecular in nature being.

As low molecular weight or higher molecular weight substances for which the method according to the invention for protection or stabilization comes into consideration, for example: organic natural substances, how they are used for pharmaceutical purposes (medicines), UV-sensitive dyes, Compounds that are decomposed as food or in food by exposure to light (unsaturated Fatty acids in oils) etc. The use of the oxalic acid derivatives mentioned has proven particularly advantageous but for the protection of polycondensation products, polyaddition products and polyvinyl chloride as well as in cosmetic preparations. As organic materials based on polymers, which can be protected according to the invention are, for example: polymers based on α, / 2-unsaturated carboxylic acids, acrylates, acrylamides and acrylonitrile; Polymers based on vinyl and vinylidene halides and vinyl esters, unsaturated Aldehydes and ketones, alkyl compounds, other polymerization products such as. B. by ring opening available e.g. B. polyamides of the polycaprolactam type, also formaldehyde polymers, or polymers that use both polyaddition and Polycondensation are available, such as polyethers, polythioethers, polyacetals, thioplasts.

Examples of the polycondensates and polyadducts which are preferred are called:

1. Polycondensation products or precondensates based on bifunctional or polyfunctional compounds with condensable groups, their homo- and mixed condensation products and products aftercare, such as B. Polyester [saturated

(e.g. polyethylene terephthalate) or unsaturated (e.g. maleic acid dialcohol polycondensates and their Crosslinking products with polymerizable vinyl monomers), unbranched and branched (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, or their precondensates and analog built products, polycarbonates, silicone resins, and others.

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

Organic materials that can be protected according to the invention also come into consideration:

a) 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;

b) natural organic materials of animal or vegetable origin, for example based on cellulose or proteins, such as wool, cotton, silk, raffia, jute, hemp, fur and hair, leather, wood masses in fine distribution, natural resins (such as rosin, in particular Varnish resins), gelatine, glues, also rubber, gutta-percha, balata, as well as their after-

treatment and modification products, degradation products, more reactive by modification Products available to groups.

The organic materials under consideration can be in the most varied of processing states (Raw materials, semi-finished products or finished products) and aggregate states are available. You can once in the form of the most varied of shaped structures, d. H. so z. B. predominantly three-dimensionally extended bodies, such as profiles, containers or a wide variety of workpieces, Schnitzel or granules, foams; predominantly two-dimensional bodies, such as films, Foils, lacquers, impregnations and coatings, or predominantly one-dimensional bodies, like threads, fibers, bristles, wires. On the other hand, said materials can also be in unformed States in the most varied of homogeneous and inhomogeneous forms of distribution and states of aggregation present, e.g. B. as powder, solutions, normal and reverse emulsions (creams), dispersions, Latices, sols, gels, putties, waxes, adhesives and fillers.

Fiber materials can be in the most varied, 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 and cardboard.

The ultraviolet stabilizers to be used in the present invention can also be used, for example, as follows can be used:

a) in cosmetic preparations such as perfumes, colored and uncolored soaps and bath additives, Skin and face creams, powders, repellants and in particular 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 the aftertreatment of dyeings, prints or etching prints ;

c) in mixtures with so-called »carriers«, antioxidants, other light protection agents, Heat stabilizers or chemical bleaches;

d) in a mixture 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 Wash baths can also be added separately;

f) in gelatin layers for photographic purposes;

g) in combination with polymeric carrier materials (polymerization, polycondensation or polyaddition products), in which the stabilizers may be dissolved in addition to other substances or dispersed form are incorporated, e.g. B. for coating, impregnating or binding agents (Solutions, dispersions, emulsions) for textiles, fleeces, paper, leather;

The novel ultraviolet stabilizers to be used in the present invention are preferred added or incorporated into the materials before or during their deformation. So you can for example in the production of films, foils, tapes or moldings of the molding compound or Add injection molding compound or dissolve, disperse or otherwise dissolve in the spinning compound before spinning finely distribute. The protective agents can also be the starting substances, reaction mixtures or Intermediate products for the production of fully or semi-synthetic organic materials are added, also before or during the chemical reaction, for example in the case of a polycondensation (including prepolymers) or a polyaddition.

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 is applied to the surface layer (a film, a fiber of a multi-dimensional molded body).

You can achieve this, for example, by a kind of dyeing process or the active ingredient in one Embed polymer (polycondensate, polyadduct film) using known surface coating methods with polymeric substances, or you can mediate the active substance in dissolved form a suitable solvent diffuse into the surface layer or allow it to swell. One Another important variant is that the ultraviolet absorber is essentially a self-supporting one two-dimensional carrier material is embedded, e.g. B. a film or a vessel wall to to prevent ultraviolet radiation from the substance behind it (examples: shop window, Films, transparent packs, 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 is reached, for example dyes, antioxidants, disinfectant additives, Antistatics and other 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 the amount of substrate to be protected. For most practical matters, this is already sufficient Amounts from about 0.2 to 2 percent by weight.

In the following production instructions and examples, parts always mean parts by weight and percentages are always percentages by weight, unless otherwise stated. Melting points are uncorrected.

Manufacturing instructions (A to C)
(especially for compounds of Table I)

h) as additives to various industrial 65 A. 37 parts of p-anisidine, 50 parts of oxalic acid diethyl products, To their aging rate ester and 0.5 parts of boric acid are at 110 to 115 ° C reduce, e.g. B. as an additive to glue, adhesive stirred for 4 hours, the resulting agents or paints. Alcohol is continuously distilled off. Subsequently

the melt is dissolved in 250 parts of boiling alcohol, insoluble diamide is filtered off and mixed the filtrate with 500 parts of water, the product of the formula

NC-COOC ₂ H ₅ ⁽¹¹⁾

The analysis data are:

C ₁₇ H ₁₇ O ₄ N:

Calculated ... C 68.21, H 5.73, N 4.68; found .... C 68.35, H 5.52, N 4.65.

C. 10.5 parts of the compound of formula

CH ₃ O _I0 ^H ° - ^ \ ^ -NH-CO-COOC ₂ H ₅

precipitates in the form of almost colorless crystals. A

twice from alcohol - water recrystallized together with 13.2 parts of lauric acid chloride analysis product melts at 107 and 108 ⁰ C and in 30 parts of chlorobenzene for 2 hours to return shows the following data: flow heated. After adding 1.5 parts of a H OM ' ⁵ silica to decolorize, it is filtered and the FiI-Ci 1 "13O ₄ N: _entered J _{n 5} qj _e ji _en hot alcohol is stirred.

Calculated ... C 59.18, H 5.87, N 6.28; crystallized product is filtered off with suction, with 20 parts

found .... C 59.26, H 6.00, N 6.02. Washed methanol and dried. You get so

15.5 parts of the compound of formula
B. 20.9 parts of the compound of formula 20

j ~ \. 9 ⁽¹³⁾

HO ^ f ^ NHCOCOOC ₂ H ₅ Il / = \

^ = / CH ₃ (CH ₂ ) _I0 -CO- \ VNH-CO-COOC ₂ H ₅

(made from p-aminophenol and oxalic acid diethyl- ^ - '
ester in the presence of catalytic amounts of boric acid 25

at temperatures from 120 to 130 ^° C.) are dissolved in with the melting point 106 to 107 ^° C. and the analysis: 50 parts of dimethyl sulfoxide at 20 ^° C. In addition

at 0 ⁰ C 14 parts of potassium carbonate (anhydrous) C ₂₂ H ₃₃ O ₅ N:

and 18 parts of benzyl bromide. The reaction- Calculated ... C 67.49, H 8.50, N 3.58;

mixture is then found for 6 hours at 0 ^° C., 30 ... C 67.43, H 8.77, N 3.56.
then 2 hours at 10 ^° C. and then · during

Stirred for 16 hours at room temperature. Then those listed in Table I below

becomes with alcohol and water the product of the for- compounds were made in the same or analogous manner

mel manufactured. In Table I means

/ - \ 35

CH ₂ - O - <^ V- NHCOCOOC ₂ H ₅ Column I Formula No.

\ = S (j 2) Column II structural formula

Column III. Melting point

precipitated from the reaction solution (22 parts). To (uncorrected) ⁰ C

Purification is the crude product from benzene - under 40 column IV analytical data

Addition of fuller's earth Tonsil NFF - and Cyclo- C, H, N
hexane recrystallized. After two recrystallizations (1st line = besation and one-time chromatography on aluminum,
Mineral oxide of activity III with benzene gives 2nd line = common melting point of 107 to 108 ⁰ C. 45 found)

Table I.

I. / Cl O ₂ N y CH ₃ O Cj O II OC ₂ H ₅ 128 HI 129 44.69
44.66 IV 4.74
4.89 Y
CF ₃ - c - O
Il (14) / Il
c - until 3.07
3.17 O O
Il OC ₂ H ₅ 171 172 50.42
50.72 11.76
11.83 Il O
Μ (15) Il until 4.23
4.47 <x O
Μ OC ₂ H ₅ 144 145 56.91
57.02 5.53
5.38 Il
- c - O
Il (16) Il
c - until 5.97
5.87 -NH -NH -NH ^V OCF

continuation

III

IV

H, C

. H, C

Cl

Br

H ₃ C

H, C

H, C

O / ^ V-NH-C-C-OC ₂ H ₅

O

Il Il

NH-CC-OC ₂ H ₅

& ■ NH - C - C - OC ₂ H ₅

0

NH - C - C - OC ₂ H ₅

O

NH-C-C-OC ₂ H ₅

O

Il Il

NH - C - C - OC ₂ H ₅

CH,

H, C

O

Il Il

NH - C - C - OC ₂ H ₅

CH ₃ - C - O - ^ V - NH - CO - COOC ₂ H ₅

(CH ₃ ) ₃ C

NH-CO —COOCH,

NH-CO —COOCH,

NH-CO- COOC ₂ H ₅ to 119.

to 153

to 158

to 61

to 71

to 52

to 114

to 60.5

to 118

to 163

to 154

up to 160

61.00 6.83 11.86 61.30 6.61 12.01

52.76 4.43 6.15 52.63 4.30 6.40

44.14 3.70 5.15 44.88 3.67 5.18

63.75 6.32 6.76 63.79 6.29 6.87

65.14 6.83 6.33 65.42 6.86 6.31

65.14 6.83 6.33 64.98 7.03 6.47

71.36 5.61 5.20 71.30 5.74 5.21

67.26 8.47 4.36 67.40 8.19 4.64

57.37 5.22 5.58

57.60 5.25 5.50

65.17 4.82 4.47

65.12 4.77 4.46

58.72 4.06 4.03

58.88 4.04 3.93

68.28 6.28 3.79

68.37 6.49 3.90

11th

continuation

12th

CH ₂ = CHCH ₂ O

C ₁₈ H ₃₇ O

C ₂ H ₅ OOCCH _{2 -C 2} H ₅ O

NH - CO - COOC ₂ H

₂ H ₅

NHCOCOOC ₂ H ₅

NHCOCOOC ₂ H ₅

NHCOCOOC ₂ H ₅

NHCOCOOC ₂ H

NHCOCOOC ₂ H ₅

ΛΛ

CH ₃ O NHCOCOOC ₂ H ₅

CH ₃

LI— NHCOCOOC ₂ H ₅ OCH,

Cl

L J - NHCOCOOC ₂ H ₅

OCH ₃ CH ₃

LI-NHCOCOOC ₂ H ₅

OC ₂ H ₅

OCH ₃

NHCOCOOC ₂ H ₅ OC ₇ H

C ₂ H ₅ O

² " ⁵

NHCOCOOC ₂ H

₂ H ₅ 1) 1

92.5 to 93

87.5 to 88

to 113

109.5 to 110.5

119.5 to 120

to 108

to 81.5

73.5 to 74

102.5 to 103.5

up to 99

to 79.5

86.5 to 87.5

IV

62.64 6.07 5.62

62.66 5.91 5.52

72.84 10.26 3.03

72.59 10.01 2.77

56.94 5.80 4.74

56.52 5.69 4.58

60.75 6.37 5.90

60.94 6.34 6.06

69.12 5.39 5.76

69.17 5.29 5.70

69.12 5.39 5.76 69.53 5.51 5.83

56.91 5.97 5.53 56.98 5.96 5.51

60.75 6.37 5.90 60.79 6.24 5.91

53.64 5.19 5.16 53.38 5.25 5.08

62.14 6.82 5.57 62.04 6.65 5.27

51.27 4.69 5.44 51.20 4.66 5.51

59.77 6.81 4.98 59.82 6.89 4.92

NH ₂ O ₂ S

continuation

NHCOCOOC ₂ H ₅
OCH ₃

NHCOCOOC ₂ H ₅
OCH ₃

'NHCOCOOC ₂ H ₅
OC ₂ H ₅

NHCOCOOC ₂ H ₅ 14

NH-CO —COOCH,

C ₁₈ H ₃₇ O - <ζ y - NH - CO - COOC ₁₈ H ₃₇ III

to 190

to 87

to 175.5

to 81

to 131

up to 99.5

IV

60.54 4.62 12.84 60.46 A64 12.90

59.18 5.87 6.28 59.24 5.93 6.26

43.70 4.67 9.27 43.79 4.73 9.18

60.75 6.37 5.90 60.68 6.27 6.05

71.36 5.61 5.20 71.35 5.44 5.22

77.02 11.61 2.04 77.97 11.77 2.12

Preparation example for Table II

11.15 parts of the compound of formula (11) are dissolved in 20 parts of alcohol and 22.3 parts Lauryl alcohol and 0.5 parts of sodium metal were added. With stirring, the mixture is heated and the and the alcohol formed is continuously distilled off. It is then refluxed for 6 hours cooked.

For working up, 400 parts of chlorobenzene and the chlorobenzene solution are added to the reaction mixture washed twice with water. The chlorobenzene is then distilled off, the remaining oil was taken up in 100 parts of acetone and water was added until the onset of cloudiness. Through Cooling in an ice bath crystallizes the compound of the formula

CH ₃ O

NHCOCOOC ₁₂ H ₂₅

(45)

in a yield of 9.1 parts. A single recrystallization from acetone-water gives the analysis product with a melting point of 61 to 62 ° C. Analysis data:
C ₂₁ H ₃₃ O ₄ N:

Calculated ... C 66.42, H 8.20, N 4.56;
found .... C 66.65, H 8.13, N 4.33.

In a completely analogous manner or by the transesterification described below are those in the following Compounds listed in Table II have been prepared, which allow the possibility of variation of the ester residue R demonstrate. In this table means

Column I formula no.

Column II ester radical-R ₃ according to

Formula (54), and structural formulas

Column III melting point in ⁰ C

(uncorrected)

Column IV analytical data, first

Line = calculated, second line = found.

Table II

Examples of type 45:

ο

CH ₃ O ^ S — NH — C —COO-R ₃ '

(46) (47) (48) (49) (50)

15th

R ₃ '= -

C ₃ H ₇ C ₄ H ₉ C ₈ H ₁₇ C ₁₈ H ₃₇

CHtCH

Table II

16

C ₂ H

₂ H ₅

R = -CH ₂ CH ₂ OCH

II!
138.5 to 139.5

73.5 to 74.5

to 76

to 62

95.5 to 96.5

66.5 to 68

104.5 to 105
86.5 to 87.5

up to 120.5

57.41
57.54

60.75
60.76

62.14
62.15

66.42
66.65

IV

5.30 6.70

5.29 6.79

6.37 5.90

6.23 5.94

6.82 5.57

6.94 5.63

8.20 4.56

8.13 4.33

72.44 10.13 3.13 72.27 10.16 3.00

66.42 8.20 4.56 66.76 8.08 4.47

67.36 5.30 4.91

67.64 5.50 4.81

56.91 5.97 5.53

56.96 5.95 5.74

64.96 6.91 5.05

65.28 6.81 5.28

C ₈ H ₁₇ O

C ₈ H ₁₇ O

C ₈ H ₁₇ O

CH,

NHCOCOOCH,

NHCOCOO-C ₈ H ₁₇

NHCOCOO -

<x sr - NH - CO - COOCH ₂ CH ₂ - to 95.5

up to 64

55.5 to 56.5

to 84

OCH,

CH,

66.42 8.20 4.56

66.54 8.34 4.76

71.07 9.69 3.45

71.17 9.73 3.68

68.74 8.94 4.01

69.06 8.88 4.30

58.42 6.41 5.24 58.53 6.30 5.22

Examples

55

In the following examples, parts also mean, unless otherwise noted, Parts by weight and the percentages are percentages by weight. In each of these examples, typical representatives used for respective subgroups of compounds according to the invention. In principle all are of the compounds mentioned in the preceding description and their equivalents in the same way Manner suitable, with only the solubility of the compound in question in the to be protected organic material must be taken into account or can be determined immediately in a manual test. Possibly Finally, the fact that the absorption maximum of the to be incorporated must be taken into account Compound is influenced by the substituents in the aromatic radical.

example 1

An acetyl cellulose film about 50μ thick is made by pouring out a 10% acetyl cellulose solution, which contains 1% (calculated on acetyl cellulose) of the compound according to formula (11), manufactured. After drying, the following values are obtained: the percentage of light transmission:

209 629/147

Light transmission in% exposed wavelength (100 hours in ηΐμ unexposed Fadeometer) 0 270 to 300 0 3 310 3 5 320 5 12th 330 12th 30th 340 30th 50 350 50

Ζ behave analogously. B. the compounds of formulas (1), (16), (22) and (36).

Example 2

A paste of 100 parts of polyvinyl chloride, 59 parts by volume of dioctyl phthalate and 0.5 parts of the compound of the formula (1) 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 340 ΐημ.

Instead of the compound of the formula (1), it is also possible, for example, to use one of the compounds of the formulas (11), (16), (32), (39), (44) or (49) can be used.

Example 3

A mixture of 100 parts of polyethylene and 0.2 parts of the compound of formula (1) is rolled out on the calender at 130 to 140 ⁰ C into a sheet and pressed at 150 ° C.

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

Instead of the compound of the formula (1), it is also possible, for example, to use one of the compounds of the formulas (11), (16), (32), (39), (41) or (44) can be used.

B e i s ρ i e 1 4

A mixture of 100 parts of polypropylene and 0.5 part of one of the compounds of the formulas (1), (11), (16), (22), (35) or (43) becomes a skin ^{on the calender at 170 ° C.} processed. This is pressed at 230 to 240 ^° 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 350 πΐμ.

Example 5

■ 0.5 parts of the compound of formula (1) are dissolved in 1.8 parts of monostyrene and 0.5 parts of a Cobalt naphthenate monostyrene solution (containing 1% cobalt) was added. Thereupon 40 parts of an unsaturated Polyesters based on phthalic acid - maleic acid-ethylene glycol - in monostyrene are added and the whole stirred for 10 minutes. After 1.7 parts of a catalyst solution have been added dropwise (Methyl ethyl ketone peroxide in dimethyl phthalate) is the well mixed, air-free mass between two Poured out glass plates. After about 20 minutes, the 1 mm thick polyester plate has solidified to such an extent that it can be taken out of shape. It is useful for UV light in the 280 to 350 πΐμ range impermeable.

Instead of the compound of the formula (1), it is also possible, for example, to use one of the compounds of the formulas (12), (19), (20), (32), (38) or (50) can be used.

Example 6 '

25 g of distilled styrene monomer can be prepolymerized in a closed bottle in an oven at 90 ⁰ C for 2 days. Then 0.5 g of a compound of the formulas (1), (11), (16), (22), (29), (44) or (56) and 0.050 g of benzoyl peroxide are slowly added to the viscous mass. The mixture is then poured into a cuboid form made of aluminum foil and ^{kept at 70 °} C. for 1 day. After the mass has completely solidified and cooled, the shape is broken apart. The block obtained in this way is then pressed 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 practical for UV light in the range from 280 to 350 ηΐμ impermeable. They are completely colorless. When exposing in the fadeometer you can see a clear Observe improvement in light stability by adding polystyrene sheets, which compounds of the above Formulas contain no yellowing during an exposure of 200 hours Plates without these additives have already yellowed.

Other connections listed in the table behave similarly.

Example 7

In 40 g of nitro clear lacquer (25%) 0.2 g of a Compound of formulas (1), (16), (22), (39), (43) or

(46) dissolved. The varnish is then evenly applied to maple wood panels with a coating squeegee applied and is completely dry after a short time. By adding the aforementioned ultraviolet absorbers the shade of the wood is not changed in relation to the lacquer. The light shade of the lacquered Wood is not changed even when exposed to a UV lamp after several days, provided that the paint contains the above compounds in a concentration of about 1%. Untreated wood darkens under the given exposure conditions after a few days.

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

B e i s ρ i e 1 8

8 g of toluene-2,4-diisocyanate / toluene-2,6-diisocyanate mixture (65:35) and 20 g of a slightly branched polyester made from adipic acid, diethylene glycol and triol (hydroxyl number 60) are 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 0.56 g of a compound of formulas (1), (11), (16), (32), (37) or (41) and stir briefly. A foam fleece is formed, which is placed in a water bath after 30 minutes. After another 30 minutes, water will be fine washed through and dried at room temperature. The addition of one of the above UV absorbers increases the resistance during exposure in the xeno

Example 10

A. Colloidal mixture of 90% cetyl alcohol and stearyl alcohol and ^parts

10% sodium lauryl sulfate 8.0

Polyethylene glycol distearate with

Molecular weight 400 5.0

Diethylene glycol monostearate 3.0

Isopropyl myristate 5.0

Vaseline oil. 5.0

Polyethylene glycol with a molecular weight of 300 20.0

Connection of formulas (11), (19), (21),

(29) or (41) 1.5

B. methyl p-oxybenzoate 0.3

Distilled water 51.9

test equipment. The above absorbers are also found in numerous other polyurethanes based on the isocyanate polyaddition process are based, easy to incorporate.

Other compounds listed in the table behave similarly.

Example 9

In 10 g of pure olive oil, 0.2 g of the connec-> ° tion of formulas (11), (14), (18) to (22), (23), (29) or (41) are solved. The solution occurs quickly and without Heat. A 50 μ thick layer of this solution absorbs the UV light up to 340 πΐμ.

Other fatty oils can also be used · 5 and creams or emulsions, which are used for cosmetic purposes, to solve the above or other compounds mentioned in the description.

Example 11

A solution of the following composition is prepared in the usual way:

Combination of formulas (11), (14), (18), ^parts

(19), (20), (22) or (23) 3

Polyethylene glycol with a molecular weight of 300 40

Propylene glycol 25

Isopropyl myristate 2.5

Ethanol 29.2

Perfume 0.3

The solution can be used as a skin protectant against ultraviolet radiation. she will expediently applied to the skin with the aid of a suitable spray device.

Claims (1)

Claim:
Use of oxalic acid ester amides ²⁰ formula φ » The 01 phase A and the aqueous phase B of the composition given below requires: NH-CO-COOR (XO) ₁ , 30th 35 40 The melted and heated to 70 ⁰ C heated oil phase A is added under vigorous stirring warmed to 75 ° C water phase B. The emulsion is stirred cold and perfumed (0.3 parts perfume). where X is an alkyl group containing 1 to 18 carbon atoms, optionally containing a carboxylic acid alkyl ester group, the allyl group, the benzyl group, a fatty acyl group or a benzyl group optionally substituted by a chlorine atom or a lower alkyl group, Y is an alkyl group containing 1 to 12 carbon atoms, a halogen atom, a halomethyl group , represents the phenyl group, the nitrile group, the nitro group, an alkylamino group or the sulfonic acid amide group or where two o-position radicals Y together form a fused benzene ring and R an alkyl group containing 1 to 18 carbon atoms, an alkoxyalkyl group containing 1 to 6 carbon atoms, the benzyl group or denotes the cyclohexyl group, and u and υ for the numbers 0, 1 or 2 with a sum for u +1; are from 1 to 3 and the value 0 for an index number (u or v) denotes a hydrogen atom, as an ultraviolet protectant for organic materials.