DE1213410B - Use of 2- (2'-hydroxy-5'-acylamido-phenyl) -benztriazole compounds for stabilizing light- and oxidation-sensitive organic materials - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN AZw PATENT OFFICE

EDITORIAL

Int. Cl .:

C07b

C08g
German class: 12 ο - 27

Number: 1213 410

File number: G 35221IV b / 12 ο

Filing date: June 15, 1962

Opening day: March 31, 1966

The present invention relates to the use of 2- (2 '- hydroxy - 5' - acylamidophenyl) - benzotriazole compounds to stabilize high and oxidation sensitive organic materials against the harmful influence of light and / or oxygen.

It has been found that light- and oxidation-sensitive organic material can be used against the action from light and / or oxygen by protecting the organic materials at least one 2- (2'-hydroxy-5'-acylamidophenyl) benzotriazole compound is incorporated.

The active ingredients correspond to the general formula

HO

(I)

In this formula, "acyl" means an organic acyl radical and R _{1 is} hydrogen or an alkyl, alkenyl, cycloalkyl or aralkyl radical, where R ₁ and "acyl" can form a ring together with the nitrogen atom and in this case R _{1 is} a carbonyl - Or represents a methylene group optionally substituted by alkyl groups and in which the nucleus A in positions 4, 5 and 6 by alkyl, alkoxy, carboxyl, carboxylic acid ester, carboxamide, sulfonic acid amide, alkylsulfonyl groups or halogens and the nucleus B in the positions 3 'and 4' can be substituted by hydrocarbon groups or halogens.

The benzene ring A can thus in positions 4, 5 or 6 even lower alkyl groups, such as methyl, ethyl, isobutyl groups, alkoxy groups such as methoxy or butoxy groups, halogens such as chlorine or bromine, carboxyl groups, carboxylic acid ester groups, namely carboxylic acid alkyl ester groups, such as Carbomethoxy, carboethoxy, carbopropoxy or carbobutoxy groups, optionally aliphatic, cycloaliphatic, araliphatic or aromatic substituted carboxamide or sulfonic acid amide groups on the nitrogen, such as carboxamide or sulfonic acid amide, methylamide, ethylamide, -cyclohexyl, -butylamide benzylamide, dimethylamide, diethylamide, -N-methyl-N-cyclohexylamide, γ-methoxypropylamide, piperidide or morpholide groups, use of 2- (2'-hydroxy-5'-acylamidophenyl) -benztriazole compounds for
Stabilizing light and
organic materials sensitive to oxidation

Applicant:

J. R. Geigy A. G., Basel (Switzerland)

Representative:

Dr. F. Zumstein, Dr. E. Assmann

and Dr. R. Koenigsberger, patent attorneys,

Munich 2, Bräuhausstr. 4th

Named as inventor:

Dr. Hansjörg Heller, Riehen;

Dr. Johann Rody, Basel;

Dr. Ernst Keller, Binningen (Switzerland)

Claimed priority:
Switzerland of June 16, 1961 (7098)

as well as alkylfonyl groups such as methylsulfonyl or ethylsulfonyl groups.

The benzene ring B can in the positions 3 'and 4' by hydrocarbon groups such as methyl, Ethyl, tert-butyl, benzyl, cyclohexyl or phenyl groups, or halogens such as chlorine or bromine, substituted be.

In the group

- N -acyl

“acyl” is in particular a radical of the formula
Y

Il

-XR ₂

in which X is a carbon atom or the radical - S = O and Y is an oxygen atom or, if X is a carbon atom, also a sulfur atom if R _{2 is} a free or substituted amino group, or an imino group which, together with X and R _{2, is} a s-triazine or pyrimidine ring forms.

R ₂ represents an alkyl, alkenyl, cycloalkyl, aralkyl or an aryl group, the aryl group, for example, by halogen atoms, alkoxy, alkyl,

609 S40 / 438

free or modified carboxyl groups can be substituted and, in particular, when X «is in the material atom, the alkyl group can be further substituted, for example, by halogen atoms, etherified mercapto, free or etherified hydroxyl groups, primary, secondary or tertiary amino groups and free or modified carboxyl groups, or if X is a carbon atom, R ₂ also denotes hydrogen or an alkoxy, alkenyloxy, cycloalkyloxy, aralkyloxy or an aryloxy group, the aryl ίο remainder of the aralkoxy or aryloxy group, for example by alkyl, alkoxy groups or halogen atoms, and the alkyloxy group can be substituted by alkoxy or alkyl mercapto groups, or an amino group which can be substituted on the nitrogen by one or two identical or different alkyl, alkenyl, cycloalkyl, aralkyl or aryl groups, or an imino group of a saturated moooeyclic heterocycle or, if R ₁ and R _? are linked, together with X and R _1, the remainder of a lactam or dioxopyrrolidine ring.

In any case, the olefinic double formation of the optionally present alkenyl group is by at least one carbon atom from the nearest heteroatom and those attached to saturated carbon atoms Heteroatoms are through at least one other carbon atom from the nearest heteroatom separated.

"Acyl" preferably represents the following groups, the preferred number in brackets Carbon atoms of this group is given:

a) an s-triazinyl radical of the formula

ZR ₃

Γ —C

ZR ₃

an aryl group (O ^ g), ah can be substituted in particular by halogen atoms, alkoxy *, alkyl, free or modified carboxyl groups,

d) a Carbatnoylrest of the form}

- C -NR ₇

wherein R _{7 is} an alkylene radical (C ₄ - ₈ ) or an oxalkylene radical (C ₄ - _e ) which, together with nitrogen, forms a five- to seven-membered saturated heterocycle,

e) a thiocarbamoyl radical of the formula

- C - 'MH - R ₅
f) a carbonic acid monoester radical of the formula

35

in which Z is an imino or an alkylimino group (Qs), an oxygen or sulfur atom and R _{3 is} an alkyl (C ₁ -I ₂ ), cycloalkyl (Q- ₈ ) or an alrakyl group (C ₇ -I ₈ ) , whereR ₅₃ together with the alkylimino group can form a five to seven-membered saturated heterocycle (and the whole group contains at most 25 carbon atoms),

b) a pyrimidyl radical which contains at most one CH group in the ring and which _{is substituted on the remaining carbon atoms by chlorine and at most one ZR 3} group (and the whole group contains at most 17 carbon atoms),

c) a carbamoyl radical of the formula

5 <>

55

OR _S

where R _{8 has} the same meaning as R ₆ , but also denotes no alkoxyalkyl (C ₃ - _iD ), a haloalkyl (Cj- ₅ ) or an alkylmercaptoalkyl radical (C ₃ -J ₀ ),

g) a carboxylic acid residue of the formula
O

Il.

-CR ₉

wherein R _{9 has} the same meaning as R ₈ , but also hydrogen or an alkenyl (C _e - ₁₈ ), a carboxyalkyl (C ₃ - ₁₀ ). a carboxyaryl (C ₇ ), carboxyalkenyl (C ₄ - _e ), a carbalkoxyalkyl (C ₃ - _{1] L} ), a carboxyalkoxyalkyl (C _e - _S ), a carboxy-kyloxyalkyl (C ₈ -J ₄ ), a carboaryloxyalkyl (C ^ ₁₄ ), an R ₆ -C
(C ₂ -U ₂ ), an R ₆ -S-alkyl- (C ₂ -O ₂ ) one

—C — n:

R ₈

where R ₄ and R _{6 are} independently hydrogen or an R ₈ group (R ₄ and R ₆ 6g together contain at most 19 carbon atoms), where R _{6 is} an alkyl (C ₁ ^ ₁₈ ), an alkenyl (C ₃ - ₅ ). a cycloalkyl ( ₅ -β) an aralkyl (C ₇ - _ia ), ¹ X,

is an alkylene (C ₄ - ^ ₈ ) or an oxalkylene radical (C _{4 -C 6} ), or

h) emen SuMonsäurerest of the formula - SO ₂ R ', where R' has the meaning given _{under R 8.}

If R ₃ to K _{9 are} aryl radicals, they are preferably monocyclic.

R ₁ is preferably hydrogen, eiae nnsubstituierte alkyl (C ₁ ^ _18), a carboxyalkyl · (CV _5), a carbalkoxyalkyl · (C ₃ ^ _14), a cycloalkyl (C ₅ _ ₈₎ or an aralkyl group (C ₇ ^ ₁₂ ).

When R ₁ and R ₂ are connected to one another, R ₁ preferably represents a carbonyl or methylene group and R _{2 represents} a 1,2-ethylene group. Preferably, R ₁ and the "acyl" radical together contain at most 26 carbon atoms, at most nitrogen atoms, a maximum of 4 oxygen atoms and a maximum of 2 sulfur atoms.

Benztriazole compounds which absorb particularly long waves are obtained when acidifying

Substituents in ring A are present. Benztriazole compounds with a particularly high molar extinction in the range from 330 to 350 μm are obtained when basic substituents are in the 5- and / or 4'-position. The molar absorption in the range of 300 ηψ. is promoted by optionally further substituted alkyl substituents in 3'-StBlIuHg. Examples of basic substituents are alkoxy groups, such as the methoxy, isopropoxy, cyclohexyloxy and benzyl oxy groups; Examples of acid-inducing substituents to are the alkylsulfonyl groups, such as the methyl and ethylsulfonyl groups, the sulfonic acid amide groups, such as the sulfonic acid methyl, butyl and ecclobexyl amide groups, and the carboxyl group and its esters or amides.

Of course, typical dye groups in the benzotriazole compounds according to the invention are such as, for example, aromatic azo groups, auxochrome-containing anthracbinone groups or phthalocyanine groups, as Exclude substituents.

The 2- (2'-hydroxy-5'-acylainidophenyl) 'benzotriazole compounds which can be used as stabilizers according to the invention and which can be further substituted within the scope of what has been said for A and B under formula I can be prepared, for example, by one of the three following methods: by oxidative ring closure of i-Ajccuno ^ '- hydroxy-S'-acylamido-ljl'-azobenzene' compounds with salts of divalent copper in a neutral to alkaline medium; by reductive ring closure of 2'nitro-2'-hydroxy-5- ^/ acylanjido-l, l'-azobenzenes ^ ζ · B. using zinc dust in an alkaline medium; by modifying functional groups in the finished 2-pbenylbenzotriazole compound, either by acylating the amino group in 2- (2 '- hydroxy- 5' - aminophenyl) benzotriazole compounds or by releasing the hydroxyl group in the 2 'position in a 2 ~ ( 2'-alkoxy-5'-acylamidophenyl) -benztriazole compound by dealkylation or in a 2- (2'-acyloxy-5'-acylamidophenyl) -benztriazole compound by saponification. The dealkylation can, for example, with aluminum chloride in boiling benzene, the saponification by heating with a solution of alkali metal hydroxides in a mixture of water and an alcohol, ζ. B. be carried out with a mixture of concentrated aqueous sodium hydroxide solution and ethylene glycol monomethyl ether.

To introduce the “acyl” radical, such as the carboxylic acid radical of the formula R ₂ - CO -, into starting materials which can be used according to the invention, anhydrides, esters, ζ, for example, are used as acyling agents. B. Esters of lower alkanols, preferably halides, in particular chlorides or ketenes of R ₂ - CO - corresponding carboxylic acids, for the introduction of a carbonic acid monoester of the formula Rg - OCO -, a sulfonic acid ester of the formula R ₆ - SO ₂ - and a cyclic carbon imide radical, in particular a l , 3,5-Triazinyl- (2) radicals, in each case the halides, especially the chlorides, of the corresponding acids; to introduce a carbamoyl or thiocarbamoyl radical, either the halides of the corresponding acids or isocyanates or mustard oils, e.g. B, phenyl isocyanate or phenyl mustard oil. The reaction of the ^{2- (2'-hydroxyphenyl) benzotriazole compound containing an acylatable amino group in the 5 y} position with the acylating agent is carried out by heating, optionally in inert organic solvents, such as, for. B. in halogenated or nitrated aromatic hydrocarbons, ζ. B. in benzene, toluene, chlorobenzene or nitrobenzene, or in a tertiary amine, such as. B. in pyridine or diethylaniline, it must be ensured in any case that the hydroxyl group in the 2'-position is not acylated, which is achieved by working in a weakly acidic to weakly alkaline agent,

Examples of particularly suitable compounds which can be used according to the invention are the following mentioned, being in this list the analytically pure substances are characterized by their melting point (uncorrected). Raw products that have been turned over and cleaned with animal charcoal on a sufficient, but insufficient purity in terms of melting point have been brought about by their characterized spectral properties, the wavelength of the longest-wave maximum (A) and the Percentage transmission (I) of a solution of Im g of substance in 100 ml of chloroform at one layer thickness 1 cm is specified.

2- (2'-Hydroxy-5'-acetylamidophenyl) -benztriazole,

M.p.> 270 ° C;
2- (2'-Hydroxy-5 ^/ -acetylamidophenyl) -5-chloro-

benztriazole, F, 268 ⁰ C;
2- (2'-hydroxy-5'-acetylamidophenyl) -5-methyl-

benzotriazole, F. 234 ⁰ C;
2- (2'-Hydroxy-5'-acetylamidophenyl) -5 »methoxy-

benzotriazole, F. 249 ⁰ C;
2 '(2'-Hydroxy-3'-methyl-5'-acetylamidophenyl) -

benztriazole-5-carboxylic acid, m.p.> 270 ° C; 2 '(2'-Hydroxy-3'-methyl-5'-pentanecarboxylic acid

amidophenyl) -benztriazo £ F. 222 ⁰ C; 2- (2'-hydroxy-5'-j3-carboxypropionylbutyl-

amidophenyl) benzotriazole, mp 154 ° C; 2- (2'-hydroxy-5'-j8-carbomethoxypropionylbutylamidophenyl) benzotriazole; A; 338 nm;

Γ: 40%;
2- (2 ^/ -hydroxy-5'-N-ß-carboxyethyl-benzoyl-

amidophenyl) benzotriazole, mp 187 ° C; 2- (2'-Hydroxy-5'-benzoyl '/ 3-cerbomethoxy-ethyl-

anüdophenyl) benzotriazole, mp 123 ° C; 2- (2'-hydroxy-5'-carbocyclohexyloxyamido-

phenyl) benzotriazole, mp 194 ° C; 2- (2'-hydroxy-5'-carbocyclohexyloxyamido-

phenyl) -5-chloro-benzotriazQl, λ: 360nm;! T: 51%; 2-t2'-hydroxy-5 '- {4 ", 6" -dibutylmercaptos-triazinyl- (2 ")} - aminophenyl] -benztriazole,

112 ° C;
2- (2'-Hydroxy-5'-methanesulfonic acid benzyl

anoidophenyl) benzotriazole, mp 215 ° C; 2- (2'-Hydroxy-3'-methyl-5'-methanesulfonic acid ' cyclohexylaraidophenyty-benztriazole-S-carbon-

allyl acid ester; λ: 353 nm; T: 49%> 2- (2'-hydroxy-5'-carbooctyloxyamidophenyl) -

benztriazole, mp 142 ° C;
2- (2'-Hydroxy ~ 5'-carbophenoxyamidophenyl) -

benztriazole; λ: 353 nm; T: 52 ° / _ο ί 2- [2'-hydroxy-5 '- {4 ", 6" -bisdibutylamino-s-tri-

azinyl- (2 ")} - aminophenyl] -benztriazole, m.p.- 88 ° C-2- [2 ^/ -hydroxy-3'-methyl-5 '- {4" _! 6 "-. Bisdibutyl-

amino-s-triazinyl- (2 ")} amidophenyl] -benz-

triazole; λ: 373 nm; T: 74%; 2-2'-Hydroxy-5'-pentanecarboxamideophenyl) -

5-methyl-benzotriazole, F. 193 ⁰ C; 2- (2'-hydroxy-5'-stearoylamidophenyl) -5-methylbenzotriazole; λ; 3 $ 0nm; T: 53%;

7 8

2- (2'-Hydroxy-5-'N-phenylcarbomylbenzyl- better light resistance and protect ζ. B. Polyester-

amidophenyl) benzotriazole, decomposition point resin plates much better before yellowing.

about 180 ⁰ C; Regarding solubility and incorporability are

2- (2'-Hydroxy-3'-methyl-5'-N-phenylcerbamoyl- such acylamido-

cyclohexylamidophenyl) -5-methylbenzotriazole; 5 2- (2'-hydroxyphenyl) benzotriazole compounds are preferred

λ: 341 µm; T: 43%; added, the acylamido groups of which differ by one second

2- (2'-Hydroxy-5'-chloroacetylbenzylamidophenyl) - derive from amine. The lightfastness generally

benztriazole, mp 185 ° C; common in the following order to: triazinyl

2- (2'-Hydroxy-5-p-methylbenzoylbenzylamido- amido - * ■ carboxylic acid amido -> sulfonic acid amido-

phenyl) benzotriazole, mp 144 ° C; ro compounds; i.e., the more acidic the acyl radical

2- (2'-Hydroxy-5'-p-toluenesulfonic acid amido- ■ speaking free acid, the better the light

phenyl) benzotriazole, mp 238 ° C; authenticity.

2- (2'-Hydroxy-5'-methanesuKonsäureamido- The stabilizers according to the invention are the to

phenyl) benzotriazole, m.p. 249 "C; protective materials in amounts of 0.001 to 5%;

2- (2'-Hydroxy-5'-N-phenylcarbamoylamido- 15 especially in amounts of 0.01 to 1% of the carrier

phenyi) -5-methyl-benzotriazole, mp> 270 ° C; materials incorporated.

2- (2'-Hydroxy-3 ^< -chlor-5'-acetyknethylamido- As a carrier material for the 2- (2'-Hydroxy-5'-acyl-

phenyi) benzotriazole, mp 138 ° C; · · Amidophenyl) benzotriazole compounds come in

2- (2'-Hydroxy-3'-methyl-5'-acetylmethylamido- ^: primarily polymers in question, such as fully synthetic

phenyl) benzotriazole, F, 158 ⁰ C. '20 polymers, eg. B. addition polymers, especially polymers of compounds with ethylenic double

If the compounds of the formula contain reactive bonds, for example those of vinyl chloride, capable groups, the latter can be post-vinylidene chloride, styrene, dienes such as butadiene, isoprene, by further reactions in 'other groups ethylene, propylene, acrylic compounds such as Acrylic transfer. So you can, for example, mobile 25 nitrile or methyl methacrylate and their copolymers; Halogen in halogen fatty acid amide groups through condensation polymers such as polyesters, for example alcohols, mercaptans, primary or polyethylene glycol terephthalate, or polyamides, secondary amines or alkali metal cyanides act against, for example, polycaprolactam, or mixed corresponding alkoxy, marcaptide, amino or polymers , ie those that exchange both polycondensates and the cyano group or represent carboxyl groups as well as polyaddition compounds, such as poly or sulfonic acid groups. optionally over the ester resins or alkyd resins, also of course polymeric acid chloride, in the corresponding acid ester or or their synthetic modifications, such as. B. transferring acid amide groups or attaching cellulose, cellulose esters and ethers as well as proteins, capable double bonds, alcohols, mercaptans, amines. In addition, there are also low molecular weight carriers or hydrocyanic acid. 35 materials into consideration, for example fats, oils or examples of such subsequent modifications are waxes. The molecular weight of the above-mentioned reactions of 2- (2'-hydroxy-5 '- /? - chloropolymer plays a subordinate role, as long as there is pionylamido-3'-methylphenyl) -benztriazole with di- within the for the characteristic mechanical ethylamine , Cyclohexylamine, benzylamine and N-Me properties of the polymers in question necessary thylcyclohexylamine to 2- (2'-hydroxy-5 '- / 3-diethyl limit values. It can, depending on the polymer, between aminopropionylamido - 3' -methylphenyl ) - benztriazole, 1000 and several million.
2- (2'-Hydroxy-5 '- ^ - cyclohexylaminopropionylamido- In nonpolar polymers, those benz-3'-methylphenyl) -benztriazole, 2- (2'-hydroxy-5' - /? - ben- triazole compounds are particularly suitable, the hydroxyl group possibly present in addition to the zylaminopropionylamido-3'-methylphenyl) -benztriazole by definition and 2- (2'-hydroxy-5 '- /? - methylcyclohexylaminopro- 45 lends a few polar groups, such as carbon or pionylamido-3'- methylphenyl) benzotriazole or the sulfonic acid amide groups, especially those additions of octyl mercaptan to 2- (2'-hydroxy-primary amines. In this case, S'-acryloyhnethylamido-S'-chlorophenyO-S-ethylbenzene are generally low-melting products because of their triazole is preferred to 2- (2'-hydroxy-5'- | S-octylmercaptopropionyl solubility.

methylamido-S'-chloropheny ^ -S-ethylbenzotriazole. 50 It is generally recommended to use the possible-for the production of the specific product to be used according to the invention by means of solubility factors Connections are not attempted to assess protection here. For example, is the product spoke. also hot in the solvents that are known for the substituted 2- (2'-hydroxy-5'-acylamidophe- protective polymers, so nyl) -benztriazole compounds are, depending on the substitution 55, an unfavorable compatibility in this poly is colorless to slightly yellowish in color. They absorb meren expected.

UV light and at the same time have an antioxidant effect, incorporating the new substituted 2- (2'-Hywodurch they differ from the related 2- (2'-hydroxyphenyl) benzotriazole compounds into these polyphenyl) benzotriazole compounds with acylamido mers happens, for example, depending on the type of polygroups Distinguish in 4'- or 5-position. The 60 mers, by incorporating at least one of these purely antioxidant effect is derived from Example 2 compounds and optionally other additives, before. They also show good fastness to sublimation and, e.g. B. plasticizers, antioxidants, heat stabilizers as long-wave absorbing light stabilizers and pigments, in the melt after the in the middle. Methods customary in technology before or during the Furthermore, the 65 to be used according to the invention have shaping or by dissolving in the corresponding benzotriazole compounds compared to the from the monomers before the polymerization or through Swiss patent 350 763 as UV ^ protective dissolving of the polymer and the additives in solvent known benzimidazole compounds mean and subsequent evaporation of the latter.

The new substituted 2- (2'-hydroxyphenyl) benzotriazole compounds can also be made from bathrooms, e.g. B. from aqueous dispersions, drawn onto films or threads will.

The photosensitive materials can be protected from the harmful effects of light as well be that they with at least one defined compound of the formula containing Protective layer, e.g. B. a varnish, or that you can with such, containing light stabilizers - Appropriately film-like - covers structures. In both of these cases, the amount is added Light stabilizers advantageously 10 to 30% (based on the protective layer material) for protective layers less than 0.01 mm thick and 1 to 10% for protective layers 0.01 to 0.1 mm thick. The benzotriazole derivatives according to the invention are all the more valuable, the more colorless they are, since they would otherwise be the end products give a yellow tint.

With certain types of use, especially when warm schnitzels have to be powdered, products are which melt above the softening temperature of the polymer in question and still in the melted state Polymers are sufficiently soluble, particularly valuable.

In general, the more colorless they are and the less they are, the more valuable the benzotriazole derivatives discolor during exposure to oxygen.

The following examples illustrate the invention. In it mean, unless otherwise noted is, the parts are parts by weight. The temperatures are given in degrees Celsius. Parts by weight to parts by volume in the same ratio as kilograms to liters.

example 1

100 parts of a commercially available liquid polyester resin, consisting of 70% of a polycondensate from Maleic acid, phthalic acid and ethylene glycol and 30% styrene are added after adding 0.3 parts 2- (2'-Hydroxy-5'-N- / ß-carbobutoxyethylberizoylamidophenyl) benzotriazole and 1 part of benzoyl peroxide poured into a mold and hardened by heating for 3 hours at 80 °. The resulting 2 mm thick colorless, transparent polyester resin plate absorbs all UV light with wavelengths of less than 380 πιμ and can be used as a UV filter.

Polyester resin plates stabilized against discoloration by the action of light are produced in the same way, if an equivalent amount of methyl methacrylate is used instead of styrene.

Used in place of maleic acid 1,4,5,6,7,7-hexachlorobicyclo-5-hepten-2,3-dicarboxylic acid (Het acid) used, flame retardant polyester resins with good absorption capacity for UV light are obtained.

Such polyester panels are suitable as roofing material.

Since the sun protection effect and the purely antioxidant effect are not readily available in one experiment can be found side by side, the present example is only intended to show that these are antioxidant is present in addition to the sun protection effect.

Example 2

The autoxidation of the petroleum distillate used as the standard test oil and known as "Regal Oil Β" (manufactured by Texas Oil Comp., USA) was used in the so-called »Continental Oil-Oxidation Test «according to the information in Ind. And Eng. Chemistry, 33, p. 339 (1941), with and without the addition of stabilizers certainly. The following shows the time after which the oxygen pressure as a result of the Oxygen consumption has decreased by 60 mm Hg due to autoxidation.

Antioxidant

None

2- (2'-Hydroxy-5'-acetylamidophenyl) -benztriazole (0.025%)

2- (2'-Hydroxy-5'-butyrylamidophenyl) -benztriazole (0.025%)

Test duration up to 60 mm pressure drop in hours

50 182 150

ao Similar results are obtained when in place of the compounds mentioned 0.075% 2- (2'-hydroxy-5 '. (4 ", 6" - bis - dibutylamino -1 ", 3", 5 "- triazinyl - (2"> amidophenyl) benzotriazole or 2- (2'-hydroxy-5'-caproylamidophenyl) -5-chlorobenzotriazole be used for auto-oxidation inhibition.

Example 3

A mixture consisting of 65 parts of polyvinyl chloride (from Lonza AG., Basel), 32 parts of dioctyl phthalate, 2 parts of barium / cadmium laurate and 0.5 parts of 2 - (2 '- hydroxy - 5' - caproylamidophenyl) -5-chlorobenzotriazole, is calendered on the two-roll mill at 150 ° to form a film 0.1 mm thick. It absorbs UV light and can be used as packaging material for UV-sensitive materials. Its UV transmission at 360 ηιμ is less than 6%.
Similar results are obtained if, instead of the compound mentioned, 0.5 part of 2- (2'-hydroxy-5'-N-benzyl-acetamidophenyl) -benztriazole, 2- (2'-hydroxy-5'-carbocyclohexyloxybenzylamidophenyl) -5 - ethylsulfonyl - benzotriazole or 2 - (2 '- hydroxy-5' - β - carbobutoxypropionylamidophenyl) - 5 - carbobutoxy-benzotriazole can be used.

In the same way, copolymers of polyvinyl chloride and polyvinyl acetate can be used to form UV-proof films are processed.

Example4

A solution of 150 parts of cellulose acetobutyrate

(Cellit BF-900 from Farbenfabriken Bayer AG, Leverkusen), 20 parts of dibutyl phthalate, 800 parts Acetone and 0.35 parts of 2- (2'-hydroxy-5'-butyrylamidophenyl) benzotriazole are drawn up on glass.

After the solvent has evaporated, a colorless film 0.4 mm thick is obtained, which is practical absorbs all UV light of wavelengths below 380 πιμ and is ideal as a protective film, ζ. Β. for shop window displays.

Cellulose acetate or propionate can be used in place of acetobutyrate with similar results will.

Similar results are obtained if, instead of the compound mentioned, 0.4 part of 2- (2'-hydroxy-5'-carbobenzyloxyamidophenyl) benzotriazole be used.

609 540/435

Example 5

ίο

100 parts polyethylene powder. (DFD 4400 from the company Union Carbide International Chemical Company, New York) "with 0.25 parts of the compound 2 - (2 '- hydroxy - 5' - benzoyl / S '- carbodecyloxyethylamidophenyl) benzotriazole mixed and processed the mixture by means of an extruder into a blown film of about 0.06 mm thickness.

The film absorbs UV light and can be used as a protective film ζ. B. used to cover greenhouses will.

Is used instead of polyethylene polypropylene (Profax 6512 from Hercules Powder Co., Wilmington, Delaware, USA.), So can by means of an extruder using a slot nozzle at 250 to 270 ° a UV-absorbing polypropylene film of high transparency in the visible range can be obtained.

Similar results are obtained if, instead of the substance mentioned, 0.3 part of 2- (2'-hydroxy-S'-N-cyclohexyl-benzoylamidopheny ^ -benztriazole or 2- (2'-Hydroxy-5'-N-butyl-benzoylamidophenyl) -benztriazole can be used.

Examples

100 parts of granulated "nylon 66" (produced by the condensation of hexamethylenediamine and adipic acid in a molar ratio of 1: 1 at about 265 ° with exclusion of oxygen) and 0.5 part of 2- (2'-hydroxy-5 ' - acetylamidophenyl) - benztriazole are dry mixed and extruded to form a continuous film. The film absorbs the ultraviolet light and is suitable as a UV absorbing packaging material. If "nylon 6" or "11" or "mixed condensate 6/10" is used instead of "nylon 66", then see Films that behave optically very similarly are obtained.

Similar results are obtained if, instead of the substance mentioned, 0.7 part of 2- (2'-hydroxy-5 ' - caproylamidophenyl) - 5 - methylbenzotriazole or 2 - (2 '- hydroxy - 5' - caproylamidophenyl) - 5 - methoxy-6-methylbenzotriazole be used.

Example7

100 parts of methyl methacrylate, 0.2 part of 2- (2'-hydroxy - 5 - ρ - methylbenzoylbenzylamidophenyl) benzotriazole and 0.2 parts of lauroyl peroxide are mixed and at 70 ° between glass plates to form a plate of 2 mm thick polymerized. The plate obtained in this way absorbs practically all UV light between 270 and 380 ηιμ, the transmission of UV light changes very little when the plate is exposed in the fadeometer for 1000 hours.

Example 8

100 parts of polyacrylonitrile (prepared by polymerizing acrylonitrile according to W. R. S ο r e η s ο η and T. W. Campbell: Preparative Methods of Polymer Chemistry, Interscience Publishers, Inc., New York, 1961) with 0.5 parts of 2- (2'-hydroxy-5'-methansiu ^ onäurehepty] antidophenyl) -5-chlorobenzotriazole mixed and suspended in 1000 parts of strongly cooled dimethylformamide with thorough stirring. The so The resulting dispersion is first placed in a wide-necked powder bottle with a screw cap for 2 hours Rolled room temperature, then the temperature in the roller apparatus is increased to 50 ° and the polyacrylonitrile solution rolled until homogeneous. The viscous solution turns into a thin one on a glass plate Layer undressed. The solvent is removed by drying in a drying cabinet with air circulation at 80 ° slowly removed, leaving a clear film. This film absorbs practically everything UV light from 270 to 370 χημ.

In the same way, UV-tight films made from copolymers of 90% acrylonitrile and 10% vinyl acetate can be produced produce.

Example 9

100 parts of polystyrene (Shell Petrochemicals Ltd., England) and 0.3 part of 2- (2'-hydroxy-5'-carbocyclohexyloxymethylamidophenyl) benzotriazole are mixed well and sprayed at 240 ° to form 2 mm thick plates. The panels thus obtained are practically absorbent all UV light from 270 to 370 ιημ and tend less for yellowing when exposed to light than plates made in the same way but without the addition of light stabilizers

Turn 20.

Example 10

• 100 parts of commercially available polyethylene glycol terephthalate (Terlenka der Generaleene Kunstzijde Unie, Arnhem, Holland) and 1 part of 2- (2'-Hydroxy-3'-propyl-5'-pentanecarboxylic acid amidophenyl) -benztriazole are mixed dry and after thorough drying by means of an extruder at 285 ° to form a continuous film of processed about 0.2 mm thickness. The transparent, practically colorless film absorbs practically everything UV light between 270 and 380 ΐημ. It is suitable as a UV-proof packaging material.

Example 11

A polyvinyl butyral film (made by acetalizing polyvinyl alcohol with butyraldehyde) "is 3 minutes in a solution of 8 parts of 2- [2'-hydroxy-5 '- {4 ", 6" - bis - dibutylamino - s - triazinyl (2 ")} - amidophenylj-benzotriazole inserted in 100 parts by volume of benzene. After the film has dried, there are two glass plates welded with it at 140 ° under pressure. The safety glass obtained in this way is UV-tight, and moreover the organic binding layer is less sensitive to yellowing than that of a safety glass panel, which has been made with an untreated polyvinyl butyral film.

Claims (1)

Claim: Use of 2- (2'-hydroxy-5'-acylamidophenyl) benzotriazole compounds the general formula HO 55 N-acyl in which “acyl” denotes an organic acyl radical and R ₁ denotes hydrogen or an alkyl, alkenyl, cycloalkyl or aralkyl radical, where R ₁ and “acyl” can form a ring together with the nitrogen atom and in this case R ₁ denotes a carbonyl - or one if necessary I 213410 Alkyl groups substituted methylene group, and wherein the nucleus A in the positions 4, 5 and 6 by alkyl, alkoxy, carboxy, carboxylic acid esters, carboxylic acid amide, sulfonic acid amide, as well as alkylsulfonyl groups or halogens and the core B in the 3 'and 4' positions can be used to stabilize light-sensitive and oxidation-sensitive organic materials against the harmful influence of light and / or oxygen. Considered publications: Hydrocarbon groups or halogens substi- Swiss patent specification No. 350 763. When the registration is announced, there is a test report (5 pages) with 12 multi-colored curve boards has been laid out.