CH634463A5 - Composition for preventing scald in apples - Google Patents

Description

The invention relates to an agent for preventing peeling of apples.

The agent according to the invention can be used for thin-skinned apples of red color, such as Jonared and Starking, particularly advantageously for the apple variety Jonathan.

The peeling of apples on the skin is usually an abnormality (change in color) due to the decomposition of the coloring matter, which in the form of spots with a diameter of 1-15 mm may form on the skin of the fruit on the tree or during storage. Pitting, on the other hand, generally shows small spots on the surface of the apple, which also extend into the pulp below. Another apple disease is, for example, the so-called scald, which arises when the fruit is stored and causes the skin to turn brown.

Several chemical or physical methods are known to prevent apples from peeling on the skin (skin spot, peel spot).

Treatment with a spray solution which contains calcium ions or calcium salts, for example calcium nitrate or calcium chloride, at least five times during the growing season can achieve at most 10-30% protection, which is of course not satisfactory in practice. Another disadvantage of this protection method is that it leads to an increase in the calcium pectate content of the cells, since it is known that the accumulation of divalent cations, so the calcium ions, in the spots is a concomitant symptom of the skin spots [E. Beyers: The Fruit. Grow. 13, 319-335 (1963); N. Schachrestany: Kaufobstbau 6, 153-154 (1964); R. Schuhmacher and F. Fankhauser: Switzerland. Z. for fruit and viticulture 102,431-441 (1966); Hungarian Patent No. 159 199].

To protect against pitting of the apples, a method is described in Israeli Patent No. 26 740, in which the apples are treated with an aqueous solution or suspension which contains calcium salts and a stop-scald preparation. The latter contains an antioxidant, for example diphenylamine or 6-ethoxy-l, 2-di-hydro-2,2,4-trimethylquinoline. The apples treated with the agent according to the above patent are stored at room temperature for 5-7 days and then brought to the cold store. According to the description, 55% of the untreated control contracted pitting, while only 2-28% of the treated apples were infected.

When stored in a controlled atmosphere (CA), the apples are stored in a room in which the oxygen-carbon dioxide ratio is kept constant. One of the disadvantages of this process is that the fragrances that form during storage, substances that accelerate ripening and other metabolic products (carbon dioxide, ethylene) have to be removed. The installation of cold stores with fans, measuring devices and technical equipment is very complex and makes the apples unnecessarily expensive. Another and decisive disadvantage of the method, however, is that the apples suddenly start to become stained after being removed from the storage room and are already extremely stained when they reach the market [P.M. Smoch and G.D. Blanpied: Proc. At the. Soc. Hoard. Be. 73-77 (1965)].

The aim of the invention is to develop a new preparation for protection against the peeling of apples, which is better, more effective and simpler than the previously known agents.

The invention is based on the knowledge that peeling of the peel can be prevented or at least reduced to a minimum if the apples are treated with a preparation which contains at least one light protection agent.

The agent according to the invention for preventing peeling of apples is characterized in that it contains at least one light protection substance and at least one formulation aid as active ingredient.

The advantages of the agent according to the invention are, for example, that - in contrast to the known agents and methods with which the problem of peeling of the peel has not hitherto been able to be solved - the peeling of the peel can generally be practically avoided with a single treatment. For large orchards, but also for smaller gardens, it is usually not at all indifferent whether spraying five times or only once is necessary. Another advantage of the invention is, for example, that the apples do not suffer any damage even after winter storage, which in contrast to storage in a controlled atmosphere (CA) means a final solution to the problem; the pulp 45 does not become soft, as is the case with protection with gamma radiation, and there is also no need for special devices. It is also advantageous, for example, that the oral toxicity of the light protection substances is low.

The light protection substances used in the agent according to the invention are usually known compounds which are used partly as UV stabilizers in the plastics industry and partly as light stabilizers in the cosmetic industry. 55 The light protection substances can be divided into the following groups according to their function:

Light filters

UV absorbers

Quenchers

6o radical seavengers

Peroxide decomposers. However, it is more appropriate to classify the light protection substances according to compound groups, because the individual light protection substances can also have multiple functions.

The light protection substances present as active ingredient in the preparations according to the invention can be, for example, representatives of the following groups of compounds:

634 463

ne, benzotriazoles, dibenztriazoles, tri-triazolobenzene derivatives, aromatic esters, substituted acrylonitriles, organometallic compounds, alicyclic dienone derivatives and some inorganic pigments etc. The preparations according to the invention can also contain several light protection substances belonging to the same connecting group or to different connecting groups.

The apples are treated with the agent according to the invention, preferably in a diluted form, generally still on the tree, before harvesting. However, the treatment can also be carried out on apples that have already been harvested.

According to the invention, for example, the following benzophenone derivatives can be used: 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sodium sulfonate,

2-hydroxy-4-methoxy-4'-methylbenzophenone,

2,2'-dihydroxy-4-methoxybenzophenone,

2-hydroxy-4-n-heptoxybenzophenone,

2-hydroxy-4-n-octyloxybenzophenone,

2-hydroxy-4-methoxy-2'-carboxybenzophenone,

2-hydroxy-4-dodecyloxybenzophenone,

2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sulfonic acid,

2-hydroxy-2'-chlorobenzophenone.

Examples of particularly preferred benzophenone derivatives are the following: 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-n-heptoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2 , 2'-Dihydroxy-4,4'-dimethoxybenzophenone-5-sulfonic acid.

According to the invention, for example, the following benzotriazole and dibenztriazole derivatives can be used:

2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-n-octylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl- 5'-methylphenyl) -5-chlorobenzotriazole,

2- (2'-Hydroxy-3 ', 5 / -di-tert-butylphenyl) -5-chlorobenzotriazole. 5.11H-5.1 r-dideshydro-benzotriazolo [2, l-a] -benztriazole.

Examples of particularly preferred benzotriazole derivatives are the following:

2- (2'-hydroxy-5'-n-octylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole,

2- (2'-Hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 5.11H-5', 11 '-didydro-benzotriazolo [2, l-a] -benztriazole.

According to the invention, the following tri-triazolobenzene derivatives can be used, for example: 2,5,8-triphenyl-tri-w-triazolo (a, c, e) benzene, 2,5,8-tri- (nitrophenyl) -tri- w-triazolo (a, c, e) benzene, 2,5,8-tri- (dinitrophenyl) tri-w-triazolo (a, c, e) benzene.

According to the invention, the following aromatic ester derivatives can be used, for example:

Digalloyl trioleate,

Phenyl salicylate,

p-octylphenyl salicylate,

tert-butylphenyl salicylate,

Resorcinol monobenzoate,

2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxy-benzoate.

Examples of particularly preferred representatives of the aromatic ester derivatives are the following:

Digalloyl trioleate,

p-octylphenyl salicylate,

s resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxy-benzoate.

For example, the following substituted acrylonitrile derivatives can be used according to the invention:

1,1'-diphenylacrylonitrile acid ethyl ester,.

1,1'-diphenylacrylonitrile 2-ethylhexyl ester,

a-Cyano-ß-methyl-4-methoxycinnamic acid methyl ester.

The following 15 of the substituted acrylonitrile derivatives are preferred:

1,1'-Diphenylacrylnitrilsäureäthylester, 1,1 '-Diphenylacrylnitrilsäure-2-ethylhexyl, a-cyano-ß-methyl-4-methoxycinnamic acid methyl ester. According to the invention, the following 20 organometallic compounds can be used, for example: [2,2 / -Thio-bis- (4-tert.-octylphenolate)] - n-butylamine-nik-kel (II),

Nickel bis-octylphenyl sulfide (Ferr AM 101 and AM 106) [3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid mono-25 ethyl ester 2: 1 nickel chelate], Irgastab 2002, Cobalt (II) dicyclohexyl dithiophosphinate.

Examples of preferred organometallic compounds are as follows:

[2,2'-thio-bis- (4-tert.-octylphenolate)] - n-butylamine-30 kel (II),

Nickel bis-octylphenyl sulfide (Ferro AM 101 and AM 106).

According to the invention, 5- (3,3-dimethyl-norbornylidene) -3-penten-2-one of the alicyclic dienone derivatives can be used very advantageously, for example. According to the invention, for example, carbon black, titanium dioxide and zinc oxide can be used from the inorganic pigments. For example, titanium dioxide and zinc oxide are preferred.

Not only 40, but also several light protection substances can be used in the preparations according to the invention, for example one or more benzophenone (s) and / or one or more benzotriazole (s) and / or one or more dibenzotriazole (s) and / or one or more tri-triazolobenzene derivative (s) and / or one or 45 more aromatic esters and / or one or more substituted acrylonitrile (s) and / or one or more organometallic compounds) and / or one or more alicyclic dienone derivative (s) and / or one or more inorganic pigment (s).

These preparations according to the invention containing more than one light protection substance contain, for example, the following light protection substances:

2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenz-55 triazole and 2- (2'-hydroxy-3 ', 5'-di-tert-butyl- phenyl) -5-chlorobenzotriazole,

Zinc oxide and 2- (2'-hydroxy-3'-tert-butyl-5'-methylphe-

nyl) -5-chlorobenzotriazole, 2,2 ', 4,4'-tetrahydroxybenzophenone and 2-hydroxy-4-60 methoxybenzophenone-5-sulfonic acid,

l, r-diphenylacrylonitrile 2-ethylhexyl and 2-hy-

droxy-4-methoxybenzophenone, 5- (3,3-dimethyl-2-norbornylidene) -3-penten-2-one and 2-hydroxy-4-n-octyloxybenzophenone, 65 2-hydroxy-4-n-octyloxybenzophenone and 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 5- (3,3-dimethyl-2-norbornylidene) -3-penten-2-one and zinc oxide ,

5

634463

5- (3,3-dimethyl-2-norbornylidene) -3-penten-2-one and digalloyl trioleate,

l, r-diphenylacrylonitrile 2-ethylhexyl and 2-hy-

doxy-4-n-octyloxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone and 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole and 5- (3.3 -Dimethyl-2-norbornylidene) -3-penten-2-one, 5- (3,3-dimethyl-2-norbornylidene) -3-penten-2-one and Nik-

kel-bis-octylphenyl sulfide (Ferro AM 101), 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and nickel-bis-octylphenyl sulfide (Ferro AM 105 ), 2- (2'-Hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and [2,2'-thio-bis- (4,6-octylphenolate)] - n-butyl -amin-nik-kel (II),

l, l'-Diphenylacrylonitrilsäure-2-ethylhexyl and [2,2'-Thio-bis- (4,6-octylphenolate)] - n-butylamine-nickel (II). However, the agent according to the invention is generally not restricted to the light protection substances mentioned in the above list or their combinations. The list is preferably intended to merely illustrate the invention, but other preparations containing light protection substances not mentioned here by name and their use also fall within the scope of the invention.

The light protection substances can be formulated individually or in combination to form preparations and can be used as such to prevent peeling of apples.

The light protection substances, or mixtures thereof, are usually processed into preparations in a manner known per se, for example wettable wettable powders (WP), liquid concentrates (flowable concentrate), expediently into water-soluble powder concentrates, water-soluble solution concentrates (WSC), emulsion concentrates (EC) , possibly also to ULV (ultra low volume) concentrates. To prepare these preparations, the light protection substances or their mixtures are generally mixed with solid or liquid inert carriers, extenders, solvents and occasionally other auxiliaries.

Examples of auxiliary substances are surface-active substances, such as wetting agents, suspending and dispersing agents, emulsifiers, substances which prevent lumping and caking (anti-cacking), substances which improve adhesion and prevent crumbling (anti-sticking) and which promote penetration Substances, anti-foaming agents and substances that maintain or increase the biological effect.

Suitable solid carriers and extenders are inactive natural and synthetic silicates, silica, modified clay minerals, bentonite, alkaline earth oxides, carbonates, phosphates etc., for example diatomaceous earth, kaolin, dolomite, calcined magnesium oxide etc.

Suitable liquid carriers and diluents are, for example, water, further optionally water-containing organic solvents or solvent mixtures, for example alcohols such as methanol and ethanol, glycols, for example glycerol, ketones such as dimethyl ketone and methyl ethyl ketone, esters such as ethyl acetate, n- and isobutyl acetate , Amyl acetate, lactones, such as y-butyrolactone, lactams, such as e-amino-caprolactam, acid amides, such as dimethylformamide, aliphatic, aromatic and cyclic hydrocarbons, such as heptane, hexane, cyclohexane, xylenes, to-luol, the solvents of the trade names Shellsol, Novasol etc.

Suitable wetting, dispersing and emulsifying agents, adhesives, substances that prevent caking and crumbling are ionic and nonionic substances. Of the ionic substances which can have an anionic, cationic or amphoteric character, particular mention may be made of, for example: sulfates and sulfonates and their salts, such as lauryl sulfate and its salts, benzenesulfates and their salts, 5 petroleum sulfonates and their salts, soaps, such as sodium stearate, etc. Of the nonionic, special mention should be made of: block polymers of ethylene oxide with propylene oxide and their esters and ethers, and also the natural and synthetic macromolecules.

Wettable wettable powders (WP) can be produced, for example, by grinding and homogenizing the solid sunscreen substances, the auxiliaries, surface-active substances, the biological activity-maintaining or increasing substances to a particle size of less than 100 (im, preferably less than 25 (im) If the surface-active substance is liquid, it can be applied, for example, by spraying it onto the powder mixture which consists of the solid, inorganic or organic vehicles and extenders and, if appropriate, already contains the active substance (s) 20. The procedure is generally similar: wettable wettable powders can also be prepared by homogenizing the ground components, then pressing them, for example, on a roller mill and then grinding them to the particle size given above.

Water-soluble powdery concentrates are produced, for example, by grinding solid, water-soluble light stabilizers, solid surface-active substances and other solid auxiliaries individually and then homogenizing the ground substances together. In the case of liquid surfactants, these can be added to an organic solvent and the ground solid components are then suspended in this solvent. The suspension can then be spray dried, for example. In this way, the surfactants are normally applied to the surface of the solid light stabilizers and carriers.

To prepare aqueous spray liquors, normally self-emulsifying liquid concentrates, so-called emulsion concentrates (EC), are prepared by dissolving the light protection substances together with one of the surface-active substances listed above in a water-immiscible solvent. This emulsion concentrate usually forms an emulsion spray broth with water by itself or by slight mechanical action, which remains unchanged even after standing for a long time.

Water-soluble liquid concentrates (WSC) can be prepared by dissolving the sunscreen substance and thus the corresponding water-soluble auxiliaries in an optionally water-containing, water-miscible solvent. The desired concentration of the spray liquor is then set, for example, by dilution with water.

ss If a suitable emulsifier is chosen, the aqueous solution concentrate of the light protection substance can also be dispersed in water-immiscible liquids, a so-called reverse emulsion being obtained. By mixing with non-water-mixed 60 bar liquids, a system of up to molecular size dispersed can be obtained, which does not change even after prolonged storage.

The spray liquors are usually prepared in a known manner from the preparations according to the invention by dilution with water. The content of light protection substance in the ready-to-use preparation is generally below 5% by weight, preferably between 1 and 0.1% by weight. You can also be spray liquors from preparations

634 463

6

riding, each containing only a single sunscreen substance, and then pour these spray broths together.

The protective treatment is generally carried out using the spray mixture prepared from the agents according to the invention. To test an agent, 10 apples are generally placed in about 1 liter of spray mixture and left there for one minute.

After the apples have dried, a mercury vapor lamp is usually placed 40 cm above them (Tungsram Germicid F, energy emission in the range 185-578 nm). Depending on the color content of the peel, the apples are irradiated for 1-5 hours, for example. More colored fruit is generally only treated for a shorter period of time. The treated apples and the unirradiated control are usually stored at +4 ° C for 2 months and then scored. On the irradiated side of the apples, the skin stains usually appear at exactly the same time as the natural skin stains, which proves that the treatment with the lamp is closely correlated with the field trials.

In the field trials, the apple trees are usually sprayed a few weeks before the apple harvest, preferably 3-6 weeks before. Depending on the amount of sunshine, spraying is generally carried out once or several times, and spraying once is usually sufficient. If the sun shines strongly during the apple harvest, it is advisable to avoid repeated spraying, which is possible, for example, by using spray liquor with a higher concentration of UV absorber.

For example, dripping wet spraying has proven particularly useful: In this unit, a quantity of 2-10 liters, preferably 3-7 liters, of spray liquor is used on an existing unit. An inventory unit is the area (irrespective of the type and age of the inventory) that can be sprayed with a single spray using a spray nozzle diameter of 1.5 mm and an initial pressure of 8 atü battery spray device kit 15 liters of liquid [Mezögazdasagi Lexicon, Mezögazdasagi Ki-adó Budapest 1958 (Lexicon of Agriculture, Agricultural Publishing House Budapest), Volume II, p. 593].

The invention can be explained in more detail with the aid of the following examples, without, however, being restricted to the examples:

Examples of wettable wettable powders (WP)

Example 1 2,4-dihydroxybenzophenone (particle size less than 10 µm)

finely divided silica *

Kaolin aliphatic-sulfonic acid sodium ** fatty alcohol polyglycol ether ***

* Untrasil, Aerosil, Durosil ** Hoe S 1880 (Hoechst)

*** Hoe S 1998 (Hoechst)

Example 2. 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (particle size less than 10 µm)

finely divided silica *

kaolin

Octylphenol polyglycol ether * * Na lauryl sulfate polyvinylpyrrolidone K-90 ***

20% 30% 42% 4% 4% 100%

20% 35% 35% 5% 4% 1% 100%

* Ultrasil, Aerosil, Durosil

** Triton X-100 (Rohm and Haas) *** GAF Corp.

5 Example 3

5,11H-5 ', 11' -dideshydrobenztriazolo- [2 ', l-a] benztriazole (particle size below 20 µm)

kaolin

10 highly adsorptive silica gel nonylphenyl polyglycol ether (EO 15) polyvinylpyrrolidone K-90 *

* GAF Corp.

15

Example 4

2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole (particle size less than 20 µm)

20 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole (particle size below 10 µm) highly adsorptive silica gel nonylphenol polyglycol ether (EO 15)

25 polyvinylpyrrolidone K-90 *

* GAF Corp.

Example 5

30 zinc oxide (particle size less than 5 (im) Gafac RM 710 *

Triethanolamine highly adsorptive silica gel ** polyvinylpyrrolidone K-90 ***

35

*, *** GAF Corp.

** Aerosil, Durosil, Supersil etc.

Example 6

40 zinc oxide (particle size less than 5 | xm) 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole highly adsorptive silica gel * octylphenol polyglycol ether (EO 10)

45 Gafac RM 10 ** in the form of the ethanolamine salt polyvinylpyrrolidone K-90 ***

* Aerosil, Durosil, Supersil **, *** GAF Corp.

80% 10% 5% 4% 1% 100%

45%

40% 10% 4% 1% 100%

90% 2% 1% 5% 2% 100%

60%

25% 5% 6% 3% 1% 100%

Water-soluble powdered concentrates

Example 7

2-hydroxy-4-methoxybenzophenone-5-55 sulfonic acid sodium carbonate sicc. Na dioctyl sulfosuccinate polyvinylpyrrolidone K-90 *

60 * GAF Corp.

75% 20% 2.5% 2.5% 100%

Example 8

2,2'-dihydroxy-4,4'-dimethoxybenzo-phenone-5-Na sulfonate 90%

65 Na dioctyl sulfosuccinate 5%

Polyvinylpyrrolidone K-90 * 5%

* GAF Corp.

100%

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Example 9

2,2'-Dihydroxy-4,4'-dimethoxybenzo-phenone-5-Na sulfonate, Na dioctyl sulfosuccinate, hydroxyethyl cellulose

Example 10 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid sodium carbonate Na dioctyl sulfosuccinate

Example 11 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid triethanolamine Gafac RM 510 *

Ethanol water

* GAF Corp.

Example 12

2,2 ', 4,4'-tetrahydroxybenzophenone

2-hydroxy-4-methoxybenzophenone-5-

sulfonic acid

Triethanolamine

Gafac RM 510 *

Methanol

water

* GAF Corp.

Example 13

2,2 ', 4,4'-tetrahydroxybenzophenone triethanolamine

Polyoxyethylene sorbitan monopalmitate methanol

Example 14 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid

2,2 ', 4,4'-tetrahydroxybenzophenone triethanolamine

Polyoxyethylene sorbitan monopalmitate Gafac RM 510 *

Triethanolamine mono oleic acid ester

Isopropanol

Methanol

* GAF Corp.

The preparation forms a colloidal solution with water.

Emulsion concentrates (EQ example 15

2-hydroxy-4-methoxybenzophenone Emuisogen IC *

Emuisogen M **

Xylene

*, ** Hoechst

90% 5% 5% 100%

75% 20% 5% 100%

2 g 1 g 0.5 g 5.9 ml 1 ml 10.0 ml

0.5 g

1.5 g 0.75 g 0.75 g 6 ml

_1 ml

10.00 ml

2 g

1 g

2 g 6.3 ml 10.0 ml

1 g 1 g 0.5 g 0.5 g 0.5 g 0.5 g 1 ml 6 ml 10.0 ml

Example 16 1,1'-diphenylacrylonitrile acid ethyl ester polyoxyethylene sorbitan trioleate polyoxyethylene sorbitan monostearate 5 xylene

Example 17

1,1'-Diphenylacrylnitrilsäureäthyl-hexyl ester io polyoxyethylene monooleate polyoxyethylene sorbitan tristearate xylene

15

2 g 0.05 g 0.05 g 7.5 ml 10.00 ml

60

65

Example 18

1,1'-Diphenylacrylnitrilsäureäthyl-hexyl ester

Polyoxyethylene sorbitan monooleate

Sorbitan oleate

Xylene

20th

Example 19 a-Cyano-β-methyl-4-methoxycinnamic acid methyl ester 25 methanol

Polyoxyethylene sorbitan oleate

Sorbitan trioleate

Xylene

30th

Example 20

5- (3,3-Dimethyl-2-norbornylidene) -3-penten-2-one

Polyoxyethylene sorbitan oleate 35 polyoxyethylene sorbitan monostearate sorbitan tristearate isopropanol propylene glycol xylene

Example 21

5- (3,3-Dimethyl-2-norbornylidene) -3-penten-2-one

Polyoxyethylene sorbitan trioleate 45 isopropanol

Example 22

5- (3,3-Dimethyl-2-norbornylidene) -3-penten-50 2-one as a 66% solution in isopropyl miristat

Polyoxyethylene sorbitan oleate polyoxyethylene sorbitan monolaurate sorbitan monostearate ss isopropanol propylene glycol xylene

Example 23

5- (3,3-Dimethyl-2-norbornylidene) -3-penten-2-one as a 66% solution in isopropyl miristat

Polyoxyethylene sorbitan oleate

Polyoxyethylene sorbitan stearate

Sorbitan stearate

Xylene

2 g 1 g 0.5 g 7.5 ml 10.0 ml

2 g 1 g 1 g 7.5 ml 10.0 ml

2 g 1 g 0.5 g 7.1 ml 10.0 ml

2 g 1.5 ml 1.0 g 1.5 g 7.2 ml 10.0 ml

2 g 1 g 0.5 g 0.3 g 0.4 ml 0.4 ml 5 ml 10.0 ml

2 g 2 g 6.4 ml 10.0 ml

3.05 g 1.60 g 0.30 g 0.3 g 0.4 ml 0.4 ml 3.25 ml 10.00 ml

3.05 g 1.0 g 0.5 g 0.5 g 3.75 g 10.00 ml

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Example 24 [2,2'-Thio-bis- (4-tert-octylphenolate)] - n-butylamine-nickel (II) nonylphenol polyglyeol ether (EO 10)

Xylene

Example 25 Nickel bis-octylphenyl sulfide (Ferro AM 101) *

Nonylphenol polyglyeol ether (EO 10)

Xylene

* Ferro Chemical

Example 26 Nickel bis-octylphenyl sulfide (Ferro AM-105) *

Nonylphenol polyglycol ether (EO 10)

Xylene

* Ferro Chemical

Example 27 Resorcinol Monobenzoate Nonylphenol Polyglycol Ether (EO 10) Sorbitan Trioleate Polyoxyethylene Sorbitanoleate Ethyl Acetate Xylene

Example 28

Digalloyl trioleate

Nonylphenol polyglycol ether (EO 10)

Sorbitan trioleate

Xylene

Example 29 2-Hydroxy-4-n-octyloxybenzophenone Nonylphenol Polyglycol Ether (EO 10) Nonylphenol Polyglycol Ether (EO 4-6)

Xylene

Example 30 2-ethylhexyl 1,1'-diphenylacrylonitrile

2-hydroxy-4-methoxybenzophenone nonylphenol polyglycol ether (EO 10)

Xylene

Example 31

5- (3,3-dimethyl-2-norbornylidene) -3-pentene-

2-one as a 66% solution in isopropylmiristate

Nickel bis-octylphenyl sulfide (Ferro AM 101) *

Nonylphenol polyglycol ether (EO 10)

Fatty alcohol polyglycol ether

Polyoxyethylene sorbitan trioleate

Xylene

* Ferro Chem.

Example 32 2-Ethylhexyl 1,1'-diphenylacrylonitrile

2-hydroxy-4-methoxybenzophenone nonylphenol polyglycol ether (EO 10)

2 g 1.8 g 7.3 ml 10.0 ml

2 g 1.8 g 7.3 ml 10.0 ml

2 g 1.8 g 7.3 ml 10.0 ml

2 g 1.0 g 0.5 g 0.5 g 5 ml 2.5 ml

10.0 ml

2g 1.5 g 0.5 g 7.5 ml 10.0 ml

2 g 1.5 g 0.5 g 7.5 ml 10.0 ml

1.5 g 0.5 g 1.5 g 7.4 ml 10.0 ml

1.5 g 1 g 1 g 0.5 g 0.5 g 5 ml 10.0 ml

1 g 1 g 0.5 g io

Fatty alcohol polyglycol ether

Polyoxyethylene sorbitan trioleate

Xylene

Example 33 2-ethylhexyl 1,1'-diphenylacrylonitrile

2-Hydroxy-4-n-octyloxybenzophenone nonylphenol polyglycol ether (EO 10) fatty alcohol polyglycol ether polyoxyethylene sorbitan trioleate xylene

15 Example 34

Nickel bis-octylphenyl sulfide * 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole

Nonylphenol polyglycol ether (EO 10) 20 fatty alcohol polyglycol ether polyoxyethylene sorbitan trioleate xylene

25th

* Ferro Chem. AM 101

Example 35 Nickel-bis-octyl-phenyl sulfide * 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole nonylphenyl polyglycol ether (EO 10) fatty alcohol polyglycol ether polyoxyethylene sorbitan trioleate Xylene

35 * Ferro Chem. AM-105

Example 36 [2,2'-Thio-bis (4-tert-octylphenolate)] - n-butylamine-nickel (II) 40 2- (2'-Hydroxy-3,5'-di-tert-butyl -phenyl) -5-chlorobenzotriazole nonylphenol polyglycol ether fatty alcohol polyglycol ether polyoxyethylene sorbitan trioleate 45 xylene

Example 37 1,1-Diphenylacrylonitrile 2-ethylhexyl ester

50 [2,2'-thio-bis- (4-tert-octylphenolate)] - 4-butylamine-nickel (II) nonylphenol polyglycol ether fatty alcohol polyglycol ether polyoxyethylene sorbitan trioleate * 55 xylene

* Hoechst AG

Example 38

5- (3,3-Dimethyl-2-norbornylidene) -3-penten-2-one

2-hydroxy-4-n-octyloxybenzophenone

Polyoxyethylene sorbitan oleate

Polyoxyethylene sorbitan stearate

Isopropanol

Propylene glycol

Xylene

60

0.5 g 1 g 6.3 ml 10.0 ml

1 g 1 g 0.5 g 0.5 g 1 g 6.3 ml 10.0 ml

1.6 g

0.4 g 0.5 g 0.5 g 1 g 7 ml 10.0 ml

1.6 g

0.4 g 0.5 g 0.5 g 1 g 7 g 10.0 ml

1.6 g

0.4 g 0.5 g 0.5 g 1 g 7 ml 10.0 ml

1 g

1 g 0.5 g 0.5 g 1 g 6.5 ml 10.0 ml

1.5 g 1.0 g 1.0 g 0.3 g 0.5 ml 0.5 ml 5 ml 10.0 ml

9

634463

Example 39

Digalloyl trioleate

Polyoxyethylene sorbitan monolaurate toluene

Example 40

5- (3,3-dimethyl-2-norbornylidene) -3 -

penten-2-one as a 66% solution in

Isopropylmiristate

Polyoxyethylene sorbitan oleate

Polyoxyethylene sorbitan monolaurate

Sorbitan monolaurate

Isopropanol

Propylene glycol

Xylene

Example 41 2- (2'-Hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole (particle size less than 5 | xm)

finely divided silica *

Kaolin aliphatic-sulfonic acid Na ** fatty alcohol polyglycol ether *

* Durosil, Supersil, Aerosil etc.

** Hoe S 1880 Hoechst AG

*** Hoe S 1998 Hoechst AG

Example 42 2- (2'-Hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole (below 5 | xm) highly disperse silica *

Kaolin aliphatic sulfonic acid Na ** fatty alcohol polyglycol ether ***

* Durosil, Supersil, Aerosil etc.

** Hoe S 1880 Hoechst AG

*** Hoe S 1998 Hoechst AG

Example 43

2,5,8-triphenyl-tri-w-triazolo (a, c, e) -benzene (less than 5 µm)

finely divided silica *

kaolin

Tributylphenol polyglycol ether ** hydroxyethyl cellulose ***

* Durosil, Supersil, Aerosil etc. ** Sapogenat T-180, Hoechst AG

*** Tylose H 20, Hoechst AG

Example 44 2,5,8-tri- (dinitrophenyl) tri-w-triazolobenzene (below 5 | xm)

finely divided silica *

kaolin

4g 4g LÄ

10 g

6.05 g

1.6 g 0.5 g 0.5 1.0 0.4 1.9

g ml ml ml

10.00 ml

50% 20% 25% 2% 3%

100%

50% 10% 33% 2% 5% 100%

50% 12% 29% 7% 2% 100%

Tributylphenol polyglycol ether ** hydroxyethyl cellulose ***

* Durosil, Supersil, Aerosil 5 ** Sapogenat T-180, Hoechst AG *** Xylose H 20, Hoechst AG

Example 45 Titanium dioxide (less than 5 µm)

10 Gafac RM 710 *

Triethanolamine polyvinylpyrrolidone K-90 ** highly adsorptive silica gel ***

15 * Gaf Corp.

** Gaf Corp.

*** Aerosil, Curosil, Supersil etc.

Example 46 2- (2'-Hydroxy-5'-methylphenyl) benzotriazole (below 5 µm) highly adsorptive silica gel *

Kaolin aliphatic-sulfonic acid Na **

Fatty alcohol polyglycol ether ***

Hydroxyethyl cellulose ***

7% 3% 100%

20th

25th

90% 2% 1% 2% 5% 100%

50% 30% 15% 2% 2% 1% 100%

50% 30% 15% 2% 2% 1% 100%

40% 40% 10%

* Aerosil, Durosil, Supersil ** Hoe 1880, Hoechst AG

*** Hoe 1998, Hoechst AG 30 **** Xylose H 20, Hoechst AG

Example 47 2- (2'-Hydroxy-5'-n-octylphenyl) benzotriazole (less than 5 µm)

35 highly adsorptive silica gel *

Kaolin aliphatic sulfonic acid Na ** fatty alcohol polyglycol ether ***

Hydroxyethyl cellulose ****

40

* Aerosil, Durosil, Supersil ** Hoe 1880, Hoechst AG

*** Hoe 1998, Hoechst AG **** Tylose H 20, Hoechst AG

45

Examples 48-67 (examples of effects)

For each of the agents described in the examples above, one trial is carried out with each of the three apple varieties (Jonathan, Jona-50 red and Starking). 10 apples are left in a spray solution containing 0.2% by weight of light protection substance for one minute and then dried at room temperature. A mercury vapor lamp is placed over the treated apples at a distance of 40 m (Tungsram Germicid F; radiation range 185-578 mm). The apples are irradiated for 4 hours and then stored together with 100 non-irradiated control apples at +4 ° C for 2 months. The rating is then carried out.

Example means according to the example of apple variety

Sunscreen substance of the agent

48

49

50

51

1

2 9

11

Jonathan 2,4-dihydroxybenzophenone

Jonathan 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone

Jonathan 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone-5-

Na sulfonate

Jonathan 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid

634463

10th

example

Means according to the example

Apple variety

Sunscreen substance of the agent

52

13

Jonathan

2,2 ', 4,4'-tetrahydroxybenzophenone

53

15

Jonathan

2-hydroxy-4-methoxybenzophenone

54

29

Jonathan

Jonared

Starking

2-hydroxy-4-n-octyloxybenzophenone

55

41

Jonathan

Jonared

Starking

2- (2'-Hydroxy-3'-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole

56

42

Jonathan

Jonared

Starking

2- (2'-Hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole

57

43

Jonathan

2,5,8-triphenyl-tri-w-triazolo- (a, c, e) -benzene

58

44

Jonathan

2,5,8-tri- (dinitrophenyl) tri-w-triazolo (a, c, e) -benzene

59

18th

Jonathan

Jonared

Starking

1,1'-diphenylacrylonitrile acid ethylhexyl

60

19th

Jonathan

Jonared

Starking a-cyano-ß-methyl-4-methoxy-cinnamic acid methyl ester

61

21st

Jonathan

Jonared

Starking

5- (3,3-Dimethyl-2-norbornylidene) -3-penten-2-one

62

24th

Jonathan

Jonared

Starking

[2,2'-thio-bis- (4-tert-octylphenolate)] - n-butylamine-nickel (II)

63

25th

Jonathan

Jonared

Starking

Nickel bis-octylphenyl sulfide

64

26

Jonathan

Jonared

Starking

Nickel bis-octylphenyl sulfide

65

20th

Jonathan

Jonared

Starking

5- (3,3-Dimethyl-2-norbornylidene) penten-2-one

66

5

Jonathan

Jonared

Starking

Zinc oxide

67

45

Jonathan

Jonared

Starking

Titanium oxide

The results of the ratings are summarized in the following table.

Example No. Means according to example Number of spotty apples

Jonathan Jonared Starking

58

44

8th

5

_

59

18th

5

10th

-

61

21st

1

2nd

-

63

25th

10th

5

-

65

20th

2nd

1

-

66

5

2nd

2nd

-

67

45

3rd

4th

-

untreated

control

10th

10th

3rd

It can be seen from the table that especially the prep 65 field experiments, which contain 5- (3,3-dimethyl-2-norbornylidene) -3-penten-2-example 68 on, zinc oxide and titanium dioxide, 24 Days before the apple harvest will have a concentration-reducing effect against peeling. level 2 Jonathan trees (10 year old; grafted onto those in East

11

634 463

Mailing selected underlay MIV) spray treated. 5 liters of spray liquor are used per tree, and the 5- (3,3-dimethyl-2-norbornylidene) -3-penten-2-one as active ingredient

0.1% by weight of polyoxyethylene sorbitan monolaurate (Tween

20) and contains 0.05% by weight of toluene. The drug concentrations are: 0.1; 0.2; 0.4; 0.6 and 1 wt%.

As a result of the favorable weather conditions,

October 1st, i.e. Harvested late for Hungarian climates. The experiments therefore took place under particularly provocative circumstances, because these climatic conditions favor the formation of the skin stains.

During the harvest, the apples (about 180 kg / tree) from the two trees treated in the same way were

collected in containers. An average sample was taken from each container, placed in the form of about 200 apples in apple crates (type Szabolcs) and the crates were stored in the cold store at +4 ° C on the day of harvest.

No peeling was observed during the harvest itself, but it was noticed that the apples from the treated trees had a more uniform color than those from the untreated ones.

At the end of the storage period, after 5 months, the degree of stain infestation was rated. The loss of stock (the number of spoiled apples) was also determined.

The results of the ratings are summarized in Table 1.

10th

Table 1

UV absorber concentration - number of apples in the broth overall spoiled peeling

% By weight many spots 1-2 spots

0.1

202

15

-

31

0.2

212

12

-

19th

0.4

185

13

-

8th

0.6

197

11

-

5

1.0

210

14

-

0

0 (control)

241

19th

66

-

0 (control)

443

23

119

-

It can be seen from Table 1 that the appearance and the development of the skin stains can be prevented or at least reduced to a minimum with the method according to the invention or the agent according to the invention.

Medium (Hungarian Patent No. 159 199) achieved protection rates of 10-30% on the same and different soils.

Example 69

The procedure described in Example 68 is followed, with the difference that the apple trees are sprayed twice with spray liquor containing 1.0% by weight of 5- (3,3-dimethyl-2-norbornylidene) -3-penten-3-one be sprayed. The second treatment is done one week after the first.

35 The results of the ratings are summarized in Table 3 below.

Table 3

Number and point in time Number of apples in the treatment total spoiled peeling many spots

1-2 spots

0 (control) 241

1 (4.IX .; control) 210 2 (4.IX. And 11.IX.) 185 0 (control) 443

19 14 17 23

66 119

It can be seen from the table that the double treatment has hardly any practical significance. The peeling of 1-2 spots perceived after the second treatment is within the error limits.

Example 70

The procedure described in Example 68 is followed, with the difference that an agent according to the invention containing digalloyl trioleate as the active ingredient is used. The spray liquor contains 0.1% by weight of active ingredient, 0.1% by weight of polyoxyethylene sorbitan monolaurate (Tween 20) and 0.05% by weight of toluene.

ss The results of the ratings are summarized in Table 4. The analysis results of the salary determinations are shown in Table 5.

Table 4

treatment

Total number of apples spoiled with many spots

1-2 spots

1

0 (control)

145 443

23

10 119

16

634 463

Table 5

12

Table 5 (continued)

parameter

UV absorber concentration in the spray liquor,% by weight 0 (control) 0.1

parameter

Ethylene production

[10-6 g / | tl - h] 3.8

Acidity fg malic acid / 100 ml press juice] 0.43 vitamin C.

[mg / 100 ml press juice]

Sugar content

[g glucose / 100 ml press juice] 9.41

Refraction [%] 12.50

3.2 0.46

8.82 14.40

UV absorber concentration in the spray mixture. % By weight 0 (control) 0.1

10th

Dye content (0.2 g peel and 100 ml juice)

Absorbance 360 nm 1.13

530 nm 0.42

0.66 0.73

Examples 71-84 The procedure described in Example 68 is followed, with the difference that spray liquors are prepared from the compositions listed in the table below and 15 trees are treated with each composition.

example

Means according to the example

Sunscreen substance of the agent

71

3rd

5.1 lH-5 ', 1 r-dideshydrobenztriazolo- [2', l-a] benzotriazole

72

5

Zinc oxide (particle size less than 5 (im)

73

6

Zinc oxide (particle size less than 5 (im)

2- (2'-Hydroxy-3 / -tert.-butyl-5'-methylphenyl) -5-chlorobenzotriazole

74

12

2-hydroxy-4-methoxybenzophenone-5-sulfonic acid;

2,2 ', 4,4'-tetrahydroxybenzophenone

75

17th

1,1'-Diphenylacrylonitrilsäure-2-ethylhexyl ester

76

24th

[2,2'-thio-bis- (4-tert-octylphenolate)] - n-butylamine-nickel (II)

77

29

2-hydroxy-4-n-octyloxybenzophenone

78

35

2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole;

Nickel bis-octylphenyl sulfide

79

36

2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole;

[2,2'-thio-bis- (4-tert-octylphenolate)] - n-butylamine-nickel (II)

80

37

1,1'-Diphenylacrylonitrilsäure-2-ethyl-hexyl ester *

81

25th

Nickel-bis-octylphenyl sulfide Ferro AM 101

82

26

Nickel-bis-octylphenyl sulfide Ferro AM 105

83

31

Nickel bis-octylphenyl sulfide

5- (3,3-Dimethyl-2-norbornylidene) -3-penten-2-one

84

40

5- (3,3-Dimethyl-2-norbornylidene) -3-penten-2-one

* 2- [2'-thio-bis- (4-tert-octylphenolate)] - 4-butylamine-nickel (II)

From the preparation apples described in the examples above until January 31 of the following year at 4 ° C. in the spray solutions with an active ingredient content of cold store were stored. The extent of the blotchiness was on

0.2% made. The apple trees were rated on September 8, February 1. The results of the rating are discussed in and the apples are harvested on October 8th. Of each 45 included in the table below.

Treatment were randomized to 100-200 samples

Example means according to

Number of apples

Example overall without stains with with many

% of stains

1-2 spots

Stains loose apples untreated control

385

73

181

131

18.9

72 5

127

104

23

-

81.0

73 6

128

88

36

3rd

68.0

74 12

132

67

48

17th

50.0

83 31

145

87

51

7

60.0

84 40

118

98

14

16

83.0

Claims (25)

634 463 Contains 1,1'-diphenylacrylonitrile 2-ethylhexyl and / or methyl a-cyano-β-methyl-4-methoxycinnamate. 1. Agent for preventing peeling of apples, characterized in that it contains at least one light protection substance and at least one formulation aid as active ingredient. Contains 2,5,8-tri (dinitrophenyl) tri-w-triazolo (a, c, e) benzene. 2,5,8-triphenyl-tri-w-triazolo (a, c, e) -benztriazole and / or 2,5,8-tri- (nitrophenyl) -tri-w-triazolo (a, c, e) benzotriazole and or 2- (2 / -hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro contains benztriazole and / or 5,11H-5 ', 11' -dideshydrobenztriazolo [2 ', l-a] benztriazole. 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and / or 2- (2'-hydroxy-5'-n-octylphenyl) benzotriazole and / or 2- (2'-hydroxy-3 ', 5 '-di-tert-butylphenyl) -5-chlorobenzotriazole and / or Contains 2-hydroxy-2'-chlorobenzophenone. 2. Composition according to claim 1, characterized in that it contains zinc oxide and / or titanium dioxide as a light protection substance. 2nd PATENT CLAIMS 3 634463 contains acid 2-ethylhexyl and [2,2'-thio-bis- (4-octyl-phenolate)] - n-butylamine-nickel (II). 3. Composition according to claim 1, characterized in that it as a light protection substance at least one benzophenone derivative and / or at least one benzotriazole derivative and / or at least one dibenzotriazole derivative and / or at least one tri-triazolobenzene derivative and / or at least one aromatic ester derivative and / or at least contains a substituted acrylonitrile derivative and / or at least one organometallic compound and / or at least one alicyclic dienone compound. 4. Composition according to claims 1 or 3, characterized in that it contains 5- (3,3-dimethyl-2-norbornylidene) -3-penten-2-one as the alicyclic dienone compound. 5 5. Agent according to claims 1 or 3, characterized in that it is 2,4-dihydroxybenzophenone and / or 2-hydroxy-4-methoxybenzophenone and / or 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and / or as the benzophenone derivative. or 2,2 ', 4,4 / -tetrahydroxybenzophenone and / or 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and / or 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sodium sul- fonate and / or 2-hydroxy-4-methoxy-4'-methylbenzophenone and / or 2,2'-dihydroxy-4-methoxybenzophenone and / or 2-hydroxy-4-n-heptoxybenzophenone and / or 2-hydroxy-4- n-octyloxybenzophenone and / or 2-hydroxy-4-methoxy-2'-carboxybenzophenone and / or 2-hydroxy-4-dodecyloxybenzophenone and / or 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sulfonic acid and / or 6. Composition according to one of claims 1 or 3, characterized in that it is a benzotriazole or dibenztriazole derivative 7. Composition according to claims 1 or 3, characterized in that it is a tri-triazolobenzene derivative 8. Composition according to claims 1 or 3, characterized in that it is digalloyl trioleate and / or as an aromatic ester derivative Contains phenyl salicylate and / or p-octylphenyl salicylate and / or tert-butylphenyl salicylate and / or resorcinol monobenzoate and / or 2,4-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate. 9. Composition according to claims 1 or 3, characterized in that it is substituted 1,1'-diphenylacrylnitrile acid ethyl ester and / or as a substituted acrylonitrile derivative 10th 10. Composition according to claim 1, characterized in that it is an organometallic compound [2,2'-thio-bis- (4-tert-octylphenolate)] - n-butylamine-nickel (II) and or Nickel bis-octylphenyl sulfide and / or nickel dibutyl dithiocarbamate and / or [3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid mono- ethyl ester 2: 1 nickel chelate] contains. 11. Composition according to claims 1 or 3, characterized in that it is 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 2- (2' -Hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole contains. 12. Composition according to one of claims 1 or 3, characterized in that it contains 2,2 ', 4,4'-tetrahydroxybenzophenone and 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid as the light protection substance. 13. Composition according to one of claims 1 or 3, characterized in that it contains 2'-ethylhexyl 1,1'-diphenylacrylonitrile and 2-hydroxy-4-methoxybenzophenone as the light protection substance. 14. Composition according to one of claims 1 or 3, characterized in that it is 5- (3,3-dimethyl-2-norbornylidene) -3-penten-2-one and 2-hydroxy-4-n- as a light protection substance contains octyloxybenzophenone. 15 15. Composition according to one of claims 1 or 3, characterized in that it is 2-hydroxy-4-n-octyloxybenzophenone and 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) - as light protection substance - Contains 5-chlorobenzotriazole. 16. Composition according to one of claims 1 or 3, characterized in that it contains 5- (3,3-dimethyl-2-norbornylidene) -3-penten-2-one and digalloyl trioleate as the light protection substance. 17. Agent according to one of claims 1 or 3, characterized in that it contains 2-ethylhexyl i.l'-di-phenylacrylonitrile and 2-hydroxy-4-n-octyloxybenzophenone as light protection substance. 18. Composition according to one of claims 1 or 3, characterized in that it is 2-hydroxy-4-n-octyloxybenzophenone and 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) - as a light protection substance - Contains 5-chlorobenzotriazole and 5- (3,3-dimethyl-2-norbornylidene) -3-penten-2-one. 19. A composition according to claim 1, characterized in that it contains zinc oxide and 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole as the light protection substance. 20th 25th 30th 35 40 45 50 55 60 65 20. Composition according to claim 1, characterized in that it contains 5- (3,3-dimethyl-2-nor-bornylidene) -3-penten-2-one and zinc oxide as the light protection substance. 21. Composition according to claim 1, characterized in that it contains 5- (3,3-dimethyl-2-nor-bornylidene) -3-penten-2-one and nickel-bis-octylphenyl sulfide (Ferro AM 101) as the light protection substance. 22. Composition according to claim 1, characterized in that it is 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and nickel-bis-octylphenyl sulfide (Ferro AM 105) contains. 23. Composition according to claim 1, characterized in that it is 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and [2,2'-thio-bis- (4-tert-octylphenolate)] - n-butylamine-nickel (II) contains. 24. Composition according to claim 1, characterized in that it is l, r-diphenylacrylonitrile 25. Use of the agent according to claim 1 for preventing peeling of apples.