DE1268295B - Production of glossy, insecticidal coatings - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

Number:
File number:
Registration date:
Display day:

C09d

German class: 22h-3

P 12 68 295.0-43
November 11, 1966
May 16, 1968

The present invention relates to improved insecticidal compositions for coating packaging materials.

It is known to use insecticidal active ingredient components in coating compositions for packaging materials Use paper, cardboard and similar fibrous packaging materials to make up the package contents to protect against insect or pest infestation. For example, the British patent describes 895 455 an aminalginate coating mass with pyrethrum extract, which by adding piperonyl butoxide is increased synergistically. This coating, while satisfactory, gives the packaging material a dull, matte appearance, which with the increasing demand for glossy cardboard or other shiny packaging material is unsuitable. Another of the numerous known plastic coating compositions also only give a semi-matt or silk-like appearance, and all so far for improvement The additives used for appearance reduced the insecticidal effect of the coating mass. Heretofore, therefore, it has been assumed that the matte appearance is due to that on the packaging material The thin synthetic resin film that is located receives fine cracks when the insecticide is released it blooms on the surface.

It has now been found, surprisingly, that with coating agents known per se from base of copolymers of styrene and maleic acid half esters and certain insecticidal synthetic resin coating compounds for fibrous packaging material can produce, which meet today's requirements correspond and at the same time are particularly effective in delivering insecticides and still the packaging material give a permanently shiny appearance.

Accordingly, the invention relates to the use of mixtures containing

a) Pyrethrum, pyrethrinoids, allethrin, 3,4,5,6-tetrahydrophthalimidomethyl ester of chrysanthemum acid ^ imethyldichlorovinylphosphate A-naph- ethyl-N-methylcarbamate, O, O-dimethyl-S- (1,2-dicarboxyethyl) - phosphorodithionate, O, O-dimethyl-O- (4-bromo-2,5-dichlorophenyl) -phosphorodithionate and / or O, O-dimethyl-O- (3-methyl-4-nitrophenyl) phosphorothionate as insecticidal active ingredient components, optionally with additions of synergistic substances, and

b) Copolymers of styrene with a half ester of a dibasic unsaturated aliphatic Acid, if necessary with solvents,

for the production of glossy, insecticidal coatings on fibrous packaging materials.

Manufacture of glossy, insecticidal coatings

Applicant:

Cooper, McDougall & Robertson Limited,

Berkhamsted, Hertfordshire (UK)

Representative:

Dr. rer. nat. J. D. Frhr. v. Uexküll, patent attorney,

2000 Hamburg 52, Königgrätzstr. 8th

Named as inventor:

James Peter Brooke,

Beauchamp, Buckinghamshire;

Philip Henry Lomax,

Berkhamsted, Hertfordshire (UK)

Claimed priority:

Great Britain 12 November 1965 (48135)

These coating compositions are particularly suitable for packaging materials for food, since they are non-toxic for humans and also for pets; For this reason, insecticides with an LD ₅₀ (rats, peroral) of at least 400 mg / kg and expediently 500 mg / kg or more are particularly preferred. The best representatives of these insecticides are the pyrethrinoids, which according to AJ L ehma η in Quaterly Bull, of Assoc. of Food & Drug Officials of the USA. (1948), 12, p. 82, have an average oral LD ₅₀ value of 1500 mg / kg animal body weight. Pyrethrinoids are understood to mean not only the compounds of the esters of 3-substituted 2,2-dimethyl-cyclopropanecarboxylic acids occurring in plant extracts, but also similar or equivalent synthetic compounds. The 3-substituent can consist either of pyrethrin I or pyrethrin II and, in particular, of allethrin or else of optically active isomers of this type of compound.

The coating compositions used according to the invention are alcohol-soluble, which is what papermaking does common paper coating machines. Furthermore, they have an almost water-light color, see above

809 549/417

3 4

that they do not affect the appearance of the packaging material in unesterified or fully esterified form adversely affect; this occurs both before and is not sufficiently alcohol-soluble. The half-esters after printing. Storage tests can also be made with a wide variety of commercially available shown that the over-alcohols used according to the invention are produced, but primary, Aliphatic alcohols mostly unsubstituted, straightforward, even after prolonged storage Show slightest yellowing and a glossy chain alcohols with 1 to 18 and preferably with Appearance although sufficient when applied in 1 to 9 carbon atoms; in particular highly volatile alcoholic solvents, ethanol and n-butanol are preferred, dry quickly. This shiny and for modern day The styrene component is generally used alone Packaging, which looks extremely desirable, is still used, but can also be mixed with a in addition, it appears to be obtained indefinitely and in small amounts of other compatible vinyl mono not affected by visible cracks or cracks or affected by mixed monomers such as methyl. Nevertheless, the insecticide is methacrylate, ethyl methacrylate, butyl acrylate, ethyl periods of time given in sufficient quantity. A hexyl acrylate, etc. can be used Another advantage is the good water and fat content. The resin component appropriately contains one resistance, which is generally much greater crosslinking catalyst, preferably a peroxide such as than with the previously used insecticides »matt varnish« - methyl ethyl peroxide and benzoyl peroxide. Coating compounds is. Further, the invention is illustrated below by way of examples coatings used in deep-freeze storage are explained in more detail, extremely stable. 20 ■.

Of the insecticides mentioned, the best examples are

suitable pyrethrum and mixtures of pyrethrum with copolymers of styrene and

synergistic compounds of methylene acid butyl maleate 30.25 parts by weight

dioxyphenyl structure, especially with piperonyl pyrethrum extract _{(50 ° / 0 pyre-}

butoxide. However, other synergistic 25 thrin) 2.70 parts by weight can also be used

active compounds such as sulfoxide isopropyl alcohol 67.05 parts by weight

and ^ (S ^ -Methylene-dioxyphenyli-S-methyl-metadi- 100.00 parts by weight

oxane, especially synergistic

Mixtures of pyrethrum or pyrethroids with. .

Piperonyl butoxide, which is 30 B e 1 s ρ 1 e 1 2

rature liquid and relatively unstable and mixed polymer of styrene and

Has a short-term effect, but after incorporation into the acidic butyl maleate as 55%

proposed copolymers an excellent solution in isopropanol-ethanol 55.0 parts by weight

Nete and long-lasting insecticidal effect. 3,4,5,6-tetrahydrophthalimido

The Chrysanthemum effect to achieve a certain biological 35 methyl ester optimal amounts of the respective insecticidal acid 0.7 parts by weight

and resin bases can be obtained by experimental Piperonyl butoxide 7.0 parts by weight

driving can be determined. The components can be isopropyl alcohol 37.3 parts by weight

be mixed together in any way; _imn r ^ A ^ tc + ^ u , however, solutions in a suitable 40
suitable organic solvents such as isopropyl alcohol. Example 3

The coating agents used according to the invention as copolymers according to

suitably have approximately the same viscosity as Example 2 55.0 parts by weight

45 parts by weight mixture used as coatings after printing.

Spirit varnishes, so that they can therefore be used without further pyrethram extract (50% pyrethrin)

use thinning in conventional paper coating machines and 6.8 parts by weight of piperonyl

let the; they are therefore generally made from butoxide of 8.2 parts by weight

Alcohols existing solvents to a ge isopropyl alcohol 36.8 parts by weight

suitable viscosity diluted. Qq ^ q i G _{ew Cii} tsteile sufficient viscosity between 40 and 220 cP, which, for example, a mixture of 55 parts by weight of _ »- In general, a 50. .. alcoholic solution of the resin base and 45 parts by weight example of an alcoholic solution of the insecticide ent- copolymer according to speaks. 55 Example 2 55.0 parts by weight

In the case of the copolymer of styrene and an O, O-dimethyl-S- (l, 2-dicarboxy-

Half ester of a dibasic unsaturated aliphatic (ethyl) phosphorodithionate 10.2 parts by weight

See acid, the ratio of the two monomers isopropyl alcohol is 34.8 parts by weight

not essential; in general, however, the two should be 100 parts by weight Components in a ratio of 20:80 to 60 ' 80:20, preferably 60:40 and 40:60 parts by weight. Example 5

The two- ,,. ,. ,,

basic unsaturated aliphatic acid can be a mixed polymer of styrene and ■

Vinyl dicarboxylic acid, such as fumaric or maleic acid, 65 acid nonanol maleate 30.25 weight stede

maleic acid in the form of its anhydride allethrin 1.40 weight s ede

is preferred. The dibasic unsaturated aliphatic isopropyl alcohol 68.35 parts by weight

Tical acid must be used as a half ester, since 100.00 parts by weight

Example 6

Copolymer according to

Example 2 55.0 parts by weight

α-Naphthyl-N-methylcarbamate .. 6.8 parts by weight Additional solvent e.g. B.

Dimethyl sulfoxide 10.0 parts by weight

Isopropyl alcohol 28.2 parts by weight

100.0 parts by weight

At the end of the test period, all of the cardboard boxes were examined and the following results were obtained became:

IO

Example 7

Copolymer of styrene and

Methyl methacrylate with acidic

Ethyl fumarate 30.25 parts by weight

O, O-dimethyl-O- (4-bromo-2,5-di-

chlorophenyl) phosphorothionate 10.25 parts by weight isopropyl alcohol 59.55 parts by weight

100.00 parts by weight

20th

Example 8

Copolymer according to

Example 2 55.0 parts by weight

O.O-Dimethyl-O-CS-methyl- (^ nitrophenyl) phosphorothionate ... 3.4 parts by weight of isopropyl alcohol 41.6 parts by weight

100.0 parts by weight

To test the insecticidal effect of the invention Various tests have been carried out on coatings, the conditions of which are more severe than were the conditions occurring in practice. The experimental methods and the results obtained are compiled in the following example.

Example 9

Twelve cardboard boxes were filled with the coating composition according to Example 3 up to an absorption of 50 mg Pyrethrins and about 500 mg piperonyl butoxide per square meter painted. These boxes were with Bags filled with wholemeal flour and all in one for 6 months at 24 ° C and 65% relative humidity Pests containing space (described by J. P. B rο ο k e in Pyrethrum Post, 6, 1, April 1961) stored. Twelve uncoated cardboard boxes were filled in the same way and stored in the same room.

Uncoated
Cardboard boxes Between
Cardboard and paper
lining In whole wheat flour Box 1 22 living 95 living Moth larvae Moth larvae 3 moths 1 fully ent dolls wrapped tri 3 living bolium spp. Moths 4 moths 3 dead moths dolls very
strong mot tengespinst Box 2 3 living very strong Ge Moths spin and pay 160 dead moths rich living and dead mot 3 dolls ten as well 1 living live larvae Moth larva and dolls

Claims (1)

Claim: Use of mixtures containing a) pyrethrum, pyrethrinoids, allethrin, 3,4,5,6-tetrahydrophthalimidomethyl ester of chrysanthemum acid, dimethyldichlorovinyl phosphate, «-naphthyl-N-methylcarbamate, O, O-dimethyl - S - (1,2 - dicarboxyethyl) - phosphorodithionate, O, O-dimethyl-O- (4-bromo-2,5-dichlorophenyl) -phosphorodithionate and / or O ₃ O-dimethyl-O- (3-methyl-4-nitrophenyl) -phosphorothionate as insecticidal active ingredient components, possibly with additives that have a synergistic effect Substances, and b) Copolymers of styrene with a half ester of a dibasic unsaturated one aliphatic acid, optionally with solvents, for the production of glossy, insecticidal coatings on fibrous packaging materials. Considered publications:
British Patent No. 895 455. M9 549/417 5.68 © Bundesdruckerei Berlin