GB2138291A - Processes and compositions of producing insecticide coatings - Google Patents

Abstract

An insecticidal surface coating composition, comprises on a weight basis: (1) 0.01 to 2.5% of one or more insecticidally active ingredients; (2) 0.1 to 1.0% of one or more non-ionic, hydrophilic protective colloids; (3) from 10.0 to 55.0 percent of one or more filming agents each comprising a dispersion of one or more homonomers and/or copolymers of vinyl acetates or vinyl acetate ester or acrylic derivatives or butadiene-styrene derivatives or alkyd derivatives; (4) 1.5 to 6.0% of one or more co-carriers; (5) 20.0 to 55.0% water; (6) 0.1 to 5.0% of one or more plasticizing agents; (7) 0.05 to 0.5% of one or more defoaming agents; and (8) 0.01 to 0.1% of one or more dispersing and/or buffering agents.

Description

SPECIFICATION Process and compositions of producing insecticide coatings Background Traditionally, eradication of household insects such as flies, ants, termites, cockroaches, spiders, silverfishes, mosquitoes, beattles etc. has been largely achieved by application of insecticidal sprays, aerosols, fumigrants and baits that kill such insects upon contact or ingestion. These methods are generally effective for a fairly short period of time and have at least the following distinct disadvantages: (1) Mists and vapors of sprays, aerosols and fumigrants and particles of baits containing active insecticidal agents are high mobile and removable. They therefore cannot stay at desired site for a long enough period of time to perform the desired insecticidal function.

(2) For reason cited in (1), these devices have a relatively short period of insecticidal activities. Practically all of them can only perform their desired function for a period of only several number of weeks. Therefore, repeated applications are necessary to ensure long-term protection against household insects. The need to repeat applications causes great inconvenience and is very time-consuming.

(3) The mobile nature of mists and vapors and particles of these devices create great opportunity of contamination. Such is highly undesirable particularly when such contamination takes place on food or food serving devices.

(4) The fact that once applied the insecticidal agents contained in these devices are only very loosely placed on the surfaces onto which these devices are applied creates undesirable danger as they may contaminate humans and household pets. The absorption of insecticidal agents through inhalation and ingestion over a long period of time may present highly undesirable hazards to human and household mammals.

(5) Applications of these devices are mostly associated with undesirable smell and odor. Such create much inconveniences and may be harmful to health.

(6) Applications of these devices normally are conducted in limited areas. Therefore they cannot be expected to provide maximum insecticidal protection to the premises wherein they are applied.

The invention provides answers to the aforesaid disadvantages of existing insecticidal devices. The invention is a process and via which the possibility to produce a range of insecticide coatings which are to be applied onto surfaces the way one does with paints, varnishes and lacquers, such surfaces could be interior and exterior walls, ceilings, and that of cabinets, wardrobes whether such surfaces are made of concrete, paper, wood, plastic, or ceramic and wh ether they are already painted or not. Once dried, the invention produces a dry, durable, water-resistant coating on the surfaces onto which it is applied. Such coating is odorless and washable.The invention presents at least the following distinct and unique properties which the aforementioned traditional insecticidal devices do not provide: (1) It is insecticidally effective for several years under normal circumstances while those traditional devices are effective for several weeks.

(2) Insecticidal agents contained in the invention are incorporated into and the particles of which are reasonably firmly held by a continuous film on its surface instead of being mobile and easily removable like that of traditional insecticidal devices.

(3) By virtue of (2), the insecticidal agents stay at place for years until the coating is artificially removed and during which insecticidal activities remain.

(4) By virtue of (2), there are practically no danger of undesirable contamination as the insecticidal agents do not float around uncontrollably like those of insecticidal sprays, aerosols or fumigrants.

(5) The invention produces an end product - continuous coating on a surface, which has no undesirable odor.

(6) The invention may be used to cover most areas in a premises where household insects are problematic and thus provides very much greater protection and coverage in the premises.

(7) The invention produces an end product - continuous coating which does not emit any significant amount, if at all, of mobile particles, vapor, mist or fume that may be inhaled or ingested accidentally by humans or household mammals and therefore greatly reduces the possibility of intoxication over a long term exposure.

(8) The invention is an insecticide coating and is totally different from the conventional type of insecticidal devices commonly available such as sprays, aerosols, fumigrants and baits.

Description of Invention and its Preferred Embodiments The invention relates to novel compositions useful for the production of a range of products which are principly embodied by the following principle compositions: (1) One or more insecticidally active ingredients presenting in the concentration of, by weight, about 0.01 to about 2.50 percent, preferably about 0.25 to about 1.0 percent; (2) One or more protective colloids presenting in the concentration of, by weight, about 0.1 to about 1.0 percent, preferably about 0.2 to about 0.5 percent; (3) One or more filming agents presenting in the concentration of, by weight, about 10.0 to about 55.0 percent, preferably about 15.0 to about 30.0 percent;; (4) One or more co-carriers presenting in the concentration of, by weight, about 1.5 to about 6.0 percent, preferably about 2.0 to about 4.0 percent; (5) Water presenting in the concentration of about 20.0 to about 55.0 percent, preferably about 25.0 to about 45.0 percent; (6) One or more plasticizing agents in the concentration of, by weight, about 0.1 to about 5.0 percent, preferably about 0.1 to about 2.5 percent; (7) One or more defoaming agents in the concentration of, by weight, about 0.05 to about 0.50 percent, preferably about 0.1 to about 0.3 percent; (8) One or more dispersing agents and buffers in the concentration of, by weight, about 0.01 to about 0.10 percent, preferably abbut 0.02 to about 0.07 percent;; (9) With or without one or more pigments which if present, in the concentration of, by weight, about 0.0 to about 60.0 percent, preferably about 2.0 to about 40.0 percent; (10) With or without one or more coalescing agents, which if present, in the concentration of, by weight, about 0.1 to about 1.5 percent, preferably about 0.5 to about 1.0 percent; (11) With or without one or more preservatives, which if present, in the concentration of, by weight, about 0.05 to a-bout 0.50 percent, preferably about 0.05 to about 0.20 percent.

and that each components, if embodied are of the following typical characteristics: (1) Insecticidally active ingredients These ingredients should be contact, systemic and stomach insecticides of low order of mammal toxicities and are derivatives of any of the following categories: (A) Organophosphates with the following common general chemical structure

where R and R' are a lower aliphatic radical, Ar is an aromatic or heterocyclic radical containing various substituents in the aromatic or heterocyclic nucleus.

(B) Carbamates with the following common general chemical structure RNHCOOR' where R is a lower aliphatic radical with or without substituents and R' is an aromatic or heterocyclic radical containing various substituents in the aromatic or heterocyclic nucleus.

(C) Derivatives of chrysanthemumum monocarboxylic acid with the following common general chemical structure

where R and R' are lower aliphatic radicals or aromatic or heterocyclic radical containing various substituents in the aromatic or heterocyclic nucleus and R" is a lower aliphatic radical with or without substituents or a simple elementary substituent.

Provided further that such ingredients are highly soluble in organic solvents, relatively insoluble or insoluble in water and with melting points of 30 to 250"C.

(2) Protective Colloids These ingredients are chemicals or dispersions of chemicals which are non-ionic, hydrophilic; dispersible in water, may or may not be dispersible in organic solvents and a 2% w/v aqueous dispersion of which renders pH of 5 to 8.5.

These ingredients are cellulose derivatives with the following common general chemical structure

where R and R' is H, -CH2CH3, or -CH2CH2OH, or other lower aliphetic radical with or without substituents.

(3) Filming agent and binders These ingredients are homonomers and/or copolymers of vinylacetates, or acrylic derivatives or vinylacetate esters or butadiene-styrene derivatives or alkyd derivatives provided that sizes of the particles of such ingredients in dispersion range from 0.10 microns to 0.60 microns and that they are suspendable or dispersible in water, carry negative particle charge and the dispersion of which has a pH of 3 to 7.

(4) Co-carriers These ingredients are aromatic or heterocylic organic solvents with or without substituents in the aromatic or heterocyclic nucleus, practically insoluble in water although probably miscible with water to a minor degree, having a boiling range from 800 to 150"C at 760 mm Hg, and a dielectric constant between 1.5 and 4.0. They should also be of a fairly low order of mammal and human toxicity.

(5) Water Water used must be of high industrial quality preferably deionized. It should meet the following specific requirement (A) Ammonium: To 20 ml add 1 ml of alkaline mercuric potassium iodide solution RAfter5 minutes the solution examined down the axis of the tube is not more intensely coloured than a referance solution prepared at the same time by adding 1 ml of alkaline mercuric potassium iodide solution R to a solution containing 2.5 ml of ammonium standard solution (1 ppm NH4) R and 7.5 ml of water.

(B) Calcium: To 10 ml add 0.2 ml of dilute ammonia R2 and 0.2 ml of ammonium oxalate solution R. The solution remainsclearfor 1 hour.

(C) Heavy metals: Heat 150 ml in a porcelain evaporating dish on a water bath until the volume is reduced to 15 ml. 12 ml of the concentrated solution complies with the limit test for heavy metals (0.1 ppm). Prepare the standard using lead standard solution (1 ppm Pb) R.

(D) Total Hardness: No more than 12 degrees.

All Reagents (R) are prepared in accordance with European Pharmacopea.

(6) Plasticizing agents These ingredients are either glycols of the following general chemical formula: HOCH2(CH20CH2)n CH2OH whereon =0to12 or an aliphatic alcoholic polymer of the following general chemical structure:

(7) Defoaming agents These ingredients are hydrophilic esters and/or aliphatic or aromatic hydrocarbon that are soluble in organic solvents, reasonably miscible with water, either colorless or of a very light shade.

(8) Dispersing and buffering agents These ingredients are sodium polyphosphate of medium chain length.

(9) Pigments These ingredients are normal commercially available pigments provided that their particle sizes range from 1 to 45 microns with a pH of 6 to 11 in a 5% w/v aqueous suspension. They are insoluble or almost insoluble in water.

(10) Coalescing agents These ingredients are water immiscible, colorless or of a very light shade, ester alcohols of 10 to 25 carbons.

(11) Preservatives These ingredients are commercially available preservatives providing that thay are not active chelating agents and are not strong alkalines.

Examples The present invention will better be understood from the following examples which are intended to be illustrative and not duly limitative.

Examples: A- 1, A-2, A-3 and A-4 Products are prepared to the percentage formulations specified in table (1) wherein example A-1, A-2, and A-3 represent Insecticide Latex coatings of flat finish containing different active insecticidal agents and mixtures; while example A-4 represents an insecticide Latex coating of gloss finish.

TABLE 1 Ingredients Formulations A-1 A-2 A-3 A-4 Aluminium silicate 5.0% 5.0 /O 5.0% Calcium carbonate 25.0% 22.0% 24.0% 25.0% (s-a-cyano-m-phenoxy benzyl (1R,3R) - 0.025% - -3-(2,2 dibromovinyl)-2,2-dimethyl cyclopropane carboxylate Defoamer 0.2% 0.2% 0.2% 0.2% 0,0-diethyl 0-(3,5,6-trichloro-2- 0.3% - 0.2% 0.35% pyridyl) thiophosphate, deodorized grade 0,0-diethyl 0-(3,5,6-trichloro-2- 0.7% - 0.5% 0.9% pyridyl) thiophosphate, technical Dowicil-75 0.1% 0.1% 0.1% 0.1% Ethylhydroxyethyl cellulose 0.4% - 0.5% Lithopone 10.0% 9.0% 10.0% 10.0% Methylcellulose - 0.5% - 0.5% Monoethyleneglycol 2.4% 2.4% 2.4% 2.4% 3-Phenoxybenzyl (+) cis-trans-2,2- - - 0.5% dimethyl-3-(2,2-dichlorovinyl) cyclopropane-1 -carboxylate Polyvinylacetate copolymerdispersion 13.63% 13.63% 13.63% 13.63% Sodium polyphosphate 0.07% 0.07% 0.07% 0.07% Talc, extra white 2.5% 2.5% 2.5% 2.5% Texanol 0.7% 0.7% 0.7% 0.7% Titanium dioxide, rutile 7.5% 6.5% 6.5% 7.5% Toluene 2.0% 2.8% 2.4% 1.8% Water 27.5% 32.575% 28.8% 32.35% Xylene 2.0% 2.0% 2.0% 2.0% The process to prepare the products are as follows:: (1) Prepare the mixture of Xylene and toluene, into which dissolve the insecticidal ingredients of 0,0-diethyl 0-(3,5,6-trichloro-2-pyridyl) th iophosphate, technical; 0,0-diethyl 0-(3,5,6-trichloro-2pyridyl)thiophosphate, deodorized grade; (s-a-cyano-m-phenoxy benzyl (1 R,3R)-3-(2,2-dibromovinyl)-2,2dimethyl-cyclopropane carboxylate; 3-phenoxybenzyl (+) cis-trans-2,2-dimethyl-3-(2,2-dichlorovinyl) cyc lopropane-1 -carboxylate; whichever is applicable.

(2) Dissolve into approximate one-third of the required quantity of water the ingredients of sodium polyphosphate, ethylhydroxyethylcellulose or methylcellulose, whichever is applicable at temperature not to exceed 32"C.

(3) Gradually add the mixtures from (1) into the water mixture from (2) with continuous high speed mixing; and then pass the final mixture through a nozzle-type homogenizer.

(4) Into the balance of the quantity of water, add, step by step, one after the other, with medium speed mixing, in a suitable stainless steel disperser, the followings: Monoethyleneglycol, defoamer, calcium carbonate, lithopone, titanium dioxide futile, Talc extra white, aluminium silicate, Texanol, Dowicil-75 whichever are applicable. Maintain temperature of mixture at below 32"C at all time.

(5) Add into the mixtures from (4) the indicated quantity of polyvinylacetate copolymer dispersion. Mix till homogenous, then add into which the mixture from (3). Mix until homogenous.

The coating qualities such as hiding powder, adhesion, scrubability, weathering, etc. are tested in accordance with industry's standards while the insecticidal activities of the preparations are tested with various household insects via a modified C.S.M.A. (Chemical Specialty Manufacturers Association, U.S.A.) method: and the stability of insecticidal activities upon storage and after applications tested via scientifically acceptable accelerated stability test methods which are matched by actual aging tests. All preparations meet all requirements and their effectiveness proven via the aforesaid tests.

Example: B- 7, B-2, B-3 and B-4 Products are prepared in similar processes as those described for Examples A-1, A-2, A-3 and A-4 and in accordance with the percentage formulations specified in table (2) wherein Example B-1, B-2 and B-3 represent Insecticide semi-transparent or transparent coatings of flat finish while Example B-4 represents an insecticide semi-transparent or transparent coating of gloss finish.

TABLE 2 Ingredients Formulations B-1 B-2 B-3 B-4 Aluminium silicate 2.4% 2.4% 2.4% (s-a-cyano-m-phenoxy benzyl (1 R,3R)- - - 0.5% 3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropane-carboxylate Defoamer 0.1% 0.1% 0.1% 0.1% 0,0-diethyl 0-(3,5,6-trichloro-2- 0.3% - 0.2% 0.35% pyridyl )th iophosphate, deodorized grade 0,0-diethyl 0-(3,5,6-trichloro-2- 0.7% - 0.5% 0.9% pyridyl)th iophosphate, technical Ethylhydroxyethylcellulose 0.4% - 0.5% Methylcellulose - 0.5% - 0.5% Monoethyleneglycol 0.1% 0.1% 0.1% 0.1% 3-phenoxybenzyl (t) cis-trans-2,2- - 0.025% - dimethyl-3-(2,2-dichlorovinyl) cyclopropane carboxylate Polyvinylacetate copolymer 50.0% 50.0% 50.0% 52.5% dispersion Sodium polyphosphate 0.02% 0.02% 0.02% 0.02% Toluene 2.0% 2.8% 2.4% 1.8% Water 41.98% 42.055% 41.28% 41.73% Xylene 2.0% 2.0% 2.0% 2.0%

Claims (21)

1. An insecticidal surface coating composition, comprising on a weight basis: (1) 0.01 to 2.5% of one or more insecticidally active ingredients; (2) 0.1 to 1.0% of one or more non-ionic, hydrophilic protective colloids; (3) from 10.0 to 55.0 percent of one or more filming agents each comprising a dispersion of one or more homonomers and/or copolymers of vinyl acetates or vinyl acetate ester or acrylic derivatives or butadiene-styrene derivatives or alkyl derivatives; (4) 1.5 to 6.0% of one or more co-carriers; (5) 20.0 to 55.0% water; (6) 0.1 to 5.0% of one or more plasticizing agents; (7) 0.05 to 0.5% of one or more defoaming agents; and (8) 0.01 to 0.1% of one or more dispersing and/or buffering agents.

2. A composition according to claim 1 further containing on a weight basis: (9) up to 60% of one or more pigments; and/or (10) up to 1.5% of one or more coalescing agents; and/or (11) up to 0.5% of one or more not strongly alkaline preservatives.

3. A composition according to claim 1 or claim 2 in which an insecticidally active ingredient is a contact or systemic insecticedal agent having any one of the following formulae:

wherein R and R' each represent a lower aliphatic radical, and Ar represents an aromatic or hetero-cyclic radical which may carry substituents in the aromatic or hetero-cyclic nucleus; (b) RNHCOOR' wherein R represents a lower aliphatic radical with or without substituents and R' represents an aromatic or heterocyclic radical which may carry substituents in the aromatic or heterocyclic nucleus;

wherein R and R' each represent a lower aliphatic radical or an aromatic or heterocyclic radical which may carry substituents in the aromatic or heterocyclic nucleus and R" represents a lower aliphatic radical with or without substituents or a simple elementary substituent.

4. A composition according to any of claims 1 to 3, in which a protective colloid has the following general structural formula:

where R and R' represent H or a lower aliphatic radical with or without substituents.

5. A composition according to any of claims 1 to 4 in which the particle size of filming agent dispersions is from 0.1 to 0.6 microns; such particles carry negative charges; and the dispersions each have a pH of 3 to 7.

6. A composition according to any of claims 1 to 5, in which a co-carrier is an aromatic or heterocyclic organic solvent with or without substituents in the aromatic or heterocyclic nucleus, having a boiling point of from 80"C to 1 500C and a dielectric constant between 1.5 and 4.0.

7. A composition according to any of claims 1 to 6 in which the plasticizing agents have either of the following general structural formulae: (a) HOCH2(CH2OCH2)nCH2OH wherein n Oto 12; or

8. A composition according to any of claim 1 to 7, comprising as a defoaming agent a hydrophilic ester or an aliphatic or aromatic hydrocarbon soluble in organic solvents, reasonably miscible with water, and either colorless or of a very light shade.

9. A composition according to any of claims 1 to 8, comprising as a dispersing and/or buffering agent a sodium polyphosphate of medium long chain.

10. A composition according to claim 2 comprising a pigment or filler having an average particle size of 1.0 to 45.0 microns, being insoluble or almost insoluble in water, but forming a 5% w/v aqueous suspension having a pH of 6 to 11.

11. A composition according to claim 2, comprising a coalescing agent that is colorless or of a very light shade and is an ester alcohol of 10 to 25 carbons.

12. A composition according to claim 2 wherein the components are present in the following ranges:- component (1) 0.25 to 1.0%; component (2) 0.20 to 0.5%; component (3) 12.0 to 50.0%; component (4) 2.0 to 4.0%; component (5) 25 to 45%; component (6) 0.1 to 2.5%; component (7) 0.1 to 0.3%; component (8) 0.02 to 0.08%; component (9) 2.0 to 50.0%; component (10) 0.5 to 1.0%; and component (11) 0.05 to 0.2%.

13. A composition according to claim 2 wherein the components are present in the following ranges: component (1) 0.25 to 1.0%; component (2) 0.20 to 0.50%; component (3)12.0 to 20.0%; component (4) 2.0 to 4.0%; component (5) 22 to 32%; component (6) 1.5 to 2.5%; component (7) 0.15 to 0.25%; component (8) 0.06 to 0.08%; component (9) 40.0 to 50.0%; component (10) 0.6 to 0.8%; and component (11) 0.07 to 0.12%.

14. A composition according to claim 2 wherein the components are present in the following ranges:- component (1) 0.25 to 1.0%; component (2) 0.20 to 0.50%; component (3) 40.0 to 50.0%; component (4) 2.0 to 4.0%; component (5) 35 to 45%; component (6) 0.1 to 0.2%; component (7) 0.07 to 0.12%; component (8) 0.02 to 0.04%; component (9) 2.0 to 5.0%; components 10 and 11 not present.

15. A composition according to any of the preceding claims in which component (1) is 0,0-diethyl 0-(3,5,6-trichloro-2-pyridyl) thiophosphate, or [S]-a-cyano-m-phenoxy-benzyl (1 R,3R)-3-(2,2 dibromovinyl)2,2-dimethyl-cyclo-propane carboxylate, or a mixture of 0.0-diethyl 0-(3,5,6-trichloro-2-pyridyl) thiophosphate and [S]-a-cyano-m-phenoxybenzyl (1 R,3R)-3-(2,2 dibromovinyl)-2,2-dimethyl-cyclopropane carboxylate, or a mixture of 0-0-diethyl 0-(3,5,6-trichloro-2-pyridyl)thiophosphate and 3-phenoxybenzyl(t) ) cis, trans-2,2-dimethyl-3-)2,2-dichlorovinyl) cyclopropane-1 -carboxylate.

16. A composition according to any of claims 1 to 15 in which component (2) is ethyl hydroxyethyl cellulose or methyl cellulose.

17. A composition according to any of claims 1 to 16 in which component (3) is polyvinyl acetate or its copolymers.

18. A composition according to any of claims 1 to 17 in which component (4) is xylene or any of its isomers, or a mixture of xylene and toluene.

19. A composition according to any of claims 1 to 18 in which component (6) is monoethylene glycol or an aliphatic polyglycol.

20. An insecticidal composition substantially as described herein any of the Examples.

21. A method of controlling insects by applying to surfaces a composition according to any of the preceding claims.