DE2340626A1 - NAGE-RESISTANT PAINTING COMPOUND - Google Patents

Description

Dr. Ing.Waiter Abitz
Dr. Dieter F. Morf
Dr. Hans-A. Browns

3 iviunchen ύυ, i-ior. <: T; jiau6.-str. 28

August 10, 1973 CASE: IC-6081

E. I. YOU PONO? DE NEMOURS AND COMPANY Wilmington, Delaware, USA.

Gnaw-resistant paint

A number of children suffer from lead poisoning every year, as a result of gnawing, sucking and biting on surfaces covered with leaded paints are coated. The National Institutes of Health estimates that 400,000 children get lead poisoning annually suffer. This is a serious public health problem that is not easy and cheap to solve. Many older ones Buildings are painted with lead-containing paints. About the danger to children from the paint to eliminate either the opportunity to gnaw or the gnawing habit must be eliminated. The only alternatives to eliminate the danger was previously either the

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Remove paint or destroy the building; both alternatives are too expensive in the majority of cases.

Recently, a paint containing a bitter substance has been introduced. If old, painted with lead Surfaces are repainted with this coat of paint, so the children no longer gnaw at it to the same extent as before Painting. Although this may work in some cases, the scope of application is limited as people rely on the different and individual ways react to bitter taste. It may be that children have the bitter taste feel less uncomfortable than adults. The gnawing or biting resistance of these paints can also be compared to Dogs and other mammals.

The present invention provides a way of preventing children, dogs and other mammals from gnawing or biting thereby to decrease that one certain irritant. Compounds incorporated into the paint; these connections create a stinging or burning sensation in the mouth. Show people, dogs, mice, rats, gerbils, guinea pigs and coyotes all irritation symptoms on exposure to small amounts of these compounds.

When a chemical compound as a means of diminution of gnawing or biting wants to be satisfactory, it must be safe, highly effective, under the ambient conditions essentially non-volatile, resistant to air and chemical oxidation, resistant to soaps and other household cleaning agents and be compatible with the paint.

The following classes of compounds have these properties: 1. Compounds of the following formula:

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OCH

wherein R is alkyl or alkenyl having 7-12 carbon atoms, or

2. 4-substituted cyclohexylamines of the formula:

I ² - A R ₁ -

wherein R _{1 is} alkyl of 3-8 carbon atoms, cycloalkyl of 4-9 carbon atoms, cycloalkylalkyl of 5-10 carbon atoms, bicycloalkyl of 7-10 carbon atoms or tricycloalkyl of 10-11 carbon atoms; R ₉ denotes hydrogen, methyl or ethyl "; -

A for

- C -

¹ V

- C

or

stands;

R represents hydrogen or alkyl of 1-4 carbon atoms;

R. and Rr, which are identical or different, are hydrogen, alkyl with 1-4 carbon atoms, cyanoalkyl with 1-4 carbon atoms, nitroalkyl with 1-4 carbon atoms, alkoxyalkyl with 1-4 carbon atoms both in the alkoxy and in the alkyl part and thioalkoxyalkyl with 1-4 carbon. represent atoms in both the thioalkoxy part and the alkyl part;

Ύ represents oxygen or sulfur; and

D, E and Z, which are identical or different, hydrogen, halogen, nitro, alkyl with 1 - 3 carbon atoms, trifluoroethyl, Mean cyano and alkoxy with 1-3 carbon atoms.

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Of the above compounds, the following compounds are preferred in terms of their effectiveness:

1. Capsaicin or

2. 4-substituted cyclohexylamines of the formula:

R ₁ -

R ₀ 0
H - 0 -

wherein R _{1 is} alkyl of 3-8 carbon atoms, cycloalkyl of 4-9 carbon atoms, cycloalkylalkyl of 5-10 carbon atoms, bicycloalkyl of 7-10 carbon atoms or tricycloalkyl of 10-11 carbon atoms;

R _{2 represents} hydrogen, methyl or ethyl; and R represents hydrogen or alkyl of 1-4 carbon atoms.

The most preferred compounds are capsaicin or N-acetyl-4-cyclohexylmethylcyclohexylamine.

As stated above, the present invention relates a method with which one prevents animals and people, especially children, from being on painted surfaces gnaw, suck, or bite. The method is particularly suitable for preventing people from working on surfaces to gnaw that were previously painted with a lead-based paint.

The method makes use of the incorporation of certain chemical compounds in paints. The resulting paints can then be applied to surfaces that have been coated with lead-based paints are. When a child gnaws at this painted surface, a stinging feeling is created and the child usually hears to gnaw on.

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Suitable chemicals are known respiratory irritants, causing an unpleasant reaction in the tissues of the mouth and throat. This unpleasant reaction is different from one another People as a stinging or burning or astringent sensation, or a combination of these Sensations described.

If these chemicals are to be effective they must be reliable, safe, cheap, essentially non-volatile in the environmental conditions, resistant to air and chemical oxidation, resistant to soaps and others Household cleaning agents and compatible with the paint.

The following compounds have been found to have the above properties and are incorporated into paints can to make them resistant to gnawing:

Compounds of the following formula:

wherein R is alkyl or alkenyl of 7-12 carbon atoms.

The compound in which

CH ₃
R stands for ^ "CH- CH = CH- (CH ₂ ) .-, that is CH ₃

Capsaicin. According to Royle, Lapworth,

J. Am. Chem. Soc. VlJj, 1109 (1919); Nelson, Dawson, J. Am. Chem.

Soc, 4.5, 2,179 (1923); U.S. Pat. 1,503,631.

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Various 4-substituted cyclohexylamine derivatives are also available suitable. These compounds are described and methods for their preparation are in the following references described:

1. US Patent No. 3,691,236, describes N-acyl-4-higher alkyl-substituted cyclohexylamines of the formula:

R ₀ 0

I ^ Il

N-C-R,

wherein R «signifies hydrogen, methyl or ethyl;

R 1 represents hydrogen or alkyl of 1-4 carbon atoms; and

R.J straight or branched chain alkyl with 3-8 carbon atoms represents.

Preferred compounds of this class are N-acetyl-cis-4-n-butylcyclohexylamine and N-acetyl-cis-4-n-hexylcyalohexylamine.

2. U.S. Patent No. 3,679,805 describes N-acyl-4-cycloalkyl-, Bicycloalkyl and tricycloalkyl substituted cyclohexylamines the formula:

Il

CR ₅

wherein R _{2 is} hydrogen, methyl or ethyl; R- is hydrogen or alkyl of 1-4 carbon atoms

R ^ for cyclobutyl, cyclopentyl, cyclohexyl, gycloheptyl, cyclo-

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octyl, cyclononyl, cycloalkylalkyl with 5-10 carbon atoms, Bicycloalkyl with 7-10 carbon atoms and iricycloalkyl with 10-11 carbon atoms.

Preferred compounds in this class include N-acetyl-4-cyclohexylmethylcyclohexylamine and N-acetyl-4-cyclotylmethylcyclohexylamine.

3. U.S. Patent 3,686,303 describes compounds the formula:

wherein R ^ for alkyl with 3-8 carbon atoms, cycloalkyl with 4-9 carbon atoms, cycloalkylalkyl with 5-10 carbon atoms, bicycloalkyl with 7-10 carbon atoms and Tricycloalkyl of 10-11 carbon atoms;

R. and Rj- independently of one another for hydrogen, alkyl with 1-4 carbon atoms, cyanoalkyl with 1-4 carbon atoms, nitroalkyl with 1-4 carbon atoms, alkoxyalkyl with 1-4 carbon atoms in the alkoxy radical and 1-4 carbon atoms in the alkyl radical and thioalkoxyalkyl with 1 -4 carbon atoms in the thioalkoxy and 1-4 carbon atoms in the alkyl radical; and .
Υ represents oxygen or sulfur.

A preferred compound of this class is 1- (cis-4-cyclohexylmethylcyclohexyl) -3-methylurea.

4. US Patent No. 3,683,001 describes compounds of the formula:

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H Y H T

H ^ vN - S - NO R ₁ -CA ^ JD "~ E H ·

wherein Y represents oxygen or sulfur;

R _{1 represents} alkyl of 3-8 carbon atoms, cycloalkyl of 4-9 carbon atoms, cycloalkylalkyl of 5-10 carbon atoms, bicycloalkyl of 7-10 carbon atoms and tricycloalkyl of 10-11 carbon atoms;

D, E and Z, each remainder for itself, for hydrogen, halogen, Nitro, alkyl with 1-3 carbon atoms, tri fluorine thyl, Cyano and alkoxy with 1-3 carbon atoms stand.

A preferred compound of this class is 1-phenyl-3- (eis-4-cyclohexylmethylcyclohexyl) urea.

Preferably, capsaicin and the compounds of US Pat. Nos. 3,691,236 and 3,679,805, in particular, are used N-acetyl-4-cyclohexylmethylcyclohexylamine.

The above compounds can be used in any paint formulation with which they are compatible, for example in latex paints or Organic solvent paints and the like are used.

For example, the paint can be in the form of a latex paint are present in which (1) the liquid phase is mainly water, (2) the resin or other film former is insoluble in the liquid phase and (3) the film-forming components and the gnawing agent. Biting decreases when very small particles are suspended or emulsified in the liquid.

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IC-6081 &

Good results can also be achieved if the liquid phase, in which the film-forming components and the agents that contain the Decrease gnaws, are dispersed, mainly composed of a volatile organic liquid and the film former exists as a solution in the liquid.

As used herein, the term "paint" is intended to include latex paints, Paints based on solvents, enamels, lacquers, varnishes or any other film-forming agent or binders known in the art to be useful in making solid (non-liquid) Films or coatings are suitable, include.

Typical formulations for paints are in the following U.S. Patent Nos. 3,261,796, 2,868,752, 2,868,754, 2,787,603, 3,113,038 and 3,032,521 and in "Formulation of Organic Coatings "by N. I. Gaynes, D Van Nostrand Co., Inc., (1967).

One type of film former for the paint, especially when the paint is a latex, is a film former, which is about 50-100 wt. # Consists of a polymeric amino ester, which can be referred to as a vinyl addition polymer, the Monovalent residues of the formulas on the carbon chain:

0 0 HR ³ H

- carries C - OH and -COCCNR ^1,

wherein R is hydrogen, benzyl and C.-C. ₀ -alkyl radicals

2 3

R and R independently of one another represent hydrogen, benzyl, aryl

and Cj-CjQ-alkyl radicals and

R represents hydrogen or Cj-C, - alkyl radicals.

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In this "preferred type of paint, for example 1-50% by weight of the film maker from another film maker "exist from the point of view of sufficient compatibility with the polymeric amino ester by the person skilled in the art can be selected. The polymeric amino ester can be prepared by various known methods; e.g. by the method described in TJS Patent No. 3,261,796.

Another type of film former that is very suitable for use in both latex and solution paints is one that is about 50-100 wt. $ from an aeryl polymer consists of poly (alkyl acrylates), poly (alkyl methacrylates) and the copolymers of an alkyl acrylate and an alkyl methacrylate is selected. ι

Other suitable film formers are alkyd resins, oil-modified ones Alkyd resins, formaldehyde condensate resins, epoxy resins, cellulose ester resins, Shellac, vinyl chloride resins, fluorine-containing resins, styrene / alkyl acrylate / methacrylic acid copolymers, polyurethanes, Acrylonitrile / alkyl acrylate copolymers, acryloxyalkyl oxazolidine resins and mixtures of two or more such film formers.

For use as an aerosol spray, the paint can be used in known Aerosol containers along with any suitable propellant such as dichlorodifluoromethane.

The paint can contain one or more of the additives known to be in film-forming compositions are useful, e.g., hardeners, desiccants, antifreezes, pigments, odor control agents Bactericidal, plasticizers, fungicides, stabilizers, viscosity controlling compounds, surface active agents and agents that counteract settling.

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These gnawing agents can be used in amounts of 0.01-1% by weight, based on the weight of the formulated paint, be incorporated into the paint. Below $ 0.01 the burning or stabbing sensation is too weak to make an impression in most ways, while above 196 the irritation symptoms are so strong that through higher contents little is gained.

The gnawing reducing compounds can be incorporated into the paint by either mixing them together mixed with the pigment in the vehicle or by dissolving them in a solvent used in the paint. For example, the compound and the paint can be added as a fine powder to the otherwise finished formulation be stirred until a uniform mixture is obtained. Alternatively, the powdered compound can be used with the film former or with the pigment if one is used prior to formulating.

Encapsulation of the gnawing compounds can be used to improve their safety and effectiveness will. Encapsulation reduces their effective vapor pressure; this helps to avoid exposure problems, e.g. in the manufacture of the chemical and also in its use. Microencapsulation is special important for the low molecular weight compounds.

A variety of techniques can be used to encapsulate the chemicals. Suitable techniques are from James E. Flinn and Herman Nock, Chemical Engineering, December 4, 1967, pages 171-178 and also by M. W. Ranney, Microencapsulation Technology, 1969, Noyes Development Corporation, Park Ridge, New Jersey. The specific technique to be used is clear to the expert and it is based on the own

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ft

shafts of the gnaw-reducing compound, the substrate and the end use. Ideally, the encapsulation material should have a continuous barrier or coating around the Make chemical to lower its effective vapor pressure.

The paints can be coated with the help of suitable known or film formation methods, e.g. by spraying, rolling, brushing, spreading with a knife, dipping, calendering, Extrusion, converted into solid films or coatings by electrical coating, Pließbeschichtttng or the like will.

The paint can be applied to any substrate such as wood, plaster of paris, metal, including materials that are already wear a coat of paint, but it is particularly useful when applied to surfaces that were previously painted on have been coated on a lead base.

The following examples serve to further illustrate the present invention. They show the making of Paints containing the irritants and how they work. In the examples, all percentages represent percentages by weight The examples are all directed to the preferred compounds, but the examples are directed to all compounds of the present invention is applicable. All of these connections have those necessary for a successful application Properties and they can be incorporated into the paint compositions in the same way.

example 1

A 49.5 g sample of an alkyd house paint (Glidden, Spred Gel FIo, 1901 Endurance White) and 0.5 g of N-acetyl-4-cyclohexylmethylcyclohexylamine (60 $ trans isomer and 40 $ cis isomer) are mixed for about 15 minutes. The paint

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/ 3

holds 0.4 $ of the active cis isomer of N-acetyl-4-cyclohexylmethylcyclohexylamine. The bottom of a new aluminum tray is then coated with it. When the paint was dry a dry platelet about 2-3 mm square was chewed Mouth immediately a burning sensation arose; _ the desire, chewing the material was then greatly reduced.

Example 2

If the amount of N-acetyl-4-cyclohexylmethyleyclohexylamine in a paint like that of Example 1 is reduced from $ 1.0 to $ 0.01, a similar burning sensation is produced, when a flake of the paint is chewed. It gets both the intensity and the duration of the burning Feel decreased compared to that of Example 1, but further chewing of the paint is hindered.

Example 3

A gnawing coating formulation is produced, which corresponds to that of Example 1 by using $ 0.02 capsaicin in place of that in Example 1 N-acetyl-4-cyclohexylmethylcyclohexylamine is used. Man notes a similar burning sensation when chewing a flake of the paint; this creates the urge to Chewing material decreases.

Example 4

A 49.5 g sample of acrylic latex paint (Glidden Spred House Paint, 3600 White) and 0.5 g of N-acetyl-4-cyclohexylmethylcyclohexylamine are mixed for about 15 minutes. A plaque from a dry, freshly painted surface is chewed and immediately creates a burning sensation, which greatly reduces the need to chew the paint.

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Example 5

A gnawing paint formulation similar to that used in Example 4 can be prepared by 0.5 g of N-acetyl - ^ - n-hexylcyclohexylamine instead of N-acetyl-4-cyclohexylmethylcyclohexylamine of Example 4 is used. · A flake of this coating causes a similarly burning one Feeling when chewing.

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Claims (1)

August 10, 1973 CASE: IC-6081 PATENT CLAIM Nagefcest-resistant coating, characterized in that that it contains 0.01-1% by weight of a compound which is selected is under: a) compounds of the following formula: OCH,
³ wherein R is alkyl or alkenyl having 7-12 carbon atoms or t) 4-substituted cyclohexylamines of the formula: , ■ - A R ₁ - CH ₂ wherein R _{1 is} alkyl with 3-8 carbon atoms, cycloalkyl with 4-9 carbon atoms, cycloalkylalkyl with 5-10 carbon 4098 3 3/0916 - 15 - material atoms, bicycloalkyl with 7-10 carbon atoms or Represents tricycloalkyl of 10-11 carbon atoms; R _{2 is} hydrogen, methyl or ethyl; ^{0 Y} ρ - C - R-; - C - N ^ ° or - C - Ή-ζ ^), wherein R represents hydrogen or alkyl having 1-4 carbon atoms; R. and Rr, which are the same or different, represent hydrogen, Alkyl with 1-4 carbon atoms, gyanoalkyl with 1-4 carbon atoms, nitroalkyl with 1-4 carbon atoms, alkoxyalkyl with 1-4 carbon atoms in both the alkoxy and in the alkyl part, and thioalkoxyalkyl with 1-4 carbon atoms both in the thioalkoxy part and in the alkyl part; Y represents oxygen or sulfur; and D, E and Z, which are identical or different, hydrogen, halogen, nitro, alkyl with 1-3 carbon atoms, trifluoroethyl, Mean cyano and alkoxy with 1-3 carbon atoms. 409833/0916
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