NO742124L - - Google Patents

Description

Procedure for painting nails and

preparation for carrying out the procedure.

The present invention relates to a process for painting nails and a resin preparation which is useful for this purpose. More specifically, the present invention relates to a method of the aforementioned kind3 whereby the nails are applied to a substrate comprising a water-soluble or water-swellable polymer in a solvent system, after which a radiation-hardening nail polish preparation is applied which is hardened with the aid of an actinic light source. The present invention also relates to a method for removing this nail coating.

It has long been practice within this technique to prepare nails for better reception of nail varnishes or enamels to help when building up. film thickness and to increase adhesion between the enamel or nail polish and the nails' first apply a substrate to the nails. The substrate preparations known from the art usually comprise a 10 percent solution of nitrocellulose as a film former. When such a substrate is applied to nails and allowed to dry and then coated with nail polish, which is also allowed to dry, a nail coating is obtained that is difficult to remove. Organic solvents are usually required to remove these coatings, which contributes to degreasing and thus drying of the nails in the process of removing the nail coating. This is clearly an undesirable result.

A very large number of different nail polish preparations are known in the art and are commercially available. These nail polishes usually consist of complicated systems containing between 6 and 8 different components. Typically, such preparations contain a primary film former such as nitrocellulose, solvents such as butyl acetate, ethyl acetate, toluene and ethyl alcohol (all of which solvents are flammable), pigments that can stain the nail, both natural and synthetic resins added to help during film formation, as well as certain materials that help with the film's wetting of the nail. All the above-mentioned components must be critically balanced in relation to each other in order to achieve a good nail polish. Even after this is achieved, however, the best nail polishes still suffer from many disadvantages.

Although the adhesion between commercially available nail varnishes and the nail surface is generally good, the varnishes are still prone to peeling and being scratched after several days of wear. As commercial varnishes also dry by solvent evaporation from the outside inwards, the gloss properties of the resulting surface are poor. In addition, several coatings are usually necessary to achieve good color coverage and acceptable gloss properties. Applying a subsequent coat of nail polish on the outside

however, the first coating will cause "the first coating to flow. This means that the user must be careful when applying the second coating. Also, the drying time for multiple coatings is extremely slow. In addition, with these known products, the user must work quickly and carefully due to the solvent evaporation. Failure to do so can result in premature curing and loss of good, even coverage. Also, as a result of solvent evaporation, the customer often has to discard a bottle of nail polish that has dried into the bottle before the contents are used up.

Commercial nail polishes are usually removed using solvents. As these solvents are usually fat-free, they can degrease and dry out both nails and skin. Commercially available nail polishes also have little resistance to wear and tear and are consequently scratched and worn by abrasive cleaning agents. In addition, repair of commercially available nail polishes on the individual nails is impossible, as the surface of nails that have not been repaired is dull and scratched compared to the newly applied surface.

It has now been shown that the disadvantages listed above are easily overcome

can be avoided by using the two-part nail polish system according to the invention, where the first part (a) consists of a substrate preparation of a water-soluble or water-swelling polymer in a solvent, and where the second part (b) is a radiation-curable nail polish preparation which is adapted to harden to a hard nail coating by being exposed to a light source described in more detail below.It has further been found that when the above base preparation is applied to nails and allowed to dry and then followed by a top layer of a radiation curable nail polish , which is hardened by

be exposed to a suitable light source, both the undercoat and the nail polish preparation are easily removed by simply soaking the nails in water for a short period of time. This causes the substrate to be released from the nail, whereby the entire coating can be easily peeled off.

According to the present invention, a radiation curable polymer system is used. It is described in more detail below as the primary film former instead of the conventional film formers, such as nitrocellulose. This radiation curable system is less complex than the conventional nitrocellulose system. Where the conventional nail polish contains nine components, the nail polish system according to the invention can contain as few as four components. In addition, the conventional nail polishes are flammable and require special treatment due to the explosive properties of nitrocellulose. The radiation curable system according to the invention contains no solvents and is relatively safe to mix and work up.

Since no solvent evaporation takes place during the curing of the radiation-curable nail polish, a smooth, perfect surface with a particularly high gloss is produced. Glare measurements have supported these observations. Full coverage can be achieved with as little as two coats. In addition, complete drying of each coat can be done in less than 1 minute, compared to 10 minutes or more for drying two coats of conventional nail polish. Red pigments seem to shorten this curing time, and no pigment shielding or staining of the nails has been shown. Besides, will

unlike conventional nail polish, subsequent coatings of the radiation-curable nail polish according to the invention do not soften or damage previous coatings that have been cured. This enables nail polish of the latest fashion to be applied on top of the pigmented substrate.

With the nail polish according to the invention, the user has complete freedom to work slowly and carefully, and then, when the result achieved is satisfactory, to dry the coating in less than 1 minute. As there is also no solvent in the system, the polymer will not dry into the bottle. However, it will harden if it is not protected from light. In addition, the polymer film that emerges during the curing has excellent wear resistance and great resistance to scratches.

The preparations according to the invention allow for repair, which is a particularly great advantage. A nail that has had the preparation according to the invention applied again 3 or 4 days after the original application cannot be distinguished from the nail varnish that has been applied several days before. The nail polish preparations according to the invention are removed by soaking the nails in warm water.' There is no need to use solvents that can degrease and dry the nails,

which is otherwise characteristic of known nail polish preparations.

As mentioned above, the substrate preparations according to the invention are characterized by the fact that a water-soluble or water-swellable polymer system is used as a film former. These base preparations serve to facilitate the removal of the nail polish when both base and radiation-curable nail polish have been placed on the nail. Soaking such over-drawn nails in water, preferably in warm water for a few minutes causes the substrate to swell with the result that the overlying layer of nail polish and the substrate can be lifted up and released from the nail.

The term "water-swellable polymer" is used here to denote a polymer material which can absorb a certain amount of water without being dissolved in it. This water uptake is accompanied by an increase in the polymer material's volume. The term "water-soluble polymer" is used here to denote a polymer which is soluble in water to an extent of at least 1% by weight.

The nail polish preparations according to the invention usually comprise

a radiation curable, liquid system containing as essential components at least one polyene, polythiol, radiation curing rate accelerator and one or more surfactants described in more detail below. This liquid system is designed to form a continuous film by being placed on nails and exposed to actinic light, particularly ultraviolet light (for example with a wavelength of 366OÅ).

A group of water-soluble or water-swellable polymers that are particularly suitable for use in substrate preparations according to the invention are water-soluble or water-swellable polymers produced by polymerization of one or more vinyl compounds with the formula:

where

(a) R1 is hydrogen, alkyl, phenyl, halogen or pyrrolidonyl, i.e. 2' 9 (b) R is hydrogen, alkyl, phenyl, halogen, -COOH or -C-, (c) R is hydrogen, alkyl, carboxyalkyl1 , phenyl or halogen. Cd) X is hydrogen, -C00 alkyl, -COOI-I, -0 alkyl, -CN, halogen or

and (e) n is 0 or 1, wherein (f) n is only 1 when both R and X are

Among these monomers is a preferred group of monomers with the same general formula as formula I above. In this case

1 2 "S

however, R , R , R" and X have the following meaning:

(a) R is hydrogen or pyrrolidonyl, (b) R 2 is hydrogen, alkyl, -C00H or

(c) R<3> is hydrogen, and

(d) X is -C00 alkyl, -C00H, hydrogen, -CN or

The term polymer is used here in the generic sense to cover the material of the polymer which results from the polymerization of one of the monomers with the formula I, or a mixture of monomers with this formula. It is thus intended to cover homopolymers, copolymers, terpolymers, tetrapolymers, etc. with the term polymer.

When R ]_ , R 2 or R 3 in the above formula denotes an alkyl group or the alkyl residue of a complex group containing an alkyl group (for example carboxyalkyl), the alkyl group or alkyl residue preferably contains from 1 to 6 carbon atoms, and can for example be methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl and n-hexyl. In addition, any other substituent, denoted by alkyl, will also contain from 1 to 6 carbon atoms in the alkyl group, which may for example be methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl and hexyl. R<1>, R<2>, R3 or X can be Cl, Br, P and I as halogen.

Examples of more particularly preferred monomers with the formula 1 can be mentioned: vinyl acetate, crotonic acid, vinyl pyrrolidone, methyl vinyl ether, maleic anhydride, maleic acid, acrylic acid and acrylonitrile.

Further examples of "special water-swellable or water-soluble polymers which are useful for use alone or in combination in the substrate preparation according to the invention are: Amphomer 2844910, PVP/VA 535 (vinylpyrrolidone/vinyl acetate copolymer 50/50 mole percent), PVP/VA 335 (copolymer vinylpyrrolidone/ vinyl acetate 35/65 mole percent), Gantrez AN 119 (methyl vinyl ether/maleic anhydride copolymer, molar ratio = 1:1, low molecular grade with average

molecular weight of 250,000), Gantrez AN 139 (methyl vinyl ether/maleic anhydride copolymer, molar ratio = 1:1, quality with medium high

molecular weight 500,000), Gantrez AN 169,. Gantrez ES 425 (monobutyl ester of poly(methyl vinyl ether/maleic acid), Gantrez ES 225 (monoethyl ester of poly(methyl vinyl ether/maleic acid), Gafquat (quaternized vinyl-pyrrolidone copolymer), National Starch Resin 26-2905- National Staren Resin 2261 , National Starch Resyn 28-2930 (terpolymer of crotonic acid (10 mole percent) and mixture of vinyl acetate and vinyl ester of C]_o~ci8~ fatty acids (90 mole percent) see US Patent 2,996,471)) and National Starch Resyn 28-1310 (copolymer of vinyl acetate (10 mole percent)/'crotonic acid (90 mole percent)).Radiation-curable polymers can also be used if they are water-swellable.

Water-swellable or water-soluble polymers that are particularly useful for use in the substrate preparation according to the invention are also characterized by the fact that they are film-forming polymers that form a flexible film and not a rigid film. As these polymers are calculated

on forming a film that sticks to nails and which at the same time forms a

, base to which a radiation-cured, polymeric top layer can adhere, it is important to choose a water-soluble or water-swellable polymer that has these adhesion properties.

Any of the above-mentioned water-soluble or water-swellable polymers or combinations thereof can be used in the composition of the substrate preparations according to the invention.

These preparations will usually consist of a solution of one or more of the polymers in a solvent system. A number of different solvents or combinations of solvents can be used for this purpose. However, the solvent system will preferably be a relatively volatile solvent of predominantly organic nature, which solvent may contain small amounts of an inorganic solvent, for example water. As examples of

solvents that can be advantageously used in this connection include ethanol, acetone, cosmetic solvents, ethyl acetate, toluene, isopropanol and methyl ethyl ketone. These solvents can be used alone or in combination.

The amount of water-soluble or water-swellable polymer in the substrate preparations can vary somewhat. Usually the amount will be between approx. 5 and approx. 30% by weight of the substrate preparations.

In addition to the above-mentioned water-soluble or water-swellable, film-forming polymers, the substrate preparation according to the invention may contain other conventional components that are usually used in such preparations. These components can be pigments, softeners, surface-active substances, auxiliary solubilizers, perfume etc. Among pigments that can be used, one can mention D&C colors, which are soluble in organic solvents••As typical examples of softeners that can be embedded in the substrate preparations according to the invention can mention is made of dibutyl phthalate, dibutyl citrate, etc. As a suitable surfactant for this purpose, sorbitan trioleate can be mentioned.

The base preparations mentioned are particularly suitable in connection with the radiation-curable nail polish preparations according to the invention. The above-mentioned radiation-curable nail polish preparations are particularly suitable for use in connection with the aforementioned base preparations due to the fact that the composition of the radiation-curable nail polish preparations, and the way in which they are applied, means that they do not mix with the base coating that has previously been placed on the nails. As a result, it did not become more difficult to release the substrate from the nails by soaking the coated nails in warm water. This is in contrast to the case where an attempt is made to use one of the known nail varnishes in connection with the base coating according to the invention, for example nitrocellulose in an organic solvent system. In this case, the application of the nail polish to the substrate causes the substrate to soften, thereby mixing the layers together. This seriously affects the substrate's ability to release from the nails when soaked in water.

In addition to the aforementioned essential components for the radiation-curable, liquid system, other auxiliary components that do not interfere with the curing process can be added to these preparations. Thus, for example, the preparations may contain pigment dyes, organic solvents (which serve as viscosity-regulating agents), softeners, etc. In these nail polish preparations, auxiliary resins can also be incorporated which do not interfere with the primary curing reaction. As these preparations are made subject to curing by exposure to light, which curing can begin by opening and closing the container in which the material is stored, it is often advisable to add a stabilizer or system to the preparation to extend the product's shelf life.

As further examples of various excipients

that can be embedded in the preparation can be mentioned:

Organic solvents: ethyl acetate, ethanol, isopropyl alcohol hol, methanol, butyl acetate, ethylene glycol dimethyl ether, (ie CH^OCH2~"CH^OCH^), diethylene glycol dimethyl ether (ie CH^OC^C^OC^C^OCH^), methyl ethyl ketone, diethyl ketone, acetone, toluene and proprietary cosmetic solvents.

Pigments:

Plasticizer: dibutyl phthalate, dibutyl citrate, etc. Resins: Santolite (copolymer of equimolar amounts of formaldehyde and p-toluenesulfonamide), vinyl pyrrolidone/vinyl acetate (respectively 50/50 and 35/65 mole percent), Gantrez AN 119 (methyl vinyl ether/maleic anhydride copolymer , molar ratio = 1:1, low molecular weight grade with average molecular weight of 250,000), Gantrez AN 139 (methyl vinyl ether/maleic anhydride copolymer, molar ratio = 1:1, medium high molecular weight grade, average molecular weight of 500,000),- National Starch Resyn 28-2930 (terpolymer of crotonic acid

(10$) and 90% of a mixture of vinyl acetate and the vinyl ester of C-^ q' C^g fatty acids), Elvamide.

Stabilizers: Hydroquinone, p-tert-butylcatechol, .2,6-di-tert-butyl-p-methylphenol, phenothiazine, N-phenyl1-2-naphthylamine.

As mentioned, the nail polish preparations according to the invention can be used in connection with a base coating or a binding layer. As is known, the latter are placed on the nails as a preliminary coating, before the nail polish is applied. They are usually applied with the aim of improving the adhesion of the nail polish to the nail. A typical undercoat or binder that can be used for this purpose is discussed in "Cosmetics, Science and Technology" by Edward Sagarin, Interscience Publishers, Inc..

New York 1957, page 687, "Formula 2 Basecoat".

However, of particular interest in connection with the nail polish preparations in question are the base preparations according to the invention.

As mentioned, these substrate preparations are characterized by the fact that they use a water-soluble or water-swellable polymer system as a film former. This serves to facilitate the removal of the top layer or nail polish when both layers are applied to the nail. Soaking the nails in warm water for a few minutes causes these substrates or bonding layers to harden

swell. The swelling bonding layer or substrate causes the overlying layer of nail polish to lift and be released. A number of different water-swellable polymers are suitable for use in this particular form of binding layer or substrate. Examples of these polymers include nitrocellulose ($14 in regular nail polish), Amphomer 2844910, PVP/VA 535 (vinyl pyrrolidone/vinyl acetate copolymer 50/50 mol percent), PVP/VA 335 (copolymer vinyl pyrrolidone/vinyl acetate 35/65 mol percent), Gantrez AN 119 (methyl vinyl ether/maleic anhydride copolymer, molar ratio 1:1, low molecular weight grade with an average molecular weight of 250,000), Gantrez AN 139 (methyl vinyl ether/maleic anhydride copolymer, molar ratio 1:1, medium high molecular weight grade, >g average molecular weight of 500,000 ), National Starch Resyn 28-2930 (terpolymer of crotonic acid (10 mole percent) and mixture of vinyl acetate and vinyl ester of C1Q-C g fatty acids (90 mole percent), National Starch Resyn 28-1310 (copolymer of vinyl acetate (10 mole percent)/ crotonic acid (90 mole percent). Each of the above-mentioned, water-soluble polymers or combinations thereof can be used in the composition of one of the aforementioned binding layers for use in connection with nail polish according to the invention. Binding corporate or

the substrate preparations will usually consist of 10-20$ polymer solutions in a volatile organic solvent, for example eta-

noi, acetone, cosmetic solvents, etc.

The viscosity of the liquid radiation-curable nail polish preparations according to the invention can vary somewhat. However, it will generally lie in the interval from approx. 20 to 10,000 CPS, measured with a Brookfield viscosirneter model LV with spindle no. 4 and at 25-28°C and 60 revolutions per minute. The preferred viscosity

is approx. 4,300 cPS at 27°C. The viscosity of the system can be varied by

.with the help of a viscosity modifier (for example ethyl acetate, ethanol, isopropyl alcohol, methanol, butyl acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, methyl ethyl ketone, diethyl ketone, acetone, toluene and proprietary cosmetic solvents). The lacquer can be applied with a brush or with the help of an •applicator■equipped with a porous tip. The polish should be applied carefully. Only when the user is satisfied with the nail polish's coverage should she expose the polish to light. The nails are then exposed to light from an actinic light source, preferably an ultraviolet light source. Examples of such light sources include the Type R.S. Sunlamps, carbon arc lamps, Xenon arc lamps, mercury lamps, tungsten halogen lamps etc. However, the most effective curing is achieved by using a light source where the light's wavelength is primarily approx. • 3660Å. When using a light source of the latter kind, the covered nails are exposed to this light for a period of from 10 seconds to 15 minutes. This is sufficient time to harden the nail polish preparation according to the invention so that a suitable hardness and gloss is achieved. A typical light source is a mercury arc lamp of the low-pressure or medium-pressure type with a suitable low-pressure arc tube which provides sufficient radiation with a wavelength of 366OÅ.

The substrate is first applied as a thin coating which is allowed to dry. A Type RS Sunlamp can facilitate the drying or curing of the substrate or bond layer. This will normally take approx. 20 seconds. The nail polish preparation is then applied in the manner described above.

US Patent 3-661,744 relates to a radiation curable liquid composition containing a polymer component, a polythiol component and a radiation cure rate accelerator. In the description, it is stated very generally that these materials can be used as sealants, coverings, adhesives and shaped objects. Example 84 in the patent document appears to be the only place in the description where information is given about the intended use of these materials as coatings, namely as coatings for clay-coated paper, cellophane, aluminum foil, steel plate starting materials, - "Mylar" polyester film, plywood and concrete blocks. The preparations described in the patent do not contain surfactants at all. In trials, it has not been possible to satisfactorily coat nails with preparations of the type indicated in US patent 3-661,744 without using surfactants from a relatively limited group, while on the other hand the preparations are obviously able to cover the various materials discussed in Example 84 without the use of surfactants at all.

This fact has been confirmed by special experiments. By using a nail polish preparation which differed from the nail polish preparation according to the present invention in that it did not contain surfactant, it was possible to obtain a coating even on surfaces made of wood, concrete, metal, glass, clay and aluminum foil. This is in sharp contrast to the preparation's behavior on nails. In this case, the preparation blistered when applied to nails, and it was not possible to form a coating that was suitable as nail polish.

In a very vague and general list of auxiliary additives in column. 11, lines 35-54 of said US patent .3. 66l. 744, which list contains approx. 40 other additives, it is mentioned that a surfactant can be embedded in the preparations to be cured. This seems to be the only place in the description where a surfactant is mentioned. It seems to be a long leap from a hint to a special group of surfactants used in the nail polish preparations according to the invention. The general mention of surface-active substances in US patent 3,661,744 suggests that it is irrelevant which particular surface-active substance is used in the coating system. In contrast to this, it has been shown that only a relatively small group of surfactants are suitable for use in a preparation for use as nail varnish.

As mentioned above, an essential component - of the nail polish ■ according to the invention is the polyene. The polyene component can be represented by the formula:

• where m is an integer and at least 2, and where X is

where f is an integer from 1 to 93 and R is hydrogen, fluorine, chlorine, furyl, thienyl, pyridyl, phenyl and substituted phenyl, benzyl and substituted benzyl, alkyl. and substituted alkyl, alkoxy and substituted alkoxy as well as cycloalkyl and substituted cycloalkyl. The substituents

on the substituted groups can be nitro, chlorine, fluorine, acetoxy, acetamide, phenyl, benzyl, alkyl, alkoxy or cycloalkyl. Alkyl and alkoxy contain from 1 to 9 carbon atoms, and cycloalkyl contains from 3 to 8 carbon atoms.

The groups (a) to (e) are connected to £A] via divalent, chemically compatible, derivative groups. The groups (a) to (e) can be connected to LA3 via a divalent, chemically compatible therein group in the form of 0

Si(R)2, carbonate, carboxylate, sulfone, -0-, -BC-, -N-, alkyl and substituted alkyl, cycloalkyl and substituted cycloalkyl, urethane and substituted urethane, urea and substituted urea, amide.and substituted amide, amine and substituted amine as well as aryl and substituted aryl. R and the substituents have the above meaning, and the alkyl groups contain from 1 to 9 carbon atoms. The aryl groups are either phenyl

or naphthyl, and the cycloalkyl group contains from 3 to 8 carbon atoms. B is a group in the form of -0-, -S- or -NR-.

The group [A] is polyvalent, free of reactive, non-aromatic, unsaturated carbon, free of strongly hydrophobic groups and consisting of atoms in the form of carbon, oxygen, nitrogen, chlorine, bromine, fluorine, phosphorus, silicon and hydrogen.

The polyene component has a molecular weight in the range from approx.• 64 to approx. 20,000, preferably in the interval from approx. 200 to approx. 10,000, and a viscosity in the range of practically 0 to 20 million cP as measured by a Brookfield viscometer at 70°C.

More specifically, the group [Al in the polyene component can primarily consist of alkyl groups, phenyl and urethane derivatives, oxygenated groups and nitrogen-substituted groups. The group LA3 can also be specified by the formula:

where j and k are whole numbers greater than 1, R p is hydrogen or alkyl with 1-9 carbon atoms, R is hydrogen or saturated alkyl with 1-9 carbon atoms, R 4 is a divalent derivative in the form of phenyl, benzyl, alkyl,. cycloalkyl, substituted phenyl, substituted benzyl, substituted alkyl or substituted cycloalkyl, where alkyl, cycloalkyl and substituted groups are defined above.

Examples of general, typical formulas for polyenes which can be used in nail polishes according to the invention are: I. Poly-(alkylene ether) polyol reacted with monoisocyanates to form polyurethane polyenes and related polymers II. Poly-(alkylene ester) polyol reacted with unsaturated monoisocyanates to form polyurethane polyenes and related polymers. III. Poly-(alkylene ether) polyol reacted with polyisocyanate and unsaturated monoalcohol to form polyurethane polyenes and related polymers. In the formulas above, the sum of x + y + z in each chain link is at least 1, P is an integer from 1 upwards, q is at least 2, n is 1 ■ ' at least 1, R is hydrogen, phenyl, benzyl,'alkyl, cycloalkyl or substituted phenyl, and R is CH^=CH, (CH2"^n'hydrogen, phenyl; cycloalkyl or alkyl.

General methods for the production of the above-mentioned polyenes are described in column 7>line 9 to column 8, line 48 in US patent 3,661,744.

Another essential ingredient in the nail polish preparation according to

■the invention is, as stated above, the polythiol. By polytipl is meant here simple or complex organic compounds with many side-styled or end-styled -SH functional groups per average molecule. ■ .

On average, the polythiol must contain two or more -SH- groups per molecule and have a viscosity in the range of practically 0 to .20 million cP, as measured by a Brookfield viscometer at 70°C, alone or in the presence of an inert solvent, an aqueous dispersion, or a plasticizer. Useful polythiols for use in nail polishes according to the invention usually have a molecular weight in the range from approx. 50 to approx. 20,000, preferably from approx. 100 to approx. 10,000.

Such groups of polythiols can be indicated by the general formula R 8 -(SH), where n is at least 2, and R 8 is a polyvalent organic residue which is free of reactive, non-aromatic, unsaturated carbon. Thus, R 8 may contain cyclic groups and heteroatoms, such as N, P and O, and contain primarily carbon-carbon, carbon-hydrogen, carbon-oxygen or silicon-oxygen containing chain bonds that are free of reactive, non-aromatic , unsaturated■carbon.

A group of polythiols which together with polyenes are useful

■to obtain practically odorless polythioether products, which are esters of thiol-containing acids with the formula HS-R^-COOH, where R^ is

an organic residue containing no reactive, non-aromatic, unsaturated carbon, with polyhydroxy compounds of the formula R<10>(OH) ,

■ 10 n ■ where R . is an organic residue containing no non-aromatic, unsaturated carbon, and n is 2 or more. These components will react under suitable conditions to form a polythiol with the general formula:

9 10

where R and R are the organic residues that do not contain reactive, unsaturated carbon, and n is 2 or more.

Certain polythiols, such as the aliphatic monomeric polythiols (ethanedithiol, hexamethylenedithiol, decamethylenedithiol, tolylene-2,4-dithiol and the like) and some polymeric polythiols, such as a thiol-terminated ethylcyclohexyl dimercaptan polymer and the like, and corresponding polythiols, which are easily and normally synthesized on a commercial basis, but with an unpleasant smell, can be used, but many of the end products cannot be accepted from a practical commercial point of view. Examples of polythiol compounds which are preferred on

due to relatively low odor level includes, but is not limited to, esters of thioglycolic acid (HS-CHgCOOH), cx-mercaptopropionic acid

■(HS-CH(CH3)-COOH) and p-mercaptopropionic acid (HS-(CH2CH2COOH) rned polyhydroxy compounds, such as glycols, triols, tetraols, pentaols, hexaols and the like. Particular examples of the 'preferred polythiols' include, but are not limited to, ethylene glycol-bis-(.thioglycolate), ethylene glycol-bis-(p-mercaptopropionate), trimethylolpropane-tris-(thioglycolate), trimethylolporpan-tris-(p-mercaptopropionate), pentaerythritol-tetrakis-'(thioglycolate) and pentaerythritol -tetrakis-(P-mercaptopropionate), all of which are commercially available, as well as dipentaerythritol-hexakis-(^-mercaptopropionate). A particular example of a preferred polymeric polythiol is polypropylene terglycol-bis-(p<->mercaptopropionate), which is prepared by polypropylene terglycol (for example Pluracpl P201) and p-mercaptopropionic acid by esterification.

The preferred polythiol compounds are characterized by a low mercaptan-like odor level to begin with and give reaction practically odorless polythioether end products which are commercially attractive and practically applicable resins or elastomers.

Likewise applicable as a polythiol compound in nail varnishes according to the invention is a group of isocyanurate-containing polythiols which are described in US patent 3,676,440. These can generally be indicated by the formula: where R is an organic, divalent residue. Usually, the total number of carbon atoms in R is not higher than 13. As typical examples of these organic residues, the following can be mentioned:

where y is hydrogen, methyl or ethyl, and z is an integer from 0 to 10. As examples of these isocyanurate-containing polythiols can

the following compounds are mentioned: tris-(3-mercaptopropionate) ester of tris-(2-hydroxyethyl)-isocyanurate. tris-(2-mercaptoethyl)-isocyanurate j tris-(2-mercaptoethoxyethyl)-isocyanurate, tris-(2-thiocarboxy-ethyl)-isocyanurate, tris-(2-mercaptoethyl)-ester of tris-(2-carboxy-" ethyl)-isocyanurate, tris-(11-mercaptodecanoate)-ester of tris-(2-hydroxyethyl)-isocyanurate} tris-(3-mercaptopropionate)-ester of tris-(2-hydroxypropyl)-isocyanurate as well as tris-( 2-mercaptopropionate) ester of tris-(2-hydroxyethyl) isocyanurate.Certain particular polyenes and polythiols are of particular interest and are preferred in the practice of the present invention.

These compounds are mentioned below together with a brief description of how they can be produced. For convenience of identification, these substances are designated with a polythiol or polyene number.

Polythiols

Polythiol No. 1: pentaerythritol-tetrakis-03-mercaptopropionate).

This material is produced by the esterification of 1 mol of pentaerythritol with 4 mol of £-mercaptopropionic acid.

Polythiol No. 2: tris-(2-hydroxyethyl)-isocyanurate-tris-(^-mercaptopropionate ). This material is produced by esterification of 1 mol of tris-hydroxyethyl isocyanurate with 3 mol of 3-mercaptopropionic acid.

Polythiol No. 3: Trimethylolpropane-tris-(/3-mercaptopropionate).

This material is produced by esterification of trimethylolpropane with 3 mol of β-mercaptopropionic acid.

Polythiol No. 4: dipentaerythritol-hexakis-(3-mercaptopropionate) This material is prepared by esterification of dipentaerythritol with 6 mol /^-mercaptopropionic acid.

Polyenes. Polyene #1: This polyene is a triene. It is produced from allyl alcohol, malic acid and toluene diisocyanate. To produce the polyene, 2 mol of allyl alcohol is first reacted with malic acid to form diallyl maleate esters. One is then transferred separately

mole of allyl alcohol with one mole of toluene diisocyanate in such a way that a monoadduct with the formula

of these two compounds are formed. One mole of this adduct is then reacted with one mole of diallyl maleate ester to form a desired tri-ene product having the formula:

Polyene #2: This polyene is a tetraene. It is produced'

from allyl alcohol, malic acid and toluene diisocyanate (TDI).

One can either use the 2,4- or 2,6-TDI isomer or mixtures thereof. To produce the polyene, diallyl maleate is first produced by esterification. Two moles of diallyl maleate ester are then reacted with one mole of TDI to form the product. A small amount of dibutyltin dilaurate is used as a catalyst. Polyene No. 2 has the following formula:

Polyene #3: This polyene is a diene. It is produced from bisphenol A and allyl chloride by a common esterification method. The formula is:

Polyene No. H: This polyene is made from malic acid, allyl alcohol and isophorone diisocyanate. Isophorone diisocyanate has the following formula:

The polyene is produced by reacting two moles of diallyl maleate

with one mole of isophorone diisocyanate in the presence of a small amount of dibutyltin dilaurate catalyst. The polyene is tetrafunctional and has the following

end' formula:

Polyene #5: This polyene is a diene. It is produced from TDI and allyl alcohol. Two moles of allyl alcohol are reacted with one mole of TDI in the presence of a small amount of dibutyltin dilaurate catalyst. The polyene has the following formula: '. Poly #6: This poly is a tri-one. The polyene is more specifically called triallyl isocyanurate. Its formula is the following:

The relative amounts of polyene and polythiol which can be embedded in nail lacquers according to the invention can vary considerably. This seems best expressed by bringing the amount of polythiol into relation with the amount of polyene by means of a mole ratio, i.e. the ratio between SH groups and unsaturated groups and bringing the total amounts of polythiol and polyene into relation with the total amount of the preparation, which a weight percentage value based on the total weight of the preparation. In accordance with this, the molar ratio between polythiol and polyene will usually lie in the interval from approx. 0.50 to 1.0 and approx. 1.5 to 1.0, preferably in the range from approx. 0.67 to 1.0 and approx. 1.0 to 1.0. Moreover, the mixture of polythiol and polyene usually amounts to between approx. 10 and approx. 99 percent by weight of the total nail polish preparation.

A third essential component in the preparation according to the invention is the radiation curing speed accelerator. It is within the scope of the invention that the radiation curing rate accelerator can be found as a special compound, such as azobenzene, as a mixture of two or more special compounds, such as benzophenone, benzanthrone, anthrone and dibenzosuberone, carbon tetrachloride and phenanthrene and the like or in chemical combination form within the molecular structure of either the pblyene or the polythiol. As an example of the latter condition, where the radiation curing rate accelerator is present not as a particular compound, but in the form of a combination of the polyene component, the following compound containing four unsaturated, reactive carbon-carbon groups and one diarylketone group per molecule.

The polyene, polythiol or radiation cure rate accelerator can be formed in situ in the radiation curable composition.

Particularly useful for use in nail polishes according to the invention are chemical radiation curing rate accelerators, such as benzophenone, acetophenone, acenaphthenquinone, o-methoxybenzophenone, thioxanthen-9-onejxanthen-9-one, 7-H-benz-UdeJ-anthracen-7-onejdibenzosuberone, 1 -naphthaldehyde, 4,4'-bis-(dimethylamino)-benzophenone, fluoren-9-one, 1'-acetonenaphthone, 2'-acetonenaphthone, anthraquinone, 1-indanone, 2-tert-butylanthraquinonejvalerophenone, hexanophenone, 8-phenyl- butyrophenone,

p-morpholinopropiophenone, 4-morpholine-benzophenone, 4'-morpholindeoxy-benzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxyacetophenone, benzaldehyde, <^-tetralone, 9~acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthrene , 3-acetylindole, 1,3,5-triacety1-benzene and the like, including mixtures of these - to a strong reduction of the lighting time.

The beam hardening rate accelerators are usually added

in an amount of from approx. 1 to approx. 10 percent by weight of the photo-curable preparation calculated from the total weight of the nail polish preparation. Preferred radiation cure rate accelerators are aldehyde and ketone carbonyl compounds having at least one aromatic nucleus directly attached to the carbonyl group, for example benzophenone.

In order to achieve maximum strength, resistance to solvents, shrinkage, heat and lack of stickiness, the reaction components consisting of the above-mentioned polyenes and polythiols are combined in such a way that upon curing the polymer systems a solid, cross-linked is formed. three-dimensional polythioether polymer network. In order to achieve such strong network formation, the individual polyenes and polythiols must have a functionality of at least 2, and the sum of functionalities for the polyene and polythiol components must always be greater than 4. Mixtures of polyenes and polythiols containing such a functionality are usable in the nail polish preparations according to the invention.

Conventional curing inhibitors or retarders can be used to stabilize the components or the curable preparations to prevent curing from starting too early. Examples of such inhibitors include hydroquinone, p-tert-butylcatechol, 2,6-di-tert-butyl-p-methylphenol, phenothiazine, N-phenyl-2-naphthylamine and inert gas atmospheres, such as helium, argon , nitrogen and carbon dioxide.

A fourth essential component of the nail polish preparations according to

■ the invention is one or more of a certain group of specific surfactants. Among the preferred surfactants in this group can be mentioned sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, pentaerythritol dioleate, pentaerythritol trioleate and non-ionic fluorocarbon esters, for example of the type manufactured by DuPont under the trade name Zonyl.

The surfactants mentioned below are less effective, but can nevertheless be used in the nail polish preparations according to the invention: alkenyldimethylethylammonium bromide, di-"coco"-dimethylammonium chloride, quaternary imidazolinium salt of stearic acid, glyceryl monooleate, glyceryl dioleate, glyceryl trioleate and polyglycerol ester of oleic acid. These surfactants are soluble in the nail polish preparation system, but this does not seem to be sufficient to explain the substance's applicability, as many surfactants that are soluble in the system without being able to fulfill the purpose were tried.

The applicability of a surface-active substance in the preparation according to the invention was tested by embedding a standard amount of the surface-active substance (usually approx. 1 percent by weight calculated from the total weight of the nail polish preparation) in the preparation containing a standard amount of polyene, polythiol and beam curing accelerator and observe the tendency of the preparation to form droplets when applied to the surface of the nail. Up to 70 surfactants were tested using this method to determine applicability, and among the tested surfactants were several substances that were closely related to the above-mentioned applicable surfactants. For some inexplicable reason, these closely related surfactants proved to be unusable. Thus, glyceryl monolaurate and glyceryl distearate had no good effect, and glyceryl monooleate a doubtful effect. When sorbitan sesquioleate, sorbitan diolst and sorbitan trioleate proved to be useful, similarly sorbitan monooleate had no effect. Furthermore, unlike pentaerythritol dioleate and trioleate, pentaerythritol distearate cannot be used as such, since

the stearate is a solid substance that is not soluble in the substance used

.system.

The surfactants listed below have been tested in accordance with the above criteria and have been found to be unusable, either because they do not improve the ability of the nail polish preparations to wet nails or are insoluble in the

current preparation:

Cationic

Do.de cy ltrimety lammonium chloride

Hexadecyltrimethylammonium chloride Octadecyltrimethylammonium chloride

"Tallow"-trimethylammonium chloride

Cetyltrimethylammonium bromide

Cetyldimethylethylammonium bromide

"Coconut" trimethylammonium chloride

■"Soya"-trimethylammonium chloride

Dilauryldimethylammonium bromide

Methyldpdecylbenzyltrimethylammonium chloride Alkyldimethyl-3j4-dichlorobenzylammonium chloride Quaternary imidazolium salts (of coconut oleic acids) Lauryl isoquindium bromide

Non-ionic

Glyceryl monolaurate

Glyceryl dilaurate Glyceryl distearate

Glyceryl monoricinoleate

Modified glyceryl phthalate resin Polyoxyethylated castor oil (20' mol ethylene oxide) Polyoxyethylated castor oil (40 mol ethylene oxide)

.Polyoxyethylated sorbitol monolaurate Polyoxyethylated sorbitan monolaurate Polyoxyethylated sorbitan monopalmitate

Polyoxyethylated sorbitan monostearate; Polyoxyethylated tert-octylphenol

Polyoxypropylene + 80% ethylene oxide

Esters of polyoxyethylated sorbitol, sorbitan or sorbjd:

Polyoxyethylated sorbitan monostearate

(20 mol ethylene oxide)

Polyoxyethylated sorbitan tristearate

(20 mol ethylene oxide)

Polyoxyethylated sorbitan monooleate Polyoxyethylated sorbitan monooleate Polyoxyethylated sorbitan monooleate

(20 mol ethylene oxide)

Polyoxyethylated sorbitan trioleate

(20 mol ethylene oxide)

Esters of other polyols:

Sorbitan monolaurate

Sorbitan monooleate

Sucrose monomyristate Sucrose monostearate

Sucrose monooleate

Sucrose dioleate

Sucrose Monothallate

Pentaerythritol distearate

Pentaerythritol tetrastearate

Ethers of polyoxyalkene glycols:

tert-octylphenoxyethanol

Polyoxyethylated tert-octylphenol (3 mol ethylene oxide)

Polyoxyethylated tert-octylphenol (5 mol ethylene oxide) Polyoxyethylated tert-octylphenol (7-8 mol ethylene oxide) Polyoxyethylated tert-octylphenol (12-13 mol ethylene oxide)

Polyoxyethylated tert-octylphenol (16 mol ethylene oxide)

■Polyoxyethylated tert-octylphenol (30 mol ethylene oxide) Polyoxyethylated tert-octyophenol (40 mol ethylene oxide) Polyoxyethylated nonylphenol (1-2 mol ethylene oxide) Polyoxyethylated nonylphenol (4 mol ethylene oxide) Polyoxyethylated nonylphenol (6 mol ethylene oxide)

Polyoxyethylated nonylphenol (8 mol ethylene oxide) Polyoxyethylated nonylphenol (9-10 mol ethylene oxide) Polyoxyethylated nonylphenone (10-11 mol ethylene oxide) Polyoxyethylated nonylphenol (12 mol ethylene oxide)..

Polyoxyethylated nonylphenone (15 mol ethylene oxide)

Oleates:

Dioleate of polyethylene glycol (200)

Dioleate of polyethylene glycol (400)

Dioleate of polyethylene glycol (600)

The amount of the surface-active ingredient that can be incorporated into the preparation according to the invention can vary somewhat. Usually it will amount to between approx. 0.5 and 1.0 percent by weight of the total weight of the preparation.

Substrate preparations

Approach:

The resin is placed in the solvent and the mixture is stirred until the resin is dissolved.

Example B- 2

Procedure: As stated under example B-l.

Example B- 3

Approach:

As stated under example B-l. ■ ' Example B- 4

Approach:

As stated under example B-l. Example B- 5

Approach:

As stated under example B-l.

Example B-6.

Approach:

As stated under example B-l.

Example B- 7

Approach:

As stated under example B-l.

Example B- 8'

■Procedure: As stated under example B-l.

Nail polish preparations

The following examples are examples of nail polish preparations according to the invention for use in connection with the base preparations according to the invention.

Example L-l

All the ingredients listed below were placed in a mixing vessel and thoroughly stirred. The mixture was then shaped to ensure the formation of a homogeneous product with evenly distributed solids:

When applying this preparation to the nails, the nails were first cleaned with a solvent to remove all dirt and decomposed materials. A substrate according to the invention was then placed on the nails. A coating of the nail polish described above was then applied with a brush to the nails. The coated nails were then exposed to light from a 4FT5BL lamp for from 1 to 11M minutes. This light source emits light with a wavelength in the range from 3500 to 3880 Å. At the end of the radiation treatment, the nail polish was

.cured to a tough coating.

The following examples are given in tabular form. The preparations were composed using the same procedure as described in example L-1. Corresponding results were obtained.

The following examples are also given in tabular form. The preparations were prepared using the method stated in example L-1. These preparations were placed and hardened on nails using the same method and apparatus as described in example L-1. The percentage content of polyene and polythiol in the preparation is given as the combined weight of polyene and polythiol, the relative amount of polyene in relation to polythiol in the preparation being expressed as the molar ratio between polythiol and polyene, i.e. the molar ratio between unsaturated groups and SH- groups.

Procedure for applying and removing substrate and nail polish preparation.

Example M- I

The nails were first cleaned with solvent, i.e. acetone or ethyl acetate to remove all dirt and waste materials. Underlay preparation B-5 was then applied to the nails. The product was applied with a brush or rubbed onto the nail using a cotton ball and allowed to air dry. A coating of nail polish preparation L-1 was then applied with a brush to the nail. The coated nails were then exposed to light from a 4FT5BL lamp for 1 to 1\1M minutes. This light source emits light with a wavelength in the range from 3500 to 3800 Å, predominantly light with a wavelength of approx. 3660 Å. At the end of this exposure, the nail polish had hardened to a tough coating.

To remove the coating, the nails were soaked in warm water for approx. 4 minutes. The nails were removed from the water and the varnish was peeled off

of; In case of resistance to the peeling, the nails were soaked for a longer period of time.

The same method as in example M-1 was used in connection with all substrate preparations B-1 to B-4 and B-6 to B-8

which is described above in connection with each of the nail polish preparations L-2 to L-32 which are also described above. The results obtained correspond to the results obtained with substrate B-5

and nail polish L-l.

It will be clear to those skilled in the art that countless variations and modifications of the particular embodiments of the invention

which is described above can be devised without deviating from the scope of the invention, and all such further variations and modifications fall within the scope of the invention as described in the following claims.

Claims (14)

1.. Procedure for applying a coating to nails, characterized in that one (a) applying a liquid substrate preparation containing a water-soluble or water-swellable, flexible film-forming polymer on the nails, (b) allowing the composition to dry on the nails whereby a film of the water-soluble or water-swellable polymer is deposited on and adheres to the nails; (c) applying another layer of a liquid nail polish to the dried film of water-soluble or water-swellable polymer, and (d) hardens the nail polish to a solid coating. 2. Method in accordance with claim 1, characterized in that the nail polish is a radiation-curable nail polish preparation which is designed to polymerize when illuminated with actinic light, and that the curing consists in exposing the layer of radiation-curable nail polish preparation to the light from an actinic light source in a sufficient time period for curing the nail varnish preparation in such a way that the varnish polymerises into a hard layer which covers and adheres to the undercoat coating. 3- Method in accordance with claim 1 or 2, characterized in that the water-soluble polymer is soluble in water at least to an extent of 1% by weight. 4. Method in accordance with one or more of the preceding claims, characterized in that the water-soluble polymer is a copolymer of vinyl pyrrolidone and vinyl acetate. 5- Process in accordance with claim 1-33, characterized in that the water-soluble polymer is a copolymer of methyl vinyl ether and maleic anhydride. 6. Method in accordance with claims 1~3> characterized in that the water-soluble polymer is a terpolymer of crotonic acid, vinyl acetate and a vinyl ester of a higher fatty acid with from 10 to 18 carbon atoms. 7. Method in accordance with claims 2-6, characterized in that the liquid, radiation-curable nail polish contains a polyene component, a polythiol component and a radiation curing speed accelerator. 8. Method in accordance with claims 2-7, characterized in that the liquid, radiation-curable nail polish preparation also contains a surfactant in the form of sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, pentaerythritol dioleate, pentaerythritol trioleate, glyceryl mono-oleate, glyceryl dioleate, glyceryl trioleate, polyglycerol ester of oleic acid, alkenyldimethylethylammonium bromide , -di-"coco"-dimethylammonium chloride, non-ionic fluorocarbon ester and quaternary imidazolinium salt (of stearic acid). 9. Method in accordance with claim 7 or 8, characterized in that (a) the polyene component is a terminally unsaturated polyene with the formula: where m is an integer of at least 2, and where X is where f is an integer from 1 to 9, R is a group in the form of hydrogen, fluorine, chlorine, furyl, thienyl, pyridyl, phenyl, substituted phenyl, benzyl, substituted benzyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl or substituted cycloalkyl, the substituents on the substituted groups consisting of nitro, chlorine, fluorine, acetoxy, acetamide, phenyl, benzyl, alkyl, alkoxy, or'' cycloalkyl, where alkyl and alkoxy contain from 1 to 9 carbon atoms, and cycloalkyl from 3 to 8 carbon atoms, where the group CA] ■is free of reactive, non-aromatic, unsaturated carbon, free of strongly hydrophilic groups and is a polyvalent, chemically compatible group in the form of carbonate, carboxylate, carbonyl, ether, silane, silicate, phosphonate, phosphite, phosphate , alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, urethane, substituted urethane, urea, substituted urea, amine, substituted amine, amide, substituted amide, hydroxyl, a heterocyclic carbonaceous group, as well as mixtures thereof, the substituents on the groups does the above mean? -which component has a molecular weight in intervals from approx. 64 to 20,000 and a viscosity in the range of practically 0 to 20 million cP at 70°C, and that (b) the polythiol component has. a molecular weight in the range from approx. 50 to approx. 20,000 and has the general formula: where R 8 is a polyvalent organic residue which is free of reactive, non-aromatic, unsaturated carbon, and n is at least 2, the sum of m and n being greater than 4, the en/thiol molar ratio being chosen in such a way that a cross-linked, firm, self-supporting, hardened product. 10. Method in accordance with claims 2-9, characterized in that the liquid radiation-curable nail polish preparation also contains a radiation-curing speed accelerator in the form of arylaldehyde, diaryl ketone, alkylaryl ketone, triarylphosphine or a mixture of carbon tetrahalide and polynuclear, aromatic hydrocarbon. 11. Method in accordance with claim 10, characterized in that the liquid, radiation-curable nail polish pre- ■ preparation contains from approx. 0.5 to 1.0 percent by weight thereof, above surfactant, from approx. 1 to approx. 10% by weight of beam the curing speed accelerator and from approx. 1 to approx. 98>5 percent by weight of a mixture of the polythiolene and the polyene, the molar ratio between polythiol and polyene in the mixture lies.in inter selected from approx. 0.50:1.0 to approx. 1.5:1-0. 12. ■ Process in accordance with claim 7, 9 or 11, characterized in that the polyene is or or 13- Method in accordance with claims 7-12, characterized in that the polythiol is pentaerythritoltetrakis-(j3-mercaptopropionate), tris-(2-hydroxyethyl)-isocyanurate-tris-O-mercaptopropionate), trimethylolpropane-tris-(i^-mercaptopropionate ) or dipentaerythritolhexakis- O>-mercaptopropionate). 14. Method for removing the nail polish applied in the preceding claims from nails, characterized by soaking the coated nails in water for a period of from 3 to 6 minutes, until the water-soluble film has swelled to a sufficient extent that the coating can be lifted off the nail, after which the coating can be pulled off the nail. 15- ' Radiation-curable, liquid nail polish preparation, comprising a polyene component, a polythiol component, a radiation curing rate accelerator and a surfactant which is soluble in the liquid preparation and which consists of at least one of the compounds sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, pentaerythritol dioleate, pentaerythritol trioleate, glyceryl monooleate, glyceryl dioleate, glyceryl trioleate, polyglycerol ester of oleic acid, alkenyldimethylethylammonium bromide, di-"coco"-dimethylammonium chloride, nonionic fluorocarbon esters or a quaternary imidazolinium salt (of stearic acid), characterized in that (a) the polyene component is a terminally unsaturated polyene of the formula:' where m is an integer of at least 2, and-where X is where f is an integer from 1 to 9, R is a group in the form of hydrogen, fluorine, chlorine, furyl, thienyl, pyridyl, phenyl, substituted phenyl, benzyl, substituted benzyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl or substituted cycloalkyl, wherein the substituents on the substituted groups consist of nitro, chlorine, fluorine, acetoxy, acetamide, phenyl, benzyl, alkyl, alkoxy- or cycloalkyl, where alkyl and alkoxy contain from 1 to 9 carbon atoms, and cycloalkyl from 3 to 8 carbon atoms, where the group A is free of reactive, non-aromatic, unsaturated carbon, free of strongly hydrophilic groups and is a polyvalent, chemically compatible group in form. of carbonate, carboxylate, carbonyl, ether, silane, silicate, phosphonate, phosphite, phosphate, alkyl, substituted alkyl, cycloalkyl, substituted, substituted cycloalkyl, aryl, substituted aryl, urethane, substituted urethane, urea, substituted urea,, amine, substituted amine, amide, substituted amide, hydroxyl, a heterocyclic carbon-containing group, as well as mixtures of these, the substituents on the groups having the meaning indicated above, which component has a molecular weight in intervals from approx. 64 to 20,000 and a viscosity in the range of practically 0 to 20 million cP at 70°C, and that (b) the polythiol component has a molecular weight in the range from about 50 to approx. 20,000 and has the general formula: where R g is a polyvalent organic residue which is free of reactive, non-aromatic, unsaturated carbon, and n is at least 2, the sum of m and n being greater than 4, the en/thiol molar ratio being chosen in such a way that a cross-linked, firm, self-supporting, hardened product. 16. ■ Preparation in accordance with claim 15, characterized in that the radiation curing speed accelerator comprises at least one of the compounds of arylaldehyde, diaryl ketone, alkylaryl ketone, triarylphosphine or a mixture of carbon tetrahalide with a polynuclear, aromatic hydrocarbon. 17- Preparation in accordance with claim 15 or 16, characterized in that it contains from approx. 0.5 to approx. 1 percent by weight of the surfactant, from approx. 1 to approx. 10% by weight of the beam hardening rate accelerator and from approx. 1 more about. ,98.5% by weight of a mixture of the polythiol and the polyene, the ideal ratio between the polythiol and the polyene in the mixture being in the interval from approx. 0.50:1.0 to approx. 1.5:1.0. l8. Preparation in accordance with claims 15-17, characterized in that the polyene is or 1'9. Preparation in accordance with claims 15-18, characterized in that the polythiol is at least one of the compounds pentaerythritol- . tetrakis-(&-mercaptopropionate), tris-(2-hydroxyethyl 1 )-isocyanurate-tris-(£-mercaptopropionate), trimethylol'lpropane-tris-(/3-mer cap t opropionate) or dipentaerythritol hexakis- Gs-mercaptopropionate).