DE2428172A1 - PROCEDURES FOR PULLING HUMAN NAILS AND COMPOSITIONS - Google Patents

Description

Method of coating human nails and assembling-} "■ · ■■ -. I

tongues for it |

The invention relates to a method for coating human _; some nails and resin compositions that can be used for this purpose. In addition, the invention is also directed to a method of removing this nail coating.

It has long been the practice to first apply one to the human nails

Apply base coat to allow for better acceptance of the < "" _ ■ - "■". i

Prepare nail varnishes or glazes to support the build-up of a certain layer thickness and the adhesion of the glaze ^! or to enlarge the nail varnish on the human nails. The known base coating compositions generally have a 10% strength solution of nitrocellulose as a film former. If ! this composition is applied to the nails and is dried and then coated with a nail polish, which is also!

-2 -

is dried, a nail coating is obtained which is very difficult to j ! is removed. Ordinarily, to remove these coatings or- j Chemical solvents required, which lead to degreasing and

so as to prevent dehydration of the nails during the removal of the nail over-j

tend to pull. i) This is of course an undesirable result. j

A wide variety of nail polish compositions are known ^! and available in the market. These nail polishes are generally

; ο ι

■ mean from complicated systems that contain at least six to eight j contain various components. Typically they contain

■ 'I

a main film former (e.g. nitrocellulose), solvents (e.g. butyl acetate, ethyl acetate, toluene and ethyl alcohol, which are all inflammable), pigments that can color the nails, natural _f and / or synthetic resins that support the film-forming properties of the primary film former, and certain

! Materials that support the wetting ability of the film with respect to the nail. All of the aforesaid ingredients must be critically coordinated in order to achieve a to get good nail polish. Even if this can be achieved, however, even the best of the known nail polishes do still have many disadvantages.

Although the adhesion of the nail varnishes available on the market to the nail surface is generally good, these nail varnishes show flaking and cracking already a few days after their application. Da-the paints available on the market by evaporation

409882 / 1U9. --3 -

^- * ο -

drying of solvents, from the outside in, ^are: beyond the gloss properties of the resulting surface-

i ■ '■■■■■■■■■ = ■. ι

! before very bad. In addition, there are usually several layers

ι j

ι required to have good color coverage and decent glare7

'to achieve business. The application of successive nail

■ ': ■ ■■ - ■■■■ .- ■■'".!

^r layers of varnish on the initial layer mean that the!

1 - ■ "- ■" ■ - ■ - "." ■■ '

Initial layer begins to flow. Therefore the nail polish must be used: Work particularly carefully when applying the second layer th. When applying several layers, the total dry,

extremely long during the spring season. _:

j In addition, the user must work quickly and carefully when processing the known products because of the evaporation of solvents. Failure to do so can result in premature curing and good, smooth coverage of the nail cannot be achieved. Also, because of the: solvent evaporation, the user will usually throw away a nail polish bottle before . ■; ..- _ -. ■. ■ i

has used all of its contents as the nail polish in the vial dries up.

The nail varnishes available on the market are generally used removed with the help of solvents. As these are usually fat solvents they can degrease and dry out both the nails and the surrounding skin. Also show the commercial available wagon varnishes have a poor resistance to-!

: i

with abrasives and can therefore easily be cleaned by cleaning!

AO988 2 / 1U 9 - 4 -

scouring agents are scratched and worn away. There is also a retouching commercial nail polishes are not possible on individual nails, as the surface parts that are not retouched Dull compared to the freshly applied surface areas and appear scratched.

J It is now the object of the present invention to provide a method

of the type mentioned above, which does not have these disadvantages.

This object is achieved in that

a) a liquid base coat composition is applied to the nails containing a water-soluble or water-swelling and flexible film-forming polymer;

b) the composition is dried on the nails, whereby on the nails a film of the water-soluble or in water swelling polymer is deposited, which attaches to the nails

■ is liable;

c) on the dried film of the water-soluble or water-swelling polymer, a second layer in the form of a liquid gen nail polish is applied and

d) the nail polish is hardened into a solid nail polish layer.

The finished nail coating is therefore a two-layer system in which

409882 / 1U9 - 5 -

! the base layer of a water-soluble or water-smoldering

i i

; lenden polymer and the second layer consists of one of one. ; Nail polish composition consists of cured hard layer. the

.] ■■ '■■. ^l

i base coat composition is applied in a solvent; \ brought, while the second layer preferably consists of a photo j

\ I

; hardening nail polish composition is built up. . |

i. ί

It was also found that after the application of the protruding ^!

i starting the above-mentioned base coating composition on human nails!

ι ι

i and subsequent drying, after coating the dried i

! Base coat composition with a photo-curing nail polish!

around subsequent hardening of this lacquer layer by exposure! I with a suitable light source the base coat and the nail '■

A layer of varnish can be easily removed by simply soaking the nails in water for a short time. Characterized deri base coat is released from the nail, so that the entire coating \

can be easily peeled off. ^:

■ ·

A special feature of the present invention is the use j formation of a photo-curable polymer system, which is described in more detail below is described as a main film former instead of the usual film former, such as nitrocellulose. The photocurable system is less complex than the usual nitrocellulose system. During the Ordinary nail polish contains at least nine components, that is

at least
system according to the invention with / four components. Furthermore

the well-known nail polishes are flammable and due to the explosive

^! 409882 / 1U9. ₆ _

Because of the character of the nitrocellulose, they must be treated with special care fait to be handled. The photocurable system according to the present invention

The invention contains no solvents and can therefore be relatively can be safely assembled and processed.

Because the process of setting the photo-curable nail polish is a solvent evaporation is not involved, becomes a smooth flawless

; Surface built with extremely high gloss. Gloss measurements have j ι. i

[confirms this observation. Complete coverage can be

can be achieved with two layers. Furthermore one dries! i. ■ i

ι every layer completely up in less than a minute, while I when applying two layers of the known nail polish ten;

, I.

Minutes and more pass. It appears as if red pigments j still shorten the hardening time; color washing and staining [of the nails could not be determined. In contrast to the bey

(Known nail polishes are used when applying another layer of j of the photo-curable nail varnish according to the invention on already existing cured layers neither softens nor damages them.

This means that fashionable nail designs can be placed on the pig- I mented lower layer possible. j

When using the composition according to the invention, it stands the user is completely free to work slowly and carefully and still cure the layer in less than a minute, if she is satisfied with the results she has achieved. In addition, since there is no solvent in the system;

409882/1149 - 7 - "

do not dry out the polymer in the vial either. But it will cure if it is not protected from light irradiation. Finally, the polymer film formed according to the invention has one; excellent abrasion resistance and increased resistance to scratching.

The compositions according to the invention also allow retouching too, which is a great advantage. A nail on which the pre-f lying composition three or four days after an initial up bring the coating to be coated again, can not of. others Nails can be distinguished, their coatings by the specified amount of time are older. The nail polish compositions can be

soft nails can be removed in warm water. There are no ^ solvents required to be used which degrease and dry out the nails, as is characteristic of the known nail polish compositions the case is.

The basecoat compositions are - as already mentioned - thereby characterized in that they contain a water-soluble or in Water swelling polymer system is used as a film former. These allow the nail polish to be removed if both the Base coat as well as the photo-curable nail polish on the nail are upset. Soaking the coated nails in hot water, preferably warm water, for a few minutes to a swelling of the base coat with the result that both the nail varnish layer covering the base coat and the

'4098827 VU9 - 8 -

The base coat itself can be lifted and removed from the nail.

> The expression "polymer swelling in water" is used in this context to identify a polymeric material,
that can absorb a certain amount of water without being dissolved in the water

Izu become. This water uptake is accompanied by an increase in volume

of the polymeric material. The term "water-soluble polymer" is used here to denote a polymer
which is at least about 1% by weight soluble in water.

'The liquid photo-curable nail polish is preferably a liquid

i]

Sige composition with at least one polyene component and ι

• i

a polythiol component is used. It is also possible that j 'also has a surface-active substance in the form of at least
one of the members of a group to be determined more precisely! · is used. Finally, an accelerator for the photo-hardening rate can also be added. |

That the above mentioned. Components containing liquid sy- j stem is adjusted so that it forms a cohesive film when it applied to human nails and exposed to actinic light j

I will. UV light is preferably used (eg 366o R).

{A class of water-soluble or water-swelling polymers,
which is particularly advantageous when carrying out the invention

409882/1 U9 _ ₉ ι

ι moderate process can be used as water-soluble:

'or polymers swelling in water are described, which by; 'Polymerization of one or more vinyl compounds of the following.

the formula can be made::

^R l

!wherein

(I) ^R 3

• n

(a) R- hydrogen, alkyl _f phenyl, halonide or
Is pyrrolidonyl (2 ^U , 2);

N-

(b) R _{2 is} hydrogen, alkyl, phenyl, halo poison, -COOH

or ι is j
- C—

(c) R _{3 is} hydrogen, alkyl, carboxyalkyl, phenyl or
Is halegonide;

(d) X hydrogen, -COO-alkyl, COOH-O-alkyl, -CN,

Is halegonide or g;

—C—

(e) η takes the value zero or 1 and

Cf) η only equals 1 if both R ^ and i

40988271 U9 '\

- Io -

X are equal to II,
-ΟΙ Within this monomer group there is a preferred monomer j ; Oi

; ren class having the same general given by the above formula (I)

; j

my formula has. In this case, however, R ₁ , R ^ ₅ -R _{3 have} j

and X have the following _values:;

(a) R ₁ is hydrogen or pyrrolidonyl; !

O: '

Cb) R ₉ is hydrogen, alkyl, -COOH or j; ^;

-C- j

(c) R ₃ is hydrogen; and '■■

(d) X is -COO-alkyl; -COOH, hydrogen, -CN or | .j

! The term "polymer" is used in the present application in its

j i

j Basic meaning uses and covers all polymer substances that-from | j the polymerization of one of those described by formula (I); Monomers or a mixture of the monomers described by the formula can originate. Therefore, both the homopolymers,

the copolymers, the terpolymers, the tetrapolymers, etc. covered j will. · {

If R ₁ , R ₂ or R ₃ in the above formula (I) is an alkyl group or the alkyl moiety (alkyMnoiety) is an alkyl group i

containing complex group (e.g. carboxyalkyl) contains the

i alkyl group or the alkyl part preferably 1 to 6 carbon atoms

me, e.g. methyl, ethyl, n-propyl, i-propyl, η-butyl, t-butyl and

409882/1 U 9 - 11 - j

j n-hexyl. Also, every other Substi -J designated as alkyl contains tuent from 1 to 6 carbon atoms, e.g. methyl, ethyl, n-propyl, ί

; -; ■ -., ■■. Ί

i ^ propyl, η-butyl, t-butyl, n-hexyl. If R ^, R ₀ , R, or X is | 12 3,

Halegonid is, Cl, Br, E, J are possible. |

\ .- ■■ '■' ■■■ '■■■!

1 ■■ "■■""■■ ^Λ !

To name preferred monomers that obey the formula (I),

- - ■ I

the following are to be listed: vinyl acetate, crotonic acid, j vinylpyrrolidone, methyl vinyl ether, maleic anhydride, maleic acid, acrylic acid, acrylonitrile Other special water-soluble or
Polymers which swell in water and which are used individually or in combination to carry out the process according to the invention
are the following:

Amphomer 2 8U> + 9-ioj PVP / VA 5 35 (vinylpyrrolidone / vinyl acetate copolymer 5o / 5o mol%); PVP / VA 3 35 (vinyl pyrrolidone / vinyl acetate copolymer 35/65 mol%) i Gantrez AN 119 (methyl vinyl ether / maleic acid ■ anhydride copolymer in a molar 1: 1 relationship with low molecular weight; average molecular weight 250, ooo); Gantrez AN 139 (methyl vinyl ether / maleic anhydride copolymer in a molar ratio of ¹ 1: 1, average molecular weight; average molecular weight 5,000); Gantrez AN 169; Gantrez ES 42 "5 (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 Resyn 26- 29o5; National Stareh | Reeyn 2261; National Stareh Resyn 28-293o (terpolymer of crotonic acid (Io%) and a mixture of vinyl acetate and vinyl ester of

M2 / 1U9 -12- i

C _lo -C ₁₈ fatty acids (90%) in mol%; see U.S. Patent 2,996,471);

j National Starch Resyn 28-13Io (copolymer of vinyl acetate (Io%)

j and crotonic acid (90%) in mol%). Photo-curable polymers can j can also be used when they swell in water.

The water-soluble or water-swelling polymers that

j can be used according to the invention with particular advantage,

j are further characterized by the fact that they are filmbil- [Dende polymers which can be distinguished from rigid films flexi-j

ble films form. As these polymers are used to form a film which adheres to human nails and which at the same time forms a base layer on which a photo-curable To be able to adhere to the polymer cover layer, it is important that the water-soluble or water-swelling polymer is a polymer is selected that has these adhesive properties.

Any of the aforementioned water-soluble or water-swelling polymers or combinations of these polymers can be used in putting together the basecoat compositions of the present invention to be used »

These compositions generally take the form of a solution have one or more of the aforementioned polymers in a solution system. A variety of solvents or combinations of solvents can be used for this purpose. The solution star is, however, preferably by a

409882 / 1U9

relatively volatile solvent formed, the predominant has an organic character, but small proportions of an inorganic: see solvents such as water. As examples some solvents should be mentioned here that are

can be used advantageously in a context:

j -

ιethanol, acetone, cosmetic solvents, ethyl acetate, toluene, i
Isopropanol, methyl ethyl ketone. These can be used alone or in combination

nation.

The amount of water-soluble or water-swelling polymer that is included in the base coating compositions according to the invention

can be set, can fluctuate. In general, the polymer makes approximately between 5 and 30% by weight of the basecoat compositions

the end* . j

! In addition to the water-soluble or water-swelling film-forming polymers of the type mentioned above, the individual base coating composition can also contain other customary ingredients, the use of which is customary in such compositions. These can include: Pigments, plasticizers, surface-active substances, auxiliary solvents, perfumes, etc. The so-called D&C colors, which are soluble in organic solvents, should be mentioned here as pigments that can be used. Typical of the plasticizers to be incorporated into the green coating compositions according to the invention are: dibutyl phthalate, dibutyl ether, etc. As a suitable one for these purposes

409882 / 1U9_ ₁₄ _

, surfactant, sorbitan trioleate can be used. J

Of particular importance in connection with the base coat j

compositions are the photo-curable nail polish compositions. The photo-curable nail varnish compositions are particularly suitable for use in conjunction with the described basic

: i

Coating compositions, since the type of their application and their composition are chosen so that the corresponding layers do not mix with the base coat previously applied to the nails. Since this is the case, there is no influence the ability of the base coat to be separated from the nails by simple ^ Soak the coated nails in warm water. This is in contrast to the case in which one would try to fine the To use known nail polishes together with the existing base coats, e.g. nitrocellulose in an organic solvent system. In this case the nail varnish is applied on the base coat to soften the base coat and to mix the two layers. This affects the Separability of the base coat from the nails by softening in the Water to a considerable extent.

In addition to the above-mentioned essential ingredients of the photocurable liquid system, other auxiliary components can also be used

len compositions are added to the curing process do not hinder. For example, the compositions can contain pigments, dyes, organic solvents (those used as reagents for adjusting serve the viscosity), plasticizers etc. are added.

409882/1149 - 15 -

Auxiliary resins can also be incorporated into these nail varnish compositions that do not interfere with the main curing reaction ren. As these compositions cured by exposure to light which begins when the container enclosing the composition is opened and only when it is closed is canceled, it is often advisable to use a stabilizer! or to add a stabilization system to the composition to to extend their processing life.

To give examples of the various auxiliary components that are included in the the composition according to the invention can be used, the following shall be mentioned:

Organic solvents: ethyl acetate, ethanol, isopropyl alcohol, methanol, butyl acetate, glyme (i.e. CH ₃ OCH ₂ CH ₂ OCH ₃ ), diglyme (i.e. CH ₃ OCH ₂ CH ₂ OCh ₂ CH ₂ OCH ₃ ), methyl ethyl ketone, diethyl ketone, acetone, Toluene and suitable cosmetic solvents.

Pigments: -

Color Index Pigment Chemical Name Number

D&C Red No. 2 16185 '

D&C Red No. 7 C.I. pigment red 57: 1 1585o: l

(Pigment red)

D&C Red No. Io CI.Pigment red 49 1563o

(Pigment red)

D&C Red No. 11 CI. Pigment red 49: 2 '1563o: 2

(Pigment Red) 'i

4 098827 11 kl _ ₁₆ - ΐ

!Pigment

D&C Red No. 12th

i
D&C Red No. 13th

'' DStC Red No. 3o

JD&C Red No. 34

j D&C Red No. 3

D&C Yellow No. 5

^! D&C Yellow No. 6 jD & C Orange No.

^! D&C blue No. 1

; D&C Blue No. δ D&C Green No. 5 D&C Green No. 6th

Cosmetic green C61-6735

Cosmetic green C61-1245

Pink 3515 B 3o9 Brown B-328 2 Yellow 317o Black A 8211 Blue C-43-W181O Rp st 3 5 51

- 16 -

Chemical name

C.I. Pigment Red 49: 1 (Pigment Red)

CI pigment red 49: 3 C pigment red)

C »I. Küpenrot (Vat Red)

C.I. pigment red 63: 1 (pigment red)

C. I. Acid Red

CI. Food Yellow

C.I. Acid Orange

CI. Vat blue

CI. Acid Green

CI. Solvent Green

40-9882 / 1 U

Color Index Number 1563o: l .1563o: 3 7336ο
1588o: l 4543ο 1914ο 15985 15 51ο 42o9o 73ooo 6157ο 61565 77289 77288 77oo7 77491 77492 ' 77499 77o77 7 7491 77788

Plasticizers: dibutyl phthalate, dibutyl citrate, etc.

-ί '" Resins: Santolite (copolymer of equimolecular j j -" ■■ "." ■ I

iren parts formaldehyde and p-toluenesulfonamide), vinylpyrrolidone / I Vinyl acetate (5o / 5o or 35/65 mol .- *); Gantrez AN 119 (copolymer ivon methyl vinyl ether / maleic anhydride with a molar ratio- nis of "1: 1; variety with low molecular weight; average molecular weight. 25o, ooo); Gantrez AN 139 (copolymer of methyl vinyl ether / maleic anhydride with a molar ratio of 1: 1; |

Variety with a medium molecular weight range

i ■ -. · Ι

i ι

each molecular weight; average molecular weight 5oo, ooo); National

I. ι

jStarch Resyn 28-293o (terpolymer of crotonic acid (Io%) and a Mixture of vinyl acetate and "vinyl esters of C. -C ^ g fatty acids j '(9o%)); Elvamide.

■ j

Stabilizers: hydroquinone, p-tert-butyl-catechol, j

2,6-di-tert-butyl-p-methylphenol, phenothiazine (tiodiphenylamine), j N-phenyl-2-naphthylamine.

If desired, these nail varnish compositions can be used with one or the other base coat. As already described above, base coats are known and are applied to the nails before the actual nail polish is applied. Primarily, such base coats are applied to improve the adhesion of the nail polish to the nail. A typical basecoat or tie coat is described in "Cosmetics, Science and Tech- ¹ ·

__ 409882/1 149 - i «-

ί - 18 -

: I.

; nology "j Edward Sagarin, Interscience Publishers, Inc., New York,

| 1957, page ü87, "Formula 2 Basecoat" described. But here I

j ί

jlen the nail polish compositions according to the invention together with ίthe base coats are used, which consist of water-soluble | or built up in water swelling film-forming polymer system! are. Some of the water-soluble or water-swelling polymers suitable for this purpose have already been listed above. j has been leading. It should also be mentioned here: Nitrocellulose,

j which is 14% contained in normal nail polishes. One of these

j water-soluble or water-swelling polymers or combinations of these can be used in the production of the base coat, the coatings usually being made of Io% strength to 20% solutions of the polymer in a volatile organic

Solvents such as ethanol, acetone, cosmetic solvents etc. can be generated.

The viscosity of the liquid nail polish compositions can vary ieren. In general, however, the viscosity will be in the range from 20 to 100,000 CPS in the temperature range from 25 ° to 28 ° C., with the measurement using the Brookfield Model LV with spindle 4 be, i 6o rpm was performed. The preferred viscosity is about 4,3oo cps at 27oc. The viscosity of the system can be adjusted with Can be changed using a viscosity converter. For this purpose, for example, those listed above under "organic solvents" are suitable th solvents, i.e. ethyl acetate, ethanol, isopropyl alcohol, methanol, butyl acetate, glyme, diglyme, methyl ethyl ketone, diethyl

409882/1 U9 - 19 -

ketone, acetone, toluene and suitable cosmetic solvents.

ι The nail polish can with; Using a brush or a spongy one, j handle-provided application tool. The varnish should be applied carefully. Only if the user

■ ■ I

If she is satisfied with the coverage of the polish, she should expose the varnish to light. The nails are then exposed to an actinic light source, which is preferably a UV light source. These include such light sources as the RS Sunlamp type lamps, carbon arc lamps, xenon arc lamps, mercury vapor lamps, tungsten halide lamps, etc. The most effective curing process is achieved when a light source is used which emits mainly with a wavelength in the range of 3.66ο Ά When such a light source is used, the coated nails can be exposed to this light for a period of 10 to 15 minutes Time is sufficient for the nail polish composition to harden to a suitable hardness and surface shape.A typical light source is a mercury arc lamp of the low pressure or medium pressure type, in the case of the low pressure arc lamp a suitable phosphor;

must be used, which radiates in the range of 3,660 Ά with sufficient intensity.

First, the base coat is applied in the form of a thin layer on ^ -j brought, which is then allowed to dry. A lamp of the type R.S .- "Sunlamp can facilitate the drying or hardening of the base coat or the binding layer · This is usually 2o see.

8 8 271 U9-2o ~

I required. After that, the nail polish composition can be used in the above ! are applied in the manner described.

; In US-PS 3,661,744 a photo-curable liquid composition is

i!

j tion described which a polyene component, a polythiol-Kom -I {component and an accelerator for the photo-curing speed When describing the possible application for j the patent proprietor first describes this composition

Composition very general in terms of their use as ι
j Sealants, coatings, adhesive materials and molded articles

i It appears as if only in example 84 of the patent certain

; Information regarding the use of these materials as an accessory Layering composition for clay coated paper cellophane, AIuj minium foil, sheet steel, "Mylar" polyester films, plywood and Concrete fittings can be found. The coating add-on referred to there The composition does not contain any surfactants. The applicant was unable to successfully coat human nails with compositions such as that disclosed in U.S. Patent 3,661,744 are described without using surfactants from a relatively limited class; apparently it was the patentee but. able to use the various materials mentioned in Example 84 to coat without using any surface-active substances (surfactants).

The applicant has this regardless of the results of the example 84 confirmed by experiments. By having a nail polish composition that differs from those of the invention just by the fact-!

MB? JM _U9 J

"I ■■■." - " ^τ ·!

! '. ■' '■ - I

one thing was that it did not contain any surfactant, ! used, she could form even layers on wood, concrete, '

Achieve metal, glass, clay and aluminum foil surfaces. This layer formation was in significant contrast to the behavior of the- ί -:

; ser composition on human nails. In this case namely

, borrowed the composition when applied to nails to I.

! ■ ■ ■. : i

j droplets together. And the applicant could not reach a shift ■ that was suitable as a nail cover. . j

; In the very vague and general list of auxiliary items that appear in

, Column 11, lines 35 to 54 appears and about Io other additions

, ze includes, the patentee mentions casually that a superficial

■ active substance incorporated into the compositions to be cured

!can be. - This appears the only place in the whole range

■ to be spelling in which a surfactant is mentioned |

i. i

!will. But this can hardly be considered a suggestion for the special class Surface-active substances are assessed, which the applicant a | puts. The patentee indicates by the general mention of the

I ■!

1 ° - - ι

surface-active substances clearly that he does not care made about which special surface-active substance (surf-j

• i

actant) is to be used in his system. The applicant now has
found that contrary to this general comment

only a relatively limited class of surfactants i

■■■■ -. · .I

is suitable for the formulation of a composition which is suitably applied as nail varnish to human nails
can be..

409882/1 U9 - 22 -

As mentioned above, an essential component is the present Nail polish composition the polyene. The polyene component

j can be represented by the following formula: i

! M.

, where m is an integer greater than or equal to 2 and X is a member of the fol-

¹ '. I.

The following group is:

4-C-4-0 = C-R

(b) B B
-0-C = C-B (e) R R
-S-C = C-R (d) -N-C = C-R
R.

JH

C-C-R

In members (a) to (e), f means an integer of 1
to 9 and R is a radical selected from the following group:

Hydrogen j fluorine, chlorine, furyl, thienyl, pyridyl, phenyl and sub ·] · substituted phenyl, benzyl and substituted benzyl, alkyl and j

ί substituted alkyl, alkyloxy and substituted alkyloxy and · |

Cycloalkyl and substituted cycloalkyl. The substituents in j the substituted radicals are from the group: Nitro, Chlpro,
Fluoro, acetoxy, acetamide, phenyl, benzyl, alkyl, alkoxy and cycloalkyl. The alkyl and alkoxy radicals have 1 to 9 carbons _T

409882 / 1U9

stoffatoine and the cycloalkyl radical has 3 to 8 carbon atoms.

i. "■ '■ - ■ - ■■". ■ -' ■■

! The members Ca) to Ce) are with [a] via divalent chemically j compatible derivative links connected. The members (a) to (e) can be replaced with [aJ by a divalent chemically compatible derivativej member of the following group: Si (R) ", carbonate, carb

0 ^l ι

oxylate, sulfone, -0-, || , -N-, alkyl and substituted alkyl,!

"- ■■.. ■; ■, .- -BC-. _ J

Cycloalkyl and substituted cycloalkyl, urethane and substituted, tes urethane, urea and substituted urea, amide and sub-substituted amide, amine and substituted amine and aryl and substituted aryl. There are also ether, phosphonate, phosphite, phosphate and heterocyclic carbon-containing radical and hy- _; droxyl in question. The alkyl derivative members have 1 to 9 carbon atoms, the aryl members are either phenyl or naphthyl

Members and the cycloalkyl members have 3 to 8 carbon atoms. R and the substituents are the same as above; B is a fellow! member of the group: -0-, -S- and -NR-.

The link [A] is polyvalent, has no reactive non-aromatic unsaturated carbon-carbon compound '(reactive non-aromatic ic carbon to carbon unsaturation) is free of 'water-sensitive members and consists of atoms selected from the group! carbon, oxygen, nitrogen, chlorine, Bromine, fluorine, phosphorus, silicon and hydrogen.

The polyene component has a molecular weight in the range of

_ _2k _ 2 ^ 28172

'"τ ■

j 64 to 2o, ooo _5, preferably in the range from 2oo to lo, ooo; the viscosity is in the range of essentially 0 to 20 million centipoises at 70 ° C. as measured with a Brookfield viscometer.

I In particular, the member [a] of the polyene composition can be

! ster line of alkyl radicals, phenyl and urethane derivatives, oxyge

ned residues and nitrogen-substituted residues are built up

jden. The term [aJ can also be represented by the following formula !will:

where j and k are integers greater than 1, R _{2 is} a member of the group | pe consisting of hydrogen and alkyl with 1 to 9 carbon atoms4

men, R _{3 is} a member of the group consisting of hydrogen and 1 saturated alkyl having 1 to 9 carbon atoms, R ^ a divalen tes derivative from the group: phenyl, benzyl, alkyl, cycloalkyl, substituted phenyl, substituted benzyl, substituted alkyl unc is substituted cycloalkyl; wherein the alkyl and the cycloalkyl and the substituents on the substituted members are already defined above.

General forms of representation for those used according to the invention Polyenes are given below by way of example:

409882/1 U9 - 25 -

. ₂₅ _

I. Poly (alkylene ether) polyol reacted i ] ■ "■ - ■ j

'with unsaturated monoisocyanates to form polyurethane poly-j

. ene and associated polymers. j

IRi-

Uv

Difunctional

Trifunctional

"I -J

Tetrafunctional

H,

Tri-to-hexafunctional

Connected-Modified Difunctional

4 09882/1 149

26 -

Connected-Modified Tetrafunctional

IK. O Bj

II. Poly (alkylene ester) polyol reacted with unsaturated monoisocyanates to form polyurethane polyenes and associated polymers'

Difunctional

Connected-Modified Difunctional

NH-C ₁ -O-

Ri

III. Poly (alkylene ether) polyol reacted j

with polyisocyanate and unsaturated monoalcohol with training

t of polyurethane polyenes and associated polymers. >

- 27 -

409882 / 1U9

Difunctional

^N V

CIi ₃ -

«T-c-

Tr! Functional

, ^ ( ¹ I-NH-I

NH I

CHj

Tetrafunctional · _t ,,.

ν η -ο

ι «--CH ₃ .-

In the above formulas, the value of the sum is + y + ζ in each 'chain segment at least 1; P is an integer equal to or greater than 1; q is at least 2; η is at least 1; R ^ is selected from the group: hydrogen, phenyl, benzyl, alkyl, cycloalkyl and substituted phenyl and R _{7 is} a member of the group: CH ₂ = Cl- (CH ₂ -H ^, hydrogen, phenyl, cycloalkyl and alkyl.

General Methods for Making the Above-mentioned Polyenes

are at column 7, line 9 through column 8, line 48 of U.S. Patent 3,661,744

described; by express reference to the U.S. Patent

3 661 744 at this point, the disclosure of which is part of the disclosure

___ ■ .___ __ ■ 409882/1 U9 -__ 8 -

, barung of the present application viewed.

As mentioned above, there is a second essential component

'of the nail varnish composition in question, the polythiol. In j of the description, all! understood simple or complex organic compounds that i j a plurality of terminally or non-terminally .arranged j i have functional groups -SH per average molecule.

j ^s

. On average, the polythiol must have two or more -SH groups per

j '

; Contain molecule and a viscosity in the range of 0 to 2o Million centipoises (cps) at 7o C, measured with a Brook-

! own field viscometer; either alone or in counter- ¹ ι. "!

^! wart an inert solvent of an aqueous dispersion or;

'ι

i of a plasticizer. Possess polythiols which can be used according to the invention usually molecular weights in the range from 50 to 20,000, and preferably in the range from about 10,000 to about 10,000,000. ;

The polythiols which can be used according to the invention can be obtained by the general Formula -.

R ₈ - (SH) _n

in which η is at least two and Rg is a polyvalent organic moiety which has no reactive non-aromatic carbon-carbon unsaturated compound. R ₈ can.

A09882 / 1U9 - ₂ a -

thus cyclic groupings and hetero-atoms like e.g. 3. N, P or i contain 0 and contains primarily ^{carbon-carbon;} Carbon-hydrogen, carbon-oxygen or silicon- j oxygen-containing connecting chains which are free of any-;

unsaturated. - ■

rather reactive non-aromatic / carbon-carbon compound are (free of any reactive non-aromatic carbon to carbon junsaturation). A class of polythiols that, together with poly-j enen for the production of essentially odorless polythioether-j Products that can be used are the esters of thiol-containing

jgen acids of the formula \

HS-R ₉ - COOH

■ where R _{Q is} an organic part that is not a reactive non-

! contains aromatic carbon-carbon compound, with poly- i

j:

hydroxy compounds of the type R> (OH), where R. is an organic

unsaturated ^! Partly free of reactive non-aromatic / carbon-carbon compounds and η is equal to or greater than 2. These ; ! Components react under suitable conditions and lead to j

a polythiol with the following general formula: ι

409882/1 U9

where Rg and R _{1 are} organic parts which do not have a reactive non-aromatic carbon-carbon unsaturated compound, and where η is 2 or more.

Certain polythiols, such as aliphatic monomeric polythiols'

I • (ethanedithiol, hexamethylene dithiol, decamethylene dithiol, tolylene-2 I,

M - dithiol and the like) and some polymeric polythiols (such as ethyl- ¹

ί ι

^! cyclohexyldimercaptan polymer with terminal thiol and the like.) and j ^! similar polythiols appropriately and commonly based on;

t are synthesized on a commercial basis, can be used

.Although they give off offensive smells; but on many <

i: these end products are from a practical commercial stand- ^:

From the point of view of ipoint, not resorted to. As examples of poly!

thiol compounds, which because of the relatively low odor level j

are preferred, the following should be mentioned here, without

ίthat this is to be understood as a limitation; Thioglycolic esters;

I acid (HS-CH ₉ COOH), £ -Mercaptopropionic acid (HS-CH (CHo) -COOH) and J.

ί ■!

Iß-mercaptopropionic acid (HS- (CH2CH ₂ COOH)) with polyhydroxy compounds, such as glycols, triols, tetraols, pentaols, hexaols and j

Like. Without limitation, particular examples of preferred j

Preferred polythiols are: ethylene glycol bis (thioglycolate),

ί J

■ Ethylene glycol bis-iß-mercaptopropionate), trimethylolpropane-tris- j (Thioglycolate), trimethylolpropane tris (ß-mercaptopropionate), penta erythritol tetrakis (thioglycolate), pentaerythritol tetrakis (ß-mercaptopropionate ), all of which are available on the market, and

14-0.

iDipentaerythritol-hexakis-Xß-Marcaptopropionat). A special addition! j. polymer i

A preferred polythiol is polypropylene ether glycol- j

i -. ■■■■■■■ .: i

jbis-Cß-mercaptopropionate), which by ester formation from polypropylene- '

■ "■" ■■■ "" · '!

weed glycol (e.g. Pluracol P2ol, Wyandotte Chemical Corporation) '

; And ß-mercaptopropionic acid can be produced.

[The preferred polythiol compounds are indicated by a

ί - ■ ■ "■ '■■■' ■ '- :.;

Initial low level of mercaptan-like odor and due to the fact that, after the reaction, essentially odorless polythiol ethers are obtained as end products, which are commercially attractive
jund are practically usable resins or elastomers.

According to the invention, a class of> can also be used as the polythiol component

ί "■ - .: ■■ - ■ '■■. ■■■ ■ ί

IsQcyamirat- containing polythiols are used, which in the
-i.US-PS 3 676 U4o. These are general through

! determines the following formula: · j

ι ■ -. - ■

R-SH
\

!,: - ■■. ■: .-. O = C "C = O. J

HSR-N N-RSH '

- 32 -

40.9882 / 1 U9

'where R is an organic divalent part. Usually the total number of carbon atoms in R is no greater than 13. Typical _; among these organic parts are, for example, the following:

CH ₀ -CH .. j • y

/ CH CH oY

I ² I i "

; .J- (CH ₂ -CH-O ^

CH ₀ -CH
² I.

j and - ^ H ₂ -CH ₂ -CO

.'here y is hydrogen, methyl or ethyl and ζ is an integer j from 0 to lo. In particular, various isocyanurate-containing Polythiols are mentioned here as examples: J

Tris (3-mercaptopropionate) ester of tris (2-hydroxyethyl) isocyanurate '; tris (2-mercaptoethyl) isocyanurate; tris (2-mercaptoethoxyethyl) iso- ι

cyanurate; tris (2-thiocarboxyethyl) isocyanurate; tris (2-mercaptoethyl) ester of tris (2-carboxyethyl) isocyanurate; trisdl mercaptoundecanoate) ester of tris (2-hydroxyethyl) isocyanurate; tris (3-mercaptopropionate) ester of tris (2-hydroxypropyl) isocyanurate; and tris (2-mercaptopropionate) ester of tris (2-hydroxyethyl) isocyanurate.

Certain particular polyenes and polythiols are of particular In- ι interest and will be used in the practice of the present invention! preferred. These are listed below and there will be a

OU? j

! A brief indication of how they can be made is given. ! So that these connections are better identified in the following j 'each will be given a polithiol number or a polyenh

i- I

j number assigned. j

ι I

Polythyols!

Polithyol No. 1: pentaerythritol tetrakis (β-mercaptopropionate). This material is made by esterification of one mole Pentaerythritol made with four moles of ß-mercaptopropionic acid.

Polithyol No. 2: Tris (2-hydroxyethyl) isocyanurate tris (β-mercaptopropionate). This material is obtained by esterifying one mole of tris-hydroxyethyl isocyanurate with 3 moles of ß-mercaptopropionic acid manufactured.

Polithyol No. 3: Trimethylolpropane-tris-Cβ-mercapto-j propionate). This material is made by esterifying one mole of trimethylpropane with 3 moles of β-mercaptopropionic acid.

Polithyol No. U: Dipentaerythritol-hexaki's-Cß-Mercaptopropio.nat). This material is made by esterifying one mole of dipentaerythritol with 6 moles of β-mercaptopropionic acid.

Polyenes

Polyene no. 1: This polyene is a triene .. It will be made from

A09882 / 1U9 _: ___ "" L ..__ .. 3H .._.

- 3M- -

■ Allyl alcohol, malic acid and toluene diisocyanate are produced. To the

j making the polyene will first be 2 moles of the allyl alcohol reacted with malic acid to form the allyl ester of the apple

to generate acid. Separately, one mole of allyl alcohol is used

j one mole of toluene diisocyanate to react in such a way that

I the monoadduct of these two compounds with the following structure

! ture formula forms:

NCO

NH-CO-CK ₂ -CH = CH ₂

1 mole of this adduct is then with one mole of the diallyl ester the malic acid to react and a triene is obtained which has the following structural formula:

■ CH ₉ -. ;

CH ₀

ι ²

! = 0 0 -0-C-HST

C = OI
0

__CH-

Polyene no. 1

.NH-CO-CH ₂ -CH = CH ₂

CH

409882 / 1U9

- 35 -

Polyene no. 2: This polyene is a tetraene. It will

■ made from allyl alcohol, malic acid and toluene isocyanate (TDI)

It can either be the 2,4- or 2,6-TDI isomer or else a mixture of the two can be used. To produce the polyene, diallyl ester of malic acid is first used by esterification manufactured. 2 moles of the diallyl ester of malic acid are then with one mole of TDI to generate the end product for the reaction

tin brings. A small amount of dibutyl dilaurate is used as a catalyst

j used. The polyene No. 2 has the following structural formula:

CH ₂ CH

CH ₂

f b ^pol y ^en

(JH- O- C- ^nU

CH ₂ CH

j polyene no. 3: This polyene is a diene. It will be out

! Bisphenol A and allyl chloride produced by standard etherification * ; It has the following structural formula:

CH ₂ = CH-CH ₂ -O-

-0-CH ₂ -CH = CH ₂

j polyene no. 4: This polyene is made from malic acid, allyl alcohol and isophorone diisocyanate. Isophorone diisocyanate

has the following structural formula:

nco

H ₃ C

CH ₂ -NCO

The polyene is obtained by reacting 2 moles of the diallyl ester of malic acid with one mole of isophorone isocyanate in the presence of Dibutyltin dilaurate produced as a catalyst. The polyene is tetrafunctional and has the following structural formula:

409882 / 1U9

- 37 -

I!

O CO-CH ₀ -CH = CH ₀
NHC-O-CH

CO-CH ₂ -CH = CH ₂
0

0-CH ₂ -CH = CH ₂

0 C = O
ι) ι

H ₀ -NH-CO-CH

• · Jl

CH ₂

C = O

Polyene no.

Polyene Mo. 5: This polyene is a diene. It becomes TDI j

and. Allyl alcohol produced. Two moles of allyl alcohol are

I- '

one mole of TDI in the presence of small 'amounts of dibutyltin dilau-' council reacted as a catalyst. The polyene is the fol- lowing;

! ■ "■■■ I

The following structural formula: I

0
U

CH ₂ = CH-CH ₂ -OC-NH-J-.

Polyene no. 6: This polyene is a triene. It is
rrially! isocyanurate It has the following structural formula:

CH-CH = CH "

O = C

40988

C = O

17TT

- 3S

49

I!

The ratio of the to be used in the present composition

The amounts of polyene and polythiol can vary considerably.

This state of affairs is best expressed by the fact that the people : ge of the polythlol to be used with the aid of a molar ratio • ses is related to the polyene, i.e. SH groups in the

! Relationship to the unsaturated groups and that the combined

; th amounts of polythiol / polyene in a ratio to Gesamtge- [

i - I

¹ · ι

can be set as a percentage of the composition, i.e. as a percentage by weight based on the total weight of the composition. | Accordingly, the molar ratio of polythiol to polyene is generally in the range from about 0.5: 1.0 to 1.5: 1.0; before- ; preferably in the range of approximately o, 67: 1, o to 1: 1, o. In addition -j

The mixture of polythiol and polyene usually makes about j

•!

Io to 99% by weight of the total nail polish composition.

A third essential component of the present composition is the photocuring rate accelerator. It
it should be noted here that under the present invention
should fall if the accelerator is used as a separate and distinguishable compound, such as azobenzene, as a mixture of
two or more separate components, such as benzophenone,

Benzanthrone, Änthron and Dibenzosuberon, carbon tetrachloride

will

and Phenantiiren or the like. Used / or when it is in chemically bound form within the molecular structure of either the polyene
or of the polythlol is present. As an example for the last
named type in which the photo-curing accelerator is not considered

separate component is present, but rather in chemical, Form is bound within the polyene component, the following structural formula should be given, the four unsaturated carbonτ Carbon groups and one diaryl ketone group per ' Average molecule contains: I.

J ■ ι

ι ο

It should also be noted here that the polyene, the Polythiol · and the photo-curing accelerator also in the photo-curing Composition can be generated in situ without deviating from the basic concept of the invention.

The following chemical photo-curing accelerators are preferred: benzophenone, acetophenone, acenaphthen-chionone, o-methoxyben * - zophenone, thioxanthen-9-one, xanthen-9-one, 7-H-benz [de] anthracen-7-one, dibenzosuberone , 1-naphthaldehyde, 4,4'-bis (dimethylamino) benzophenone, fluoro-en-9-one, l'-acetonaphthone, 2'-acetonaphthone, anthraquinone, 1-indenone, 2-tert.-butylanthraquinone, valerophenone, hexanophenone, 8-phenylbutyrophenone, p-morpholinopropiophenone, 4-morphiolinobenzophenone, 4'-morpholinodeoxybenzoin, p-diacetylbenzoi., (Diacetophenone). 4-aminobenzophenone, 4'-methoxyacetophenone, benzaldehyde, 06-tetralone, 9-acetylphenanthrene, 2-Äcetylphenanthren, lo- thioxanthenone, 3-acetylphenanthrene, 3-acetylindole, 1,3,5-triacetyl-

40988 2/1149 - * o -

- 4ο -

j benzene (triacetophenone). Mixtures of these accelerators can also be used are used, all of which shorten the exposure times considerably. !

The curing accelerators are usually used in an amount of

• about 1 to 10% by weight of the photo-setting composition ί
based on the total weight of the nail polish composition

■ set. Preferred accelerators are the aldehyde and ketone car- ! bony! compounds in which at least one aromatic nucleus is

i O

'■ is bound directly to the | (group, e.g. benzophenone (diphenyl-; ketone).

I '

j UnT maximum strength, solvent resistance, creep resistance, heat-J resistance and to achieve freedom from tack, the group consisting of the \ polyenes and polythiols according to the invention the reaction components a dreidimenp dimensional network be formulated so as to cross-linked solid constituent polythioether-Polymersysterne establish if they cure . In order to achieve such an unlimited network formation, the individual polyenes and polythiols must have at least two ifunctional groups (functionality of at least 2) and the sum of the functional groups of the polyene and polythiol components must always be greater than U. Mixtures and blends of the polyenes and the polythiols which have this functionality can also be used.

Known curing inhibitors or retarders can also be used

: 409882 / 1U9 __- Ji_ ..-_ J

i will add the components or the curable compositions

I stabilize to prevent the onset of premature curing !impede. For example, should be mentioned here: Hydroquinone, p-tert-butylcatechol, 2,6-di-tert-butyl-p-methylphenol; Phenothiazine; N-phenyl-2-naphthylamine; and protective gas atmospheres such as helium, argon, nitrogen and carbon dioxide.

A fourth essential component of the nail varnish composition according to the invention is a substance or several from a certain class of certain special surface-active substances. To this preferred surfactants in the group include: ■ sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, pentaerythritol dioleate, Pentaerythritol trioleate and nonionic surfactants of the eluorocarbon ester group of surfactants Fabrics that are manufactured and sold by DuPont under the trademark, legally protected name Zonyl.

The following surfactants are less effective, but can still be used for the purposes of the invention: Alkenyldimethylethylammonium bromide; dI "coco" dimethylammonium chloride; quaternized imidazole salt (of stearic acid); Glyceryl monooleate; Glyceryl dioleate; Glyceryl trioleate and polyglycerol residues ^ of oleic acid.

These surfactants are in the present system soluble, but this is not a sufficient reason for the explanation

409882/1 H9 ^: - «-

the fact that they can be used according to the invention, since ! Many other surfactants have been studied that were also soluble in the system, but for the

y y

: This purpose could not be used. \

i - i

(j

¹ ι

The usability of the surface-active substance for the inven- ^! ! proper purpose in the present composition was under ^ -

; ι

! sucat by adding a standard amount of the ^! j (generally 1 wt. t based on the total weight of the nail no

I ι

: lacquer composition) was added to the composition, the one

j. I.

ι Standard amount of polyene, polythiol and photo-curing accelerator Iger contained, and meanwhile the tendency of the composition to form ! formation of a "drop" was observed when this on the upper ' ■ the surface of the nail was applied. With the help of this technique j

j up to 70 surfactants have been tested to improve their j 'ι

¹ determine operational capability; of these some were that already! Structurally closely related substances mentioned above and found to be usable. However, for reasons which the applicant cannot explain, it was found that these substances are not suitable for the

J can be used according to the invention. Glyce-

Ryl monolaurate and glyceryl distearate were of no benefit, while glyceryl monooleate gave results that were at least partially satisfactory. Similarly, it was found that sorbitan can not be used, sorbitan _i whereas sesquioleate, sorbitan trioleate and can be used for the inventive purpose. In addition, was

4Q9882 / 1U 9 - H3 -

found that Pentaer.ythritdioleate and trioleate very well integrated ι can be set, while the pentaerythritol dustearate is a solid j

I "" ■ - ■ "■■■ -.-. 'Ί

Is substance that is not soluble in the system used and therefore also cannot be used.

'ί

The following is a list of surfactants; leads that are investigated according to the above criteria has been and which cannot be used for the purpose according to the invention because they either reduce the wettability of the nail polish

{"- ■ .. : '■■;' ■ " - ■■■■■■■■ -

[compositions on human nails do not improve or

The following cannot be used in the composition according to the invention:

iCation-active substances

Dod e c y It r ime t hy lammon iumch lor id Hexadecyltrimethylaminonium chloride

Octadecyltrimethylammonium chloride "Tallow'V-Trimethylammonium Chloride Cetyltrimethylammonium bromide

Cetyldimethylethylammonium bromide "eoco ^II -trimethylammonium chloride

''Soya'V-trimethylammonium chloride ■ _; Dilauryldimethylammonium bromide Hethyldodeeylbenzyltrimethylammonium chloride Alkyldimethyl-SH-dichlorotipenzylammonium chloride Quaternary imidazoline salts (of coco acids) Lauryl isoquindium bromide

409882/1 U9:

Non-ionic substances

Glyceryl monolaurate

Glyceryl dilaurate

Glyceryl distearate

Glyceryl monoricinoleate Modified glyceryl phthalate resin Polyoxyethylated castor oil (2o moles of ethylene oxide) Polyoxyethylated castor oil (4o moles of ethylene oxide) Polyoxyethylated sorbitolin monolaurate Polyoxyethylated sorbitan monolaurate Polyoxyethylated sorbitan monopalmitate Polyoxyethylated sorbitan monostearate Polyoxyethylated tert. Octy! Phenol polyoxypropylene + 80% ethylene oxide

Non-ionic substances

Esters of polyethylated sorbitol, sorbitan or sorbide:

Polyoxyethylated sorbitan monostearate

(2o moles of ethylene oxide)

Pcfyoxyethylated sorbitan tristearate (2o moles of ethylene oxide)

Polyoxyethylated sorbitan monooleate Polyoxyethylated sorbitan dioleate

Polyoxyethylated sorbitan monooleate (.Zo moles of ethylene oxide)

Polyoxyethylated sorbitan trioleate (2o moles of ethylene oxide)

409882/1 H9 - 45 -

Esters of other polyalcohols: "

Sorbitan monolaurate
Sorbitan monooleate
Sucrose monomyristate
Suerose monostearate
Sucrose monooleate
Sucrose dioleate
Sucrose monotallowate
Pentaerythritol distearate
Pentaerythritol tetrastearate

Ethers of polyoxyalkylene glycols;
tert. Octylphenoxyethanol

Polyoxyethylated tert. Octylphenol (3 moles of EthyXene oxide)

Polyoxyethylated tert. Octylphenol: C-S moles of ethylene oxide)

Polyoxyethylated tert. Octylphenol (7-8 moles of ethylene oxide)

Polyoxyethylated tert. Octylphenol ■ = - ■■ (12-13 moles of ethylene oxide)

Polyoxyethylated tert. Octylphenol (16 moles of ethylene oxide)

. Polyoxyethylated tert. Octylphenol (3o moles of ethylene oxide)

Polyoxyethylated tert. Octylphenol • (Uo Mole Ethylene Oxide)

Polyoxyethylated nonyphenol
(1-2 moles of ethylene oxide)

Polyoxyethylated nonylphenol

(4 moles of ethylene oxide)

409882 / 1U9 - "6 -

Polyoxyethylated nonylphenol (6 moles of ethylene oxide)

Polyoxyethylated nonylphenol (8 moles of ethylene oxide)

Polyoxyethylated nonylphenol (9-lo moles of ethylene oxide)

Polyoxyethylated nonylphenol (lo-ll moles of ethylene oxide)

Polyoxyethylated nonylphenol (12 moles of ethylene oxide)

Polyoxyethylated nonylphenol (15 moles of ethylene oxide)

Oleates:

.üioleate of polyethylene glycol (2oo) Dioleate of polyethylene glycol (4oo) dioleate of polyethylene glycol (6oo)

The amount of represented by the surfactant Component incorporated into the composition according to the invention may fluctuate a little. Usually it is approximately between 0.5 to 1 wt .-% based on the total weight of the Make up composition.

Basecoat Compositions Example B-I

Fabrics% by weight

PVP / VA 3 35 (copolymer of vinyl pyrrolidone and vinyl acetate; 35/65 mole%)

409882/1 149 - 47 -

Ethanol (95%) 80

Continuation of example B-I

Fabric % by weight

Procedure: The resin is added to the solvent and the The mixture is stirred until all of the resin has dissolved.

Example B-2

Amphomer 2 8 "+ 9Io 2o

Ethanol (95%) 80

Procedure: As in example B-I

Example B-3

National Starch Resyn 28-131o (copolymer of
Vinyl acetate crotonic acid; lo / 9o mol%) Io

Ethanol (95%) "9o

Procedure: As in example B-I

- 48 -

AÖ1M.2JL1

Example B-4

Fabric% by weight

National Starch Resyn 2 8-2 93o

(Terpolymer made from crotonic acid and a mixture

of vinyl acetate and vinyl ester of

^c -i -C. "-Fatty acids; lo / 9o mol% Io

XO Io

Ethanol (95%) 9o

Procedure: As in example B-I.

Example B-5
i

'' Gantrez AN 119 (copolymer of methyl vinyl

! ether / maleic anhydride; molar ratio 1: 1 j average molecular weight 25o, ooo 2o

Acetone 8o

Procedure: As in example B-I.

Example B-6

Gantrez AN 13 9 (polymer of methyl vinyl ether /
Maleic anhydride; molar ratio 1: 1;
Average molecular weight 5oo, ooo 2o

Acetone 8ο

Procedure: - As in example B-I

409887./J JX9

Example 3 -7 ι

! National Starch Resyn 2 6-2 9o5 _:

■ (Resyn 28-293o (So%) in ethanol (95%)) Io j

j i

cosmetic solvent (Shellsolve 146o) ■

i |

■ C5o% ethanol (95%) / 5o% isopropanol (anhydrous)) 9o!

ι 1

; ι

! Procedure: For example B-I j

I Example B-8 ;

National Starch Resyn 2261 "

. (Acrylic copolymer latex suspension in
'Water; 47% solids; with 0.04% formaldehyde as a protective agent. Io

! Cosmetic solvent (Shellsolve 146o)
(5o% ethanol (95%) / 5o% isopropanol (anhydrous)) 9o

Procedure: As in example B-I

Nail varnish compositions

Examples of nail varnish compositions will now be given below
which can be used in conjunction with the base-over-pull compositions of the present invention.

- 5o - ·

409882/1119 J.

- 5ο -

Example L-I

All of the ingredients in the list below are made into one

Put in the mixing vessel and stir well together «This mixture ^; was then ground in order to ensure the construction of a homogeneous product in which the solids are evenly distributed: j

Ingredients per cent

Polyene no. 2 47.75

Polythiol no. 1 ■ 43.2o

ßenzophenone 5.42

Hydroquinone o _/ 12

Sorbitan trioleate · l, oo

Rubine Lake (CI 1585o) o, 95

Black (CI 77499) ο, οδ

iDSC Red No. 3o (CI 7336o? O, 52

D&C yellow No. 5 (CI 1914o) o, 13

Titanium dioxide ο, 8 5

Before applying this composition to human nails the nails are first cleaned with a solvent to remove all dirt and grime. After that, a base coat is applied applied to the nails. A coating of the nail varnish described above was then brushed onto the nails .; The coated nails were then exposed to the light of an HFTSBL lamp

409882 / 1IAJ zI ^ L

exposed for a period of one minute to 1 minute for 15 seconds. This light source emits mainly in the range from 35oo to 388o Ä. At the end of that exposure, the nail polish was at one hardened hard nail coating.

The following examples are given in tabular form, The formulations were prepared using the same procedure as described in connection with Example L-I. Similar results were obtained.

- 52 -

A09882 / 1 U9

!Ingredients

- 52 - Examples L-3 L-4 y Weight, L-5 .-% Table I. 48.298 48.3ο 48.44 L-6 43.715 43.61 43.79 48.25 L-2 5,481 5.62 5.49 43.68 48.178 ο, 128 ο, 13 ο, 13 5, 47. 43,598 1, ooo Ι, οο 1, oo ο, 13 5.468 1, oo ο, 127 1, ooo

jPolyene No.

jPolythiol No.

j
Benzophenone Hydroquinone Sorbitan Trioleate! Sorbitan dioleate j sorbitan sesquioleate; pentaerythritol dioleate! Pentaerythritol trioleate! Rubine Lake (CI 1585o)

(Black (CI 77499) I.
D&C Red No. 3o (CI 7336o)

D&C yellow No. 5 (CI 1914o) Titanium dioxide D&C Red No. 6 (CI 1585o) D&C Red No. 7 (CI 1585o: l) Cosmetic Umber (CI 77491) D&C Red No. 13 (CI 1563o: 3) pure oxy red (CI 77491) o, o43

1,586

o, 953 o, oo4

O , oo9 1 , o7 O , 412 O , 27

1.15

- 53 -

409882 / 1U9

Table I (continued)

ingredients

Examples - by weight ^;

L-7

L-8

L-9

L-Io

; Polyene No. ■ Polythiol No.

iBenzophenone

.Hydroquinone iSorbitan trioleate jSorbitan dioleate ^! Sorbitan sesquioleate, ipentaerythritol dioleate

iPentaerythritol trioleate JRubine Lake (CI 1585o) ! black (CT 774 99) Ü & C Red No. 3o (CI 7336o) D&C Yellow No. 5 (GI 1914o) Titanium dioxide

D&C Red No. 6 (CI 1585o) D&C Red No. 7 (CI 1585o.:l) Cosmetic Umber (CI 77491) D&C Red No. 13 (CI 1563o: 3) pure oxy red (CI 77491)

47.75 43.2o 5.42o, 12

1, oo

o, 95 o, o6 o, 52 o, 13 o, 85

l, oo

l, oo

l, oo

- 54 -

409882/1149

j The following examples are also given in tabular form. Also j

! i

these compositions are used in connection with example * L-I described manner produced. The compositions are

^! on the human nails with the aid of the method and the aj

^1st ι

I directions applied as they have been described in connection with example LI j j. The percentages of polyene and polythiol ^! in the composition are as the combined weight of polyene

! and polythiol indicated; the relative amounts of polyene and poly-

': thiol in the composition are given as the molar ratio of poly-thiol to polyene, ie as the molar ratio of the SH groups to the unsaturated groups.

- 55 -

409882/1 149 J

■ - ■ - -. - «. - 55 - 2428172 No. 1
I. Table II No. 4th ingredients L-Il Examples
L-12 L-13 1: 1 Polyene no. .-..- No. 1 No. 1 9o, 95 Polythiol no. No. 1 No. 3 Molar ratio of polythiol
Polyene : 1: 1
from here 1: 1
in% by weight Polyene + polythiol 9o, 95 31.9o ßenzophenone Acetophenone 5.42 o-methoxybenzophenone 5.62

Dibenzosuberone ——— ——— 5.42 Hydroquinone o, 12 o, 13 o, 12 Sorbitan trioleate 1, oo Sorbitan dioleate -__ l, oo- Sorbitan sesquioleate l, oo Pentaerythritol dioleate Pentaerythritol trioleate - Rubine Lake (CI 1585o) o, 95 o, 95 Black (CI 77499) o, o6 o, o6 D&C Red NO. 3o (CI 7336o) o, 52 o, 52 D&C yellow No. 5 (CI 1914o) o, 13 o, 13 Titanium dioxide o, 85 o, 85 Cosmetic umber (CI 77491) I, o7 . D&C Red No. 13 (CI 1563o: 3) o, 28 - 409882/1 149 - 56 -

- if -

Table II (continued;) . ^τ

j - ** examples

'Ingredients . L-14 L-15 L-16 L-17 L-18 L-i

Ι ι

! Polyene No. No. 2 No. 2 No. 2 No. 3 No. 3 No.

jPolythiol No. No. 2 No. 3 No. H No. 1 No. 2 No.

'Sorbitan trioleate l, oo

Sorbitan dioleate.

Sorbitan sesquioleate

Pentaerythritol dioleate l, oo

Pentaerythritol trioleate - l, oo ---

Rubine Lake (CI 1585o) o, 95

Black (CI 77499) 0.06

D&C Red No. 3o (CI 7336o) o, 52

D&C yellow No. 5 (CI 1914o) o, 13

Titanium dioxide o.85

Cosmetic umber

(CI 77491)

D&C Red No. 13 (CI 1563o: 3)

! Molar ratio 1: 1 o, 8o: lo, 8t: l 1: 1 _a l: l 1: 1 polythiol: polyene. j

from here in% by weight j

Polyene + polythiol 9o, 95. - ^ j

Benzophenone 5.4 2 _a

Acetophenone

o-methoxybenzophenone

Dibenzosuberone

■ Hydroquinone 0.12 "" _a

- 57 -

409882 / 1U9

• - 57 L-21 2428172 L-23 L-24 :
ι Table II (continued) No. 4th Examples No.4 No.4 ι
I. L-2o No.l L-2 2 No.3 No.4 i ingredients No. 3 1: 1 No.4 1: 1 1: 1 i
I. Polyene no. No. 4th No. 2 ! Polythiol no. 1: 1 o, 67: I.
I. Molar ratio i
!

'Polythiol: polyene

jpolyene + polythiol 9o, 95

iBenzophenone 5.4

! Acetophenone

; O-methoxybenzophenone

jdibenzosuberone

'Hydroquinone ο,

Sorbitan trioleate 1, oo

jsorbitan dioleate

Sorbitan sesquioleate

Pentaerythritol dioleate

Pentaerythritol trioleate

Rubine Lake (CI 1585o) o, 95

! Black (CI 7 74-9 9) o, o6

D&C Red No. 3o (CI 7336o) o, 52

D&C yellow No. 5 (CI 1914o) o, 13

Titanium dioxide ο, 85

Cosmetic umber (CI 77491)

D&C Red No. 13 (CI 1563o: 3)

from here in weight- '

-.58 -

409882/1 U9

Table II (continued)

ingredients

.5 L-26 T φ
Examples L-28 L-29 .1 No. 5 L-2 7 No. 5 No. 6th L-2 5 1 No. 2 No. 5 No.4 No.l No 1: 1 No. 3 1: 1 1: 1 No , 95 away o, 8o: 3% by weight 1: , 42 here in C 9o 5

Polyene no. Polythiol no.

Polythiol: polyene molar ratio

Polyene + Polythiol fJenzophenone Acetophenone o-methoxybenzophenone

Dibenzosuberone

hydroquinone sorb itantr i ο1eat

Sorbitan dioleate, sorbitan sesquioleate, pentaerythrx dioleate Pentaerythritol trioleate Rubine Lake (CI 1585o) o, 12 1, oo

black (CI 77499) o, 95 o, o6

D&C Red No. 3o (CI 7336o) o, 52 J * D&C Yellow No. 5 (CI 1914o) o, 13 S. Titanium dioxide o, 85 Cosmetic umber (CI 77491) - 59 - D&C Red No. 13 (CI 1563o: 3) 40988 2/1149

Table II (continued)

L-3o

Examples
L-31 ° L-32

'olyen No. 'olythiol No. Polar ratio of polythiol:

Polyene

'olyen + polythiol

No.6. No.2 1: 1

No.6
No.3
1: 1

No.6 j

I No.4 j

ο, 75: 1, ο

from here in% by weight

9o, 95

Benzophenone 5.42 • U9 ?
¹ p Acetophenone
p-methoxybenzophenone i
Dibenzosuberone iydroquinone Sorbitan trioleate o, 12 Sorbitan dioleate l, oo Sorbitan sesquioleate « Pentaerythritol dioleate ^ \ Pentaerythritol trioleate S. kubin Lake (CI 15 85o) Black (CI 77499) o, 95 D&C Red No. 3o (CI 7336o) ο, 06 DSC Yellow Mo. 5 (CI 1914o) o, 52 - 60 - ritanium dioxide o, 13 Cosmetic umber (CI 77491) 0.8 5 D&C Red No. 13 (CI 1563o: 3) ——— 409882/1

Method of applying and removing the base coat and nail

varnish compositions

Example M-I

A person's nails are first treated with a solvent

j such as acetone, ethyl acetate cleaned to remove all dirt

and remove dirt. Thereafter, the base coat B-5 was applied to the Nails applied. The product is brushed onto the nail or rubbed with a cotton ball and then air-dried. A layer of the nail polish L-I was then brushed onto the nails. The coated nails were then exposed to the light , a 4FT5BL lamp for a period of one minute to 1 min. 15 sea

l exposed. This light source emits in the range from 3.5oo to 3.88ο R , whereby the main part of the emitted light has a wavelength of approximately 3.66o Ä. At the end of the exposure time, the nail polish had hardened to form a hard nail coating.

To remove the coating, the nails were used for a period of immersed in hot water for approximately 4 minutes. Then the nails were taken out of the water and the varnish peeled off. if the nails were soaked for an extended period of time to resist peeling.

The same procedure of this Example M-I was used in connection with all of the other above-described and coatings B-I through B-U and

409882 / 1ΛΑ9 "__ ⁶ L.1_

409882/1 U9

Β-6 to Β-8 along with each of the nail polishes L-2 to L-3 2

performed, which have been described above. There were j Results are obtained which are comparable to the results obtained with Basecoat B-5 and Nail Polish L-I.

! Although the invention has only been described on the basis of special embodiments has been, the large number of connections shows that deviations and changes can be made without that the basic idea of the present invention is left.

Claims (19)

Claims ! 1..A method for coating human nails, characterized in that
, a) a liquid base coat composition on the nails is applied that has a water-soluble or water-smoldering t »
i ! contains lende and flexible film forming polymer; ι b) the composition is dried on the nails, whereby on the nails a film of the water-soluble or in water
swelling polymer is deposited that adheres to the nails; c) on the dried fiIn of the water-soluble or in water swelling polymer a second layer in "form of a liquid Nail polish is applied and d) the nail polish hardened into a solid nail polish layer will. 2. The method according to claim 1, characterized in that as Na- I A09882 / 1U9 - 63 - gellack uses a photo-curable nail varnish composition | is, which is polymerizable by an actinic light source, and that when curing the layer of photo-curable nail varnish composition of the actinic light source for a time; is permanently exposed, which is sufficient for a hardening of the nail polish composition, whereby a hard polymerized nail ^: lacquer layer is obtained, which covers the base coat and adheres to it. 3. The method according to claim 1 or 2, characterized in that the water-soluble polymer is at least 1% by weight soluble in water. 4. The method according to any one of claims 1 to 3, characterized gekennzeictv net that a copolymer of vinyl pyrrolidone and vinyl acetate is used as the water-soluble polymer. 5. The method according to any one of claims 1 to 3, characterized net that the water-soluble polymer is a copolymer of methyl vinyl ether and maleic anhydride is used. 6. The method according to any one of claims 1 to 3, characterized in that the water-soluble polymer is a terpolymer of crotonic acid, Vinyl acetate and a vinyl ester of a high quality Fatty acid with 10 to 18 carbon atoms is used. 40JL8 ____ / _. LlA9 -JA. "J 7. The method according to any one of claims 1 to 6, characterized in that that as a liquid photo-curable nail varnish a liquid j composition with at least one polyene component and one Polythiol component is used. 8. The method according to any one of claims 1 to 7, characterized in that that the liquid photo-curable nail polish composition also has a surfactant in the form of at least ^ one of the members of the following group: sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, pentaerythritol dioleate, Pentaerythritol xoleate, glyceryl monooleate, glyceryl dioleate, Glyceryl trioleate, polyglycerol esters of oleic acid, alkenyldimethylethylammonium bromide, di- "Coco" -dimethylammonium chloride, Surfactants in the form of nonionic fluorocarbon esters and quaternary imidazoline salt (of stearic acid). 9. The method according to any one of claims 1 to 8, characterized , that a) a terminally unsaturated polyene according to the following formula is used as the polyene component: where m is an integer of at least 2, where (X) has the following formula: - 65 - 409882/1 U9; R RR I I I ■ C \ - C = C — R I.
R. where f is an integer from 1 to 9, R is a radical selected from the following group: hydrogen, fluorine, chlorine, furyl, | Thienyl, pyridyl, phenyl and substituted phenyl, alkoxy and | substituted alkoxy, cycloalkyl and substituted cycloalkyl J where the substituents in the substituted radicals from I. the following group are selected: nitro, chloro, fluoro, acetoxy, acetamide, phenyl, benzyl, alkyl, alkoxy and cycloalkyl, the Alkyl and alkoxy radicals 1 to 9 carbon atoms and the cyclo • alkyl radical Have 3 to 8 carbon atoms, j and wherein [[A] is not a reactive "non-aromatic unsaturation" Has carbon-carbon compound, is free of highly water-sensitive components and a polyvalent ι lentes chemically compatible member of the following group: Carbonate, carbdxylate, carbonyl, ether, silane, silicate, phosphonate, Phosphite, phosphate, alkyl and substituted alkyl, cycloalkyl and substituted cycloalkyl, aryl and substituted Aryl, urethane and substituted urethane, urea and substituted urea, amine and substituted amine, amide and substituted, amide, hydroxyl, heterocyclic carbon containing radicals and mixtures thereof, the substituents of the members of the above-mentioned group having the above i correspond to those mentioned in (X), the component has a molecular Benzyl and substituted benzyl, alkyl and substituted alkyl ', 409882/1 J_4J .... ... -. 66 ..-_ j weight in the range from about 6 ¹ to 2o, oooo and a viscosity j in the range from substantially 0 to 2o million centipoises at 70 ° C, and that b) the polythiol component has a molecular weight in the range of is about 5o to 2o, ooo and has the following general formula: ^R 8 where Rg is a polyvalent organic compound part which no reactive non-aromatic unsaturated carbon-carbon compound has ^ and η is at least 2, the sum of m and η is greater than U and the molar ratio: Ene / Thiol is selected so that a chained solid self-supporting cured product is obtained. 10. The method according to any one of claims 4 to 9, characterized in that the liquid photo-curable nail polish composition also has an accelerator for the photo-curing rate from the following group: aryl aldehyde, diaryl ketone, alkyl aryl ketone, triaryl phosphine and a mixture of carbon tetrahalide with a polynuclear aromatic hydrocarbon. 11. The method according to any one of claims 1 to Io, characterized in, that the liquid photo-curable nail polish composition I O 1 7 H ί fI - 67 - 2A28172 approximately ο.5 to Ι, ο% by weight of the surfactant, 1 to 10% by weight of photo-setting rate acceleration niger and from 1.0 to 98.5% by weight of the mixture of polythiol and polyene, the molar ratio of polythiol to. Polyene in the mixture in the range of about 0.5o: 1.0 to 1.5: 1, ο lies. 12. The method according to claim 7, 9 or 11, characterized in that the polyene is selected from the following group: U ^ώ CH CH f _O _CH-C-HN. 0 C = O ■ ¹ ^ /. NH _- JO-CHp-CH ^ CH ₂ CH ₀ Ah A ¹ H. or 409882/1 JL4_9 j S ^H 2 '" CH CH ₂ C = * 0 I « CH-O-C-HN; f C = O f ₂ CH OH. CH OH CH -> C = O ο k TiH-C-O-CH CH OH, CH ₂ = CH-CH ₂ -O- 0-CH ₂ -CH = CH ₂ 409882 / TU9 - 69 - -0-CH ₂ -CH = CH ₂ 'NHC-O-CH . CO-CH ₂ -CH = CH ₂ -CH ₀ -CH = CH ₁ C. C = O r-c-o- ( .CH ₀ -NH-CO-CH -CH
CH ₂ C = O
0-CH ₂ -CH = CH ₂ CH- CH ₂ = CH-CH ₂ -OC-NH 0
NH-CO-CH ₂ -CH = CH ₂ O = C
I. CH ₅ -CH = CH
² C = O i C W 0 CH ₂ -CH = CH ₂ - 7o- 13. The method according to any one of claims 1 to 12, characterized in that that the polythiol is selected from the following group: pentaerythritol tetrakis (β-mercaptopropionate); Tris (2-hydroxyethyl) isocyanurate tris (ß-mercaptopropionate); Trimethylolpropane-tris-Cß-mercaptopropionate), dipentaerythritol hexakis- (ß-mercaptopropionate). to remove 14. The method / according to the method according to any one of claims 1 to 13 applied coating of human nails, characterized in that the nails provided with the coating soaked in water for a period of 3 to 6 minutes until the water-soluble or the water-swelling Film is so swollen that the nail cover from the Nails is lifted, and then the nail coating is peeled off the nails. 15). Photo-curable nail polish composition characterized by a polyene component, a polythiol component, an accelerator component to accelerate the photo-curing rate and a surfactant that is present in the liquid composition is soluble, the surface-active Substance is at least one member of the following group: sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, pentaerythritol dioleate, Pentaerythritol trioleate, glyceryl monooleate, GIy ceryldioleate, glyceryl trioleate, polyglycerol esters of oleic acid, alkenyldimethylethylammonium bromide, di- "Coco" dimethyl 409882/1 149 ^ _21_ = ammonium chloride, surfactants in the form of nonionic fluorocarbon esters and quaternary imidazoline salt (of stearic acid), whereby
(A) the polyene component is a terminally unsaturated polyer according to the following formula: C ^A 3 where m is an integer of at least 2, where (X) the following. Formula has: R I --C I R RR II C = C-R where f is an integer from 1 to 9, R is a radical selected from the following group: hydrogen, fluorine, chlorine, furyl, thienyl, pyridyl, phenyl and substituted phenyl, alkoxy and substituted alkoxy, cycloalkyl and substituted cycloalkyl, where the Substituents in the substituted radicals are selected from the following group: nitro, chloro, fluoro, acetoxy, acetamide, phenyl, benzyl, alkyl, alkoxy and cycloalkyl, the alkyl and alkoxy radicals 1 to 9 carbon atoms and the cycloalkyl radical 3 to 8 Have carbon atoms and in which [Ä \ has no reactive non-aromatic unsaturated carbon-carbon formation, free of benzyl and substituted benzyl, alkyl and substituted alkyl, 409882 / 1UU - 72 - is highly water-sensitive components and is a po- is: carbonate, carboxylate, carbonyl, ether, silane, silicate, lyvalentes chemically compatible member of the following group} Phosphonate, phosphite, phosphate, alkyl and substituted alkyl, ί Cycloalkyl and substituted cycloalkyl, aryl and substituted-j tes aryl, urethane and substituted urethane, urea and substituted urea, amine and substituted amine, amide and substituted amide, hydroxyl, heterocyclic carbon i-containing radicals and mixtures thereof, the substituents of the members of the above-mentioned group having the above correspond to those mentioned in (X), the component is a molecule ^ lar weight in the range of about 64 to 2o, ooo and a vis- viscosity in the range of essentially to 20 million centi poises at 70 ° C and the (b) the polythiol component has a molecular weight in the range from about 5o to 2o, ooo and the following generally « Formula has: R ₈ wherein Rg is a polyvalent organic connecting part of the carbon-carbon compound having no reactive unsaturated non-aromatic, and η at least equal to 2, the sum of m and η is greater than 4 and the molar ratio; Ene / thiol is selected so that an interlinked solid self-supporting cured product is obtained. 16. The composition according to claim 15, characterized in that the Photoaushärtungsbeschleuniger a compound from the following group: aryl aldehyde, diaryl ketone, alkyl aryl ketone, j triarylphosphine and a Mischung.von Kohlenstofftetrahaloge- 'nid with a polynuclear aromatic hydrocarbon. j 17. Composition according to claim 15 or 16, characterized in that I. . ι records that it contains approximately: 0.5 to 1.0 wt .- * of the J surfactant, 1 to 10% by weight photo-curing! speed accelerator and l, o to 98.5 wt .-% of the Mi- j mixture of polythiol and polyene, the molar ratio of I Polythiol to polyene in the mixture in the range of approximately o, 5'o: l, o to 1.5: 1, ο lies. j 18. Composition according to one of claims 15 to 17, characterized
characterized in that the polyene is a polyene from the following J group: CH NH-CO-CHp-CH = CH ₂ 2JL114.9. .. 74-. or F, ^H 2 t 0 CH _C 0
Il CH ₉ CH
ι I Il
ηττ / -j η τττντ. j Il ² CH ₉ Ay CH i ² \ έ
C = O
I. CH ₅ O
I. 0 T 2 C = O CH ₂ 0 CH
UH ₂ C = O
I. CH ₂ ^J. KH-CO-CH C = O
I. 0 or 'CH ₂ = CH-CH ₂ -O- (f. Y ^ CH 0-CH ₂ -CH = CH ₂ - 75 - CO-CH ₀ -CH = CH ₀ I ^{2 2 s} NKC-O-CH CH ₂ 0 'C = O .CH ₂ -NH-CO-CH CO-CH ₂ -CH = CH ₂ 0-CH ₀ -CH = CH, Γ 2 £ . QH CH ₂ = CH-CH ₂ -OC-NH-J- 4 - [- NH-CO-CH ₂ -CH = CH ₂ CH ₂ -CH = CH 'CH ₂ -CH = CH ₂ - 76 - 409882/1149 19. Composition according to one of claims 15 to 18, characterized in that the polythiol is at least one compound from the following group: pentaerythritol tetrakis (ß-mercaptopropionate); Tris (2-hydroxyethyl) isocyanurate tris (β-mercaptopropionate); Trimethylolpropane-tris-Cß-mercaptopropionate), Dipentaerythrilrhexakis-Cß-mercaptopropionate). _O ΜΆΆΆΆ2ΙΛ