DD141870A5 - INSTALLATION OF AN ADVERTISING SUBSTANCE INTO ORIGINAL ORGANIC BASE SUBSTRATES - Google Patents

Description

Installation of a coloring substance in transparent organic substrates

Field of application of the invention

This invention relates generally to the coloring articles or articles, i. h, the articles or articles containing a coloring substance which may reversibly change color or transparency when exposed to a given radiation and, in particular, but not exclusively, pail, which is an organic material eye lens and especially the one sold under the trade name "CR 39", hand e11 ·

Characteristic of the known technical solutions

The Parbaugenlinsen brought up to date for the production γοη sunglasses in aen Handel are generally made of inorganic glass and the coloring matter they contain is also of an inorganic nature.

Ss is mostly silver halide.

Attempts have been made to use such a coloring matter for organic material lenses.

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In practice there is an incompatibility between the substances concerned. Within an organic substance, silver halide does not respond properly to the external radiation. .

For "CR 39 ^w , this incompatibility is due to the nature of the catalyst required to polymerize the base monomer." The only catalyst currently used satisfactorily for this polymerization is isopropyl percarbonate, which, by oxidation, destroys the coloring properties of silver halide.

To overcome this difficulty, it was attempted to provide the silver halide particles with an inorganic protective coating, ζ. B. of silicon dioxide, which is impermeable to the organic products to coat. It is an expensive solution that also lacks effectiveness.

It was then attempted to replace the silver halide by an organic-type coloring substance in such organic material ophthalmic lenses. ;

Various proposals have been made in this direction according to which such a substance is dispersed into the mass within the organic matter constituting the corresponding lenses. No one was really satisfying until today.

One of the reasons may be as above in the incompatibility of the proposed coloring substances with the polymerization catalysts used and in the practical

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Difficulties in the application of the methods, in particular the coating methods proposed to overcome this difficulty.

Other proposals have been to place the coloring substance within a particular intermediate layer between two outer layers of organic material. The practical application is not easy.

Other proposals eventually included ready-to-use lenses, d. H. after polymerization of their organic base material. This avoids the contact between the coloring matter used and the catalyst which has ensured this polymerization.

According to a first of these last proposals, the coloring substance is applied as a pial to the eye lenses to be treated. Such a film is inevitably exposed to shocks, scratches and abrasion to the detriment of its completeness and, consequently, the homogeneous color rendering it is intended to provide.

According to a second of the proposals in question, the ophthalmic lenses to be treated are immersed in a concentrated solution of the proposed coloring matter in solvent, in practice toluene, which has been boiled, in practice 70 ^° C. This coloring substance can, ζ. Example, a spiropyran, as proposed in the French patent, filed on November 29, 1973 under the number 73 43536 and published under the number 2 211 666, or a Dithizonatmetall, as in the French

patent, filed June 29, 1973, No. 73 24497 and published under No. 2 236 479.

However, in order to achieve adequate soaking of the treated ophthalmic lenses, it is necessary to immerse them for at least 24 hours, and by boiling the solution used, special measures must be taken to obtain a satisfactory recovery of the solvent vapors, so that their practical application Such a dipping process becomes uncomfortable.

Moreover, the results that can be achieved in practice are often disappointing.

Moreover, the currently known coloring substances of organic nature are subject to aging. After a relatively short time, which in any case is less than the life considered normal for sunglasses, they become inert and no longer react to the external radiation.

If it is a substance dispersed within the subject's ophthalmic lens, such aging inevitably results in its rejection.

Of course, when it comes to a substance applied to such eye lenses as a film, one might think of regenerating such a film after aging. In practice, however, such regeneration proves to be too uncomfortable and too expensive for the reasons set out above with the application methods known to date

2 1 O 5 f 4 -5-

expensive, which also leads to the final committee of these lenses.

Aim of the invention

The aim of the invention is to increase the life of colored eyeglasses and to be able to bring in new easily and cheaply when aging the coloring substance contained in them.

Darlegimg dea-essence of the invention

It is an object of the present invention to provide a process for incorporating a coloring substance into a transparent organic base substrate in which a reaction between the coloring substance used and the polymerization catalyst is avoided and the coloring substance can penetrate into the organic base substrate. -

The object is achieved according to the invention in that a contact between the organic substrate and your coloring material is produced and the coloring material is transferred to the organic substrate with the application of heat Layer, eg filter paper or kraft paper, from which it is transferred to the substrate to be treated.

The substrate to be treated is advantageously preheated to a temperature below the transfer temperature prior to contact with the colorant. As a coloring substance

a spiropyran or a dithizonate metal is used. After the thermal transfer, the treated substrate is washed with a solvent.

This invention relates generally to a process for easily incorporating a coloring matter into any organic substrate, in particular "CR 39", the use of which is readily enough to provide a fast, if desired, dyeing substance subject to aging and it is also convenient to provide the transparent base and ophthalmic lenses of organic material, particularly "CR 39", which have been treated using this method.

It is based on the otherwise unexpected observation that the coloring substances of organic nature or at least some of them are advantageous for easy application by thermal transfer, for. B. from the temporary subcarrier on the final support, according to a known method, since its vapor tension is so high that it satisfies such a method and their compatibility with the relevant final support material, in this case an organic material sufficient in that they can be absorbed into this material in 3 or of steam, and thus remain anchored in it after return to the solid state. The unexpected aspect of this observation is that it has normally had to be assumed that the application of the heat required for such thermal transfer to dyeing

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Substances are such that their coloring properties are disturbed, even destroyed.

This is not so, at least under the practical conditions of use of the invention where the heat application to the treated products is relatively short.

The method according to the invention can easily be applied to any optician without too complicated and / or expensive equipment and makes only a short-term activation, e.g. in the order of a minute, required.

A colored eye lens according to the invention can therefore, if desired, be easily and cheaply re-coated after aging of the coloring matter containing it, of course provided that this substance undergoes any aging.

In addition, and being an additional feature of the invention, the substance, while being substantially close to the surface of such a lens, remains anchored in the bulk of that lens except for an outer pial, thus benefiting as regards its protection Butting, scratches and abrasion from the mechanical properties of the organic material that makes up this lens.

As with immersion impregnation, the thermal transfer process of the present invention is particularly useful for a final product, i. H. an already polymerized, interesting, whereby any reaction between the coloring material used and the polymerization catalyst is avoided, since this is no longer active after the polymerization, which he has ensured.

Apart from the fact that the gas-phase chemical diffusion process that it meets is different, its ease and speed of application, as well as its actual effectiveness, enable its effective use in the products concerned.

embodiments

The invention will be explained in more detail below by exemplary embodiments. In the accompanying drawing show:

Pig. Fig. 13 is a perspective view of a colored eye lens made of an organic material;

Pig. FIG. 2: on a larger scale, a partial view of this lens in section, corresponding to line II-II of FIG. 1; FIG.

Pig. Figure 3 is a sectional view illustrating one possible application of a method of incorporating a coloring matter into an ophthalmic lens of organic material according to the present invention.

These figures illustrate the application of the invention to ophthalmic lenses.

In Figure 1, under the general reference 10, such an eye lens can be seen.

By eye lens is meant here the blank with circular circumference, which allows the optician to mount in any spectacle frame, after the rim of this optician

21 o 51

was appropriately cut, is delivered.

Bs is in this Pail an eye lens made of organic material, eg. It may also be a poly (ethylene glycol di-allyl-di-carbonate) ophthalmic lens commonly sold under the trade designation "CR 39". It could also be a polycarbonate or polymethylmethacrylate ophthalmic lens or a transparent polyurethane act. ·

The object of the invention is to enable the incorporation of a coloring substance in the transparent base substrate of organic material constituting such a lens.

For this purpose, it is proposed to work with thermal transfer _s ie a colorant _s which at least consists of such a substance in part, to bring a lens of organic material into contact and subjecting the fabric simultaneously to heat.

Of course, the chosen substance must be compatible with the organic matter.

In addition, it must have a vapor tension, which allows the use for thermal transfer '.

Especially, those of the coloring substances belonging to the group of spiropyranes satisfactorily satisfy this double requirement.

As is well known, substances are those of the following general formula:

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in which the symbols indicated have the following meaning:

A = O, S, C with two substitution alkyl radicals; B = S, H substituted by an alkyl, hydroxyalkyl,

AlkoxyalkyIradikal; IL = H, alkyl radical, aromatic, alkoxy, halogen,

Hitril-, Phenoxyradikal; S = aromatic radical with one or more Rp

Substituentenj

R ₂ = halogen, nitro, alkoxy radical; Q = aromatic cyclic system or a heterocycle

for incorporation of R 1 alkyl, halo substituents.

Other coloring substances, which are also satisfactory, belong to the group of dithizonate metals.

These are certain internal complexes between different metals and dithizone, which corresponds to the following general formula:

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C ₆ H ₅ - % =

~ C = SC ₆ H ₅ - H - ϊ ^

H H.

In practice, the application of these substances preferably takes place in liquid form or in paste form.

In general, the procedure is thus such that the chosen coloring substance dispersed in a suitable solvent and the resulting mixture evt. A binder is added, which plays the role of a densifying agent and allows obtaining the desired viscosity.

When used in liquid form, such a binder may be nitrocellulose. In the application variant P ^ benform this binder z. As collodion or plasticized nitrocellulose.

In one case as in the other case, especially if the chosen coloring substance is a spiropyran, the solvent may be amyl acetate, butyl acetate, a mixture of these two solvents or else an aromatic solvent.

The application of the resulting coloring matter to the lens 10 may, if desired, directly, for. However, the application is preferably carried out with the aid of a temporary auxiliary carrier to which this coloring material is initially applied.

Such a procedure becomes ζ. Β. in Pig. 3, on which the lens 10 to be treated can be seen.

As a temporary subcarrier z. B.ν a layer of kraft paper 11 or a layer of filter paper can be selected.

Such a layer of paper is entirely coated with a coloring matter coating 12, as defined above, then dried by evaporation of the solvent (s) initially contained in that substance.

Apart from the fact that this solvent makes it easier to disperse the coloring matter used for the preparation of the desired coloring matter, its evaporation makes it possible to dry the paper layer 11 to which it is applied faster.

Regardless of whether this coloring material is applied directly to the lens 10 or applied to a paper layer 11, which in turn is applied to such a lens 10, the method according to the invention also includes exposing this substance to arms when it is in contact with the thin lens becomes.

In the example of application illustrated in FIG. 3, this application of heat is carried out by means of a mold heater 13 which has the shape of the lens 10 to be treated in order to transfer the paper layer 11 with the coating of dyeing substance 12 au according to arrow F of FIG.

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The device 13 is a short time, z. B. 45 seconds, applied, with a pressure sufficient that the desired contact between the coloring material and the lens 10 sets under proper conditions.

The temperature of the device 13 is chosen so that the temperature of the temporary auxiliary carrier layer 11 remains limited and z. B. between 180 " ⁰ C and 220 ⁰ C.

If desired, the lens 10, before being brought into contact with the coloring matter coating 12, may be preheated to a temperature lower than that of the later-to-be-achieved thermal transfer and of the order of, for example, 100 ^° C.

However, this lens may also be left at ambient temperature until it is treated.

Also, if desired, it is possible to avoid any contact between the heater 13 and the temporary subcarrier layer 11, to interpose a layer of the same type as the last one (not shown) between this device and this layer.

However, in the heat application to the coloring matter 12 by the heater 13, at least a part of the coloring matter constituting this cloth is sublimated, and since this sublimation is in contact with the lens 10 to be treated at least part of the vapor formed is absorbed by the organic material constituting this lens.

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After thus ensuring incorporation of such a coloring substance into the organic substance of the lens, the treated lens 10 is washed with a solvent which enables elimination of the excess coloring matter which has not been sublimated and eventually the binder initially associated with this substance ,

The part of the coloring substance which, after sublimation, has migrated into the organic material constituting the lens 10 and has been absorbed here, then forms in the mass of this lens on the surface thereof in the vicinity of which it is arranged, as in FIG Figure 2 illustrates a zone 15 which forms an integral part of this lens as it results from migration of an external substance into it and has the desired parabolic properties due to that substance.

For a better illustration of the invention, practical examples of color mixtures which are used according to the invention and can be satisfactory under their conditions of use follow below.

In addition, for each mixture, a visual check is carried out as follows:.

The subject lens is subjected to ultraviolet radiation for one minute, this radiation coming from a mercury vapor lamp of 400 W, which reproduces the solar spectrum by means of an interference filter, and the optical density of this lens before irradiation (Dq), then measured after irradiation (D),

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The difference Δ D = DD _Q characterizes the effectiveness of the corresponding color mixture ·

Mixture 1 Composition Coloring substance s

Tri2-N-ethoxy-2,4 ₉ 6-phenyl-mercury - dithizonate 2%

Λ Solvents »

Ethyl alcohol 59 %

Ethyl acetate '19 %

Thickener:

Nitrocellulose softened with dibutyl phthalate 20 %

Procedural lessons:

- A filter paper is soaked with this mixture and allowed to dry until completely dried;

- The paper is then placed on the lens to be treated and by means of a metal plate, a Fonn-

_N heater forms, for 45 seconds at 210 ⁰ C heated; After transfer, the lens is washed with acetone.

Results

D ₀ S 0.1146 D = 0.2628 ^ D = 0.1482

Mixture 2

composition

Identical with mixture 1, with trifluoroethyl-2-phenyl-mercuric dithizonate as coloring substance.

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Procedure steps: Same as mixture 1

- Results D ₀ = 0.0836 D = 0.1864 ^ D = 0.1028

Mixture 3 . , '

composition

Identical with mixture 1, but with cyclohexyl mercuric dithizonate as coloring substance.

Method steps;

As with mixture 1

Results

D ₀ = 0.1379 D = 0.2328 AD = 0.0949

Mixture 4

composition

Identical with mixture 1, but with phenyl-quecks overdithizonate as coloring substance.

Procedure as for mixture 1

Results

D ₀ = 0.1403 D * 0.2219 AD = 0.0816

Mixture 5

Zusammenset Zung Coloring substance:

-2-spiro- ^2f -nitro-6 * -methoxy- ^8f -

210 Si

benzopyran ° 1 %

Solvents and thickeners:

Benzene '10 %

Glyzorophthalic varnish ° 89 %

Method steps; As with mixture 1

Results

D ₀ = 0.1278 D = 0.4330 AD = 0.3052

Gemis ch 6

'' Ii · ».ι in * ii« ι ^

Composition Coloring substance s

[i) imethyl-3 _s 3-isopropyl-1-indolino [] -2-spiro-2'-nitro-6-methoxy-e'-benzopyran 1%

Solvents and thickeners:

Benzene 10%

Glycerophthalic varnish 89 %

Process steps: J Same as for mixture 1

Results

D ₀ = 0.9545 D = 0.2104 AD = 0.156

Mixture 7.

composition

Coloring substance:

£ diBiethyl ~ 3i3-isopropyl-1-indolines] -2-spiro-2'-nitro-6-

methyl thioisopropyl 8'-benzopyran 1 %

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Dissolving and thickening agents:

Benzene 10 %

Glycerophthalic varnish 89 %

Procedure as in mixture 1

Results

D ₀ = 0.0696 D - 0.1349 AD = 0.0753

Mixture 8 Composition Coloring substance:

Methyl 3-benzothiazole -2-spiro- ^2f -nitro-6 · methoxy-8 * -benzopyran 5 %

Benzene 95 %

Steps:

The mixture is applied to the lens and the solvent is allowed to evaporate. On the surface of the lens to be treated, an aluminum foil is applied, which serves as an intermediate layer between the same and a heating plate. It is heated to about 210 ^° C. for 30 seconds.

Results

D ₀ = 0.0362 D m 0.0835 B D = 0.0473

Mixture 9

composition

Coloring substance:

[Methyl 3-benzothiazole J -2-spiro-2 ^L -propoxy-3'-nitro-6 ^L -

methoxy-8'-benzopyran 5%

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Lb'sungsmittel:

Benzene 95%

Operating procedure As for mixture 8

Results

D ₀ = 0.0362 D «0.0706 ^ D = 0.0464

Mixture 1Q

composition

Coloring substance:

[Methyl-3-benzo-3-co-1,3-1,3] -2-spiro-2'-phenoxy- ^ ^f -nitro-

6 * -aiethoxy-8'-benzopyran. · 5 %

solvent:

Benzene. 95 %

Yerfahrenssohritte t

A filter paper is wetted with the mixture. The dried paper is then brought into contact with the lens to be treated, then 45 s is heated to 200 ⁰ G.

Results

D ₀ «0.0605 D = 0.1238 AD = 0.0633

Mixture 11

Zusai a xnenee t Zung

Coloring substance:

[Trimethyl-3,4,4-oxazo]] -2-spiro-2'-propoxy-3 * -nitro-

6 * -methoxy-8'-benzopyran 5

21 Ö. S14 " ² ° -

Solvent: *

Benzene 95 %

Verfahrensschrittei

As with mixture 10

Results

D ₀ = 0.0530 D 0.0942. ^ D = 0.0412

J Mixture 12

Composition

Coloring substance ί

[Hexamethyl-3,4,5,5,6,6-oxazine-1,33,2-spiro-2 »-methyl-

3 ^l -nitro-6i-inethoxy-8 ^t-benzopyran · 5%

Solvent:

Benzene 95 %

Procedure: Same as mixture 10

Results .

J D ₀ = 0.0540 D = 0.0757 ^ D = 0.0217

Of course, this invention is not limited to the types of applications described above, but includes any variant. In particular, it is possible to carry out the thermal transfer in a vacuum, whereby the required temperature for such a transfer can be reduced.

In addition, as was to be understood, the depth of penetration of

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coloring matter: unimportant in the eye lens in question, Important is the global density of this substance in such a lens, seen across, ά. H. global parallel to the optical axis of the same.

Claims (9)

21 0 514 -22- claim for invention A method for incorporating a coloring substance into transparent organic base substrates, in particular an eye lens, characterized in that a contact between such a substrate and a coloring material, which is formed at least in part from such a substance, and the coloring material transferred to the organic substrate with the application of heat. 2 ί Ο 51 2. The method according to item 1, characterized in that the dyeing substance from a temporary support made of a thin layer, for. As filter paper or kraft paper is transferred to the substrate to be treated. Method according to item 1 or 2, characterized in that the heat is transferred by means of a mold heater, which has the overall shape of the substrate to be treated. 4. The method according to any one of the items 1 to 3, characterized in that the substrate to be treated is preheated to a temperature below the transfer temperature before contact with the coloring material. 5. The method according to any one of the items 1 to 4, characterized in that a spiropyran is used as a coloring substance. 6. Method according to one of the items 1 to 4 »characterized in that a dithizonatatme metal is used as the coloring substance. 7. The method according to any one of items 1 to 6, characterized in that the treated substrate is washed after the thermal transfer with a solvent. 8 »Method according to items 1 to 7> characterized in that a transparent substrate of organic material is colored. 9. The method according to item 1 to 8, characterized in that the coloring material is introduced into the vicinity of the surface of the organic substrate. See "7 page.