DE2443164C2 - THERMOPLASTIC PLASTIC FILM WITH RADIATION CHANGING PARTICLES - Google Patents

Description

3. Thermoplastic plastic film according to claims 1 and 2, characterized in that that it contains mixtures of various radiation-modifying particles.

4. Thermoplastic plastic film according to claims 1 to 3, characterized in that the radiation-modifying particles are grains, rods, threads or fibers, the

of the same kind, with the naked eye on non-luminous or possibly differently luminous underground can be perceived.

The particles are generally added to the film in amounts of preferably 0.03 to 10 percent by weight, preferably 0.3 to 2 percent by weight, based on the total weight of the film, additional weight. In principle it is also possible to reduce amounts below

Contains amounts of 0.001 to 1%, based on the total film weight.

7. Plastic film according to claims 1 to 6, characterized in that it does not convert radiation Pigments is colored in a shade that is visible when viewed: m Light largely corresponds to the hue of the radiation-changing particles.

8. Plastic film according to claims 1 to 7, 55 0.03 percent by weight and over 10 percent by weight characterized in that they can be used as radiation; for amounts below 0.03 percent by weight however, changing particles with traces of heavy metals result in a poor optical activation Salts of metals of group II of pressure, and in amounts of more than 10 percent by weight contains periodic table. on the one hand difficulties arise with the thermo-

9. Plastic film according to claims 1 to 8, 60 plastic processing of the mass to film, characterized in that they are radiative and, on the other hand, the individual particles are not changing particles with heavy metal traces can be perceived more completely separately from each other, contains activated zinc sulfide. The strength range of thermoplastic

10. Use of plastic films according to the stoffoiien is variable within wide limits. He lies in Claims 1 to 9 as information carriers, in particular in the range from about 2 to 2000 μ, especially for the production of ID cards, Sckeck- preferably 15 to 1000 μ, in particular 25 to 750 μ. or credit cards. The lower film thicknesses from 2 to 20 μ.,

preferably 3 to 15 μ, are preferred by loading

Layering of solutions or dispersions on one suitable carrier material, such as. B. a thermoplastic plastic film or paper, according to itself known processes, for example by roller or anilox roller application, caster, flower, with or without dosage, e.g. B. by squeegee or air brush, and subsequent drying of the solution or Dispersant generated.

From about 20 to about 2000 μ, the known manufacturing processes for thermoplastics are preferred Plastic films, such as extrusion, calendering or pressing, are used to make the films that convert the radiation Particles incorporated therein to produce, being a composite production with others In some cases, foils or paper are advantageously used together or immediately after production the films according to the invention can be carried out. Also a combination of the coating and Incorporation process is possible, for example in the case of a coated film Cause luminous effects in the layer and in the carrier film. The coating method is preferred used when the radiation-changing particles are exposed to higher temperature and shear loads, as they occur in thermoplastic processing methods, cannot withstand.

As particles that convert invisible, electromagnetic radiation into visible light (hereinafter "Radiation-changing particles" called) are preferably those that, when excited fluoresce with ultraviolet light in visible light; z. B. inorganic phosphors, such as sulfides, Selenides, silicates and tungstates of alkaline earth metals, zinc and cadmium, as well as calcium halophosphates, those used to activate heavy metal traces, for example copper, silver, antimony, bismuth, tin, lead, titanium or manganese as individual components or in a mixture with one another, as well as the so-called "Lenard phosphates". Activating zinc sulfide is particularly suitable.

Organic luminescent pigments are also suitable, provided they are produced under the film or coating production conditions do not go into solution largely homogeneously, for example 2,5-bis [5'-tertiary buty! benzoxazolyl (2 ')] thiophene and dibenzoxazolylnaphthalene when used in aqueous dispersion in the coating process.

The known substances or bodies can also be used as radiation-changing particles, if they are not largely homogeneous under the film or coating production conditions go into solution that contain inorganic or organic radiation-modifying substance, for example Plastic particles (grains, rods, fibers) that have been provided with optical brighteners.

The radiation-changing particles are not bound to any particular shape or size they can vary within wide limits. For the size of the particles downwards there is one The limit is set when the luminous effect of the individual particle is low or too small if the particles are too small. seems too weak for the human eye without aids. Conveniently own them the shape of grains, the geometric shape not being critical, rods or of threads; included the grain diameter or the rod or thread thickness is generally in the range of about 0.3 to 600 μ, preferably from 0.5 to 100 μ, in particular from 1 to 30 μ, and the length of the rods or the threads in the range from 0.03 to 20 mm, preferably from 0.5 to 5 mm.

In order to avoid processing difficulties, the particle size (diameter) should in general not exceed * / s of the thickness of the film in which the particles are contained. Mixtures of different radiation-modifying particles can also be used in a film according to the invention.

The insolubility of the radiation-changing particles in the Foüen mass can either be a basic property the radiation-changing substance (e.g. ZnS). It can also be achieved by one in themselves in the film mass soluble or dispersible radiation-changing substances in substances, z. B. in the film mass insoluble polymers, dissolves or dispersed or to this by absorption or chemical reaction binds, as a result of which it does not go into solution or goes into solution only slightly if the in the Film mass largely insoluble substances, such as polymer particles, in the processing of the Foil mass are distributed.

The radiation-changing particles are the ready-to-use plastic mixture according to known Procedure, e.g. B. in a fluid mixer to mix. The mixture can be used for homogenization in special cases it is then gently ground, however, it is important to ensure that that the particles are not crushed too much. The same also applies to subsequent processing steps, provided that high shear stresses occur.

All conventional thermoplastics are suitable as thermoplastics for the production of the films Polymers that are largely inert to the radiation-converting particles, such as. B. polystyrene, its mixed and graft polymers with acrylonitrile, butadiene and acrylic esters, polyvinyl chloride, its mixed and graft polymers with vinyl esters, vinyl ethers, acrylates, methyl methacrylates, Styrene, α-olefins such as ethylene, propylene and butylene, butadiene and acrylonitrile, polyvinylidene halides, such as polyvinylidene chloride and polyvinylidene fluoride, polyamides, polyolefins, polyacrylic and vinyl esters, thermoplastic polyurethanes and cellulose esters. These thermoplastics can can be used alone or in admixture with one another. Furthermore, the usual processing aids, such as stabilizers, inhibitors, lubricants, plasticizers, solvents, dispersants, etc. be added, care must be taken that the effect of the radiation-changing particles is preserved remains and not through chemical change or too high general absorption for the effective, invisible electromagnetic radiation is prevented.

If the use requires or permits, the films according to the invention can advantageously also be used pigments that do not change radiation are colored, whereby a color is preferably chosen, which comes very close to the inherent color of the radiation-changing pigments in visible light, which means the presence of these radiation-modifying pigments is largely unrecognizable without aids will.

In addition to the radiation-changing particles not dissolved in the film composition, those according to the invention can be used Slides one or more when loading

5 6

radiation with ultraviolet light fluorescent parts by weight

Substances in amounts from 0.001 to 1 · / », preferred dibutyltin dithioglycolate

from 0.005 to 0.2% based on the total film stabilizer 1

weight, containing these substances in the titanium dioxide 6

Plastic compound soluble or in as fine and equal 5 phosphor based on zinc sulfide,

moderate distribution must be dispersible that mean particle size 18 μ 0.5

their fluorescence to the naked eye largely beyond

the entire surface is perceived evenly. is for 2 minutes in a fluid mixer. Particularly suitable for this are optical * brighteners, homogenized, plasticized on a roller mill at 150 ° C, for example compounds with aromatic or IO, and on a four-roll calender for heterocyclic ring systems, which with, given temperatures of 160 to 180 ⁰ C with brief, if nuclear-substituted, benzoxazolyl residues are substituted, heating to 220 ° C to a 0.3 mm thick film, or derivatives of coumarin or processed. This film is pressed between heated stilbene with optionally substituted benzotriazole plates at 170.degree. It shows after cooling or triazine residues, which are far i; are soluble when illuminated with normal daylight or artificially. Which prefers a uniform, pure white color with light from other light. According to the invention, at a wavelength fluorescing in the ultraviolet radiation source, the film appears dark. Particles present in the plastic film then appear littered with bright greenish dots. One as a "starry sky" on a different and preferably foil made of the same mixture without a background that shines less brightly. 20 additive appears evenly in ultraviolet light

The production of composites, the foils with dark,
Containing radiation-modifying particles occurs in

Usually by thermoplastic compression, example 2
Welding or gluing, whereby at the same time

or subsequently embossings are applied 25 A mixture of

can. Parts by weight

The thermoplastic synthetic according to the invention polyvinyl chloride 56.5

Foils can be used wherever mixed polymer made of acrylonitrile,

inconspicuously marked foils are required, butadiene and styrene (ABS) 40

For example, as an information carrier for receiving 30 dibutyltin dithioglycolate

a printed and / or embossed image, a descriptive stabilizer 1.5

ble layer or a magnetic sound layer, with 0.5 in montanic acid ester wax

the latter two cases a one-sided coverage of stearic acid 0.5

According to the invention, markings optionally in glycerol monooleate 1

Must be bought if it is not 35 Titanium Dioxide 10

prefers the layer itself with radiation-modifying phosphor based on zinc sulfide,

to provide the particle. The mean particle size is preferably 18μ 2

Films according to the invention as a component of composites with other films and / or paper is used, as described in Example 1, to form a film, these films in turn or the paper 40 of 0.15 mm thickness being processed, with the calender being used as Information carriers in temperatures of about 200 ^° C. described above can be used. can serve ben kind. Photographs or other The film shows after cooling when illuminated with photomechanical reproductions are also a similar to normal daylight or artificial light a color which is relatively pure white with the films according to the invention. Reversible under an ultraviolet. 45 radiation source, the film appears dark with a

The large number of bright greenish dots according to the invention are particularly suitable.

Foils for the production of ID cards, checks or a foil from the same mixture without luminous

Credit cards and in similar areas of application, the addition of substances appears the same in ultraviolet light.

but their application is not moderately obscure in these areas,
limited. 50

Advantages of the films according to the invention are Example 3
among other things, the little elaborate production that

inconspicuous labeling with simple, zer- A mixture of

If the methods work properly, parts by weight are tested

can. For higher demands on the marking 55 polyvinyl chloride 92.4

can be red dot counters that also have a copolymer made of vinyl acetate

on certain wavelengths of the radiation and ethylene 6

light emitted from converting particles- dibutyltin dithiocarboxylic acid ester ... 1

are correct. Montanic acid ester wax 0.3

In the following, the invention is explained using "o stearic acid 0.3

Examples explained in more detail without referring to this titanium dioxide 10

restrict games. Di-benzoxazolylnaphthalene 0.05

_n . -11 phosphor based on zinc sulfide,

^{a e i s} P » ^e ' ^l mean particle size 18 μ 4

A mix of 65

As described in Example 2, parts by weight become a film

Polyvinyl chloride 96 of 0.5 mm thickness processed. The slide shows

Montanic acid ester wax 3 cooling when lighting with normal Taees-

light an evenly white color. The film glows moderately under a source of ultraviolet rays light bluish-purple and is covered with a multitude of bright yellow-green luminous points, which are clearly visible from shining in a different color. Lift off the ground.

. Example 4

A mix of

Parts by weight

Mixed polymer made of acrylonitrile,

Butadiene and Styrene (ABS) 100

Montanic acid ester wax 0.3

Stearic acid 0.3

Titanium dioxide 12

2,5-bis [5'-tertiary butyl

benzoxazolyl (2 ')] thiophene 0.005

Phosphor based on zinc sulfide with

an average particle size of 18 μ ... 8

is heated to 140 ° C in a heating-cooling mixer, cooled and on a single screw extruder with 90 mm screw diameter and slot die at housing temperatures of 170 to 180 ° C to form a film, which after treatment in a Smoothing roller mill at 85 ° C a thickness of 0.7 mm having. The film shows the same behavior in daylight and ultraviolet light as in Example 3 described.

Example 5

ίο A film as described in Example 2, but without a phosphor, is treated with an aqueous dispersion containing 40 percent by weight of a methyl methacrylate polymer with other vinyl compounds and 0.15 percent by weight of dispersed di-benzoxazolylnaphthalene with an average particle size of 2 μ. contains, coated with 5 g / m ² dry weight (about 4 μ layer thickness) and dried at about 70 ° C in a stream of air. The coated film shows a practical effect on both sides in normal daylight or artificial light

ao same white coloring. Under an ultraviolet ray source the film appears evenly dark on the uncoated side and on the coated side On the side it is covered with a multitude of fine, bluish, bright dots.

«096361

Claims (2)

Claims - articles of daily use that represent a certain value, such as documents, means of payment, etc., should be designed in such a way that their forgery or falsification is on the one hand as difficult to accomplish as possible, on the other hand it is as easy and quick to identify as possible. Lately, thermoplastic plastic films for the production of such consumer goods, such as. B. ID cards, check 1. Thermoplastic plastic film, which contains undissolved particles, which irradiated, invisible, convert electromagnetic radiation into visible light, characterized in that, that the film changes the radiation Contains particles in so small an amount that when irradiated by an io cards, credit cards, used. Here are above all Individual particles generated luminous effect separately from composites of such films with each other and with other mostly printed, written or coated information carriers, such as. B. paper, Photographs, magnetic layer carriers, common, whereby these composites also metal foils, over the entire surface or in Strips, may contain. It is known to increase the security against counterfeiting difficult-to-copy print patterns and certain specialty inks. Further in 2 to 20 μ thickness on a carrier material ao is known, the print carrier by watermarks is present. or to mark with colored fibers. Especially at Plastic films, the latter methods are not applicable because z. B. when incorporating. Fibers in the usual form with paper, processing difficulties arise due to flow disturbances, etc.; in addition, a partially differently colored background is often undesirable because it, for example the clear visibility of the print especially; impaired in unfavorable light conditions and The grain diameter or the thickness in the range of 30 is also often not aesthetically satisfactory. Also will range from 0.3 to 600 μ and the length of a marking that is visible without any aids Rods, threads or fibers in the area easily recognized by a possible forger, what the 0.03 to 20 mm. Protective effect reduces and the possibility of the 5. Thermoplastic plastic film after the user of a forged document; or number claims 1 to 4, characterized in that being caught red-handed is reduced It has now been found that these disadvantages of violet light fluorescent substances can be avoided by a thermoplastic polymer quantities from 0.001 to 1%, based on the fabric film, which contains undissolved particles, which are a Total film weight, contains invisible electromagnetic radiation emitted in art Convert mass of matter in such a fine and even distribution into visible light, with the mark, that the fluorescence largely causes the film to contain these particles in such a small amount, evenly over the entire surface of the film, optionally in the presence of soluble or unmit visible to the naked eye. soluble, finely divided, not separately perceptible, 6. Plastic film according to claims 1 to 5, containing fluorescent substances, that when irradiated characterized in that the luminous effect produced by individual particles is 45 in the film, mass largely soluble, optical brighteners in separate from the luminous effect of other particles of the the luminous effect of other particles of the same kind with the naked eye on non-luminous or differently luminous background can be perceived. 2. Thermoplastic plastic film according to claim 1, characterized in that it is used as Layer is part of composites with other foils and / or paper or that it is used as a layer