DE1446828A1 - Reflex reflective transfer film - Google Patents

Description

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Heflex reflective transfer film

The present invention relates to a reflex-reflecting transfer film which is provided with a carrier layer on its reflex-reflecting surface which can be peeled off in the dry state. The present invention also relates to a novel method of making reflective articles. ^!

The objects produced according to the invention can particularly be used as reflective markings and signs be used on flexible substrates such as a wide variety of clothing, fabrics and fabrics. Jackets, Coats, headgear, raincoats, shoe covers and the like Finished items of clothing can be marked with the characters proposed according to the invention.

So far, no successful reflex-reflective transfer film has been proposed from which the required

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Such protective carrier coating on the reflective surface could be peeled off in the dry state, with a firmly adhering, weather- and heat-resistant, flexible marking or the like remaining on an item of clothing, which is directly effective as a reflective device and of contamination of the lens-shaped reflective device Surface was free. The surface of the lenticular reflex-reflecting structure, from which the carrier material must be completely detached, is an irregular surface with projections which extend into the material to be detached from the protective carrier arranged thereon. The mechanical detachment of the surface of a carrier coating to be detached from the lens-shaped surface of a reflex-reflecting structure was "previously difficult; it was therefore necessary to wash off contaminants from the lens-shaped surface with a solvent. Although lens-shaped reflex-reflecting structures have been known for many years Such structures were previously inaccessible in the form of a flexible transfer film with a protective carrier layer on the lens-like surface of the structure that could be peeled off in the dry state.

According to the invention, a transfer film structure is proposed which, according to a method, is firmly attached to a fabric can be attached, in which a hot iron firmly pressed onto the support of the structure and then the support, which can be peeled off in the dry state, from the reflective

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Transfer film is peeled off. The behavior of reflective transmission films of the present invention, that have been applied to children's washable clothing by this method has been investigated, these being a repeated washing with the usual household cleaning agents and repeated ironing and wearing over a trial period of withstood about 6 months without losing the brilliant reflective properties or the adhesive strength on the underlying tissue was reduced, so that here proposed transfer film have the properties necessary for practical use. Proportions of fabric covered with a reflective marking wear and fold essentially like the fabric in other proportions of the same garment.

Reflex reflective fabrics are from Canadian Patent 475,177, issued July 10, 1951, is known. In contrast to the structure described there however, the transfer film proposed by the present invention has a dry strippable backing; where the proposed transfer film is suitable for applying reflective signs and markings to already finished garments. This can be called with the help of a Iron or optionally by means of an organic solvent, which is the adhesive of the reflex-reflective transfer film of the structure described here activate. Activation with the help of a solvent is

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especially useful when the transfer film of the present invention on plastic raincoats or similar items of clothing as should also be applied to overshoes and the like. As with mass production, when the transfer film in To be applied in large numbers to clothes and the like, the transfer film formation can usually be dielectric Welding can be applied to the underlying substrate.

The proportion of the composite proposed according to the invention Structure that is transferred to or attached to an item of clothing using the methods described above, is extremely thin and delicate. This portion is so delicate that it cannot be comfortably handled with the fingers alone. This delicate reflex-reflecting transfer film includes a layer of small glass spheres that are in a Flexible and stretchable rubber binder layer partially embedded and permanently bonded therein, reflective Means underlying the glass beads of the structure and a layer of adhesive on the back of the structure. Although the structure can be stretched very easily, the glass beads of the structure are permanently bound in it, so that few, if any, beads in bending or stretching (such as splitting the tissue) in practical use jump off or peel off. The general optical principles of reflex reflection, which also apply to this structure, are in Canadian Patent 420,676, which issued on Jan.

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June 1944 is described. In the re-ironable structure of the present invention, a thermal barrier film or primer coat is sandwiched between the reins bond coat and the adhesive coat placed on the back of the transfer film. In its As a whole, the transfer film is pliable and stretchable and, in separate form, practically impossible to handle.

about making the transfer film manageable is on A removable support is arranged on the protruding optical elements of the reflex-reflecting structure. In addition Carriers include a dimensionally stable carrier pad and a coating of a plastic material on that carrier pad that is coated with the glass beads and the rubber binder in which the glass beads are partially embedded have poor adhesive strength. In the finished structure, the plastic coating surrounds the carrier base removes the protruding portion of the optical elements (i.e., the glass beads of the transfer film structure) and avoids a Wrinkling or shrinking of the transfer film. Without the carrier would fold up the delicate transfer film and be very difficult to spread after a procedure, necessary to fix this film on a surface. In practical use, it has proven to be impossible to place the delicate reflex-reflecting transfer structure on a carrier without the aid of the required carrier To attach pad. The carrier will also

ORlGINAL INSPECTEO

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sheet structure according to the invention the desired dimensional stability so that variously shaped reflective markings from the composite sheet material can be cut off and applied to garments. Outlines of plug witnesses, Indian heads, girl scout badges, For example, letters and numbers can be cut out of the sheet material and applied to the underlying tissue will.

In the drawings, in which a preferred embodiment of the present invention is explained

Pig. 1 shows a cross section through the finished structure proposed according to the invention and

Pig. Figure 2 is a cross-section through the transfer film portion of the in Pig. 1 structure shown, which is on an underlying Tissue surface is applied.

In Fig. 1, the finished layer structure proposed according to the invention is shown in cross section. The structure is shown in the reverse position, with the layer that can be peeled off when dry is at the bottom in the drawing. The carrier 3 consists of a dimensionally stable backing pad or sheet material with a dimensionally stable one on top adhesive plastic coating. This carrier can be removed as a unit from the rest of the structure. To the transfer film portion des in Pig. 1 include transparent beads 1c (with associated reflective pigment masses in the binder layer for the beads), the binder

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layer 1b for the beads, the heat barrier film 1d and the Adhesive layer 1a. On the adhesive layer of the structure A removable layer 2 is arranged so that the adhesive is protected from contamination when it is applied to a substrate.

It is essential that the adhesive protective The removable layer has a lower adhesive strength to the adhesive than the carrier which can be peeled off in the dry state opposite the surface of the reflective transfer film, so that the removal of the adhesive is easily possible without the temporary and Dissolvable connection between the surface of the reflective pile and the plastic coating of the carrier is affected. A surface of the protective coating which is less adhesive than the adhesive layer is obtained, by removing the surface of the non-sticky, removable cover Tor the application on the adhesive layer is embossed. This also reduces the contact area between the removable cover and the adhesive layer but still achieved another surprising advantage. After cutting up the in Flg. 1 structure shown in the for Applied to a desired shape, the portions of the removable embossed protective layer can be removed from the Stick out adhesive layer because of the embossing, by means of a Fingernails or the like peeled off slightly to remove the temporary, removable protective layer from the adhesive will.

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In Pig. 2 of the drawing is the transfer film portion of the figure shown in Fig. 1 on a tissue paper shown = It should be noted that the adhesive content of the transfer film structure is pressed into the depressions of the cloth, so that only a very small amount of the Portion of the transfer film structure lifts or protrudes from the surface of the cloth. Thanks to the flexible thermal barrier film 1d and the binder layer 1b for the balls are the very slight irregularities in the fabric structure balanced; however, the clear beads 1c of the structure remain firmly in the binder layer for the beads bound and the composite structure remains in the position suitable for a brilliant reflex reflection. The one in Pig. The arrangement shown is indicative of a structure made by ironing a transfer film according to the invention on a woven cloth backing is obtained. The adhesive "layer" on the transfer film becomes, of course, a flexible plastic base, e.g. a plastic raincoat, not penetrated to a noticeable extent; A good adhesive strength is nevertheless achieved on such garments without that the transfer film from the surface of the garment stands out significantly.

The following is the process for making the in Fig. 1 described composite structure shown. A suitable dimensionally stable support pad (available under the Manufacturing and use conditions not thermoplastic

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is) is covered with a layer of plastic material, which has only a low adhesive strength compared to the glass beads and the binding material used for the production of the transfer film. For best results, the plastic coating should preferably be thermoplastic and have a melting point between approximately 65 and 177 ^° C., preferably between 107 and 149 ^° C. The coated backing is passed around a hot drum with the dimensionally stable backing pad against the hot drum and the drum being heated to a temperature sufficient to tackify the thermoplastic coating to the backing. The heat-tackified coating of the carrier is simultaneously brought into contact with a mass of small glass spheres located in a trough below the hot drum (ie the drum is immersed in a mass of small glass beads in a trough). The adhesive plastic coating a, uf the carrier absorbs glass beads in a single layer. In a practically flat position, the carrier with the single layer of beads arranged on it - namely the dimensionally stable carrier base preferably lies at the bottom - is heated to a temperature sufficient to soften the plastic coating on the carrier and allow the beads to sink in. The extent to which the beads sink into the plastic coating is surprisingly easy to regulate and can be further regulated by the heating time and temperature. the

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The temperature used is of course determined by the particular melting properties of the plastic coating used on the carrier. It is essential that the balls are allowed to sink into the plastic by at least $ 15 (preferably at least 30 fo) and up to about 50 fo their diameter.

The plastic coating is preferably only about half the main diameter on the carrier applied to the KÜgelehen used. If, for example, glass beads with a diameter of about 0.005 cm are used, a plastic coating with a thickness of 0.0025 cm is preferably used so that a easier melting of the plastic coating and sufficient Sinking of the KÜgelehen is made possible, this even can come into tangential contact with the surface of the underlying dimensionally stable substrate. A Another reason for the use of relatively thin plastic coatings is that the invention Structures that can be attached to clothing by ironing on have good heat transfer properties through the should have peelable backing, which is easier to achieve when using thinner coatings.

Although the term "sinking in" has been used above, partial embedding of the Beads in the plastic coating can also be achieved by heating the structure when it is in the reverse position

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"is found. Those that occur when removing the plastic coating Ejapillary forces are apparently responsible for that the egg yolks are partially drawn into the coating even if the balls are heated when the image is heated lying down. In another embodiment, the GlaskUgelchen with the help of heat and pressure in the one described above Extent to be partially embedded.

The small glass balls used to produce the structure can be of various diameters, but with beads with a diameter of more than about 0.013 cm a rough, grain-like reflective surface the reflective transfer film portion of the object is obtained. Glaskugeleheη with a diameter greater than 100 microns are usually inconvenient, so those up to about 75 microns in diameter are preferred be used. Although globules with an outer nest small diameters (e.g. about 5 microns) are useful for making the structure, beads with a Diameters above 25 microns found most useful in making the structure.

In the manufacture of the reflex-reflecting structures Glass corners are preferred with a lens-like surface with a refractive index (np) of about 1.9 is used, where useful results have also been obtained with spheres with an index of refraction as low as 1.7 and up to 2.0. For the purpose of However, the greatest possible reflex reflection should be achieved

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Spheres with an effective index of refraction of about 1.9 used.

Each partial embedding of the beads in the plastic will cool the plastic to room temperature calmly. The beads are then coated with a hemispherical, reflective coating of silver, aluminum or a other light reflective metal coated by vapor deposition; or the required reflective components The glass beads are created with the aid of a binder for the beads which contains a reflective pigment. So s.B. Pigment flakes made of aluminum, copper or another reflective metal can be incorporated into the binder for the beads; optionally, a reflective pigment, such as l'ita, ndioxyd, can be used. If a reflective pigment is used in the bead binder (this embodiment is preferred), then a rubber adhesive composition containing the reflective pigment to produce the bead binder layer, used, wherein the beads are provided at the same time with the associated reflective components. the , reflective facilities lie under the beads when the reflective reflective transfer film is at the practical use has been applied. The rubber binder composition containing the reflective pigment: e is usually applied to the protruding glass beads of the plastic sch.io.ut with the aid of a diluent, e.g.

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an organic solvent applied. The solvent is then evaporated from the coating at moderately elevated temperatures} it being possible for the coating to be cured or partially cured at this stage of manufacture.

Then the other layers of the structure are brought up, wherein the thermal barrier film is preferably applied with the aid of a solution in a suitable solvent and then is dried and hardened and finally the adhesive layer is applied with the help of a solution in a solvent and dried, whereupon on the exposed back a protective coating with low adhesive strength is applied to the adhesive.

In order to produce a composite structure proposed according to the invention, a calendered paper with a thickness of about 0.015 cm was coated with a 0.03 cm thick layer of polyethylene with a molecular weight of about 18,000. The coated with polyethylene paper was then passed to a, heated to about 77 ⁰ C hot cylinder nourishing the same time the tackified by heat PoIyäthylenoberfläohe was passed through a trough filled with CHaakUgelehen and disposed below the cylinder "* r" Dl "Glaekügelchen had a size between about 45 and 75 microns and an index of refraction of about 1.9. The calendered paper with the single layer of ilaektlgelchen arranged on it, which had been taken up by the polyethylene coating and stuck to it, was then passed through an oven

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passed and there subjected to a temperature of about 132 ⁰ C, with each unit of Polyäthylenüberzugs was suspended about 2 minutes .This temperature By this heating, the polyethylene was softened and the globules were drawn into the coating. They were "drawn into the coating up to about 40-50 $ of their diameter. Since the" calendered paper had a polyethylene coating about half the diameter of the sphere, the glass spheres were able to pass essentially through the polyethylene coating and the one underneath Touch the surface of the calendered paper tangentially. The heating step described here surprisingly causes the spheres to sink into the polyethylene coating to approximately the same extent, regardless of their size. The polyethylene-coated tape was then cooled, whereupon a spherical binder composition containing a reflective pigment was applied to the protruding globules of the carrier structure.

G-e weight parts

Rubber-like butadiene-acrylonitrile copolymer, that from the B.P. Goodrich Company under the trade designation

"Hycar 1001" is marketed

about 55 parts of butadiene and 45 parts of acrylonitrile 9.5

Dioctyl phthalate plasticizer 1.8

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Parts by weight ketone soluble, heat convertible (heat curable)

Phenol aldehyde resin (50 ^a jo plague ingredients

in methyl isobutyl ketone) 15.6

Ethylene glycol monoethyl ether as an organic solvent (Cellosolve) 5.6

Methyl isobutyl ketone as an organic

Solvent 56.0

The composition having the above composition WUR the then 11.5 parts of large, non-sheet-forming of aluminum flakes having a particle size of less than 150 microns, and more was added as about 20 microns. Usually must Heflektion be used aluminum flakes or metal powder having a size below 200 microns in order to achieve a brilliant reflex, which is required for the structure described here | Metal flakes or reflective pigments as small as 2 or 3 microns are also useful.

The adhesive compound was produced according to a known method in which the rubber-like copolymer and the plasticizer were ground to dissolve the compound in the solvent mixture of cellosolve and methyl isobutyl ketone . The dissolved or finely divided rubber and plasticizer were then mixed with the phenol aldehyde resin solution , whereupon the aluminum flakes were dispersed in the mass. The mass was then applied to the glass beads protruding from the polyethylene coating using a blade.

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worn so that a film of the reflective and pigmented binder at a dry thickness of about 0.0025 cm zur iic kb dear, this cover had a weight of et via

p
2.1 - 2.9 mg per cm. This was then EHgelchenbindemittelliberzug by evaporation of the solvent at moderately elevated temperatures that are gradually increased to 65 ⁰ C, dried. When heated to around .65 C it becomes a substantial

not

Hardening of the bead binder coating / achieved; one slight hardening, which is not disadvantageous, can be found on prolonged heating. The hardening of the globular binder can, however, be added at this point Can be carried out using elevated temperatures.

It should be noted that the bead binder coating produced by this process, as can be seen from the drawing, has an irregular or contoured exposed surface after the solvent has evaporated, where this is more or less corrugated and adapts to the Ball of the structure lifts off. If very small glass balls may be used and / or a relatively thicker bead binder layer is used, these irregularities can go unnoticed.

Then a thermal barrier coating or a coating often viewed as a primer adhesive coating, is applied to the bead binder coating. One for this one Purpose of suitable coating has the following composition:

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Parts by weight

Rubbery butadiene-acrylonitrile copolymer as used in the bead-binder coating 12

Ketone-soluble, heat-convertible (heat- curable)
Phenol aldehyde resin (sold by the Varcum Company under the trade designation "Varcum 5476" ) 12.2

Diootyl phthalate plasticizers 2.4

Methyl isobutyl ketone 73.0

This barrier compound was mixed homogeneously using a conventional process in which the rubber-like copolymer was combined with the plasticizer on a rubber mill for easy dispersion in the methyl isobutyl ketone and the phenol aldehyde resin powder was mixed with it homogeneously by stirring,

The flowable Sperruberzugsmasse was then applied by a blade on the KUgelchenbindemittelschicht in such a thickness that a dry film was obtained having a thickness of about 0.001 cm, was evaporated and the solvent by gradually increasing the temperature of the structure to about 65 ⁰ C. Then the thermal barrier cover and the KÜgeloheri binder layer were cured by further increasing the temperature to about 132 ⁰ C for a time of about 10-15 minutes. Suitable hardening can also be achieved by a longer or shorter heating time , however, the heat hardening stage described above is considered to be ideal.

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widely regarded and provides a stretchable and elastic Structure that is solvent-proof and heat-resistant and therefore washed • when used in practice on fabrics or dry-cleaned and ironed repeatedly.

A heat and solvent activated adhesive was then applied to the barrier coating at a dry film thickness of -0.007 cm. The Klebmittelmasse consisted of about 25! Parts of a thermoplastic copolymer of 85 i> vinyl chloride and vinyl acetate 15 ^, about 16.7 parts of dioctyl phthalate as a plasticizer and about 0.5 parts of an aluminum powder pigment as it has been used in the bead bond layer. This oil was dissolved or dispersed in a mixture of about 38 parts of methyl ethyl ketone and 19.8 parts of toluene. This mixture was then applied to the thermal barrier film by means of a blade, whereupon the solvent was evaporated from the coating ^{at moderately elevated temperatures up to about 65 ° C.}

A temporary protective coating is then applied to the exposed dry adhesive coating, the one made from a 0.01 cm thick sheet of embossed polyethylene film duration.

The resulting structure could easily be handled and trimmed for the purpose of making badges and markings will. The temporary protective coating on the adhesive could easily be removed, whereupon the obtained Structure applied to an item of clothing, e.g. a cloth coat could be. Exposure to a hot household

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bttgeleisens (temperature setting for cotton) on the support surface "with moderate iron pressure for a period of 20-30 seconds, the structure was effectively attached to the underlying fabric Area has dropped somewhat, for example to about 38 ^{° C.}

Those involved in making the masses for the diverse Layers of the structure described above can of course be changed without leaving the scope of the invention. The Higelohenbinderschioht and the thermal barrier film can e.g. also consist of natural or synthetic rubber and do not need to consist of the butadiene-acrylonitrile copolymer described above to pass. A suitable heat activatable adhesive or a Solvent-activatable adhesive (with or without pigment, extender and the like) can also, for example, from the conventional thermoplastic adhesive materials in place of plasticized polyvinyl chloride or the like. Manufactured will. Optionally, other thermoplastic materials can be used as part of the dry strippable Carrier used) also the composition of the temporary For example, protective coating with poor adhesive strength for the adhesive can be changed. The essential Relationships between the carrier, the transfer film and

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the removable protective cover for the adhesive layer must, however, "be observed. It is essential that the removable protective coating for the adhesive has a lower bond strength to the adhesive than the backing opposite the lenticular exposed surface of the reflective reflective transfer film structure, In contrast, the carrier base and the associated plastic cover must be separated from the delicate, practically unmanageable, reflex-reflecting transfer film structures with lenticular surface by peeling off in the dry state be completely removable. By such a reflex-reflective A structure with a lens-shaped surface, which has a carrier which can be peeled off in the dry state, is a Substantial progress has been made because "for impurities avoided, which impair the optical effect of the excellent glass beads of the transfer film became.

In the G-picture you can also use colored clear glass beads can be used. Also combinations of colored binders (or different colored layers of a binder layer) and various Colored spheres can be used to achieve certain effects, including a different one visual appearance under reflective conditions compared to normal daytime viewing.

- Claims _{909809/0125 eAD} ORIGINAL

Claims (3)

M 1055 claims ι 1. Transfer film made of a) a transfer layer, made up of an adhesive layer and one on top of it chewy-like binder layer with embedded, partially outstanding microspheres with a refractive index of 1.7 2.0 ", and b) one on the adhesive side e of the transfer layer located removable protective layer, thereby characterized in that the transfer layer (1) is so thin that it cannot be handled alone when in use, and on its front also c) one dry after gluing has peelable backing layer (3), the parts of the microspheres protruding from the transfer layer (1) (1c) are embedded in the carrier layer (3). · 2. Transfer film according to claim 1, characterized in that that the proportion of the dry-peelable carrier layer (3)> in that which protrudes from the transfer layer (1) Parts of the microspheres (1c) are embedded, consists of polyethylene. 3. Transfer film according to claim 1 or 2, characterized in that the transfer layer (1) has an between the adhesive layer (1a) and the rubbery binder layer (1b) has incorporated thermal barrier layer (1d) and that the adhesive layer (1a) consists of a heat-activatable Glue. New documents (Art 7, Paragraph I, Paragraph 2, No. I, Clause 3 of the amendment gu. Of 4.9.1967) 90 9 80 9/0125