DE2250395A1 - HEAT APPLICABLE STICKER AND METHOD OF ITS MANUFACTURING - Google Patents

Description

DENNISON MÄNUFACTURINC COMPANY

Framingham, Massachusetts / V.St.A.
Our reference: D 661

Heat-Applicable Stickers and Processes to

its manufacture

The invention relates to heat-attachable stickers for labeling; it relates in particular to improvements regarding the release properties of dry thermal stickers, when printing such stickers and when applying such stickers to the surface to be labeled, such as e.g. a plastic bottle.

Labeling by means of heat transfer (heat transfer labeling) is very old and has already been described in US Pat. No. 1,030,9.88, in which a heat-applicable Sticker (label) with a "paper backing ^ a Resin c the wax transfer layer and a print and dye pattern on the transfer layer is described. Such transfer layers as described in U.S. Patents 1,331,581, 1,882,593, 2,219,071, and 2,667,003 are but are not for a number of reasons

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completely satisfactory, especially when used on plastic containers transferred and applied.

Improved heat transfer sticker (s) that can be used on based on the use of oxidized waxes as a release layer are widely used in commerce and are described in US Pat 2 862 832 in which a heat transfer sticker (heat transfer label) is described, which consists of a wax release layer on a suitable carrier, a Printer color layer on top of the wax release layer and one through Heat activatable thermoplastic adhesive layer is made on top of the printer ink layer. Although such a heat transfer sticker is used to a considerable extent in practice, certain disadvantages arise in its use on. For example, when transferring to a surface, for example a plastic tab, at least part of the wax separating layer is transferred and undergoes a change in state from molten to solid state. When solidifying, this wax coating causes a cloudiness (known as the HaIo effect or Atrial effect), which to a certain extent at least the imprint pattern is made invisible. In order to avoid this HaIo effect, attempts have already been made to create a Achieve dry separation by making relatively incompatible films from resinous, film-forming materials placed on top of each other, which have such a low affinity for each other have that the two films can be easily separated from each other during use. So is for example has been proposed to use a paper backing (paper carrier) with a polyethylene or vinyl resin release coating (in both Cases are thermoplastic resins) with a layer of varnish over the polyethylene or vinyl resin coating to use «The print pattern (the imprint) is then

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printed onto the varnish coating and the adhesive that can be activated by ^ poor is then applied to the print pattern. Because of the release properties of the polyethylene or vinyl resin for the varnish, although the varnish layer adheres sufficiently firmly to the polyethylene or vinyl coating to permit handling of the sticker as a whole, it is nevertheless dry stripped from the coated substrate during heat labeling (heat transfer) easily detachable. It was "found, however, that it is not only difficult to print such a polyethylene or vinyl resin, but also that the thermoplastic polyethylene and vinyl resins have a tendency under the heat labeling conditions (heat transfer conditions), such as 14-9 to 232 ⁰ C (300 to 4-50 ⁰ I), in particular at 163 to 204 ⁰ C (325 to 400 ⁰ F), which are necessary for a technically feasible dry heat separation labeling The consequence of this is that when stripping a part of the polyethylene or polyvinyl resin is removed at least in some areas with the lacquer layer and the printed pattern, which remains adhered to the labeled surface by the heat-activated adhesive, ie the cohesion the resin separating layer is reduced to less than the increased adhesion in these B at least in certain areas reach between the separating layer and the lacquer layer and the consequence of this is that the break between the separating layer and the lacquer layer is not reliably and uniformly clear ο Although the oxidation of the polyethylene reduces the problem of printing on the same, the problem of achieving a clear break becomes Reinforced in the thermal separation between the dry paper, which is provided with a separating layer, and the lacquer layer. -

For many uses of a thermal release sticker (label)

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it is highly advantageous that the sticker can be produced quickly and in large quantities, for example by gravure printing (etching printing). As stated above, the basic characteristic of a dry heat release sticker is that the pattern transfer layer is printed on an auxiliary carrier which has only a relatively low affinity or adhesion to the pattern layer, so that it can be easily separated therefrom by dry separation during heat labeling (heat transfer) is. In the tape gravure printing method, the carrier, for example a provided with a release paper is successively brought into pressure contact with a plurality of printing cylinders to the required layers of the label (label) applied, thereby obtaining a finished composite layer, usually a plurality of different colors having. It has been found that if it is attempted to provide a carrier with a dry release coating, for example with a material other than one made of wax or wax-like materials, which crack during the heat separation and accordingly have the disadvantageous halo effect mentioned above, with a To provide a variety of films by the gravure printing process, particularly serious difficulties arise in both printing and heat transfer. The first layer, which is printed onto the dry, release lined paper, must necessarily be relatively incompatible with the release coating on the carrier and only have a low affinity for this release coating so that the desired dry release properties are achieved in the finished article will. Accordingly, when this and the subsequent layers are applied, there is a marked tendency that, because of the greater affinity of this layer and the subsequent layers for the printing cylinder than for the separator

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Coating on the carrier can be detached or lifted off from the dry release layer. This difficulty is particularly severe when using a gravure printing method because the support or pad is in contact with the printing cylinder or printing plate under pressure. Accordingly, the manufacture of a relatively inexpensive dry thermal release label by printing a plurality of superimposed films on a dry release liner using a belt gravure press or the like has not proven technically suitable. Where such attempts have been made and tape gravure printing techniques have been used, the finished thermal label was such that high speed labeling could not be performed without difficulty in separating the label from the labeled surface, ie »When the adhesive bond between the release coated paper and the first printing layer was made strong enough to prevent the above-mentioned peeling _f such delamination occurred»

Although this problem is not as severe with wax or wax-like (non-dry) release coatings because the adhesive bond between the wax layer and the transfer or printing layer is strong enough to separate to prevent during the printing, this strong adhesion, which is advantageous during the printing, makes separating the release liner from the transfer layer (Labeling layer) required by breaking the heat-softened wax layer, which leads to the disadvantageous HaIo effect and which requires further heating to remove the surface on top of the print pattern attached to the labeled surface adheres, making residual wax transparent (clear).

In summary, it should be noted that the use of conventional

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dry release layers, for example those made of silicone, transparent Teflon, polyethylene, vinyl resins, etc., problems related to sufficient adhesion of the print, ie the transfer layer, on the dry release layer during high-speed gravure printing or high-speed screen printing and during subsequent handling brings. Moreover, the material, etc. appears when using conventional thermoplastic dry separation material! S such as _o polyethylene, vinyl resins, cellulose materials, v / verifiable or it changes its shape in such a way during heat transfer, probably due to increased temperature between 149 "and 232 ⁰ C (JOO to 4-50 F), which is used in such a dry release transfer, whereby the cohesion of the release layer is reduced and the adhesion of the same to the transfer layer (release layer) is increased too much. As a result, part of the release material remains on the print pattern transferred to the labeled surface, which is highly undesirable, or in some cases a part of the print pattern remains ai;: f of the separating layer "

It has been found that in other cases when using of resinous dry release liners under the Heat transfer conditions the cohesion between the separation layer and the transfer layer (release layer) adhered thereto and the adhesive strength therebetween change and cause the transmission layer_switch itself in some places separates from the separating layer, which is highly undesirable. Another problem exists with heat transfer labeling in that the use of heat activated rubbery thermoplastic adhesives used for transferring the print pattern on certain types of plastic surfaces to be glued, such as those made of polyvinyl chloride, is necessary to distort the print because of the

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rubbery nature of the adhesive. The exposed print pattern is also subject to a chemical Attack and can also be damaged by rough handling and handling.

Another problem with printing on dry peel heat transfer stickers is the difficulty in obtaining an exact registration (match) * between the clear adhesive layer and the print pattern onto which the adhesive is being pressed, especially if the auxiliary backing (auxiliary carrier) is white or almost white, _{or the like} The non-registration (non-registry) of the print pattern has a number of disadvantages, in particular that the print pattern (design print) is not completely covered and that the adhesive also comes into contact with the dry separating layer and during the Heat transfer does not separate therefrom because the adhesion between the adhesive and the release layers is much greater than that between the transfer layer and the release layer. An exact match (coverage) in not so important (non-dry Deduction) wax release layer, since even if the adhesive comes with the release layer in contact with the separation during heat transfer by replacing the softened wax coating still comes about _c Accordingly, the adhesive layer printed on the print pattern may be significantly too large in relation to the print pattern to ensure that the print pattern is completely covered, even if the registration (match) is poor, without the risk of the separation layer separating during the Heat transfer is prevented «

Also, the use of a clear coat of varnish that put together with the print pattern is part of the transfer layer and is located in the vicinity of the dry release layer is highly preferred because the composition of the paint

* (registry)

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layer can be selected so that a good separation from the release layer is achieved during heat transfer is, while at the same time a sufficiently strong bond is achieved to prevent the separation of the same during printing, to prevent during storage and handling «This gives you greater freedom in the Use of common print sample components that are found in other Are more appropriate. The use of a clear varnish that is printed on the release liner and on which the print pattern is printed in coverage increases (adds up) the problems of the exact coverage of the lacquer coating, the pattern print and the adhesive.

The Trerm Dry Heat Transfer Sticker and Procedure for the manufacture and transmission of the same according to the invention eliminates the above-mentioned difficulties.

According to one aspect, the present invention relates to a dry release heat transfer label (dry release heat transfer label) in which the adhesive bond between the release layer and the transfer layer (peel layer), which the print pattern (the imprint) with or without a layer of varnish adjacent to the dry Has separating layer, (1) is sufficient to allow printing (by the gravure or screen printing method) of the transfer layer on the separating layer, which, however, (2) at heat transfer ^{temperatures of up to 14-9 to 232 0} C (300 to 450 ⁰ F ) and higher (a) is considerably weaker than the cohesive forces of the dry release layer, the transfer layer and the heat activated adhesive layer and (b) is considerably weaker than the adhesive bonds between the release layer and the auxiliary carrier, between the transfer layer and the heat activated adhesive layer and between the heat activated adhesive layer and the glued surface, for example a plastic tab.

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Accordingly, during heat transfer (heat labeling) the dry separating layer with the carrier film adhering to it can be easily and cleanly peeled off from the 'transfer layer that is on the glued surface remains adhered by the clear, heat activated adhesive without removing any part of the release liner remain on the transfer layer (peel layer) as in the case of wax or wax-like or polyethylene release layers and without removing any parts of the transfer layer with the release layer. Accordingly Wax-like separating layers are avoided and it occurs. no HaIo effect associated with heat transfer (heat transfer) is linked.

According to a preferred embodiment, this is achieved in that in the dry release layer (this is preferred) and / or in the transfer layer (release layer) a crosslinked, thermoset polymeric resin, preferably a non-silicone, is present around the layer in which it is present to impart a softening temperature which is wesentlich.höher than the temperature of the dry release label, ie, about 14-9 to 232 ⁰ G (300 to 4-5O ⁰ F)., preferably 163 to 204- ⁰ C (325 to 4-00 ⁰ to impart excellent release properties for transmitting (sticking · ^ on plastic surfaces, such as polyvinyl or _{Polyalkylenoberflachen}} is applied, and also to the surface of such a layer in contact with the other layer while allowing F), and a printing without delamination. Although such thermoset resins are highly preferred, certain thermoplastic resins such as polyprop ylene, as long as they have a softening temperature above the temperature of the dry heat release sticker

The one here referring to the resin as well as the dry

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Separating layer and the Ubertragungsschicht used term "softening temperature" means that the material at the dry Tremiwärmeübertragungstemperaturen, ie at temperatures up to about 149-232 ⁰ C (3OO to 450 ⁰ P) is not sufficiently softened to cause the material of its cohesive strength loses and that its adhesive strength to adjacent layers increases to such an extent that it ruptures under the dry heat transfer conditions of separation. Accordingly, there is always a clear break between the separating layer and the transfer layer (peeling layer).

An indication that the bond between the transfer layer and the dry release layer is sufficient to permit printing the transfer and adhesive layers on the release liner without delamination of the transfer layer from the To allow release liner means that the peel strength is significantly higher between the transfer layer and the separating layer; than the peel strength between the transfer layer and the untreated Teflon release surface, between the transfer layer and the untreated silicone release surfaces and between the transfer layer and the untreated polyethylene release surfaces. Of the As used herein, the term "clear" includes both the terms transparent and translucent. The transmission layer preferably also comprises one or more clear lacquer layers, at least one of which is between the printed pattern and the dry separating layer (peel layer) is arranged. These Lacquer layer adheres to the dry separating layer, which is printed on the dry separating surface (print surface), wherein the printing pattern is printed onto the lacquer layer and the adhesive which can be activated by heat is printed onto the printing pattern will.

Where such a lacquer layer is provided as part of the transfer layer and the thermoset resin in the transfer layer

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layer is present is such a thermoset Resin arranged in the lacquer layer adhering to the separating layer. When so arranged, the varnish layer gives since it is made relatively hard (rigid) by the thermoset resin compared to an elastomeric resin j and da them on top of the print pattern after transfer and after peeling off the backing sheet and the dry Separation layer (release layer) adheres and covers this, the print pattern a resistance to rough treatment and chemical resistance. If the heat activated adhesive is elastomeric or flexible, such as polyamide, as desired for use on a labeled polyvinyl chloride surface, it gives the print pattern dimensional stability on the pasted or labeled surface, and thereby the above-mentioned problem becomes the distortion of the print avoided. This is another Aspect of the present invention.

The thermosetting resin is preferably a crosslinked resin from the group of acrylic resins, polyamide resins, polyester resins, vinyl resins, epoxy resins, epoxy acrylate resins, ally resins, aldehyde resins, such as e.g., the phenol-formaldehyde resins, and the aminoaldehyde resins such as urea-formaldehyde and melamine-formaldehyde, and combinations of that. When the thermoset resin is used as a release coating, it preferably does not become up to one plasticized to such an extent that it no longer has the cohesive and adhesive properties specified above "

Examples of thermoset aminoaldehyde resins are copolymers of amino aldehydes with alkyds, styrylated alkyds, Esters, acrylic acids, polyamides and cellulose esters, which are preferred, the copolymers of amino aldehydes with cellulose esters, such as cellulose acetate or cellulose acetate butyrate, are most preferred. The most preferred aminoaldehyde is melaminealdehyde, such as hexametÜoxy-

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methylmelamine. Copolymers deliver optimal results of hexainethoxymethylmelamine and cellulose esters, preferably cellulose acetate butyrate or cellulose acetate.

When the thermoset or other resin is present in the release coating, a preferred material for those on it is i.e. a cellulose ester, such as cellulose acetate, printed onto the release coating. In this case, the However, the lacquer layer consists of other resins (1) as long as it has a softening temperature above the dry separation heat transfer temperatures and (2) as long as the adhesive bond between it and the release layer (release layer) is sufficient to allow the transfer and Allow adhesive layers on the release liner without delaminating the transfer layer from the release liner and (3) as long as this adhesive bond is weaker than the cohesions of the release layer, the transfer layer (including the lacquer and print pattern layers and the bond between them) and the heat activated adhesive layer and as long as it is weaker than the adhesive bonds between the separating layer (peel layer) and the carrier film, between the transfer layer and the heat activated adhesive layer and between the latter Layer and the plastic surface to be glued.

When the thermoset or other resin is added to the varnish layer, i.e., the transfer layer, the preferred separating layer made of polypropylene. However, it can also consist of any other resinous material, as long as (1) their softening temperature is above the dry separation heat transfer temperatures and (2) as long the adhesive bond between the separating layer and the lacquer layer meets the minimum and maximum requirements specified above. Regardless of which of the two Layers containing thermoset or the other resin, the other layer will of course vary in each case

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depending on the resin used to achieve an adhesive bond between the two layers and cohesion of the other layer with those noted above Strength values. Conversely, the thermoset or other resin used in any of the layers can be varied depending on the structure of the other layer to achieve the above-mentioned adhesive bond strength between the two layers and the above-mentioned cohesion of the layer, which contains this resin. In any case, it is highly preferred that neither the separating layer nor the lacquer layer. at least as long as they are in contact with each other, contains a substance that is at the heat transfer temperatures is oily or liquid in that the oil or liquid, like the wax, will split up in the wax separating layers, wherein part remains on the paint surface and part remains on the peeled release surface.

According to a further aspect of the invention is in the clear, thermoplastic, heat-activatable adhesive an indicator compound (tracer compound) is present, which under normal light has sufficient clarity that it does not interfere with the clarity of this adhesive layer,. which, however, becomes clearly visible under light of a certain wavelength or by some other excitation, so as long as it is exposed to this light of a certain wavelength or some other excitation. Accordingly is the glue when you look at the glue layer and the print pattern under this light of the selected wavelength or under some other excitation during or after printing of the sticker (label) is clearly visible to the eye and can therefore be printed on the print pattern be that both exactly coincide, which ensures that no adhesive is printed on the release liner and that the print pattern is completely covered with the adhesive. Such an indicator compound is a fluorescent color

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material of any usual composition or structure, which becomes fluorescent and therefore clearly visible under ultraviolet light. Accordingly, by the Adhesive layer during the printing of the sticker prints on the printed pattern under ultraviolet light, or ultraviolet on the printed sticker Allowing light to act to test its coincidence (consistency), an exact coverage of the normally clear Adhesive imprint on the print pattern achieved while at the same time the adhesive in the finished sticker (label) remains clear.

If a clear lacquer layer is present in the transfer layer (release layer), as is preferred, so is also the above-mentioned indicator compound is present in the varnish printed on the dry separating layer and each full printing operation is performed under the above-mentioned light of a selected wavelength or the finished sticker is exposed to such light the coverage (correspondence) between the paint layer, the

-Layer print pattern and the glue f / in relation to each other too check. In any case, if there is a mismatch (registration), the printing device is switched to usual Way manually or "automatically adjusted to the required Make corrections to achieve an exact match. As the print pattern usually is colored and is therefore normally visible, is not an indicator compound, for example a fluorescent dye, Such an indicator compound is required to achieve an exact coverage between the lacquer layer and / or the adhesive layer but can be present in the print pattern if desired. This is particularly advantageous in a Carrier and a separating layer which are brightly colored, for example white or transparent. By magnification the surface of the lacquer layer compared to that of the printing

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pattern and the adhesive layer and by suitable printing in congruence (correspondence), as mentioned above, Chances are that the print pattern or clear adhesive will be accidentally printed on the dry release liner become to a negligibly small factor with the result that they stick during the dry heat separation decreased. Complete coverage of the print pattern by the adhesive is also ensured. From the above It can be seen from the explanations that the printed pattern and the adhesive imprint both have their edges completely within of the varnish imprint. The adhesive layer can die have the same area or an area larger than that of the printed pattern as long as their area is smaller than that of the paint imprint ο

The use of such a fluorescent or other indicator compound in the adhesive and lacquer layers can also be helpful when transferring the sticker (label) to the surface to be labeled under ultraviolet Light or under some other light of a selected wavelength under which the compound is clearly visible. The clear one Lacquer layer and the adhesive layer of the sticker transferred to the bottle or other surface to be glued remain clearly visible under the light of the selected wavelength.

Indicator compounds can be used that are normally used have sufficient clarity that they do not interfere with the clarity of the paint and adhesive layers that however, under the action of energy waves, especially light waves with a light other than ultraviolet light Wavelength, temporarily become clearly visible, in which case the overlap (correspondence) of the layers under this energy is monitored at a different wavelength, e.g. the normally clear scintillation compositions become in the layers by radioactive

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Rays excited, which causes them to emit visible light. Also usually clear thermochromatic compounds in the layers respond to thermal energy, such as infrared radiation, which temporarily changes their color tone or color changes.

Connections that are usually clear, but those below Ultraviolet light fluorescent and therefore visible are known, such as that from the company Ciba-Geigy under substituted phenylbenzotriazole sold under the trade name UVITEX OB and other triazoles sensitive to ultraviolet light. This also includes the triazines, the diazines, the imidazoles, the oxazoles, the coumarins, the aminocoumarins, the sulfonsulfonic acids, the pyrazolines, the cationic ones Oxacyanines, the imidazolones, the pyrazines, the aminonaphthalimides, the oxadiazoles, the stilbenes and the triazoles, such as 4,4'-dimainosti, lben-2,2'-disulfonic acid, N, N'-diacylstilbene derivatives, N, N'-dibenzoyl-4,4'-diaminostilbene-2,2'-disulfonic acid, 4,4'-bis- (2-hydroxy »4-anilino-1,3,5-triazinyl) diaminostilbene-2,2'-disulfonic acid» 2-naphthotriazolylstilbene, vinylenebisbenzimidazole, Vinylenebisbenzoxazole, 4-methyl-7-hydroxycoumarin, 4-alkyl-7-dialkylaminocoumarins, benzidinesulfone disulfonic acid and Diphenylpyrazoline. All of these compounds are known per se and can be used according to the invention. Many these compounds are excited by radioactive rays and emit visible light.

With the design print according to the invention, it can be in one layer or several individual layers and it can be any conventional thermal transfer printing pattern composition act as long as they have such cohesion and adhesion to the nearest neighboring Layers on v / eist which do not lead to splitting or detachment under dry separating heat transfer conditions. The sticker of the invention is thereby in one aspect

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characterized in that it consists of a release layer and a transfer layer which are composed so that they adhere sufficiently tightly to one another that a pattern can be printed using a tape gravure printing process, and which can be transferred (glued) to a surface as a unit, but with the layers during the transfer can easily be peeled off from each other without detaching the sticker from the glued surface » The subject of the present invention,

heat transferable sticker (label) is suitable

especially for high-speed labeling devices. The type of dry heat transfer ₉ in which the present invention is particularly advantageous is that in which the release layer is in the form of a continuous layer on the substrate, e.g. in the form of a roll or an endless or large film, the sticker (the transfer ) is applied in the form of a print to which the surfaces of the separating layer between the printed India paper (India) are exposed. With this type of thermal adhesive, the fact that it is not possible to achieve precise registration between the adhesive layer and the print pattern layer is a serious problem. "

As stated above}, according to the invention, a heat transfer sticker is specified which consists essentially of 5 layers and is provided with an auxiliary carrier or underlay, a polymeric dry release layer which is arranged on the upper surface of the auxiliary carrier, a clear lacquer layer which is applied to the upper surface of the polymer separating layer is printed on, a print pattern which can have a plurality of layers, which is arranged on the upper surface of the lacquer layer, and is provided with a clear, heat-activatable adhesive layer printed thereon on: j

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-18- 775 (1395

Adhesive top layer

Print sample

printed lacquer layer

Separation layer

carrier

Diagram 1

In the case of heat transfer (labeling), the sticker (consisting of the adhesive cover layer, the print pattern and the printed lacquer layer) (whereby the carrier and the dry release layer during the transfer of the lacquer layer peeled dry) firmly on the label to be labeled Surface, in the cone of a plastic surface, e.g. a plastic tab, 'attached to which he with the through Heat activated adhesive cover layer is transferred, which adheres to the surface to be labeled and wherein the The printed varnish layer is exposed and protects the print pattern. The transferred sticker has an improved chemical resistance and improved resistance to rough treatment is optically clear with the exception of the print pattern (imprint), which may or may not be optically clear, it is free from print distortion and free from a coating layer made of the separating layer material in contrast to the previously known, heat transferable Stickers.

The auxiliary carrier or the auxiliary documents can be of any one suitable material, as it is usually used for carriers for heat transfer (heat labeling), for example from a plastic film, a metal foil or made of paper. However, it has been different from the standpoint of economy and from the standpoint of ease of handling A smooth, clay-coated paper, preferably such a paper, has proven particularly advantageous to use, which holds the applied dry separating layer mass well during manufacture. As you can read above,

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is the heat release layer and / or the printed lacquer layer preferably made of a siliconfreiea _s cross-linked heat-cured en polymeric resin "that is, with the application of heat, as applied in the heat labeling the at 149 to 232 ° C (300 to 450 ⁰ P) does not melt according to the process according to the invention, ie which has a softening temperature of above 149 to 232 ⁰ C (300 to ^ 50 ⁰ F), a preferred heat-cured resin being an aminoaldehyde resin, such as a urea formaldehyde and / or melamine formaldehyde resin . .

As is known, these amino aldehydes are often copolymerized or modified with a cellulose ester, such as cellulose acetate, cellulose butyrate ₃ cellulose propionate or cellulose acetate butyraf in an amount of up to about 80 or 90% by weight of the total polymer composition. According to a preferred embodiment of the invention, the aminoaldehyde is copolymerized with such Celluloseharzj preferably with cellulose acetate butyrate ^ in an amount of 10 to 80, preferably from 25 to 5O ₉ in particular from 30 to 40 wt .-% "It is also known that these uncured aminoaldehyde resins containing a curing catalyst en which causes that the resin hardens (thermosets) and becomes rigid with the application of heat or over time. " A free acid or a salt or an ester of a free acid ₉ which releases the acid at high temperature is preferably used as such a catalyst. A preferred thermosetting catalyst for this purpose is p-toluenesulfonic acid. Preferably, the uncured aminoaldehyde resin is a catalyzed resin. Incidentally, any conventional thermosetting catalyst can be used.

Below is first the production of "the dry, by The heat transferable sticker of the invention with the thermoset resin in the release liner and then the sticker with it

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the thermoset resin in the paint layer.

(A) When the thermoset resin is used in the release liner (release liner), the release liner can be applied to the paper base in an amount of 0 / 1-5 to 2.27 kg (1 to 5 pounds) per ream of paper (where a ream of paper is 500 sheets of 50.8 cm by 63.5 cm (20 by 25 inches) in size). Now, if the paper backing is made up of 7 »26 kg (16 pounds) paper about 0.06 / 5 mm (2.5 mils) thick, the thickness of the thermal barrier layer is about 0.0127 mm (0.5 mils) in a Coating thickness of 2.27 kg (5 pounds) per ream or about 1/4 the thickness of the paper backing after drying and curing. The dry, thermosetting separating layer resin, for example the aminoaldehyde resin, v / ie polyalkoxyalkylmelamine, is applied together with a cellulose ester with which the melamine is to be copolymerized, v / ie eg “cellulose acetate butyrate, and together with a curing catalyst such as p-toluenesulfonic acid paper support applied in the form of a partially cured or uncured solution and then the coated layer on the paper support at the normally recommended for the thermoset resin curing temperatures 121-177 ⁰ C (250 to 35O ⁰ F) heat cured. The resulting ^x cured, dry separating layer made of the thermoset resin has a cohesive strength at the dry heat transfer temperatures which is significantly higher than the adhesive strength on the lacquer layer after printing the same. After the application of the separating layer coated with the release substrate is then coated with the printed clear varnish, vorzugsv / else a clear cellulose resin, such as a Celluloseester coated with a softening point well above 149 to 232 ⁰ C (300 to 45O ⁰ F), ie the cellulose resin used is one which does not noticeably soften or become sticky at the transfer temperatures (labeling temperatures).

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A preferred cellulose ester is cellulose acetate.

The clear cellulose ester can be applied to the separating layer in a common form of lacquer in the form of a solution (with a solids content suitable for the printing conditions used) be applied by a gravure printing process in such a way that its printed (printed) surface is greater than that of the print pattern and the following heat-activated adhesive. This layer serves after drying as a primary coat and as a primer coat for the print pattern and prevents the printing ink from the print pattern (imprint) from migrating or penetrating into the separating layer during the production of the sticker (label). In addition, this makes the sticker resistant to chemical and harsh mechanical treatment after he has been transferred. The dried paint layer has a cohesive strength at the heat transfer temperatures and an adhesion strength to the subsequently printed print pattern which is substantially higher than that Adhesion strength of the same to the separating layer,

As stated above, the combination of the dry release layer results from the thermoset amino aldehyde resin with the lacquer layer from the cellulose resin to a bond between the two layers, which are sufficiently strong to adhere during printing, storage and handling to achieve, which, however, breaks easily when the subcarrier is peeled from the sticker during the heat transfer without delamination of the sticker, i.e. the adherent Lacquer layer, the print pattern and the adhesive layer occurs from the labeled surface. As a result, it is not necessary that the separating layer (release layer) is melted during the transfer and therefore no part of the separating layer is entrained during the transfer and the problem of lack of clarity and appearance

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a HaIo effect is avoided.

The print pattern (the imprint) is printed directly onto the printed lacquer layer in the usual way and as a function dried by the nature of the pattern. The ink used for the print pattern may vary depending on the label and these separate levels vary between 1 and 6 colors, common heat transfer printer colors used, such as nitrocellulose and / or polyamide printing inks, which contain pigments and / or dyes of the desired color dispersed or dissolved therein and which a cohesive strength at the heat transfer temperatures and adhesion strength to the lacquer layer and the subsequently printed, heat-activatable Have adhesive layer that is significantly higher than the adhesive strength between the dry release layer and the lacquer layer. The size of the area of the print pattern is smaller than that of the lacquer layer. The print pattern is arranged with its edge within the lacquer layer so that no part of it with the thermoset separating layer (Peel layer) comes into contact «

After the pattern is applied to the varnish layer, a heat-activatable thermoplastic adhesive layer of a conventional composition is applied to the printing pattern in the form of a solution and then dried. The adhesive layer may consist of a thermoplastic polyamide which is non-tacky under normal conditions, however, (300 to 45O ⁰ F) becomes tacky when heat transfer temperatures from 149 to 232 ⁰ C and which is known per se and are preferably applied in the form of a lacquer is . Such a layer is suitable for labeling pretreated, for example flamed, polyolefin bottles. If polyvinyl chloride surfaces, for example polyvinyl chloride bottles, are to be labeled, then is indicated by

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Heat-activatable adhesive, preferably a conventional plasticized polyamide resin or a conventional yinylacryl resin used. The adhesive layer is applied so that the printed area of the adhesive is larger than that of the print pattern, but that it is smaller than that of the lacquer layer, whereby the pattern between the Lacquer layer and the adhesive layer is included, so that no part of the adhesive is in contact with the dry release liner, i.e. the printed adhesive layer with its edge within the printed lacquer layer. The task of the adhesive layer is to provide a to achieve heat-activated adhesion of the label (sticker) when it is on the surface to be labeled is transmitted.

The vinyl acrylic material used as the adhesive is either a mixture or a copolymer of a vinyl resin such as ZoB. Polyvinyl butyrate, with an acrylic resin such as one formed from acrylic acid or a derivative thereof such as methyl methacrylate ₉ "These vinyl acrylic materials are commercially available products and are in the form of a powder or in the form of a varnish, if both the" vinyl resin Any conventional heat-activatable adhesive, usually a thermoplastic "resin", which is capable of strong, heat-activated (activated at the heat transfer temperature) adhesion to the plastic surface to be labeled can be used to which the sticker is to be transferred can be used as long as this strong adhesion, as well as the adhesion of the heat activated adhesive to the print pattern and the cohesive strength of the heat activated adhesive, are all higher than the adhesive strength of the lacquer and dry release bond .

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The heat transfer label is used to bring the adhesive cover layer into contact with the surface to be labeled, for example a plastic container. While the label (sticker) and the container are in mutual contact, heat and pressure are applied, preferably on the back of the auxiliary carrier, for example by using a heated roller at a temperature between about 149 and 232 ⁰ C (JOO to 450 ⁰ F), preferably üe at a temperature of about 177 ° C (35O ° F)><transmission accomplished. The sticker can also be preheated if desired. After transfer, the carrier and release layers can immediately be peeled off as a unit from the sticker, which now adheres to the labeled surface, or they can be allowed to cool and then peeled off without the risk of delamination of the sticker from the labeled surface . In any case, the unit of lacquer layer, print pattern (imprint) and adhesive layer remains adhered to the labeled surface A suitable apparatus for performing the transfer (labeling) is described in US Pat. No. 3,434,902. Another device is described in U.S. Patent Application No. 857,268. When the transfer or labeling is complete, the sticker consists of three layers. The first layer is the thermoplastic adhesive with the help of which the sticker is connected to the surface to be labeled, for example a plastic bottle, the second layer is the decorative print and the third layer is the paint layer.

(B) The following is the manufacture of a thermal transfer label described, in which the thermoset resin in the transfer layer, i.e. in the lacquer layer of the over-

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The dry resin thermal barrier layer may be a layer of thermoset or thermoplastic resin selected to bond with the layer of varnish containing the thermoset resin which is then printed on sufficient to enable the transfer layer and the adhesive layer to be printed on this release layer without delamination of the transfer layer from the release layer, as stated above have, which is substantially higher than the adhesive strength of the same to the transfer layer containing the thermoset resin ο It has been found that the higher non-rubbery polyalkylenes, ie the higher polyalkylenes than polyethylene, such as polypropylene, these E have properties. Polypropylene is preferred. Polypropylene has a softening temperature that is above 149 to 232 ⁰ C (300 to

P) lies. The polypropylene can be in the form of a sheet in an amount of 0.45 Ms 4.54 kg (1 to 10 pounds) per Eies paper (with a ream of 5OO sheets of paper one The size is 50.8 cm 63.5 cm (20 25 inches) on the

Paper carrier are applied. Now, when the paper carrier consists of a 7 _S 26 kg (16 pounds) paper with a thickness of about 0.0635 now (2.5 mils), which thickness of the heat release layer is about 0.0254 mm (1 mil) 4.54 10 pounds of coating per egg of paper with a thickness about half the thickness of the paper backing. The polypropylene is preferably applied by extrusion.

After applying the dry release layer to the paper backing, this layer is cured with the varnish from the thermoset Resin, for example a non-hardened aminoaldehyde and a cellulose ester and a catalyst · coated and then the printed coating is applied to the carrier

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thermoset. The lacquer applied to the dry release coating preferably contains in addition to the aminoaldehyde and cellulose esters or vinyl acrylic resins, which are a mixture or copolymer of a vinyl resin, such as e.g., polyvinyl chloride, polyvinyl alcohol or polyvinyl butyral and an acrylic resin such as from acrylic acid or a derivative thereof, such as methyl methacrylate, is formed «, The acrylic and vinyl resins and the amino aldehyde resins have such a composition in the paint, that after curing, the composite paint layer has a softening temperature has, which is above the heat transfer temperature, so that its adhesive strength during the heat transfer to the surface to be labeled is significantly lower than its cohesive and adhesive strength compared to the subsequently applied print pattern (imprint).

It is believed that the vinyl acrylic resin makes the amino formaldehyde resin tough and lowers its brittleness so that it can better withstand rough mechanical treatment and handling. It also helps maintain proper adhesion between the transfer layer and the release layer; to be achieved when polypropylene is used for the separating layer. The ratio of vinyl acrylic resin to urea-formaldehyde resin can be varied within relatively wide limits. In general, the vinyl acrylic resin 10 makes to 90 wt .-%, preferably 40 to 80 wt -.% _Y in particular 60 to 70 wt .- ä of the total weight of the dry, cured coating layer, wherein the urea formaldehyde resin making up the balance, wherein even lower? Amounts of other materials such as a catalyst for curing the resin and the like may be present. The urea-formaldehyde resin / vinyl acrylic resin mixture can be applied to the separating layer by the gravure printing process. The print pattern is applied directly to the lacquer layer in a smaller area and the through

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Heat activatable adhesive is applied to the print pattern in the same way as described above if that thermoset resin is used in the release liner.

(G) In a preferred embodiment, whether the thermoset resin is used in the dry release layer or in the lacquer layer, a fluorescent dye is in the clear lacquer applied to the release coating and in the clear heat-activatable adhesive applied to the print pattern in an amount ranging from "about 0.1 and about 10 wt .-%, preferably between about 1 and about 3 or 5 wt -.% _t available, based on the solids in the varnish or adhesive layer, and the printing of all Laying, i.e. the lacquer layer, the print pattern (print) and the adhesive layer, is carried out under ultraviolet light so that the dye fluoresces so that it is clearly visible when printing, or after the printing is finished, the printed sticker is exposed to ultraviolet light, so that it fluoresces and the accuracy of the coverage of the printed layers can be visually observed.

The minimum amount of fluorescent dye is only determined by the amount required to obtain sufficient visibility under ultraviolet light so that an accurate Correspondence (coverage) is achieved, and the maximum amount is only determined by the amount beyond which the dye is used begins, the desired cohesion properties of the layers, in which it is present, and the adhesive properties of these layers with respect to adjacent layers are disadvantageous to influence. Even in the case of the adhesive layer that can be activated by heat, the amount of dye should not be so large that that the stickiness thereof, which can be activated by heat, is adversely affected «, although the fluorescent dye in the design print. can be used, it is in most cases to achieve an exact coverage

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(Match) not required, as in most cases the print pattern is colored and therefore clear is visible.

The fluorescent dye or other indicator material, which is used to achieve an exact print match can be used to advantage in the lacquer and adhesive layers used v / ground, even if customary wax and v / axis-like separating layers are used, and that thereby The advantages achieved are independent of the structure of the lacquer and separating layers and of the structure of the adhesive layer. They are also independent of the dry stripping aspects of the invention. However, the use of such an indicator material is to achieve an exact pressure match not so necessary with wax separating layers, since there is a perfect pressure match (pressure registration) is not so critical. The principle of using an indicator compound in the clear printing layers can be used in any printing process in which clear ... layers are used will. It is suitable, for example, for the production of pressure-sensitive (self-adhesive) transfer labels as well as solvent- or moisture-sensitive transfer labels, when clear overprint layers are used. It is also suitable for overprint processes in which clear Layers unrelated to transfer labels are used.

The present invention is illustrated in more detail by the following examples, without, however, being restricted thereto.

example 1

A paper backing made of a smooth, clay coated Sheets of paper weighing approximately 7 »26 kg (16 pounds) per ream (500 sheets of 50.8 cm 63.5 cm (20 inches χ 25 inches)) was made by coating with a varnish with a

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30 % solids content from an uncured, catalyzed urea-formaldehyde resin modified with 36% cellulose acetate butyrate (S-1028, Haffi-Swanson, Inc.) coated with a dry release coating (Mayer rod # 20). The catalyst used consisted of 4 parts of a p-toluenesulfonic acid solution (catalyst 7909 from Raffi-Swanson, Inc.) per 100 parts of resin. The urea formaldehyde and cellulose acetate butyrate in the applied release layer were removed by heating on a hot drum to 177 ° C (35O ⁰ F) for a period of 20 seconds, after which the applied lacquer for one minute at a temperature of 60 ⁰ C (14- 0 ⁰ Ii ¹ ) had been dried, cured to a crosslinked, thermoset resin. The dry release layer of the cured urea-formaldehyde resin was then coated with a clear lacquer (with a solids content of 15%) of cellulose acetate (E 3983 from Eastman Chemicals) in methyl ethyl ketone 40 microns, with a 120 stridv grid and a 15-20 wall (equivalent to a # 8 Mayer rod). The applied lacquer coating was dried for ^{one minute at 60 °} C. (140 ^{° F.)}

Then the "clear lacquer layer" was applied using a with polyamide-nitrocellulose modified printing ink that contained a pigment or dye of the desired color (ZYROTO WHITE from Gotham Ink and Color Co., which contained a titanium dioxide pigment) · a print pattern printed on »The area of the print pattern was smaller than that of the imprinted lacquer layer and it was completely within the edge of the lacquer layer.

A clear adhesive layer was then applied to the printing ink as a coating layer, which consists of a solution of a thermally activated thermoplastic polyamide resin in the form of a varnish (VERSAtllDE 940 from General Mills)

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passed, and then the glue was applied to dry, dried non-sticky state. The area of the adhesive on print was smaller than that of the paint and it was completely within the edge of the lacquer layer. No peeling occurred during the three printing operations (Sticking) on.

The heat transfer sticker produced as above was then brought into contact with a polyethylene bottle, the surface of which had been pretreated in the usual way, for example by contact with flamin, in order to make it more receptive to the printing ink. Heat and pressure were applied to the sub-carrier to press the adhesive layer against the polyethylene surface. In the application of heat, about 177 ° C (35O ⁰ F), no softening of the release layer or the cellulose acetate layer occurred, however, the adhesive coating was prepared by the heat activated at a high-tack state, so that it adhered to the Polyäthylenoberfläche the bottle. The auxiliary carrier could then be stripped from the transfer sticker (label) or it could be left on the label and later stripped off without the risk of the label becoming detached from the polyethylene surface. After the auxiliary carrier had been stripped off, no part of the release layer remained on the label and no part of the lacquer was removed together with the release layer. After cooling and peeling off the auxiliary carrier, the bottle coated in this way was treated with the flame and the adhesion of the label to the same was tested. The adhesion was excellent.

Example 2

The procedure of Example 1 was repeated, but this time the urea-formaldehyde resin content was reduced to 25% by weight was, while the content of cellulose acetate butyrate increased

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75 wt% was increased. Similar results were obtained.

Example 3

The procedure of Example 1 was repeated, this time increasing the content of urea-formaldehyde resin to 80% by weight while the content of cellulose acetate butyrate was decreased to 20% by weight. Similar results were obtained.

Example 4

The procedure of Example 1 was repeated, this time the polyamide adhesive by a heat-activated polyvinyl acrylic adhesive (R0-120-S from Frederick H. Levy Co.) were replaced and a glass bottle coated with a polyvinyl chloride made from a plastisol was labeled, No surface preparation of the bottle was required as with polyethylene. The results obtained were similar or identical to the results obtained in Example 1.

Example 5

Example 1 was repeated, this time using an acrylic release coating solution instead of urea formaldehyde cellulose acetate butyrate, which was prepared by mixing 33 parts of a self-crosslinking acrylic resin (consisting of a solution of the acrylic resin in a xylene / butanol / methyl cellulose (60/22 / 18) solvent mixture with a solids content of 5 % (AT-50 from Rohm and Haas Co.)) with 67 parts of toluene and this time using a cellulose acetate lacquer solution with a solids content of 10%. After applying the separating layer

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(stretched) to the carrier film and, after drying, the coating was cured in an oven for 35 minutes at 160 ⁰ C (32O ⁰ F). The results obtained were similar to those obtained in Example 1 at heat transfer temperatures from 157 to 182 ⁰ C (315 and 36O ⁰ F).

Example 6

Example 5 was repeated, this time the release coating solution of 85 parts AT-50, 15 parts of an epoxy resin mixture consisting of 85 % of a liquid diglycidyl ether of bisphenol A (Bakelite EEL 277 oiler Union Carbide) and 15% of a solid one Addition product of diglycidyl ether of bisphenol A having a higher molecular weight (Epon 1004 from Shell Chemical Co.), and 100 parts of toluene. The cure (crosslinking) was carried out after drying for 60 minutes at 160 ° C (320 ⁰ F). The results were the same as in Example 5

Example 7

Example 5 was repeated, this time the release coating solution being prepared from 75 parts of the epoxy resin mixture of Example 6, 25 parts of a polyamide derived from the condensation product of the "dimeric acid" and an aliphatic polyamine (Versamid 125 from General Mills, Amin-Yfert = 330 -360) and from 100 parts of methyl ethyl ketone. The curing vairde 30 minutes carried out at 160 ° C (32O ⁰ F). The results were the same as in Example 5

Example 8

Example 5 was repeated, this time using the Trermbeschichtuncslösung consisted of 14 parts of hexamethoxymethylmelamine (Cymel 301 of American Cyanajnid), 75 parts of Ccllulone-

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company
acetate butyrate (EAB 500-5 der / Eastman) (15 % in methyl ethyl ketone), 2 parts of catalyst No. 1010 (25 % p-toluenesulfonic acid in butanol from American Cyanamid) and 60 parts of ethyl acetate. The curing was carried out for 20 seconds in a hot drum at 177 ° C (35O ⁰ F). The used cellulose lacquer it was cellulose acetate (E-398-3, F. 230-250 ⁰ C., from Estman). The release results were "better than those in Example 1 or 5" In addition, the use of this release coating solution had the advantage over Example 1 that there was no excess of semi-toxic formaldehyde which evaporates during transfer and has an unpleasant odor.

Example 9

Example 8 was repeated using (-17I-4-0 EAB, F _9230-240 C ⁰ Eastman) was used this time as paint cellulose acetate butyrate. The results were the same as in Example 5 »

Example 10

Example 5 was repeated, this time the release coating solution consisted of a mixture of 30.2 parts butylated urea formaldehyde (60 % solids in butanol / xylene (3/1), Eesimene U-920 from Monsanto Co.), 9.8 parts Cellulose acetate butyrate (EAB 500-5, from Eastman), 58 parts of ethanol and 2 parts of ethyl acetate 65.8 parts of the above mixture were catalyzed with 2.7 parts of p-toluenesulfonic acid (60% in butanol) and diluted with 19.5 parts of ethyl acetate . Curing was carried out in a hot drum for 20 seconds at 177 ° C (35O ⁰ F). The results were the same as in Example 5

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Example 11

Example 10 was repeated, this time the lacquer layer made of cellulose acetate butyrate (EAB 171-40 from Estman) duration. The results were the same as in Example

Example 12

Example 5 was repeated, this time the coating solution consisting of a mixture of 25 parts of a solid epoxy resin (Araldite 7097 from Ciba-Geigy Corp.), 25 parts of a liquid epoxy resin (Bakelite ERL 2774), 50 parts of methyl ethyl ketone and 3 parts of diethylenetriamine as hardener or crosslinking agent, the hardening or crosslinking was carried out for 50 minutes at 154 ⁰ C (JIO ⁰ F). The results were the same as in Example 5

Example 13

Example 5 was repeated, but this time the release coating solution consisted of 15 parts of a melamine (Cymel 301), 85 parts of a modified polyester (Cyplex 1473-S, 65 % in xylene (American Cyanamid), 2 Parts of a catalyst consisting of 25 % p-toluenesulfonic acid in butanol (catalyst 1010 from American Cyanamid) and 50 parts of methyl ethyl ketone. Curing was carried out for 30 minutes at 154 ^° C. (310 ^° F.) The results were the same as in the example 5 ·

Example 14

Example 5 was repeated, this time using the release coating solution consisted of 60 parts of a butylated urea formaldehyde solution (50% in xylene / butanol (1/1), Beetle XB-1047 from American Cyanamid), 40 parts of one

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2250195

Acrylic resin (50 % in xylene / cellosolve acetate (3/1), AT-70 from Rohm and Haas Co.), 50 parts of methyl _{ethyl ketone and 2 parts of catalyst No. 1010 e} ° C (315 ° F) cured, results were the same as Example 5

Example 15

Example 5 was repeated, this time the release coating solution consisted of 60 parts of butylated urea formaldehyde (XB-1047), 25 parts of an alkyd resin (50 % in xylene, 320-5 from Koppers Co.), 18 parts of methyl ethyl ketone and 2 parts of the catalyst no. 1010. the coating was cured for 30 seconds in a hot drum at 157 ° C (315 ^O F). The results were the same as in Example 5

Example 16

Example 5 was repeated, this time the release coating solution consisting of 60 parts of butylated urea ormaldehyde resin (XB-1047), 40 parts of a styrylated alkyd resin (60 % in xylene, S112-4 from Koppers Co.), 25 parts of methyl ethyl ketone and 2 parts of Catalyst No. 1010. The coating was cured in a hot drum at 157 ° C (315 ° F) for 30 seconds. The results were the same as in Example 5

Example 17

Example 5 was repeated except that the release coating solution, a mixture of 60 parts ΣΒ - 1047, 40 parts of a bisphenol A plasticized Epo: cyacrylats (60% 'ln Kethyläthv ketone, Epocr-1 25-3-60 Shell! Chemical Co.), 2 parts of the catalyst No. 1010 and 50

0 9 8 17/0789 bad original

Parts represented methyl ethyl ketone. The hardening turned 30 Performed at 149 ° C (300 ° F) for minutes. The results were the same as in Example 5

Example 18

Example 5 was repeated, this time the release coating solution being a mixture of 62 parts of XB-1047, 28 parts of an epoxy resin (Bakelite EHL 2774), 2 parts of Catalyst No. 1010 and 50 parts of methyl ethyl ketone. Cure was carried out at 149 ° C (30O ⁰ F) for 30 minutes. The results were the same as in Example 5

Example 19

A paper backing made from a smooth, clay-coated sheet of paper weighing approximately 7 »26 kg (16 pounds) per ream (5OO sheets by 50.8 cm by 63.5 cm (20 inches by 25 inches)) was attached to a polypropylene coating extrusionsbe-> coated. The coated polypropylene paper was then provided with a paint coating which consisted of 67 wt -.% Of a vinyl acrylic resin (R0-120-S from Frederick H. Levey Co.) and 33 wt .-% of a 4- 3 % cellulose acetate butyrate-modified, uncured, catalyzed urea-formaldehyde resin (S-487 from Raffi-Swanson). )

The paint had a solids _{content of about 30%} diluted with ethyl acetate. The catalyst used \ If it were 0.12 parts of p-toluenesulfonic acid solution (cata- lyst I 7909 of the company Raffi-Swanson, Inc.) to 100 (

Parts of resin. Coating was carried out using a regular varnish etching cylinder with a depth

- A line of about 40 microns and a 12O / grid and a 15-20 wall with a paint solution with a solids content of about 20%. After drying at 60 ^oC (140 ° F) for 1 minute, {'

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the ureaimaldehyde cellulose acetate butyrate in one Drum cured at 1-7 ° C (350 ° F) for 20 seconds. Of the Varnish coating was clear «Then it was applied to the paint layer Pattern printed using a polyamide nitrocellulose modified printing ink as in Example 1 and dried. The dried ink was then covered with a clear layer of adhesive provided, which is made from a solution of a heat-activatable, plasticized, thermoplastic polyamide resin in In the form of a varnish, and then dried as in Example 1. No peeling occurred during the three prints (Hold on).

The heat transferable label prepared as above was then attached to a polyethylene bottle or a polyvinyl chloride bottle brought into contact, the surface of which is pretreated in the usual way, for example by flame contact had been made to make them more pressure-receptive. The auxiliary carrier was subjected to heat and pressure in order to to press the adhesive layer against the polyethylene surface. The sub-carrier could then be removed from the surface label can be peeled off or you could leave it on the label (sticker) and only peel it off later without the There was a risk of the label becoming detached from the polyethylene surface. After peeling off the auxiliary carrier remained no part of the release liner is left on the label. After the auxiliary carrier had cooled down and peeled off, it was labeled in this way Bottle tested with a flame to check the adhesion of the label to the same. The adhesion was excellent.

Example 20

The procedure of Example 19 was repeated, this time the urea formaldehyde content was increased to 50% by weight, while the vinyl acrylic resin content is decreased to 50% by weight

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became. Similar results were obtained. Example 21

The procedure of Example 19 was repeated except that the content of the urea-formaldehyde resin to 60 wt .-% was increased while the content of the vinyl acrylic resin to 40% .-- n Qc & lowered "There were obtained similar results.

Example 22 .

A roll of white paper with the cured release coating of Example 8 became a decorative coating (sticker) made for plastic bottles »Using a rotogravure press (six stations) first became a clear one Imprinted and dried varnish, consisting of 10 parts of cellulose acetate (E398-3 from Eastman), dissolved in 90 parts Methyl ethyl ketone / acetone (9/1), and 0.1475 parts of one Fluorescent dye (a substituted phenylbenzotriazole sold under the trade name Intrawite OB by the company Intracolor Corp. is sold). Thereafter, within the scope of the first printed, dried clear lacquer printed four different colors, each with a polyamide cellulose nitrate base, each one different colored pigment, and finally at the sixth station on the whole (but within the Circumference of the clear varnish printed first) a clear, heat activated adhesive varnish printed on that existed from 30 parts of a mixture of a heat activatable Polyamids (Versamid 940 from General Mills) and nitrocellulose (SS, 1/4 second from Hercules Chemical Co.) in a ratio of 85:15 "and 70 parts a solvent mixture consisting of isopropanol, toluene and ethyl acetate in a ratio of 4: 1: 1. to this mixture was 4 parts of a before printing

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Triphenyl phosphate plasticizer and 0.14-75 parts of the fluorescent dye were added. The applied heat activatable adhesive topcoat was dried to a non-tacky but heat activatable state. The finished print was checked after the sixth station under ultraviolet light, in which the dye fluoresced in order to make it clearly visible, which made it possible to print the two clear varnishes containing the fluorescent dye and the color prints in a perfect print match (coverage) "hold. While pressing occurred no peeling (adhesion) and the release liner was in the heat transfer temperature of 157" to be deducted to 182 ⁰ C (315 to 360 ° F) of the layer of lacquer clean ·

Example 23

The procedure of Example 1 was repeated, this time using the fluorescent dye of Example 22 of the lacquer layer and the heat-activated adhesive layer in oil the same amount as in Example 22 was added. The results were similar to those of Example 22,

Example 24 "

Example 19 was repeated, this time using the fluorescent dye of Example 22 of the varnish layer and the adhesive layer in the same amount as in Example 19 was added

Example 25

Example 19 was repeated, this time using a wax composition instead of a polypropylene release liner which consisted of a mixture of paraffin and montan

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grow (70:30), and also the lacquer layer and the adhesive layer contained the fluorescent dye of the example in the same amount. By examining in the ultraviolet Light, a perfect pressure match (coverage) * could be achieved.

The invention has been described above on the basis of specific embodiments explained in more detail, but it is clear that it is not limited to this, but that these in many ways Aspects can be changed and modified without departing from the scope of the present invention.

* (print registration)

Patent claims:

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Claims (20)

Claims Λ . Heat-transferable sticker for labeling a surface, characterized in that it consists of an auxiliary carrier, a resin release layer, a transfer layer having a printed pattern or an imprint and a heat-activatable adhesive layer, with between the transfer layer and the separation layer there is an adhesive bond sufficient to make the Aufr print the transfer and adhesive layers on top of the To enable the separation layer without the transfer layer becoming detached from the separation layer, and wherein the adhesive bond between the separation layer and the transfer layer at heat transfer temperatures up to about 14-9 G (F) is significantly weaker than the cohesions of the separating layer, the transfer layer and the heat-activated adhesive layer which have been applied to the surface to be labeled, and which is also considerably weaker than the adhesive bonds between the separating layer and the auxiliary carrier, between the transfer layer and the heat activated adhesive layer and between the heat activated adhesive layer and the surface to be labeled _o 2. Sticker according to claim 1, characterized in that at least one of the surfaces of the separation and transfer layers which are in adhesive bonding contact with one another stand, as an essential component an inert, cross-linked, thermoset polymeric resin and that each of these surfaces has a softening temperature which is essential is higher than the temperature of the heat transfer. 3 «sticker according to claim 2, characterized in that the thermoset resin is present in the separation layer. 4 ·. Sticker according to claim 3, characterized in that 309817/078 9 _ 4-2 - the transfer layer contains a cellulose ester. 5. Sticker according to claim 4, characterized in that that the cellulose ester is a cellulose ester of a carboxylic acid. 6. Sticker according to claim 4, characterized in that that the cellulose ester is selected from the group cellulose acetate and cellulose acetate butyrate. 7. A notice according to claim 2, characterized in that that the thermoset resin is selected from the group of crosslinked acrylic resins, polyaniid resins, polyester resins, Vinyl resins, epoxy resins, allyl resins, epoxy acrylate resins, aldehyde resins, Aminoaldehyde resins including copolymers of aminoaldehydes with alkyds, styrylated alkyds, Polyesters, acrylates, polyamides and cellulose esters and Combinations of these. 8. Sticker according to claim 7 »characterized in that the thermoset resin is an amino aldehyde resin acts. 9. Sticker nacfi. Claim 8, characterized in that the aminoaldehyde resin has been copolymerized with a cellulose ester o 10. Sticker according to claim 9, characterized in that the thermoset resin made from a resin selected from the urea group ormaldehyde and melamine formaldehyde, which with a Cellulose ester of a carboxylic acid has been copolymerized, 11. Sticker according to claim 9ν, characterized in that the thermoset resin consists of a polyalkoxymelamine, which is bonded with a compound from the group of cellulose acetate 309817/0789 tyrate and cellulose acetate has been copolymerized. 12. Sticker according to claim 2, characterized in that the thermosetting resin is present in the separating layer and that the transfer layer has a lacquer layer which is connected to the separating layer by means of an adhesive, the lacquer layer being printed with a printed pattern and the adhesive layer on the printed pattern is printed and wherein the areas of the print pattern and the adhesive layer are less than the area of the lacquer layer and are within the limits of the lacquer layer _o 13. Sticker according to claim 2, characterized in that the thermoset resin is present in the transfer layer. 14. Sticker according to claim 13j, characterized in that the transfer layer, in addition to the print pattern, has at least one lacquer layer on it, which is essentially through an adhesive bond is connected to the separating layer, which is / is weaker as the adhesive bond between the paint layer and the Printing pattern, with the thermoset resin in the varnish layer is present, and that the lacquer layer together with the print pattern and the adhesive layer from the auxiliary carrier and the separating layer is transferred to the surface to be labeled, so that the print pattern is chemically resistant and resistant to rough treatment. 15. Sticker according to claim 14, characterized in that the separating layer is made of polypropylene. 16. Sticker according to claim 14, characterized in that the thermoset resin is an amino aldehyde resin acts. 17. Sticker according to claim. · 16, characterized in that the lacquer layer is also a resin from the group of vinyl resins _% 309817/0789 Our reference: D Dennison Manufacturing igegang Contains acrylic resins and combinations thereof. 18. sticker according to claim 14, characterized in that the area _f of the print pattern and the adhesive layer is smaller, so that neither the printing pattern or the adhesive layer are used as the surface of the resist layer with the release layer in contact. 19 · Process for making a heat transferable Sticker for labeling a surface, characterized in that a separating layer is applied to an auxiliary carrier applies, prints a transfer layer on the separating layer, then on the transfer layer in coincidence with it, a layer of a heat-activated adhesive is printed on by means of a printing surface, v / obei one this layer with the release layer with an adhesive bond bonds whose adhesive strength is greater than the adhesive strength between the adhesive layer and the printing press surface, but with heat transfer Temperatures of up to 149 C (JOO F) are much weaker is essential as the cohesive strength of the release layer, the transfer layer and the adhesive layer and the is weaker than the bond between the separating layer and the submount, between the transfer layer and the warning activated adhesive layer, and between the heat activated adhesive layer and the to etil'ct tier en that surface. 20. The method according to claim 2 ^, characterized in that a separating layer is applied to a hat trowel the separating layer prints a layer of lacquer, by means of a BAD ORIGINAL 309 8 1 7 / 07f! Ü received m ... ß> ί -. & φ Drueköberflache a Druckmus t he on dieLacksohicht in registration with the lacquer layer imprints, and then by means of a Drucköberflache on the print pattern in cover DA _t with a layer of an activatable by heat adhesive imprints to give the Laokschicht irish layer having interconnecting so 'that the strength The adhesive bond between the iJaökschicht and the separating layer is higher than the strength of the adhesive bond between the print pattern and the print surface and between the adhesive layer and the print surface, which, however, at heat transfer temperatures of up to 149 ° Ö CgOO ⁰ J ¹ ) is significantly weaker than the eohesion strength the release layer, the paint layer, the printing pattern and the adhesive layer and significantly weaker than the bond between the release layer and the submount, between the varnish layer and the print layer between dei ⁴ print layer and the heat-activated adhesive layer and between the Pieter h heat activated adhesive layer and the 2u labeling surface. 3098 17 / ÖT89