KR100484357B1 - Method of providing images on an image receptor medium - Google Patents

Abstract

The present invention relates to a method of forming an image on an image receiving medium, comprising forming the image on the image transfer medium and then transferring the image to the image receiving medium. By using the hot roll lamination method as the transition method, acceptable phase transfer characteristics can be obtained under a transition rate of 0.3 m / min to 3.0 m / min, preferably 0.3 m / min to 4.6 m / min. The image receiving medium includes a phase receiving layer containing at least one polymer having a Bicat softening point and melting point higher than room temperature to a degree sufficient to prevent sticking and handling difficulties. The image receiving medium may optionally include a base layer, an undercoat layer, and an adhesive layer for improving properties such as durability and weather resistance.

Description

METHODS OF PROVIDING IMAGES ON AN IMAGE RECEPTOR MEDIUM

The present invention relates to films useful as image receptive media, such as those used in advertising and promotional displays, and more particularly, to methods of forming images on such media.

Advertisement and sales promotion displays are often used on a graphic surface that is produced on the side of a truck, a structure such as a tent, or installed alone as a banner. To produce the display, an image is formed on an adhesive supported image receiving medium (also sometimes referred to as a graphic marking film) and then adhered to the desired substrate. An alternative method is to first form an image on the phase transfer medium and then transfer to the phase receiving medium. The image receiving medium usually comprises a base material with an additional receiving layer superimposed thereon. As the base material, a plasticized vinyl film is usually used, but paper may be used.

Graphic displays may be installed for long-term use of more than 5 years, but in outdoor installations their life is usually relatively short (3 months to 1 year). As the image receiving medium of the short-term display, a low-cost graphic marking film having weather resistance, durability and good printability and excellent adhesion to ink and / or toner that is easy to apply and remove on the surface is preferable. Polyvinyl chloride (PVC) -based film used in the current graphics marking film is expensive to be used for a short period of time, and usually has problems such as migration of the plasticizer, staining of the plasticizer and adhesive fixing. There may also be a problem with the vinyl composition itself. For example, chlorinated compositions of vinyl have environmental difficulties associated with their use in fire hazard applications and vinyl disposal, and cadmium in stabilizers used in most vinyl formulations is restricted or prohibited in many countries. will be. On the other hand, paper-based media do not have sufficient durability or weather resistance and are easily torn upon removal. Polyolefin-based films are inexpensive and contain no plasticizer, while ink / toner adhesion is poor. Application of the acceptor film on the base film usually requires additional processing steps, thus adding to the cost of the manufacturing process.

Electrography is a well-known phase forming method. BACKGROUND OF THE INVENTION An electrography method involves passing a substrate (usually an insulating material) through an electrographic printing device (eg, an electrostatic printer). In the printer, a latent image is formed on the substrate by an electrostatic charge (for example, by a stylus), and then developed by a suitable toner. This technique is particularly suitable for forming large scale images that can be used for posters and signs.

With the completion of the electrography method of developing an image dyed by toner on an insulating substrate, the printing substrate is enclosed between two layers of transparent vinyl plastic films, which can be directly used for outdoor use (eg signs). However, since the usual insulating base material mainly consists of paper, the weather resistance required for outdoor signs is often insufficient. More durable substrates, such as polyvinyl chloride (PVC) films and polyvinylacetate (PVA) films, are difficult to form phases directly on these substrates due to their electrical and mechanical properties.

In the case of producing a large-scale sign suitable for outdoor display, it is possible to transfer the dyed image deposited on the insulating substrate by the electrographic method to a weather-resistant image receiving medium. Insulating substrates are known as carriers or phase transfer media. This technique is discussed in US Pat. No. 5,262,259.

In order to transfer the dyed phase from the phase transfer medium to the phase receiving medium, there is a need for a method of applying pressure and heat, for example via lamination (hot roll lamination) in a heated press roll system. Phase transfer techniques of this kind are described in US Pat. No. 5,114,520. The hot roll lamination system was effective, but was considered to be slow in transition (typically from 0.5 m / min to 1.0 m / min).

1 is a schematic diagram showing one form of a printing section used to form an image in the method of the present invention.

2 is a schematic diagram of a method for transferring an image from a phase transfer medium to an image receiving medium according to the present invention.

3 is a cross-sectional schematic view of an image receiving medium (media optionally comprising a substrate layer) used in the method of the present invention.

4 is a cross-sectional schematic diagram of an image receiving medium (a medium optionally including a base layer and a bottom layer) used in the method of the present invention.

Embodiment of the invention

One method of forming an image on a phase transfer medium is electrographic printing in the form of electrostatic printing, as shown in FIG. In FIG. 1, the phase transfer medium 1 comprises a conductive paper substrate 2 having a first insulating layer 4 and a release coating 6 on at least one side. In addition, the phase transfer medium may optionally include a conductive layer (not shown) between the insulating layer 4 and the substrate 2, or on the substrate surface opposite the release coating 6, or both. In the phase transfer medium 1, the side with the release coating 6 passes through the printing portion in the direction 8 so that the coated side of the paper first passes through the stylus writing head 10 and is charged by this head 10. (12) is deposited and a space 14 is formed over the uncharged surface. After passing through the writing head 10, the image transfer medium 1 passes through the toner processing unit 20 provided with the toner applicator 16 in contact with the toner liquid bath 18 in the container 20. The toner liquid 22 is held in the toner applicator 16 and deposited on the entire surface of the phase transfer medium 1, and then the toner liquid in the uncharged area is removed by the vacuum channel 28, whereby the dyeing portion 24 ) And non-staining portion 26 are provided. These series of processing portions of the printer each deposit separate images (images of one of four different colors, usually black, cyan, magenta and yellow). The finished color image (also called dye) appears on the release surface of the phase transfer medium. This technique is described in US Pat. No. 5,262,259. Such electrostatic printers are known in the art and are commercially available, for example, from 3M, Xerox Engineering Systems, Raster Graphics, Inc. and Nippon Steel Corporation.

In the method of the present invention, after the image is formed on the phase transfer medium, the image is transferred to the image receiving surface of the image receiving medium. The transition can be accomplished by passing the sheets together through the heated nip rolls through a number of methods known in the art, for example, by hot roll lamination, or on a heated plate of a vacuum drawdown frame. This can be done by placing them together. In order for the final image on the image receiving medium to have good characteristics and good color fidelity, there should be no distortion and a generally complete transition (meaning little or no ink or toner remaining intact on the image transfer medium). . Therefore, the phase should be easily released from the surface of the phase transfer medium under the transition process conditions and should adhere well to the phase receiving surface of the image receiving medium.

2 is a schematic diagram of a preferred phase transfer device 31. The feed roll 33 is arranged to continuously feed the image receiving medium web 37 with the image receiving surface 38 around a series of cylindrical idler rolls 41, 43, 45, 47. The cylindrical press roll 49 draws the roll 49 toward the backup roll 51 while applying sufficient pressure to form the nip region 53 and attract and compress the web material fed into the nip region 53. The distal end is supported by a movable support (not shown). One or more of the rolls 49, 51 is driven by a drive means (e.g., a variable speed electric motor, etc.) such that the rolls 49, 51 rotate back at the desired speed while the web is tensioned through the nip at the desired speed (aka transition speed). (Not shown). It is desirable that the transfer rate be as fast as possible to maximize productivity while not so fast as to unacceptably sensitize the quality of the transferred phase.

The roll 35 is arranged to continuously supply the previously formed image transfer medium 39 in contact with the image receiving medium 37, so that the roll 35 is in contact with the image receiving surface 38 of the image receiving medium. When the webs 37, 39 reach the nip region 53, they are tensioned and squeezed together between the rolls 49, 51 so that the image received on the webs 39 is in intimate contact with the webs 37 and the image receiving surface 38 is present. Is pressed). Further, at least the roll 49 in contact with the web 39 from which the phase is released must be heated so that the temperature of these materials rises as the web material passes through the nip region. Alternatively, both rolls 49 and 51 may be heated.

The nip pressure between the rolls 49 and 51 is usually controlled by an air or hydraulic cylinder impinging on the axial end of the roll 49. Useful nip pressure is usually 45-100 lbs / in ² (psi) or a 3~7 kg / ㎠, which are affected by the material on which the transition. The web is fed on the support table 59 for cooling after exiting the nip region 53. The webs 37, 39 are then separated and the phase is transferred to the web 37.

This phase transfer technique (known as "hot roll lamination") is described in detail in U.S. Patent No. 5,114,520 (King et al.) And is available from Scotchprint ™ Electronic Graphics Systems commercially available from 3M Commercial Graphics. Forms part of it.

The choice of phase transfer medium, phase material and phase receiving medium is important to ensure that the phase is completely transferred without damage. Phase transfer media and toner solutions useful for electrostatic printing are described in US Pat. Nos. 5,114,520 and 5,262,259.

The phase receiving medium is usually a flexible sheet having phase water solubility as described above. This medium should have chemical and physical properties suitable for its intended use. For example, where the intended use is an outdoor advertising display, the image receptive medium should have good weather resistance and sufficient strength to withstand the manipulation of the application and removal process. To achieve the rapid transition rate of the present invention, the image receiving medium 60 shown in FIG. 3 includes an image receiving layer 64 and any substrate layer 68 superimposed to contact one side of the image receiving layer. The image receiving layer 64 has an outer surface 66 for receiving the image.

Phase receiving layer

The image receiving layer 64 is one or more polymers suitable for providing water solubility for the inks and toners used in the printing process described above, and for providing good phase transfer properties under the desired phase transfer rate when using hot roll lamination. Of these components. Good image transfer quality refers to a good quality phase that is fully transitioned without significant pinholes, scratches or distortions. In addition, the phase receiving layer is maintained intact as a whole, and it is preferable that the tendency to adhere to the non-imaged portion of the phase transfer medium is minimal. The polymer component of the phase receiving layer preferably contains at least one resin that can be extruded or coextruded into a substantially two-dimensional sheet. These resins can be bonded to these layers without peeling when coextruded or laminated with any adjacent substrate layers. Alternatively, the polymer component may be present in the form of a polymer dispersion that can be coated onto the substrate layer via a method such as roll coating,

The polymer (s) constituting the phase receiving layer may be characterized by melting point and Vicat softening point (ASTM D-1525) as measured by differential scanning calorimetry (DSC) according to ASTM D-3418. Typically, these temperatures should be higher than room temperature to be sufficient to prevent sticking and handling difficulties, but low enough to provide acceptable phase receiving properties. Each polymer in the phase receiving layer preferably has a Bikat softening point of less than about 100 ° C and a melting point of less than about 150 ° C. More preferably, the Vicat softening point is less than about 93 ° C. and the melting point is less than about 121 ° C.

Suitable polymers include ethylene vinyl acetate (EVA) (e.g., resins sold under the trade name ELVAX by E.I.Dupont de Nemours & Company ("Dupont")); Acid-modified, anhydride-modified or acid / acrylate-modified EVA copolymers (eg, resins sold under the trade name BYNEL by DuPont); Acid-modified or anhydride-modified ethylene acrylate copolymers (eg, resins sold under the trade name BYNEL by DuPont); Ethylene-ethyl acrylate (EEA) copolymers (eg, DPDA resins available from Union Carbide Chemicals & Plastics, Inc.); Ethylene methyl acrylate (EMA) (eg, OPTEMA TC-120 resin available from Exxon Chemical Company); Ethylene acrylic acid (EAA) (eg, PRIMACOR resins available from Dow Chemical Company, or ADCOTE aqueous dispersions available from Morton International); Ionomers (eg, SURLYN ethylene methacrylic acid copolymer resins available from DuPont); Polyesters (eg BOSTIK resins available from Bostik, Inc.); And mixtures of these materials. The modified EVA resin of BYNEL CXA series 3000, available from DuPont, is one of the preferred polymer components of the phase receiving layer. This series of resins contains EVA-based resins blended with polymers having acids and acrylate functional groups. Due to the chemical functional groups of the BYNEL resin series, their printability and ink adhesion are excellent. These resins are usually used as relatively thin adhesive bond layers interposed between thicker working layers in coextrusion processes. Another preferred polymer component of the phase receiving layer is the SURLYN series, an ethylene methacrylic acid copolymer ionomer resin available from DuPont.

The polymer component may comprise 100 weight of the phase receiving layer, or may comprise slightly less. The amount of polymer component in the phase receiving layer is preferably set to the maximum amount within the limit performance requirements of the phase receiving medium for the intended use. Optimizing this amount may require daily effort. The appropriate amount will depend on the intended use, and the performance of the polymer component can be influenced by other additives in the phase receiving layer as described below.

The phase receiving layer may contain other components (e.g. carrier resins for additives such as pigments, fillers, ultraviolet (UV) absorbers and stabilizers, slippers, antistatic agents and pigments), all of which are known to those skilled in the art. Things. When the image receiving layer 64 is used in combination with the substrate layer 68, the image receiving layer 64 is relatively thin compared to the substrate layer 68, and the thickness thereof is about 2.5 microns to about 127 microns (0.1 mil to 5 mils). Is preferably. If the image receiving layer 64 is not combined with the substrate layer 68, it may be necessary to make the image receiving layer 64 thicker than the above range in order to provide the durability and dimensional stability necessary for the intended use.

Any substrate layer

For example, if additional layers are needed to provide sufficient durability and dimensional stability, the substrate layer 68 may be included in the image receiving medium structure. For graphic display applications, it is most common for the substrate layer to be opaque white, but may also be transparent, opaque color, or translucent. The base layer may contain any polymer material having physical properties required for the intended use. Examples of these physical properties are flexibility (or rigidity), durability, burst resistance, heat resistance, conformity to non-uniform surfaces, die cutability, weather resistance and elasticity. For example, graphic marking films used for short-term outdoor sales displays can typically withstand outdoor conditions for a period of about 3 months to about 1 year, and have burst resistance and durability to facilitate application and removal. Can be.

As a material of a base material layer, resin which can be extruded or coextruded into a substantially two-dimensional film is preferable. Examples of suitable materials are polyesters, polyolefins, polyamides, polycarbonates, polystyrenes, acrylics, polyurethanes and polyvinyl chlorides. The substrate layer preferably contains an unplasticized polymer so as to avoid the disadvantages associated with migration of the plasticizer and stain formation.

The base layer may also contain other components known to those skilled in the art (eg pigments, fillers, ultraviolet absorbers, slippers, anti-shielding agents, antistatic agents and processing aids). Typical thickness of the substrate layer 10 is from about 12.7 μm to about 254 μm (0.5 mil to 10 mil). However, it is possible to exceed the ranges set forth above to the extent that the resulting phase receptive media is not too thick to feed into the selected phase transfer device. Useful thicknesses are usually determined based on the requirements of the intended use.

Any subsurface

As shown in FIG. 4, the image receiving medium 70 has an optional undercoat 69 on the surface of the substrate layer 68 opposite the image receiving layer 64. This undercoat layer acts to improve this strength when the bond strength between the substrate layer and the adhesive layer (not shown) in the absence of the undercoat layer is not strong enough. If an adhesive layer is present, the image receiving medium has utility as a graphic marking film.

Although it is preferable to use a pressure-sensitive adhesive, any adhesive that is particularly suitable for the base layer and the selected application may be used. Such adhesives are known in the art and examples include strong adhesive adhesives, pressure sensitive adhesives, repositionable or deployable adhesives, hot melt adhesives and the like. Such adhesives are commercially available at 3M.

The adhesive layer is preferably applied with a release liner (not shown) that protects the adhesive until just before the image receiving medium is applied to the surface. Undercoat 69 also acts as an adhesive layer in itself in some applications. The undercoating layer comprises an ethylene vinyl acetate resin containing from about 5% to about 28% by weight of vinyl acetate, and a filler (e.g. talc) that provides surface roughness to the undercoating layer to prevent adhesion of the adhesive and promote adhesion. It is preferable to contain. The content of the filler is usually from about 2% by weight to about 10% by weight.

It is also within the scope of the present invention to include other layers in addition to the image receiving layer 64, any base layer 68, and any subconducting layer 69. Additional layers may be useful for purposes such as adding color, improving dimensional stability, or improving adhesion between polymers of different species of the aforementioned layers. After the phase has transitioned to the image receiving medium, any protective overlap layer (not shown) can be adhered to the imaged surface. The superimposition layer can protect the image receiving medium from the influence of ambient humidity and direct sunlight and can also prevent scratches, scratches and stains on the image. In addition, the superimposition layer can give a desired finishing feeling (eg, high gloss or matteness) on the image. Any overlapping layer is suitable as long as it is a suitable transparent plastic sheet material having an adhesive on one surface. The use of such overlapping layers is described, for example, in US Pat. No. 4,966,804.

Image receiving media 60,70 can be manufactured in a number of ways. Layer 64 and optional layers 68,69 may be extruded simultaneously using any suitable type of extrusion or coextrusion die and any suitable film making method (eg, expansion film extrusion or molded film extrusion). have. The adhesive layer may be coextruded with the other layers, transferred from the liner to the image receiving medium, or coated directly on the image receiving medium in a further processing step. In order to provide the best performance in coextrusion, the polymeric material of each layer is chosen to have similar properties (eg melt viscosity). Coextrusion techniques are described in references related to many polymer treatments, such as Progelhof, RC and JL Throne, "Polymer Engineering Principles", Hanser / Gardner Publications, Inc., Cincinnati, Ohio, 1993].

Alternatively, one or more layers may each be extruded into separate sheets, and then these sheets may be laminated together to form an image receiving medium. An aqueous dispersion or solvent based dispersion may be coated over one or more layers previously extruded to form one or more layers. This method is less desirable as it involves additional processing steps and additional waste.

When the finished image receiving medium is treated with a surface treatment method such as corona treatment, ink and toner water solubility of the image receiving layer for a specific application can be improved.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the specific materials mentioned in these examples and their amounts, other conditions and details.

There is a need for a method of transferring a phase to a low-cost, phase-receiving medium having durability and weather resistance at a much higher transfer rate than a conventional roll lamination method.

The present invention solves the above problems in the art by providing a method of forming an image on an image receiving medium in which the rate of transition is considerably faster than conventional methods, while the properties of the transitioned phase can be maintained well. This method is a method of first forming an image on an image transfer medium and then transferring the image to the image receiving surface of the image receiving medium. The image receiving medium comprises an image receiving layer having two opposing major surfaces, one of which is an image receiving surface.

The phase receiving layer contains at least one polymer having a melting point and a Vicat softening point higher than room temperature to a degree sufficient to prevent sticking and handling difficulties. Each of these polymers preferably has a Bikat softening point of less than about 100 ° C and a melting point of less than about 150 ° C. More preferably, the Vicat softening point is less than about 93 ° C. and the melting point is less than about 121 ° C.

The phase receiving layer provides phase water solubility to the phase receiving medium. By “image receptivity” is meant the property that a phase formed on or applied to an image receptive medium, when subjected to a tape snap test, is present in a fully or almost completely adherent state. The tape snap test is a test in which 3M SCOTCH tape 610 (commercially available from 3M Campani, St. Paul, MN) is applied firmly onto and then removed through a quick snap action. Suitable polymers for the phase receiving layer include ethylene vinyl acetate, acid modified ethylene vinyl acetate, acid / acrylate modified ethylene vinyl acetate, anhydride modified ethylene vinyl acetate, acid modified ethylene acrylate, anhydride modified ethylene acrylate, ethylene ethyl It can be selected from acrylate, ethylene methyl acrylate, ethylene acrylic acid, ionomers, polyesters and mixtures thereof.

The image receiving medium may further comprise any polymeric substrate layer on the second major surface opposite the image receiving surface in the image receiving layer. Examples of suitable polymers for the substrate layer are non-plasticized polymers (eg, low density polyethylene, straight chain low density polyethylene, high density polyethylene, polypropylene, polyesters, polyamides, polycarbonates, polyurethanes, polystyrenes, and acrylics). . The base layer may also contain polyvinyl chloride.

It is preferable to form an image by an electrography method (for example, electrophotographic method or electrophotographic method). Phase transition is preferably carried out via hot roll lamination as described in US Pat. No. 5,114,520. Using this technique in the method of the invention, it is possible to obtain acceptable phase transfer properties under a transition rate of 0.3 m / min to 3.0 m / min, more advantageously 0.3 m / min to 4.6 m / min. Such a transfer speed is faster than that obtained using a commercially available image receiving medium, which can increase productivity and reduce costs in the printing process.

It may be advantageous for the image receiving medium to consist of only a single layer, which can be produced by a relatively simple and inexpensive method. In the case where the image receiving medium includes a base layer in addition to the image receiving layer, the image receiving medium may have all the best properties of several kinds of resins present in each layer. For example, the base layer may be made of a resin which is usually inexpensive and provides physical properties specific to the intended use. The physical properties include dimensional stability, conformity, elasticity, die cutability, rigidity and flexibility. Since the image receiving medium does not need to contain a plasticizer anywhere in these layers, problems associated with migration of the plasticizer and staining of the plasticizer are prevented. In addition, a non-halogenated polymer can be used as a polymer contained in an image receiving medium. Thus, certain regulations (eg, regulations relating to polyvinyl chloride (PVC)) in the disposal of waste can be avoided.

Another embodiment of the present invention is the image receiving medium.

Example 1

Four samples of the image receiving medium of the present invention each containing a base layer and an image receiving layer were prepared as follows. Two of these film samples were prepared using a molding extrusion method. The resin pellets were fed to a 4.45 cm (1.75 inch) Prodex single screw extruder with a temperature profile of 171 to 232 ° C. (340 to 450 ° F.) and a melting point of 207 ° C. (405 ° F.). Using a drop die, the extrudate was molded on a polyethylene terephthalate (PET) based film to a width of about 30 cm (12 inches) and a thickness of 0.05 mm (0.002 inches). The resulting film structure flowed between a steel chill roll and a rubber back up roll to solidify the molten resin into a layer about 0.05 mm (0.002 inches) thick. Sample 1A prepared by this method contained BYNEL CXA 3101 acid / acrylate modified EVA resin (provided by DuPont) and no additional additives, while sample 1B was acid modified EVA of BYNEL CXA 1123 (provided by DuPont) Only resin was contained. All of these samples were corona treated using a handheld Corona Treatment Unit Model # BD-20C (Electro-Technic Products, Chicago, Illinois, Inc.).

The remaining two samples (Samples 1C and 1D) were prepared using a conventional expanded film coextrusion method with a comparative film sample (Sample C-1). Three extruders A, B and C, respectively, fed the melt blend into an annular die to synthesize these melts, forming a single melt stream consisting of three separate layers in the form of a sleeve. For each sample, the melt of extruder A formed the phase receiving layer, the extruder B formed the substrate layer, and the melt of extruder C formed the undercoat layer. For comparative sample C-1, each layer contained only LLDPE as the polymer component or a mixture of LDPE and LLDPE. Air was then injected into the molten polymer sleeve and secured to the final diameter and thickness by securing this sleeve between the die and the nip roll at the top of the expanded film tower. This film sleeve was then divided into two flat film webs, each of which was corona treated on the image receiving layer face and wound around the core. Each thickness of the resulting sample was about 0.1 mm (0.004 inches), but the distribution of the layer thicknesses varied. The composition and thickness of the layers are shown in Tables 1a to 1c below.

Composition of layers ingredient Sample 1C (parts by weight) Sample 1D (parts by weight) Sample C-1 (parts by weight) Phase receiving layer ELVAX 3135 ethylene vinyl acetate (EVA) resin (Dupont) 100 - - BYNEL CXA 3101 Acid / Acrylate Modified EVA Resin (Dupont) - 100 - AMPACET 11976 TiO ₂ Pigment Concentrate (Ampace Corp., Tarrytown, NJ) 20 20 25 POLYFIL MT5000 talc concentrate (Polyfil Corporation, Dover, NJ) 20 5 10 AMPACET 10407 UV Inhibitor Concentrate (Ampace Corp., Tarrytown, NJ) 5 5 5 ESCORENE 108.37 Low Density Polyethylene Resin from Exxon Chemical Company - - 60 6109T Straight Chain Low Density Polyethylene Resin with Chevron Chemical Company - - 40 Substrate layer DOWLEX 2256A Straight Chain Low Density Polyethylene Resin (Dow Chemical, Minnesota Midland) 100 100 - 6109T Straight Chain Low Density Polyethylene Resin with Chevron Chemical Company - - 100 AMPACET 11976 TiO ₂ Pigment Concentrate (Ampace Corp., Tarrytown, NJ) 30 30 - AMPACET 10407 UV Inhibitor Concentrate (Ampace Corp., Tarrytown, NJ) 5 5 5 AMPACET 19270 Black Pigment Concentrate (Ampace Corporation, Tarrytown, NJ) - - One Subfloor ELVAX 3135B Ethylene Vinyl Acetate (EVA) Resin (Dupont) 100 100 - ESCORENE 108.37 Low Density Polyethylene Resin from Exxon Chemical Company - - 60 6109T Straight Chain Low Density Polyethylene Resin with Chevron Chemical Company - - 40 POLYFIL MT5000 talc concentrate (Polyfill Corporation, Dover, NJ) 20 20 10 AMPACET 10407 UV Inhibitor Concentrate (Ampace Corp., Tarrytown, NJ) 5 5 5 AMPACET 19270 Black Pigment Concentrate (Amsetet Corporation, Tarrytown, NJ) 5 3 - AMPACET 11976 TiO ₂ Pigment Concentrate (Ampace Corporation, Tarrytown, NJ) - - 25

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Layer thickness layer Sample 1C (% of total film thickness) Sample 1D (% of total film thickness) Sample C-1 (% of total film thickness) Phase receiving layer 40 40 30 Substrate layer 45 45 40 Subfloor 15 15 30

All samples were evaluated in terms of phase transfer properties. To this end, multicolor weathering bar graphics were imaged on a SCOTCHPRINT ™ 8601 transition medium (commercially available at 3 m) in a SCOTCHPRINT ™ 9512 electrostatic printer. The stained image on the transition medium was then placed in contact with the image receptive layer of the multilayer film, and then the two sheets were hot rolled on a Pro-Tech model EGS-692 set at 96 ° C. (205 ° F.) and 441 kPa (64 psi). Passed through the laminator. For each sample, the transition rate was slowly increased until the transition characteristics were poor. The properties of the transferred phase were visually classified as "bad", "good", "good" or "excellent". The results are shown in Table 2 below.

Sample Properties of the phase Permissible transfer rate on the phase [m / min (fpm)] 1A Great 3.7 (12) 1B Great 3.7 (12) 1C Great 2.6 (8.5) 1D Great 3.1 (10) C-1 Good to excellent 0.5 (1.5)

Only comparative sample C-1 showed acceptable phase transfer characteristics at very low transition rates. It is important to note that Sample 1D containing modified EVA resin of BYNEL CXA 3101 and about 13% by weight of LDPE in the form of a carrier resin showed good ink adhesion and phase transfer properties. Since LDPE and LLDPE (illustrated as Sample C-1) are poor ink receptors, the above results are rather surprising.

Example 2

After the phases were formed in accordance with the present invention on 12 phase receiving media samples, the phase transfer properties were evaluated. Each sample was a 25 micron to 254 micron thick film prepared through standard extrusion, which included a single phase receiving layer. For comparison, an LDPE film and a commercially available image receptor film (SCOTCHPRINT ™ CONTROLTAC ™ marking film 8620 commercially available at 3 m) were evaluated. Images were formed on the SCOTCHPRINT ™ 8601 transition media using a standard SCOTCHPRINT ™ toner in a SCOTCHPRINT ™ 9512 electrostatic printer. All of these products are commercially available at 3 m. The dyed phases were then transferred to each film sample using the hot roll laminator of the Pro-Tech model EGS-692 set at 96 ° C. (205 ° F.) and 441 kPa (64 psi). The transfer operation was carried out at a speed of 0.6 m / min to 3.1 m / min (2-10 feet / minute).

The samples were evaluated for the transition properties of the phases under low and high transition rates using a visual standard method grading system (VSM). This method examined the transition medium after the transition when evaluating the residual of the toner and the receiving medium when evaluating the presence of the characteristics of the transition phase, the uniformity of color, and the presence of absorption. The medium was classified numerically in comparison to standard samples. The minimum grade of acceptable transfer was 8.5, while the perfect toner transfer grade was 10.0. The lowest rating was 4.0. Polymers and corresponding results are summarized in Tables 3A and 3B below.

Phase Transition Characteristics (VSM) Under Transition Rates Sample Polymer film 0.6 m / min (2 fpm) 3.1 m / min (10 fpm) 2A Extruded film containing ELVAX 3124-2 ethylene vinyl acetate resin (EVA) (provided by E.I. DuPont de Nemours & Company) 10.0 8.5 2B Extruded Film with ELVAX 4260 EVA Resin (Dupont) 10.0 9.0 2C Extruded Film with ELVAX 4355 EVA Resin (Dupont) 10.0 8.5 2D Extruded film containing BYNEL 1123 acid-modified EVA resin (Dupont) 10.0 9.0 2E Extruded film with BYNEL CXA 3101 acid / acrylate modified EVA resin (Dupont) 10.0 9.0 2F Extruded film containing BYNEL 2002 acid-modified ethylene acrylate resin (Dupont) 10.0 9.0 2G Hot melt pressed film containing DPDA 9169 ethylene ethyl acrylate copolymer (EEA) (Union Carbide Chemicals & Plastics, Inc.) 10.0 7.5 2H Extruded film containing TC-120 ethylene methyl acrylate resin (EMA) (Exxon Chemical Corporation) 10.0 9.0

2I Extruded 51 micron (2 mil) thick film containing Primacor 3440 ethylene acrylic acid resin (EAA) (Dow Chemical) and a UV stabilizer package including a pair of UV absorbers, disturbing amine light stabilizers and antioxidants 10.0 7.5 2J SURLYN 1705-1 EMA Copolymer Ionomer Resin (Dupont) and TiO ₁ 12 wt. film 10.0 7.0 2K Extruded film containing SURLYN 1705-1 EMA copolymer ionomer resin (Dupont) and a UV stabilizer package including a pair of UV absorbers, disturbing amine light stabilizers and antioxidants 10.0 4.0 2L Hot melt crimp film containing BOSTIK 4189 polyester resin (Bosstick Inc.) 10.0 9.5 C-2 SCOTCHPRINT ™ CONTROLTAC ™ Marking Film 8620 (3 m) 9.5 <4.0 C-3 Extruded film containing low density polyethylene resin (LDPE) and TiO ₂ pigment concentrate <4.0 <4.0

All samples except comparative sample C-3 (LDPE) showed good transition properties at 0.6 m / min. All samples except sample 2K showed significantly better transition properties at 3.1 m / min compared to comparative samples C-2 and C-3.

Example 3

Two samples of phase receiving media evaluated the lamination temperature, lamination pressure, transition rate and phase transition characteristics for the phase transfer medium using a hot roll lamination technique. The first sample was a film of Sample 1D described in Example 1. The phase receiving layer contained a BYNEL CXA 3101 acid / acrylate modified EVA resin (provided by DuPont) and a titanium dioxide (TiO ₂ ) -based white pigment concentrate containing 50% LDPE as a carrier resin (function to whiten the layer). The undercoating layer contained ELVAX 3135B EVA resin (provided by DuPont) and a black pigment concentrate which blackened the layer.

The second film was prepared by extruding a 102 micron (4 mil) thick layer containing SURLYN 1705 ethylene acid copolymer ionomer resin (provided by DuPont). The film was dyed white using about 20% by weight TiO ₂ -based pigment concentrate containing 8.55% by weight of LDPE, and a UV stabilizer package (pair of UV absorbers, disturbing amines) similar to that recommended by the resin manufacturer. (hindered amine light stabilizer and antioxidant). Next, one side of this film was subjected to corona discharge treatment. This corona treated surface was laminated with a 15.4 mil thick acrylic pressure sensitive adhesive layer using a pair of heated nip rolls, and then a release liner was added to protect the adhesive layer. This film was called Sample 3A.

In a manner similar to that described in Example 1, SCOTCHPRINT ™ 8601 and SCOTCHPRINT ™ 8603 A weather resistant bar graphic image was formed on the transition medium (all of which are commercially available at 3M). The phases are then combined with high and low lamination temperatures (96 ° C. and 88 ° C.), high and low lamination pressures (441 kPa and 276 kPa), and high and low transition rates (1.5 m / min and 0.5 m / min). In one condition, a hot roll laminator was used to transfer samples 1D and 3A with a comparative sample of comparative sample SCOTCHPRINT ™ CONTROLTAC ™ marking film 8620. Phase transfer properties were evaluated using the grading system of the visual standard method of Example 2. The results are summarized in Table 4 below.

Sample Phase transition medium Lamination Temperature [° C] Lamination Pressure [kPa (psi)] Transition rate [m / min (fpm)] Transitional Characteristics [VSM] Scotchprint ™ 8620 Scotchprint ™ 8601 96 (205) 441 (64) 0.5 (1.5) 10.0 3A Scotchprint ™ 8601 96 (205) 441 (64) 1.5 (5.0) 10.0 1D Scotchprint ™ 8601 96 (205) 441 (64) 1.5 (5.0) 9.5 ^* 1D Scotchprint ™ 8601 96 (205) 276 (40) 1.5 (5.0) 9.0 ^* 1D Scotchprint ™ 8601 88 (190) 441 (64) 1.5 (5.0) 8.5 ^* 1D Scotchprint ™ 8601 88 (190) 276 (40) 1.5 (5.0) 6.5 ^* 1D Scotchprint ™ 8603 96 (205) 441 (64) 0.5 (1.5) 10.0 1D Scotchprint ™ 8603 96 (205) 441 (64) 1.5 (5.0) 7.0 1D Scotchprint ™ 8603 96 (205) 276 (40) 1.5 (5.0) 6.5 1D Scotchprint ™ 8603 88 (190) 441 (64) 1.5 (5.0) 7.0 1D Scotchprint ™ 8603 88 (190) 276 (40) 1.5 (5.0) 6.0 ^* A receiving layer was bonded to the transition part is a white area of the secret medium.

SCOTCHPRINT ™ When using 8601 transition medium, both samples 1D and 3A showed good transition properties at higher transition rates. However, Sample 1D (containing BYNEL modified EVA resin) adhered to the unstained white area of the transition medium. Sample 2E of Example 2 containing a film 100% composed of BYNEL modified EVA resin was SCOTCHPRINT ™ 8601 without sticking. The result was surprising because the images were received from the transition medium. At the time of corona treatment of Sample 1D, it was judged that no adhesion was achieved.

Example 4 Four phase receiving media samples were prepared by coating a polymer aqueous dispersion onto a polymer film to form a phase receiving layer. Each coating solution was prepared by adding a butyl carbitol coating agent and two kinds of ultraviolet (UV) stabilizers with stirring to the polymer aqueous dispersion. The composition is shown in Table 5 below.

ingredient Amount of Solution # 1 (g) Amount of Solution # 2 (g) SURLYN Ionomer Dispersions 56220,31 Solids from DuPont 200 - ADCOTE 50T4983 Ethylene Acrylic Acid Dispersion, 25 Solids, available from Morton International. - 200 Butyl Carbitol Coating 10.7 10.65 TINUVIN 1130 UV Stabilizer (Shiba Kaigi Corporation) 1.62 1.3 TINUVIN 123 UV Stabilizer, powered by Ciba Geigy Corporation 1.1 0.89

Each solution was coated on a polyester substrate and a vinyl substrate using the knife rod coating method and setting the wet gap to 3.0 mils. Each of these coatings was dried at 93 ° C. (200 ° F.) for 4 minutes to prepare an image receiving medium comprising an image receiving layer and a substrate layer. This sample was called 4A-4D. After forming a phase on each sample, the SCOTCHPRINT ™ under deposition rates of 1.2, 2.1, 3.1 and 3.8 m / min as described in Example 1 The transition properties of the phase formed on the 8601 transition medium were evaluated.

Sample Polymer of the phase receiving layer Substrate layer Phase transition characteristics under the following transition rates 1.2 m / min (4 fpm) 2.1 m / min (7 fpm) 3.1 m / min (10 fpm) 3.8 m / min (12.5 fpm) 4A Ionomer Polyester 9.5 7.0 6.0 - 4B EAA Polyester 9.5 ^* 9.0 ^* 8.0 ^* - 4C Ionomer vinyl - 9.5 9.0 8.0 4D EAA vinyl - 9.5 ^* 9.0 ^* 8.5 ^{* *} Part of the image receptive layer adhered to the unstained white area of the transition medium

All samples showed good transition properties, especially on more flexible vinyl substrates. Samples 4B and 4D (containing EAA) adhered to unstained white areas of the phase transfer medium. Previously, it was thought that a flexible conformal film was needed to accommodate the dyed phase, but it was important that both Samples 4A and 4B (including the harder polyester substrate) showed good toner solubility under a transition rate of 2.1 m / min or less. Do.

Comparative Example 5

For comparison with the above examples, commercially available multilayered coextruded adhesive support label film samples were evaluated in terms of ink adhesion and phase transfer properties. This sample included FASCLEAR and PRIMAX label films available from Avery International Corporation, Pasadena, CA. In order to evaluate each of these films, these pieces of film were transferred to 3M SCOTCHCAL ™. Adhered onto a 30 cm x 30 cm sheet of 18010 graphic marking film.

The phase transfer properties of each label film sample were evaluated. SCOTCHPRINT ™ multicolor weatherproof bar graphics SCOTCHPRINT ™ from 9512 Power Failure Printer It was printed on 8601 transition media. The dyed phase was then transferred to the sample film using a Pro-Tech model EGS-692 hot roll laminator set at 96 ° C. and 441 kPa (64 psi). Phases were transferred to each sample at 0.5 m / min (1.5 fpm) and 1.2 m / min (4 fpm). For phased samples, phase transfer characteristics were examined using visual standard method (VSM) ratings. All samples were then evaluated using the crosshatch adhesion test as follows. Each sample was engraved with 10 parallel lines at intervals of about 1.6 mm (1/16 inch) using the corners of a sharp razor blade. Only the toner layer was imprinted, not the base film. Another similar set of lines was inscribed into the toner layer at right angles to the first set to form a crosshatch pattern. Subsequently, a 2.5 cm × 10.2 cm (1 inch × 4 inch) piece of 3 m SCOTCH tape # 610 was applied onto the crosshatch pattern and then wiped in two reciprocations using a 3 m PA-1 applicator squeegee. Then, the tape was pulled using a sharp jerk to observe the crosshatch-shaped sample in terms of toner removal. The results are shown in Table 7 below.

exam PRIMAX label film FASCLEAR label film Phase transition characteristics at 0.5 m / min <4.0 9.5 Phase transition characteristics at 1.2 m / min <4.0 <4.0 Toner Adhesive at 0.5 m / min Non-removable Non-removable Toner Adhesive at 1.2 m / min Remove some Non-removable

PRIMAX films showed poor phase transfer properties (lower than the lowest possible grade) at both rates. The FASCLEAR film showed good phase transfer properties at slower transition rates, but poorer phase transfer properties at faster transition rates. As a result of the comparison, the films described in the previous examples showed acceptable phase transfer characteristics at transition rates of 3.8 m / min (12.5 fpm) or less.

This invention is not limited by the said embodiment. The claims are set forth below.

Claims (8)

(a) forming an image on the phase transfer medium, (b) transferring the phase of step (a) onto the phase receiving medium at a rate of 1.2 m / min to 4.6 m / min via hot roll lamination; Including, The image receiving medium comprises an image receiving layer having two opposing major surfaces, the first major surface being a surface for receiving the image, And the phase receiving layer comprises a polymer component comprising at least one polymer having a Vicat softening point of less than 100 ° C. and a melting point of less than 150 ° C. The polymer component of the phase receiving layer is ethylene vinyl acetate, acid modified ethylene vinyl acetate, acid / acrylate modified ethylene vinyl acetate, anhydride modified ethylene vinyl acetate, acid modified ethylene acrylate, anhydride modified Characterized in that it is selected from the group consisting of ethylene acrylate, ethylene ethyl acrylate, ethylene methyl acrylate, ethylene acrylic acid, ionomers, polyesters and combinations thereof. The method of claim 1 or 2, wherein the polymer component of the phase receiving layer is an acid / acrylate modified ethylene vinyl acetate or ethylene methacrylic acid copolymer ionomer. The method of claim 1 or 2, wherein the image receiving medium further comprises a polymeric substrate layer having an outer surface on a second major surface opposite the image receiving surface in the image receiving layer. The method of claim 4, wherein the image receiving medium further comprises an undercoat having an outer surface on the outer surface of the substrate layer. 6. The method of claim 5, wherein the image receiving medium further comprises an adhesive layer on the outer surface of the undercoating layer. delete delete