KR20050098938A - Dry paint transfer laminate - Google Patents

Abstract

The disclosed invention relates to a dry paint transfer (or multi-layer) laminate (100) which comprises: a dry paint layer (110) which includes a color layer comprising a binder and a pigment, the dry paint layer (110) having an upper surface (112) and a lower surface (114); a pressure-sensitive adhesive layer (120) overlying the upper surface (112) of the dry paint layer (110); and a release liner (130) overlying the lower surface (114) of the dry paint layer (110). The release liner (130) includes a first release coating layer (or carrier release coat layer or matte release coat layer) (135) that contains particles that project into the surface (114) of the dry paint layer (110) for transferring a matte finish to the surface (114) when the adhesive layer (120) adheres the laminate (100) to a substrate under the application of pressure and the release liner (130) is peeled away from the dry paint layer (110).

Description

Dry Paint Transfer Laminates {DRY PAINT TRANSFER LAMINATE}

The present invention relates to dry paint transfer laminates. These laminates are multilayer laminates comprising a dry paint layer, an adhesive layer overlying one side of the dry paint layer, and a release liner overlying the other side of the dry paint layer.

Conventional painting using liquid paint requires setup steps that include masking off areas that should not be painted and spreading drop cloths. Conventional painting also requires a thorough cleaning of brushes, rollers and the like, and causes problems of leakage, exposure to smoke and delays in paint drying. When special effects such as artificial finish are required, additional time and effort is required to apply additional coats.

The present invention provides an answer to these problems. According to the invention, there is no need to mask off areas that should not be painted and no need to use drop cloths. Difficult cleaning of brushes, rollers, etc. can be avoided. Leakage and exposure to smoke can be avoided. You can also avoid the delay of waiting for the paint to dry. Special effects such as artificial finishing can be performed with a single application.

The present invention provides a dry paint layer comprising a color layer comprising a binder and a pigment, the dry paint layer having an upper surface and a lower surface; A dry pressure sensitive adhesive layer overlying the top surface of the dry paint layer; And a release liner detachably adhered to the lower surface of the dry paint layer, the release liner adhering the laminate to the substrate under pressure applied with an adhesive layer and exposing the dry paint layer when the release liner is peeled from the dry paint layer. And a carrier release coat layer containing particles protruding into a dry paint layer detachably bonded to transfer the matte finish to the finished surface.

In one embodiment, the release liner further comprises an adhesive release coat layer on one side of the liner opposite from the release liner coat layer.

In one embodiment, the dry paint layer comprises a transparent layer positioned between the color layer of the dry paint layer and the release liner, wherein the carrier release coat layer is detachably adhered to the transparent layer.

In one embodiment, the invention provides a dry paint layer comprising a color layer comprising a binder and a pigment and a transparent layer overlying the color layer; A dry pressure sensitive adhesive layer overlying the surface of the dry paint layer on its side opposite from the transparent layer; And a release liner detachably contacting the surface of the dry paint layer opposite the adhesive layer, wherein the release liner has a dry matt release coat layer bonded to the release liner, After the release liner is released from contacting the dry paint layer to expose the matt surface of the transparent layer, when pressure is applied to the adhesive layer to adhere the laminate to the substrate, on the exposed surface of the transparent layer To a dry paint transfer laminate containing particles in contact with the transparent layer to produce a matt or flat or semi-gloss surface finish.

In one embodiment, the invention provides a matte release liner comprising a flexible polymer carrier film and a dry matte release coat bonded to the carrier film; A flexible dry paint layer in detachable contact with the matte release coat on the release liner; And a dry adhesive layer bonded to a dry paint layer on its side opposite the matte release liner, the dry paint layer comprising a pigment dispersed in a polymer binder, the matte release coat adhesive of the laminate contacting the substrate. It has a level of tack detachably attaching the matte release liner to the dry paint layer to provide a support for the laminate when placing the side, the adhesive layer having a dry paint layer on the substrate by applying pressure to the dry paint transfer laminate. A pressure sensitive adhesive for adhering the adhesive, wherein the matte release coat is dried to transfer the matte finish to the exposed surface of the dry paint layer when the release liner is released from contact with the dry paint layer after the laminate is adhered to the substrate. Containing particles protruding into the paint layer It relates to a dry paint transfer laminate.

In one embodiment, the release liner comprises a thin flexible polymeric carrier film and a matte release coat made from a thermosetting resinous material bonded to the carrier film, the dry paint when the release liner is removed from the paint layer at room temperature. The layer forms a matte surface that transfers the matte surface finish.

In one embodiment, the release liner comprises a matte release coat on the carrier film in overlapping contact with the thin flexible polymer carrier film and the dry paint layer, wherein the matte release coat comprises a coating material (1) on the dry paint layer. Forming a detachable matt surface, (2) releasing from the dry paint layer at room temperature, and (3) transferring the matt surface finish to the exposed surface of the dry paint layer when the release liner is removed from the dry paint layer. It is made from a resinous coating material having a hard state at room temperature.

In one embodiment, the invention provides a release liner having a flexible polymer carrier film and a matte release coat bonded to the carrier film; A flexible dry paint transfer layer detachably bonded to the matte release coat; And a dry pressure sensitive adhesive layer bonded to the dry paint transfer layer on the opposite side of the release liner, the dry paint transfer layer comprising a color layer comprising a pigment included in a polymeric binder; The matte coat has a level of tack that preferentially bonds the release liner with a dry paint transfer layer sufficient to provide a level of structural support for the dry paint layer when placing the adhesive side of the dry paint layer in contact with the substrate; The matte release coat includes a resinous material hardened or cured to form a fine-rough surface for transferring the matte surface finish to the exposed surface of the dry paint layer when the release coat is released from contact with the dry paint layer. and; The adhesive layer has a suppressed initial level of tack at room temperature that allows the laminate to adhere to the substrate following removal of the release liner from the dry paint layer, the adhesive layer having a time sufficient to permanently bond the dry paint layer to the substrate. It relates to a multilayer laminate that performs the subsequent reinforcement of adhesion due to the passage.

In one embodiment, the gloss level transferred from the matte release coat to the dry paint layer is less than 30% at 85 degrees.

In one embodiment, the dry paint transfer layer includes a clear coat layer overlying the color layer, and the clear coat contacts the matte emission coat to transfer the fine-rough surface to the clear coat layer.

In one embodiment, the release liner comprises a polyester film that is essentially non-stretchable at room temperature.

In one embodiment, the laminate includes a reinforcement polymerizable support layer between the dry paint layer and the adhesive layer, wherein the support layer has a greater tensile strength than the dry paint layer.

In one embodiment, the laminate has a self-winding form in which the release force required to separate the matte release coat from the dry paint layer is greater than the release force needed to separate the adhesive release coat layer from the pressure sensitive adhesive layer.

In one embodiment, the matte release coat is a tack that preferentially bonds the release liner with a dry paint transfer layer sufficient to provide a level of structural support for the dry paint layer when placing the adhesive side of the dry paint layer in contact with the substrate. Have a level; This matte release coat provides a fine-rough surface for transferring the matte surface finish to the exposed surface of the dry paint layer when the matte release coat material is hardened or cured so that the particles are released from contact with the dry paint layer. A resinous material containing dispersed particulate material to form, the uniform finish of the transferred matte having a gloss level of less than 30% at 85 degrees; The adhesive layer has a suppressed initial level of tack at room temperature that allows the laminate to adhere to the substrate subsequent to the removal of the release liner from the dry paint layer, which adhesive layer has sufficient time to permanently bond the dry paint layer to the substrate. The subsequent reinforcement of the adhesion is to be performed.

In one embodiment, the present invention provides an indoor dry paint layer comprising a binder and a pigment, a pressure sensitive adhesive layer placed on one surface of the dry paint layer for adhering the dry paint layer to a wall, a dry paint opposite the adhesive layer. And a release liner overlying the surface of the layer, the release liner being removable from the dry paint layer by attaching a dry paint layer to the wall via a pressure sensitive adhesive, the dry paint layer being matt on its exposed surface. Having a finish, the release liner comprises a matte release coat on the carrier film in overlapping contact with the thin flexible polymer carrier film and the dry paint layer, the matte release coat having an adhesive layer adhered to the wall and the release liner Matte surface on the exposed surface of the dry paint layer when removed from the paint layer at room temperature The multilayer laminate is made from a resinous coating material having a hardened state at room temperature where the coating material forms a matte surface for transferring the finish, and the transferred matte surface has a gloss level of less than 30% at 85 degrees. It is about.

In one embodiment, the present invention provides a dry paint layer detachably attached to a release liner to provide a support for the dry paint layer, and a pressure on one side of the dry paint layer opposite the release liner to attach the paint layer to the inner wall. A sensitive adhesive layer, wherein the release liner has a release coat that can be removed from the dry paint layer to expose the dry paint layer as a painted inner wall covering, the release liner opposite the release coat in contact with the dry paint layer. Having an adhesive release coat on one side of the liner, wherein the release liner comprises a polymeric carrier film, the release coat thereon comprising a matte release coat bonded to the carrier film and in contact with the dry paint layer; The release coat is a space separated from the carrier film in the rigid state. It has an adhesion level that forms a fine-rough surface and adheres the release liner to the dry paint layer, but the adhesive layer adheres the laminate to the wall and when the release liner is released from contact with the dry paint layer at room temperature. Made of a material that transfers a matte finish to an exposed surface, the laminate having a release force greater than the release force needed to separate the matte release coat from the dry paint layer and greater than the release force needed to separate the adhesive release coat from the adhesive layer. Has a self-winding form that removes the liner and has an ejection force level sufficient to transfer the matte surface to the dry paint layer while maintaining the integrity of the dry paint layer on the wall without releasing from its attachment to the wall. Dry paint transfer of indoor as phosphorus, interior wall It relates to a laminate.

In one embodiment, the invention applies a paint layer on one side of a release liner, and drying or curing the paint layer on the release liner to form a dry paint layer (the release liner is a thin film flexible polymer carrier film Wherein the paint layer comprises a binder and a pigment, and the release liner has a release surface in contact with the dry paint layer); And applying a pressure sensitive adhesive layer to the side of the paint layer opposite the release liner (applying the matte release coat to the release liner, wherein the matte release coat comprises a resinous material having dispersed particle filler material). And having a cured state at room temperature to form a matt surface; And applying a paint layer to the matte surface of the matte release coat and drying or curing the dry paint layer in contact with the matte surface to releasably adhere the dry paint layer to the matte surface (the matte surface is a laminate wherein the laminate is pressure sensitive). Bonded to the substrate via an adhesive and adapted to be released from the dry paint layer at room temperature to transfer the matte surface finish to the exposed surface of the dry paint layer when the release liner is removed therefrom). It is about.

In one embodiment, the present invention comprises applying one or more adhesive paint layers on one side of a release liner and drying or curing the adhesive paint layer or layers on the release liner to form a dry paint layer thereon (the The dry paint layer comprises a colored layer comprising a binder and a pigment, and has a top surface and a bottom surface, wherein the release liner comprises a matte release coat containing a resinous binder and dispersed particles forming thereon a matte emitting surface. Wherein the bottom surface of the dry paint layer is over and in contact with the matte emissive surface of the release liner; And applying a pressure sensitive adhesive layer over the top surface of the dry paint layer, the pressure sensitive adhesive layer being adapted to adhere the dry paint layer to the substrate surface as pressure is applied to the release liner, the release liner being Dry paint transfer, which may be released from the adhered dry paint layer to transfer the matte finish from the matte emissive surface to the exposed surface of the dry paint transfer layer when the release liner is released from contact with the dry paint layer. It relates to a method for producing a laminate.

In one embodiment, the present invention provides a method of applying a matte release coat to a release liner, wherein the matte release coat is made from a resinous material that has a rigid state at room temperature and has a matte surface spaced apart from the carrier film. ; And applying a paint layer to the matte surface and drying or curing the paint layer thereon, the matte release coat material providing adhesion of the matte surface to the dry paint layer, wherein the dry paint layer is applied to the substrate surface via a pressure sensitive adhesive. And release from contact with the dry paint layer at room temperature to transfer the matte surface finish to the exposed surface of the dry paint layer when bonded to the layer.

In one embodiment, the invention provides a step of applying a thermosetting resinous matte release coat to a release liner and curing the release coat thereon at room temperature (the composition of release coat material forming a bond to a release liner and Forming a matte emissive surface in a hard state and forming a tack level in its hardened state); And applying a paint layer to the matte surface, and drying or curing the paint layer thereon (the matte release coat is detachably adhered to the dry paint layer, and the laminate is adhered to the substrate surface via a pressure sensitive adhesive, And the transfer of the matte surface finish to the dry paint layer at room temperature when the release liner is subsequently removed from the dry paint layer.

In one embodiment, the present invention comprises applying a matte release coat to a release liner and drying or curing the release coat thereon to form a matte surface on the liner, wherein the release coat is bonded to the liner, Made from a thermosetting resinous material containing dispersed particulate material thereon forming a matte surface, and applying a paint layer to the matte surface, and drying or curing the paint layer thereon (the matte surface is The dry paint layer is adhered to the substrate surface via a pressure sensitive adhesive, and transfers the matte surface finish to the dry paint layer when the release liner is subsequently removed from the paint layer.

Brief description of the drawings

In the accompanying drawings, like reference numerals refer to like parts of features.

1 is a schematic illustration of a side view of a dry paint transfer laminate embodying certain aspects of the present invention.

FIG. 2 is a schematic illustration of the dry paint transfer laminate illustrated in FIG. 1 partially wound with a roll. FIG.

3 is a schematic illustration of a side view of another embodiment of a dry paint transfer laminate of the present invention.

4 is a schematic illustration of a side view of another embodiment of a dry paint transfer laminate of the present invention.

5 is a schematic illustration of a side view of another embodiment of a dry paint transfer laminate of the present invention.

6 is a schematic illustration of a side view of another embodiment of a dry paint transfer laminate of the present invention.

7 is a schematic illustration of a side view of another embodiment of a dry paint transfer laminate of the present invention.

8 is a schematic illustration of a side view of another embodiment of a dry paint transfer laminate of the present invention.

9 is a schematic illustration of a side view of another embodiment of a dry paint transfer laminate of the present invention.

10 is a schematic illustration of a side view of another embodiment of a dry paint transfer laminate of the present invention.

11 is a schematic illustration of the process of co-extrusion of the support layer and the adhesive layer used in one embodiment of the laminate of the present invention.

12 is a schematic illustration of another embodiment of a process of coextrusion of a support layer and an adhesive layer used in one embodiment of a laminate of the present invention.

Similar terms such as "on" and "on" and "on" refer to one layer or to a relationship between another layer or a second layer of a first layer, where the first layer is partially or completely It means the fact that it lies on the second layer. The first layer overlying the second layer may or may not be in contact with the second layer. For example, one or more additional layers may be located between the first layer and the second layer. Similar terms such as "below" and "below" and "below" have a similar meaning except that the first layer is placed below rather than partially or completely above the second layer. .

The term "dry paint" means a paint composition that is sufficiently dried and cured so that the paint composition applied to the substrate does not stain or become soiled when touched or handled by the user. The dry paint composition may be derived from a liquid (ie, solvent based or water based) coating or film forming composition or hot melt coating or film forming composition. In one embodiment, the dry paint composition may be derived from a composition containing one or more volatile components (eg, organic solvents, water, etc.), wherein the paint composition is applied to a substrate, and the volatile components are fully or sufficiently It is removed to allow the paint to adhere to the substrate and to a degree that does not stain or stain when the user touches it. The term "volatile" is used herein to mean materials that are volatile at drying temperatures and atmospheric pressure.

When referring to a transparent film layer overlying one or more dry paint film layers of the dry paint transfer laminate of the present invention, the term "transparent" means that one or more dry paint film layers can be seen through the transparent film layer. . The transparent film layer can be translucent.

Referring to FIG. 1, the dry paint transfer laminate of the present invention is generally indicated by reference numeral 100, in one of its illustrated embodiments, which is a dry paint having an upper surface 112 and a lower surface 114. Layer or film layer 110; An adhesive layer 120 overlying and adhered to the top surface 112; And a release liner 130 overlying and adhered to the bottom surface 114. The release liner 130 includes a backing liner 132 having an upper surface 133 and a lower surface 134; A first release coating layer 135 overlying and adhered to top surface 133; And a second release coating layer 136 overlying and adhered to the bottom surface 134. The first release coating layer 135 may be referred to as a carrier release coating layer or a matte release coating layer. The first release coating layer 135 is located between the top surface 133 of the backing liner 132 and the bottom surface 114 of the dry film layer 110, preferably the top surface of the backing liner 132 ( 133). Thus, when the release liner 130 is peeled off from the dry paint film layer 110, the release coating layer 135 is separated from the dry paint film layer 110 and remains attached to the backing liner 132. The bottom surface 127 of the emissive layer 136 is adapted to contact the top surface 122 of the adhesive layer 120 when the laminate 100 is wound in roll form as illustrated in FIG. 2.

Referring to FIG. 2, the dry paint transfer laminate 100 is wound in the form of a roll having a bottom surface 137 of the release coating layer 136 in contact with the top surface 122 of the adhesive layer 120. This release coating layer 136 is first adhered to the backing liner 132. Thus, when the dry paint transfer laminate 100 illustrated in FIG. 2 is not wound, the release coating layer 136 is separated from the adhesive layer 120 and left attached to the backing liner 132.

The dry paint transfer laminate 100A illustrated in FIG. 3 has the dry paint transfer laminate illustrated in FIG. 1 except that a transparent film layer 140 is positioned between the dry paint film layer 110 and the release coating layer 135. Same as (100). The release coating layer 135 is adhered to the transparent film layer 140 on one side, adhered to the backing liner 132 on the other side, and preferentially to the backing liner 132. Thus, when the release liner 130 is peeled off from the transparent film layer 140, the release coating layer 135 is separated from the transparent film layer 140 and remains attached to the backing liner 132.

The dry paint transfer laminate 100B illustrated in FIG. 4 is the dry illustrated in FIG. 3 except that the printed adhesive layer 150 is positioned between the dry paint film layer 110 and the transparent film layer 140. Same as the paint transfer laminate 100A.

The dry paint transfer laminate 100C illustrated in FIG. 5 is FIG. 4 except that a second printed adhesive layer 160 is positioned between the printed adhesive layer 150 and the transparent film layer 140. Same as the dry paint transfer laminate 100B illustrated in.

Additional printed adhesive layers may be used beyond the layers 150 and 160. For example, the laminates of the present invention may include five or more printed adhesive layers that overlap each other, in one embodiment about three or four printed adhesive layers. The printed adhesive layers can provide the desired print or design and can be applied using conventional printing methods such as gravure, iron plate printing, silk screen, ink jet, and the like.

The dry paint transfer laminate 100D illustrated in FIG. 6 is illustrated in FIG. 1 except that no release coating layer 136 is present and an additional release liner 170 is added to overlie the adhesive layer 120. It is the same as the laminate 100. The release liner 170 includes a backline liner 172 having an upper surface 173 and a lower surface 174; And a release coating layer 176 overlying and adhered to the bottom surface 174. The emissive layer 176 is positioned between the bottom surface 174 of the backline liner 172 and the top surface 122 of the adhesive layer 120 and preferentially adheres to the bottom surface 174 of the backline liner 172. do. Thus, when the release liner 170 is peeled off from the adhesive layer 120, the release coating layer 176 is separated from the adhesive layer 120 and remains adhered to the backing liner 172.

The dry paint transfer laminate 100E illustrated in FIG. 7 has the exception that the laminate 100E includes a support layer 180 positioned between the dry paint film layer 110 and the adhesive layer 120. Same as the laminate 100 illustrated in.

The dry paint transfer laminate 100F illustrated in FIG. 8 has the exception that the laminate 100F includes a barrier layer 190 positioned between the dry paint film layer 110 and the adhesive layer 120. Same as the laminate 100 illustrated in.

The dry paint transfer laminate 100G illustrated in FIG. 9 has the exception that the laminate 100G includes a support layer 180 positioned between the dry paint film layer 110 and the adhesive layer 120. Same as the laminate 100 illustrated in. The laminate G also includes printed adhesive layers 150, 160, and 165 positioned between the dry paint film layer 110 and the first release coating layer 135.

The dry paint transfer laminate 100H illustrated in FIG. 10 has no release liner 130 present in the laminate 100C, the release liner 170 overlies the adhesive layer 120, and the release layer 176 releases. Same as laminate 100C illustrated in FIG. 5 except that it is located between liner 170 and adhesive layer 120.

Dry paint layer or film layer 110 may have a thickness of about 0.5 to about 1.5 mils, in one embodiment about 0.5 to about 1.2 mils, in one embodiment about 0.5 to about 0.9 mils, and in one embodiment about 0.7 mils. have. The thickness of the adhesive layer 120 may range from about 0.4 to about 1 mil, in one embodiment from about 0.4 to about 0.8 mil, and in one embodiment from about 0.4 to about 0.6 mil. The thickness of the backlash liner 132 may range from about 0.5 to about 2 mils, in one embodiment from about 0.5 to about 1.5 mils, and in one embodiment from about 0.85 to about 1.05 mils. The thickness of the first release coating layer 135 may range from about 0.05 to about 0.3 mils, in one embodiment about 0.1 to about 0.2 mils. The thickness of the second release coating layer 136 may range from about 0.04 to about 0.2 mils, in one embodiment from 0.04 to about 0.15 mils, and in one embodiment from 0.04 to about 0.08 mils. The thickness of the transparent film layer 140 may range from about 0.05 to about 0.4 mils, in one embodiment about 0.05 to about 0.3 mils, and in one embodiment about 0.2 mils. The thickness of the printed adhesive layer 150 may range from about 0.02 to about 0.15 mils, in one embodiment about 0.02 to about 0.08 mils. The thickness of the second printed adhesive layer 160 may range from about 0.02 to about 0.15 mils, in one embodiment from about 0.02 to about 0.1 mils. The thickness of the backliner liner 172 may range from about 0.5 to about 2 mils, in one embodiment from about 0.5 to about 1.5 mils, and in one embodiment from about 0.85 to about 1.05 mils. The thickness of the release coating layer 176 may range from about 0.04 to about 0.2 mils, in one embodiment about 0.04 to about 0.15 mils, and in one embodiment about 0.04 to about 0.08 mils. The support layer 180 may have a thickness of about 0.3 to about 1.4 mils, in one embodiment about 0.3 to about 1.1 mils, in one embodiment about 0.3 to about 0.8 mils, and in one embodiment about 0.3 to about 0.5 mils. . When the support layer 180 is used, the overall thickness of the dry paint film layer 110 and the support layer 180 combined is about 0.5 to about 1.5 mils, in one embodiment 0.5 to about 1.2 mils, and in one embodiment about 0.5 To about 0.9 mil, in one embodiment about 0.7 mil. Barrier layer 190 may have a thickness in the range of about 0.01 to about 0.1 mils, in one embodiment about 0.05 to about 0.1 mils, and in one embodiment about 0.01 to about 0.02 mils. Each of these thicknesses is a dry film thickness. Laminates 100-100H can have any width and length suitable for ease of use by a user. For example, the width may range from about 1 to 200 cm, in one embodiment from 10 to 100 cm, in one embodiment from about 30 to about 40 cm. The length may range from about 10 to about 6500 meters, in one embodiment from about 15 to about 1000 meters. In one embodiment, the length may range from about 19 to about 6500 meters. In one embodiment, the length may range from about 17 to about 20 meters. In one embodiment, the laminate may have a width of about 10 to about 20 cm and a length of about 10 to about 30 cm. The laminates may be provided in the form of a flat sheet or roll as illustrated in FIG. 2.

Layers 110, 150, 160, and 165 may independently comprise one or more binders or resins, and one or more pigments. The support layer 180 may comprise one or more binders or resins, and optionally one or more pigments. The transparent film layer 140 may include one or more binders or resins. These layers may contain additional additives for controlling properties such as one or more binders or resins, one or more pigments (if used), water or one or more organic solvents, and optionally rheological properties. It can be prepared from a liquid coating or paint compositions comprising. Each of layers 110, 140, and 180 may independently include one or more extruded film layers.

The binder or resin can include any binder or resin commonly used in coating or paint formulations. The binder may comprise a thermoplastic or thermoset resin. The binder or resin may be a synthetic resin or a natural resin. The binder or resin may comprise a film forming material which may be an extrudable film forming material in one embodiment. Examples of useful binders or resins include acrylic resins, vinyl resins, polyester resins, alkyd resins, butadiene resins, styrene resins, phthalic or anhydride resins, urethane resins, epoxy resins and the like. The binder or resin may be selected from vinyl and vinylidene polymers or copolymers containing units such as vinyl acetate, vinyl chloride, vinylidene chloride and the like; Hydrocarbon polymers and copolymers containing ethylene or propylene units and ethers, oxygenated or halogenated derivatives of butadiene, oxygenated butadiene, isoprene, oxygenated isoprene, butadiene-styrene, butadiene vinyl toluene, isoprene Styrene and the like; Polymers or copolymers containing acrylic acid, methacrylic acid, esters or acrylonitrile units thereof; Vinyl hydrocarbon monomers reacted with unsaturated substances such as maleic acid or the reaction product of anhydride with styrene; And broadly, various other dendritic rubbery elastomeric latex polymers and copolymers of ethylenically unsaturated monomers and polymers that can be obtained in the form of suitable aqueous latexes. The binder or resin may comprise a copolymer of vinyl chloride and vinyl acetate. The binder or resin may include diphenylmethane diisocyanate, methylene diethyl diisocyanate, isocyanurate, urea-formaldehyde, phenolformaldehyde, phenolic glue, animal halide glues, and the like. Other examples of binders or resins that can be used include fluorine resins, silicone resins and fibrin resins.

The binder or resin may comprise one or more polystyrenes, polyolefins, polyamides, polyesters, polarcarbonates, polyvinyl alcohols, polyethylene vinyl alcohols, polyurethanes, polyacrylates, polyvinyl acetates, ionomers And mixtures thereof. The polyolefins are characterized by having a melt index or melt flow rate of less than about 30, in one embodiment less than about 20, and in one embodiment less than about 10 as measured by ASTM test method 1238.

Polyolefins include polymers and copolymers of ethylene, propylene, 1-butene and the like or blends of mixtures of such polymers and copolymers. Polyolefins may include polymers and copolymers of ethylene and propylene. Polyolefins may include propylene homopolymers and copolymers such as propylene-ethylene and propylene-1-butene copolymers. Blends of polypropylene and polyethylene with one another or with one or both of them and a polypropylene-polyethylene copolymer can be used. Polyolefin film forming materials are high propylene content, polypropylene homopolymer or propylene-ethylene copolymers or polypropylene and polyethylene and low ethylene content blends or propylene-1-butene copolymers or polypropylene and poly-1-butene And a low butene content blend.

Various polyethylenes can be used, including low density, medium density and high density polyethylenes. The low density range for polyethylenes can be about 0.910 to about 0.925 g / cm ³ , the medium density range can be about 0.925 to about 0.940 g / cm ³ , and the high density range is about 0.940 to about 0.965 g / cm Can be ^three . An example of a useful low density polyethylene (LDPE) is Rexene 1017, available from Huntsman.

Propylene homopolymers that can be used alone or in combination with propylene copolymers include various propylene homopolymers such as those having a melt flow rate (MFR) of about 0.5 to about 20 as measured by ASTM Test D 1238, Condition L. do. In one embodiment, propylene homopolymers having an MFR of less than about 10 and in one embodiment from about 4 to about 10 may be used. Propylene homopolymers can be characterized as having a density in the range from about 0.88 to about 0.92 g / cm ³ . Many useful propylene homopolymers are commercially available from various sources, some useful polymers are available from Union Carbide, 5A97 with a melt rate of 12.0 g / 10 min and a density of 0.90 g / cm ³ ; DX5E66, available from Union Carbide, having an MFI of 8.8 g / 10 min and a density of 0.90 g / cm ³ ; And WRD5-1057, available from Union Carbide, having a MFI of 3.9 g / 10 min and a density of 0.90 g / cm ³ . Useful commercial propylene homopolymers may also be available from Fina and Montel.

Polyamide resins include resins available from EMS American Grilon Inc., Sumter, SC. Under the common trade names Grivory such as CF6S, CR-9, XE3303 and G-21. Grivory G-21 is an amorphous nylon copolymer having a glass transfer temperature of 125 ° C., a melt flow rate of 90 ml / 10 minutes (DIN53735) and an elongation at break of 15 (ASTM D638). Grivory CF65 is a nylon 6/12 film grade resin having a melting point of 135 ° C., a melt flow rate of 50 ml / 10 minutes and an elongation at break exceeding 350%. Grilon CR9 is another nylon 6/12 film grade resin having a melting point of 200 ° C., a melt flow rate of 200 ml / 10 minutes and an elongation at break of 250%. Grilon XE3303 is a nylon 6.6 / 6.10 film grade resin with a melting point of 200 ° C., a melt flow rate of 60 ml / 10 minutes and an elongation at break of 100%. Polyamide resins are, for example, those available from Union Camp of Wayne, NJ under the Uni-Rez product line, and dimers available from Bostik, Emery, Fuller, Henkel (under Versamid product line). Base polyamide resins. Polyamides include those produced by condensing dimerized vegetable acids and hexamethylene diamine. Examples of polyamides available from Union Camp are Uni-Rez 2665; Uni-Rez 2620; Uni-Rez 2623; And Uni-Rez 2695.

Polystyrenes include copolymers as well as homopolymers of substituted styrenes such as styrene and alpha-methyl styrene. Examples of styrene copolymers and triple polymers include acrylonitrile-butene-styrene (ABS); Styrene-acrylonitrile copolymers (SAN); Styrene butadiene (SB); Styrene-maleic anhydride (SMA); And styrene-methyl methacrylate (SMMA) and the like.

Polyurethanes include aliphatic as well as aromatic polyurethanes.

Polyesters can be prepared from various glycols or polyols and one or more aliphatic or aromatic carboxylic acids. Polyethylene terephthalate (PET) and PETG (PET modified with cyclohexanedimethanol) are useful film forming materials available from various commercial sources including Eastman. For example, Kodar 6763 is PETG available from Eastman Chemical. Another useful polyester available from DuPont is Selar PT-8307, a polyethylene terephthalate.

Acrylate polymers and copolymers and alkylene vinyl acetate resins (eg EVA polymers) can be used. Examples include Escorene UL-7520 (Exxon), copolymers of ethylene and 19.3% vinyl acetate; Nucrell 699 (DuPont), ethylene copolymers containing 11% methacrylic acid, and the like.

Ionomers (polyolefins containing ionic bonds in the molecular chains) can be used. Examples of ionomers include ionomer ethylene copolymers such as Surlyn 1706 (DuPont), which are believed to contain interchain ionic bonds based on zinc salts of ethylene methacrylic acid copolymers. Surlyn 1702, available from DuPont, is an ionomer that can be used.

Polycarbonates are also useful, which are Dow Chemical Co. (Calibre), G.E. Available from Plastics (Lexan) and Bayer (Makrolon). These polycarbonates can be obtained by the reaction of bisphenol A with carbonyl chloride in the contacting process. Molecular weights can vary from about 22,000 to about 35,000, and melt flow rates can range from about 4 to about 22 g / 10 minutes.

The pigment can be any pigment used to make adhesive coatings. These include carbon black, yellow oxides, brown oxides, tan oxides, raw and baked sienato or umber, chromium oxide green, phthalocyanine green, phthalocyanine blue, ultramarine blue, as well as opaque pigments such as titanium dioxide and zinc oxide. Cadmium pigments, chromium pigments and the like. These pigments include organic reds such as azo reds, quinacridone red and perylene red as well as organic yellows such as diarylide yellow. Mixed metal oxide pigments can be used. Filler pigments such as clay, silica, talc, mica, wollastonite, wood flour, barium sulfate, calcium carbonate, aluminum silicate and the like can be added in conventional amounts as well as conventionally used in coating and paint formulations.

The solvent may be an organic-based solvent such as ketones, esters, aliphatic compounds, aromatic compounds, alcohols, glycols, glycol ethers and the like. These include methylethyl ketone, methyl isobutyl ketone, ethyl acetate, white solvents, alkanes, cycloalkanes, benzene, hydrocarbon substituted aromatic compounds (e.g. toluene, xylene, etc.), isoparaffin solvents and two or more thereof. Combinations. Alternatively, water or a water-based solution can be used to form an emulsion with the binder or resin. Water-based solutions include water-alcohol mixtures and the like. Since the solvent or water is sufficiently volatile, when applied to the substrate, the solvent evaporates, leaving the binder or resin, pigment (if used) and any other nonvolatile components.

Additional ingredients that can be used include moisturizers; Plasticizers; Suspension aids; Thixotropic agents such as silica; Propellant-free additives such as polysiloxane compounds; Flame retardant additives; Biocides; Defoamers; Flow agents and the like.

The pigment concentration for the liquid paint or coating composition used to provide the layers 110, 150, 160, and 165 may range from about 10 wt% to about 30 wt%, in one embodiment from about 13 wt% to about 27 wt%. The binder or resin concentration may range from about 20 to about 40 weight percent, in one embodiment from about 22 to about 37 weight percent. The water or organic solvent concentration may range from about 30% to about 70% by weight, in one embodiment from about 40% to about 60% by weight. Additional ingredients such as moisturizers, suspending agents, etc. may be provided in concentrations known in the art, for example at about 5% by weight and in one embodiment at a concentration of about 0.1 to about 5% by weight. The coating or paint compositions used to make the layers 110, 150, 160 and 165 may have a pigment volume concentration (PVC) in the range of about 5 to about 35%, in one embodiment in the range of 10 to about 30%. The liquid paint or coating compositions used to make the film layers 110, 150, 160, 165 and 180 may be mixed using known techniques.

The dry paint layer or film layer 110 may comprise a single coat or multiple coats of paint in the form of a continuous layer, while the printed adhesive layers 150, 160 and 165 are independently of continuous or discontinuous layers. It may be in the form. When multiple coats for layer 110 are used, each coat may have the same or different formulation. Layers 150, 160 and / or 165 may have the same or different color as layer 110. Layers 150, 160 and / or 165 may have the same color or they may have different colors from each other. Layer 110 may be used to provide a background color, while layers 150, 160 and / or 165 may be used to provide a pattern or design. For example, layers 150, 160 and / or 165 may be used to provide a fake finish or “lagging” or “sponging” appearance. Layers 150, 160 and / or 165 may be used to provide a desired print or design image (eg, floral design) with one or multiple colors. Designs may be in the form of repeating designs or random non-repeating designs.

The transparent layer or film layer 140 may comprise a single coating layer or multiple coats and may include any of the resin materials. When multiple coats are used, each coat may have the same or different formulation. The transparent layer 140 may be extruded. Specific examples of resins that can be used include polyvinyl chloride and copolymers of vinyl chloride and acrylic acid or methacrylic acid. Transparent layer 140 may be distinguished from phosphorus dry paint film layer 110 primarily by the fact that it is transparent or translucent. Transparent layer 140, in one embodiment, provides enhanced scuff resistance, fouling resistance and / or recoating potential for a dry paint film layer or underlying layers. The enhanced recoating potential encourages the presence of the transparent layer 140 in subsequent application of another dry paint film layer or adhesive layer printed thereon or application of conventional paint or wall coverings (eg, wallpaper) thereon.

The support layer 180 may be formed from any of the above binders or resin materials. The support layer can be formed from a solution or emulsion and can be applied using any of the coating techniques described below. The support layer 180 may be extruded. The support layer 180 may contain one or more of these pigments. In one embodiment, the support layer 180 contains sufficient pigment to have neutral colors such as grey, light blue, bright red, and the like. When used, the concentration of the pigment in the support layer 180 may range from about 6 wt% to about 10 wt%, in one embodiment, up to about 10 wt%.

Layers 110, 140 and 180 may independently contain inorganic fillers or other organic or inorganic additives to provide the desired properties such as appearance properties (transparent, opaque or colored film), durability and processing properties. have. Examples of useful materials are calcium carbonate, titanium dioxide, metal particles, fibers, flame retardants, antioxidant compounds, heat stabilizers, light stabilizers, ultraviolet stabilizers, antiblocking agents, processing aids, acid acceptors And the like.

Nucleating agents may be added to one or more layers 110, 140 or 180 to increase crystallinity and thereby increase stiffness. Nucleating agents that can be used include mineral nucleating agents and organic nucleating agents. Examples of mineral nucleating agents include carbon black, silica, kaolin and activity. Examples of organic nucleating agents are salts of aliphatic mono- or di-basic acids or salts of arylalkyl acids, for example sodium succinate, sodium glutarate, sodium caproate, sodium 4-metalvalate, aluminum phenyl acetate And sodium cinnamate. Alkali metal and aluminum salts of aromatic and alicyclic carboxylic acids such as aluminum benzoate, sodium benzoate or potassium, sodium betanaphtholate, lithium benzoate and aluminum tert-butyl benzoate are also useful organic nucleating agents. Substituted sorbitol derivatives such as bis (benzylidene) and bis (alkylbenzylidene) sorbitols, wherein the alkyl groups contain about 2 to about 18 carbon atoms, are useful nucleators. Sorbitol derivatives such as 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di-para-methylbenzylidene sorbitol and 1,3,2,4-di-para-methyl Benzylidene sorbitol can be used. The amount of nucleating agent incorporated into the film forming formulations may range from about 100 ppm to about 6000 ppm of the film. In one embodiment, the amount of nucleating agent may range from about 1000 to 5000 ppm.

The one or more layers 110, 140, and 180 may contain a minimum amount of adhesive resin to promote adhesion of the layers 110 to the layers 140 and / or 180. Also or alternatively, tie layers of adhesive resin may be located between layers 110 and 140 or between layers 110 and 180. Adhesive resins may be ethylene / vinyl acetate copolymers, such as those available from DuPont under the trade name Elvax. Adhesive resins available from DuPont under the trade name Bynel may be used.

In one embodiment, layers 110, 140 and / or 180 are non-stretch and inelastic at room temperature.

The adhesive layer 120 may comprise a pressure sensitive adhesive (PSA) layer, a moisture active adhesive layer or a thermally active adhesive layer. The adhesive can include any pressure sensitive, moisture active or thermally active adhesive known in the art for use with film substrates. The adhesive layer 120 may be in the form of a continuous or discontinuous layer and may comprise one adhesive or a mixture of two or more adhesives. The adhesive layer may be in the form of a patterned adhesive layer having relatively strong adhesion in some areas and relatively weak adhesion in other areas. In one embodiment, the adhesive layer provides an initial tack and allows some movement of the laminate to allow placement control prior to forming permanent bonds. In one embodiment, the adhesive allows inspired stripping of the dry paint film layer from the substrate when the use of the paint film layer is no longer desirable. In one embodiment, the adhesive layer is characterized as producing only a limited amount of emissions beyond the boundaries of the substrate when the laminate is applied to the substrate. In one embodiment no emissions are produced. The adhesive may comprise a rubber base adhesive, an acrylic adhesive, a vinyl ether adhesive, a silicone adhesive, or a mixture of two or more thereof. The adhesive can be applied as a hot melt solvent-based or water-based adhesive. Useful adhesive materials include, as main components, adhesive polymers such as acrylic type polymers; Block copolymers; Natural, regenerated or styrene-butadiene rubbers; Adhesive natural or synthetic rubbers; Copolymers of ethylene and vinyl acetate; Ethylene-vinyl-acrylic triple polymers; Polyisobutylene; Poly (vinyl ether) and the like. Other materials may be included in the adhesive, such as tacky resins, plasticizers, antioxidants, fillers, waxes and the like.

Adhesives are random copolymer adhesives such as those based on the following categories: acrylate and / or methacrylate copolymers, α-olefin copolymers, silicone copolymers, chloroprene / acrylonitrile copolymers, and the like. field; Block copolymer adhesives including those based on linear block copolymers (ie, A-B and A-B-A types), branched block copolymers, star block copolymers, graft or radial block copolymers, and the like; And natural and synthetic rubber adhesives. A description of useful pressure sensitive adhesives can be found in Willie-Interscience, New York, 1988, Vol. 13, Encyclopedia of Polymer Science and Engineering. Further description of useful pressure sensitive adhesives can be found in the first issue of Encyclopedia of Polymer Science and Technology, published by Interscience (New York, 1964).

Pressure sensitive adhesives that may be used include H.B., St. Paul, Minn., Such as HM-1597, HL-2207-X, HL-2115-X, HL-2193-X. High temperature melt pressure sensitive adhesives available from Fuller Company. Other useful pressure sensitive adhesives include those available from Century Adhesives Corporation, Columbus, Ohio.

Conventional PSAs are useful, including silicone-based PSAs, rubber-based PSAs, and acrylic-based PSAs. An example of another commercially available hot melt adhesive is H2187-01, sold by Ato Findley, Inc., Wowwatu, Wisconsin. In addition, rubber base block copolymer PSAs described in US Pat. No. 3,239,478 (Harlan) can also be used, which is incorporated herein by reference for the disclosure of such hot melt adhesives.

In one embodiment, the pressure sensitive adhesive are rubber-based elastic body materials, for example, diblock structures AB, triblock ABA, radial or coupled structures of (AB) linear indicated by _n, branched, graft or radial block copolymer Coalescers and combinations thereof, where A represents a hard thermoplastic phase or block that is non-rubber or glassy or crystalline but fluid at high temperature, and B represents a soft block that is rubbery or elastic in service or at room temperature . These thermoplastic elastomers may comprise about 75 to about 95 weight percent of the rubbery segments and may comprise about 5 to about 25 weight percent of the non-rubber segments.

Non-rubber segments or hard blocks include polymers of mono- and polycyclic aromatic hydrocarbons, more particularly vinyl-substituted aromatic hydrocarbons which may be monocyclic or bicyclic in nature. The rubbery blocks or segments are typically polymer blocks of homopolymers or copolymers of aliphatic conjugated dienes. Gummy materials such as polyisoprene, polybutadiene, and styrene butadiene rubbers may be used to form the gummy blocks or segments. The rubbery segments include saturated olefin rubbers of polydienes and ethylene / butylene or ethylene / propylene copolymers. The latter rubbers can be obtained from the corresponding unsaturated polyalkylene moieties, for example polybutadiene and polyisoprene by hydrogenation thereof.

Block copolymers of vinyl aromatic hydrocarbons and conjugated dienes that may be used include any of those exhibiting elastic properties. The block copolymers can be diblock, triblock, multiblock, starblock, polyblock or graftblock copolymers. Throughout the specification and claims, the terms diblock, triblock, multiblock, polyblock and grafted or grafted-blocks with respect to the structural features of the block copolymers are referred to in the Encyclopedia of Polymer Science and Engineering Volume 2 (1985) John Willie & Sons Inc, New York, pp. 325-326 and JE It should be given in the usual sense as defined in McGrath's Block Copolymers, Science Technology, Dale J. Meier, Compilation, Howard Academic, 1979, pages 1-5, and the like.

Such block copolymers may contain various ratios of conjugated dienes to vinyl aromatic hydrocarbons, including those containing up to about 40 weight percent vinyl aromatic hydrocarbons. Thus, multi-block copolymers can be used, which are linear or radial symmetrical or asymmetrical and have structures represented by the formulas AB, ABA, ABAB, BAB, (AB) _0,1,2 ... BA, etc., wherein A is a polymer block of vinyl aromatic hydrocarbon or conjugated diene / vinyl aromatic hydrocarbon tapered copolymer block, and B is a rubbery polymer block of conjugated diene.

Block copolymers are described, for example, in US Pat. No. 3,251,905; 3,390,207; 3,390,207; 3,598,887; 3,598,887; And sequential addition of monomers, increasing addition of monomers, or coupling techniques, as illustrated in US Pat. No. 4,219,627, by any of the well known block polymerization or copolymerization processes. As is well known, tapered copolymer blocks can be incorporated into multi-block copolymers by copolymerizing a mixture of conjugated diene and vinyl aromatic hydrocarbon monomers using the difference in their copolymerization reactivity rates. US Patent No. 3,251,905; 3,639,521; US Pat. And several patents, including US Pat. No. 4,208,356, disclose the preparation of multi-block copolymers containing tapered copolymer blocks, the disclosure of which is incorporated herein by reference.

Conjugated dienes that can be used to prepare polymers and copolymers are those containing 4 to about 10 carbon atoms and more generally 4 to 6 carbon atoms. Examples include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, chloroprene, 1,3-pentadiene, 1,3-hexadiene, and the like. It includes. Mixtures of these conjugated dienes may also be used. Conjugated dienes are isoprene and 1,3-butadiene.

Examples of vinyl aromatic hydrocarbons that can be used to prepare the copolymer are styrene and o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,2-dimethylstyrene, alpha-methylstyrene, beta-methyl Various substituted styrenes such as styrene, p-isopropylstyrene, 2,2-dimethylstyrene, o-chlorostyrene, p-chlorostyrene, o-bromostyrene, 2-chloro-4-methylstyrene and the like. Preferred vinyl aromatic hydrocarbons are styrene.

Many of these copolymers of conjugated dienes and vinyl aromatic compounds are commercially available. The number average molecular weight of the block copolymers before hydrogenation is about 20,000 to about 500,000, preferably about 40,000 to about 300,000.

The average molecular weights of the individual blocks in the copolymers can vary within certain limits. In most cases, the vinyl aromatic block will have a number average molecular weight of about 2000 to about 125,000, preferably about 4000 to 60,000. Hydrogenated transfer or later conjugated diene blocks will have a number average molecular weight of about 10,000 to about 450,000, more preferably about 35,000 to 150,000.

In addition, prior to hydrogenation, the vinyl content of the conjugated diene moiety is generally from about 10% to about 80%, and the vinyl content is preferably from about 25% to about 65%, in particular the modified block copolymer being rubbery elastomeric. When it represents 35% to 55%. The vinyl content of the block copolymer can be measured by nuclear magnetic resonance means.

Specific examples of diblock copolymers include styrene-butadiene (SB), styrene-isoprene (SI) and their hydrogenated derivatives. Examples of triblock polymers include styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), alpha-methylstyrene-butadiene-alpha-methylstyrene and alpha-methylstyrene-isoprene alpha-methylstyrene. Examples of commercially available block copolymers useful as adhesives in the present invention include those available from Shell Chemical Company, and are listed in Table II below.

Table II

Kraton type Styrene / Rubber Ratio (w) Melt index

D1101 Linear SBS 31/69 <1

D1107P Linear SIS 15/85 11

D1111 Linear SIS 22/78 3

D1112P Linear SIS 15/85 23

D1113P Linear SIS 16/84 24

D1117P Linear SIS 17/83 33

D1320X Multi-arm (SI) n 10/90 NA

Vector 4111 is a SIS block copolymer available from Dexco of Houston, Texas.

Following the hydrogenation of SBS copolymers in which the 1,4 and 1,2-isomers comprise the rubbery segments of the mixture, a styrene-ethylene-butylene styrene (SEBS) block copolymer is obtained. Likewise, hydrogenation of the SIS polymer produces styrene-ethylene propylene-styrene (SEPS) block copolymers.

Selective hydrogenation of the block copolymers can be carried out by a variety of well known processes including hydrogenation in the presence of Raney nickel, precious metals such as platinum, palladium and the like and soluble transfer metal catalysts. have. Suitable hydrogenation processes that can be used are those in which the diene-containing polymer or copolymer is dissolved in an inert hydrocarbon diluent such as cyclohexane and hydrogenated by reaction with hydrogen in the presence of a soluble hydrogenation catalyst. Such processes are disclosed in US Pat. Nos. 3,113,986 and 4,226,952, the disclosures of which are incorporated herein by reference. Such hydrogenation of the block copolymers is in some way up to the extent to selectively produce hydrogenated copolymers having residual unsaturation content in the polydiene blocks whose native unsaturated content prior to this hydrogenation is from about 0.5% to about 20%. Is performed.

In one embodiment, the conjugated diene of the block copolymer is at least 90% saturated, more often at least 95% saturated, but the vinyl aromatic moiety is not significantly hydrogenated. Useful hydrogenated block copolymers include hydrogenated products of block copolymers of styrene-isoprene-styrene, for example styrene- (ethylene / propylene) -styrene block polymers. When the polystyrene-polybutadiene-polystyrene block copolymer is hydrogenated, the ratio of 1,2-polybutadiene to 1,4-polybutadiene in the polymer is preferably about 30:70 to about 70:30. When such block copolymers are hydrogenated, the resulting product resembles regular copolymer blocks of ethylene and 1-butene (EB). When conjugated dienes are used as isoprene, the resulting hydrogenated product resembles regular copolymer blocks of ethylene and propylene (EP).

The number of optionally hydrogenated block copolymers is commercially available from Shell Chemical Company under the general trade name "Kraton G". One example is Kraton G1652, a hydrogenated SBS triblock comprising about 30% by weight styrene end blocks and a midblock copolymer of ethylene and 1-butene (EB). Low molecular weight versions of G1652 are available from Shell under the trade name Kraton G1650. Kraton G1651 is another SEBS block copolymer containing about 33% styrene by weight. Kraton G1657 is a SEBS diblock copolymer containing about 13% styrene by weight. This styrene content is lower than the styrene content in Kraton G1650 and Kraton G1652.

In another embodiment, the selectively hydrogenated block copolymer has the formula

B _n (AB) _o A _p

Where n is 0 or 1; o is from 1 to 100; p is 0 or 1; Each B before hydrogenation is predominantly a polymerized conjugated diene hydrocarbon block having a number average molecular weight of about 20,000 to about 450,000; Each A is predominantly a polymerized vinyl aromatic hydrocarbon block having a number average molecular weight of about 2000 to about 115,000; The A blocks constitute about 5% to about 95% by weight of the copolymer; Unsaturation in block B is less than about 10% of primitive unsaturation. In other embodiments, the unsaturation of block B is reduced to less than 5% of the raw value with hydrogenation and the average unsaturation of the hydrogenated block copolymer is reduced to less than 20% of its raw value.

The block copolymers react an alpha, beta-olefin unsaturated monocarboxylic or dicarboxylic acid reagent onto selectively hydrogenated block copolymers of vinyl aromatic hydrocarbons and conjugated dienes as described above. It may also comprise functionalized polymers as can be obtained by. The reaction between carboxylic acid reagents in the graft block copolymers can be carried out by melting process or in solutions in the presence of free radical initiators.

The preparation of various selectively hydrogenated block copolymers of dienes conjugated with vinyl aromatic hydrocarbons grafted with carboxylic acid reagents is described in US Pat. No. 4,578,429; 4,657,970; 4,657,970; And 4,795,782, the disclosures of which are directed to grafted and optionally hydrogenated block copolymers of conjugated dienes and vinyl aromatic compounds and to the preparation of such compounds. Hereby incorporated by reference. US Patent 4,795,782 discloses and provides examples of the preparation of block copolymers grafted by a solution process and a melt process. U.S. Patent 4,578,429 provides an example of grafting of Kraton G1652 (SEBS) with maleic anhydride and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane by melt reaction in a twin screw extruder. Include.

Examples of commercially available maleated and selectively hydrogenated copolymers of styrene and butadiene include Kraton FG1901X, FG1921X, and FG1924X, available from Shell, often malened and optionally hydrogenated SEBS polymers are called. FG1901X contains about 1.7% by weight bound functionality and about 28% by weight styrene as succinic anhydride. FG1921X contains about 1% by weight bound functionality and about 29% by weight styrene as succinic anhydride. FG1924X contains about 1% bound functionality as about 13% styrene and succinic anhydride.

Useful block copolymers are also available from Nippon Seon Co., Marunochi 2-1, Chiyoda-ku, Tokyo, Japan. Quintac 3530, for example, is available from Nippon Zeon and is believed to be a linear styrene-isoprene-styrene block copolymer.

The adhesive compositions may contain at least one adhesive resin component. Solid adhesives are defined herein as having a softening point of at least 80 ° C. When the solid adhesive resin component is present, the adhesive compositions may comprise about 40 to about 80 weight percent and about 20 to about 60 weight percent of the thermoplastic elastomer component, and in one embodiment about 55 to about 65 weight percent of the solid adhesive resin component. Can be. Solid adhesive reduces the modulus of the mixture sufficiently to form a tack or adhesion. In addition, the solid adhesives (particularly, high molecular weight solid adhesives (eg, Mw of about 2000 or more) and those having low dispersibility (Mw / Mn = less than about 3)) are less sensitive and move into the polymer film layer. This is desirable because the movement of the adhesive into the layer 110 or 180 can cause dimensional instability.

Solid tackifier resins include hydrocarbon resins, rosin, hydrogenated rosin, rosin esters, polyterpene resins and other resins exhibiting appropriate balance properties. Various useful solid tackifier resins are commercially available as petroleum hydrocarbon resins such as terepene resins sold by Arizona Chemical Company under the trade name Zonatac and resins sold by the Exxon Chemical Company under the trade name Escorez. One particular example of a useful solid adhesive is Escorez 2598, a C ₅ -C ₉ (aromatic modified aliphatic) synthetic adhesive having a Mw of 2100 and a dispersibility (Mw / Mn) of 2.69. Another useful solid tackifier is Escorez 1310LC and is identified as an aliphatic hydrocarbon resin having a Mw of 1350 and a dispersibility of 1.8. Wingtack 95 is a synthetic adhesive resin available from Goodyear, Akron, Ohio, consisting primarily of polymerized structures derived from piperylene and isoprene.

The modulus of the adhesive mixture to be coextruded can be lowered by incorporating liquid rubbers, ie rubbers that are liquid at room temperature. Liquid rubbers will generally have a Mw of at least 5,000, and more often will have a Mw of at least 20,000. Incorporating liquid rubber in an amount of less than 10% and even less than 5% by weight based on the total weight of the adhesive formulation results in adhesives that can be coextruded with the polymeric film materials. Incorporation of the liquid rubber can produce adhesives with increased tack and adhesion. Liquid block copolymers such as liquid styrene-isoprene block copolymers can be used. Examples include Kraton LVSI-101 available from Shell Chemical Company. Another example is liquid polyisoprene obtained by depolymerization of high molecular weight polyisoprene. An example of a commercially available depolymerized high molecular weight polyisoprene is D-400 from Elementis Performance Polymers, Belleville, NJ, and this liquid rubber has a Mw of about 20,000. Other liquid rubbers that may be incorporated into the adhesive mixture include liquid styrene-butadiene rubbers, liquid butadiene rubbers, ethylene-propylene rubbers, and the like.

The adhesive layer 120 may contain one or more pigments to enhance the opacity of the paint film layers overlying it, allowing the use of thinner paint film layers to achieve the desired opacity level. Any of the above identified pigments can be used. Specific examples include titanium dioxide and carbon black. Pigment volume concentrations can range from about 5 to about 10% in one embodiment, and from about 2 to about 8% in one embodiment, up to about 10%.

Adhesive compositions may also include other materials such as antioxidants, heat and light stabilizers, ultraviolet absorbers, fillers, colorants, antiblocking agents, reinforcing agents, processing aids and the like. Stereolyzed phenol and amine antioxidant compounds may be included in the adhesive compositions, and a wide variety of such antioxidant compounds are known in the art. Various antioxidants are available from Ciba-Geigy under the common trade names "Irganox" and "Irgafos". For example, the sterically hindered phenolic antioxidant n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenol) -proprionate can be obtained under the trade name "Iranox 1076". Iranox 1010 is identified as tetrakis (methylene 3-3 ', 5'-di-tert-butyl-4'-hydroxyphenol) proprionate) methane. Irgafos 168 is another useful antioxidant from Ciba-Geigy. Hydroquinone-based antioxidants may also be used, one example of such an antioxidant being 2,5-di-tertiary-amyl-hydroquinone. Light stabilizers, heat stabilizers and UV absorbers may also be included in the adhesive compositions. Ultraviolet absorbers include benzo-triazole derivatives, hydroxybenzylphenones, esters of benzoic acid, oxalic acid, diamides and the like. Light stabilizers include sterically hindered amine light stabilizers, and heat stabilizers include dithiocarbamate compositions such as zinc dibutyl dithiocarbamate.

Adhesive compositions may contain inorganic fillers and other organic and inorganic additives to provide the desired properties. Examples of useful fillers include calcium carbonate, titanium dioxide, metal particles, fibers, and the like. An example of a useful end-block enhancer is Cumar LX509 from Neville Resins.

Barrier layer 190 is any of the acrylate polymers or copolymers, polyvinyl alcohol, copolymers derived from ethylene and vinyl acetate, and copolymers derived from ethylene, vinyl acetate, and polyvinyl alcohol. It may include. The barrier layer is identified as polyvinyl alcohol, urethane, Cymel 385 (from Cytec, identified as melamine formaldehyde resin) and polyaziridine (eg, trimethol-tris N (methyl aziridinyl) proprionate, Avecia Polymer blends, available from Resins, Inc., in one embodiment the weight ratio of polyvinyl alcohol to urethane is about 20:80. The barrier layer may be provided to inhibit or reduce the migration of dyes or pigments and other materials from the substrate until the laminate of the present invention is applied into the dry paint film layer 110. The following examples illustrate certain coating compositions that can be used to form the barrier layer 190.

weight%

Barrier Layer 1

Elvacite 2042 (ethyl methacrylate 20

Manufactured by Ineos as a Copolymer)

Toluene 48

Methyl Ethyl Ketone 32

Barrier Layer 2

Adcote 61WG178 (0.10 as solution of acrylic polymer

Rohm & Haas products identified)

Syloid 234 (identified as synthetic amorphous silica

Grace Davison Products)

N-propanol 44.35

Barrier Layer 3

Adcote 61WG178 74.07

N-propanol 25.83

Syloid 234 0.10

Barrier Layer 4

Adcote 61WG178 55.55

N-propanol 44.35

Syloid 234 0.10

Desmodur CB 75N (Oligomer Toluene 0.44

From Bayer, identified as diisocyanate)

Barrier Layer 5

Adcote 61WG178 74.07

N-propanol 25.83

Syloid 234 0.10

Desmodur CB 75N 0.44

Barrier Layer 6

Adcote 61WG178 58.0

R-900 TiO ₂ (15.00 as rutile titanium dioxide

DuPont products identified)

N-propanol 24.00

Isobutanol 3.00

Barrier Layer 7

Adcote 61WG178 58.00

R-900 TiO ₂ 15.00

N-propanol 24.00

Isobutanol 3.00

Desmodur CB 75N 0.44

Barrier layer 8

Air Vol 523 (5.0, identified as polyvinyl alcohol)

Air Products)

N-propanol 25.83

Syloid 234 0.10

Water 47.5

Isopropanol 47.5

Backhold liners 132 and 172 may independently comprise paper, polymer film, or a combination thereof. These backliner liners are thermally stable, inelastic, and non-stretchy at room temperature in one embodiment. Paper liners are useful because of the wide range of applications in which they can be used. The paper is also relatively expensive and has desirable properties such as antiblocking, antistatic, dimensional stability and the like and can be potentially recycled. Any type of paper with sufficient tensile strength to be handled in conventional paper coating and handling devices can be used as the backing liner. Thus, any type of paper can be used depending on the end use and the preference of the particular individual. Types of paper that can be used include clay coated paper, glassine, polymer coated paper, hemp, and soda, sulfite or sulphate (craft) processes, neutral sulfide cooking processes, alkali-chlorine processes, nitrous acid processes, Similar cellulose materials prepared by processes such as semi-chemical processes are included. Although any weight of paper can be used as the backing liner, paper having a weight in the range of about 30 to about 120 pounds per ream is useful and paper having a weight in the range of about 60 to about 100 pounds per streak. Can be used. As used herein, the term "ream" is equivalent to 3000 square feet.

Alternatively, the backing liners 132 and 172 independently comprise a polymer film, examples of polymer films meaning polyolefins, polyesters, and combinations thereof. Polyolefin films have polymers and copolymers of monoolefins having from 2 to about 12 carbon atoms per molecule, in one embodiment having from 2 to about 8 carbon atoms, and in one embodiment having from 2 to about 4 carbon atoms. It may include. Examples of such homopolymers include polyethylene, polypropylene, poly-1-butene and the like. Blends of copolymers or films made from blends of copolymers and homopolymers can be used. These films can be extruded in mono or multiple layers.

Another type of material that can be used as the backing liners 132 and 172 is a polycoated kraft liner that basically consists of a kraft liner coated on one or both sides by polymer coating. Polymeric coatings, which may be composed of high density, medium density or low density polyethylene, propylene, polyester or other similar polymer films, are coated onto the substrate surface to add strength and / or dimensional stability to the liner. The weight of these types of liners ranges from about 30 to about 100 pounds per year, with about 94 to about 100 pounds per year useful. In total, the final back liner 132 may comprise about 10% to about 40% polymer and about 60% to about 90% paper. For two side coatings, the quantitation of the polymer can be divided almost uniformly between the top and bottom surfaces of the paper.

Backhold liners 132 and 172 provide structural integrity to the laminate in one embodiment until they are removed as they apply the laminate to the substrate. As a result of using one or two of these liners, there is no need to use a semi-rigid or reinforced backing sheet with the laminates of the present invention.

The release coating layer 135 may comprise a single coat or multiple coats of release coating material. When multiple coats are used, each coat may have the same formulation or different formulations may be used. This release coating layer 135 may be applied to the dry paint film layer 110 to prevent separation of the release coating layer 135 from the film layer 110, 140 or 165 during and during the manufacture of the dry paint transfer laminate. 1 or 6-8), but provides sufficient tack or adhesion between the transparent film layer 140 (FIGS. 3-5) or the printed adhesive layer 165 (FIG. 9) and the release coating layer 135, It can include any of the above binders or resins that have sufficient release properties to provide inspired separation between the release coating layer 135 and the layers 110, 140 or 165 when using a laminate. The release coating layer 135 may include an alkyd resin and / or a vinyl resin crosslinked with melamine resin. Alkyd resins include resins formed by condensation of one or more polyhydric alcohols with one or more polybasic acids or anhydrides. Polyhydric alcohols include glycols, and polybasic acids or anhydrides include phthalic anhydride. Modified alkyds in which the polybasic acid is partially substituted with monobasic acids such as acrylic acid or vegetable oil fatty acids can be used. Vinyl resins that can be used include polyvinyl chloride, polyvinyl acetate, copolymers of vinyl chloride and vinyl acetate, acrylic resins, methacrylic acid resins, polystyrene resins, and the like. Melamine resins include amino resins prepared by condensation of melamine with formaldehyde or a compound capable of providing methylene bridges. Crosslinking of alkyd and / or vinyl resins with melamine resins typically occurs when the release coating 135 is applied to the backing liner and dried or cured. In one embodiment, the release coating comprises 0 to about 80 weight percent solids base, in one embodiment about 10 to about 30 weight percent alkyd resin; 0 to about 80 weight percent, in one embodiment about 10 to about 30 weight percent vinyl resin; And from about 10 to about 30 weight percent, and in one embodiment from about 20 to about 25 weight percent melamine resin.

The release coating layer 135 is a surface 114, a transparent film layer 140, or a printed adhesive layer 165 of the dry paint film layer 110 to provide layers 110, 140 or 165 with a matte or flat finish. May comprise one or more solid particles protruding into the surface 141. When particles are present, the emissive coating layer 135 may be referred to as a matte emissive coat or matte emissive layer. The particles that can be used can be any of the filler pigments for use in paint film layers. Particles with irregular shapes (eg platelet shapes) can be used. By controlling the use of these particles, the surface finish of the dry paint film layer, the transparent film layer or the printed adhesive layer can be controlled. For example, by using these particles, the dry paint film layer, transparent film layer, or printed adhesive layer can have a flat or semi-gloss finish. The paint film layer, transparent film layer or printed adhesive layer may have a glossy finish by not using these particles or minimizing their use. The weight ratio of particles to resin or binder is about 1.1: 1, in one embodiment about 0.7: 1 to about 1.1: 1, in one embodiment about 0.7: 1 to about 0.9: 1, in one embodiment about 0.9: 1. To about 1.1: 1.

The release coating layers 136 and 176 can independently include any release coating composition known in the art. Silicone release coating compositions can be used. Silicone release coating compositions typically include polyorganosiloxanes such as polydimethylsiloxanes. The silicone release coating composition used in the present invention may be room temperature cured, thermally cured, or radiation cured. Generally, compositions that can be cured at room temperature and thermally include at least one polyorganosiloxane and at least one catalyst (or curing agent) for such polyorganosiloxane (s). These compositions may include at least one cure accelerator and / or adhesion promoter. As is known in the art, some materials act as cure accelerators to perform both functions, ie increase speed or reduce cure temperature, and also improve adhesion of the silicone composition to the substrate. Has the ability to act as a sex promoter. The use of such dual function additives where appropriate falls within the scope of the present invention.

In the embodiments illustrated in FIGS. 1-9, the release force required to separate the release coating layer 135 from the dry paint film layer 110, the transparent film layer 140, or the printed adhesive layer 165 is an adhesive layer. It is advantageous to be larger than the ejection force required to separate the emissive coating layer 136 from 120. In the embodiment illustrated in FIG. 6, the release force required to separate the release coating layer 135 from the dry paint film layer 110 is greater than the release force required to separate the release coating layer 176 from the adhesive layer 120. It is advantageous. In one embodiment, the release force required to separate the release coating layer 135 from the dry paint film layer 110, the transparent film layer 140, or the printed adhesive layer 165 is about 20 to 180 grams per inch. / 2in), in one embodiment 30 to about 150g / 2in, in one embodiment 40 to about 120g / 2in, in one embodiment 50 to about 100g / 2in, in one embodiment 50 to about 90g / 2in, one embodiment Examples may range from 70 to about 90 g / 2 in, and in one embodiment 50 to about 65 g / 2 in. In one embodiment, the ejection force required to separate the release coating layer 136 or 176 from the adhesive layer 120 is 10 to about 150 g / 2 in, in one embodiment 20 to about 150 g / 2 in, in one embodiment 20 to about 90 g / 2 in, in one embodiment from 30 to about 150 g / 2 in, in one embodiment from 30 to about 100 g / 2 in, in one embodiment from 30 to about 70 g / 2 in. Test methods for determining these release forces include measuring the release force required to separate a 2-inch wide release coated liner from layers 110, 140 or 165 or from an adhesive coated substrate, provided that the release coated liner Extends at a 90 ° angle relative to the layer or substrate and is pulled at a speed of 300 inches per minute. The test can be performed at room temperature.

Each of the layers 110, 120, 135, 136, 140, 176, 180 and 190 may be applied independently, dried and / or cured using known techniques. Application techniques include gravure, reverse gravure, offset gravure, roll coating, brushing, knife-over roll, measuring bar, reverse roll coating, doctor knife, dipping, die coating, slot die coating, spraying, curtain coating, slide coating, slide curtain Coating, extrusion, co-extrusion, sheet printing, letter press, rotary screen, flat screen, and the like. In one embodiment, the adhesive layer 120 is a pressure sensitive adhesive layer and may be applied using transfer lamination. Adhesive layers 150, 160 and 165 may be applied using known printing techniques including gravure, iron plate printing, silk screen, ink jet, and the like. The applied layers can be dried and / or cured by exposure to heat or known forms of ionizing or actinic nonionic radiation. Drying or curing temperatures that may be used may range from about 115 ° C. to about 160 ° C., in one embodiment from about 140 ° C. to about 150 ° C. Useful types of radiation include ultraviolet rays and electron beams. Equipment for generating, drying and / or curing these forms of heat or radiation is well known to those skilled in the art. One or more of the layers 110, 120, 140, and 180 may be extruded. Layers 110 and / or 180 may be coextruded with adhesive layer 120. In one embodiment, the support layer 180 may be coextruded with the adhesive layer 120, and the dry paint film layer 110 is coated onto the support layer 180 (eg, gravure).

Each of layers 110, 140 or 180 may independently comprise a single layer film or a multilayer film of two or more adjacent coextruded layers. For example, layers 110, 140 or 180 may comprise one layer of a blend of one layer of polyolefin and polyolefin and a copolymer of ethylene and vinyl acetate (EVA). In one embodiment, layers 110, 140, or 180 may comprise three layers, for example, a base or core layer of polyolefin, skin layers within two sides of the base or core layer, which may comprise the same or different polymer blends. It may include.

Dry paint layer or film layer 110 or support layer 180 may be coextruded with adhesive layer 120 using separate extruders as illustrated in FIG. 11 or dual die extruder as illustrated in FIG. 12. Can be. Referring to FIG. 11, the release liner 200 is unrolled from the roll 240, proceeds to the past extrusion die 210 when coated with an adhesive layer 120, and then the support layer 180 is the adhesive layer ( 120 is then passed to the last extrusion die 220. The resulting co-extrusion is collected in roll form as indicated by collection roll 250. Referring to FIG. 12, the release liner 200 proceeds to the last double extrusion die 230 which simultaneously coats the release liner 200 with the adhesive layer 120 and the support layer 180. The resulting co-extrusion is collected in roll form as indicated by collection roll 250. When the desired quantity of co-extruded has been produced, the collection roll 250 is removed from the process and stored for subsequent processing (eg, coating, printing, etc.) during separate operations at the same or different geographic location, thereby enhancing Provides manufacturing flexibility. Alternatively, rather than being collected, co-extrudates can be routed for coating, printing, etc. during the same manufacturing operation. The dry paint film layer 110 may be coextruded with the adhesive layer 120 according to the above process. Multi-die application methods useful for applying both pressure sensitive adhesives and film forming layers to substrates are disclosed in published PCT International Application No. PCT / US95 / 11807; PCT / US95 / 11733; PCT / US95 / 11734; And PCT / US95 / 11717, which is incorporated herein by reference. Coextruded polymeric film materials and adhesive compositions can be clean and they can be emulsions or solvent-based. Emulsions and solvent-based acrylic base PSAs are known and are described, for example, in US Pat. Nos. 5,639,811 and 5,164,444, respectively, which are incorporated herein by reference for their disclosure. When emulsions of film materials and / or adhesive compositions are used, water can be removed in an extruder by using the process described and claimed in US Pat. No. 5,716,669 (LaRose et al.). In one embodiment, the coextruded film materials and adhesives are compositions that are substantially free of water and / or solvents (eg, less than about 1 weight percent). The presence of water or solvents during the coextrusion process can result in pinholes and bubbles in the coextruded film. The presence of voids in the film due to steam may be referred to as "moisture slits".

When the polymerizable film material and the adhesive are coextruded, the hot melt viscosity of the polymerizable film material and the adhesive is continuous in the polymerizable film material and the adhesive to avoid mixing and film defects of the polymerizable film material and the adhesive during the coextrusion process. It may be within a window or viscosity range that can produce uniform co-extrudes. The polymerizable film material may have a hot melt viscosity that is within a factor of about 0.07 to about 15 times the hot melt viscosity of the adhesive at the shear rate that occurs during the coextrusion process. Shear rate can be between about 100sec ^-1 to 10,000 sec ^-1 range. The factor may be about 1 to about 15, in one embodiment about 1 to about 10. It is also preferred that the polymerizable film material and the adhesive have a relatively similar melt viscosity at the extrusion temperature. For example, when the adhesive is a conventional hot melt adhesive, the extrusion temperatures of the adhesive may range from about 150 ° C to about 200 ° C, in one embodiment from about 175 ° C to about 200 ° C. The polymerizable film material selected for use with the adhesive may have an extrusion temperature of about 200 ° C. or less, and in one embodiment an extrusion temperature in the range of about 150 ° C. to about 180 ° C.

The dry paint transfer laminate 100 illustrated in FIG. 1 uses one of the application techniques above to apply a release coating 136 to the lower surface 134 of the backing liner 132 and then cure the release coating. Can be prepared. The coat weight for the release coating layer 136 may range from about 0.1 to about 1 gram (gsm) per square meter, in one embodiment from about 0.25 to about 0.35 gsm. The release coating layer 135 is then applied to the top surface 133 of the backing liner 132 using one of the indicated application techniques (eg, gravure) and then dried or cured. The coat weight of the release coating layer 135 may range from about 2.5 to about 6.5 gsm, in one embodiment from about 4.5 to about 5.5 gsm. Subsequently, the liquid paint or coating composition for forming the dry paint film layer 110 is applied to the surface of the release coating layer 135 using one of the application techniques indicated above (eg, reverse roll or slot die), It is then dried or cured. The coat weight of the dry paint film layer 110 may range from about 20 to about 60 gsm, in one embodiment from about 30 to about 40 gsm. One or more coats may be applied. A pressure sensitive adhesive layer 120 is then applied to the top surface 112 of the dry paint film layer 110 using one of the indicated application techniques (eg, slot die) and then dried or cured. Pressure sensitive adhesives can be applied using transfer lamination. The coat weight for the pressure sensitive adhesive layer 120 may range from about 10 to about 30 gsm, in one embodiment from about 11 to about 17 gsm. The dry paint transfer laminate 100 may then be wound in roll form as illustrated in FIG. 2 using known techniques.

The dry paint transfer laminate 100A illustrated in FIG. 3 is applied except that the transparent film layer 140 is applied to the surface of the release coating layer 135 and then dried or cured prior to application of the dry paint film layer 110. It can be made using the same process used to make the laminate 100. The dry paint film layer 110 is then applied to the surface of the transparent film layer 140. The transparent film layer 140 may be applied using one of the application techniques (eg, gravure). The coat weight for the transparent film layer 140 may range from about 1 to about 5 gsm, in one embodiment from about 2.5 to about 3.5 gsm. One or more coats may be applied. The dry paint transfer laminate 100A may then be wound into a roll as illustrated in FIG. 2 using known techniques.

The dry paint transfer laminate 100B illustrated in FIG. 4 is a liquid paint composition for forming the printed adhesive layer 150 is applied to the surface of the transparent film layer 140 and then of the dry paint film layer 110. It can be made using the same process used to make laminate 100A except that it is cured prior to application. The dry paint film layer 110 is then applied to the surface of the printed adhesive layer 150. The printed adhesive layer 150 may be applied using any of the above printing techniques (eg, gravure, iron plate printing, silk screen, ink jet, etc.). The coat weight for the printed adhesive layer 150 may range from about 0.3 to about 2 gsm, in one embodiment from about 0.3 to about 0.7 gsm. The dry paint transfer laminate 100B may then be wound into a roll as illustrated in FIG. 2 using known techniques.

The dry paint transfer laminate 100C illustrated in FIG. 5 is a liquid paint composition for forming the second printed adhesive layer 160 is applied to the surface of the transparent film layer 140 and then the printed adhesive layer ( It can be made using the same process used to make laminate 100B except that it is dried or cured prior to application of 150). The printed adhesive layer 150 is then applied over the surface of the second printed adhesive layer 160. The second printed adhesive layer 160 may be applied using any of the above printing techniques (eg, gravure, iron plate printing, silk screen, ink jet, etc.). The coat weight for the second printed adhesive layer 160 may range from about 0.3 to about 2 gsm, in one embodiment from about 0.3 to about 0.7 gsm. The dry paint transfer laminate 100C may then be wound into a roll as illustrated in FIG. 2 using known techniques.

The dry paint transfer laminate 100D illustrated in FIG. 6 is illustrated in FIG. 1 except that release liner 170 is adhered to adhesive layer 120 by release coating layer 176 in contact with adhesive layer 120. It can be made using the same process used to make the laminate (100).

The dry paint transfer laminate 100E illustrated in FIG. 7 performs the same process used to manufacture the laminate 100 illustrated in FIG. 1 except that the support layer 180 is adhered to the dry paint film layer 110. It can be prepared using. The support layer 180 may be coextruded with the adhesive layer 120, and then the dry paint film layer 110 may be coated onto the support layer 180 (eg, gravure). The dry paint transfer laminate 100E may then be wound into a roll as illustrated in FIG. 2 using known techniques.

The dry paint transfer laminate 100F illustrated in FIG. 8 is the same process used to manufacture the laminate 100 illustrated in FIG. 1 except that the barrier layer 190 is coated on the dry paint film layer 110. It can be prepared using. The dry paint transfer laminate 100F may then be wound into a roll as illustrated in FIG. 2 using known techniques.

The dry paint transfer laminate 100G illustrated in FIG. 9 performs the same process used to manufacture the laminate 100 illustrated in FIG. 1 except that the support layer 180 is adhered to the dry paint film layer 110. It can be prepared using. The support layer 180 may be coextruded with the adhesive layer 120. The printed adhesive layers 150, 160, and 165 may be sequentially coated onto the dry paint film layer 110. The dry paint transfer laminate 100G may then be wound into a roll as illustrated in FIG. 2 using known techniques.

The dry paint transfer laminate 100H illustrated in FIG. 10 has the laminate illustrated in FIG. 5 except that the release liner used in the laminate 100C is removed, and the release liner 170 and accompanying release liner are included. It may be prepared using the same process used to prepare 100C). The dry paint film layer 110 and the adhesive layer 120 may be coextruded onto the release layer 176 of the release liner 170.

The dry paint transfer laminate of the present invention can be produced in a single production line or in multiple production lines or in multiple production facilities. By means of multiple production lines or facilities, part of the laminate is produced as a roll laminate, dried or cured, rolled up, transferred to the next production line or facility, released and added by application of additional layers Can be treated as For example, dry paint film layer 110 and adhesive layer 120 may be deposited in multiple lines, or they may be deposited sequentially in a single line, or they may be co-extruded or multi-die coating methods. Can be deposited simultaneously. Production on a single production line may be more efficient by avoiding extra handling, storage, and transport steps for what may comprise relatively thin, subtle film materials in at least one embodiment.

The dry paint transfer laminate 100 may be used by releasing the laminate from the roll illustrated in FIG. 2 and applying the laminate to a substrate (eg, a wall) to be covered at the same time. The substrate may comprise any flat surface. Flat surfaces can include wall boards, plastic sheets, metal sheets, composites, and the like. The substrate may comprise an inner (ie indoor) surface or an outer (ie outdoor) surface. The laminate is placed on the substrate with the adhesive layer 120 in contact with the substrate. The release liner 130 is then peeled off leaving a dry paint film layer 110 adhered to the substrate by the adhesive layer 120. The advantage of using such a laminate is that, in at least one embodiment, due to the fact that the seams are substantially disappeared and thus unrecognizable, it is then possible to overlap a part of the dry paint film layer applied with the next applied dry paint film layer It is. This advantage is provided at least in part due to the fact that the dry paint film layer 110 is relatively thin. In addition, the gloss and opacity of the dry paint film layer 110 contributes to this ability to hide seams.

Dry paint transfer laminate 100A may be applied to the substrate in the same manner as laminate 100. When the release liner 130 is peeled off, the dry paint film layer 110, the transparent film layer 140, and the adhesive layer 120 are left attached to the substrate by the adhesive layer 120 in contact with the substrate. .

Dry paint transfer laminate 100B may be applied to the substrate in the same manner as laminate 100. When the release liner 130 is peeled off, the dry paint film layer 110, the printed adhesive layer 150, the transparent film layer 140, and the adhesive layer 120 are in contact with the substrate 120. Left to adhere to the substrate.

Dry paint transfer laminate 100C may be applied to the substrate in the same manner as laminate 100. When release liner 130 is peeled off, layers 110, 150, and 160, transparent film layer 140, and adhesive layer 120 remain adhered to the substrate by adhesive layer 120 in contact with the substrate. Lose.

The dry paint transfer laminate 100D advantageously provides the laminate in the form of a flat sheet other than a roll, except that the release liner 170 is peeled off before the adhesive layer 120 is adhered to the substrate. It can be applied to the substrate in the same manner as.

The dry paint transfer laminate 100E may be applied to the substrate by adhering the adhesive layer 120 to the substrate and then removing the release liner 130.

The dry paint transfer laminate 100F may be applied to the substrate by adhering the adhesive layer 120 to the substrate and then removing the release liner 130.

The laminate 100G may be applied to the substrate by adhering the adhesive layer 120 to the substrate and then removing the release liner 130.

Laminate 100H may be applied to a substrate by coating release liner 170, carrying a release coating 176 from the laminate, and applying adhesive layer 120 to the substrate. This laminate can be applied by using a special applicator to wind or coil the release liner 170 and entrain the release layer 176 as the rest of the laminate is applied to the substrate.

Examples 1 and 2

The polyethylene terephthalate film backing liner corresponding to the backing liner 132 is coated on one side by a silicone release coating corresponding to the second release coating layer 136. The thickness of the release coated liner is 0.92 mils.

The matte release coat corresponding to the first release coating layer 135 is applied to the other side of the backing liner using gravure with a coating weight of 6.5-7.75 gsm. The formulation for the matte release coat is as follows: 26% by weight methyl isobutyl ketone, 6% by weight isopropanol, Lankyd 13-1425 (product supplied by Akzo Resins, identified as acrylic modified alkyd), 34.8% by weight, Elvacite 2042 ( 2.6 wt% from Lucite International, identified as a polyethyl methacrylate polymer), 30 wt% from Microtalc MP 15-38 (available from Barrett's Minerals, identified as a talcum thickener pigment), Cycat4040 (identified as paratoluene sulfonic acid) 2.5% by weight of the product supplied by Cytec, and 8.7% by weight of Cymel 303 (product supplied by Cytec, identified as melamine resin). The matte release coat is dried using forced hot air at a temperature of 149 ° C.

The transparent layer corresponding to the transparent layer or film layer 140 is applied to the matte release coat using gravure with a coat weight of 2.7-2.9 gsm and dried using forced hot air at a temperature of 120 ° C. The formulation for the clear layer is as follows: 46.7 weight% methyl ethyl ketone, 31.3 weight% toluene, 11 weights VYNS (Product of Union Carbide, identified as vinyl chloride / vinyl acetate copolymer containing 5-20 weight% vinyl acetate) %, And 11% by weight of Vitel 2200B (product of Bostict, identified as polyester copolymer).

The following paint compositions are used to form a dry paint layer corresponding to the dry paint layer or film layer 110 on the transparent layer, one for Example 1 and the other for Example 2. Example 1 has a dark brown tone while Example 2 has an orange pastel tone. In the following table, all numerical values are parts by weight.

Example 1 Example 2

Methylethyl Ketone 66.7 66.7

Toluene 33.3 33.3

VYHH (50.05 30.55 as vinyl chloride / vinyl acetate copolymer

Union Carbide company identified)

Edinol 9790 (24.65 15.05, identified as polyester plasticizer

Cognis company)

Yellow pigment 42 (iron oxide) 17.8 2.3

Orange pigment 36 (monoazo benzimidazolin) 2.5 0.38

Black 7 (carbon black) 0.1 0.02

White 6 (titanium dioxide) 4.9 51.7

The pigment volume ratio for Example 1 is 10% and for Example 2 is 27%. The paint formulations are applied to the clear layer using a reverse roller coater and dried at a temperature of 135 ° C. to remove the solvents. The dry film thickness of each of the dry paint layers is 0.7 mils.

The pigmented pressure sensitive adhesive is then applied to the dry paint layer with a coat weight of 14-20 gsm using a transfer lamination to provide an adhesive layer corresponding to the pressure sensitive adhesive layer 120. The formulation for the pressure sensitive adhesive is as follows: 70-90% by weight 2-ethylhexyl acrylate, 1-10% by weight acrylic acid, 10-20% by weight methyl acrylate, UCD 1106E (identified as titanium dioxide dispersion concentrate) 3.7% by weight of Rohm & Haas) and 0.3% by weight of UCD 1507E (product of Rohm & Haas, identified as carbon black dispersion concentrate).

Example 3

The procedure used in Examples 1 and 2 is repeated except that the following liquid paint composition is used to form a dry paint layer corresponding to the dry paint layer or film layer 110. In the following table, all numerical values are parts by weight.

Methylethyl Ketone 29.6

Toluene 19.5

Vitel 2200 b 11.6

Vitel 2650 (11.5 as polyester copolymer

Bostic's product identified)

R-900 (manufactured by DuPont, Inc. identified as titanium dioxide) 27.5

955-39230 (0.2 identified as shading black

Gibraltar Chemical Works)

99-34520 (0.1 identified as phthalo blue GS

Gibraltar Chemical Works)

955-37470 (tint identified as carbazole violet

Gibraltar Chemical Works)

The paint composition is light blue. The dry film thickness of the dry paint film layer is 0.6-0.8 mils.

Example 4

The polyethylene terephthalate film backing liner corresponding to the backing liner 132 is coated on one side with a silicone release coating corresponding to the second release coating layer 136. The release coating layer is 0.92 mils thick.

The matte release coat corresponding to the first release coating layer 135 is applied to the other side of the backing liner using gravure at a coating weight of 4.4-4.6gsm. The formulation for the matte release coat is as follows: 50.54 weight percent methyl isobutyl ketone, 7.84 weight percent isopropanol, 8.93 weight percent Lankyd 13-1425, VAGH (identified as hydroxy modified polyvinyl chloride / polyvinyl acetate copolymer) Union Carbide) 10.68%, Microtalc MP 15-38 22%, Cycat4040 2%, and Cymel 303 6.8%. The matte release coat is dried using forced hot air at a temperature of 149 ° C.

The first coat of clear layer corresponding to clear layer 140 is applied to the matte release coat using gravure with a coat weight of 1.3-2 gsm and dried using forced hot air at a temperature of 120 ° C. The dry film thickness is 0.05-0.1 mils. Formulations for this first clearcoat are as follows: 41.5 weight percent methyl ethyl ketone, 41.5 weight percent methyl isobutyl ketone, and 17 weight percent Elvacite 2042 (from Lucite International, identified as polymethyl methacrylate).

The second coat of the transparent layer corresponding to the transparent layer or the film layer 140 is applied onto the first coat of the transparent film layer using gravure with a coat weight of 1.0-1.5 gsm and forced hot air at a temperature of 120 ° C. Is dried using. The dry film thickness is 0.03-0.7 mils. The formulation for this second clear layer coat is as follows: 41.5% methyl ethyl ketone, 41.5% methyl isobutyl ketone, and VYHH (identified as vinyl chloride / vinyl acetate copolymer containing 5-20% vinyl acetate). Union Carbide's products) 17% by weight.

The adhesive layer corresponding to the second printed adhesive layer 160 is printed onto the second coat of the transparent coating layer with a coat weight of 3.0-3.2 gsm and dried in hot air at a temperature of 120 ° C. The paint compositions used in this adhesive layer have the following formulations (all numerical values are by weight):

Methylethyl Ketone 42.6

Methyl Isobutyl Ketone 38.7

VYHH 15.86

DP 80110 (Methylethyl Ketone, Toluene, Carbon Black 2.1

And as containing an acrylic polymer

Gibraltar Chemical Works)

DP 36640 (methylethyl ketone, toluene, quinacridone red 0.22

And as containing an acrylic polymer

Gibraltar Chemical Works)

18977 (methylethyl ketone, toluene, R.S. phthalo blue 0.10

And as containing an acrylic polymer

Gibraltar Chemical Works)

18980 (methylethyl ketone, toluene, isoindolinone yellow 0.38

And as containing an acrylic polymer

Gibraltar Chemical Works)

The adhesive layer corresponding to the printed adhesive layer 150 is printed onto the indicated adhesive layer corresponding to the second printed adhesive layer 160 with a coat weight of 0.8 gsm and heated at a temperature of 120 ° C. Dried in air. The paint composition used in this adhesive layer has the following formulation (all numerical values are by weight):

Methylethyl Ketone 42.85

Methyl Isobutyl Ketone 39.1

VYHH 16.0

DP 80 110 1.71

DP 36640 0.18

18977 0.18

The paint composition is then coated onto the indicated adhesive layer corresponding to the adhesive layer 150 printed with a coat weight of 30-32 gsm and dried in hot air at a temperature of 120 ° C. to dry film layer or film layer 110 It provides a dry paint layer corresponding to). In the following table, the numerical values are parts by weight.

Methylethyl Ketone 34

Toluene 16.7

VYHH 18.3

Edinol 9790 9

AVI-0301-3 Orange (methyl ethyl ketone, toluene, 8.9

Containing diarylide orange, VYHH and Edinol 9790

From Gibraltar Chemical Works, Inc.)

AVI-0301-5 magenta (methyl ethyl ketone, toluene, 5.3

Contain metal azo red, VYHH and Edinol 9790

From Gibraltar Chemical Works, Inc.)

AVI-0301-6 Iron Red (Methyl Ethyl Ketone, Toluene, 3.7

Containing iron oxide red, VYHH and Edinol 9790

From Gibraltar Chemical Works, Inc.)

AVI-0301-1 TiO ₂ White (methyl ethyl ketone, toluene, 3.52

Containing titanium dioxide, VYHH and Edinol 9790

From Gibraltar Chemical Works, Inc.)

AVI-0301-2 Carbon Black (Methyl Ethyl Ketone, Toluene, 0.03

Containing carbon black, VYHH and Edinol 9790

From Gibraltar Chemical Works, Inc.)

The colored pressure sensitive adhesive is then applied using a transfer lamination over the dry paint layer or the dry paint layer corresponding to the film layer 110 at a coat weight of 17 gsm to provide an adhesive layer corresponding to the pressure sensitive adhesive layer 120. do. The formulation for the pressure sensitive adhesive is as follows: 96% by weight non-tacky acrylic emulsion containing crosslinked copolymer of butyl acrylate and ethyl hexyl acrylate, 3.7% by weight UCD 1106E and 0.3% by weight UCD 1507E.

Example 5

The polyethylene terephthalate film backing liner corresponding to the backing liner 132 is coated on one side with a silicone release coating corresponding to the second release coating layer 136. The thickness of the release coated liner is 0.92 mils.

The matte release coat corresponding to the first release coating layer 135 is applied to the other side of the backing liner using gravure at a coating weight of 4.4-4.6gsm. The matte release coat is dried using forced hot air at a temperature of 149 ° C. The formulation for the matte release coat is as follows (all numerical values are by weight):

Methyl Isobutyl Ketone 52.54

Elvacite 4402 (hydroxy ethyl methacrylate 20.98

Lucite identified as modified acrylic resin

International Corporation)

VYNS 1.35

Microtalc 15-38 22.85

Byk 451 (2.2 identified as blocked acid catalyst)

Products from Byk Chemie)

Cymel 303 6.38

The transparent layer corresponding to the transparent layer or film layer 140 is applied to the matte release coat using a reverse roll coater with a coating weight of 13 gsm and dried using forced hot air at a temperature of 120 ° C. The dried film thickness is 0.4 mils. The formulation for the clear film layer coat is as follows (all numerical values are by weight):

Rucothane CO-A-5002L (52.54 as polyester urethane

Identified products of Ruco Chemical)

Toluene 18.75

Isopropanol 18.75

The adhesive layer corresponding to the printed adhesive layer 150 is printed onto a layer of transparent film indicated by a coat weight of 1 gsm and dried in hot air at a temperature of 120 ° C. The paint compositions used in this adhesive layer have the following formulations (all numerical values are by weight):

Methylethyl Ketone 25.67

Methyl Isobutyl Ketone 22.0

VYHH 9.17

18980 3.5

DP 37251 (Perylene Red, Methylethyl Ketone, Toluene, 0.99

And as containing an acrylic polymer

Gibraltar Chemical Works)

DP80110 1.0

DP39600 (Ti2O, methylethyl ketone, toluene, 37.47

And as containing an acrylic polymer

Gibraltar Chemical Works)

18977 0.20

The paint composition is then coated onto the indicated adhesive layer corresponding to the adhesive layer 150 printed at a coat weight of 66 gsm and dried in hot air at a temperature of 138 ° C. to the dry paint layer or film layer 110. Provide a corresponding dry paint layer. In the following table, all numerical values are parts by weight:

Methyl Isobutyl Ketone 24.11

Toluene 20.65

VYHH 11.54

R-900 38.4

Acroloid B-72 (3.86 identified as acrylic resin

Rohm & Haas product)

18980 2.6

DP37251 0.21

DP80110 0.40

The pressure sensitive adhesive is then applied using a transfer lamination over the dry paint layer or the dry paint layer corresponding to the film layer 110 at a coat weight of 15-20 gsm to provide an adhesive layer corresponding to the pressure sensitive adhesive layer 120. do. The pressure sensitive adhesive is a non-tacky acrylic emulsion. Formulations for this pressure sensitive adhesive are as follows: 70-90% by weight 2-ethylhexyl acrylate, 1-10% by weight acrylic acid, and 10-20% by weight methyl acrylate.

Example 6

The polyethylene terephthalate film backing liner corresponding to the backing liner 132 is coated on one side with a silicone release coating corresponding to the second release coating layer 136. The thickness of the release coated liner is 0.92 mils.

The matte release coat corresponding to the release coating layer 135 is applied to the other side of the backing liner using gravure. This release coat is dried using forced hot air at a temperature of 148.9 ° C. The matte release coat is applied with a coat weight of 4.0-5.0 gsm. The formulation for the matte release coat is as follows (all numerical values are by weight):

Methyl Isobutyl Ketone 42.03

Isopropanol 8.51

Microtalc 15-38 23.87

Cymel 303 7.36

Cycat 4040 1.8

VROH (Vinyl Chloride / Vinyl Acetate with OH Functional Group 16.43

Union Carbide supplied product identified as copolymer

The transparent layer corresponding to the transparent layer or film layer 140 is applied over the matte release coat No. 2 using a 2 mil byrd bar with a coat weight of 30 gsm and dried using hot air at a temperature of 126.7 ° C. The formulation for the transparent film layer is as follows (all numerical values are by weight):

Water 7.98

N-methyl pyrrolidone 4.79

Texanol (Eastman 4.79, identified as ester alcohol)

Chemicals company)

BYK 333 (manufactured by Byk Chemie, Inc. identified as a moisturizer) 0.4

Vycar 351 (polyvinyl chloride copolymer 79.81

From Noveon, identified as an emulsion)

Antifoam PD-218 (0.32 identified as an antifoaming agent

Magrabar Chemical)

Rheolate 350 (Rjeox, 1.92, identified as thickener)

Inc. product)

The paint composition is then coated onto the above indicated transparent film with a coat weight of 96 gsm and dried in hot air at a temperature of 126.7 ° C. to provide a dry paint layer corresponding to the dry paint layer or film layer 110. In the following table, all numerical values are parts by weight:

Water 18.28

Surfynol CT-324 (Air 0.98 identified as Surfactant

Products company)

R-900 32.88

Vycar 460x45 (34.72 as vinyl chloride / acrylic copolymer)

Noveon products identified)

Vycar 460x46 (11.57 as vinyl chloride / acrylic copolymer)

Noveon products identified)

Antifoam PD-218 0.19

Byk 333 0.23

Rheolate 350 1.2

The pressure sensitive adhesive is then applied using a transfer lamination over the dry paint film layer corresponding to the dry paint layer or film layer 110 at a coat weight of 17 gsm to provide an adhesive layer corresponding to the pressure sensitive adhesive layer 120. . The formulation for the pressure sensitive adhesive is as follows: 96% by weight non-tacky emulsion containing crosslinked copolymer of butyl acrylate and ethyl hexyl acrylate, 3.7% by weight UCD 1106E and 0.3% by weight UCD 1507E.

Example 7

The polyethylene terephthalate film backing liner corresponding to the backing liner 132 is coated on one side with a silicone release coating corresponding to the second release coating layer 136. The thickness of the release coated liner is 0.92 mils.

The matte release coat corresponding to the first release coating layer 135 is applied to the other side of the backing liner using gravure at a coat weight of 4.4-4.6gsm. The formulation for the matte release coat is as follows: 50.54 weight percent methyl isobutyl ketone, 7.84 weight percent isopropanol, 8.93 weight percent Lankyd 13-1425, VAGH (identified as hydroxy modified polyvinyl chloride / polyvinyl acetate copolymer) Union Carbide) 10.68%, Microtalc MP 15-38 22%, Cycat4040 2%, and Cymel 303 6.8%. The matte release coat is dried using forced hot air at a temperature of 149 ° C.

The transparent layer corresponding to the transparent layer or film layer 140 is applied to the matte release coat using gravure with a coat weight of 12-16 gsm and dried using forced hot air at a temperature of 165 ° C. The dry film thickness is 0.35-0.5 mils. The formulation for this transparent film layer is as follows (all numerical values are by weight):

Cyclohexanone 69.3

Elvacite 2042 10.5

Solsperse 17000 (0.1 identified as moisturizer)

Avecia company)

Tinuvin 234 (product of Ciba company identified as light stabilizer) 0.6

Kynar 301F (27.0 as polyvinyl fluoride homopolymer

Atofina company identified)

N-methyl-2-pyrrolidone 2.5

The adhesive layer corresponding to the second printed adhesive layer 160 is printed onto the transparent coating layer with a coat weight of 0.3-1.2 gsm and dried in hot air at a temperature of 105 ° C. The paint compositions used in this adhesive layer have the following formulations (all numerical values are by weight):

Methylethyl Ketone 36.0

Methyl Propyl Ketone 35.1

Kynar 7201 (SL) (27.0 as polyvinyl fluoride copolymer

Atofina company identified)

Elvacite 2010 (3.4 as polymethyl methacrylate

Lucite International's product identified)

Tinuvin 234 0.27

DP 35740 (Pale Yellow Mixed Metal Oxide Pigment 0.10

Gibraltar Chemical Identified as a Concentrate

Works product)

DP 35820 (Brown Mixed Metal Oxide Pigment 11.7

Gibraltar Chemical Identified as a Concentrate

Works company)

DP 39040 (Black Mixed Metal Oxide Pigment 3.3

Gibraltar Chemical Identified as a Concentrate

Works product)

The adhesive layer corresponding to the printed adhesive layer 150 is printed over the indicated adhesive layer corresponding to the second printed adhesive layer 160 with a coat weight of 0.3-1.2 gsm and at a temperature of 105 ° C. In hot air. The paint composition used in this adhesive layer has the following formulation (all numerical values are by weight):

Methylethyl Ketone 34.0

Methyl Propyl Ketone 33.0

Kynar 7201 (SL) 9.6

Elvacite 2010 3.2

Tinuvin 234 0.25

DP 35740 14.4

DP 35820 5.0

DP 39040 3.2

The paint composition is then coated onto the indicated adhesive layer corresponding to the adhesive layer 150 printed with a coat weight of 6-10 gsm and dried in hot air at a temperature of 105 ° C. to dry film or film layer 110 It provides a dry paint layer corresponding to). In the following table, all numerical values are parts by weight:

Methyl Ethyl Ketone 27.6

Methyl Propyl Ketone 26.3

Kynar 7201 (SL) 7.4

Elvacite 2010 2.5

Tinuvin 234 0.2

DP 35740 4.1

DP 35820 7.8

DP 39040 0.6

DP39600 (23.6 as white titanium dioxide pigment concentrate

Identified by Gibralter Chemical Works)

The colored pressure sensitive adhesive is then applied using a transfer lamination over the dry paint film layer corresponding to the dry paint layer 110 at a coat weight of 17 gsm to provide an adhesive layer corresponding to the pressure sensitive adhesive layer 120. The formulation for the pressure sensitive adhesive is as follows: 96% by weight non-tacky acrylic emulsion containing crosslinked copolymer of butyl acrylate and ethyl hexyl acrylate, 3.7% by weight UCD 1106E and 0.3% by weight UCD 1507E.

Example 8

The polyethylene terephthalate film backing liner corresponding to the backing liner 132 is coated on one side with a silicone release coating corresponding to the second release coating layer 136. The release coating layer is 0.92 mils thick.

The matte release coat corresponding to the first release coating layer 135 is applied to the other side of the backing liner using gravure at a coating weight of 4.4-4.6gsm. The formulation for the matte release coat is as follows: 50.54 weight percent methyl isobutyl ketone, 7.84 weight percent isopropanol, 8.93 weight percent Lankyd 13-1425, VAGH (identified as hydroxy modified polyvinyl chloride / polyvinyl acetate copolymer) Union Carbide) 10.68%, Microtalc MP 15-38 22%, Cycat4040 2%, and Cymel 303 6.8%. The matte release coat is dried using forced hot air at a temperature of 149 ° C.

The adhesive layer corresponding to the second printed adhesive layer 160 is printed onto the matte release coat with a coat weight of 0.3-1.2 gsm and dried in hot air at a temperature of 105 ° C. The paint compositions used in this adhesive layer have the following formulations (all numerical values are by weight):

Methylethyl Ketone 36.0

Methyl Propyl Ketone 35.1

Kynar 7201 (SL) (10.2 as polyvinyl fluoride copolymer)

Atofina company identified)

Elvacite 2010 (3.4 as polymethyl methacrylate

Lucite International's product identified)

Tinuvin 234 0.27

DP 35740 (Pale Yellow Mixed Metal Oxide Pigment 0.10

Gibraltar Chemical Identified as a Concentrate

Works company)

DP 35820 (Brown Mixed Metal Oxide Pigment 11.7

Gibraltar Chemical Identified as a Concentrate

Works company)

DP 39040 (Black Mixed Metal Oxide Pigment 3.3

Gibraltar Chemical Identified as a Concentrate

Works company)

The adhesive layer corresponding to the printed adhesive layer 150 is printed over the indicated adhesive layer corresponding to the second printed adhesive layer 160 with a coat weight of 0.3-1.2 gsm and at a temperature of 105 ° C. In hot air. The paint composition used in this adhesive layer has the following formulation (all numerical values are by weight):

Methylethyl Ketone 34.0

Methyl Propyl Ketone 33.0

Kynar 7201 (SL) 9.6

Elvacite 2010 3.2

Tinuvin 234 0.25

DP 35740 14.4

DP 35820 5.0

DP 39040 3.2

The paint composition was then coated using rotogravure over the indicated adhesive layer corresponding to the adhesive layer 150 printed with a coat weight of 5-16 gsm and dried in hot air at a temperature of 105 ° C. to dry layer A dry paint film layer corresponding to 110 is provided. In the following table, the numerical values are parts by weight.

Toluene 19.0

Methylethyl Ketone 23.6

VYHH 5.8

Edinol 9790 2.9

DV39600 (48.6 as Iron Oxide Red Pigment Dispersion

Identified by Gibraltar Chemical Works)

DV39420 (0.07 as Carbon Black Pigment Dispersion

Identified by Gibraltar Chemical Works)

DV36500 (0.03 as pigment red 178 pigment dispersion

Identified by Gibraltar Chemical Works)

DV34130 (0.10 as phthalo blue RS pigment dispersion

Identified by Gibraltar Chemical Works)

The coating composition was then coated onto the indicated dry paint film layer using a roll coating with a coat weight of 20-30 gsm and dried in hot air at a temperature of 105 ° C. to provide a support layer corresponding to the support layer 180. . In the following table, the numerical values are parts by weight.

Toluene 14.1

Methylethyl Ketone 21.1

VYHH 13.2

Edinol 9790 6.6

DV39600 44.96

DV39420 0.04

The colored pressure sensitive adhesive is then applied using a transfer lamination over the coated layer corresponding to the support layer 180 at a coat weight of 17 gsm to provide an adhesive layer corresponding to the pressure sensitive adhesive layer 120. The formulation for the pressure sensitive adhesive is as follows: 96% by weight non-tacky acrylic emulsion containing crosslinked copolymer of butyl acrylate and ethyl hexyl acrylate, 3.7% by weight UCD 1106E and 0.3% by weight UCD 1507E.

While the present invention has been described in connection with its preferred embodiments, it should be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Accordingly, it should be understood that the invention disclosed herein is intended to cover modifications that fall within the scope of the appended claims.

Claims (62)

A dry paint layer comprising a color layer comprising a binder and a pigment, said dry paint layer having a top surface and a bottom surface; A dry pressure sensitive adhesive layer overlying the top surface of the dry paint layer; Particles protruding into the detachably bonded dry paint layer to adhere the laminate to the substrate under pressure applied with a pressure sensitive adhesive layer and to transfer the matte finish to the exposed surface of the dry paint layer when the release liner is peeled from the dry paint layer. Release liner detachably adhered to the bottom surface of the dry paint layer, having a carrier release coat layer containing Dry paint transfer laminate comprising a. The laminate of claim 1, wherein the release liner further comprises an adhesive release coat layer on one side of the liner opposite from the carrier release coat layer. The laminate of claim 1 wherein the dry paint layer comprises a transparent layer positioned between the color layer of the dry paint layer and the release liner, wherein the carrier release coat layer is detachably adhered to the transparent layer. 4. The laminate of claim 1, 2 or 3 wherein the dry paint layer comprises a printed adhesive layer located on one side of the color layer adjacent to the release liner. The method of claim 1, wherein the binder is one or more acrylic resins, vinyl resins, polyester resins, alkyd resins, butadiene resins, styrene resins, phthalic acid or anhydride resins, urethane resins, epoxy resins. , Fluoropolymer resins, or polymers or copolymers containing ethylene and propylene units. A laminate according to claim 1 wherein the dry paint layer is derived from a liquid composition containing water or a water-alcohol mixture or an organic solvent. 4. The laminate of claim 3, wherein said transparent layer comprises an acrylic resinous material and said colored layer comprises a plasticized vinyl resinous material. The adhesive of claim 1 wherein the adhesive comprises a rubber based adhesive, an acrylic adhesive, a vinyl ether adhesive, a silicone adhesive or a mixture of two or more thereof, wherein the adhesive layer is derived from a hot melt adhesive, an organic solvent based adhesive or a water based adhesive. Laminate characterized in that the. The laminate of any one of the preceding claims wherein the carrier release coating layer comprises an alkyd resin and / or a vinyl resin crosslinked with a melamine resin. 3. The laminate of claim 2, wherein said adhesive release coat layer comprises a silicon-based material. 3. The laminate of claim 2, wherein the ejection force required to separate the release coat layer from the dry paint layer has a self-winding form that is greater than the release force required to separate the adhesive release coat layer from the adhesive layer. The release force required to separate the carrier release coat layer of the release liner from the dry paint layer ranges from about 20 to about 180 grams per two inches, and the two inch wide sample of the release liner is 300 per minute at a 90 degree angle. And a self-winding form that separates from the dry paint layer by pulling at an inch speed. 13. The method of claim 2 or 12, wherein the ejection force required to separate the adhesive release coating layer of the release liner from the adhesive layer ranges from about 30 to about 150 grams per two inches, and the two inch wide sample of the release liner is at a 90 degree angle. And a self-winding form that separates from the dry paint layer by pulling at a speed of 300 inches per minute. Applying a paint layer comprising a binder and a pigment to a release liner comprising a thin flexible polymer carrier film and drying or curing the paint layer on the release liner to form a dry paint layer, wherein the release liner is combined with the dry paint layer. Having an emitting surface in contact; A method of manufacturing a multi-pack laminate comprising the step of applying a pressure sensitive adhesive layer from the release liner to the opposite paint layer side, Applying a matte release coat to the release liner, the resinous material having a dispersed particle filler material and comprising a resinous material at room temperature in a cured state forming a matte surface; Apply a layer of paint on the matte surface of the matte release coat and dry paint at room temperature to transfer the matte surface finish to the exposed surface of the dry paint layer when the laminate is adhered to the substrate via a pressure sensitive adhesive and the release liner is removed therefrom. Drying or curing the dry paint layer in contact with the matte surface to detachably adhere the dry paint layer to the matte surface, the adhesive being adapted to be released from the layer; Method for producing a multilayer laminate comprising a. A matte release liner comprising a flexible polymer carrier film and a dry matte release coat bonded to the carrier film; A flexible dry paint layer detachably contacting the matte release coat on the release liner; And Opposite the matte release liner includes a dry adhesive layer bonded to the dry paint layer on one side thereof, The dry paint layer comprises a pigment dispersed in a polymerizable binder, The matte release coat has a level of tack detachably attaching the matte release liner to the dry paint layer to provide a support for the laminate when placing the adhesive side of the laminate in contact with the substrate, The adhesive layer comprises a pressure sensitive adhesive for adhering the dry paint layer to the substrate under room temperature conditions by applying pressure to the dry paint transfer laminate, The matte release coat contains particles protruding into the dry paint layer to transfer the matte finish to the exposed surface of the dry paint layer when the release liner is released from contact with the dry paint layer after the laminate is adhered to the substrate. Characterized by dry paint transfer laminate. The method of claim 15, wherein the dry paint layer comprises one or more resins selected from the group consisting of vinyl acetate / vinyl chloride copolymer or acrylics, urethanes, polyesters, alkyds, butadienes, fluoropolymers, polyolefins or vinyl resins. Laminate comprising a resinous binder. 16. The laminate of claim 15, wherein said release coat is selected from the group consisting of vinyl resins, acrylic resins, polyester resins, alkyd resins, and vinyl chloride / vinyl acetate copolymers. The method of claim 15 wherein the dry paint layer comprises a colored coat layer and a clear coat layer in which the clear coat layer detachably contacts the matte release coat, the clear coat layer comprising an acrylic resin, the color coat layer Laminate comprising a plasticized vinyl resin. The laminate of claim 15 wherein the matte release coat comprises a polymerizable binder in which particles are dispersed, and the ratio of particles to the resin binder is from about 0.7 to 1.0 to about 1.1 to 1.0. A dry paint layer comprising a binder and a pigment, said dry paint layer having a top surface and a bottom surface; A dry pressure sensitive adhesive layer overlying the top surface of the dry paint layer; And Matte on a carrier film made from a thin polymer carrier film and a thermosetting resinous material bonded to the carrier film and forming a matte surface that transfers the matte surface finish to the dry paint layer when the release liner is removed from the paint layer at room temperature. Release liner overlying the bottom surface of the dry paint layer, including the release coat Multilayer laminate comprising a. 21. The laminate of claim 20, wherein said matte release coat is selected from the group consisting of acrylic resins, polyester resins, alkyd resins and vinyl chloride / vinyl acetate copolymers. 21. The laminate of claim 20, wherein the clear coat layer comprises an acrylic resin, the color coat layer comprises a plasticized vinyl resin, and the adhesive layer comprises a crosslinked acrylic resinous material. Applying a paint layer comprising a binder and a pigment to a release liner comprising a thin flexible polymer carrier film and drying or curing the paint layer on the release liner to form a dry paint layer, wherein the release liner is combined with the dry paint layer. Having an emitting surface in contact; A method of manufacturing a multi-pack laminate comprising the step of applying a pressure sensitive adhesive layer from the release liner to the opposite paint layer side, The release liner releases a thermoset resinous matte release coat, wherein the composition of release coat material forms a bond to the release liner, forms a matte release surface in the cured state at room temperature and forms a level of tack in its cured state. Applying to and curing the release coat thereon at elevated temperature; Apply a paint layer on the matte surface, the laminate is adhered to the substrate surface via a pressure sensitive adhesive and detachably bonded to the dry paint layer when the release liner is subsequently removed from the dry paint layer and finish the matte surface to the dry paint layer at room temperature Or curing the paint layer on the matte release coat, which transfers Method for producing a multilayer laminate comprising a. A dry paint layer comprising a color layer comprising a binder and a pigment, said dry paint layer having a top surface and a bottom surface; A dry pressure sensitive adhesive layer overlying the top surface of the dry paint layer; And A release liner overlying the bottom surface of the dry paint layer, The release liner includes a thin, flexible polymeric carrier film and a matte release coat on the carrier film in overlapping contact with the dry paint layer, wherein the matte release coat allows the coating material to detachably adhere to (1) the dry paint layer. A hardened state that forms a matte surface, (2) is released from the dry paint layer at room temperature, and (3) transfers the matte surface finish to the exposed surface of the dry paint layer when the release liner is removed from the dry paint layer. Multilayer laminate, characterized in that it is prepared from a resinous coating material having. 25. The release liner of claim 24, wherein the release liner has a top surface and a bottom surface, the matte release coat overlies the top surface of the release liner, and the outer release coat layer detachably contacts the adhesive in the laminate's self-winding form. Laminate over the lower surface of the release liner. 26. The laminate of claim 24 or 25, wherein the laminate further comprises a barrier layer positioned between the dry paint layer and the adhesive layer, the barrier layer comprising an acrylate containing polymer or copolymer, polyvinyl alcohol, ethylene and vinyl acetate. And copolymers derived from ethylene, vinyl acetate and polyvinyl alcohol, or polymer mixtures derived from polyvinyl alcohol and urethane. 25. The method of claim 24, wherein the ejection force required to separate the release liner from the dry paint layer ranges from about 20 to about 180 grams per two inches, and the two inch wide sample of the release liner is pulled at a speed of 300 inches per minute at a 90 degree angle. And separated from the dry paint film layer. The release coat of claim 24, wherein the release coat comprises a thermoset resin material rigid or cured on the release liner, wherein the release coat material is less than 30% at 85 degrees relative to the dry paint layer when the release liner is removed therefrom. And forming a matte emissive surface at its cured conditions at room temperature to transfer a matte surface finish having a gloss of. 29. The method of claim 28, comprising a transparent layer positioned between the bottom surface of the dry paint layer and the release liner, wherein the matte surface is transferred to a transparent layer, and the release coat layer protrudes into the surface of the transparent layer to form a matte surface. A laminate comprising solid fine particles. To a release liner having a flexible polymer carrier film and a matte release coat bonded to the carrier film, a flexible dry paint transfer layer detachably adhered to the matte release coat, and a dry paint transfer layer on the opposite side of the release liner. A combined dry pressure sensitive adhesive layer, wherein the dry paint transfer layer comprises a color layer comprising a pigment contained in a polymeric binder, The matte coat has a level of tack that preferentially bonds the release liner with a dry paint transfer layer sufficient to provide a level of structural support for the dry paint layer when placing the adhesive side of the dry paint layer in contact with the substrate, The matte release coat includes a resinous material hardened or cured to form a fine-rough surface for transferring the matte surface finish to the exposed surface of the dry paint layer when the release coat is released from contact with the dry paint layer. and, The adhesive layer has a suppressed initial level of tack at room temperature that allows the laminate to adhere to the substrate following removal of the release liner from the dry paint layer, the adhesive layer having a time sufficient to permanently bond the dry paint layer to the substrate. Multilayer laminate characterized by performing subsequent reinforcement of adhesion due to passage. 32. The laminate of claim 30, wherein the gloss level transferred from the matte release coat to the dry paint layer is less than 30% at 85 degrees. 31. The laminate of claim 30, wherein the dry paint transfer layer comprises a clear coat layer overlying the colored layer, wherein the clear coat is in contact with the matte release coat for transferring the fine-rough surface to the clear coat layer. 31. The laminate of claim 30, wherein the release liner comprises a polyester film that is essentially non-stretchable at room temperature. 31. The laminate of claim 30, wherein the laminate comprises a reinforcement polymerizable support layer between the dry paint layer and the adhesive layer, the support layer having a greater tensile strength than the dry paint layer. 31. The laminate of claim 30, wherein the release liner further comprises an adhesive release coat on one side of the liner opposite from the matte release coat. 36. The laminate of claim 35, wherein the release force required to separate the matte release coat from the dry paint layer is greater than the release force required to separate the adhesive release coat layer from the pressure sensitive adhesive layer. . 37. The laminate of claim 36, wherein the adhesive layer comprises a crosslinked acrylic resinous material. A dry paint layer comprising a color layer and a transparent layer comprising a binder and a pigment; A dry pressure sensitive adhesive layer overlying the color coat side of the dry paint layer; And Matte surface, where the matte release coat material is cured in a hard state on the carrier film and the matte included in the release coat material transfers the matte surface finish to the transparent layer when the adhesive layer is adhered to the substrate and the release liner is removed therefrom. A matte release coat made from a resinous binder material overlying the transparent layer and containing a thin polymeric flexible carrier film and a matte binder material bonded to the carrier film and detachably adhered to the transparent layer, Release liner with less than 30% gloss level transferred from the matte release coat to the clear layer at 85 degrees Multilayer laminate comprising a. 39. The laminate of claim 38, wherein the transparent layer comprises an acrylic resinous material and the binder contained in the color coat layer comprises a vinyl resinous material. A dry paint layer comprising a binder and a pigment, said dry paint layer having a top surface and a bottom surface; A dry pressure sensitive adhesive layer overlying the top surface of the dry paint layer; And Having a matte release coat made from a resinous material coated on a liner and cured thereon to a hard state whereby the cured hardened release coat material forms a fine-rough matte surface separated from the carrier film. Wherein the matte surface comprises a release liner overlying the bottom surface of the dry paint layer that transfers the matte surface finish to the dry paint layer when the release liner is removed therefrom. 41. The laminate of claim 40, wherein the gloss level transferred from said matte release coat to said dry paint layer is less than 30% at 85 degrees. 41. The laminate of claim 40, wherein the release liner further comprises an adhesive release coat on one side of the liner opposite from the matte release coat. 43. The laminate of claim 42, wherein the release force required to separate the release coat layer from the dry paint layer is greater than the release force required to separate the adhesive release coat layer from the adhesive layer. 41. The laminate of claim 40, wherein the matte release coat material consists essentially of crosslinked acrylic modified alkyd resins and vinyl resinous materials and dispersed particulate materials. To a release liner having a flexible polymer carrier film and a matte release coat bonded to the carrier film, a flexible dry paint transfer layer detachably adhered to the matte release coat, and a dry paint transfer layer on the opposite side of the release liner. A combined dry pressure sensitive adhesive layer, the dry paint transfer layer comprising a colored layer comprising a pigment contained in a polymeric binder, The matte release coat has a tack level that preferentially bonds the release liner with a dry paint transfer layer sufficient to provide a level of structural support for the dry paint layer when placing the adhesive side of the dry paint layer in contact with the substrate, The matte release coat hardens or cures the matte release coat material to form a fine-rough surface for transferring particles of the matte surface finish to the exposed surface of the dry paint layer when the particles are released from contact with the dry paint layer. Comprising a resinous material containing dispersed particulate material, the uniform finish of the transferred matte having a gloss level of less than 30% at 85 degrees, The adhesive layer has a suppressed initial level of tack at room temperature that allows the laminate to adhere to the substrate subsequent to the removal of the release liner from the dry paint layer, which adhesive layer has sufficient time to permanently bond the dry paint layer to the substrate. Multilayer laminate, characterized in that the subsequent reinforcement of adhesion is carried out due to the passage of 46. The laminate of claim 45, wherein the release liner further comprises an adhesive release coat on one side of the liner opposite from the matte release coat. 47. The self-winding form of claim 46, wherein the ejection force required to separate the release coat layer from the dry paint layer is greater than the release force required to separate the adhesive release coat layer from the adhesive layer. Laminate. 48. The laminate of claim 45, 46 or 47, wherein the pressure sensitive adhesive comprises a crosslinked acrylic resinous material. 46. The laminate of Claim 45, comprising a reinforced polymeric support layer between the dry paint layer and the adhesive layer, the support layer having a greater tensile strength than the dry paint layer. An indoor dry paint layer comprising a binder and a pigment, a pressure sensitive adhesive layer overlying one surface of the dry paint layer to adhere the dry paint layer to a wall, and a release liner overlying the surface of the dry paint layer opposite the adhesive layer. Wherein the release liner is removable from the dry paint layer by attaching a dry paint layer to the wall via a pressure sensitive adhesive, the dry paint layer having a matte finish on its exposed surface, the release liner A thin polymeric flexible carrier film and a matte release coat on a carrier film made from a thermosetting resinous material bonded to the carrier film, drying at a gloss level of less than 30% at 85 degrees when the adhesive layer is adhered to the wall Forms fine-rough matt surfaces when transferring matt surface finishes with paint layers And, a release liner is laminated multiple layer characterized in that the paint removed from the layer at room temperature. 51. The laminate of claim 50, wherein the finely roughened surface is formed by dispersed particulate material contained in the matte release coat. 51. The laminate of claim 50, wherein the adhesive has an initial tack level suppressed at room temperature and performs an increase in adhesion over time with permanent bonding to the wall. 51. The laminate of Claim 50, wherein the pressure sensitive adhesive comprises a crosslinked acrylic resinous material. A dry paint layer detachably attached to the release liner to provide a support for the dry paint layer, and a pressure sensitive adhesive layer on one side of the dry paint layer opposite the release liner to attach the paint layer to the inner wall; The release liner has a release coat that can be removed from the dry paint layer to expose the dry paint layer as a painted inner wall covering, which release liner has an adhesive release coat on one side of the liner opposite the release coat in contact with the dry paint layer. Wherein the release liner comprises a polymerizable carrier film, wherein the release coat thereon comprises a matte release coat bonded to the carrier film and in contact with the dry paint layer, the matte release coat being in a rigid state To form a fine-coarse surface spaced apart from the film It has an adhesive level that adheres the release liner to the dry paint layer, but the adhesive layer is made of a material that transfers the matte finish to the exposed surface of the dry paint layer when the laminate adheres to the wall, and the release liner is dry paint at room temperature. Released from contact with the layer, the laminate has a greater ejection force needed to separate the matte release coat from the dry paint layer than the release force needed to separate the adhesive release coat from the adhesive layer, and the matte release coat removes the liner and dries out. Jade as an interior wall, characterized in that it has a self-winding form that maintains the integrity of the dry paint layer on the wall without releasing from its attachment to the wall while having a sufficient level of ejection force to transfer the matte surface to the paint layer. Dry Paint Transfer Laminate of Contents . 55. The laminate of claim 54, wherein said finely roughened surface is formed by dispersed particulate material contained in said matte release coat. 55. The laminate of claim 54, wherein the gloss level transferred from the matte release coat to the dry paint layer is less than 30% at 85 degrees. 55. The laminate of Claim 54, wherein said pressure sensitive adhesive comprises an internally crosslinked acrylic emulsion. Applying one or more adhesive paint layers on one side of the release liner and matting the resinous binder and matt thereon to form a dry paint layer comprising a color layer comprising a binder and a pigment thereon and having a top surface and a bottom surface Dry or cure an adhesive paint layer or layers on a release liner with a matte release coat containing dispersed particles forming a release surface, wherein the bottom surface of the dry paint layer lies on and contacts the matte release surface of the release liner. step; And Applying a pressure sensitive adhesive layer adapted to adhere the dry paint layer to the substrate surface as pressure is applied to the release liner over the top surface of the dry paint layer, The release liner can be released from the adhered dry paint layer to transfer the matte finish from the matte emissive surface to the exposed surface of the dry paint transfer layer when the release liner is released from contact with the dry paint layer. Method of producing a dry paint transfer laminate. 59. The system of claim 58, wherein the release liner comprises a backing liner having a top surface and a bottom surface; The matte release coat lies on the top surface of the backing liner; The outer release coating overlies the bottom surface of the backing liner; The exterior release coating is in contact with a layer of pressure-sensitive adhesive in the form of a self-winding laminate. Applying a paint layer comprising a color layer comprising a binder and a pigment to a release liner comprising a thin flexible polymer carrier film, and drying or curing the paint layer on the release liner to form a dry paint layer, wherein The liner has a release surface in contact with the dry paint layer; A method of making a multilayer laminate comprising applying a pressure sensitive adhesive layer from the release liner to an opposite paint layer side, Applying a matte release coat to the release liner, the matte release coat made from a resinous material having a matte surface that is rigid at room temperature and spaced apart from the carrier film; Apply a paint layer to the matte surface and dry or cure the paint layer thereon, wherein the matte release coat material provides adhesion of the matte surface to the dry paint layer, and the dry paint layer is adhered to the substrate surface via a pressure sensitive adhesive. Capable of releasing from contact with the dry paint layer at room temperature when transferring a matt surface finish having a gloss less than 30% at 85 degrees to the exposed surface of the dry paint layer Method for producing a multilayer laminate comprising a. Applying a paint layer comprising a color layer comprising a binder and a pigment to a release liner comprising a thin flexible polymer carrier film, and drying or curing the paint layer on the release liner to form a dry paint layer, wherein The liner has a release surface in contact with the dry paint layer; A method of making a multilayer laminate comprising applying a pressure sensitive adhesive layer to a side of a paint layer opposite the release liner, A release on top of the thermoset resinous material, which is applied from a release liner and is made from a thermoset resinous material containing dispersed particulate material that is bonded to the liner to form a matte surface on the liner and forms a matte surface thereon Drying or curing the coat; Apply the paint layer on the matte surface and apply the paint layer on the matte surface, which transfers the matte surface finish to the dry paint layer when the dry paint layer is adhered to the substrate surface via a pressure sensitive adhesive and the release liner is subsequently removed from the dry paint layer. Drying or curing step Method for producing a multilayer laminate comprising a. Applying a paint layer to a release liner comprising a thin flexible polymer carrier film and drying or curing the paint layer on the release liner to form a dry paint layer comprising a color layer comprising a binder and a pigment, wherein the release layer is dried or cured. The liner has a release surface in contact with the dry paint layer; A method of making a multilayer laminate comprising applying a pressure sensitive adhesive layer to a side of a paint layer opposite the release liner, Applying a matte release coat to the release liner and drying or curing the release coat thereon to form a micro-rough matte surface whose cured and rigid state of the matte release coat material is space separated from the liner; An active material and release liner that applies a layer of paint to the matte surface and dries or cures the layer of paint in contact with the matte emitting surface, wherein the matte release coat adheres the layer of dry paint to the matte surface to support the dry paint layer at room temperature. Transferring a matte surface finish to the dry paint layer when the dry paint layer is adhered to the substrate surface via a pressure sensitive adhesive and the release liner is subsequently released while the adhesive layer of the spheres on top Method for producing a multilayer laminate comprising a.