JP7201389B2 - Method for manufacturing multilayer products - Google Patents

Description

The present invention relates to a method of manufacturing multi-layer printed marks or stencils.

Printed marks and stencils are commonly used materials for decorating and marking various articles. However, today such materials can have drawbacks such as poor adhesion, interlayer adhesion and migration of volatile compounds, which can lead to shrinkage, edge curling and, after removal such as wall paint, paper or glass. It can appear as a residue that remains on the surface to which it is applied. Another phenomenon that occurs during removal is tearing into small pieces or separation of layers.

US Pat. No. 6,541,561 discloses a method for preparing plastic films or transfers.

US Pat. No. 6,143,407 discloses a decal comprising a plastisol ink, a carrier sheet and an adhesive.

U.S. Pat. No. 6,541,561 U.S. Pat. No. 6,143,407

There is a need to provide new materials and new manufacturing methods that overcome the aforementioned problems.

The present invention provides a way to overcome adhesion and/or adhesion problems and provides long-term strength and durability during use. Furthermore, the present invention provides a sustainable solution, for example by allowing recycling and preventing volatility of components such as plasticizers and solvents. Also, halogen-free polymer powders can be used to provide an environmentally friendly alternative.

The present invention provides a layer that gels after application in order to absorb the plasticizer/monomer/oligomer mixture into the polymer powder in order to avoid premature polymer curing. This gelation step provides good interlaminar penetration and layer homogenization. Interlayer diffusion provides good interlaminar adhesion upon cross-linking of all printed layers, including applied inks and pressure sensitive adhesives.

The present invention comprises the steps of (1) optionally forming a release coating on a substrate; (2) optionally forming a printing ink layer on said release coating; ) forming a coating of a curable composition comprising a polymer powder, at least one plasticizer and at least one monomer and/or oligomer on a substrate or a layer or coating previously applied thereon; (4) heating the curable coating composition to a temperature of from about 70° C. to about 120° C. to form a gel-like curable coating; (6) forming a coating film of another curable composition comprising a polymer powder, at least one plasticizer and at least one monomer and/or oligomer on the pre-applied layer or coating; forming on the coating; and heating the other curable composition coating to a temperature of about 70 to about 120° C. to form a second gel-like curable coating; (7 ) heating the formed multi-layer coated substrate to a temperature of about 130 to about 160° C. before cross-linking is performed; and (8) subjecting the heated multi-layer coated substrate to irradiation and/or about cross-linking by exposure to heat at a temperature of from 165 to about 190° C.; or, if more than one is present, the last formed gel polymer coating.

Embodiments of the invention will now be described, by way of example, with reference to the accompanying schematic drawings.

Fig. 2 is a cross-sectional view of a decorative wall transfer disclosing its different layers; FIG. 4 is a cross-sectional view of the weatherable sign transfer disclosing its different layers. FIG. 4 is a cross-sectional view of a peel decal graphic disclosing its different layers; FIG. 2 is a cross-sectional view of a flexible stencil mask disclosing its different layers; FIG. 3 is a cross-sectional view of a decorative stencil mask disclosing its different layers;

The method of manufacturing a multi-layer printed mark or stencil can include several steps. First, a substrate is provided. The substrate can be a plastic film, such as a polyethylene terephthalate film or a polyoxyethyleneoxyterephthaloyl film; or heat resistant paper or cardboard, which can be stabilized with a polymer; or a fiberglass material such as a web or sheet. For non-adhesive stencils, reusable glass fiber PTFE coated membrane materials such as sheets or webs can be used.

A release coating can be formed on the substrate, eg, coated thereon. The substrate can temporarily adhere to the present multi-layer printed mark or stencil, which means that when the multi-layer printed mark or stencil is used, the substrate can be peeled off from the layered structure and applied, for example, onto a wall. show. Release coatings can be applied on substrates with controlled surface tension to obtain the appropriate level of applied release while avoiding pre-release. The controlled surface tension of the substrate can be a surface tension within the range of 5-45 Dyne/cm, such as 10-40 Dyne/cm, 15-35 Dyne/cm or 12-38 Dyne/cm. Release coatings may include polydimethylsiloxane, epoxy resins and polytetrafluoroethylene surface tension modifiers to obtain adequate release levels while avoiding pre-release.

A printing ink or adhesive is then applied onto the release coating or of this release coating to form a printing ink layer or adhesive layer, as discussed further below. It may optionally be applied over any other previously applied layers. Printing inks can be selected from conventional UV or hybrid offset and screen inks, flexographic and digital inks. Note that one or more types of printing ink can be used to form this printing ink layer. The printing inks may contain different colorants to give different colors of the printing ink layer. Printing inks, if not used at this stage, can be applied later in the layering sequence even if they are used.

On the substrate, or optionally after the release coating, or optionally after the printing ink layer, or optionally after the pressure sensitive adhesive composition coating disclosed below, the polymer A coating of a curable composition comprising a powder, at least one plasticizer and at least one monomer and/or oligomer is applied on or over a substrate of any previous coating or layer. given above. The curable coating film may include, for example, a photoinitiator that may be activated by UV, or a thermally activated initiator, such as an organic peroxide. The applied curable coating composition is heated to a temperature of 70-120° C., such as 70-110° C., 75-100° C. or 80-90° C., to form a gel-like curable coating film. Heating is carried out such that the polymer powder particles present in the liquid mixture of said plasticizer, monomer and/or oligomer are swollen by the absorbent portion of the liquid mixture, which allows interpenetration for interlayer adhesion. Gives a tack-free gel-like structure that

Optionally, printing ink may be applied onto said gel-like polymer coating, for example to form a printing ink layer, if not pre-formed. The same types of printing inks mentioned above can be considered in this application. When more than one layer of printed ink is formed in the present multi-layer printed mark or stencil, the printed inks need not be identical, but may be of different types and colors. If this optional printing ink layer is formed by one of the group consisting of conventional UV or hybrid offset and screen inks, flexographic and digital inks, the previous printing ink layer, if present, Note that it can be formed by different types of inks selected from

Another curable coating composition comprising a polymer powder, at least one plasticizer and at least one monomer and/or oligomer is added to a previous coating or layer, e.g., a first gel-like curable coating or print. It may be applied over an ink layer or, optionally, a pressure sensitive adhesive coating composition disclosed below. If a printed ink layer is formed at this stage, said printed ink layer is preferably followed by another layer of curable coating composition. The same or similar coating compositions disclosed for the first curable coating composition can be used herein. Although there may be differences between the curable compositions disclosed herein, they fall within the same ranges noted herein above within the previous disclosure of coatings of curable compositions. . After coating film application, to form another second gel-like curable coating film, the same as the previous curable coating composition, i. etc., to temperatures of 70-120° C., other curable coating compositions are carried out. Another same or similar curable coating composition may be applied in a similar manner such that a third or fourth coating may be heated after each coating application or forming step. In part of the layering sequence, at least two curable coating compositions comprising polymer powder, at least one plasticizer and at least one monomer and/or oligomer are preferably applied one after the other, immediately after each other. In another embodiment, at least three curable coating compositions comprising polymer powder, at least one plasticizer and at least one monomer and/or oligomer are applied sequentially and immediately after each other.

After formation of the desired amount of gel-like curable coating(s), the partially completed multi-layer coated substrate proceeds to the next step. The formed multilayer coated substrate is heated to a temperature of 130-160°C, such as 140-160°C, before cross-linking is performed. Further heating of the multilayer coated substrate allows the swollen polymer powder particles to dissolve, preferably completely, in the mixture of plasticizer, monomer and/or oligomer to form a homogeneous phase. Note that at this stage the components of the different layers applied to the substrate are also interconnected with each other by migration of components, which increases interlayer bonding during subsequent fixing. This separate heating step to a higher temperature improves interlayer adhesion and adhesion. The ratio between the polymer powder particles and the liquid mixture of plasticizer, monomers and/or oligomers can be chosen in such a way that no excess liquid or polymer is present, which is initially wet and and/or will give a brittle cold coating at a later stage.

After another heating step, cross-linking of the heated multilayer coated substrate is carried out by irradiation and/or exposure to heat at a temperature of 165-190°C, such as 170-180°C. Crosslinking can be accomplished by, for example, cationic or free radical polymerization. Irradiation can be performed, for example, by UV and/or EB, which forms a unique network of components of the multilayer coated substrate. The irradiation energy can be 5-500 mJ/cm ² , such as 20-500 mJ/cm ² , 100-450 mJ/cm ² or 200-400 mJ/cm ² . Irradiation using wavelengths of about 300-500 nm may be carried out, such as 350-450 nm or 370-400 nm. Cross-linking in the sense of chemical cross-linking forming chemical bonds between molecules takes place at this stage of the production of said multi-layer printed mark or stencil. Prior gelation and separate heating physically dissolve the components together while avoiding functionally significant cross-linking. This final chemical cross-linking gives the composition of the layer its ultimate strength. This chemical cross-linking can be done by cationic or radical polymerization, which requires that particular initiator. To achieve cross-linking, for example, a multi-layer coated substrate comprising a mixture of polymers, monomers and/or oligomers is polymerized to form a unique network and heated by IR for thermosetting, or other conventional heating means. may need to be implemented. Heating is important for achieving free-radical polymerization using thermal initiators such as organic peroxides to crosslink the incoming components of the multi-layer printed mark or stencil. Crosslinking is carried out after application of all curable composition coatings suitable for a particular type of product. Exposure to heat and/or UV/EB irradiation forms a hard coating with desirable physico-chemical and mechanical properties. Note that when electron beam (EB) irradiation is used, no initiator is required in the cured composition, as the composition can be crosslinked with EB irradiation alone. However, initiators may be present in the composition even when EB irradiation is used. Upon cooling, the finished multilayer coated substrate is a solid with excellent mechanical properties and does not migrate or evaporate the contained plasticizers. Due to this strongly improved mechanical properties, edge adhesion failures will be eliminated. The plasticizer no longer evaporates or migrates into the wall in the case of wall decals. Therefore, no significant change in dimensions, reduced adhesion at the edges, or discoloration of the walls is seen after removal of the mark or stencil.

The pressure sensitive adhesive composition coating may be applied to the release coating on the substrate before another coating or layer is applied, or separate heating and crosslinking is performed. Note that it may be applied to the gelled polymer coating formed last if more than one is present before.

The multi-layer print or stencil comprises (1) at least one substrate and (2) a polymer powder, at least one plasticizer and at least one monomer and/or oligomer which may contain different ingredients in different coating layers. at least two curable coating compositions, such as three or more. An optional layer of multi-layer print or stencil may be applied on the substrate before another coating or layer is applied; directly on the release coating, or as a final A pressure sensitive adhesive composition coating that may be applied over the final curable composition coating film comprising polymer powder, at least one plasticizer and at least one monomer and/or oligomer prior to the heating and curing steps. coating; and, when present, on a release coating before another coating or layer is applied, or on a release coating, or comprising a polymer powder, at least one plasticizer and at least one monomer and/or oligomer. can be applied on the curable composition coating film, preferably between two curable coating compositions each comprising a polymer powder, at least one plasticizer and at least one monomer and/or oligomer It may be selected from the group consisting of printing ink layers. When the pressure-sensitive adhesive coating composition is applied at the end of preparation of the multi-layer printed mark or stencil, a protective foil may be applied over it. The protective foil may be made of paper, plastic or any combination thereof.

Different compositions can be provided as coating films or layers by printing or coating processes. As noted above, the curable composition is provided as a coating film and then subjected to elevated temperatures to swell the polymer powder particles by partial penetration of the liquid mixture of plasticizer and monomers and/or oligomers. . This swelling transforms the coating film into a non-sticky gel, which allows overprinting, ie, printing multiple layers, without back-trapping. In the manufacture of a multi-layered print or stencil, the formation of different coatings and layers can be referred to as printing, i.e., different coatings and layers were printed to provide said multi-layered print or stencil. . After printing (coating) of the multilayer coated substrate is completed, the multilayer coated substrate is heated. During this process, the swollen polymer powder particles are preferably completely dissolved in the plasticizer, monomer and/or oligomer composition to form a homogeneous layered structure. Subsequent exposure to, for example, UV and/or EB radiation at this higher temperature crosslinks the coating film, or the temperature is further increased, for example, by multi-layering using organic peroxides. The coated substrate is polymerized to form a unique network across multiple layers, greatly improving mechanical properties. The changes between the various steps can be described as a so-called sol-gel transformation process. A "sol" is a polymer powder dispersed in a liquid mixture of the type(s) of polymer(s) and type of liquid component, and the "gel" phase is a complete polymer with the required dimensional and mechanical properties. swelling of the polymer particles by the liquid component until a homogeneous structure is finally obtained.

Several layers of curable composition coatings, including printing inks and polymer powders, can be used in the production of multi-layer printed marks or stencils, so that UV curing is performed between the coatings and lamination. Note that it is important to consider If UV curing is used while building the layer structure, any curable coating composition containing polymer powder under such a UV cured layer will also be affected and the multi-layer printed mark or stencil will You may have problems with poor adhesion between the layers of a multi-layer print or stencil. Therefore, if UV is used not only at the end of lamination, but also during lamination, the curable composition coating film comprising the polymer powder located below the propellant UV-treated layer To avoid premature cross-linking, any resulting curable coating composition containing polymer powder should not contain a UV initiator, but instead use other initiators such as thermal initiators (e.g. organic peroxides). of cross-linking initiators should be used. Alternatively, the curable coating composition comprising the printing ink layer(s) and/or polymer powder which may be present may comprise formulations comprising high amounts of pigments such as white pigments, e.g. titanium dioxide. Thus, the pigments are such that any UV radiation penetrates through or penetrates into such layers to cure and crosslink said layers or any underlying curable coating composition comprising polymer powders. make it difficult. If the curable composition coating film comprising polymer powder is highly pigmented and/or covered by a highly pigmented printing ink, then the coating composition contains in such cases a UV initiator, a pigment Even with curable coating compositions containing polymer powders which are covered by high amounts and/or highly pigmented printing inks, UV penetrates inside highly pigmented formulations, Such a curable coating composition comprising a polymer powder would not be able to penetrate through it and exposure to UV would not be sufficient to crosslink, so such a curable coating composition comprising a polymer powder would not be able to react with the heat disclosed above. A thermal initiator, such as an organic peroxide, is preferably included to achieve sufficient cross-linking by .

Provided herein are curable coating compositions comprising polymer powder, at least one plasticizer, and at least one monomer and/or oligomer. The composition may further comprise ingredients selected from the group consisting of initiators, dyes, pigments, stabilizers and fillers. A curable coating composition is provided by mixing the ingredients, which composition is then used in the process to form the coating film. At least one curable composition is used in making the multilayer coated substrate.

The curable coating composition can include:
30-75 wt% polymer powder(s),
5-50 wt% plasticizer(s),
1-40 wt% monomer(s) and/or oligomer(s),
0.5-5 wt% initiator(s).

Any other component composition may be present in the following amounts:
0.5-20 wt% dye(s) and/or pigment(s),
0.5-5 wt% stabilizer(s) and 0.5-5 wt% filler(s).

The polymer powder particles present in the curable coating composition are preferably insoluble in the monomer/oligomer and plasticizer mixture at ambient temperature, but form a tack-free gel when heated. Therefore, this multi-layer printing becomes possible.

The polymer powder is preferably selected from acrylate polymers and/or vinyl polymers. Vinyl polymers may be selected from the group consisting of polyvinyl chloride, polyvinyl acetate, and copolymers of vinyl chloride and vinyl acetate. Acrylate polymers can be homopolymers and/or copolymers of C _3-25 alkyl acrylates and/or C _2-25 alkyl methacrylates. Acrylate polymers are alkyl (meth)acrylates; hydroxyalkyl (meth)acrylates (wherein the alkyl in the preceding compound can be methyl, ethyl, butyl, 2-ethylhexyl, lauryl, stearyl, etc.); (meth)acrylic acid; malein acid; itaconic acid; and any combination thereof.

Polymer powders can include other polymers such as polystyrene, polyvinyl alcohol, polyacrylonitrile, acrylonitrile butadiene styrene and polyethylene terephthalate copolymers and any combination thereof.

The polymer powder is present in the curable coating composition at 35-70 wt%, 40-68 wt%, 40-66 wt%, 35-66 wt%, 35-50 wt%, 40-50 wt%, 45-75 wt%, 50-70 wt%. % or 30-75 wt%, such as 55-68 wt%. The amount of polymer powder present may vary with the type of polymer powder used. For example, when an acrylate polymer powder is used, the acrylate polymer powder can be present in an amount of 35-66 wt%, such as 35-50 wt% or 40-50 wt%. When vinyl polymer powder is used, the vinyl polymer powder may be present in an amount of 45-75 wt%, such as 50-70 wt% or 55-68 wt%.

The at least one plasticizer present in the curable coating composition is preferably at least two plasticizers. The plasticizer is preferably phthalate-free. Plasticizers include polyglycol benzoates such as polyoxyethylene glycol dibenzoate and polyoxypropylene glycol dibenzoate; trimellitate; pyromellitate; adipates such as dioctyl adipate, diisodecyl adipate; sebacate esters such as dibutyl sebacate and dioctyl sebacate; e.g. alkyl-substituted diphenyls, alkyl-substituted terphenyls, partially hydrogenated alkyl terphenyls, aromatic process oils, hydrocarbons such as pine oil; and any combination thereof.

The plasticizer(s) may be present in the curable coating composition in an amount of 5-50 wt%, such as 10-45 wt%, 15-40 wt%, 19-40 wt% or 20-40 wt%. .

At least one monomer and/or oligomer present in the curable coating composition is preferably polymerizable. They may also be soluble in plasticizers at ambient temperature. At least one monomer and/or oligomer may be selected from acrylate monomers and acrylate oligomers. Acrylate oligomers may be selected from the group consisting of epoxy acrylates, polyester acrylates, urethane acrylates, silicone acrylates, amine functional polyether acrylates, chlorinated acrylates and any combination thereof. Preferably, urethane acrylate oligomers such as urethane acrylates and ethoxylated trimethylolpropane triacrylates or urethane acrylates and 2-(2-ethoxyethoxy)ethyl acrylate. Monomers include ethoxylated phenol monoacrylate, tripropylene glycol diacrylate, trimethylpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, epoxy acrylate, polyether acrylate, vinylpyrrolidone, silicone acrylate, polyester acrylate. , methacrylate, acrylic acid dimer, beta carboxyethyl acrylate, isobornyl acrylate, osyl acrylate, decyl acrylate, aliphatic acrylate, pentaerythritol acrylate, 1,6-hexanediol acrylate, polyethylene diacrylate and any of these It may be selected from the group consisting of combinations.

The monomers and/or oligomers are present in the curable coating composition in an amount of 1-40 wt%, such as 1-25 wt%, 2-24 wt%, 4-22 wt%, 5-20 wt% or 5-15 wt%. obtain.

Initiators that may be present in the curable coating composition may be selected from photoinitiators and thermal initiators. Photoinitiators may include cationic polymerization initiators such as diaryldiiodonium salts or triarylsulfonium salts. Thermal initiators may include substituted benzylphosphonium salts.

Acenaphthenequinone; methyl ethyl ketone; valerophenone; hexanophenone; alpha-phenylbutyrophenone; p-morpholinopropionphenone; dibenzosuberone; 4'-methoxyacetophenone; benzaldehyde; alpha-tetralone; 9-acetylphenanthrene; 2-acetylphenanthrene; 10-thioxanthenone; 9-fluorenone; 1-indanone; 1,3,5-triacetylbenzene; thioxanthen-9-one; xanthren-9-one; 7-H-benzo[de]anthracen-7-one; 4,4′-bis(dimethylamino)benzophenone; fluoren-9-one; 1′-acetonaphthone; 2′-acetonaphthone; 2,3-butanedione; ] anthracene-7,12-dione; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzoin isobutyl ether; 2,2-dimethoxy-2-phenylacetophenone or 2,2-diethoxy-2-phenyl 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzyl dimethyl ketal; and any combination thereof.

Thermal initiators may be selected from the group consisting of substituted or unsubstituted pinacols, azo compounds, thiurams, organic peroxides and any combination thereof. Preferably, organic peroxides may be used as thermal initiators. Even more preferably the peroxide is a blocked peroxide. Examples of organic peroxides are 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butylperoxyisopropyl)benzene, 1,3-bis(cumylperoxy isopropyl)benzene, 2,4-dichlorobenzoyl peroxide, caprylyl peroxide, lauroyl peroxide, t-butyl peroxyisobutyrate, benzoyl peroxide, p-chlorobenzoyl peroxide, hydroxyheptyl peroxide, di-t-butyl diperphthalate, t -butyl peracetate, t-butyl perbenzoate, dicumyl peroxide, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane and di-t-butyl peroxide. Examples of azo compounds are 2-t-butylazo-2-cyanopropane; 2,2′-azobis(2,4-dimethyl-4-methoxyvaleronitrile); 2,2′-azobis(isobutyronitrile); 2,2′-azobis(2,4-dimethylvaleronitrile) and 1,1′-azobis(cyclohexanecarbonitrile). Examples of thiurams are tetramethylthiuram disulfide, tetraethylthiuram disulfide, di-N-pentamethylenethiuram disulfide, tetrabutylthiuram disulfide, diphenyldimethylthiuram disulfide, diphenyldiethylthiuram disulfide and diethyleneoxythiuram disulfide. Examples of pinacols are benzopinacol, 4,4′-dichlorobenzopinacol, 4,4′-dibromobenzopinacol, 4,4′-diiodobenzopinacol, 4,4′,4″,4′″- Tetrachlorobenzopinacol, 2,4-2′,4′-tetrachlorobenzopinacol, 4,4′-dimethylbenzopinacol, 3,3′-dimethylbenzopinacol, 2,2′-dimethylbenzopinacol, 3,4 -3',4'-tetramethylbenzopinacol, 4,4'-dimethoxybenzopinacol, 4,4',4'',4'''-tetramethoxybenzopinacol, 4,4'-diphenylbenzopinacol, 4 ,4′-dichloro-4″,4′″-dimethylbenzopinacol, 4,4′-dimethyl-4″,4′″-diphenylbenzopinacol, xanthone pinacol, fluorenone pinacol, acetophenone pinacol, 4, 4'-dimethylacetophenone pinacol, 4,4'-dichloroacetophenone pinacol, 1,1,2-triphenylpropane-1,2-diol, 1,2,3,4-tetraphenylbutane-2,3-diol, 1,2-diphenylcyclobutane-1,2-diol, propiophenone pinacol, 4,4′-dimethylpropiophenone pinacol, 2,2′-ethyl-3,3′-dimethoxypropiophenone pinacol, 1,1 , 1,4,4,4-hexafluoro-2,3-diphenyl-butane-2,3-diol, benzopinacol monomethyl ether, benzopinacol monophenyl ether, benzopinacol and monoisopropyl ether, benzopinacol monoisobutyl ether and Benzopinacol mono(diethoxymethyl) ether.

The initiator may be present in the curable coating composition in an amount of 0.5-5 wt%, such as 0.8-4 wt%, 1-3.5 wt% or 1-3 wt%.

Pigments and dyes that may be present in the curable coating composition can be selected from titanium oxide, red iron oxide, iron black and carbon black, and these pigments and dyes are preferably transparent to UV radiation and the like. . If they are used solely as fillers, it may be desirable for the material to have a very small particle size, because minimal loss of transparency of coating films or layers containing such may be desirable. because it would be suppressed to

Dyes and/or pigments may be present in the curable coating composition in an amount of 0.5-20 wt%, such as 1-15 wt% or 1-10 wt%.

Stabilizers that may be present in the curable coating composition may be selected from metal-containing stabilizers. Calcium and/or zinc containing stabilizers may be used.

Stabilizers may be present in the curable coating composition in an amount of 0.5-5 wt%, such as 1-4 wt% or 1.5-3 wt%.

Suitable fillers that may be present in the curable coating composition are clays such as bentonite, which may or may not be modified; e.g., ground calcium carbonate, precipitated calcium carbonate, surface-treated calcium carbonate, etc. titanium oxide; barium sulfate; zinc white; silicic acid; mica powder talc;

Fillers may be present in the curable coating composition in an amount of 0.5-5 wt%, such as 1-4 wt% or 1-3 wt%.

Another layer of the final product can be formed with a printing ink. Printing inks may include:
30-60 wt% monomer(s),
10-35 wt% dye(s) and/or pigment(s),
5-25 wt% prepolymer(s),
1-15 wt% resin(s),
1-10 wt% initiator(s) and 1-10 wt% other additives.

The printing ink monomers can be selected from the same types mentioned for the curable coating composition. Monomers may be selected from acrylate monomers. The monomer may be present in the printing ink in an amount of 30-60 wt%, such as 35-55 wt% or 40-50 wt%. The dyes and/or pigments of the printing ink can be selected from the same types mentioned for the curable coating composition. Dyes and/or pigments may be present in the printing ink in an amount of 10-35 wt%, such as 15-30 wt% or 20-25 wt%.

The printing ink prepolymer may be selected from diallyl phthalate prepolymers. The unsaturated prepolymer polymerizes upon initiation of cross-linking and is incorporated into the polymer network. The prepolymer may be present in the printing ink in an amount of 5-25 wt%, such as 10-20 wt% or 12-18 wt%.

The printing ink resin may be selected from polyester resins. The resin may be present in the printing ink in an amount of 1-15 wt%, such as 3-10 wt% or 5-8 wt%.

Initiators for printing inks may be selected from photoinitiators and thermal initiators. Preferably a mixture of photoinitiators is used, such as two or three different initiators. The initiator may be present in the printing ink in an amount of 1-10 wt%, such as 2-8 wt% or 4-7 wt%.

Printing ink additives may be selected from stabilizers, fillers and the like. The additive may be present in the printing ink in an amount of 1-10 wt%, such as 2-8 wt% or 4-6 wt%.

Another layer of the final product may be formed of an adhesive, preferably a pressure sensitive adhesive (PSA). Adhesives may include:
30-95 wt% copolymer(s),
0.5-15 wt% propylene glycol,
1-50 wt% solvent(s),
1-15 wt% silicon dioxide, and 10-50 wt% rosin.

The adhesive copolymer may be selected from vinyl acetate, ethylene and acrylate copolymers. The copolymer may be present in the adhesive in an amount of 30-95 wt%, such as 40-90 wt%, 45-85 wt%, 40-70 wt%, 40-65 wt% or 60-90 wt%.

Propylene glycol in the adhesive may be present in the adhesive in an amount of 0.5-15 wt%, such as 1-10 wt% or 2-8 wt%.

The adhesive solvent may be selected from water and hydrocarbon solvents such as mineral spirits type hydrocarbon solvents, for example D40 solvent. The solvent may be present in the adhesive in an amount of 1-50 wt%, such as 2-45 wt%. The amount of solvent present can vary with the type of solvent used. For example, if water is used, it may be present in an amount of 5-50 wt%, such as 10-45 wt%. If a hydrocarbon solvent is used, it may be present in an amount of 1-10 wt%, such as 1-5 wt% or 2-5 wt%.

The silicon dioxide of the adhesive may be present in the adhesive in an amount of 1-15 wt%, such as 1-10 wt% or 2-8 wt%. Silicon dioxide is used herein as a rheology modifier.

The adhesive rosin may be present in the adhesive in an amount of 10-50 wt%, such as 20-40 wt% or 25-35 wt%.

Alternatively, the adhesive can be a UV pressure sensitive permanent tack adhesive that can include:
20-65 wt% urethane acrylate(s), preferably aliphatic urethane acrylate(s),
1-30 wt% of alkyl acrylate(s), preferably 2-ethylhexyl acrylate,
1-30 wt% hydrogenated hydrocarbon resin(s),
1-15 wt% reactive monomer(s) diluent, preferably isobornyl acrylate 1-15 wt% vinylamide monomer(s), preferably vinylcaprolactam 1-15 wt% silica , preferably amorphous silica 0.1-5 wt% UV photoinitiator(s).

While various embodiments of the invention have been described and illustrated, the invention is not limited thereto and may be embodied in other ways within the scope of the subject matter defined in the following claims.

The examples described herein should not be considered as limiting the invention, but are described as optional embodiments thereof.

Example 1: UV offset/hybrid or screen printed decorative wall transfer.
To enable printing and to avoid accidental ink peeling, a 50 μm thick or 75 μm thick polyethylene terephthalate film or polyoxyethylene oxyterephthaloyl film carrier was coated with a polydimethylsiloxane matte containing a controlled release additive vinyl group. and the film was temperature stabilized and cured at a temperature of 140-150°C. Wall Transfer Full color halftone graphics were printed using the formulation at a thickness of between 1-2 μm onto a matte modified release coating. The plasticizers used are phthalate-free.

Formulation 1.0 - UV offset full color halftone printing ink:
Acrylic acid ester monomer 42 parts
^* Pigment 25 parts Diallyl phthalate prepolymer 15 parts Polyester resin 7 parts UV photoinitiator 6 parts Additive 5 parts
^* Cyan PB 15:2, Magenta PR 122, Yellow PY 12, Black 7
The multicolored printed sheet is partially UV-cured and tack-dry. A second white pigmented 12-15 μm film forming 1.3 layers was screen printed over the halftone graphic image.

Formulation 1.1 - Hybrid Offset Full Color Halftone Printing Inks:
In this example, a sheet-fed UV offset ink printed on a matte release sheet is replaced with a UV hybrid ink from TOKA, a Japanese ink company. Hybrid inks are intermediate between UV inks and conventional offset inks. Hybrid inks contain monomer/oligomer moieties in addition to conventional oil-based offset inks and, if selected, 1.3. Improved adhesion to white screen printed ink marks and transparent layer 1.4. The layers were individually heated to about 80-100° C. to swell the polymer particles with the plasticizer/monomer/oligomer composition and make them dry to the touch.

Formulation 1.2 - Screen Printable Sol-Gel Acrylate Full Color Halftone Curable Composition Containing Polymer Powder:
Optionally, the wall transfer full color halftone graphics can be screen printed at a thickness between 3-4 μm for improved mechanical strength and color density. The plasticizers used are phthalate-free.

Acrylate polymer powder 43 parts Plasticizer 32 parts Secondary plasticizer 7 parts
^* Full color pigment 6 parts Acrylate monomer 5 parts Urethane acrylate oligomer 3 parts Modified bentonite clay 2 parts Silicon dioxide 1 part UV photoinitiator 1 part
^* Cyan PB 15:2, Magenta PR 122, Yellow PY 12, Black 7
The printed carrier sheet was heated up to about 80-100° C. to swell the polymer particles with the plasticizer/monomer/oligomer composition and make them dry to the touch.

Formulation 1.3—Screen-printable sol-gel acrylate white curable composition with polymer powder:
Acrylate polymer powder 48 parts Plasticizer 25 parts White pigment PW2 ^* 12 parts Urethane acrylate oligomer 5 parts Secondary plasticizer 5 parts Acrylate monomer 4 parts UV photoinitiator 1 part
^* Rutile type titanium oxide (IV)
The printed carrier sheet was heated up to about 80-100° C. to swell the polymer particles with the plasticizer/monomer/oligomer composition and make them dry to the touch. Optionally, to enhance mechanical strength, a transparent sol-gel layer was prepared with the following formulation and subsequently printed over the marks.

Formulation 1.4—Printable Sol-Gel Acrylate Transparent Curable Composition Containing Polymer Powder:
Acrylate polymer powder 49 parts Plasticizer 31 parts Secondary plasticizer 7 parts Acrylate monomer 8 parts Amorphous fumed silica 2 parts Ca/Zn heat stabilizer 2 parts UV photoinitiator 1 part Depending on the plasticizer/monomer/oligomer composition The printed carrier sheet was heated up to about 80-100° C. to swell the polymer particles and make them dry to the touch. A pressure sensitive adhesive was prepared having the following formulation.

Formulation 1.5 - Medium Tacky Pressure Sensitive Adhesive:
Vinyl acetate, ethylene and acrylate copolymer 90 parts Monopropylene glycol 7 parts Solvent D40 2 parts Silicon dioxide 1 part Subsequently, a sheet containing a 7-10 μm pressure sensitive adhesive is printed and oven dried, after which the temperature is further increased. C. to about 140-150.degree. C. followed immediately by exposure to UV light to crosslink the sol-gel layer of the monomer/oligomer mixture containing the adhesive. A protective silicone coated liner paper was laminated to the adhesive side. Multilayer marks could be transferred to all types of materials, wall coverings and painted surfaces. The transferred marks exhibited excellent adhesion and dimensional stability, especially the edges of the marks remained well adhered without curling.

An example of a decorative wall decal is disclosed in FIG. To better understand the present multi-layer printed mark or stencil, the composition disclosed herein in Example 1 is described in FIG.

Disclosed in FIG. 1 are:
1. Glossy polyethylene terephthalate carrier foil 2 . 3. Matte polydimethylsiloxane release coating. ^* Full color and single color graphic layers Layer: Formulation, 1.0-1.1-1.2
4. White sol-gel: layer, formulation: 1.3
5. Transparent: sol-gel layer, formulation: 1.4
6. PSA layer formulation, 1.5
7. protective liner paper
^* Coating layers with different UV offset/hybrid and screen printing inks are disclosed.

Example 2: To enable weatherable sign transfer printing and to avoid accidental ink stripping, a 50 µm or 75 µm thick polyethylene terephthalate film or polyoxyethylene oxyterephthaloyl film carrier was treated with a controlled release additive. Treated with a glossy surface energy control release coating of polydimethylsiloxane containing vinyl groups, the film was temperature stabilized and cured at a temperature of 160-170°C. In the formulation below, the sol-gel photoinitiator is replaced with an organic peroxide that has an activation temperature of about 170°C. It may be preferred to use acrylate polymer powders in the formulation to improve outdoor weatherability and UV resistance. The plasticizers used are phthalate-free.

A clear 4-7 μm film-forming layer of the following formulation containing UV filters and stabilizers was screen printed.

Formulation 2.0—Screen-Printable Sol-Gel Acrylate Transparent Curable Composition Containing Polymer Powder:
Acrylate polymer powder 49 parts Plasticizer 26 parts Acrylate monomer 12 parts Secondary plasticizer 7 parts Peroxide 3 parts Ca/Zn heat stabilizer 2 parts Silicon dioxide 0.5 parts UV/UVA absorber 0.5 parts Plasticizer/ The layer was heated up to about 80-100° C. to swell the polymer particles with the monomer/oligomer composition and make them dry to the touch.

A pigmented 8-12 μm ink layer of the following formulation was screen printed.

Formulation 2.1 - Screen Printable Sol-Gel Acrylate Black Curable Composition Containing Polymer Powder:
Acrylate polymer powder 46 parts Plasticizer 25 parts Acrylate monomer 12 parts Secondary plasticizer 9 parts Carbon pigment ^* C.I. I. Black 7 4 parts Peroxide 3 parts Silicon dioxide 1 part
^* Optional Pigment Selection This sign transfer is marked with a low UV light penetrating color, e.g. There is a need for protective UV light absorbers that are pigmented and improve weatherability and UV resistance. Gelation of all sol-gel layers is required. For coloring herein, a limited depth of penetration of UV radiation into the filtered layer or opaque ink layer will be obtained. This leads to under-crosslinking in all layers. To avoid uncured material, organic peroxides with activation temperatures above 160° C. were introduced into the formulation. Curing of the individual sol-gel layers into a coherent film was carried out at 170°C to 180°C. Contains high tack water-based pressure sensitive adhesives or high solids UV adhesives of the following formulations.

Formulation 2.2 - High Tack Water Based Pressure Sensitive Adhesive:
40 parts water 38 parts vinyl acetate, ethylene and acrylates copolymer 15 parts rosin 6 parts solvent D40 1 part monopropylene glycol Alternatively, a UV permanent tack adhesive can be used:
Formulation 2.3 - UV Pressure Sensitive Permanent Tack Adhesive:
Aliphatic urethane acrylate 47 parts 2-ethylhexyl acrylate 20 parts Hydrogenated hydrocarbon resin 18 parts Isobornyl acrylate 7 parts Vinyl caprolactam 5 parts Amorphous silica 2 parts UV photoinitiator mixture 1 part Subsequent printing at 7-10 μm Print a sheet using a selected type of high tack pressure sensitive formulation 2.2 printed at 10-12 μm thickness or a UV permanent tack formulation 2.3 printed at a thickness of 10-12 μm to print the sheet, monomer/oligomer The temperature was further increased to about 160-170° C. to crosslink the sol-gel layer of the mixture, followed immediately by UV exposure to crosslink the UV adhesive. A protective silicone coated liner paper was laminated to the adhesive side. Multilayer decals could be transferred to all types of materials and objects.

FIG. 2 discloses an example of a weatherable sign transfer. To better understand the present multi-layer printed mark or stencil, the composition disclosed herein in Example 2 is described in FIG. Two different options for the PSA layer are disclosed in FIG.

Disclosed in FIG. 2 are:
1. Glossy polyethylene terephthalate carrier foil 2 . Polydimethylsiloxane release coating 3 . Transparent film-forming layer, formulation: 2.0
4. ^* Vector color image layer, formulation: 2.1
5. WB PSA layer, formulation: 2.2 (left side of Figure 2)
6. UV PSA layer, formulation: 2.3 (Figure 2 right)
7. protective liner paper
^* Screen printing, resistance to wool scale greater than 8.

Example 3: Release Decal Graphics A 50 μm thick or 75 μm thick polyethylene terephthalate film or polyoxyethylene oxyterephthaloyl film carrier is treated with a surface energy modified release coating of polydimethylsiloxane containing vinyl controlled release additives. bottom. The film was temperature stabilized and cured at a temperature of 160-170°C. Release decals were first printed using Pressure Sensitive Adhesive 3.0 and contained a white image printed with a clear 3.1 film forming ink followed by a 3.2 UV or hybrid 1.1 offset ink. Protective printed with full color and cover printed with 3.3 and 3D 3.4 sol gel varnish layers.

Pressure sensitive adhesives were prepared using the following formulations.

Formulation 3.0 - Repositionable Pressure Sensitive Adhesive:
Water 44 parts Vinyl acetate, ethylene and acrylate copolymer 46 parts Silicon dioxide grit 5 parts Silicon dioxide 2 parts Monopropylene glycol 3 parts A carrier sheet containing a 4-7 μm pressure sensitive adhesive is printed and dried at about 70-80°C. Oven dried. The following transparent film-forming layers of the following formulations were prepared. The plasticizers used are phthalate-free.

Formulation 3.1 - Screen Printable Sol-Gel Vinyl Transparent Curable Composition Containing Polymer Powder:
Vinyl polymer powder 60 parts Plasticizer 24 parts Acrylate monomer 6 parts Secondary plasticizer 4 parts Organic peroxide 3 parts Urethane acrylate oligomer 3 parts Ca/Zn heat stabilizer 2 parts heated. The polymer particles were swollen and tack-free by the plasticizer/monomer/oligomer composition and were prepared to be UV or hybrid offset printed over white or clear indicia of the following formulations.

Formulation 3.2 - UV Offset Full Color Halftone and White Printing Inks:
Acrylic acid ester monomer 42 parts
^* Pigment 25 parts Diallyl phthalate prepolymer 15 parts Polyester resin 7 parts UV photoinitiator mixture 6 parts Additive 5 parts
^* Cyan PB 15:2, Magenta PR 122, Yellow PY 12, Black 7, White PW 2
The printed UV offset or hybrid ink was cured and tack-dry. A sol-gel varnish layer was subsequently prepared with the following formulation. The plasticizers used are phthalate-free.

Formulation 3.3 - Screen Printable Sol-Gel Vinyl Clear Curable Varnish Composition Containing Polymer Powder:
Vinyl polymer powder 57 parts Plasticizer 14 parts Urethane acrylate oligomer 20 parts Secondary plasticizer 5 parts Ca/Zn stabilizer 2 parts Acrylate monomer 1 part UV photoinitiator mixture 1 part The printed sheet was heated up to about 100-110° C. to swell and dry to the touch. A second 3D sol-gel varnish layer was prepared having the following formulation. The plasticizers used are phthalate-free.

Formulation 3.4 - 3D Screen Printable Sol-Gel Vinyl Transparent Curable Varnish Composition Containing Polymer Powder:
Vinyl polymer powder 66 parts Plasticizer 15 parts Acrylate monomer 10 parts Secondary plasticizer 6 parts Ca/Zn stabilizer 2 parts UV photoinitiator mixture 1 part Heat the multi-layer decal to about 160-170°C immediately followed by The polymer and monomer/oligomer mixture sol-gel layers containing the adhesive were exposed to UV light to crosslink. Multilayer 3D imprint decals could be peeled off and adhered to all types of materials and surfaces. The decals exhibited good adhesion and dimensional stability without shrinkage.

An example of peel off decal graphics is disclosed in FIG. To better understand the present multi-layer printed mark or stencil, the composition disclosed herein in Example 3 is described in FIG.

Disclosed in FIG. 3 are:
1. Glossy polyethylene terephthalate carrier foil 2 . Polydimethylsiloxane release coating 3 . WB PSA layer, formulation: 3.0
4. Transparent film-forming layer, formulation: 3.1
5 ^* Single color/full color graphic layer, formulation: 3.2
6. Film forming layer, formulation: 3.3
7. Film-forming 3D layer, Formulation 3.4
^* UV offset or hybrid inks.

Example 4: Flexible stencil mask Glossy 50 μm thick or 75 μm thick polyethylene terephthalate film or polyoxyethylene oxyterephthaloyl film carrier coated with surface energy controlled release coating of polydimethylsiloxane containing controlled release additive vinyl group processed with The film was temperature stabilized and cured at a temperature of 160-170°C. A release stencil is printed first using a pressure sensitive adhesive, followed by one color mask and then one or more printed stencil masks, whereby the final printed mask is durable. become solvent-based. Pressure sensitive adhesives were prepared using the following formulations.

Formulation 4.0 - Repositionable Pressure Sensitive Adhesive:
Water 44 parts Vinyl acetate, ethylene and acrylate copolymer 43 parts Silicon dioxide grit 6 parts Silicon dioxide 4 parts Monopropylene glycol 3 parts A carrier sheet containing a 4-7 μm pressure sensitive adhesive is printed and dried at about 70-80°C. Oven dried. A colored stencil ink layer of the following formulation was prepared. The plasticizers used are phthalate-free.

Formulation 4.1 - Screen Printable Sol-Gel Vinyl Clear Color Curable Composition Containing Polymer Powder:
Vinyl polymer powder 65 parts Plasticizer 21 parts Secondary plasticizer 7 parts Acrylate monomer 3 parts Ca/Zn stabilizer 2 parts Red pigment PR 122 ^* 1 part UV photoinitiator mixture 1 part
^* Optional red pigment PR 122
The printed carrier sheet was heat gelled and dried to the touch. A second unpigmented 60-80 μm stencil mask of the following formulation was screen printed on top of the colored ink stencil layer. The plasticizers used are phthalate-free.

Formulation 4.2 - Screen printable sol-gel vinyl transparent curable composition containing polymer powder stencil mask:
Vinyl polymer powder 66 parts Plasticizer 23 parts Secondary plasticizer 5 parts Acrylate monomer 3 parts Ca/Zn stabilizer 2 parts UV photoinitiator mixture 1 part The printed carrier sheet was heat gelled and dried to the touch. A third unpigmented 60-80 μm rigid stencil mask of the following formulation was screen printed. The plasticizers used are phthalate-free.

Formulation 4.3 - Screen printable sol-gel vinyl hard curable composition containing polymer powder stencil mask:
Vinyl polymer powder 65 parts Plasticizer 18 parts Acrylate monomer 10 parts Secondary plasticizer 4 parts Ca/Zn stabilizer 2 parts UV photoinitiator mixture 1 part The multilayer stencil mask was heated to about 160-170°C. The multilayer stencil mask was then directly exposed to UV light to crosslink the sol-gel polymer and monomer mixture containing the adhesive. The stencil mask can be peeled from the carrier and applied to all types of materials and surfaces for decorative purposes, and the stencil exhibits dimensional stability, interlayer adhesion, and resistance to washing for repeated multiple reuse. It was solvent soluble.

An example of a flexible stencil mask is disclosed in FIG. To better understand the present multi-layer printed mark or stencil, the composition disclosed herein in Example 4 is described in FIG.

Disclosed in FIG. 4 are:
1. Glossy polyethylene terephthalate carrier foil 2 . Polydimethylsiloxane release coating 3 . Repositionable WB PSA Layer, Formulation: 4.0
4. Clear color layer, formulation: 4.1
5. Clear stencil mask, formulation: 4.2
6. Clear rigid stencil mask, formulation: 4.3
7. Stencil open design.

Example 5: Durable Stencil Mask A stencil multi-masking layer was printed using a temporary glass fiber PTFE carrier and removed after printing, gelling and cross-linking. This type of carrier is reused for the next production batch and a second option uses polyethylene terephthalate film treated with a surface energy modified release coating for smaller stencil sizes and a stencil mask. It supplies a sheet containing One color mask is then used to print the carrier using two or more printed stencil masks so that the final printed mask is durable and solvent resistant.

A clear color layer was prepared using the following formulation.

Formulation 5.0 - Screen Printable Sol-Gel Vinyl Clear Color Curable Composition Containing Polymer Powder:
Vinyl polymer powder 65 parts Plasticizer 21 parts Secondary plasticizer 7 parts Acrylate monomer 3 parts Ca/Zn stabilizer 2 parts Red pigment PR 122 ^* 1 part UV photoinitiator mixture 1 part
^* Optional red pigment PR 122
The printed carrier sheet was heat gelled and dried to the touch. A second unpigmented 60-80 μm stencil mask of the following formulation was screen printed on top of the colored ink stencil layer. The plasticizers used are phthalate-free.

Formulation 5.1 - Screen printable sol-gel vinyl hard curable composition containing polymer powder stencil mask:
Vinyl polymer powder 65 parts Plasticizer 21 parts Acrylate monomer 8 parts Secondary plasticizer 3 parts Ca/Zn stabilizer 2 parts UV photoinitiator mixture 1 part , dry to the touch. A third unpigmented 70-90 μm stencil mask was screen printed on top of the previous stencil layer of the following formulation. The plasticizers used are phthalate-free.

Formulation 5.2 - Screen printable sol-gel vinyl durable curable composition containing polymer powder stencil mask:
Vinyl polymer powder 60 parts Plasticizer 21 parts Acrylate monomer 9 parts Copolyester powder 5 parts Secondary plasticizer 2 parts Ca/Zn stabilizer 2 parts UV photoinitiator mixture 1 part Durable multi-layer stencil mask to about 160-170°C heated. The durable multilayer stencil mask was then directly exposed to UV light to crosslink the sol-gel polymer and monomer mixture. The stencil mask was removed from the carrier and packaged for distribution. Advantages compared to laser cut and die cut stencils are better copy reproduction offering finer detail and better flexibility, stencil masks can be used on all types of materials and surfaces for decorative purposes. Upon application, the stencils exhibited optimal dimensional stability, interlayer adhesion, and solvent resistance to withstand washing for repeated multiple reuses.

An example of a durable stencil mask is disclosed in FIG. To better understand the present multi-layer printed mark or stencil, the composition disclosed herein in Example 5 is described in FIG.

Disclosed in FIG. 5 are:
1. Glass fiber PTFE carrier foil 2 . Transparent color layer, formulation: 5.0
3. Transparent stencil mask, formulation: 5.1
4. Clear Permanent Stencil Mask, Formulation: 5.2
5. Stencil open design.

Claims (14)

forming a release coating on a substrate;
optionally forming a printed ink layer on said release coating;
Forming a coating of a curable composition comprising a polymer powder, at least one plasticizer and at least one monomer and/or oligomer on said substrate or a layer or coating previously applied thereon. ;
heating the coating film of the curable composition to a temperature of 70 to 120° C. to form a gel-like curable coating film;
optionally forming a printing ink layer on said gel-like curable coating ;
forming on said pre-applied layer or coating a coating of another curable composition comprising polymer powder, at least one plasticizer and at least one monomer and/or oligomer;
heating the coating of said another curable composition to a temperature of 70-120° C. to form a second gel-like curable coating;
the release coating on the substrate, any printed ink layer thereon, the gel-like curable composition, any printed ink layer on the gel-like curable coating, before crosslinking is performed; and heating the second gel-like curable coating forming a multilayer coated substrate to a temperature of 130-160° C .; cross-linking by exposure to heat at a temperature of ~190°C ;
including
Optionally, a pressure sensitive adhesive composition coating is applied to said release coating on said substrate before another coating is applied, or if more than one is present Provided on the gel-like curable coating film last formed in
A method for producing a multilayer print mark or stencil. The method of claim 1, wherein said substrate has a surface tension within the range of 5-45 Dyne/cm . A further polymer powder coating comprising a curable coating composition that is heated to a temperature of 70-120° C. to form a third gel-like curable coating before cross-linking is performed. 3. The method of claim 1 or 2, wherein the second gel-like curable coating comprises . The curable composition(s) comprises
30-75 wt% polymer powder,
5-50 wt% plasticizer,
1-40 wt% of monomers and/or oligomers,
A method according to any one of claims 1 to 3, comprising 0.5-5 wt% initiator. 5. The method of any one of claims 1-4, wherein the polymer powder comprises an acrylate polymer and/or a vinyl polymer . 6. The method of any one of claims 1-5, wherein the plasticizer is phthalate- free . 7. A method according to any one of claims 1 to 6, wherein said monomers and/or oligomers are selected from acrylate monomers and acrylate oligomers respectively. wherein said initiator is selected from a photoinitiator and a thermal initiator, claim 4 , claim 4 depending on claim 4, claim 6 depending on claim 4; Claim 4 quoted through claim 4, Claim 4 quoted through claim 7, Claim 6 quoted from claim 4, and Claim 4 quoted through claim 5 Claim 4 depending on claim 7 and claim 5, claim 4 depending on claim 7 and claim 6 depending on claim 4, or claim 4 depending on 5. A method as claimed in any one of claims 4 to 4, recited through claims 7-5 . The curable composition(s) comprises
0.5-20 wt% of dyes and/or pigments,
A method according to any one of claims 4 to 8, further comprising 0.5-5 wt% stabilizer and 0.5-5 wt% filler. said dyes and/or pigments are selected from the group consisting of titanium oxide, red iron oxide, iron black and carbon black;
said stabilizer is selected from the group consisting of metal-containing stabilizers; and said filler is clay, calcium carbonate, magnesium carbonate, titanium oxide, barium sulfate, zinc white, silicic acid, mica powder talc, silica, diatomaceous earth selected from the group consisting of glass powder, graphite powder, alumina, metal powder and talc;
and any combination thereof. When the pressure-sensitive adhesive composition coating film is provided on the finally formed gel-like curable coating film , the pressure-sensitive adhesive composition coating film has a protective substrate after the crosslinking . A method according to any one of claims 1 to 10 provided. The pressure sensitive adhesive composition is
30-95 wt% copolymer(s),
0.5-15 wt% propylene glycol,
1-50 wt% solvent(s),
1-15 wt% silicon dioxide, and 10-50 wt% rosin,
or 20-65 wt% urethane acrylate(s),
1-30 wt% alkyl acrylate (s),
1-30 wt% hydrogenated hydrocarbon resin(s),
1-15 wt% reactive monomer(s) diluent
1-15 wt% vinylamide monomer (s)
1-15 wt% silica
12. The method of any one of claims 1 to 11, comprising 0.1-5 wt% UV photoinitiator(s). The method according to any one of claims 1 to 12, wherein said heating to form a gel-like curable coating is carried out for a period of 10 seconds to 2 minutes . A method according to any one of the preceding claims, wherein said cross-linking of said gel-like curable coating (s) is carried out for a period of 10 seconds to 2 minutes .

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