KR100322459B1 - Transcription Printing Media - Google Patents

Abstract

A transfer printing medium that includes a carrier to which is applied a curable laser-transferrable ink having one or more layers. The transfer medium is capable of converting laser energy to heat. The ink includes: (a) at least one colorant; (b) at least one polymerization initiator; and (c) at least one curable prepolymer.

Description

Transcription printing media

Background of the Invention

The present invention relates to laser-induced transfer printing.

In laser-induced transfer printing, irradiating an ink-containing carrier with laser light transfers ink from the carrier to a surface, such as the surface of a microelectronic device, audio cassette, computer diskette, or syringe body. By manipulating the scanning parameters of the laser beam, the ink can be deposited (transcribed) in a programmed pattern.

Summary of the Invention

In a first form, the invention features a transfer printing medium comprising a carrier to which a curable laser transfer ink having one or more layers thereon is applied. The transfer medium can convert laser energy into heat. The ink may comprise (a) at least one colorant; (b) at least one polymerization initiator; And (c) at least one curable prepolymer. "Colorant" means any additive that imposes on the ink a color comprising white and black.

Colorants include dyes and pigment protons as well as metal coils. "Prepolymer" means all species that can be polymerized following a thermal or photochemical initiator to form a polymer.

In a preferred embodiment, the ink of the present invention is cured at once by transferring to the surface and applying laser energy. In one preferred embodiment at least one polymerization initiator is a thermal polymerization initiator and at least one prepolymer is thermoset. In another preferred embodiment, at least one polymerization initiator is a photoinitiator and at least one prepolymer is photochemically curable.

One example of a preferred prepolymer is an epoxy-functionalized prepolymer. A second example is an epoxy functionalized prepolymer combined with a vinyl ether functionalized prepolymer. A third example is an epoxy-functionalized prepolymer combined with an acrylate-functionalized prepolymer. A fourth example includes the acrylic-functionalized prepolymer itself. The fifth example is a blocked isocyanate-functionalized prepolymer and the sixth example is a mixture of vinyl ether-functionalized prepolymer and maleic acid- or maleimide-functionalized prepolymer.

The at least one ink layer can be a curable size coat comprising a polymerization initiator and a curable prepolymer. The size coat (surface layer) is used with the color coat layer. In a preferred configuration, the color coat (layer) is non-curable and comprises a colorant and a thermoplastic film-forming resin. In another preferred configuration, the colorcoat is curable and includes a colorant, a polymerization initiator, and a curable prepolymer. In the case of curable colorcoats used with curable size coats, the polymerization initiators and prepolymers found in each layer may be the same or different from each other.

In a second aspect, the invention features a laser-induced transfer printing method using the transfer printing medium described above. The method includes irradiating a specific transfer print medium with a laser light of a predetermined wavelength to transfer the ink from the carrier to the object surface, and curing the ink to adhere the ink to the object surface. Transfer and curing of the ink can be performed at once by irradiating the laser light. Curing may be performed in a separate process following transfer.

The present invention provides a transfer printing medium characterized by curable ink that adheres well to the surface to be deposited following laser irradiation. The ink is transferred cleanly from the support carrier (carrier) and cured quickly; In some cases, transfer and curing takes place at one time. There is no need to add a separate self-oxidizing agent, such as nitrocellulose, to effect transcription. In addition, the ability to use a non-curable layer (e.g. a non-curable color coat (layer)) in combination with a curable layer (e.g., a curable size coat) has a bearing on the type of material that can be used as the ink. In turn, the properties of the ink are adapted to the application in the particular field.

Other features and advantages of the invention will be apparent from the following preferred embodiments and claims.

Description of the Preferred Embodiments

The present invention is characterized in that a curable laser-transcribed ink having at least one layer is a transfer print medium capable of being deposited on a carrier to convert laser energy into heat. The carrier must have a surface energy low enough for the ink to be transferred. In addition, the carrier must not melt or otherwise deform upon laser irradiation. Examples of suitable carriers include stretchable plastic films such as polyethylene, polypropylene and polyester.

The transfer medium can convert laser energy into heat to promote the transfer of ink from the carrier to the surface of interest. At least one thermal transducer is in turn bound to a carrier, ink or each. The thermal converter can be part of a separate additive or prepolymer.

For separately added converters included in the ink, the amount of converter is from about 0.25% to about 30% by weight (based on the total solids of the ink). The specific converter is selected based on the specific laser energy used for the irradiation. In the case of CO ₂ lasers, preferred variants include carbon black, polyethylene glycol (e.g., commercially available PEG3000 from Union Carbide), talc (e.g., Nytal400, commercially available from RT van der Wilt), and Idemichu Petrochemical. Commonly used phosphotriazine PPZ; PPZ also acts as a prepolymer. In the case of Nd: YAG lasers, preferred converters are the commercial dyes of Glendal Protective Technology, exclusive dyes IR99, IRA980, and IR165. IR dyes 14,617 (exclusive dyes from Eastman Kodak) The commercial product is Project900NP, a proprietary dye. For diode lasers, the preferred converters are IR dyes 14,617 and IR980.

The ink may have at least one layer, of which layers have certain components (eg, polypolymer, polymerization initiator, etc.) in a layer. One example of an ink is a single layer ink (called a "one-pass" coating) having a curable color coat containing a curable prepolymer, a polymerization initiator and a colorant in a single layer. Another example is a two layer ink (" two-pass " coating) having a color layer (which can be curable or non-curable) that binds on a curable surface cost comprising a curable prepolymer and a polymerization initiator. This is called.

Since the ink is curable, transfer adhesiveness to the surface is enhanced. The advantage of the sige coat (the color layer is transferred by laser irradiation) is that the adhesion is also enhanced, making even the non-curable color layer usable.

The ink comprises at least one curable prepolymer, and the total amount of the curable polypolymer is 25 to 95% by weight (based on the total solids of the ink). Curable prepolymers useful in the present invention have at least two functional groups that are useful for crosslinking (whereby the transfer takes place simultaneously by providing the next laser irradiation or laser radiation in a separate thermal or photochemical curing step).

One class of suitable curable prepolymers is epoxy-functionalized prepolymers such as epoxy functionalized novolac resins (e.g., Shell Oil's commercial Epon 164) and bisphenol A diglycidyl ether (Epon 1001's commercial products of Shell Oil). It includes. Low molecular epoxides, such as UVR6100 (liquid diepoxide, commercially available from Union Carbice Inc.) may also be added.

A second class of suitable curable prepolymers includes epoxy functionalized prepolymers that bind with at least one vinylether-functionalized prepolymer that is cured with the epoxy-functionalized prepolymer. Examples of suitable vinyl ether-functionalized prepolymers include bisphenol A-divinyl ether adducts; 2,4-toluene diisocyanate / hydroxybuyl vinyl ether adduct; Commercially available cyclohexyl divinyl ethers from CAF or ISI Product; Vinyl ethyl ether, vinyl isobutyl ether, vinyl octadecyl ether, polyethyleneglycol divinyl ether, polytetrahydrofuran / 350 / divinyl ether, and trimethylol propane trivinyl ether, which are commercially available from BASF; And vectormeters 2010, 2031, 2032, 4010, 4020, and 4030 commercially available from Alid-Signal.

A third class of suitable curable prepolymers includes the above-described epoxy-functionalized prepolymers that combine with at least one acrylate functional prepolymer. Examples of acrylate-functionalized prepolymers include RDX29522 and Ebecryl 639 (commercially available from Radcure Inc.); Sartomer 351 (commercially available from Sartomer); And NR440 (commercially available from Genca Resin).

The fourth class of suitable curable prepolymers includes the acrylate-functionalized prepolymers themselves without epoxy-functionalized prepolymers.

The fifth class of suitable curable prepolymers includes blocked isocyanate-functionalized prepolymers. Examples include B1299 (commercially available from Horses) and BL4165A (commercially available from Miles).

The sixth class of suitable curable prepolymers includes the aforementioned vinyl ether-functionalized prepolymers that bind with maleic acid- or maleimide-functionalized prepolymers. Examples of maleic acid-functionalized prepolymers include 89-8902 (commercially available from Cargill Products); And Astrocure 78HV and Astrocure 78LV (commercially available from Zircon, respectively). Maleimide-functionalized prepolymers include BMI / S / M / 20 / TDA (commercially available from Mitsui Toarts Chemicals).

At least one non-curable layer may be used in combination with at least one curable layer. For example, the non-curable color layer can be combined to overlap with the curable surface layer. Suitable non-curable resins are thermosetting film-forming resins. Examples include acrylic resins such as Loflex B85 (acrylic dispersant from Rohm & Haas) and Alsco 3011 (acrylic dispersant from Rohm &Haas); Urethane resins such as QW-16 (K, J, Quinsa's commercially available film dispersant); Phenoxy resins such as PKHW35 (commercially available from Union Carbite); And combinations thereof. The amount of non-curable prepolymer in the ink is about 15 to 35% by weight (relative to the total solids of the ink).

The ink also contains about 0.1 to 5 weight percent (based on the total solids of the ink) of the polymerization initiator. Initiators (stock free groups or cationic initiators) can be photochemical or thermal initiators; In some cases, the same initiator can act as a thermal and photochemical initiator, respectively. In a multilayer ink comprising a plurality of cured layers, the layer comprising the photochemical initiator can be combined with the layer comprising the thermal initiator. Some initiators may also be used in combination with accelerators such as benzpinacol, copper II salts (eg copper benzoate).

In the case of thermal initiators, there must be good stability at ambient temperature to prevent precure of the prepolymer. In addition, the initiator temperature should be within the range obtained by laser irradiation. Examples of suitable thermal initiators for anionic initiators include arylsulfonium salts (for example salts described by WO90 / 11303, which are incorporated herein by reference); Aryl iodonium salts (e.g., UVE9310 and U479 which are commercially available from General Electric); And ammonium salts (eg, Commercial FC 520 from 3M).

Examples of suitable thermal initiators for free group initiators include the class of compounds which induce peroxy groups such as, for example, hydroperoxides, peroxy esters and peroxyketals; Each compound is a commercial item of Elf-Atochem.

Suitable free radical initiators are also Wako's commercially available azo polymerization initiators.

In the case of photochemical initiators, the initiator should have good stability of ambient temperature to prevent precure of the prepolymer. In addition, the initiator should exhibit a maximum absorption in the region of the electromagnetic field different from the region where the colorant exhibits the maximum absorption.

Examples of suitable photochemical initiators for cation initiation include aryl sulfonium salts (e.g. commercial UVI 6974 from Union Carbide) and aryl iodonium salts (e.g. UVE9310 and U 479 from General Electric).

Another example of a suitable initiator for the cationic initiator is hydroxy naphthylimide sulfonate ester. Examples of suitable photochemical initiators for free phase initiation include CPTX and ITX (commercially available from Siva-Geigy Corporation, respectively),

Each is combined with methyl diethanolamine (commercially available from Aldrich Chemical); Lucerine TPO (commercially available from BASF) in combination with diethanolamine; Darcure 4265 (commercially available from Ciba-Geigy Company), and Irugacure 369 in combination with ITX.

The ink may comprise at least one colorant, which may be a dye, a pigment, or a metal coating (eg an aluminized coating). In the case of dyes and pigments, the colorant is present in an amount of about 35 to 65% by weight (based on the total solids of the ink). The particular colorant is chosen according to the desired color on the final printed surface. Examples of suitable colorants include talc, TiO ₂ (white), phthaloline (GT-674-D), chrome green oxide (6099), ultramarine blue (RS-9), black oxide (BK-5099D), Pigments such as Chromared 7097, and Nova Firm Yarrow (HR-70), and dyes such as dynonicidine 2915 and Diannel Orange, as well as the metal platings described above.

In the case of ink-containing photocurable prepolymers, about 0.5 to 8% by weight (sensitizer of ink) can be added to widen the photoinitiated irradiation wavelength to the visible area. Such photosensitizers are useful, for example, in schemes involving large amounts of TiO ₂ pigments that absorb light up to 400 nm and compete with the initiator. Examples of suitable photosensitizers, all of which are commercially available products of Aldrich Caical, include perylene, rubrene, phenothiazine, anthracene derivatives and thioxanthones, as well as lucerin TPO ( Commercially available from BASF.

Other additives that may be added to the ink to enhance coatability, printability, printability, and durability of the ink include various surfactants, dispersants, and polymer dispersants. The amount of each additive is selected based on the desired properties. Examples of suitable surfactants (which may be anions, cations or nonions :) include Triton X-100 (commercially available aryl ethoxylates from Rohm & Haas) and FC430 (commercially available fluoro aromatic polymeric esters from 3M) (fluoroaliphatic polymeric ester)). Examples of suitable dispersants include polyacrylate salts such as Daxad30, a 30% aqueous solution of polysodium acrylate commercialized by W.R.Grace. Examples of suitable dispersants include Shamrock 375 and Aquacer 355, both commercially available polyethylene wax dispersants from Diamond Shamrock.

The transfer medium according to the present invention is provided by adding an ink raw material to a water-soluble or organic solvent (preferably an aqueous solvent) and applying the obtained composition to a carrier. If a surface coating is used, a surface coating is applied to the surface of the color layer.

To facilitate coating, the total solids of the ink are adjusted to be 10-50% by weight of the ink. The coated carrier is irradiated with a laser light (e.g., filed simultaneously with this application and assigned by Frank A. Meneghini, et al., To U.S. Application No. 08 / 565,417, incorporated herein by reference. The ink is transferred from the carrier to the desired surface, for example the surface of the semiconductor element. Suitable lasers include CO ₂ lasers (irradiation wavelength is 10.6 mu m), Nd: YGA lasers (irradiation wavelength is 1.06 mu m) and diode lasers (irradiation wavelength is 0.9 mu m, for example). The specific irradiation wavelength, power and time of the applied parameter is chosen to ensure clean transfer.

For some inks, the ink is simultaneously transferred and cured at the same time upon laser irradiation. In other inks, separate thermal or photochemical curing is performed following transfer. Curing conditions are selected depending on the particular prepolymer and initiator used in the reaction.

The invention will now also be described by the following examples.

Example 1

This embodiment is a one-pass; A method for producing a transfer medium having thermosetting, cation initiation, and ink is described.

The following additives are combined to form a laser-transferable ink (all amounts in weight percent):

1. Water-soluble dispersant of bisphenol A-epichlorohydrin as an additive from Rhone-Poulene.

Polyethylene glycol (Mn = 3000), a commercial product of 2- Union Carbide.

3. An aryl sulfonium salt thermal initiator of the type described in WO90 / 11303.

4. Commercialized surfactants from Rohm & Haas.

Water is added to adjust the total solids to 35% by weight, and the resulting ink is then coated onto a 1.2 mil thick polypropylene carrier film using a # mayer rod. The coated film surface is placed in direct contact with the surface of the molded semiconductor device. The CO ₂ laser is then irradiated through the uncoated side of the carrier film to cause the ink to be transferred to the surface of the semiconductor device. The laser stops at the specified pixel for 16μsec. At the point of contact with the coated film the laser power is 14.5 W.

The device with the transferred image is placed in a hot air oven at 170 ° C. for 30 minutes to cure the ink. After hardening, the transferred images were found to withstand 1, 1, 1-trichloroethane treatment (3 min immersion, 10 brush strokes, 3 cycles).

Example 2

This embodiment describes a method for producing a transfer medium in which the color layer and the surface layer each have a two-pass, cationic starting ink that is photochemically curable.

The following components are combined to form a photochemically curable color layer (all amounts in weight percent);

1. Hydroxy Butyl Divinyl Ether Additive.

2. A commercially prepared pre-made urethane dispersant from K. J. Quinn.

3. Idemitsu Petrochemicals Co. Ltd. merchandise.

4. Commercialized surfactants from Rohm & Haas.

5. Triaryl sulfonium salts based on commercially available initiators of Union Carbide.

Water is added to adjust the total solids to 35% by weight, and the resulting color layer is then applied to a 1.2 mil thick polypropylene carrier film using # 13 Mayor rods.

The following components are combined to form a photochemically curable surface layer (all amounts in weight percent):

1.Commercialized bisphenol A diglycidyl ether of Shell Oil Co.

2. Commercially available liquid diepoxide from Union Carbide.

3. A commercially available fluoroarific polymeric ester of 3M Co.

4. Triaryl sulfonium salts based on commercially available initiators of Union Carbide.

5. Commercially available photosensitizers from Aldrich Chemical Co.

6. Merchandise of Idemitsu Petrochemicals Co.

Methyl ethyl ketone was added to adjust the total solids of the surface layer to 25% by weight, and the resulting surface layer was applied to the top surface of the color layer using # 5 Meyer Rod.

The coating surface of the film was placed in intimate contact with the surface of the molded semiconductor device. The CO 2 laser was then irradiated through the uncoated side of the carrier film to transfer the ink (the surface layer added to the color layer) onto the surface of the semiconductor device. The laser was irradiated at each designated pixel for 20 mu sec. At the point of contact with the coated film the output power of the laser was 14.5 W. The device with the transferred image was then cured (UV radiation for 3.6 seconds after preheating at 150 ° C. for 5 minutes). The resulting cured print image was found to be resistant to 1,1,1-trichloroethane treatment (immersion for 3 minutes, 10 brush strokes, 3 cycles).

Example 3

This embodiment describes a method for producing a transfer medium having a two-pass, cationic curable ink in which the color layer is non-curable and the surface layer is thermoset.

The following components were combined to form a non-curable color layer (all amounts are in weight percent);

1. W.R. Grace commercially available polyacrylate dispersant.

2. Commercialized surfactants from Rohm & Haas.

3. Commercially available polyethylene wax dispersant from Diamond Shamrock.

4. Commercialized acrylic dispersant from Rohm & Haas.

5. Commercialized acrylic dispersant from Rohm & Haas.

Sufficient ammonium hydroxide was added to adjust the pH to 8.5 and then the final color layer was applied to a 1.2 mil thick polypropylene carrier film with a layer weight of 69 mg / m 2.

The following components were combined to form a photochemically curable surface layer (all amounts are in weight percent):

1. Shell Oil Co. Commercially available bisphenol A diglycidyl ether.

2. Commercially available liquid diepoxide from Union Carbide.

3. 3M Co. Commercially available fluoroaripatic polymer ester surfactants.

4. A commercially available iodonium salt thermal initiator from General Electric.

5. Commercially available dyes from Glendale Protective Technologies.

6. A commercially available promoter of Aldrich Chemical Co ..

Methyl ethyl ketone was added to adjust the total solids of the surface layer to 25% by weight, and then the added surface layer was applied to the surface of the color layer using # 5 Mayer rod.

The coated surface of the film was placed in intimate contact with the surface of the molded semiconductor device. Subsequently, an Nd: YAG laser was irradiated to the uncoated side of the carrier film to transfer the ink (the surface layer added to the color layer) to the surface of the semiconductor device. The laser was irradiated to each designated pixel for 18 mu sec. The "laser output power was 4.5 W at the point of contact with the coating film. The device with the transfer image was then cured (4 minutes at 175 ° C). The final cured printed image was 1,1,1-trichloroethane. The treatment was found to be resistant (3 min immersion, 10 blows, 3 cycles).

Example 4

This embodiment describes a method for producing a transfer medium having a one-pass, thermosetting, cation initiated ink in which transfer and curing occur at one time upon laser irradiation.

The following ingredients were combined to form a laser-transferable ink (all amounts in weight percent):

1. R.T. Commercialized Nytal 400 by Vanderbilt

2. Commercialized light and thermal initiators from General Electric

3. Aldrich Chemical Co. Commercially available accelerators.

4. Epoxy noblock resin with commercial epoxy equivalent 200-240 from Shell Oil.

5. Commercialized cyclohexyl divinyl ether from GAF or ISI Products.

Methyl ethyl ketone was added to adjust the total solids to 50% by weight, and the resulting ink was coated onto a 1.2 mil thick polypropylene carrier film top using 10 Mayer rods.

The coating surface of the film was placed in intimate contact with the glass slide. The CO ₂ laser was then irradiated through the uncoated side of the carrier film to transfer the ink to the surface of the glass slide. The laser was irradiated at each designated pixel for 80 μsec. Next, the transferred coating layer was removed to form a glass slide and analyzed by differential scanning calorimetry. There was no trace of reaction residual heat, indicating that the transfer coating cured during the transfer process.

Example 5

This embodiment is a two-pass wherein the color layer and the surface layer are photocurable. A method of making a transfer medium having free-initiated inks is described.

The following components were combined to form a photocurable color layer (all amounts are in weight percent);

1. Commercialized polyethylene wax dispersant from Diamond Shamrock.

2. Commercially available acrylate-functional prepolymer from Zeneca Resins.

3. Merchandise of Idemitsu Petrochemicals Co.

4. Commercialized surfactants from Rohm & Haas.

5. Commercially available photochemical free group initiator from Ciba Geigy.

Water was added to adjust the total solids to 40% by weight and then the final color layer was applied to a 1.2 mil thick polypropylene carrier film using # 13 Meyer Rod.

The following components were combined to form a photochemically curable surface layer (all amounts are in weight percent):

1. Commercially available acrylate-functionalized prepolymer from Zeneca Resins.

2. A commercially available acrylate-functionalized prepolymer from Radcure,

3. Commercially available photochemical free group initiator from Ciba Geigy.

Water was added to adjust the total solids of the surface layer to 40% by weight, and the resulting surface layer was applied to the top surface of the color layer using # 5 Meyer Rod.

The coating surface of the film was placed in intimate contact with the surface of the molded semiconductor device. The CO ₂ laser was then irradiated through the uncoated side of the carrier film to transfer the ink (the surface layer added to the color layer) to the surface of the semiconductor device. The laser was irradiated at each designated pixel for 20 μsec. At the point of contact with the coated film the output power of the laser was 14.5 W. The device with the transferred image was then cured (after preheating at 100 ° C. for 5 minutes, passing through a UV fusion oven installed with an H bulb at a rate of 100 in./min). The print image obtained was found to be resistant to 1,1.1-trichloroethane treatment (immersion for 3 minutes, 3 cycles of 10 brush strikes), other configurations are within the following claims.

Claims (23)

A transfer printing medium comprising a carrier to which a curable laser-transferable ink having at least one layer is applied, wherein the ink is (a) at least one colorant; (b) at least one polymerization initiator; And (c) at least one curable prepolymer, said transfer medium being capable of converting laser energy into heat. The transfer printing medium according to claim 1, wherein the ink is transferred onto a target surface and cured at once upon providing laser energy. The transfer printing medium of claim 1, wherein the at least one polymerization initiator comprises a thermal polymerization initiator and the at least one prepolymer is thermosetting. The transfer printing medium of claim 1, wherein at least one polymerization initiator comprises a photoinitiator and the at least one prepolymer is photochemically curable. The transfer printing medium of claim 1, wherein at least one of said prepolymers comprises an epoxy-functionalized prepolymer. The transfer printing medium of claim 5, wherein the prepolymer also comprises a vinylether-functionalized prepolymer. The transfer printing medium of claim 5, wherein the prepolymer also comprises an acrylate-functionalized prepolymer. The method of claim 1, wherein at least one of said prepolymers comprises an acrylate-functionalized prepolymer. The transfer printing medium of claim 1, wherein the at least one prepolymer comprises a blocked isocyanate-functionalized prepolymer. The transferprinting medium of claim 1, wherein the prepolymer comprises a mixture of vinyl ether-functionalized prepolymer and maleate- or maleimide-functionalized prepolymer. 12. The transfer print medium of claim 11 wherein at least one layer of the ink is a curable size coat comprising a curable prepolymer and a polymerization initiator. The transfer printing medium of claim 1 wherein at least one of said ink layers is a curable size coat comprising a polymerization initiator and a curable prepolymer and at least one of said ink layers is a non-curable color comprising a colorant and a thermoplastic film-forming resin. It is a floor. The transfer printing medium of claim 1, wherein at least one of the ink layers is a size coat comprising a polymerization initiator and a curable prepolymer and at least one of the ink layers is a curable color layer comprising a colorant, a polymerization initiator, and a curable prepolymer. (size coat). (a) providing a transfer printing medium comprising a carrier for providing a curable laser-transcribed ink having at least one layer and capable of converting laser energy into heat, wherein the ink comprises (i) at least one colorant; (ii) at least one polymerization initiator; And (iii) at least one curable prepolymer; (b) irradiating a laser light of a wavelength set on the medium to transfer the ink to a corresponding surface; And (c) curing the ink to adhere the ink to a corresponding surface. The method of claim 14, wherein the transfer and curing of the ink is performed in a single step by irradiating the laser light. The method of claim 14, wherein at least one of the at least one polymerization initiator comprises a thermal polymerization initiator and at least one of the at least one of the prepolymers is heat curable. The method of claim 14 wherein at least one of the polymerization initiators comprises a photoinitiator and at least one of the polypolymers is photochemically curable. The method of claim 14 wherein at least one of the ink layers is a curable surface layer comprising a polymerization initiator and a curable prepolymer. The method of claim 14 wherein at least one of the ink layers is a curable size coat comprising a polymerization initiator and a curable prepolymer and at least one of the ink layers is a non-curable color layer comprising a colorant and a thermoplastic film-forming resin. To be. The method of claim 14 wherein at least one of the ink layers is a curable surface layer comprising a polymerization initiator and a curable prepolymer and at least one of the layers of the ink is a curable color layer comprising a colorant, a polymerization initiator, and a curable prepolymer. To be. The method of claim 14 wherein the transfer and curing of the ink is performed in a single process through the laser light irradiation. The method of claim 14 wherein the transfer and curing of the ink is carried out in a separate process. (a) providing a transfer print medium comprising a carrier to which a curable laser-transferable ink is applied and capable of converting laser energy into heat; And (b) irradiating the medium with laser light of a set wavelength, wherein the laser light hardens the ink to transfer the ink to the surface and adhere the ink to the surface. .