JPH07232480A - Transfer printing medium - Google Patents

Abstract

PURPOSE: To provide a transfer printing medium used for laser guided transfer printing and a method therefor. CONSTITUTION: The transfer printing medium that has a carrier to which is applied a curable laser-transferable ink having one or more layers. The medium is capable of converting laser energy to heat. The ink contains (a) at least one colorant, (b) at least one polymerization initiator, and (c) at least one curable prepolymer. Accordingly, types of materials capable of being used for the ink can be increased, and characteristics of the ink to be prepared to need specific application can be validated.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to laser induced transfer printing.

[0002]

2. Description of the Related Art In laser-induced transfer printing, by irradiating a carrier carrying ink with laser light, the ink is ejected from the carrier, for example, on a surface of a microelectronic device, an audio cassette, a computer diskette, or a syringe body. Etc. can be transferred to the surface. By manipulating the operating parameters of the laser beam, the ink can be arranged in a programmed pattern.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a transfer printing medium used in laser induced transfer printing and a method thereof.

[0004]

In a first aspect of the invention, the transfer print medium comprises a carrier provided with one or more layers of curable laser transfer ink. This transfer medium has the ability to convert laser energy into heat. The ink comprises (a) at least one colorant, (b) at least one polymerization initiator, and (c) at least one curable prepolymer. By "colorant" is meant an additive that imparts color, including colors, white and black, to the ink. Colorants also include dyes and pigments, and also metallized coatings. "Prepolymer" refers to anything that can be polymerized by thermal or photochemical initiation to form a polymer.

In the preferred embodiment, the application of laser energy causes the ink to transfer to the surface of interest and solidify in one step. In one of the preferred embodiments, at least one polymerization initiator is a thermopolymerization initiator and at least one of the prepolymers is thermosetting. In another preferred embodiment, at least one of the polymerization initiators is a photopolymerization initiator and at least one of the prepolymers is photochemically curable.

The first of the preferred prepolymers is an epoxy functionalized prepolymer. The 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. The fourth example is the acrylate functionalized prepolymer itself. The fifth example is a blocked isocyanate functionalized prepolymer and the sixth example is a mixture of a vinyl ether functionalized prepolymer and a maleate functionalized prepolymer or a maleinimide functionalized prepolymer.

At least one of the ink layers is a curable size coat, which contains a polymerization initiator and a curable prepolymer. This size coat is used in combination with the color coat layer. In one of the preferred embodiments, the color coat is non-curable and contains a colorant and a thermoplastic film forming resin. In another preferred embodiment, the color coat is curable and comprises a colorant, a polymerization initiator and a curable prepolymer. In the case of the curable color coat used with the curable size coat, the polymerization initiator and the prepolymer in each layer may be the same as or different from each other.

A second feature of the invention is laser-induced transfer printing using the transfer printing medium. This method includes the steps of irradiating the transfer printing medium with laser light having a predetermined wavelength to transfer the ink from the carrier to the target surface, and curing the ink to adhere the ink to the target surface. The transfer and curing of the ink may be performed in a single step by irradiation with the laser light. Curing may be performed in a separate step following transfer.

The present invention provides a transfer print medium featuring a curable ink that adheres well to the surface to be deposited after laser irradiation. The ink transfers cleanly from its holding carrier and cures quickly, in some cases transfer and curing occur in a single step. It is not necessary to add a separate auto-oxidizing material such as nitrocellulose to effect the transfer.
Also, the ability to use a non-curable layer (e.g., non-curable color coat) in combination with a curable layer (e.g., curable size coat) expands the types of materials that can be used in the ink, and The properties of the ink to be adjusted as required for the application can be enabled.

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

[0011]

Embodiments of the present invention will be described below in detail with reference to the drawings. The present invention features a transfer print medium in which one or more layers of curable laser transferable ink are deposited on a carrier and capable of converting laser energy to heat. The carrier must have a sufficiently low surface energy to allow transfer of the ink. It must not melt or deform during laser irradiation. Examples of suitable carriers are flexible plastic films, polyethylene,
Examples include polypropylene and polyester.

The transfer medium can convert the laser energy into heat and facilitate the transfer of ink from the carrier to the target surface. To this end, one or more heat exchange materials are used in the carrier, the ink, or both. The heat exchange material may be part of a separate additive or prepolymer. When the replacement material is added to the ink separately, the amount of replacement material ranges from about 0.25 to 30% by weight (based on total solids of the ink). The exchange material is selected based on the laser energy applied. For CO ₂ lasers, the preferred replacement materials are carbon black, polyethylene glycol (e.g. UnionCa
rbide PEG3000), talc (for example, RTVanderbilt
Nytal 400), and PPZ (e.g. Idemitsu Petrochem)
phosphotriazine manufactured by icals Co. Ltd.)
And PPZ also functions as a prepolymer. For Nd: YAG lasers, the preferred replacement materials are IR99, IRA980, and IR16.
5 (these are all proprietary dyes from Glendale Protective Technologies), IRdye14,617, (this is a proprietary dye from Eastmen Kodak), and Projet 900NP (a proprietary dye from ICI). For diode lasers, the preferred replacement materials are IRdye 14,617 and IRA980.

In any layer of the ink, a specific component (eg, prepolymer, polymerization initiator, etc.) is present 1.
The above layers may be used. The ink of one example is a single ink layer (") having a curable color coat containing a curable prepolymer, a polymerization initiator, and a colorant in a single layer.
Another example is a one-pass "coating." Another example is a two-ink layer (") having a curable or non-curable color coat associated with a laminating curable size coat containing a curable prepolymer and a polymerization initiator. It is a two-pass "film".

Since the ink is curable, the adhesiveness of transfer to the target surface is improved. The effect of the size coat transferred with the color coat by laser irradiation is that the adhesiveness is further improved, which makes it possible to use the non-curable color coat. The ink comprises one or more curable prepolymers containing the curable prepolymer in an amount ranging from 25 to 95% by weight (based on total solids of the ink). Effective curable prepolymers in the present invention have two or more functional groups capable of cross-linking that occur on simultaneous transfer by the application of laser irradiation or on transfer after laser irradiation in separate thermal or photochemical curing steps. ing.

A first class of suitable curable prepolymers is bisphenol A diglycidyl ether (Ep from Shell Oil).
on1001) and epoxy functionalized novolac resin (e.g. Sh
Includes epoxy functionalized prepolymers such as Epon164) from ellOil. Small molecule epoxides such as UVR6110 (UnionCarbi
Liquid diepoxide from de) is likewise added. Second
Suitable curable prepolymers of this class include those epoxy functionalized prepolymers that combine with one or more vinyl ether functionalized prepolymers that cure with the epoxy functionalized prepolymer. Examples of suitable vinyl ether functionalized prepolymers include bisphenol A-divinyl ether adducts,
2,4-toluene diisocyanate / hydroxybutyl vinyl ether adduct, cyclohexyl divinyl ether or ISI product manufactured by GAF, vinyl ethyl ether manufactured by BASF, vinyl isobutyl ether, vinyl octadecyl ether, polyethylene glycol divinyl ether,
Polytetrahydrofuran / 350 / divinyl ether, and trimethylolpropane trivinyl ether, and Rapi / cure divinyl ether / 3, Rapi / cure cyclohexyl vinyl ether, Rapi / cure PEPC, and Rapi / cure made by ISP.
Hydroxybutyl vinyl ether and Allied-Sig
nal Vectomers 2010, 2031, 2032, 4010, 4020, and 4030.

A suitable curable prepolymer of the third class is 1
Includes the above epoxy functionalized prepolymer combined with the above acrylate functionalized prepolymer. The acrylate functionalized prepolymers of the examples were RDX29522 and Ebecryl639 (both Rad
cure), Sartomer351 (Sartomer), and NR440
(Zeneca Resin). A fourth class of suitable curable prepolymers includes acrylate functionalized prepolymers that are free of epoxy functionalized prepolymers.

Suitable curable prepolymers of the fifth class are:
Includes a blocked isocyanate functionalized prepolymer. Examples include B1299 (Huls) and BL4165A (Miles).
A sixth class of suitable curable prepolymers include the vinyl ether functionalized prepolymers described above in combination with maleate functionalized prepolymers or maleinimide functionalized prepolymers. The maleate functionalized prepolymers of the examples are 89-890
2 (manufactured by Cargil Products), and Astrocure 78HV and Astr
ocure78LV (both manufactured by Zircon) is included. The maleimide functionalized prepolymers of the examples are BMI / S / M / 20 / TDA (MitsuiToa
tsu Chemical, Inc.).

The one or more non-curable layers are used in combination with the one or more curable layers. As an example, a non-curable color coat is used in combination with a laminating curable size coat. A suitable non-curable resin is a thermoplastic film forming resin. Examples are acrylic resins such as Rhoplex B85 (acrylic dispersant manufactured by Rohm & Haas) and Amsco3011 (acrylic dispersant manufactured by Rohm & Haas), QW-16 (urethane dispersant known as film forming agent manufactured by KJ Quinn). And urethane resins, phenoxy resins such as PKHW35 (manufactured by Union Carbide), and combinations thereof. The amount of uncurable prepolymer in the ink is about 15 to about 35% by weight (based on the solid components of the ink).

The ink contains about 0.1 to 5% by weight of a polymerization initiator.
Includes amounts in the range (based on total solids of the ink). A polymerization initiator (which is typically a free radical or cationic polymerization initiator) is a photochemical or thermal polymerization initiator, and in some cases the same thermal and photochemical Acts as a polymerization initiator. In the case of a multi-curable multi-layered ink, the layer containing the photochemical polymerization initiator may be combined with the layer containing the thermal polymerization initiator. Also, some polymerization initiators may be used in combination with accelerators such as benzpinacol, copper II salts (eg copper benzoate), and hexaphenylethane.

In the case of a thermal polymerization initiator, a polymerization initiator that is stable at ambient temperature is used in order to prevent early vulcanization of the prepolymer. Also, the polymerization initiation temperature must be within the range achieved by laser irradiation.
Examples of suitable thermal initiators for initiating cationic polymerization include arylsulfonium salts (e.g., WO90 / 11303).
Of the above), aryliodonium salts
(Eg UVE9310 and U479, both from General Electric) and ammonium salts (eg FC520 from 3M). Examples of suitable thermal initiators for free radicals are the types of compounds that lead to peroxy radicals, such as hydroperoxides, peroxyesters, and peroxyketals, which are Elf-Atoche.
The one manufactured by m company is typical. Suitable for initiating free radical polymerization is the azo polymerization initiator manufactured by Wako.

In the case of a photochemical polymerization initiator, a polymerization initiator which is stable at ambient temperature is used in order to prevent early vulcanization of the prepolymer. Also, its maximum absorption in the electromagnetic spectrum must be different from the maximum absorption exhibited by the colorant. Examples of suitable photochemical initiators for initiating cationic polymerization include arylsulfonium salts (e.g., UVI6974 from Union Carbide) and aryliodonium salts (e.g., UVE9310 and U479, both
General Electric). A suitable polymerization initiator in another embodiment for initiating cationic polymerization is hydroxynaphthylimide sulfonate ester. Suitable photochemical initiators in the examples for initiating free radical polymerization include methyldiethanolamine (Aldrich Chemical
Co.) CPTX and ITX (both are Ciba-Geigy), and lucerinTP combined with methyldiethanolamine
O (manufactured by BASF), Darcure 4265 (manufactured by Ciba Geigy), and ITX
Includes Irgacure 368 combined with.

The ink contains one or more colorants, which may be dyes, pigments, or metallized coatings (eg, aluminized coatings). In the case of dyes and pigments, the colorant comprises an amount in the range of about 35 to 65% by weight (based on total solids of the ink). The colorant is selected based on the desired color on the final printed surface. Suitable colorants for the examples are pigments such as talc, TiO ₂ (white), phthalogreen (G).
T-674-D), chrome green oxide (6
099), ultramarine blue ultramarine blue (RS-9),
Black oxide black oxide (BK-5099D), chroma red
Kromared (7097) and Nova Palm Yellow Novapermyell
ow (HR-70), and as a dye, dinonicidin d
ynonicidine (2915) and Dianellorang
e, as well as the metallized coatings described above.

In the case of an ink containing a photocurable prepolymer,
The sensitizer is added in an amount in the range of about 0.5 to 8% by weight (based on the total solid components of the ink) in order to extend the irradiation wavelength to the visible light region due to the photopolymerization initiation reaction. Such sensitizers are effective for the examples, where the formulation contains a large amount of TiO ₂ pigment, which absorbs light below 400 nm and competes with the polymerization initiator. All suitable sensitizers in the examples are Aldrich Chemi
manufactured by calCo., these are perylene, rubrene, phenothiazine, anthracene derivative and thioxanthone and
Includes TPO (manufactured by BASF).

Other components added to improve the coatability, printability, printing performance and weather resistance of the ink include surfactants, dispersants, and polymer dispersants. Each component and its amount are selected based on the desired properties. Suitable surfactants of the examples (which may be anionic, cationic or nonionic) include triton X-100 (Aryl ethoxylate from Rohm & Haas) and FC430 (a fluoroaliphatic polymeric ester from 3M). included. Suitable dispersants of the examples include polyacrylate salts such as Daxad30,
This is 3 of polysodium acrylate from WR Grace.
It is a 0% aqueous solution. Suitable dispersants for the examples are Shamrock 37
5 and Aquacer 355, both of which are polyethylene wax dispersants from Diamond Shamrock.

The transfer medium according to the invention is prepared by combining the ink components in an aqueous or organic solvent, preferably an aqueous solvent, and the resulting composition is applied to a carrier. If a size coat is used, it is applied on top of the color coat. To facilitate coating, the total solids content of the ink is adjusted between 10 and 50% by weight of the ink. The coated carrier is irradiated with laser light, and the ink is transferred from the carrier to a desired surface, for example, the surface of a semiconductor device. Suitable lasers are CO ₂ lasers (irradiation wavelength of 10.6 micrometers), Nd: YAG lasers (irradiation wavelength of 1.06 micrometers), and diode lasers (e.g.,
(Irradiation wavelength of 0.9 micrometer). The irradiation wavelength, power, and application time parameters are selected to ensure clean transfer.

For some inks, laser irradiation simultaneously transfers and cures the ink. In other inks, a separate thermal or photochemical cure occurs after transfer. Curing conditions are selected based on the prepolymer and polymerization initiator used in the formulation. Examples according to the present invention are described in detail below. Example 1 This example illustrates a one-pass, thermosetting, transfer medium having an ink by a cationic polymerization initiation reaction.

The following components (all in weight percent amounts) were combined to form a laser transferable ink. TiO ₂ 55.0 Bisphenol A-DVE adduct 13.0 35201 ¹ 24.8 PEG3000 ² 5.0 Aryl sulfonium salt ³ 2.0 tritonX-100 ⁴ 0.2 1: Aqueous dispersant of bisphenol A-epichlorohydrin adduct manufactured by Rhone-Poulenc. 2: Polyethylene glycol manufactured by Union Carbide (M _n = 300
0). 3: Aryl sulfonium salt thermal polymerization initiator described in WO90 / 11303. 4: Surfactant manufactured by Rohm & Haas.

After adding water to adjust the total solids content to 35% by weight, the resulting ink was applied to a # 15 Meyer rod (m
ayerrod) was applied to a 1.2 mil thick polypropylene carrier film (1 mil = 0.0254 mm). And
The film-coated surface was brought into close contact with and adhered to the surface of the molded semiconductor device. Next, a CO ₂ laser was irradiated through the uncoated side of the carrier film to transfer the ink to the surface of the semiconductor device. The laser was illuminated onto the pixels at each location for 16 seconds. The output power of the laser was 14.5 W at the point of contact with the coated film. The semiconductor device bearing the transferred image was placed in a forced hot air oven at a temperature of 175 degrees for 30 minutes to cure the ink. After curing, the transferred image is 1,1,1-trichloroethane
It was found that it can withstand the treatment even after (3 minutes immersion, 10 brushes, 3 cycles). Example 2 This example illustrates a transfer medium that is two- pass, photochemically curable in color and size coats, and has an ink by cationic polymerization initiation reaction.

The following components (all in weight percent amounts) were combined to form a photochemically curable color coat. TiO ₂ 55.0 2,4-Toluene diisocyanate / HBVE adduct ¹ 35.8 QW-16 (urethane dispersant) ² 2.0 PPZ ³ 5.0 TritonX-100 ⁴ 0.2 UVI6974 ⁵ 2.0 1: Hydroxybutyl divinyl ether adduct. 2: KJ Quinn pre-made urethane dispersant (Pre-made
urethane dispersion). 3: Product made by Idemitsu Petrochemicals Co. Ltd. 4: Surfactant manufactured by Rohm & Haas. 5: A polymerization initiator based on a triarylsulfonium salt manufactured by Union Carbide.

After the addition of water to adjust the total solids to 35% by weight, the resulting color coat was applied to a 1.2 mil thick polypropylene carrier film using a # 13 Meyer rod. The following components (all in weight percent amounts) were combined to form a photochemically curable size coat.

EPON1001 ¹ 89.1 UNI6110 ² 5.45 FC-430 ³ 2.47 UVI6974 ⁴ 1.68 Perylene ⁵ 0.3 PPZ ⁶ 1.0 1: Bisphenol A diglycidyl ether manufactured by Shell Oil Co. 2: Liquid diepoxide manufactured by Union Carbide. 3: 3MCo fluoroaliphatic polymeric ester surfactant. 4: Polymerization initiator based on triarylsulfonium salt manufactured by Union Carbide. 5: Photosensitizer manufactured by Aldrich Chemical Co. 6: Product made by Idemitsu Petrochemicals Co. Ltd.

After the addition of methyl ethyl ketone to adjust the total solids of the size coat to 25% by weight, the resulting size coat was applied on top of the color coat using a # 5 Meyer rod. And, the film coating surface,
The surface of the molded semiconductor device was brought into close contact with and adhered to it. Next, a CO ₂ laser is irradiated through the uncoated side of the carrier film to ink (color coat and size coat).
Was transferred to the surface of the semiconductor device. The laser was irradiated onto the pixels at each location for 20 seconds. The output power of the laser was 14.5 W at the point of contact with the coated film. Preheat the semiconductor device that bears the transferred image with ink for 5 minutes at a temperature of 150 degrees, and then
It was cured by UV irradiation for 2 seconds. After curing, the transferred image was found to survive treatment with 1,1,1-trichloroethane (3 minutes soak, 10 brushes, 3 cycles). Example 3 This example illustrates a transfer medium that is two-pass, has a color coat that is non-curable and a size coat that is thermosetting, and that has a curable ink by a cationic polymerization initiation reaction.

The following components (all in weight percent amounts) were combined to form a non-curable color coat. Water 54.0 Daxad30 ¹ 0.5 TiO ₂ 38.4 tritonX-100 ² 0.5 Shamrock375 ³ 6.2 RhoplexB85 ⁴ 1.4 Amsco3011 ⁵ 7.7 1: Polyacrylate dispersant manufactured by WR Grace. 2: Surfactant manufactured by Rohm & Haas. 3: Polyethylene wax dispersant manufactured by Diamond Shamrock. 4: Acrylic dispersant manufactured by Rohm & Haas. 5: Acrylic dispersant manufactured by Rohm & Haas.

After addition of ammonium hydroxide to adjust the pH to 8.5, the resulting color coat was applied at a coat weight of 69 mg / m ² to a 1.2 mil thick polypropylene carrier film. The following components (all in weight percent amounts) were combined to form a photochemically curable size coat.

EPON1001 ¹ 88.2 UVR6110 ² 11.6 FC-430 ³ 3.0 UV479 ⁴ 1.6 IR99 ⁵ 0.5 Benzpinacol ⁶ 0.47 1: Bisphenol A diglycidyl ether manufactured by Shell Oil Co. 2: Liquid diepoxide manufactured by Union Carbide. 3: 3M Co. Fluoroaliphatic Polymeric Ester Surfactant 4: General Electric Iodonium Salt Thermal Initiator. 5: Dye manufactured by Glendale Protective Technologies. 6: Accelerator manufactured by Aldrich Chemical Co.

25% by weight of all solid components of the size coat
After adding methyl ethyl ketone to adjust, get
Size coat with # 5 Mayer rod
It was applied to the table. Formed semi-conductive surface of film coating
It was attached in intimate contact with the surface of the body device. Then N
Irradiate the d: YAG laser through the uncoated side of the carrier film
The ink (color coat and size coat) on the semiconductor device.
It was transferred to the surface of the table. Laser for 18 seconds on each pixel
It was irradiated for a while. The output power of the laser contacts the coated film
It was 4.5W at the point. Install the semiconductor device that bears the transferred image.
The ink is cured by heating at a temperature of 175 degrees for 4 minutes.
It was After curing, the transferred image was 1,1,1-trichloroethane (soaked for 3 minutes
Even if it is pickled, brushed 10 times and treated for 3 cycles)
I found that Example 4 This example is a one-pass, thermosetting, transfer and
The cation weight is set by laser irradiation in a single step.
The transfer medium having the ink by the reaction of initiating the reaction will be described.

The following components (all in weight percent amounts) were combined to form a laser transferable ink. Talc ¹ 30.0 UVE9310 ² 7.0 Copper benzoate ³ 0.14 Epon164 ⁴ 51.43 CHVE5 ⁵ 11.43 1: Nytal 400 from RT Vandebilts. 2: Light and thermal polymerization initiator manufactured by General Electric Company. 3: Accelerator manufactured by Aldrich Chemical Co. 4: Epoxy novolac resin with 200-240 equivalents of epoxy from Shell Oil. 5: Cyclohexyldivinyl ether manufactured by GAF or ISI Products.

After the addition of methyl ethyl ketone to adjust the total solids content to 50% by weight, the resulting ink was
A 1.2 mil thick polypropylene carrier film was applied using a Mayer rod. Then, the film-coated surface was brought into close contact with and adhered to the surface of the glass slide. Then, the CO ₂ laser is irradiated through the uncoated side of the carrier film, the ink was transferred onto the surface of the glass slide. The laser was irradiated onto the pixels at each location for 80 seconds. After irradiation, the transfer coating was removed from the glass slide and analyzed by a differential scanning calorimeter. It was found that the transfer coating was cured during the transfer process with no evidence of residual thermal reaction. Example 5 This example illustrates a transfer medium that is two-pass, photochemically curable in color coat and size coat, and has a free radical polymerization initiated reaction ink.

The following components (all in weight percent amounts) were combined to form a photochemically curable color coat. _{^{TiO 2 65.0 Aquacer355 1 11.0 NR440 2}} 18.8 PPZ 3 3.0 tritonX-100 4 0.2 Daracure4265 5 2.0 1: DiamondShamrock Co. polyethylene wax dispersant. 2: Acrylate functionalized prepolymer from Zenecaresin. 3: Product made by Idemitsu Petrochemicals Co. Ltd. 4: Surfactant manufactured by Rohm & Haas. 5: Photochemical free radical polymerization initiator manufactured by Ciba Geigy.

After adding water to adjust the total solids to 40% by weight, the resulting color coat was applied to a 1.2 mil thick polypropylene carrier film using a # 13 Meyer rod. The following components (all in weight percent amounts) were combined to form a photochemically curable size coat.

NR440 ¹ 78.0 Ebecryl639 ² 20.0 Daracure4265 ³ 2.0 1: Acrylate functionalized prepolymer from Zeneca Resin. 2: Radcure acrylate functionalized prepolymer. 3: Photochemical free radical polymerization initiator manufactured by Ciba Geigy.

The resulting size coat was prepared by adding water to adjust the total solid content of the size coat to 40% by weight.
It was applied on a color coat using a # 5 Meyer rod. Then, the film-coated surface was brought into close contact with and adhered to the surface of the molded semiconductor device. Next, a CO ₂ laser was irradiated through the uncoated side of the carrier film to transfer the ink (color coat and size coat) onto the surface of the semiconductor device. The laser was irradiated onto the pixels at each location for 20 seconds. The output power of the laser is at the point of contact with the coated film.
It was 14.5W. The semiconductor device bearing the transferred image was preheated at a temperature of 100 ° C. for 5 minutes, and then passed through an ultraviolet fusion furnace equipped with an H bulb at a rate of 100 inches / minute to cure the ink. After curing, the transferred image was found to survive the treatment with 1,1,1-trichloroethane (3 minutes soak, 10 brushes, 3 cycles).

[0043]

A transfer printing medium comprising a carrier to which a curable laser transferable ink having one or more layers is added, comprising:
The transfer medium is capable of converting laser energy into heat and the ink has (a) at least one colorant, (b) at least one polymerization initiator, and (c) at least one curable prepolymer, The types of materials that can be used in the ink can be expanded to enable the properties of the ink to be adjusted as needed for a particular application.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C08F 2/46 MDY C09D 11/00 PTA 9121-2H B41M 5/26 Q (72) Inventor John Jay ． Drake United States New Hampshire 03431 Keene Robins Road 20

Claims (23)

[Claims] 1. A transfer printing medium comprising a carrier to which a curable laser transferable ink having one or more layers is attached, wherein the ink is (a) at least one colorant, and (b) at least one. A transfer printing medium comprising a polymerization initiator and (c) at least one curable prepolymer, wherein the transfer medium is capable of converting laser energy into heat. 2. The transfer print medium of claim 1, wherein the ink moves to a target surface and cures during application of laser energy in one step. 3. The transfer print medium of claim 1, wherein at least one of the polymerization initiators is a thermal polymerization initiator and at least one of the prepolymers is thermosetting. 4. The transfer print medium of claim 1, wherein at least one of the polymerization initiators is a photopolymerization initiator and at least one of the prepolymers is photochemically curable. 5. The transfer print medium of claim 1, wherein at least one of the prepolymers comprises an epoxy functionalized prepolymer. 6. The transfer print medium of claim 5, wherein the prepolymer further comprises a vinyl ether functionalized prepolymer. 7. The transfer print medium of claim 5, wherein the prepolymer further comprises an acrylate functionalized prepolymer. 8. The transfer print medium of claim 1, wherein at least one of the prepolymers comprises an acrylate functionalized prepolymer. 9. The transfer print medium of claim 1, wherein at least one of the prepolymers comprises a blocked isocyanate functionalized prepolymer. 10. The transfer print medium of claim 1, wherein at least one of the prepolymers comprises a mixture of a vinyl ether functionalized prepolymer and a maleate or maleimide functionalized prepolymer. 11. The transfer print medium of claim 1, wherein the ink of at least one of the layers is a curable size coat comprising a polymerization initiator and a curable prepolymer. 12. The at least one layer of the ink is a curable size coat comprising a polymerization initiator and a curable prepolymer, and the at least one layer of the ink comprises a colorant and a thermoplastic film forming resin. The transfer printing medium according to claim 1, which is a non-curable color coat. 13. The ink of at least one layer is a curable size coat comprising a polymerization initiator and a curable prepolymer, and the ink of at least one layer is a colorant, a polymerization initiator, and a curable resin. The transfer printing medium according to claim 1, which is a curable color coat made of a prepolymer. 14. A laser-induced transfer printing method comprising: (a) (i) at least one colorant, (ii) at least one polymerization initiator, and (iii) at least one curable prepolymer. A step of supplying a transfer printing medium capable of converting laser energy into heat, which comprises a carrier having a curable laser transfer ink having one or more layers attached thereto, and (b) supplying a laser beam of a predetermined wavelength to the medium. A method comprising: irradiating to move the ink to a target surface; and (c) curing the ink to adhere the ink to the target surface. 15. The method of claim 14, wherein the transferring and curing of the ink is performed in a single step through the irradiation of the laser light. 16. The method of claim 14, wherein at least one of the polymerization initiators comprises a thermal polymerization initiator and at least one of the prepolymers is thermosetting. 17. The at least one polymerization initiator comprises a photopolymerization initiator, and the at least one prepolymer is photochemically curable.
4. The method described in 4. 18. The method of claim 14, wherein the ink of at least one of the layers is a curable size coat consisting of a polymerization initiator and a curable prepolymer. 19. The ink of at least one of the layers is a curable size coat comprising a polymerization initiator and a curable prepolymer, and the ink of at least one of the layers comprises a colorant and a thermoplastic film forming resin. 15. The method of claim 14, which is a non-curable color coat. 20. The ink of at least one of the layers is a curable size coat comprising a polymerization initiator and a curable prepolymer, and the ink of at least one of the layers is a colorant, a polymerization initiator, and a curable resin. 15. The method of claim 14, wherein the curable color coat comprises a prepolymer. 21. The method of claim 14, wherein the transferring and curing of the ink is performed in a single step through the irradiation of the laser light. 22. The method of claim 14, wherein the transferring and curing of the ink is performed in separate steps. 23. Laser induced transfer printing, comprising the steps of: (a) providing a transfer printing medium capable of converting laser energy into heat, the carrier comprising a carrier to which a curable laser transfer ink is added; and (b) a predetermined wavelength. Irradiating the medium with the laser light of
Wherein the laser light causes the ink to move to the target surface and causes the ink to adhere to the target surface.