KR20120138691A - Liti donor film - Google Patents

Abstract

PURPOSE: A donor film for a laser induced thermal transfer method is provided to secure an intermediate layer with a uniform surface by setting the optimum thickness of the intermediate layer according to the surface illumination of a photothermal conversion layer. CONSTITUTION: A primer layer(20) is formed on a base film(10). A photothermal conversion layer(30) is formed on the primer layer and includes a resin composition with thermosetting resin and photothermal conversion materials. An intermediate layer(40) is formed on the photothermal conversion layer. A transfer layer(50) is formed on the intermediate layer.

Description

Donor film for laser thermal transfer method {LITI DONOR FILM}

TECHNICAL FIELD The present invention relates to a thermal transfer donor film and to a thermal transfer donor film having a thermal transfer image forming element for use in a laser induced thermal imaging or similar process.

Recently, the trend of the development of the display device technology is the development of a technology that is excellent in visibility while using less energy. Accordingly, the development of a display device using an organic light emitting display device (OLED), which is known to consume less energy than a conventional light emitting method, is being made competitively.

In order to realize full color of the display device using the OLED, a method of patterning color on the light emitting device is very important, and as a result, an organic film layer of the organic light emitting display device that determines the color of the light emitting device. Depending on how to form the difference in implementation effect occurs. The method of forming an organic film layer in an OLED includes a deposition method, an inkjet method, a laser thermal transfer method (LITI), and the like. Among them, a laser thermal transfer method commonly used as LITI is a method of converting light from a laser into thermal energy, transferring a transfer layer to a substrate of an OLED by the converted thermal energy, and forming an organic layer on the OLED. Such a transfer method is described in Korean Patent Publication No. 10-0700828. The LITI method has advantages such as high resolution pattern formation, film thickness uniformity, multi-layer implementation capability, and scalability to large mother glass.

In this LITI method, the critical medium for converting light into thermal energy to form a pattern on the substrate of the light emitting device includes a transfer layer having a red pixel region (R), a green pixel region (G), and a blue pixel region (B). LITI donor film. The LITI donor film has a structure in which a base film, a light-to-heat conversion layer, and a transfer-directing layer are stacked in this order. The LITI donor film optionally includes an interlayer between the light-to-heat conversion layer and the transfer layer to prevent the material contained in the light-to-heat conversion layer from being transferred to the transfer layer.

In the LITI process, when the laser is irradiated to the LITI donor film, the light energy of the laser is converted into thermal energy in the light-to-heat conversion layer, and the volume expansion of the light-to-heat conversion layer and the blocking layer is generated by the thermal energy and transferred by volume expansion. The layer is transferred to the OLED substrate.

Republic of Korea Patent Publication No. 10-0700828 (2007.03.21)

The present inventors have completed the present invention in that the surface transferred from the transfer layer can be smoothly and uniformly formed by allowing the volume expansion of the light-to-heat conversion layer to expand evenly to implement the transfer pattern more preferably.

That is, an object of the present invention is to make the surface to be transferred from the transfer layer smooth and uniform when the transfer layer is transferred by the LITI method.

The present invention for achieving the above object relates to a donor film for a laser thermal transfer method consisting of a base film, a primer layer, a light-to-heat conversion layer, an intermediate layer and a transfer layer, the composition and thickness of the light-to-heat conversion layer and the intermediate layer It is characterized by.

In particular, the inventors of the present invention, when using the UV-curable resin in the light-to-heat conversion layer is not foamed by excessive curing, or the edge open phenomenon (edge open) on the transfer surface transferred after the transfer by foaming, that is, Figure 1 As a result of researches to solve the problem that the bending layer or the angled corners are not transferred when the transfer layer is transferred, the edge-opening phenomenon is improved by using a thermosetting resin instead of a UV curing resin. Found. FIG. 1 is a cross-sectional view illustrating an edge open phenomenon on a transfer surface transferred after being transferred, and illustrates an acceptor 200, a transfer layer 300, and an edge open 100.

However, when the light-to-heat conversion layer is formed using a thermosetting resin, when the light-to-heat conversion material is not uniformly distributed but partially agglomerated, excessive heat is generated in the agglomerated portion during laser irradiation, or burned. After coating, a telegraphic phenomenon occurs in which the surface shape of the conversion layer remains in the intermediate layer.

In addition, the coating of the layer forming the pixel on the light-to-heat conversion layer and then the transfer is a problem that the surface of the transferred transfer layer is not smooth occurs to study this problem. As a result, in the range in which the coating amount after drying of the light-heat conversion layer is adjusted to 1 to 3.5 g / m 2, and the thickness of the intermediate layer is adjusted to 1.0 to 3.5 μm, the light-heat used in the light-to-heat conversion layer It was found that this problem can be solved by adjusting the content of the conversion material to 20 to 40% by weight.

In addition, it was confirmed that the coagulation problem can be solved by undergoing first kneading or mixing, second milling, and third filtering to prevent the photo-thermal conversion material from generating excessive heat due to coagulation. In addition, to maximize the milling effect, an oxidation-treated carbon black or an additive such as an aluminum dispersant may be used. Through solving the carbon black coagulation problem, the surface of the transfer layer was found to be very smooth and the edge open phenomenon did not occur so that the transfer was very well formed and completed the present invention.

The smooth surface of the transferred transfer layer and no edge open phenomenon are very important for forming a high resolution display. In the present invention, the coating amount after drying the light-to-heat conversion layer is 1 to 3.5 g / m 2 as described above. When adjusting the content of the intermediate layer in the range of 1.0 ~ 3.5㎛ thickness, the surface used for the light-to-heat conversion layer modified content of the light-to-heat conversion material to 20 to 40% by weight, It can be seen that the surface energy of the light-to-heat conversion layer is 35 mN / m or less, and the surface roughness is formed to 20 nm or less. The surface of the transfer layer transferred in a range where the surface roughness of the light-to-heat conversion layer satisfies the above range is formed smoothly and uniformly.

Specifically, the present invention includes a base film, a primer layer, a light-to-heat conversion layer, an intermediate layer, and a transfer layer, wherein the light-to-heat conversion layer includes a resin composition including a thermosetting resin and a light-to-heat conversion material. The intermediate layer relates to a donor film for a thermal transfer method comprising a UV curable resin, a silicone resin or a fluorine resin and having a surface energy of 35 mN / m or less.

The present invention also relates to a donor film for a thermal transfer method wherein the surface energy of the intermediate layer is 18mN / m to 35mN / m.

The present invention also relates to a donor film for a thermal transfer method wherein the surface energy of the intermediate layer is 18mN / m to 25mN / m.

The present invention also relates to a donor film for a thermal transfer method, wherein the surface roughness Ra of the light-to-heat conversion layer is 20 nm or less.

The present invention also relates to a donor film for a thermal transfer method wherein the thermosetting resin in the light-heat conversion layer is a polyurethane-based resin, and the light-heat conversion material is carbon black.

The present invention also relates to a donor film for a thermal transfer method wherein the polyurethane-based resin is selected from polyester polyurethane and polycarbonate polyurethane.

The present invention also relates to a donor film for a thermal transfer method, the light-to-heat conversion material is contained in 20 to 40% by weight.

In another aspect, the present invention is a donor film for thermal transfer method using the light-heat conversion material dispersed in any one or two or more resins and solvents selected from polyvinyl chloride, polyvinyl chloride polyvinylacetate copolymer, thermosetting polyurethane It is about.

The present invention also relates to a donor film for a thermal transfer method, wherein the light-to-heat conversion layer further comprises less than 50% by weight of the thermoplastic resin in the total resin composition.

The present invention also relates to a donor film for a thermal transfer method wherein the light-to-heat conversion layer has a coating amount of 1 to 3.5 g / m 2 after drying.

The present invention also relates to a donor film for a thermal transfer method, wherein the intermediate layer has a thickness of 1.0 to 3.5 μm.

By selecting the optimal thickness of the intermediate layer according to the surface roughness of the light-to-heat conversion layer through the present invention it is possible to ensure the shape of the intermediate layer of the uniform surface. This results in a uniform transfer surface when the final transfer layer is transferred, ultimately optimizing the resolution of the display.

1 is a cross-sectional view illustrating an edge open phenomenon occurring in a conventional transfer surface.
2 is a cross-sectional view showing an example of a laminated structure of the donor film of the present invention.
Description of the main parts of the drawing-
10: base film
20: primer layer
30: light-heat conversion layer
40: middle layer
50: transfer layer
100: edge open
200: acceptor
300: transfer layer

Hereinafter, a donor film for a thermal transfer method of the present invention will be described in detail with reference to the accompanying drawings.

One aspect of the present invention includes a base film 10, a primer layer 20, a light-to-heat conversion layer 30, an intermediate layer 40 and a transfer layer 50, as shown in FIG. The thermal conversion layer 30 includes a resin composition including a thermosetting resin and a photo-thermal conversion material, and the intermediate layer 40 includes a UV curable resin, a silicone resin or a fluorine resin, and has a surface energy of 35 mN / m. It is a donor film for the thermal transfer method of the following.

More specifically, in one aspect of the present invention, the light-to-heat conversion layer includes a resin composition and a light-to-heat conversion material including a thermosetting resin, and the light-to-heat conversion material is included in 20 to 40% by weight, after drying The present invention relates to a donor film for a thermal transfer method having a coating amount of 1 to 3.5 g / m 2.

In addition, the intermediate layer includes a UV-curable resin, including a silicone resin or a fluorine-based resin thickness of 1.0 ~ 3.5㎛, a surface energy of 35mN / m or less relates to a donor film for the thermal transfer method.

In another embodiment of the present invention, the surface roughness of the light-to-heat conversion layer is 20 nm or less.

In another embodiment of the present invention, the thermosetting resin in the light-heat conversion layer is a polyurethane-based resin, the light-heat conversion material is carbon black.

In another embodiment of the present invention, the light-to-heat conversion material may be used dispersed in any one or two or more resins and solvents selected from polyvinyl chloride, polyvinyl chloride polyvinylacetate copolymer, thermosetting polyurethane. .

Hereinafter, the structure of each layer of this invention is demonstrated more concretely.

Base film

In the present invention, the base film may be a glass, a transparent film or a polymer film. Examples of the polymer film may include polyester, polycarbonate, polyolefin, polyvinyl resin, and the like, but are not limited thereto. More specifically, it is preferable to use polyethylene terephthalate or polyethylene naphthalate because it is excellent in processability, thermal stability and transparency. More preferably, in order to increase the transmittance of light irradiated during the execution of the LITI method, it is preferable to use a light transmittance of 90% or more.

The surface of the base film may be modified by a surface treatment known to those skilled in the art, for example, a surface treatment such as corona or plasma, to adjust adhesion and surface tension in a subsequent process.

The thickness of the base film is preferably 0.025 to 0.15 mm, more preferably 0.05 to 0.1 mm, but is not limited thereto.

Primer layer

In the present invention, the primer layer is to control the temperature transfer between the base film and the adjacent layer, to improve the adhesion between the base film and the adjacent layer, and to control the image forming radiation transfer to the light-heat conversion layer, In the case of forming the layer, the phenomenon in which the substrate and the light-to-heat conversion layer are separated in the transfer process using a laser can be improved, which is more preferable. As a suitable material for such a primer layer, any one selected from acrylic resin, polyurethane resin, polyester resin or a mixed resin thereof may be used. If the heat-resistant adhesion between the primer layer and the base film or between the primer layer and the light-to-heat conversion layer is poor, the base film and the light-to-heat conversion layer may be separated in the transfer process using a laser.

More specifically, in the present invention, the primer layer may be formed by coating on one side or both sides of the base film by an inline coating process when manufacturing the base film.

That is, in the present invention, when the base film is a polyethylene terephthalate film, it may be formed by applying a water-dispersible primer coating liquid in the stretching step of the film to uniaxial or biaxial stretching.

The water-dispersible primer coating liquid may be used without limitation as long as it is used in the art. More preferably, it is preferable that the resin has a small refractive index difference from that of the polyethylene terephthalate film, which is a base film, since the light transmittance is improved. Examples of such water-dispersible primers include acrylic resins, polyurethane resins, polyester resins, and the like. Coating liquids are preferred.

The thickness of the primer layer is preferably 0.01 ~ 0.5 ㎛, but is not limited thereto.

Light-To-Heat Conversion layer (LTHC layer)

The light-to-heat conversion layer of the present invention absorbs light in the infrared-visible light region and converts a part of the light into heat, and includes a resin composition including a thermosetting resin and a light-to-heat conversion material.

In the present invention, the resin composition may be made of a thermosetting resin alone or a mixed resin of a thermosetting resin and a thermoplastic resin. In the case where a thermosetting resin and a thermoplastic resin are mixed and used, it is preferable that the thermosetting resin contains 50% by weight or more of the total resin components including a curing agent. When the content of the thermosetting resin is less than 50% by weight, solvent resistance of the intermediate layer may penetrate into the light-to-heat conversion layer during coating of the intermediate layer, and also may not be smoothly dispersed in the light-heat conversion material dispersion process Pinholes may occur during coating.

In the resin composition, the thermosetting resin preferably includes a polyurethane-based thermosetting resin, and specifically, for example, the thermosetting polyurethane includes polycarbonate polyurethane, polyester polyurethane, polyurethane, and the like. It is preferable that the polyurethane resin has a glass transition temperature (T _g ) of 10 ° C. or more, and more specifically, a glass transition temperature of 10-50 ° C. may be used. If the glass transition temperature is less than the above range, the coating layer may be partially transferred to the opposite side in the aging process after coating the light-to-heat conversion layer. If the glass transition temperature is exceeded, the expansion of the desired shape may be reduced due to the small volume expansion during laser irradiation. It can be difficult.

Examples of the curing agent include an isocyanate curing agent, a peroxide, an epoxy crosslinking agent, a metal chelate crosslinking agent, a melamine crosslinking agent, an aziridine crosslinking agent and a metal salt. These crosslinking agents can be used individually by 1 type or in combination of 2 or more types. In addition, a thermoplastic resin can be added to the present composition.

The thermoplastic resin uses an amount smaller than the sum of the thermosetting resin and the crosslinking agent solids based on the solids content. Specifically, it is used in less than 50% by weight of the total content of the resin composition. The thermoplastic resin may be polyvinyl chloride vinyl acetate copolymer, polyvinyl chloride homopolymer, polymethyl methacrylate, isobutyl methacrylate, polybutyl methacrylate, polymethyl acrylate- butyl acrylate copolymer, etc. It is preferable to use a glass transition temperature of 40 ℃ or more. If the glass transition temperature is less than 40 ℃ blocking may occur.

The light-to-heat conversion material means a material that absorbs incident laser light and converts it into heat, and dyes such as visible light dyes, ultraviolet dyes, infrared dyes, fluorescent dyes, and radiation polarizing dyes, pigments, metals, metal compounds, and metals. Films, carbon blacks, metal oxides, metal sulfides and the like can be used, and more preferably carbon black is used in the present invention.

In addition, dyes such as visible light dyes, ultraviolet dyes, infrared dyes, fluorescent dyes, and radiation-polarized dyes, pigments, organic pigments, inorganic pigments, metals, metal compounds, metal films, and iron cyanide pigments may be used. , Phthalocyanine pigments, phthalocyanine dyes, cyanine pigments, cyanine dyes, metal dithiolene pigments, metal dithiolene dyes and other absorbent materials may be further added.

It is preferable to use the carbon black having an average particle diameter of 10 to 30 nm because a flat surface can be obtained. In addition, if necessary, the carbon black is first dispersed with one or two or more resins selected from polyvinyl chloride, polyvinyl chloride-polyvinylacetate copolymer, thermosetting polyurethane, surface treatment by dispersing in resin It can be further improved.

As the method of primary dispersion, carbon black may be added to a resin such as polyvinyl chloride to perform primary dispersion by kneading or mixing. Kneading includes a solvent, and kneading may be performed by using a kneading machine after preparing a preparation liquid having a solid content of 30 to 70 wt%. If the solid content is less than 30 wt%, the viscosity may be low and the dispersion of carbon may be reduced. If the solid content is more than 70% by weight, too much torque is applied, making dispersion difficult. Kneaded crude can add additional milling and filtering processes to optimize dispersion. The solvent used for kneading preferably uses a solvent capable of dissolving the resin according to the kind of resin used. More specifically, for example, toluene: methyl ethyl ketone: cyclohexanone is 1 to 5 : 1-5: The mixed solvent mixed in 1-5 weight ratio can be used.

In the present invention, the content of the light-to-heat conversion material is preferably included in 20 to 40% by weight, when the content of the light-to-heat conversion material is less than 20% by weight, the transfer process using a laser is a light-to-heat conversion layer Since there is a limit to swelling, the desired pattern may not be uniformly transferred, and if it exceeds 40% by weight, an excessive amount of heat may be generated in the laser transfer process and the light-to-heat conversion layer may be burned and not transferred.

In the present invention, the photothermal conversion layer may be formed by a kneading, milling, filtering, and coating process, and may also be formed by a milling, filtering, and coating process. Kneading and milling are performed to optimize the dispersion of the particles, and milling methods can be utilized in various ways such as ring mills and send mills.

Milling may be used in various ways, for example, in the case of using a ring mill, a crude liquid or resin / addition of residual resin and solvent so that the solid content of the total liquid is 10% to 20% by weight of the first kneaded crude liquid. A carbon black / solvent mixture (solid content of 10% to 20% by weight) is injected into the main container of the mill, and 50-80% by volume of 0.5-2.0 mm zirconium particles are filled in the ring portion, followed by stirring. Agitation is carried out in duplicate. One is carried out for the purpose of injecting the inside of the ring portion into the ring while the main milling vessel is circulated, and the other is carried out for the purpose of dispersing particles in the ring. As the particles filled in the ring portion, other milling particles other than zirconium may be used. If necessary, milling can be carried out in several stages. First milling with 2.0mm zirconium particles and first milling, then second milling with 1.5mm particles and third milling with 0.5mm particles can achieve more uniform dispersion of carbon black particles. have.

Alternatively, milling may be performed sequentially using a milling machine in which particles of each size are sequentially filled.

The solid content during milling is preferably carried out in the range of 10% to 20% by weight. There is a difference depending on the composition ratio of the resin, but if less than 10% by weight particle dispersion efficiency is lowered, if it exceeds 20% by weight may cause a problem that the liquid stability of the milled liquid is lowered.

The filtering process aims at removing large particles having a particle size of 2.5 μm or more. The coating process may use a bar coating, a die coating method and a roll coating method, and various coating methods may be applied when necessary. If additional crosslinking is required after the coating process, the degree of crosslinking can be controlled through separate aging.

The light-to-heat conversion layer is prepared by applying and drying on a substrate including a primer layer. Since this layer is a thermosetting type, crosslinking treatment is required by appropriate heat treatment. Crosslinking process may be performed at the temperature of a drying process, and you may form and perform crosslinking processing process separately after a drying process.

The photothermal conversion layer is preferably a dry coating amount of 1 ~ 3.5g / ㎡. If the coating amount after drying of the light-to-heat conversion layer is less than 1g / ㎡, the light-to-heat conversion layer burns out in the transfer process, if it exceeds 3.5g / ㎡ it is not properly heat transfer transfer is not properly transferred May cause problems.

In addition, the light-to-heat conversion layer preferably has a surface roughness Ra of 20 nm or less, and more preferably 10 to 20 nm. When the surface roughness exceeds 20 nm, the surface of the transfer layer may not be formed smoothly and uniformly.

Interlayer

In the present invention, the intermediate layer is used to prevent the transfer of the light-to-heat conversion material present in the light-to-heat conversion layer together when the transfer layer is transferred by the heat generated in the light-to-heat conversion layer, and the light-to-heat conversion The heat generated in the layer is formed to prevent the transfer of heat to the transfer layer and burned out by the heat.

In the present invention, the intermediate layer is made of a UV-curable resin, and should simultaneously perform a release function to separate the transfer layer, the surface energy is lower than 35mN / m by adding a fluorine-based or silicon-based resin having a low surface energy, more specifically 18mN. / m to 35mN / m, more preferably 18mN / m to 25mN / m is preferably adjusted to. If the surface energy exceeds 35mN / m, the transfer layer may not be transferred because the intermediate layer does not perform a release function in the transfer process and the transfer layer is not separated. Accordingly, the lower the surface energy of the intermediate layer, the lower the adhesive strength with the transfer layer, so that smooth transfer can be achieved in the transfer process. The higher the surface energy of the intermediate layer, the higher the adhesive force with the transfer layer, the more difficult the transfer process can be. In performing the release function, the preferred range is 18mN / m to 35mN / m, more preferably in the range of 18mN / m to 25mN / m can be smoothly transferred.

In addition, it is preferable that the intermediate layer has a coating thickness of 1.0 to 3.5 μm after drying. When the intermediate layer is less than 1.0 μm, the transfer layer is burned off due to poor thermal barrier effect, and the transfer layer may not be obtained. The transferred surface may be non-uniform, resulting in a lower resolution of the display. If the thickness exceeds 3.5 μm, too much heat may be blocked and the transfer layer may not transfer.

More specifically, the thickness of the intermediate layer should be increased to ensure a flat surface shape when the surface roughness of the light-to-heat conversion layer is increased. When the surface roughness (Ra) value of the light-to-heat conversion layer is in the range of 10 nm to 20 nm, and the surface roughness value of the light-to-heat conversion layer is in the range of 5 to 10 nm, the thickness of the intermediate layer is 2 to 3.5 μm, and the light- If the surface roughness value of the heat conversion layer is 5nm or less, it is preferable to have a range of 1 to 3㎛.

UV curable resins usable in the intermediate layer include urethane acrylates, epoxy acrylates, polyester acrylates, etc., and grafting substituents containing fluorine to the backbone of the UV curable resins to control the surface tension to less than 35 mN / m. Grafting or additives may be used as reactive or non-reactive fluorine and silicone additives. In addition, the intermediate layer may be added various additives for removing static electricity.

Specifically, for example, a fluorine-based compound and a non-reactive fluorine-based additive having a vinyl reactor may be used as the fluorine-based additive. The silicone additives may be polyether modified polydimethyl siloxane, polyether modified dimethylpolysiloxane copolymer, dimethylpolysiloxane-based and modified dimethylpolysiloxane-based, methyl alkylsiloxane-based and reactive silicone acrylate additives. BYK-300, BYK-301, BYK-302, etc. are not limited thereto.

The intermediate layer may be formed by a method such as bar coating, roll coating, die coating or the like.

In addition, the intermediate layer may be formed in a two-layer structure if necessary, and may further form an aluminum deposition layer on top of the intermediate layer.

Transfer layer

The transfer layer is formed on top of the intermediate layer by coating a uniform layer by a method such as evaporation, sputtering, solution coating, or the like. The transfer layer typically includes one or more layers for transferring to the receptor. For example, it may be formed using organic, inorganic, organometallic and other materials, including electroluminescent materials or electrically active materials.

More specifically, for example, poly (phenylenevinylene), poly-para-phenylene, polyfluorene, polydialkylfluorene, polythiophene, poly (9-vinylcarbazole), poly (N-vinyl Carbazole-vinyl alcohol) copolymer, triarylamine, polynorbornene, polyaniline, polyarylpolyamine, triphenylamine-polyetherketone and the like can be used, but are not limited to these.

The transfer layer may further include at least one material selected from a known light emitting material, a hole transporting organic material, and an electron transporting organic material so as to match the characteristics of the organic light emitting device to be manufactured. It may include a compound comprising at least one of a non-luminescent charge transfer polymer material and a curable organic binder material.

The configuration of such a transfer layer is not particularly limited in the present invention, and can be used without limitation as long as it is a configuration generally used in the art.

In addition, the transfer layer may be formed in a two-layer structure including an aluminum deposition layer to improve releasability.

Hereinafter, the present invention will be described in detail by way of example. However, the present invention is not limited to the following examples, and it is obvious that the present invention can be modified within the same or equivalent material range.

Hereinafter, physical properties were measured by the following measuring method.

1) Surface roughness

Using a two-dimensional surface roughness measuring instrument (Kousaka Lab. Surfcorder SE-3300), the conditions were measured under the conditions of 1 탆 radius, load 0.7 mN, and cutoff value of 80 µm. After selecting a total of five times, the average value was calculated. When the illuminance curve was expressed as y = f (x) with the center line as the x-axis and the vertical direction as the y-axis, the following equation was calculated.

Surface Roughness (Ra) = (1 / L) ∫f (x) dx

2) surface energy

The surface energy is measured using a contact angle meter, the contact angle is measured using pure water and diiodomethane, and the surface energy is obtained using the Owens-Wendts method. The value is measured 10 times and then averaged.

3) Transcription

After coating 500 Tri of Tris (8-hydroxyquinolinato) aluminium (Alq3) as a transfer layer on the intermediate layer, the transfer was performed in an energy range of 100 to 130 W using a Nd YAG laser having a wavelength of 1064 nm.

If the appearance after transfer coincides with the portion irradiated with the laser; O

If the transferred appearance after the transfer coincides with the part irradiated with the laser partly; △

If transfer is not possible in the part irradiated with the laser; X

4) Blocking property

Overlapping the prepared sample 10 is added to the load of 200gf / ㎠ and left for 3 days in a 40 ℃ oven to determine the occurrence of blocking.

-If blocking occurs: X

-If some blocking occurs: △

-If it does not occur: O

Example 1

Preparation of the composition for preparing a photothermal conversion layer (A-1)

Polyvinyl chloride vinyl acetate copolymer (Dow Chemical, VMCH grade) 18 wt%, Polyurethane resin (Lubzizol, ESTANE 5715 grade) 43 wt%, Polyisocyanate (Aekyung Chemical, AK75 grade) 9 wt%, Carbon black (Degussa) , 30% by weight of PRINTEX L6 grade) was added to a mixed solvent of toluene: methyl ethyl ketone: cyclohexanone = 1: 1: 1 by weight so as to have a solid content of 15% by weight to prepare a composition for preparing a photothermal conversion layer.

At this time, the preparation of the crude liquid was prepared through a kneading and milling filtering process as follows.

First, kneading was carried out by heating and dissolving the polyvinyl chloride vinyl acetate copolymer at 50 ° C. in a mixed solvent mixed with a toluene: methyl ethyl ketone: cyclohexanone = 1: 1: 1 weight ratio to prepare a 13 wt% polyvinyl chloride vinyl acetate solution. Prepared. After putting a certain amount of carbon black into the kneading machine, the polyvinyl chloride vinyl acetate solution was added little by little while the kneading machine was operated, and kneading was performed for 1 hour.

After kneading was finished, the kneaded liquid was put into a ring milling container of a ring mill filled with 80% of 1.2 mm zirconium particles, and a mixed solvent was prepared in a toluene: methyl ethyl ketone: cyclohexanone ratio of 1: 1: 1 by weight. 20 wt% polyurethane resin and a mixed solvent (toluene: methyl ethyl ketone: cyclohexanone = 1: 1: 1 weight ratio) heated and dissolved at 50 ° C. were added thereto to prepare a solution having a solid content ratio of 15 wt%. After the prepared liquid was added, two stirrers were operated in the mill to perform milling. The stirrer used to mix the coating solution into the mill was adjusted to 1000 rpm, and the stirrer installed in the ring part for particle dispersion was stirred at 2000 rpm for 6 hours.

The milled liquid was filtered using a filter capable of filtering particles larger than 2.5 μm. The filtered solution was coated with Meyer Bar # 8, dried at 120 ° C. for 30 seconds, and the surface was examined under a microscope to confirm that there were no particles of 2.5 μm or more, and then filtering was completed. After filtering, polyisocyanate as a curing agent was added thereto, and stirred for 1 hour to prepare a composition for preparing a photothermal conversion layer.

Preparation of the intermediate layer composition (B-1)

A silicone-based additive (BYK, BYK-302) was added to UV curable urethane acrylate resin (Toyo ink, Lioduras LCH) to prepare a composition for preparing an intermediate layer.

Production of LITI Donor Film

A double-sided acrylic primer-treated PET film (Kolon Industries Co., Ltd., H11F) was prepared as a base film.

The photothermal conversion layer prepared composition (A-1) was coated on the acrylic primer layer of the prepared base film by a microgravure coating method and dried to form a photothermal conversion layer. At this time, the coating amount after drying was 1.5 g / m 2. Additional aging was carried out at 50 ° C. for 3 days.

The intermediate layer composition (B-1) prepared on top of the photothermal conversion layer was coated and dried using a microgravure coater to form an intermediate layer. At this time, the coating thickness was adjusted to be 2.0 μm.

The physical properties of the produced film were measured and shown in Table 1 below.

[Example 2]

Except that the thickness of the intermediate layer was adjusted to 3.0㎛ was prepared in the same manner as in Example 1.

The physical properties of the produced film were measured and shown in Table 1 below.

[Example 3]

Except for adjusting the coating amount after drying the light-to-heat conversion layer was prepared in the same manner as in Example 1.

The physical properties of the produced film were measured and shown in Table 1 below.

Example 4

Except for changing the light-heat conversion layer composition was prepared in the same manner as in Example 1.

Preparation of the composition (A-2) for photothermal conversion layer manufacture

Polyvinyl chloride vinyl acetate copolymer (Dow Chemical, VMCH grade) 16 wt%, Polyurethane resin (Lubzizol, ESTANE 5715 grade) 37 wt%, Polyisocyanate (Aekyung Chemical, AK75 grade) 7 wt%, Carbon black (Degussa) , 40% by weight of PRINTEX L6 grade) was added to a mixed solvent of toluene: methyl ethyl ketone: cyclohexanone = 1: 1: 1 by weight so as to have a solid content of 15% by weight to prepare a composition for preparing a photothermal conversion layer.

The physical properties of the produced film were measured and shown in Table 1 below.

[Example 5]

Except for changing the light-heat conversion layer composition was prepared in the same manner as in Example 1.

Preparation of the composition (A-3) for manufacturing a photothermal conversion layer

Polyvinyl chloride vinyl acetate copolymer (Dow Chemical, VMCH grade) 20wt%, Polyurethane resin (Lubzizol, ESTANE 5715 grade) 46wt%, Polyisocyanate (Aekyung Chemical, AK75 grade) 9wt%, Carbon black (Degussa , 25% by weight of PRINTEX L6 grade) was added to a mixed solvent of toluene: methyl ethyl ketone: cyclohexanone = 1: 1: 1 by weight so as to have a solid content of 15% by weight to prepare a composition for preparing a photothermal conversion layer.

The physical properties of the produced film were measured and shown in Table 1 below.

[Example 6]

It was prepared in the same manner as in Example 1 except for changing the intermediate layer composition.

Preparation of the composition for manufacturing the intermediate layer (B-2)

To 100 parts by weight of the solid content of the fluorine-substituted UV-curable urethane acrylate resin (KY11M-45CF from Negami, Inc.), 3 parts by weight of an initiator (Shiga Irgacure 184) was added to prepare a composition for producing an intermediate layer.

The physical properties of the produced film were measured and shown in Table 1 below.

[Example 7]

It was prepared in the same manner as in Example 1 except for changing the intermediate layer composition.

Preparation of the intermediate layer composition (B-3)

To 100 parts by weight of solids of the UV-curable urethane acrylate resin (Negami, KY11M-45C), 3 parts by weight of a photoinitiator (Irgacure 184, Ciba) was added, and 3 parts by weight of a silicone additive (Amter, USO-100). By addition, the composition for preparing the interlayer was prepared.

The physical properties of the produced film were measured and shown in Table 1 below.

[Example 8]

It was prepared in the same manner as in Example 1 except for changing the intermediate layer composition.

Preparation of the intermediate layer composition (B-4)

To 100 parts by weight of solids of the fluorine-substituted UV-curable urethane acrylate resin (Negami KY11M-45CF), 3 parts by weight of a photoinitiator (Irgacure 184, Ciba) was added, and a silicone-based additive (Amtra, USO-100) was added. 3 parts by weight was added to prepare a composition for preparing the intermediate layer.

The physical properties of the produced film were measured and shown in Table 1 below.

[Example 9]

It was prepared in the same manner as in Example 1 except for changing the light-to-heat conversion layer composition.

Preparation of the composition for preparing a photothermal conversion layer (A-4)

Polyvinyl chloride vinyl acetate copolymer (Dow Chemical, VMCH grade) 18 wt%, Polyurethane resin (Lubzizol, ESTANE 5715 grade) 43 wt%, Polyisocyanate (Aekyung Chemical, AK75 grade) 9 wt%, Carbon black (Degussa) , 30% by weight of PRINTEX L6 grade) was added to a mixed solvent of toluene: methyl ethyl ketone: cyclohexanone = 1: 1: 1 by weight so as to have a solid content of 15% by weight to prepare a composition for preparing a photothermal conversion layer.

At this time, the preparation of the crude liquid was prepared through a kneading and milling filtering process as follows.

First, kneading was carried out by heating and dissolving the polyvinyl chloride vinyl acetate copolymer at 50 ° C. in a mixed solvent mixed with a toluene: methyl ethyl ketone: cyclohexanone = 1: 1: 1 weight ratio to prepare a 13 wt% polyvinyl chloride vinyl acetate solution. Prepared. After putting a certain amount of carbon black into the kneading machine, the polyvinyl chloride vinyl acetate solution was added little by little while the kneading machine was operated, and kneading was performed for 1 hour.

After kneading was finished, the kneaded liquid was put into a ring milling container of a ring mill filled with 80% of 1.2 mm zirconium particles, and a mixed solvent was prepared in a toluene: methyl ethyl ketone: cyclohexanone ratio of 1: 1: 1 by weight. 20 wt% polyurethane resin and a mixed solvent (toluene: methyl ethyl ketone: cyclohexanone = 1: 1: 1 weight ratio) heated and dissolved at 50 ° C. were added thereto to prepare a solution having a solid content ratio of 15 wt%. After the prepared liquid was added, two stirrers were operated in the mill to perform milling. The stirrer used to mix the coating solution into the mill was adjusted to 1000 rpm, and the stirrer installed in the ring part for particle dispersion was stirred at 2000 rpm for 6 hours.

The milled liquid was filtered using a filter capable of filtering particles of 3.0 µm or more. The filtered solution was coated with Meyer Bar # 8, dried at 120 ° C. for 30 seconds, and the surface condition was checked under a microscope. After filtering, polyisocyanate as a curing agent was added thereto, and stirred for 1 hour to prepare a composition for preparing a photothermal conversion layer.

The physical properties of the produced film were measured and shown in Table 1 below.

[Example 10]

Except for adjusting the coating amount after drying of the light-to-heat conversion layer was prepared in the same manner as in Example 1.

The physical properties of the produced film were measured and shown in Table 1 below.

[Example 11]

Except that the thickness of the intermediate layer was adjusted to 3.5㎛ was prepared in the same manner as in Example 1.

[Example 12]

Except that the thickness of the intermediate layer was changed to 4.0㎛ was prepared in the same manner as in Example 1.

The physical properties of the produced film were measured and shown in Table 1 below.

[Example 13]

Except that the thickness of the intermediate layer was changed to 0.5㎛ was prepared in the same manner as in Example 1.

The physical properties of the produced film were measured and shown in Table 1 below.

Example 14

Except for changing the coating amount to 4.0g / ㎡ after drying the light-heat conversion layer was prepared in the same manner as in Example 1.

The physical properties of the produced film were measured and shown in Table 1 below.

Example 15

Except for changing the coating amount to 0.5g / ㎡ after drying the light-heat conversion layer was prepared in the same manner as in Example 1.

The physical properties of the produced film were measured and shown in Table 1 below.

[Example 16]

Except for changing the light-heat conversion layer composition was prepared in the same manner as in Example 1.

Preparation of the composition for preparing a photothermal conversion layer (A-5)

Polyvinyl chloride vinyl acetate copolymer (Dow Chemical, VMCH grade) 43wt%, Polyurethane resin (Lubzizol, ESTANE 5715 grade) 18wt%, Polyisocyanate (Aekyung Chemical, AK75 grade) 9wt%, Carbon black (Degussa , 30% by weight of PRINTEX L6 grade) was added to a mixed solvent of toluene: methyl ethyl ketone: cyclohexanone = 1: 1: 1 in a weight ratio to prepare a composition for preparing a photothermal conversion layer.

The physical properties of the produced film were measured and shown in Table 1 below.

Example 17

Except for changing the light-heat conversion layer composition was prepared in the same manner as in Example 1.

Preparation of the composition for preparing a photothermal conversion layer (A-6)

12% by weight of polyvinyl chloride vinyl acetate copolymer (Dow Chemical, VMCH grade), 30% by weight of polyurethane resin (Lubzizol, ESTANE 5715 grade), 8% by weight of polyisocyanate (Aekyung Chemical, AK75 grade), carbon black (Degus) , 50% by weight of PRINTEX L6 grade) was added to a mixed solvent of toluene: methyl ethyl ketone: cyclohexanone = 1: 1: 1 by weight to prepare a composition for preparing a photothermal conversion layer.

The physical properties of the produced film were measured and shown in Table 1 below.

Comparative Example 1

A primer film was prepared in the same manner as in Example 1 except that the PET film was not used.

The physical properties of the produced film were measured and shown in Table 1 below.

Comparative Example 2

It was prepared in the same manner as in Example 1 except for changing the composition of the intermediate layer and the light-heat changing layer.

Preparation of the composition for photothermal conversion layer (A-7)

12% by weight of polyvinyl chloride vinyl acetate copolymer (Dow Chemical, VMCH grade), 30% by weight of polyurethane resin (Lubzizol, ESTANE 5715 grade), 8% by weight of polyisocyanate (Aekyung Chemical, AK75 grade), carbon black (Degus) , 80% by weight of PRINTEX L6 grade) was added to a mixed solvent of toluene: methyl ethyl ketone: cyclohexanone = 1: 1: 1 in a weight ratio to prepare a composition for preparing a photothermal conversion layer.

Preparation of the composition for manufacturing the intermediate layer (B-5)

UV curable urethane acrylate resin (Toyo ink, Lioduras LCH series) was used. The coating was diluted with a methyl ethyl ketone solvent to prepare a 20% by weight solid solution, followed by coating.

The physical properties of the produced film were measured and shown in Table 1 below.

[Table 1]

As shown in the table, the surface energy is 35mN / m or less, the thickness of the intermediate layer is 3.5㎛ or less, the coating amount after drying of the light-to-heat conversion layer 3.5g / ㎡ or less, 40% by weight of carbon content was used In Examples 1 to 11 it can be seen that the best transferability and blocking properties can be achieved.

In addition, Comparative Example 1, which did not form a primer layer, was poor in transferability, and Comparative Example 2 was found to have high carbon content, poor surface energy, and thus poor transferability, and poor blocking properties.

Claims (13)

A base film, a primer layer, a light-to-heat conversion layer, an intermediate layer, and a transfer layer,
The light-heat conversion layer comprises a resin composition containing a thermosetting resin and a light-heat conversion material, the intermediate layer comprises a UV curable resin and the surface energy of 35mN / m or less donor film for the thermal transfer method. The method of claim 1,
A donor film for thermal transfer method of which the surface energy of the intermediate layer is 18mN / m to 35mN / m. The method of claim 2,
A donor film for thermal transfer method of which the surface energy of the intermediate layer is 18mN / m to 25mN / m. The method of claim 1,
The donor film for thermal transfer methods whose surface roughness Ra of the said light-to-heat conversion layer is 20 nm or less. The method of claim 1,
The thermosetting resin in the light-heat conversion layer is a polyurethane-based resin, the light-heat conversion material is a carbon black donor film for the thermal transfer method. 6. The method of claim 5,
The polyurethane resin is a donor film for thermal transfer method selected from polyester polyurethane, polycarbonate polyurethane. The method of claim 1,
The light-to-heat conversion material is a donor film for thermal transfer method comprising 20 to 40% by weight. The method of claim 1,
The light-heat conversion material is a donor film for a thermal transfer method using a polyvinyl chloride, polyvinyl chloride polyvinylacetate copolymer, one or more resins selected from thermosetting polyurethane and dispersed in a solvent. The method of claim 1,
The light-heat conversion layer is a donor film for a thermal transfer method further comprises a thermoplastic resin less than 50% by weight of the total resin composition. The method of claim 1,
The light-to-heat conversion layer is a donor film for thermal transfer method having a coating amount of 1 ~ 3.5g / ㎡ after drying. The method of claim 1,
The intermediate layer is a donor film for thermal transfer method is 1.0 ~ 3.5㎛ thickness. The method of claim 1,
UV curable resin in the intermediate layer is a thermal transfer method donor film is a fluorine-substituted UV curable resin. The method of claim 1,
The intermediate layer is a donor film for thermal transfer method further comprising a silicone resin or a fluorine resin.

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