KR100946201B1 - Method of manufacturing thermal transfer film - Google Patents

Abstract

The present invention is coated with a first release agent layer and a second release agent layer on both sides of the synthetic resin film of 5 to 200㎛ thickness, the hard coating composition is coated on the second release agent layer is provided with a hard coating layer formed by curing, It relates to a transfer film and a method of manufacturing the print layer is formed on the hard coating layer.

According to the present invention, it is possible to provide a transfer film capable of realizing vivid colors with excellent printability, adhesion, and solvent resistance, and to realize three-dimensional molding with high hardness, and inserting into an injection mold after forming a printing layer. When the injection, the hard coat layer may be provided with a transfer film which is cleanly separated from the film together with the print layer and transferred to the injection molded product, and a method of manufacturing the same.

Transfer film, semi-hardening, thermal transfer, injection, photoinitiator, soft acrylate, hard acrylate, monomer acrylate

Description

Manufacturing Method of Transfer Film {METHOD OF MANUFACTURING THERMAL TRANSFER FILM}

The present invention relates to a transfer film capable of realizing vivid colors with excellent printability, adhesion, and solvent resistance, and to realize three-dimensional molding with high hardness, and more particularly, after the printing layer is formed, it is inserted into an injection mold. It relates to a transfer film and a method of manufacturing the hard coating layer is cleanly separated from the film with the printing layer at the time of injection and transferred to the injection.

As a method for treating a pattern for decorative purposes on a metal or plastic surface, a screen printing method, a pad printing method, a thermal transfer printing method using a transfer paper, and the like are used.

The screen printing method is useful for printing on the surface of a product having a smooth surface such as a synthetic resin plate because of the simple printing equipment and the simple printing method. However, when the surface to be printed is curved or multicolor printing is required There is a disadvantage that the precision of the pattern and the painting is inferior.

The pad printing method is to engrave a three-dimensional pattern on a flexible pad, and to print on the printed surface by applying ink to the three-dimensional pattern, which is printed on a ceramic product, such as a plate, on which the surface to be printed is not smooth and curved. Although it is used when printing multicolored patterns, it is not only hassle to print several times according to colors using multiple pads, but also when the printed layer is dried each time the printed layer is dried, Since printing requires a long printing time and difficult to match the boundary of the pattern, there is a problem in that precise printing is not obtained.

In addition, the general screen printing method can be applied only to products with a smooth surface, the pad printing method has a problem that the productivity is reduced by replacing the pad when implementing a multi-color by three-dimensional curved printing.

Accordingly, in order to solve the problems caused by the printing of multi-colored patterns and the problems of three-dimensional curved printing in the screen printing method and the pad printing method described above, a thermal transfer printing method using a transfer film is mainly used as a printing on a synthetic resin product. It is used.

In the thermal transfer printing method using a transfer film, a transfer film is prepared by sequentially laminating a hot melt release agent layer, a print protection layer, a patterned print layer, and a hot melt adhesive layer on a surface of a base film made of paper or a synthetic resin film. And the transfer film is brought into close contact with the surface of a transfer object, for example, a synthetic resin product, and heat-compressed so that the print layer is transferred to the transfer object, and then the base film is separated from the print layer.

In the transfer printing method, since the pattern printed on the printing layer of the transfer paper is transferred as it is to the transfer object, a relatively sophisticated multicolored pattern appears on the surface of the transfer body in a simple manner.

In addition, the transfer printing method may be applied to the silk screen printing method that can produce a product with a smooth surface, as well as after printing in gravure by laminating a hot melt adhesive layer is transferred to the surface of the injection molding to adhere to the surface of the product It is possible to print a three-dimensional curved surface by heat compression.

In the conventional method of manufacturing a thermal transfer film, a color paint is printed on a plastic product in order to realize color on an injection molded article, and then a hard coating composition is applied to protect a printed layer, and the UV coating is performed. . However, this has a harmful effect on the environment due to the spray coating method, there is a limit in the color implementation, there is a problem that must be produced separately for each accessory.

In order to overcome this problem, a hard coating composition composed of an ultraviolet curable resin, a photoinitiator and an organic solvent, which is cured by ultraviolet irradiation, is coated on the surface of a synthetic film such as polyethylene terephthalate (PET) resin film, and a 400 nm long wavelength ultraviolet ray is applied thereto. The transfer film was prepared by curing the hard coating composition to form a hard coating layer, forming a printing layer of various colors by a conventional printing method, and then applying a hot melt adhesive layer thereon.

The transfer film is to form a printing layer on the hard coating composition is completely cured, so that not only the adhesion between the hard coating composition and the printing layer is lowered, but also the hardness is high and the elasticity is low, so that the crack when bonding to the curved surface It can also occur. Therefore, the adhesion between the hard coating layer and the printing layer is weak, so that the delamination between the hard coating composition and the printing layer is likely to occur, and when the transfer layer is transferred to the printed object using the transfer film, the printing layer is broken. There is a problem that incomplete transcription occurs.

In order to solve the above problem, a transfer film was formed by forming a stable layer on the hard coating layer and forming a printing layer thereon to increase the adhesion between the hard coating layer and the printing layer.

However, even when the stabilized layer is utilized, although the adhesion between the hard coat layer and the printed layer can be improved, the problem of cracking when the surface is adhered due to its high hardness still remains, There are disadvantages.

Thus, in Korean Patent Laid-Open Publication No. 2005-11833, a semi-hardened transfer film was introduced to solve problems of adhesion between the hard coating layer and the printing layer and high hardness of the hard coating layer.

The semi-cured transfer film constitutes a hard coating composition using a short wavelength initiator and a long wavelength initiator, and in the curing step irradiates short wavelength ultraviolet rays of 250 nm or less to semi-harden the ultraviolet resin composition, and then prints on the semi-cured ultraviolet resin composition. After forming the layer is a method of completely curing by irradiating 400nm long wavelength ultraviolet rays to the printed layer.

However, in the method of manufacturing the semi-cured transfer film, the materials used as the long-wavelength initiator have a problem of low stability at room temperature storage, causing a crack in the hard coating layer as the storage time elapses, and after the UV coating in the semi-cured state. In the process of winding the transfer film, a blocking phenomenon occurs between the semi-hardened layer and the back surface of the base film, thereby causing a problem of forming a stain on the coating layer.

In addition, due to the tacky of the semi-cured layer due to the semi-cured, there is a problem that the semi-cured material is transferred to the back of the base film.

The present invention is to solve the above problems, its purpose is to prevent harmful effects on the environment due to the conventional spray coating method, to prevent the occurrence of cracks due to the high hardness characteristics of the hard coating layer, the quality of the three-dimensional curved surface The present invention provides a transfer film capable of high printed matter transfer and a method of manufacturing the same.

In addition, an object of the present invention is to provide a transfer film including a hard coating composition capable of improving the adhesion between the hard coating layer and the printing layer without a stable layer and a method of manufacturing the same.

In addition, while using the manufacturing method of the semi-hardened transfer film, the transfer film can be stored for a long time, the staining is not formed on the coating layer during the winding, and the semi-cured material on the back of the base film does not transfer and a method for manufacturing the same The purpose is.

Method for producing a transfer film according to the present invention for solving the above problems is the first release agent layer coating step of coating the first release agent layer on the lower surface of the synthetic resin film which is a base film; A second releasing agent layer coating step of coating a second releasing agent layer on an upper surface of the base film; Curing resin coating step of mixing and coating a hard coating composition comprising a semi-cured acrylate, photoinitiator on the second release agent layer; A semi-curing step of drying the hard coating composition at 50 to 150 ° C. for 30 seconds to 5 minutes and irradiating ultraviolet rays with a light amount of 20 to 450 mJ / cm ² to form a hard coating layer in a semi-cured state; A printing layer coating step of coating a printing layer on the hard coating layer; It comprises an adhesive layer coating step of coating a hot melt adhesive layer on the printed layer.

Here, the first release agent layer is made of a silicone-based release agent, the second release agent layer is preferably made of a melamine-based release agent in order to exhibit an effective peeling characteristics.

In addition, the release force of the first release agent layer is preferably 5 to 1,500 N / mm in order to prevent slipping during roll running, and to prevent the blocking phenomenon of the hard coating layer.

In addition, the synthetic resin film is made of any one of the synthetic resin of PET, PVC, PP, PE, PMMA, PC, the thickness is 5 to 200㎛ to prevent the bending or folding phenomenon during the process, the cracking of the hard coating layer It is desirable to prevent.

In addition, the semi-curable acrylate is composed of a hard and soft photocurable oligomer acrylate, the hard coating composition, in the 100% by weight of the hard coating composition, the hard photocurable oligomer acrylate is 5 to 90 weight %, The soft photocurable oligomer acrylate is 5 to 90% by weight, the photoinitiator comprises 0.2 to 10% by weight, the hard coating composition is mixed with an organic solvent, the 100 parts by weight of the hard coating composition 50 to 500 parts by weight of an organic solvent is preferably coated on the second release agent layer to maximize the semi-curing properties.

In addition, the hard and soft photocurable oligomer acrylate, urethane acrylate, urethane methacrylate, epoxy acrylate, epoxy methacrylate, ester acrylate, ester methacrylate, acrylic acrylate, polyester acrylate At least one of the amine-modified acrylates is the most preferred composition choice for semi-curing properties.

In addition, the semi-cured acrylate further comprises a hard monomer acrylate, in 100% by weight of the hard coating composition, the hard photocurable oligomer acrylate is 3 to 55% by weight, the hard monomer acrylate is 5 to 40% by weight, 5 to 50% by weight of the soft photocurable oligomer acrylate, 0.2 to 10% by weight of the photoinitiator is composed of oligomer acrylate of the convenience and resin simplicity of the resin synthesis and desired viscosity It is preferable to obtain.

In addition, the hard monomer acrylate is 1,6 hexanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, At least one of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, lauryl acrylate, isobornyl acrylate and isodecyl acrylate is preferable to achieve the best ultraviolet curable resin.

In addition, the transfer film according to the present invention, the first release agent layer and the second release agent layer is coated on both sides of the synthetic resin film of 5 to 200㎛ thickness, the hard coating composition is coated on the second release agent layer and then cured A formed hard coating layer is provided, and a printing layer and a hot melt adhesive layer are sequentially formed on the hard coating layer, and the hard coating composition is made of hard and soft photocurable oligomer acrylate, and the hard coating composition is 100 weight In%, the hard photocurable oligomer acrylate is 5 to 90% by weight, the soft photocurable oligomer acrylate comprises 5 to 90% by weight, the photoinitiator comprises 0.2 to 10% by weight.

Here, the semi-cured acrylate further comprises a hard monomer acrylate, in 100% by weight of the hard coating composition, the hard photocurable oligomer acrylate is 3 to 55% by weight, the hard monomer acrylate is 5 to 40% by weight, 5 to 50% by weight of the soft photocurable oligomer acrylate, 0.2 to 10% by weight of the photoinitiator is composed of oligomer acrylate of the convenience and resin simplicity of the resin synthesis and desired viscosity It is preferable to obtain.

In addition, the hard and soft photocurable oligomer acrylate, urethane acrylate, urethane methacrylate, epoxy acrylate, epoxy methacrylate, ester acrylate, ester methacrylate, acrylic acrylate, polyester acrylate At least one of the amine-modified acrylate, the hard monomer acrylate is 1,6 hexanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylol triacrylate, pentaerythritol triacryl At least one of latex, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, lauryl acrylate, isobornyl acrylate, and isodecyl acrylate has the best properties. It is preferable to.

According to the transfer film and the manufacturing method according to the present invention, due to the conventional spray coating method to prevent harmful effects on the environment, to prevent the occurrence of cracks due to the high hardness characteristics of the hard coating layer, and the quality of the three-dimensional curved surface It is possible to provide a transfer film capable of high printed matter transfer and a method of manufacturing the same.

In addition, even without a stable layer, it is possible to provide a transfer film including a hard coating composition capable of improving the adhesion between the hard coating layer and the printing layer and a manufacturing method thereof.

In addition, while using the manufacturing method of the semi-hardened transfer film, it can be stored for a long time, the stain is not formed on the coating layer during winding, and the transfer film and the method of manufacturing the semi-cured material on the back of the base film does not transfer. Can be.

Hereinafter, a transfer film and a manufacturing method according to the present invention will be described with reference to the drawings.

1 is a cross-sectional view of a transfer film according to the present invention, Figure 2 is a flow chart showing a method of manufacturing a transfer film according to the present invention.

As shown in FIG. 1, the transfer film 1 according to the present invention has a second release agent layer 300, a hard coating layer 400, a printing layer 500, and an adhesive on an upper surface of a synthetic resin film which is a base film 100. The layers 600 are stacked in this order, and the first release agent layer 200 is coated on the bottom surface thereof.

As shown in FIG. 2, the method of manufacturing a transfer film according to the present invention includes a first release agent layer coating step (S10), a second release agent layer coating step (S20), a cured resin coating step (S30), and a semi-curing step (S40). ), The print layer coating step (S50), including the adhesive layer coating step (S60).

The first release agent layer coating step (S10) is a step of coating the first release agent layer 200 on the bottom surface of the synthetic resin film which is the base film 100.

The second release agent layer coating step (S20) is a step of coating the second release agent layer 300 on the opposite surface, that is, the upper surface of the base film 100, on which the first release agent layer 200 is coated.

Here, the first release agent layer 200 and the second release agent layer 300 is to form a thickness of 0.1 to 20㎛, preferably 0.5 to 5㎛.

Curing resin coating step (S30) is a step of forming a hard coating layer 400 by coating a hard coating composition containing a semi-cured acrylate and a photoinitiator on the second release agent layer (300).

In the hard coating composition, an organic solvent, a leveling agent, and other additives may be coated by mixing together an extender pigment, a colorant, an octane powder as an antimicrobial agent, zeolite, and the like.

Semi-step (S40) is that the drying is a hard coating composition in the 50 to 150 ℃ 30 seconds to 5 minutes, preferably from 20 to 450mJ / cm ^2, and more preferably It is a step of forming a hard coat layer of the semi-cured state by irradiating ultraviolet light with a light amount of 40 to 350mJ / cm ^{2 ,} .

Herein, the amount of ultraviolet light is to allow the hard coating composition to be semi-cured, and when the amount of light is less than 20 mJ / cm ^2, the transfer film in the wound state is increased because the adhesiveness is increased to the semi-cured hard coating layer 400. Pollution of the roll, or the hard coating layer 400 or the print layer 500 has a problem that the transfer or transfer to the roll, 450mJ / cm ² Amount of light If it exceeds, the hardness is increased, there is a problem that the crack or cracking phenomenon of the hard coating layer 400 occurs during the three-dimensional curved surface.

In general, when the amount of ultraviolet light is irradiated at 350 mJ / cm ² or more, the hard coating composition is often completely cured. However, in the present invention, a soft and hard resin composition is suitably mixed, and thus the amount of ultraviolet light is 350 mJ / cm. even when irradiation with cm ² or more, the hardness of the cured resin composition in some cases to obtain a resin which is low elongation.

Printing layer coating step (S50) is a step of coating a printing layer 500 containing a printing ink on the hard coating layer 400.

There is no particular limitation on the printing method used in the printing layer coating step (S50), a conventional method such as gravure printing, offset printing, silkscreen printing can be applied.

Adhesive layer coating step (S60) is a step of coating the hot melt adhesive 600 on the printing layer 500.

The transfer film 1 thus prepared is inserted into an injection mold, and the molten resin of the transfer object is injected and filled through a nozzle in the mold, cooled by cooling, the resin is solidified, and the mold is opened. When the base film 100 is peeled off from the subsequent molded article, a three-dimensional molded article obtained by transferring a pattern including the hard coat layer 400, the print layer 500, and the hot melt adhesive layer 600 is obtained.

The material to be transferred is not particularly limited in material or shape, and examples thereof include acrylic resins, vinyl chloride resins, acrylonitrile butadiene styrene copolymers (ABS resins), polycarbonate resins, polyethylene, polypropylene, and phenol resins. Resins or metals or metal compounds such as aluminum, iron, stainless steel, pearls, woods such as plywood, wood boards, medium density fiberboard (MDF), ceramics such as glass, ceramics, tiles, etc. , Cement, such as GRC (fibre-reinforced concrete), calcium silicate, asbestos slate and the like.

Next, the transfer film 1 manufactured by the manufacturing method will be described in detail.

Base Film (100)

As the base film 100, a synthetic resin film such as PET, PVC, PE, or PMMA film may be used, and in particular, the PET film may be made of a material that is not melted or deformed by heat applied in a subsequent transfer process. Mainly used.

It is preferable that the thickness of the base film 100 is 5-200 micrometers, More preferably, it is 10-125 micrometers, More preferably, it is 20-100 micrometers. When the thickness of the base film 100 is less than 5㎛, it is difficult to handle each process, so that bending or folding may occur, and bending or curling may occur during coating of a release agent layer or coating of a hard coating layer. Can be. In addition, in the case of 200 μm or more, it is necessary to apply high temperature and high pressure for forced forming in the injection mold. Therefore, it is difficult to perform perfect three-dimensional molding, and in particular, the hard coating layer 400 may be cracked or cracked due to high pressure. Phenomenon may occur.

The present invention uses a method of semi-hardening the hard coating composition as a method of forming the hard coating layer 400, since the semi-hardened hard coating composition has a predetermined viscosity, that is, tacky.

Therefore, the semi-hardened hard coat layer 400 is formed, and the semi-hardened hard coat layer 400 due to the adhesion in the process of winding it by contacting the back surface ('lower' in the present invention) of the base film 100 The semi-cured UV curable resin may be partially transferred to the lower surface of the base film 100, thereby causing a problem in that an uneven coating layer may be formed.

First release agent layer (200)

The first release agent layer 200 is to solve the above problem, and serves to prevent the semi-cured layer before the hard coat layer 400 is transferred to the bottom surface of the base film 100.

The first release agent layer 200 may be used alone or mixed with silicon, paraffin wax, fluorine, melamine-based release agent, but preferably a silicone-based release agent having the best release properties. Melamine-based, paraffin wax-based or fluorine-based releasing agent has a high release force so that the semi-hardened hard coating layer 400 is partially transferred to the lower surface of the base film 100 when the semi-hardened hard coating layer 400 is wound, so that an uneven coating layer Problems that can be formed can arise.

In a state in which the first release agent layer 200 is in contact with the lower surface of the base film 100, the release force for peeling the first release agent layer 200 is 5 to 1,500 N / mm, preferably 10 to 1,000 N / mm, more preferably 15. Should be from 800 N / mm.

When the release force is less than 5N / mm, the surface frictional force of the first release agent layer 200 may not be sufficient when the roll travel in the transfer film manufacturing process may cause a sliding phenomenon. When the release force exceeds 1,500 N / mm, a blocking phenomenon of the hard coat layer may occur during the winding of the transfer film, and the radius of the semi-hardened hard coat layer 400 may be reduced. The hard coating layer 400 is partially transferred to the lower surface of the base film 100 may cause a problem that a non-uniform coating layer can be formed.

2nd release agent layer (300)

The second release agent layer 300 is formed on the upper surface of the base film 100, that is, on the opposite side of the surface on which the first release agent layer 200 is formed. The second release agent layer 300 serves to allow the hard coating layer 400 to be easily separated from the base film 100 so as to be easily transferred to the printing layer 400.

The second release agent layer 300 may be used alone or in combination with silicone, paraffin wax, fluorine, melamine-based release agent, preferably melamine-based release agent. The silicone, paraffin wax, and fluorine-based releasing agent may have poor wettability when the hard coating composition is applied on the second releasing agent layer 300, thereby preventing the coating from being properly formed, and the semi-hardened hard coating layer 400 may not be peeled off. May occur.

Hard coating layer (400)

In general, the hard coating composition constituting the hard coating layer 400 is made of a material having excellent coating properties, sufficient strength, and excellent light transmittance, for example, a thermosetting resin, a thermoplastic resin, an ultraviolet curable resin, and an electron beam curable resin. And a two-liquid mixed resin.

Among them, an ultraviolet curable resin that can be cured by ultraviolet curing to form a hard coat layer efficiently by a simple processing operation is suitable.

UV curable resins generally used include polyesters, acrylics, urethanes, amides, silicones, epoxys, and the like, and UV curable monomers, oligomers, polymers, and the like.

Hard coating  Composition

In the present invention, the hard coating layer 400 is formed by applying a hard coating composition including an ultraviolet curable resin on the second release agent layer 300, and semi-curing the hard coating composition, the hard coating composition is a semi-curable acrylate and It comprises a photoinitiator, it is mixed with an organic solvent and a leveling agent to form a coating layer.

The semi-cured acrylate is a material having a property that does not completely cured when the UV cured, as it is after the coating, and consists of a material that minimizes the adhesion.

Conventional UV-curable resins are intended to be completely cured and use only hard materials having a pencil hardness of H or more. However, the semi-cured acrylates used in the present invention are mixed with acrylate-based materials and photoinitiators having hard and soft properties, respectively. It is through.

(1) semi-cured acrylate

As the semi-curable acrylate, a hard photocurable oligomer acrylate and a soft photocurable oligomer acrylate are used in combination, and a photoinitiator is added thereto to form a hard coating composition. In addition, it may be made by further comprising a hard monomer acrylate.

The content is 100% by weight of the hard coating composition, 5 to 90% by weight of the hard photocurable oligomer acrylate, 5 to 90% by weight of the soft photocurable oligomer acrylate, 0.2 to 10% by weight photoinitiator It includes, the organic solvent is made by mixing 50 to 500 parts by weight based on 100 parts by weight of the hard coating composition, 0.1 to 3 parts by weight of a leveling agent may be added thereto.

 Here, when the hard monomer acrylate is included, the hard coating composition is 3 to 55% by weight of the hard photocurable oligomer acrylate, 5 to 40% by weight of the hard monomer acrylate, the soft photocurable 5 to 50% by weight of oligomer acrylate, the photoinitiator may comprise 0.2 to 10% by weight.

1) Hard Photocurable Oligomeric Acrylate

The hard photocurable oligomer acrylate is a material exhibiting high hardness properties, the pencil hardness of H or more, and is used in the form of a low molecular weight polymer, that is, an oligomer with fewer repeating units.

2) soft photocurable oligomer acrylate

The soft photocurable oligomer acrylate is a material that gives an elongation to the resulting hard coat layer 400. Pencil hardness is less than H and is an elongated flexible material.

The hard and soft photocurable oligomer acrylates include urethane (meth) acrylates, epoxy (meth) acrylates, ester (meth) acrylates, acrylic acrylates, polyester acrylates, amine modified acrylates, and the like. These are used alone or in combination.

3) Hard monomer acrylate

The hard monomer acrylate is used for reasons of convenience of resin synthesis, simplicity of process, etc., and is a monomer (monomer) having a low molecular weight of liquid or semisolid, that is, a molecular weight of less than 500. By using the hard monomer acrylate, an ultraviolet curable resin having a desired viscosity can be obtained.

The hard monomer acrylate is 1,6 hexanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipenta Erythritol pentaacrylate, dipentaerythritol hexaacrylate, lauryl acrylate, isobornyl acrylate, isodecyl acrylate can be used alone or in combination.

In order to minimize the possibility of being limited to a neat coating because there is a possibility that some yellowing phenomenon occurs in the material, it is most preferably used by mixing a hard and soft urethane acrylate with the hard monomer acrylate.

4) content

The hard photocurable oligomer acrylate is 5 to 90% by weight, preferably 10 to 80% by weight, and the soft photocurable oligomer acrylate is 5 to 90% by weight in 100% by weight of the hard coating composition. 10 to 80% by weight is added.

Herein, when the hard monomer acrylate is included, the hard photocurable oligomer acrylate is added in an amount of 3 to 55% by weight, preferably 5 to 50% by weight, and the hard monomer acrylate is 5 to 40%. By weight, preferably 10 to 35% by weight, the soft photocurable oligomer acrylate is added 5 to 50% by weight, preferably 10 to 45% by weight.

The values given in parentheses below are for the case where hard monomer acrylates are included.

When the hard photocurable oligomer acrylate is less than 5% by weight (3% by weight) or when the soft photocurable oligomer acrylate is added in excess of 90% by weight (50% by weight) of the hard coat layer 400 produced. There is a problem that the mechanical properties such as hardness and wear resistance is weakened, on the contrary, when the hard photocurable oligomer acrylate is more than 90% by weight (55% by weight) or the soft oligomer acrylate is less than 5% by weight of the hard coating layer ( Although 400 is manufactured as a semi-hardened type, when formed into a three-dimensional curved shape, cracking or cracking may occur due to high hardness characteristics.

(2) photoinitiator

The photoinitiator used in the present invention is an organic photoinitiator in which benzotriazole-based, benzophenone-based compound, benzyl dimetal, ketan-based compound, acetophenone-based compound, or the like is used alone or in combination, or zinc oxide or oxide on fine particles having a particle diameter of 0.2 μm or less. Inorganic substances such as cerium and titanium oxide may be used.

The content of the photoinitiator may be adjusted according to the working conditions, that is, the working speed, the amount of ultraviolet light, etc., and includes 0.2 to 10% by weight in 100% by weight of the hard coating composition, when less than 0.2% by weight does not complete curing There exists a problem and when it exceeds 10 weight%, it is difficult to adjust the ultraviolet light quantity for making a resin composition semi-cured.

(3) organic solvent and leveling agent

An organic solvent and a leveling agent may be added to the UV resin composition including the semi-cured acrylate and the photoinitiator. The organic solvent is 50 to 500 parts by weight, and the leveling agent is 0.1 to 3, based on 100 parts by weight of the hard coating composition. Add parts by weight.

1) Organic Solvent

The organic solvent is used to appropriately lower the viscosity of the resin composition, and ketone-based compounds, aromatic compounds, and mixtures thereof are used. Preferably, MEK (methyl ethyl ketone), toluene, MIBK (methyl isobutyl ketone) and the like may be used, and when the content is less than 50 parts by weight with respect to 100 parts by weight of the hard coating composition, the viscosity of the composition may be increased during coating operation. If the thickness of the coating layer is not easy to control, and if it exceeds 500 parts by weight, the content of solids in the coated coating layer is too low, which results in the deterioration of all physical properties of the coating layer.

2) Leveling agent

In the present invention, the leveling agent is applied to even the surface of the hard coating layer 400, it may be used by mixing a ketone or ester-based solvent in the silicone resin. Among the silicone leveling agents, a silicone compound, a modified acrylate, and the like are particularly preferable, and slip is imparted to the surface by adding reactive silicone, so that scratch resistance is maintained.

The leveling agent may be added in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the hard coating composition, and preferably 0.2 to 2 parts by weight. When the leveling agent is added in less than 0.1 part by weight it is difficult to expect the leveling effect, when added to more than 3 parts by weight may be a weak surface hardness of the hard coating composition, or the leveling agent may bleed (bleeding).

In addition to the hard coating composition of the present invention, well-known additives such as a matting agent for improving adhesion with the print layer 500 may be further added.

Adhesive layer (600)

The adhesive layer 600 is a hot-melt adhesive having a thickness of about 10 μm coated on the printing layer 500, and does not contain water or an organic solvent, and is an adhesive composed only of solid content and easily melted by heating. It refers to the adhesive that is cured when it is cooled down. After drying it, it is pressed into a plastic bottle, and then the transfer film is separated, or inserted into an injection mold and then injected, and the printing layer 500 is transferred onto the surface of the plastic (injected product).

In the present invention, since the transfer film is manufactured in a state in which the hard coating layer 400 is semi-cured, it is preferable to form the print layer 500 together with the hard coating layer 400 in the injection molding by the latter injection molding method.

Hereinafter, the characteristics of the transfer film 1 produced by the above-described manufacturing method and a comparative example of the present invention will be described.

Example  One

The melamine-based second release agent layer 300 was coated on the top surface of the base film 100 on which the first release agent layer 200 was formed by the silicon-based release agent. Here, melamine was diluted with 25% including a curing agent and then coated with wire bar # 3. Here, the synthetic resin film used as the base film 100 used PET and PMMA.

After coating the second release agent layer 300, it was thermoset in an oven at 120 ° C. for 2 minutes and left at room temperature for at least 5 minutes.

58 wt% of the hard urethane acrylate and 39 wt% of the soft urethane acrylate and 3 wt% of the photoinitiator Irgacure 184D are mixed on the second release agent layer 300 to prepare 100 wt% of the hard coating composition, and the hard coating composition 100 After mixing and stirring 200 parts by weight of MEK and 200 parts by weight of MIBK with respect to parts by weight, 2.5 parts by weight of the acrylic leveling agent was added and sufficiently mixed, and then the hard coating composition was coated with wire bar # 10.

The coated hard coating composition was dried in an oven at 60 ° C. for 2 minutes, and then irradiated with a metal halide lamp at a light amount of 80 mJ / cm 2 to form a hard coating layer 400, wherein the printing layer 500 and the hot melt adhesive layer ( 600) was sequentially coated to prepare a transfer film (1), it was inserted into the injection mold together with the transfer molten resin to prepare a molded article having a three-dimensional pattern.

Example  2

A transfer film was manufactured in the same manner as in Example 1, except that the hard coating composition was prepared in Example 1 below.

100 wt% of the hard coating composition is made by mixing 67 wt% of soft urethane acrylate, 28 wt% of dipentaerythritol pentaacrylate, 2.5 wt% of Irgacure 184D, and 2.5 wt% of benzophenone, and mixing the hard coating composition. With respect to 100 parts by weight, 200 parts by weight of MEK and 200 parts by weight of MIBK were mixed and stirred, and then coated with wire bar # 10. The coated UV cured layer was dried in an oven at 60 ° C. for 2 minutes, and then irradiated with a metal halide lamp at a light amount of 400 mJ / cm 2.

Comparative example  One

Same as Example 1 except that the base film 100 was used as a double-sided untreated PET film, and the hard coating layer 400 was completely cured by irradiating 400mJ / cm 2 of light instead of 80mJ / cm 2 of the semi-curing step. To prepare a transfer film in the same manner as in Example 1.

Pencil hardness, three-dimensional processability, transfer force, and winding properties of the three-dimensional molded article using the transfer film manufactured through the above Examples and Comparative Examples were measured as follows.

Pencil hardness

After coating the UV resin solution on each substrate and making it into a specimen (100 * 100mm), place it on an iron plate and fix it with a tape. Take a Mitsubishi pencil and grind it vertically on # 1000 sandpaper. By repeating the 50mm section five times at a rate of 0.5 mm / sec with a 45 ° inclination with respect to the plane of the sample was recorded the hardness of the pencil marks do not remain at the end three times except the initial two times.

3D processability

After the transfer film 1 is inserted into a mold having a different three-dimensional processing depth, there is no crack of the hard coating layer 400 at a depth of 7 mm or more, and there is no crack of the hard coating layer 400 at a depth of 3 to 7 mm or more. In the case of good, when the hard coating layer 400 is not broken in the depth of 3mm or less, usually, when the cracking phenomenon occurs even in the flat type was measured as bad.

Transcription

When the 3M Tape 810 is in close contact with the hard coating layer 400 on the second release agent layer 300 and then peeled off instantaneously, the entire adhered portion is exfoliated from the second release agent layer 300. When good, 40% to 80% when peeled off, usually 40% or less when peeled off was evaluated.

Winding

In order to evaluate the transfer property of the hard coating layer 400 on the second release agent layer 300 to the lower surface of the base film 100 when the transfer film 1 is coated, a circular weight having a diameter of 65 mm is pressed at 1000 g for 24 hours. After the addition of the hard coating layer 400 was determined whether the transition.

Table 1 below shows the results of the evaluation of the characteristics of the transfer film.

Evaluation item Pencil hardness 3D processability Transcription Winding PET PMMA Example 1 2H 4H ○ ◎ ◎ Example 2 H H ◎ ◎ ◎ Comparative example 2H 4H △ ◎ Ｘ

◎: excellent, ○: good, △: normal, Ｘ: poor

As shown in Table 1, the transfer film using the semi-curing method according to the present invention can be seen that the three-dimensional processability and winding properties are better than the transfer film produced by the comparative example using the full curing, in particular constant hardness It can be seen that the case of Example 1 in which is secured is most preferable.

In addition, the transfer film thus produced has a haze value of 2% or less, enabling free color implementation, excellent transmittance of the transferred hard coat layer, and excellent mechanical strength and three-dimensional processability.

Although the preferred embodiment of the present invention has been described above, the present invention may use various changes, modifications, and equivalents. It is clear that the present invention can be applied in the same manner by appropriately modifying the above embodiments. Accordingly, the above description does not limit the scope of the invention as defined by the limitations of the following claims.

1 is a cross-sectional view of the transfer film according to the present invention

2 is a flow chart showing a method of manufacturing a transfer film according to the present invention.

* Description of the major symbols in the drawings *

1: transfer film 100: base film

200: first release agent layer 300: second release agent layer

400: hard coating layer 500: printing layer

600: adhesive layer

Claims (11)

A first releasing agent layer coating step of coating a first releasing agent layer made of a silicone-based releasing agent on a lower surface of the synthetic resin film which is a base film and having a releasing force of 5 to 1,500 N / mm; A second release agent layer coating step of coating and thermosetting a second release agent layer made of a melamine-based release agent including a curing agent on an upper surface of the base film; Curing resin coating step of mixing and coating a hard coating composition comprising a semi-cured acrylate, photoinitiator on the second release agent layer; A semi-curing step of drying the hard coating composition at 50 to 150 ° C. for 30 seconds to 5 minutes and irradiating ultraviolet rays with a light amount of 20 to 450 mJ / cm ² to form a hard coating layer in a semi-cured state; A printing layer coating step of coating a printing layer on the hard coating layer; A method of manufacturing a transfer film comprising an adhesive layer coating step of coating a hot melt adhesive layer on the printed layer. delete delete The method of claim 1, The synthetic resin film is made of any one of the synthetic resin of PET, PVC, PP, PE, PMMA, PC, the thickness of the synthetic resin film is a manufacturing method of the transfer film, characterized in that 5 to 200㎛. The method of claim 1, The semi-cured acrylate is composed of hard and soft photocurable oligomeric acrylate, the hard coating composition, In 100% by weight of the hard coating composition,   1) the hard photocurable oligomer acrylate is 5 to 90% by weight,   2) the soft photocurable oligomer acrylate is 5 to 90% by weight,   3) the photoinitiator comprises 0.2 to 10% by weight, 50 to 500 parts by weight of an organic solvent based on 100 parts by weight of the hard coating composition is mixed and coated on the second release agent layer. The method of claim 5, The hard and soft photocurable oligomer acrylate, It is at least one of urethane acrylate, urethane methacrylate, epoxy acrylate, epoxy methacrylate, ester acrylate, ester methacrylate, acrylic acrylate, polyester acrylate, amine-modified acrylate Method for producing a film. The method of claim 1, The semi-cured acrylate is composed of hard and soft photocurable oligomer acrylate and hard monomer acrylate, the hard coating composition, In 100% by weight of the hard coating composition,   1) the hard photocurable oligomer acrylate is 3 to 55% by weight,   2) the hard monomer acrylate is 5 to 40% by weight,   3) the soft photocurable oligomer acrylate is 5 to 50% by weight,   4) The method of manufacturing a transfer film, characterized in that the photoinitiator comprises 0.2 to 10% by weight. The method of claim 7, wherein The hard and soft photocurable oligomer acrylate, At least one of urethane acrylate, urethane methacrylate, epoxy acrylate, epoxy methacrylate, ester acrylate, ester methacrylate, acrylic acrylate, polyester acrylate, amine-modified acrylate, The hard monomer acrylate is 1,6 hexanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipenta Method for producing a transfer film, characterized in that at least one of erythritol pentaacrylate, dipentaerythritol hexaacrylate, lauryl acrylate, isobonyl acrylate, isodecyl acrylate. delete delete delete

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