WO2015194856A1 - Coating composition, plastic film prepared by using same, and preparation method therefor - Google Patents

Abstract

The present invention relates to: a coating composition; a plastic film prepared by using the same; and a preparation method therefor and, more specifically, to: a coating composition capable of forming a plastic film exhibiting high hardness and excellent processability; a plastic film prepared by using the same and exhibiting a three-dimensional structure; and a preparation method therefor.

Description

 【Specification】

 [Name of invention]

 Coating composition, plastic film produced using the same, and a method of manufacturing the same [Cross-reference with Related Application (s)]

 This application is filed with Korean Patent Application No. 10-2014-0073636, filed on June 17, 2014.

Claims the benefit of priority based on Korean Patent Application No. 10-2014-0073637 dated June 17, 2014 and Korean Patent Application No. 10-2015-0085227 dated June 16, 2015, and is disclosed in the literature of the Korean patent applications. All content is included as part of this specification. Technical Field

 The present invention relates to a coating composition, a plastic film produced using the same and a method of manufacturing the same. More specifically, the present invention relates to a coating composition capable of forming a plastic film exhibiting high hardness and excellent processability, a plastic film prepared by using the same, and a three-dimensional structure, and a method of manufacturing the same.

 Background Art

 Recently, with the development of mobile devices such as smartphones and tablet PCs, thinning and slimming of display substrates are required. Glass or tempered glass is generally used for display windows or front panels of such mobile devices. It is used. However, the glass causes the mobile device to be heavier due to its weight and there is a problem of breakage due to external impact. Therefore, plastic resin is being researched as a substitute material for glass. Plastic resin films are lightweight and less prone to break, making them suitable for the trend toward lighter mobile devices. In particular, in order to achieve a film having properties of high hardness and wear resistance, a film for coating a hard coat layer made of a plastic resin on a supporting substrate has been proposed.

As a method of improving the surface hardness of the hard coating layer, a method of increasing the thickness of the hard coating layer may be considered. In order to secure the surface hardness to replace the glass it is necessary to implement the thickness of the hard coating layer. However, as the thickness of the hard coating layer is increased, the surface hardness may be increased. However, since wrinkles or curls increase due to hardening shrinkage of the hard coating layer, cracks or peeling of the hard coating layer are likely to occur. Is not easy. Korean Patent Publication No. 2010-0041992 discloses a plastic film composition excluding a monomer and using a binder resin including an ultraviolet curable polyurethane acrylate oligomer. However, the plastic film disclosed above is not strong enough to replace the glass panel of the display with a pencil hardness of 3H.

 On the other hand, for aesthetic and functional reasons, a display having a curved or partially curved three-dimensional shape of the display device has recently attracted attention, and this trend is particularly prominent in mobile devices such as smartphones and tablet PCs. However, when the glass is used as a cover plate for protecting such a three-dimensional display, there is a high risk of breakage due to the high weight of the glass and the weak characteristics of the outer layer.

 Although the plastic resin film is lighter and less brittle than glass, it is difficult to manufacture a film having a three-dimensional structure and high hardness as glass.

 [Content of invention]

 Problem to be solved

 In order to solve the above problems, the present invention exhibits high hardness after curing, and does not generate curls or cracks and is excellent in workability, thereby forming a plastic film having a three-dimensional structure in which not only a flat type but also at least a part is bent. It provides a coating composition that can be.

 In addition, the present invention provides a plastic film having a three-dimensional structure while showing a high hardness and a manufacturing method thereof.

 [Measures of problem]

 One aspect of the present invention to solve the above problems,

 Provided are a coating composition comprising a dual curable binder, photoinitiator, thermosetting agent, and inorganic fine particles contained in one molecule comprising a thermosetting functional group and a photocurable functional group.

 In addition, another aspect of the present invention

 Supporting substrate; And

It includes a coating layer formed on at least one side of the support substrate, The coating layer includes a cured product of a dual curable binder and inorganic fine particles included in one molecule including a thermosetting functional group and a photocurable functional group, and provides a plastic film having at least a part of a curved form.

 In addition, another aspect of the present invention,

 Applying to the at least one side of the supporting substrate a coating composition comprising a dual curable binder, photoinitiator, thermosetting agent, and inorganic fine particles contained in one molecule comprising a thermosetting functional group and a photocurable functional group;

 Performing a first curing on the applied coating composition to form a semi-cured coating layer;

 Performing thermoforming on the support substrate on which the semi-cured coating layer is formed; And

 It provides a method for producing a plastic film comprising the step of performing a second curing for the semi-hardened coating layer.

 【Effects of the Invention】

 According to the coating composition of the present invention, it is possible to provide a plastic film having a three-dimensional structure that exhibits high hardness, layer resistance, scratch resistance, high transparency, has low curling or cracking with excellent processability, and is not only a flat film but also at least a part of a curved shape. Can be.

 According to the present invention, it is possible to provide a film that exhibits high hardness, layer resistance, scratch resistance, and high transparency, and has excellent curling properties, less curl or crtack, and at least a part of which is curved.

 Accordingly, the plastic film of the present invention may be a plastic film having a three-dimensional shape, for example, one edge or an opposite edge portion is bent, all four edge portions are curved, or are entirely curved. It is possible to provide a film having a curved shape and high hardness.

 The plastic film may be usefully applied to cover plates such as mobile devices of various shapes, display devices, front panels of various instrument panels, display units, etc., as well as flat displays, which are replaced by cover plates made of glass or tempered glass.

In addition, according to the method for producing a plastic film of the present invention, the plastic film as described above can be produced in a low cost and a simple process. [Brief Description of Drawings]

 1 is a perspective view showing a plastic film according to an embodiment of the present invention.

 FIG. 2 is a cross-sectional view illustrating the plastic film of FIG. 1. FIG.

 3 is a perspective view showing a plastic film according to another embodiment of the present invention.

 4 is a cross-sectional view illustrating the plastic film of FIG. 3.

 5 is a perspective view showing a plastic film according to another embodiment of the present invention.

 6 is a cross-sectional view illustrating the plastic film of FIG. 5.

 [Specific contents to carry out invention]

 The present invention provides a coating composition comprising a binder, a photoinitiator, a thermosetting agent and inorganic fine particles contained in one molecule including a thermosetting functional group and a photocurable functional group.

 Moreover, this invention is a support base material; And a coating layer formed on at least one surface of the support substrate, wherein the coating layer includes a cured product of the dual curable binder and an inorganic fine particle included in one molecule including a thermosetting functional group and a photocurable functional group, and at least a part of which is curved. To provide a plastic film.

 In another aspect, the present invention comprises the steps of applying a coating composition comprising a double curable binder, a photoinitiator, a thermosetting agent, and inorganic fine particles contained in at least one surface of the supporting substrate in one molecule comprising a thermosetting functional group and a photocurable functional group; Performing a first curing on the applied coating composition to form a semi-cured coating layer; Performing thermoforming on the supporting substrate on which the semi-cured coating layer is formed; And it provides a method for producing a plastic film comprising the step of performing a second curing for the semi-hardened coating layer.

 In the present invention, terms such as first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.

In addition, the terminology used herein is for the purpose of describing example embodiments only and is not intended to be limiting of the invention. Singular expressions are contextual Including plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise", "comprise" or "have" are intended to indicate that there is a feature, step, component, or combination thereof, and one or more other features or steps, It is to be understood that the present invention does not exclude the possibility of adding or presenting elements, or a combination thereof.

 Also, in the present invention, when each component is referred to as being formed "on" or "on" of each component, it means that each component is directly formed on each component, or other components are each It can be formed additionally between the layer, the object, the substrate.

 As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to a specific disclosed form, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

 Hereinafter, the coating composition, the plastic film, and a manufacturing method of the present invention will be described in more detail. Coating composition

 One aspect of the present invention provides a coating composition comprising a double curable binder, a photoinitiator, a thermosetting agent and inorganic fine particles contained in one molecule including a thermosetting functional group and a photocurable functional group. Throughout this specification, the thermosetting functional group means a functional group capable of crosslinking polymerization with each other by heating at a predetermined temperature or more to form a cured product. For example, an epoxy group, a vinyl group, a hydroxyl group, an alkoxy group, a thi ( thiol), melamine (melamine), or a siloxane (siloxane) group may be included, but the present invention is not limited thereto. Throughout the present specification, the photocurable functional group means a functional group capable of crosslinking polymerization with each other by ultraviolet (UV) irradiation to form a cured product. For example, an acrylate group, a methacrylate group, a vinyl group, or a thiol Groups, and the like, but the present invention is not limited thereto.

In addition, the thermosetting functional group and the photo-curable functional group throughout the present specification The binder included in one molecule to be included may also be referred to as a double curable binder, and is used in the same sense.

 According to one embodiment of the invention, the dual curable binder may have a weight average molecular weight in the range of about 10,000 to about 300,000 g / mol, or about 15,000 to about 200,000 g / mol, or about 20,000 to about 50,000 g / md have. In addition, the equivalent weight of the thermosetting functional group and the photocurable functional group of the dual curable binder are the same or different, independently from each other, about 80 to about 1,500 g / eq, or about 100 to about 1,000 g / eq, or About 200 to about 600 g / eq.

 In the case of using the above-mentioned double curable binder, that is, a coating composition in which two single curable binders, that is, a binder containing only a thermosetting functional group and a binder containing only a photocurable functional group, are used, the coating layer after primary curing Since the tackness of the is good, secondary processing such as thermoforming is easy, and the crosslinking density can be increased, thereby improving mechanical strength. However, the present invention does not exclude the use of a binder containing only a thermosetting functional group and a binder containing only a photocurable functional group, and additionally, in order to further improve the physical properties of the coating layer, other photocurable binders and / or in addition to the double curable binder. It may comprise a thermosetting binder.

 The double curable binder having the above physical properties can be purchased directly or polymerized. In addition, the double curable binder may include only one type, or may be used by mixing two or more different types of double curable binders.

According to one embodiment of the present _invention. Within the dual curable binder, the thermosetting functional group and the photocurable functional group are included in a molar ratio of about 1: 9 to about 9: 1, or about 3: 7 to about 7: 3, or about 4: 6 to about 6: 4. Can be. When the thermosetting functional group and the photocurable functional group are included in the above range, it is possible to provide a plastic film having good processability while maintaining high hardness.

 The dual curable binder may be included in about 10 to about 50 parts by weight based on 100 parts by weight of the coating composition. By including the dual curable binder in the above range, it is possible to bend molding while maintaining a high hardness, it is possible to provide a plastic film having good processability.

The coating composition of the present invention comprises a photoinitiator. Examples of the photoinitiator include 1-hydroxycyclohexyl-phenyl ketone,

2-hydroxy-2-methyl-1-phenyl-1-propanone,

 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propanone,

Methyl benzoyl formate, _{α, α} - dimethoxy hydroxy _ _ _α-phenyl acetophenone, 2-benzoyl-2- (dimethylamino) -1- [4- (4-morpholine-yl) phenyl] -1-butanone,

2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone

Diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide, or bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like, but are not limited thereto. Commercially available products include Irgacure 184, Irgacure 500, Irgacure 651, Irgacure 369, Irgacure 907, Darocur 1173, Darocur MBF, Irgacure 819, Darocur TPO, Irgacure 907, and Esacure KIP 100F. These photoinitiators can be used individually or in mixture of 2 or more types different from each other.

 The content of the photoinitiator is not particularly limited, but may be included in an amount of about 0.1 to about 5 parts by weight based on 100 parts by weight of the coating composition to achieve effective photopolymerization without inhibiting the physical properties of the entire coating composition.

 The coating composition of the present invention comprises a thermosetting agent.

 The thermosetting agent may be used by selecting an appropriate compound according to the type of the thermosetting functional group, for example, when the thermosetting functional group is a hydroxy group (-OH), monomer, dimer, tri, containing isocyanate group (-NCO) what,. Or a polymer type material may be used as a thermosetting agent, and more specifically, toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), or isophorone diisocyanate (IPDI). Although may be used, the present invention is not limited thereto. In this case, dibutyl tin dilaurate (DBTDL, dibutyltindilaurate) may be added and used as a catalyst for promoting the thermal curing reaction.

In addition, the thermosetting agent that can be used according to the type of the thermosetting functional group, zinc octoate, iron acetyl acetonate, Ν, Ν-dimethyl ethanolamine, tri Ethylene diamine and the like, but are not limited thereto. These thermosetting agents can be used individually or in mixture of 2 or more types different from each other. The content of the thermosetting agent is not particularly limited, but may be included in an amount of about 10 to about 50 parts by weight based on 100 parts by weight of the coating composition to achieve effective heat curing without inhibiting the physical properties of the entire coating composition.

 The coating layer of the present invention contains inorganic fine particles. The inorganic fine particles serve to further improve the hardness of the coating layer.

 According to one embodiment of the present invention, as the inorganic fine particles, inorganic fine particles having a particle size of nanoscale, for example, a particle diameter of about 100 nm or less, or about 10 to about 100 nm, or about 10 to about 50 nm, may be used. . As the inorganic fine particles, for example, silica fine particles, aluminum oxide particles, titanium oxide particles, zinc oxide particles, or the like can be used.

 According to one embodiment of the present invention, the inorganic fine particles may be included in about 1 to about 40 parts by weight, or about 5 to about 30 parts by weight based on 100 parts by weight of the coating composition. By including the inorganic fine particles in the above range, it is possible to achieve the effect of improving the hardness of the plastic film according to the addition of the inorganic fine particles within the range of not lowering the physical properties such as flexibility.

 The coating composition may optionally further comprise an organic solvent for proper fluidity and applicability.

 According to an embodiment of the present invention, the organic solvent may be an alcohol solvent such as methanol, ethane, isopropyl alcohol, butanol, 2-methoxyethanol, 2-ethoxyethane, such as 1-methoxy-2-propanol. Ketone solvents such as alkoxyalcohol solvents, acetone, methyl ethyl ketone methyl isobutyl ketone, methyl propyl ketone, cyclonucleanone propylene glycol monopropyl ether, propylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monopropyl ether ethylene glycol Ether solvents such as monobutyl ether, diethylene glycol monomethyl ether diethyl glycol monoethyl ether, diethyl glycol monopropyl ether diethyl glycol monobutyl ether, diethylene glycol-2-ethyl nucleosil ether, benzene, toluene, Aromatic solvents, such as xylene, etc. can be used individually or in mixture.

According to one embodiment of the present invention, since the content of the organic solvent can be variously adjusted within a range that does not lower the physical properties of the coating composition, Although not limited, the weight ratio of solids: organic solvent may be included in a range of about 70:30 to about 99: 1 based on 100 parts by weight of the solids contained in the coating composition. When the organic solvent is in the above range, it may have appropriate flowability and applicability.

 On the other hand, the coating composition of the present invention, in addition to the above-described components, may further include additives commonly used in the art to which the present invention belongs, such as surfactant, yellowing inhibitor, leveling agent, antifouling agent. In addition, since the content can be variously adjusted within a range that does not lower the physical properties of the coating composition of the present invention, it is not particularly limited, for example, may be included in about 0.1 to about 10 parts by weight based on 100 parts by weight of the total coating composition. have.

 According to one embodiment of the invention, the coating composition may include a surfactant as an additive, the surfactant may be a 1 to 2 functional fluorine-based acrylate, fluorine-based surfactant or silicone-based surfactant. In this case, the surfactant may be included in the form of being dispersed or crosslinked in the crosslinked copolymer.

In addition, the additive may include a yellowing inhibitor, and the yellowing inhibitor may include a benzophenone compound or a benzotriazole compound. According to an embodiment of the present invention, the coating composition may further include a photocurable binder such as a 3 to 6 functional acrylate-based ^' monomer as a photocurable binder.

 The 3 to 6 functional acrylate monomers include trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxy triacrylate (TMPEOTA), glycerin propoxylated triacrylate (GPTA), pentaerythritol tetraacrylate (PET A) or the dipentaerythrite includes nuxaacrylate (DPHA) and the like. The 3 to 6 functional acrylate monomers may be used alone or in combination with each other.

 The 3 to 6 functional acrylate-based monomers are cross-polymerized with each other by ultraviolet irradiation to form a cross-linked copolymer, including the cross-linked copolymer can be given a higher hardness to the coating layer.

According to an embodiment of the present invention, the 3 to 6 functional acrylate-based The monomer may be included in an amount of about 5 to about 50 parts by weight, or about 10 to about 40 parts by weight, based on 100 parts by weight of the coating composition. By including the 3 to 6 functional acrylate monomer in the above range, it is possible to achieve the hardness improvement effect of the plastic film according to the addition of the acrylate monomer within a range that does not lower the physical properties such as flexibility.

According to one embodiment of the present invention, the viscosity of the coating composition is not particularly limited as long as it has a range of appropriate fluidity and applicability, for example, may have a viscosity of about l, 200 cps or less at a silver degree of 25 ^° C. have.

 The film including the coating layer formed using the coating composition of the present invention exhibits high hardness, high processability, impact resistance, flexibility, scratch resistance, high transparency, durability, light resistance, high transmittance, etc., and thus may be usefully used in various fields. Can be.

 According to an embodiment of the present invention, a film of a flat type or three-dimensional shape may be manufactured by a thermosetting and photocuring process using the coating composition.

 The plastic film formed by using the coating composition of the present invention can be utilized in various fields. For example, the present invention can be used for a flat panel or three-dimensional cover substrate or element substrate of a mobile communication terminal, a touch panel of a smartphone or a tablet PC, and various displays. Plastic film and its manufacturing method

 According to another aspect of the invention, the support substrate; And a coating layer formed on at least one surface of the support substrate, wherein the coating layer includes a cured product of the dual curable binder and an inorganic fine particle included in one molecule including a thermosetting functional group and a photocurable functional group, and at least a part of which is curved. To provide a plastic film.

In the plastic film of the present invention, the supporting substrate on which the coating layer is formed is a transparent plastic resin which is commonly used, and has a resin having a glass transition temperature (Tg) of about 80 to 250 ^° C., or about 100 to 150 ^° C. Can be used. If the glass transition temperature of the support substrate is lower than the above-mentioned range, there is a fear that the thermal stability and durability of the product is lowered, if higher than the above-mentioned range to form a curved shape There is a possibility that the coating layer may be modified during the thermoforming process.

 If it is a transparent plastic resin which has a glass transition temperature of the said range, it can use without a restriction | limiting in particular in the manufacturing method or material of a supporting base material, such as a stretched film or a non-stretched film. More specifically, according to one embodiment of the present invention, for example, the support substrate is a polyester such as polyethylene terephthalate (PET), a cyclic olefin polymer (cyclic olefin polymer, COP), cyclic Cyclic olefin copolymer (COC), polyacrylate (PAC), polycarbonate (PC), polymethylmethacrylate (PMMA), polyetheretherketon (PEEK), Polyethylenenaphthalate (PEN), polyetherimide (PEI), polyimide (PI), triacetylcellulose (TAC), MMA (methyl methacrylate), or fluorine resin Can film. The support substrate may be a single layer or a multilayer structure including two or more substrates made of the same or different materials as necessary, but is not particularly limited.

 According to one embodiment of the invention, the supporting substrate is a multi-layered structure of polyethylene terephthalate (PET), the structure of two or more layers formed by co-extrusion of polymethyl methacrylate (PMMA) / polycarbonate (PC) It can be a substrate.

 In addition, according to an embodiment of the present invention, the support substrate may be a substrate including a copolymer of polymethyl methacrylate (PMMA) and polycarbonate (PC).

 Although the thickness of the support substrate is not particularly limited, a substrate having a thickness of about 100 to about 1,000 Pa, or about 200 to about 500 Pa can be used as a range that can satisfy the hardness and workability of the plastic film. .

 The plastic film of the present invention includes a coating layer formed on at least one surface of the support substrate.

Alternatively, the plastic film of the present invention includes a coating layer formed on both sides of the supporting substrate. In addition, according to an embodiment of the present invention, the ratio of the thicknesses of the support substrate and the coating layer may be independently about 1: 0.1 to about 1: 2, or about 1: 0.5 to about 1: 1.5. When the ratio of the thickness is in the above range, it is possible to form a plastic film exhibiting high hardness while generating less curl or cracks.

 In the plastic film of this invention, the said coating layer contains the hardened | cured material of the double curable binder contained in one molecule containing a thermosetting functional group and a photocurable functional group, and an inorganic fine particle.

 The coating layer is coated with the coating composition as described above, that is, a coating composition comprising a double curable binder, a photoinitiator, a thermosetting agent, and inorganic fine particles contained in one molecule containing a thermosetting functional group and a photocurable functional group to the support substrate and the radius It can be formed by carrying out curing, thermoforming and complete curing.

 Detailed description of the coating composition and the dual curable binder, photoinitiator, thermosetting agent, inorganic fine particles, and other components that may be included in the coating composition and specific examples thereof are as described above.

 When using the double curable binder of the present invention, the tackness of the coating layer after the first curing is good, as compared with the case of using a coating composition in which a thermosetting functional group and two kinds of binders each containing a photocurable functional group are mixed. Therefore, secondary processing such as thermoforming is easy, and the crosslinking density can be increased, so that mechanical strength is improved. However, the present invention does not exclude the use of a binder containing only a thermosetting functional group and a binder containing only a photocurable functional group, and additionally other photocurable binders and / or in addition to the double curable binder to further improve the physical properties of the coating layer. It may comprise a thermosetting binder.

 According to one embodiment of the present invention, the thermosetting functional group and the thermosetting functional group are in a ratio of about 1: 9 to about 9: 1, or about 3: 7 to about 7: 3, or about 4: 6 to about 6: 4. May be included. When the thermosetting functional group and the thermosetting functional group are included in the above range, it is possible to provide a plastic film having good processability while maintaining high hardness.

Coating compositions comprising the aforementioned components can form the plastic films of the invention by semi-curing, thermoforming and fully curing after application to the support substrate. According to one embodiment of the invention, the coating layer has a thickness after curing of about 20 // m or more, for example, about 20 to about 300 kPa, or about 50 to about 300 / ΛΙΙ, or about 20 to about 200 / im , Or about 50 to about 200, or about 20 to about 150 // m, or. Or from about 50 to about 150 / Λ 50, or from about 20 to about 150 / ΛΠ, or from about 70 to about 150. If the thickness range of the coating layer is less than the appropriate range may not be obtained a sufficient mechanical strength, if exceeding the appropriate range there is a fear that the tensile force applied to the bent portion in the thermoforming process increases beyond the limit. According to an embodiment of the present invention, the coating layer may be formed only on one surface of the supporting substrate.

 According to one embodiment of the invention, the coating layer may be formed on both sides of the support substrate.

 According to the present invention, it is possible to provide a plastic film including a cured product of the double curable binder and inorganic fine particles, and at least a part of which is bent.

 That is, thermoforming is possible in a state where only a part of the thermosetting functional group and the photocurable functional group are cured by adjusting the degree of curing of the dual curable binder, thereby providing a plastic film having at least a part of which is bent.

 More specifically, after curing only a part of the thermosetting functional group and the photo-curable functional group contained in the binary curable binder applied to the supporting substrate to a semi-cured state, the supporting substrate having the semi-cured coating layer in a mold of a certain shape By placing and applying heat, at least a portion of the film may be formed into a curved shape according to the shape of the mold. This is called thermoforming process. By curing the uncured functional group, a plastic film can be obtained in which the three-dimensional structure is fixed in the form of a mold.

In the coating composition using only an acrylate monomer conventionally used as a binder of plastic resin, when the acrylate monomer is molded into a three-dimensional shape in a partially cured state and the other is cured, cracks may be formed due to stress of the bent portion. It is difficult to produce a curved or curved film due to a problem that occurs, or the adhesion to the support substrate is reduced and the coating layer falls from the support substrate. In addition, the uncured acrylate monomer exhibits tackness, so that the surface of the coating layer is deteriorated upon contact with the mold. The molding method was extremely limited.

 However, the plastic film of the present invention uses a cured product of a double curable binder included in one molecule containing a thermosetting functional group and a photocurable functional group, thereby preventing the occurrence of a stack during or after molding without deterioration of adhesion to the supporting substrate. And bends having a wide range of radii of curvature.

 In addition, it is possible to form a coating layer of a high thickness to exhibit high hardness without cracking. That is, according to the plastic film of the present invention, in addition to the photocurable functional group, by further comprising a thermosetting functional group to prevent the occurrence of curl due to curing shrinkage while maintaining a high hardness, it is possible to form a coating layer of a high thickness.

 In addition, when the coating layer is formed of only a photocurable resin, the higher the thickness of the coating layer, the less ultraviolet rays do not reach the lower part of the coating layer, which may cause incomplete curing of the coating layer. According to the present invention, however, the coating layer may include both a thermosetting functional group and a photocurable functional group to compensate for incomplete photocuring by performing curing with heat and ultraviolet rays. Accordingly, it is possible to further strengthen the high hardness and physical properties of the coating layer.

 In addition, compared to the case of using a coating composition in which a binder containing only a thermosetting functional group and a binder containing only a photocurable functional group are used, when using such a double curable binder, the tackness of the coating layer after the first curing is higher. It is advantageous that secondary processing such as thermoforming is easy, and the crosslinking density can be increased, thereby improving mechanical strength.

 The plastic film of the present invention may be at least partially curved. By "at least partly curved," it is meant that when the plastic film of the present invention is viewed from the side in the thickness direction, part or all of the side faces are curved, preferably part of the arc. Thus, part or all of the face portions of the plastic film of the present invention have a curved shape.

1 is a perspective view showing a plastic film according to an embodiment of the present invention, Figure 2 is a cross-sectional view showing the plastic film of FIG. In more detail, Figure 2 shows a cross-sectional view of the plastic film of Figure 1 viewed in the direction Τ-Γ. 1 and 2, the plastic film 1 may be formed of the substrate 10 and the substrate 10. It includes a coating layer (20, 30) formed on both sides.

 Plastic film according to an embodiment of the present invention shown in Figures 1 and 2 may be a curved form of two opposite edges of the four (edge). Radius (R1, R2) of the edge of each of the edges are each independently the same or different, but may be in the range of 2.5 to 15, the present invention is not limited to this, the shape, size, And the use thereof.

 In the plastic films of FIGS. 1 and 2, the angles Θ1 and Θ2 formed by the front and side portions are each independently the same or different, and the shape and size of the plastic film required within a range of more than 0 degrees to 90 degrees or less. Subject to change.

 3 is a view showing a plastic film according to another embodiment of the present invention. 4 is a cross-sectional view illustrating the plastic film of FIG. 3. More specifically, FIG. 4A illustrates a cross-sectional view of the plastic film of FIG. 3 viewed in the direction of Τ1-ΤΓ, and FIG. 4B illustrates a cross-sectional view of the plastic film of FIG. 3 viewed from the direction of T2-T2 '. will be. 3 and 4, the plastic film 100 includes a substrate 40 and coating layers 50 and 60 formed on both surfaces of the substrate 40.

 3 and 4, the plastic film according to the embodiment of the present invention may have a curved shape with all four edges and corners. Radius (R3, R4, R5, R6) of each of the edges of the edge is independently the same or different, and may range from 2.5 to 15, the present invention is not limited thereto, and the shape of the plastic film required , Size, and use.

 In the plastic films of FIGS. 3 and 4, the angles Θ3, Θ4, Θ5, and Θ6 formed by the front and side portions are each independently the same or different, and the plastic film is required within a range of more than 0 degrees to 90 degrees. It can be changed according to the shape, size, and use of the.

 5 is a view showing a plastic film according to another embodiment of the present invention. 6 is a cross-sectional view illustrating the plastic film of FIG. 5. In more detail, FIG. 6 illustrates a cross-sectional view of the plastic film of FIG. 5 viewed in the T3-T3 'direction. 5 and 6, the plastic film 200 includes a substrate 70 and coating layers 80 and 90 formed on both surfaces of the substrate 70.

5 and 6, the plastic film according to an embodiment of the present invention is one The entire surface may be curved. The radius of curvature of the curved plastic film may be in the range of 2.5 to 900, but the present invention is not limited thereto, and may be changed according to the shape, size, and use of the plastic film.

 In addition, the plastic film of the present invention has been described with reference to FIGS. 1 to 6, but the present invention is not limited thereto and may have various shapes of three-dimensional structures. For example, the plastic film of the present invention, such as curved shape of one edge, curved shape of three edges, curved shape of only edge, curved shape of the entire surface, hemispherical shape, etc. It can be a three-dimensional form.

 According to another embodiment of the present invention, at least one surface of the support substrate for applying a coating composition comprising a dual curable binder, photoinitiator, thermosetting agent, and inorganic fine particles contained in one molecule comprising a thermosetting functional group and a photocurable functional group step; Performing a first curing on the applied coating composition to form a semi-cured coating layer; Performing thermoforming on the support substrate on which the semi-cured coating layer is formed; And it provides a method for producing a plastic film comprising the step of performing a second curing for the semi-hardened coating layer.

 Detailed description of the coating composition and the dual curable binder, photoinitiator, thermosetting agent, inorganic fine particles, and other components that may be included in the coating composition and specific examples thereof are as described above.

 A coating composition comprising the aforementioned components is applied on at least one side of the support substrate. At this time, the method of applying the coating composition is not particularly limited as long as it can be used in the technical field to which the present technology belongs, for example, bar coating method, knife coating method, coating method, blade coating method, die coating method, micro A gravure coating method, a comma coating method, a slot die coating method, a lip coating method, or a solution casting method may be used.

In addition, the coating composition may have a thickness of about 20 // m or more, such as about 20 to about 300 / ΛΠ, or about 50 to about 300 / zm, or about 20 to about 200 / m, or about 100% after being fully cured. 50 to about 200, or about 20 to about 150 // ΙΠ, or about 50 to about 150, or about 20 to about 150, or about 70 to about 150. Next, first curing is performed on the applied coating composition. The first curing is a step for curing the egg of the applied coating composition to make a thermoforming, which is a subsequent step.

 The coating composition applied by the first curing process as described above forms a semi-cured coating layer. In the specification of the present invention, the semi-cured coating layer means that the degree of curing calculated by Equation 1 is about 10 to about 70%.

[Equation ^1]

Sir _. G number of learned functional groups

 Hardness <<%) = X 100

 Nominal number of photocurable functional groups [* ¾ curable ¾ functional groups] In other words, the semi-cured coating layer comprises a curable functional group included in the coating composition, that is, a thermosetting functional group and a photocurable functional group. With respect to 100 moles of all curable functional groups, about 10 to about 70 moles, or about 40 to about 60 moles of functional groups are cured. If the cured degree of the semi-hardened coating layer is too low out of the range, the adhesion of the surface is strong so that the coating layer may be adsorbed with the mold or the coating layer may be deformed, and if it is too high, it may be bent in a subsequent thermoforming process due to excessive hardness. Molding is difficult or there is a risk of cracking.

 According to an embodiment of the present invention, the first curing may be a thermosetting process. In the case where the first curing is a thermosetting process, the semi-cured coating layer is mainly in a state in which the thermosetting functional group is cured, but does not exclude the curing of the photocuring functional group.

The thermosetting is a process for curing the thermosetting functional groups contained in the coating composition. The thermosetting may be accomplished by heating at a temperature of about 90 to about 150 ^° C, or about 1 10 to about 130 ^° C for about 1 minute to about 30 minutes, or about 1 minute to about 5 minutes. If the thermosetting is performed at a temperature lower than the temperature range, the restoring force of the substrate may be high, which may cause difficulty in subsequent thermoforming and second curing processes. If the temperature is out of the temperature range, the supporting substrate, which is weak in overall heat, may be affected. This can lead to deterioration of the overall plastic film properties.

 According to another embodiment of the present invention, the first curing may be a photocuring process.

The photocuring is a process for curing the photocurable functional groups contained in the coating composition. The irradiation amount of ultraviolet light during the photocuring is, for example, about 20 to about 600 mJ / cm ² , or about 50 to about 500 mJ / cm ² . The light source for ultraviolet irradiation is not particularly limited as long as it can be used in the art to which the present technology belongs, and for example, a high pressure mercury lamp, a metal halide lamp, a black light fluorescent lamp, or the like can be used. The photocuring step may be performed by irradiating for about 30 seconds to 15 minutes or about 1 minute to about 10 minutes with the above irradiation amount.

 In the case where the first curing is a photocuring process, the semi-curing coating layer is mainly in a state where the photocuring functional group is cured or does not exclude the curing of the thermosetting functional group.

 The semi-cured coating layer formed by the first curing as described above has a degree of cure that can be flexibly smoothed without cracking when functional groups included in the coating composition are partially cured to apply a constant pressure and heat, and the surface of the coating composition before curing The tackness of the resin is lowered, so that subsequent thermoforming is possible. Next, thermoforming is performed on the supporting substrate on which the semi-cured coating layer is formed.

 The thermoforming is a process for making the semi-hardened coating layer and supporting substrate into the desired three-dimensional shape.

The thermoforming is performed by applying a constant heat to the supporting substrate on which the semi-cured coating layer is formed, that is, the semi-cured coating layer and the supporting substrate including the same. In this case, the thermoforming may be performed by heating to a temperature of about 90 to about 250 ^° C, or about 100 to about 150 ^° C. If the thermoforming is performed at a temperature lower than the temperature range, the restoring force of the substrate may be so high that a three-dimensional shape of a desired shape may not be obtained, and when the temperature is out of the temperature range, the support substrate may be affected and the physical properties of the overall plastic film may be reduced. May occur.

 Thermoforming may be accomplished by reaching within the aforementioned temperature range and holding for a period of time, for example, for about 30 to about 600 seconds, or for about 120 to about 300 seconds, but the holding time is not limited thereto. It may vary depending on the type of substrate, the thickness, the thickness of the coating layer, the molding state, the pressure applied from the mold and the like.

According to an embodiment of the present invention, the thermosetting during the thermoforming process may be performed together. That is, in the thermoforming process, the support substrate on which the semi-cured coating layer is formed may be cured by a thermosetting functional group included in the coating composition. Since it is heated to a temperature, at the same time thermoforming is performed, additional curing of the thermosetting functional groups included in the coating composition can be made.

 According to an embodiment of the present invention, thermoforming may be performed by placing the supporting substrate on which the semi-cured coating layer is formed in a mold having a suitable shape according to a desired three-dimensional shape, and heating the mold to a thermosetting temperature.

 More specifically, by placing the supporting substrate on which the semi-cured coating layer is formed between the upper and lower female and female molds, heating the mold to the above-mentioned temperature range, and then contacting the heated female and female mold to the supporting substrate on which the semi-cured coating layer is formed. ^ Thermoforming can be performed. Alternatively, thermoforming may be performed by placing the specimen in one of the male and female molds and then applying vacuum and air pressure to close the mold. At this time, a constant pressure, for example, about 1 to about 10 MPa, or about 2 to about 3 MPa, may be applied to the support substrate for more efficient thermoforming.

 According to another embodiment of the present invention, the core portion of the support substrate on which the semi-cured coating layer is formed is fixed to a flat support portion, and a portion or part, for example, a mold or rod, in which only the edge portion is heated, to be bent. The thermoforming can be performed by allowing it to come in contact with and holding it for a period of time.

 Next, second curing is performed on the semi-hardened coating layer.

 remind. Second curing is a process for curing functional groups that remain uncured in the semi-cured coating layer. The Crab 2 cures the remaining functional groups contained in the coating composition in the semi-cured coating layer.

 The semi-cured coating layer is completely cured by the second curing, thereby forming a plastic film of high hardness while having a three-dimensional shape by the thermoforming process of the previous step. 100% of all curable functional groups contained in the coated coating composition, that is, the thermosetting functional group and the total curable functional group including the photocurable functional group, as well as the cured state of at least about 80 moles, that is, the degree of curing of at least about 80% If it is completely cured.

 The second curing may be performed in a state in which the thermoformed film is detached from the mold or is not detached.

According to an embodiment of the present invention, the second curing may be a thermosetting process. The thermal curing is at a temperature of about 90 to about 150 ^° C, or about 110 to about 130 ^° C By heating for about 1 minute to about 30 minutes, or for about 1 minute to about 5 minutes.

 According to another embodiment of the present invention, the second curing may be a photocuring process.

The irradiation amount of ultraviolet light during photocuring may be, for example, about 20 to about 600 mJ / cm ² , or about 50 to about 500 mJ / cm ² . The ultraviolet light source is not particularly limited as long as it can be used in the art to which the present technology belongs, and for example, a high pressure mercury lamp, a metal halide lamp, a black light fluorescent lamp, or the like can be used. The photocuring step may be performed by irradiating for about 30 seconds to 15 minutes or about 1 minute to about 10 minutes with the above irradiation amount.

 When the coating layer is formed on both sides of the support substrate, applying a coating composition to one surface of the support substrate; Performing heat curing on the coating composition applied to the one surface to form a semi-cured coating layer; Applying the coating composition to the back side of the support substrate; Performing heat curing on the coating composition applied to the rear surface to form a semi-cured coating layer; Performing thermoforming on the supporting substrate having the semi-cured coating layer formed on both surfaces thereof; And it is possible to produce a plastic film of the present invention by performing a photocuring for the semi-cured coating layer.

 Or, applying the coating composition to one side of the supporting substrate; Simultaneously performing thermosetting and thermoforming on the coating composition applied to one surface to form a semi-cured coating layer; And it is possible to produce a plastic film of the present invention by performing a photocuring for the semi-cured coating layer.

 Or, applying the coating composition to one side of the supporting substrate; Performing a photocuring on the coating composition applied to one surface to form a semi-cured coating layer; Applying the coating composition to the back side of the support substrate; Performing photocuring on the coating composition applied to the rear surface to form a semi-cured coating layer; Performing thermoforming on the supporting substrate having the semi-cured coating layer formed on both surfaces thereof; And thermosetting the semi-hardened coating layer to produce the plastic film of the present invention.

Or, applying a coating composition to one side of the support substrate; The applied Thermally curing the coating composition to form a semi-cured coating layer; Performing thermoforming on the support substrate on which the semi-cured coating layer is formed; Applying the coating composition to the back side of the support substrate; Performing heat curing on the coating composition applied to the rear surface to form a semi-cured coating layer; And it is possible to produce a plastic film of the present invention by performing a photocuring for the semi-cured coating layer. At this time, since the state of forming a coating layer on one side is already molded into a desired three-dimensional shape of the plastic film, the thermoforming process may be excluded after forming the semi-cured coating layer on the back side.

 Or, applying a coating composition on one side of the support substrate; Photocuring the coated coating composition to form a semi-cured coating layer; Performing thermoforming on the support substrate on which the semi-cured coating layer is formed; Applying the coating composition to the back side of the support substrate; Performing photocuring on the coating composition applied to the rear surface to form a semi-cured coating layer; And thermosetting the semi-hardened coating layer to produce the plastic film of the present invention.

 Plastic film of the present invention prepared according to the above manufacturing method can be usefully used in various fields by showing three-dimensional shape, high hardness, layer resistance, scratch resistance, high transparency, durability, light resistance, light transmittance and the like.

 For example, the plastic film of the present invention, the pencil hardness at 1kg load may be 3H or more, or 4H or more, or 6H or more.

 In addition, the plastic film of the present invention may have a good layer resistance to replace the glass. For example, in the plastic film of the present invention, cracks may not occur when 22 g of iron balls are freely dropped at a height of 40 cm.

 In addition, when the steel wool # 0000 is mounted on the friction tester, when reciprocating 400 bar with a load of 500g, only two scratches may be generated, thereby showing excellent scratch resistance.

In addition, ^"the plastic film of the present invention is a light transmittance of 92% or more can have a haze less than or equal to 1.0%, or 0.5%, or 0.4%.

In addition, the plastic film of the present invention may have an initial color b * (b * due to CIE 1976 L * a * b * color space) of 1.0 or less. In addition, the initial color b * and ultraviolet in the UVB wavelength range After 72 hours of exposure to the lamp, the difference in color b * may be less than or equal to 5, or less than or equal to 0.4. The plastic film of the present invention can be used in various fields. For example, the present invention may be used for a touch panel of a mobile communication terminal, a smartphone or a tablet PC, and a three-dimensional cover substrate or an element substrate of various displays. Hereinafter, the operation and effects of the invention will be described in more detail with reference to specific examples of the invention. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined. <Example>

 Production Example of Double Curable Binder

 Preparation Example 1

 SMP-220A is a double-curable binder containing hydroxyl and acrylate groups in the molecule (obtained from: Gongyoung Chemical Co., Ltd., Japan), solid content 50% (in MIBK), equivalent weight of acrylate = 220 g / eq, equivalent weight of hydroxyl = 220 g / eq, Mw = 30,000-40,000 g / mol). Preparation Example 2

 SMP-360A is a binary curable binder containing hydroxy group and acrylate group in the molecule (obtained from: Gongyoung Chemical Co., Ltd., Japan), solid content 50% (in MIBK), equivalent weight of acrylate = 360 g / eq, equivalent weight of hydroxyl = 360 g / eq, Mw = 30,000-40,000 g / mol). Preparation Example 3

SMP-550A is a double curable binder containing hydroxy and acrylate groups in the molecule (obtained from: Gongyoung Chemical Co., Ltd., Japan), solid content 50% (in MIBK), equivalent weight of acrylate = 550 g / eq, equivalent weight of hydroxyl = 550 g / eq, Mw = 30, 000 40,000 g / mol). Example 1 6 g of the double curable binder (Product name: SMP-220A) of Preparation Example 1, 12 g of silica-trimethyl to propane triacrylate (TMPTA) composite (50 g of silica, 6 g of TMPTA), in which 50% by weight of nano silica having a particle diameter of 20 to 30 nm was dispersed. 6.47 g of hydroxy-pentaerythrelli nucleoacrylate (trade name: A-9750W, manufacturer: NK Chemical), alicyclic polyisocyanate (trade name; MF-K60X, manufacturer: AsahiKasei) 7.1 lg, dibutyl as a thermosetting agent 0.15 g of tindilaurate (BDTDL, 0.1 wt% in MEK), 0.15 g of Tego 410 ^® 0.1 wt% in MEK, Tego 450 ^® 0.1 wt% in MEK as a flow improver, photoinitiator (trade name) : Darocur TPO) 0.2g, 0.1g of benzotriazole yellowing inhibitor (trade name: Tinuvin 400) was mixed to prepare a first coating composition.

The first coating composition was applied onto a PET support substrate of 15 cm × 20 cm, thickness 188 / kg. Next, thermosetting was carried out for 30 minutes at a temperature of 130 ^° C. A second coating composition was also prepared in the same manner, and the second coating composition was applied to the back side of the supporting substrate. Next, the specimen was prepared by performing thermal curing at a temperature of 130 ^° C for 30 minutes. After the thermosetting was completed, the thicknesses of the first and second coating layers formed on both surfaces of the substrate were 100, respectively.

Two edges facing the specimen prepared as described above were placed between the male and female molds to be bent to have a curvature of 2.5 R, 90 degrees, and left at 120 ^° C. for 1 minute, and then the upper and lower molds were joined at a pressure of 2 MPa. After standing for 3 minutes in the bonding is completed, the molded specimen was recovered by separating the upper and lower molds. The recovered specimen was completely cured under an ultraviolet lamp having a wavelength of 280-350 nm, and as a result, a plastic film having a three-dimensional structure with two opposite edges bent at 2.5R and 90 degrees was prepared. Example 2

6 g of the double curable binder (Product name: SMP-220A) of Preparation Example 1, and silica-defenterieryri (nuclear acrylate) (DPHA) composite containing about 50% of the nano silica having a particle diameter of 20 to 30 nm, 48 g (silica 3.74 _& DPHA 3.74 g), hydroxy-pentaerythritol nucleoacrylate (trade name: A-9750W, manufacturer: NK Chemical) 2.64 g, alicyclic polyisocyanate (trade name; MF-K60X, manufacturer: AsahiKasei) 7.1 lg, 0.15 g of dibutyltindilaurate (BDTDL, 0.1wt% in MEK) as a thermosetting agent, 0.15g of Tego 410 ^® 0.1wt% in MEK) Tego 450 ^® 0.1 wt% in MEK) 0.15g , 0.2 g of photoinitiator (trade name: Darocur TPO) and 0.1 g of benzotriazole anti-yellowing agent (trade name: Tinuvin 400) were mixed to prepare a first coating composition.

The first coating composition was applied on a PET support substrate 15 cm × 20 cm, 188 mi thick. Next, heat curing was performed for 30 minutes ^{at a} temperature of 130 ^° C. A second coating composition was also prepared in the same manner, and the second coating composition was applied to the back side of the supporting substrate. Next, the specimen was prepared by performing thermal curing at a temperature of 130 ^° C for 30 minutes. After the thermosetting was completed, the thicknesses of the first and second coating layers formed on both surfaces of the substrate were 100, respectively.

The specimen prepared as described above was placed between the male and female molds to be bent to have four edges of 2.5R, 90 degrees of bending, and left at 120 ^° C. for 1 minute, and then the upper and lower molds were joined at a pressure of 2 MPa. After standing for 3 minutes in the bonding is completed, the molded specimen was recovered by separating the upper and lower molds. The recovered specimen was completely cured under an ultraviolet lamp having a wavelength of 280-350 nm, and as a result, a plastic film having a three-dimensional structure with four edges bent at 2.5R and 90 degrees was prepared. Example 3

Specimens prepared in the same manner as in Example 1 were placed between the male and female molds having 700 R in the longitudinal direction and 300 R in the width direction, and left at 120 ^° C. for 1 minute, and then the upper and lower molds were joined at a pressure of 2 MPa. After standing for 3 minutes in the bonding is completed, the molded specimen was recovered by separating the upper and lower molds. The recovered specimen was completely cured under an ultraviolet lamp having a wavelength of 280-350 nm, and as a result, a plastic film having a three-dimensional structure bent at 300R to 700R over the entire surface of the specimen was prepared. Example 4

6 g of the double curable binder of Preparation Example 2 (trade name: SMP-360A), 50 g of nano silica having a particle diameter of 20 to 30 nm, and an increase of ⁰ / ^° . 12 g of silica-trimethyl dispersed propane triacrylate (TMPTA) composite (6 g of silica, TMPTA) 6g) hydroxy-pentaerythrelli nucleoacrylate (trade name: A-9750W, manufacturer: NK Chemical) 6.47g, alicyclic polyisocyanate (trade name; MF-K60X, manufacturer: AsahiKasei) 4.35g, 0.15 g of dibutyltindilaurate (BDTDL, 0.1 wt% in MEK) as a thermosetting agent, 0.15 g of Tego 410 ^® 0.1 wt% in MEK additive from Tego as a flow improving agent, 0.2 g of a photoinitiator (trade name: Darocur TPO) In combination, a first coating composition was prepared.

The first coating composition was applied on a PET support substrate 15 cm × 20 cm, 188 m thick. Next, thermosetting was carried out for 30 minutes at a temperature of 130 ^° C. A second coating composition was also prepared in the same manner, and the second coating composition was applied to the back side of the supporting substrate. Next, the specimen was prepared by performing thermal curing at a temperature of 130 ^° C. for 30 minutes. After the thermosetting was completed, the thicknesses of the first and second coating layers formed on both surfaces of the substrate were 100, respectively.

Two edges facing the specimen prepared as described above were placed between the male and female molds to be bent to have a curvature of 2.5 R, 90 degrees, and left at 120 ^° C. for 1 minute, and then the upper and lower molds were joined at a pressure of 2 MPa. After standing for 3 minutes in the bonding is completed, the molded specimen was recovered by separating the upper and lower molds. The recovered specimen was completely cured under an ultraviolet lamp having a wavelength of 280-350 nm, and as a result, a plastic film having a three-dimensional structure with two opposite edges bent at 2.5R and 90 degrees was prepared. Example 5

6 g of the double curable binder of Preparation Example 3 (trade name: SMP-550A), and 12 g of silica-trimethyl-propane triacrylate (TMPTA) composite containing 6 wt% of nano silica having a particle diameter of 20 to 30 nm (silica 6 g, TMPTA 6 g) 6.47 g of hydroxy-pentaerythrelli nucleoacrylate (trade name: A-9750W, manufacturer: NK Chemical), 2.85 g of alicyclic polyisocyanate (trade name; MF-K60X, manufacturer: AsahiKasei), dibutyl as a thermosetting agent 0.15 g tindilaurate (BDTDL, 0.1 wt% in MEK), 0.15 g Tego 410 ^® 0.1 wt% in MEK additive from Tego as a flow improver, 0.2 g photoinitiator 1 (trade name: Darocur TPO) 1 coating composition was prepared.

The Crab 1 coating composition was applied on a 15 cm x 20 cm, 188 thick PET support substrate. Next, thermosetting was carried out for 30 minutes at a temperature of 130 ^° C. A second coating composition was also prepared in the same manner, and the second coating composition was applied to the back side of the supporting substrate. Next, the specimen was prepared by performing thermal curing at a temperature of 130 ^° C. for 30 minutes. First and second surfaces formed on both sides of the substrate after thermal curing is completed; The thickness of the 2nd coating layer was 100, respectively.

Two edges facing the specimen prepared as described above were placed between the male and female molds to be bent to have a curvature of 2.5 R, 90 degrees, and left at 120 ^° C. for 1 minute, and then the upper and lower molds were joined at a pressure of 2 MPa. After standing for 3 minutes in the bonding is completed, the molded specimen was recovered by separating the upper and lower molds. The recovered specimen was completely cured under an ultraviolet lamp having a wavelength of 280-350 nm, and as a result, a plastic film having a three-dimensional structure with two opposite edges bent at 2.5R and 90 degrees was prepared. Comparative Example 1

 10 g of trimethylolpropane triacrylate (TMPTA), 0.1 g of photoinitiator Irgacure 127, and 0.1 g (10 wt% in MEK) of flow improver Tego Flow 410 were mixed to prepare a coating composition. The coating composition was applied onto a 188 卿 thick PET support substrate, and then completely cured under an ultraviolet lamp having a wavelength of 280 to 350 nm.

Two edges facing the specimen thus prepared were placed between the male and female molds to be bent to have a curvature of 2.5 R and 90 degrees, and left at 120 ^° C. for 1 minute, and then the upper and lower molds were joined at a pressure of 2 MPa. After standing for 3 minutes in a state where the bonding is completed, the upper and lower molds were spaced apart to recover the molded specimen to prepare a plastic film. Comparative Example 2

 10 g of propane triacrylate (TMPTA), 0.1 g of photoinitiator Irgacure 127, and 0.1 g (10 wt% in MEK) of flow improver Tego Flow 410 were mixed to prepare trimethyl. The coating composition was applied on a thickness of 188 PET support substrate and then semi-cured so that the curing degree was about 40% under an ultraviolet lamp having a wavelength of 280-350 nm.

Two edges facing the specimen thus prepared were placed between the male and female molds to be bent to have a curvature of 2.5 R and 90 degrees, and left at 120 ^° C. for 1 minute, and then the upper and lower molds were joined at a pressure of 2 MPa. After the bonding was completed for 3 minutes, the upper and lower molds were separated and the molded specimens were recovered and completely cured under an ultraviolet lamp having a wavelength of 280 to 350 nm to prepare a plastic film. Comparative Example 3 ^'

 As in Example 1, the first and second coating compositions were prepared.

Next, the first coating composition was applied onto a PET support substrate having a thickness of 15 cm X 20 cm, 188. Then, thermal curing was performed for 6 hours at a temperature of 130 ^° C.

A second coating composition was also prepared in the same manner, and the second coating composition was applied to the back side of the supporting substrate. Next, the specimen was prepared by performing thermal curing at a temperature of 130 ^° C. for 6 hours. After the thermosetting was completed, the thicknesses of the first and second coating layers formed on both surfaces of the substrate were 100, respectively.

 Two edges facing the specimen prepared as described above were placed between the male and female molds to be bent to have a curvature of 2.5 R and 90 degrees, and then left and held at 12 CTC for 1 minute, and then the upper and lower molds were joined at a pressure of 2 MPa. After standing for 3 minutes in the bonding is completed, the molded specimen was recovered by separating the upper and lower molds. The recovered specimen was completely cured under an ultraviolet lamp having a wavelength of 280 ~ 350nm to prepare a plastic film.

Experimental Example

 <Measurement method>

 1) pencil hardness

 After measuring three times with a 1.0kg load according to the measurement standard JIS K5400 using a pencil hardness tester, the hardness without the groove was confirmed.

2) formability

After adjusting the upper and lower mold temperature of the thermoforming machine to 130 ^° C., the specimen was placed between the molds and thermoforming was performed at a pressure of 2-3 MPa. Deformation of the flatness of the mold surface after molding, crack formation of the bent portion, discoloration, and evaluation of the formability by the maximum separation of less than 0.5mm when combined with the structure of the same shape as the mold, if all of them are satisfied, If it was not satisfied, it was evaluated by NG.

3) tackness

After primary curing, before thermoforming, property analyzer (texture analyzer, stable micro System, UK) to measure the degree of adhesiveness by measuring the peel force (unit: N / 2cm) between the primary cured film and the protective film under the conditions of a peel rate of 50 mm / min and a peel angle of 90 degrees. .

 In the case where the peeling force is less than 0.1, the adhesiveness ©, the peeling force in the case of 0.1 or more and less than 0.5, o, 0.5 or more and less than 1, represented by X in the case of 1 or more.

4) Light resistance

 The difference in color b * before and after 72 hours exposure to UV lamps in the UVB wavelength range was measured and evaluated as OK when <1.

5) Transmittance and Haze

 The transmittance and haze were measured using a spectrophotometer (device name: COH-400), and the evaluation was OK when the transmittance was> 91% and OK when the haze was <1.0%. 6) Impact resistance

 The initial height of crack generation was measured when 22 g of iron ball was dropped from 10 cm height to 5 cm intervals and free-falled 10 times on the film. Physical property measurement results are shown in Table 1 below.

 Table 1

As shown in Table 1, the plastic films of Examples 1 to 5 of the present invention exhibited a high hardness, but also exhibited various three-dimensional structures due to good moldability and adhesiveness. However, Comparative Examples 1 and 3, which performed thermoforming on the fully cured coating layer instead of semi-curing, were incapable of forming due to poor moldability such as cracking of the bent portion. In addition, in the case of Comparative Example 2 using a coating composition containing only an acrylate monomer as the binder, but the thermoforming after the semi-curing process, the adhesiveness of the semi-cured coating layer is high, so that the coating layer is adsorbed with the mold or the surface of the coating layer is deformed. Again, moldability was not good.

Claims

[Patent Claims]

 Claim 1-A coating composition comprising a double curable binder, a photoinitiator, a thermosetting agent, and inorganic fine particles contained in one molecule containing a thermosetting functional group 'and a photocurable functional group.

[Claim 2]

 The method of claim 1,

 The thermosetting functional group and the photocurable functional group are included in a molar ratio of 1: 9 to 9: 1.

[Claim 3]

 The method of claim 1,

 10 to 50 parts by weight of the double curable binder, 0.1 to 5 parts by weight of the photoinitiator, 10 to 50 parts by weight of the thermosetting agent, and 1 to 40 parts by weight of the inorganic fine particles, based on 100 parts by weight of the total coating composition. Coating composition.

[Claim 4]

 According to claim 11,

 Coating composition further comprising a 3 to 6 functional acrylate monomer.

[Claim 5]

 The method of claim 4,

 The 3 to 6 functional acrylate monomer is a coating composition comprising 5 to 50 parts by weight, based on 100 parts by weight of the total coating composition.

[Claim 6]

 The method of claim 1,

Equivalent weights of the thermosetting functional group and the photocurable functional group of the double curable binder are independently the same or different from 80 to 1,500 g / eq.

[Claim 7]

 Supporting substrate; And

 And a coating layer formed on at least one surface of the support substrate, wherein the coating layer includes a cured product of the dual curable binder and inorganic fine particles included in one molecule including a thermosetting functional group and a photocurable functional group, and has at least a part of a curved shape. Plastic film.

[Claim 8]

 The method of claim 7, wherein

 The thermosetting functional group and the photocurable functional group are plastic films included in a molar ratio of 1: 9 to 9: 1.

[Claim 9]

 The method of claim 7,

 Two opposite edges are curved, the radius of each curved edge is independently the same or different, the plastic film ranges from 2.5 to 15.

[Claim 10]

 The method of claim 7,

 All four edges are curved, and the radius of curvature of each curved edge is independently the same or different, and the plastic film ranges from 2.5 to 15.

[Claim 11]

 The method of claim 7,

A plastic film having one side curved in its entirety and having a radius in the range of 2.5 to 900.

[Claim 12]

 The method of claim 7,

The glass transition temperature of the support substrate is 80 to 250 ^° C. Plastic film.

[Claim 13]

 The method of claim 7, wherein

 The coating layer has a thickness of 20 to 300 plastic film.

[Claim 14]

 According to claim 17,

 Plastic film with a pencil hardness of at least 3 H at a load of l kg.

[Claim 15]

 Applying the coating composition of claim 1 to at least one side of the support substrate;

 Performing a first curing on the applied coating composition to form a semi-cured coating layer hole; '

 Performing thermoforming on the support substrate on which the semi-cured coating layer is formed; And

 Method for producing a plastic film comprising the step of performing a second curing for the semi-hardened coating layer.

[Claim 16]

 The method of claim 15,

The semi-cured coating layer is a method of producing a plastic film, wherein 10 to 70 moles of functional groups are cured with respect to 100 moles of all curable functional groups including the thermosetting functional group and the photocurable functional group. [Claim 17] The method of claim 15,

The thermoforming is a method for producing a plastic film made at a temperature of 90 to 250 ^° C. [Claim 18]

 The method of claim 15,

 At least a portion of the plastic film is bent by the thermoforming. [Claim 19]

 The method of claim 15,

 Wherein the first curing is thermosetting and the second curing is photocuring. [Claim 20]

 The method of claim 15,

 And wherein the first curing is photocuring and the second curing is thermosetting.