WO2015076567A1

WO2015076567A1 - Plastic film laminate

Info

Publication number: WO2015076567A1
Application number: PCT/KR2014/011145
Authority: WO
Inventors: 강준구; 최항석; 장영래; 정혁
Original assignee: 주식회사 엘지화학
Priority date: 2013-11-19
Filing date: 2014-11-19
Publication date: 2015-05-28

Abstract

The present invention relates to plastic film laminate and, more specifically, to a plastic film laminate exhibiting impact resistance and excellent characteristics. According to the present invention, a plastic film laminate exhibiting high hardness, impact resistance, scratch resistance, and high transparency and having excellent processability can be provided.

Description

【Specification】

[Name of invention]

Plastic film laminate

Technical Field

The present invention relates to a plasma film laminate. More specifically, the present invention relates to a plastic film laminate exhibiting high hardness and excellent properties.

This application is filed with the Korean Patent Application No. 10-2013-0140664 filed with the Korea Intellectual Property Office on January 19, 2013, and Korean Patent Application No. 10-2014-0161 177 filed with the Korean Patent Office on February 18, 2014. Claims the benefit of the filing date of the issue, the entire contents of which are incorporated herein.

Background Art

Recently, with the development of mobile devices such as smartphones and tablet PCs, thinning and slimming of the display base material are required. Glass or tempered glass is generally used as a material having excellent mechanical properties in the display window or the front plate of the mobile device. However, the glass is. Due to its own weight, the mobile device becomes heavy, and there is a problem of damage caused by external stratification. Therefore, plastic resin is being researched as a substitute material for glass. Plastic resin compositions are suitable for the trend toward a lighter mobile device because they are lightweight and less prone to breakage. In particular, compositions have been proposed for coating a hard coat layer on a support substrate to achieve compositions having high hardness and wear resistance properties.

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 can be increased, but it is easy to apply practically because it becomes easy to cause cracks or peeling of the coating layer at the same time as wrinkles and curls increase due to the curing shrinkage of the hard coating layer. Not.

In recent years, several methods have been proposed to achieve high hardness of plastic films and to solve the problem of curling due to cracking and curing shrinkage of the hard coat layer. Korean Unexamined Patent Publication No. 2010-0041992 is UV curable without the monomer A coating composition using a binder resin containing a polyurethane acrylate oligomer is disclosed. However, the hard coat composition disclosed above is not strong enough to replace the glass panel of the display with a pencil hardness.

[Content of invention]

[Problem to solve]

In order to solve the above problems, the present invention provides a plastic film laminate having high hardness and excellent properties.

[Measures of problem]

In order to solve the above problems, the present invention,

A first plastic film comprising at least one coating layer; And a second plastic film including at least one coating layer, wherein the first and second plastic films are bonded to each other by an adhesive layer. 【Effects of the Invention】

According to the plastic film laminate of the present invention, it exhibits high hardness, layer resistance, scratch resistance, and high transparency to replace glass in cover panels or device substrates of mobile communication terminals, touch panels of smartphones or tablet PCs, and various displays. It can be used for the purpose.

[Specific contents to carry out invention]

The plastic film laminate of the present invention,

A first plastic film comprising at least one coating layer; And a second plastic film comprising at least one coating layer, wherein the first and second plastic films are bonded to each other by an adhesive layer.

Also, the terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise.

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 between the layer, the object, the substrate additionally.

The present invention may be variously modified and may have various forms. It is intended to illustrate the specific embodiments of the bar and to be described in detail below. However, this is not intended to limit the present invention to a particular disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, the plastic film laminate of the present invention will be described in more detail. According to the invention, the first plastic film comprising at least one coating layer; And a second plastic film including at least one coating layer, wherein the first and second plastic films are bonded to each other by an adhesive layer.

According to one embodiment of the present invention, the first and second plastic films each independently include the same or different, the support substrate, and a coating layer formed on one or both sides of the support substrate, the coating layer is photocurable Cross-linked copolymers.

That is, the first plastic film may include a coating layer on only one surface of the support substrate and the support substrate, or may include a coating layer on both surfaces of the support substrate. In addition, the second plastic film may further include a coating layer on only one surface of the support substrate and the support substrate, or may include a coating layer on both surfaces of the support substrate. In the first and second plastic films, the support substrate on which the coating layer is formed can be used without particular limitation as long as it is a transparent plastic resin substrate that is commonly used. More specifically, according to one embodiment of the present invention, the support substrate may include, for example, polyester such as polyethylene terephthalate (PET), polyethylene such as ethylene vinyl acetate (EVA) polyethylene), cyclic olefin polymers (COPs), cyclic olefin copolymers (COCs), polyacrylates (polyacrylates, PACs), polycarbonates (PCs), polyethylene PE), polymethylmethacrylate (PMMA), polyetheretherketon (PEEK), polyethylenenaphthalate (PEN), The film may include a polyetherimide (PEI), a polyimide (PI), a triacetylcellulose (TAC), a methyl methacrylate (MMA), a fluorine resin, or the like. 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) The substrate can be.

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).

The thickness of the support substrate is not particularly limited, but a support substrate having a thickness of about 30 to about 1,200, or about 50 to about 800 may be used.

The first and second plastic films of the present invention each independently include the same or different coating layers formed on one or both sides of the support substrate.

In addition, according to an embodiment of the present invention, the coating layer includes a photocurable crosslinked copolymer, the photocurable crosslinked copolymer is a 3 to 6 functional acrylate monomer, 1 to 2 functional acrylate monomer, 1 to 6-functional acrylate monomer ^■,. And the optical path there is a chemical conversion elastomer at least one of ⁱ binder is selected from the group consisting of may be each cross-linked polymerization.

Each coating layer formed on one or both surfaces of the first and second plastic films may independently include the same or different photocurable crosslinked copolymers.

For example, the photocurable crosslinked copolymer may be a crosslinked copolymer of 1 to 6 functional acrylate monomers and a photocurable elastomer, or a crosslinked copolymer of 3 to 6 functional acrylate monomers and a photocurable elastomer. It may be coalescing.

In the present specification, the acrylate-based is not only an acrylate but also a methacrylate, or a substituent is introduced into the acrylate or methacrylate. All derivatives.

In addition, throughout the present specification, the photocurable elastomer means a polymer material that exhibits elasticity and includes a functional group capable of crosslinking polymerization by ultraviolet irradiation.

According to one embodiment of the invention, the photocurable elastomer is ASTM

It may have an elongation of at least about 15%, for example about 15 to about 200%, or about 20 to about 200%, or about 20 to about 150%, as measured by D638. When using a photocurable elastomer having a range of the above range, it is possible to form a coating layer that satisfies both high hardness and high impact resistance.

When the photocurable crosslinked copolymer is a crosslinked polymerization of the photocurable elastomeric polymer and 1 to 6 functional acrylate monomers, it provides high hardness and flexibility to the coating layer including the same, and in particular, damages caused by external impact It can prevent and ensure excellent layer resistance.

According to one embodiment of the invention, the photocurable elastomer may be a polymer or oligomer having a weight average molecular weight in the range of about 1,000 to about 600,000 g / mol, or about 10,000 to about 600,000 g / mol.

The photocurable elastomer may be, for example, at least one member selected from the group consisting of polycaprolactone, urethane acrylate polymer, and polyrotaxane.

Among the materials that can be used as the photocurable elastomer, polycaprolactone is formed by ring-opening polymerization of caprolactone and has excellent physical properties such as flexibility, impact resistance, and durability.

The urethane acrylate polymer has excellent elasticity and durability, including urethane bonds.

The polyrotaxane refers to a compound in which a dumbbell shaped molecule and a cyclic compound are structurally fitted. The dumbbell shaped molecule includes a constant linear molecule and a blocking group disposed at both ends of the linear molecule, the linear molecule penetrates the interior of the cyclic compound, and the cyclic compound can move along the linear molecule. And the departure is prevented by the blocker. According to one embodiment of the present invention, a cyclic compound in which a lactone compound having a (meth) acrylate compound introduced therein is bound; Linear molecules penetrating the cyclic compound; And a rotasein compound disposed at both ends of the linear molecule and including a blocking group to prevent the cyclic compound from being separated.

In this case, the cyclic compound may be used without any limitation as long as it has a size enough to penetrate or surround the linear molecule, and may be a hydroxyl group, an amino group, a carboxyl group, a thiol group or an aldehyde group that may react with other polymers or compounds. It may also contain a functional group. Specific examples of such cyclic compounds include _α -cy-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, or a combination thereof.

In addition, as the linear molecule, a compound having a straight chain form having a molecular weight of a predetermined or more may be used without great limitation, and a polyalkylene compound or a polylactone compound may be used. Specifically, a polyoxyalkylene compound containing a oxyalkylene repeating unit having 1 to 8 carbon atoms or a polylactone compound having a lactone repeating unit having 3 to 10 carbon atoms may be used.

On the other hand, the containment group can be appropriately adjusted according to the properties of the rotacein compound to be prepared, for example one selected from the group consisting of dinitrophenyl group, cyclotextrin group, adamantane group, trityl group, fluorescein group and pyrene group or Two or more kinds can be used.

The 1 to 6 functional acrylate monomers include, for example, hydroxyethyl acrylate (ΗΕΑ), hydroxyethyl methacrylate (ΗΕΜΑ), nucleic acid diol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA). ), Ethylene glycol diacrylate (EGDA), trimethyl to propane triacrylate (ΤΜΡΤΑ), trimethyl to propane specific triacrylate (ΤΜΡΕΟΤΑ), glycerin propoxylated triacrylate (GPTA), pentaerythritol tetra An acrylate (PETA) or a dipentaerythrium can be mentioned nucleated acrylate (DPHA). The 1 to 6 functional acrylate monomers may be used alone or in combination with each other.

When the photocurable crosslinked copolymer is a crosslinked copolymer in which the photocurable elastomer and the 1 to 6 functional acrylate monomer are crosslinked, the content ratio thereof is Although not particularly limited, when the total weight of the photocurable crosslinked copolymer is 100 parts by weight, 20 to 80 parts by weight of the photocurable elastomer and 80 to 20 parts by weight of the 1 to 6 functional acrylate monomers Or, 20 to 60 parts by weight of the photocurable elastomer, 40 to 80 parts by weight of the 1 to 6 functional acrylate monomer may be a copolymer cross-linked. As described above, when the high elastic photocurable elastomer includes a photocurable crosslinked copolymer crosslinked with a high content, high impact resistance and good physical properties can be achieved.

According to one embodiment of the invention, the coating layer formed on one side or both sides of the support substrate are each 50 or more, for example about 50 to about 300 ^ m, or about 50 to about 200, or about 50 to about 150 j Or, from about 70 to about 150.

According to another embodiment of the present invention, the photocurable crosslinked copolymer may be a crosslinked copolymer of 3 to 6 functional acrylate monomers.

According to another embodiment of the present invention, the photocurable crosslinked copolymer may be a crosslinked copolymer of 3 to 6 functional acrylate monomers and 1 to 2 functional acrylate monomers.

According to another embodiment of the present invention, the photocurable crosslinked copolymer may be a crosslinked copolymer of a 3 to 6 functional acrylate monomer and a photocurable elastomer.

The 3 to 6 functional acrylate monomers include trimethylolpropane triacrylate (TMPTA), trimethyl to propane specific triacrylate (TMPEOTA), glycerin propoxylated triacrylate (GPTA), and pentaerythritol tetra Acrylate (PETA) or dipentaerythrium can be mentioned nucleated acrylate (DPHA). The 3 to 6 functional acrylate monomers may be used alone or in combination with each other.

In addition, in the plastic film of the present invention, the coating layer may further include inorganic fine particles dispersed in the photocurable crosslinked copolymer. In particular, it may be preferable that the coating layer located at the outermost part contains inorganic fine particles in order to improve surface hardness.

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

By including the inorganic fine particles, the hardness of the coating layer can be further improved.

According to one embodiment of the present invention, when the coating layer comprises inorganic fine particles, about 40 to about 90 parts by weight of the photocurable crosslinked copolymer and about 10 to about 60 parts by weight of the inorganic fine particles Or about 50 to about 80 parts by weight of the photocurable crosslinked copolymer and about 20 to about 50 parts by weight of the inorganic fine particles. By including the photocurable crosslinked copolymer and the inorganic fine particles in the above range, it is possible to form a plastic film of excellent physical properties.

On the other hand, in addition to the photocurable crosslinked copolymer and inorganic fine particles described above, the coating layer may further include additives commonly used in the technical field of the present invention, such as surfactants, anti-yellowing agents, leveling agents, antifouling agents. In addition, since the content can be variously adjusted within a range that does not lower the physical properties of the plastic film of the present invention, it is not particularly limited, for example, about 0.1 to about 10 weight by weight based on 100 parts by weight of the photocurable crosslinked copolymer It can be included as a wealth.

According to one embodiment of the invention, for example, the coating layer 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. The coating layer may be formed by applying the above-described binder, a photoinitiator, and optionally a coating composition including an organic solvent, inorganic fine particles, and additives on a supporting substrate and then photocuring the same.

Examples of the photoinitiator include 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone and 2-hydroxy-1- [4- (2-hydroxy Phenyl] -2-methyl-1-propane, Methylbenzoylformate, α, α-dimethoxy-α-phenylacetophenone, 2-benzoyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2 ᅳ methyl-l- [4- (methylthio) phenyl] -2- (4-morpholinyl) -l-propanone diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide, or bis ( 2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like, but is not limited thereto. Commercially available products include Irgacure 184, Irgacure 500, Irgacure 651, Irgacure 369, Irgacure 907, Darocur 1 173, 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.

Examples of the organic solvent include methane, an alcoholic solvent such as ethanol, isopropyl alcohol and butane, an alkoxy alcohol solvent such as 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone, cyclo hex rice fields ^based, solvent, 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, Aromatic solvents, such as luene and xylene, can be used alone or in combination.

In the coating composition, the organic solvent may include a weight ratio of the solid content: the organic solvent to about 70:30 to about 99: 1 based on a solid content including a binder, a photoinitiator, and other additives. As described above, when the coating composition contains a high content of solids, a high viscosity composition may be obtained, thereby enabling thick coating to form a coating layer having a high thickness, for example, 50 μπι or more.

The first and second plastic films described above are laminated in a form bonded to each other by an adhesive layer.

The thickness of the adhesive layer may be about 1 to about 200, or about 1 to 100 ΙΜ, or about 5 to 50 _/ .

To bond the first and second plastic films. The storage modulus of the adhesive layer (Storage modulus, G ') is measured by dynamic viscoelasticity according to the conventional measurement method. When measured using an instrument, the storage modulus at room temperature (25 ^° C.) after curing is about 40 to about 700 kPa, preferably about 40 to about 500 kPa, more preferably about 40 to about 200 kPa. It features. If the storage elastic modulus of the adhesive layer is less than 40 kPa, bubbles are more likely to occur in the adhesive layer, and if it exceeds 700 kPa, the interfacial adhesion of the first and second plastic films may be deteriorated due to the too hard property. , Layer resistance, and flexibility may be lowered.

With a composition satisfying the storage elastic modulus range as described above, it may include a light (UV) curable resin or a thermosetting resin. For example, the adhesive layer may be formed by photocuring and / or thermosetting an adhesive layer composition including a photocurable acrylate polymer, an oligomer, a monomer, or a mixture thereof as an acrylate monomer component.

_. As said acrylate-type monomer component, it is (meth) acrylate, the alkyl (meth) acrylate which has a C1-C14 linear or branched alkyl group, for example, methyl (meth) acrylate, ethyl (meth) ) Acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, butyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, nuclear chamber (meth Acrylate, 2-ethylnuclear (meth) acrylate, ethylbutyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) Examples include, but are not limited to, ligomers or polymers including acrylates and / or tetradecyl (meth) acrylates or polymerized with one another.

The acrylate monomer may have a weight average molecular weight of 1 million to 5 million g / mol, preferably 1 million to 4 million g / ii) l, more preferably 1.5 million to 3 million g / m.

When the adhesive layer composition is a thermosetting composition, it may further include a curing agent capable of crosslinking the acrylate monomer component.

The curing agent may be used commonly used in the field of adhesive layer production, for example, may be used at least one selected from epoxy-based and isocyanate-based.

The curing agent is based on 100 parts by weight of the acrylate monomer component. 0.01 parts by weight to 10 parts by weight may be included, but the ratio may be changed according to the desired elastic modulus and tackiness.

When the adhesive layer composition is a photocurable composition, it may further include a photoinitiator.

The adhesive composition may further include additives such as _¾ other curable resins, monomers, UV stabilizers, or antioxidants as necessary.

The adhesive layer may refer to any filling having adhesiveness while satisfying the above conditions regardless of its name or form, such as a freestanding layer, a film, a film, or a cured resin layer of a coating composition.

The total thickness of the plastic film laminate of the present invention in which the above-mentioned first and second plastic films are laminated by an adhesive layer is about 0.3 to about 1.5 mm, or about 0.5 to about 1.5 mm, or about 0.7 to about 1.0 mm. Can be.

In addition, the plastic film laminate of the present invention may be a laminate in which five or more layers or substrates distinguished from each other are laminated. For example, the plastic film laminate of the present invention may have a structure of a coating layer-a supporting substrate-an adhesive layer-a supporting substrate-a coating layer, or a coating layer-a supporting substrate-a coating substrate-an adhesive layer-a structure of a supporting substrate-a coating layer, or a coating layer-a supporting substrate- The structure of the adhesive layer-coating layer-supporting substrate-coating layer or the structure of the coating layer-supporting substrate-coating layer-adhesive layer-coating layer-supporting substrate-coating layer. At this time, the components constituting the coating layer are independent of each other, each may be the same or different.

According to an embodiment of the present invention, the plastic film stacker of the present invention is another plastic resin film, adhesive film, release film, conductive film, conductive layer on at least one plastic film of the first or second plastic film In addition, the coating layer, the cured resin layer, a non-conductive film, a metal mesh layer or a layer such as a patterned metal layer may further include one or more. In addition, the layer, film, film or the like may be in any form of a single layer, a double layer or a laminate. The layer, film, or film may be laminated on the coating layer by a method such as laminating a freestanding film using an adhesive or an adhesive film, or by coating, vapor deposition, sputtering, or the like. It is not limited to this.

At this time, in order to increase the adhesion to the layer in contact with the other layer, film, or film, the plasma (plasma) treatment on the surface of the plastic film in contact, Corona discharge treatment or surface treatment with a basic solution such as sodium or potassium hydroxide may be performed.

According to one embodiment of the present invention, the first and second plastic films may be prepared by coating and photocuring the coating composition on one or both surfaces of the support substrate, respectively.

When the coating layer is formed using the coating composition, the coating layer may be formed by a conventional method used in the art. For example, first, a coating composition comprising the aforementioned components is applied to 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.

Next, the coating composition is formed by irradiating the coated composition with ultraviolet light to photocuring the same.

The irradiation amount of ultraviolet light may be, 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. Irradiation for about 30 seconds to about 15 minutes, or about 1 minute to about 10 minutes with the above irradiation amount may be performed to photocuring.

The thickness of the coating layer may be about 50 to about 300 urn, or about 50 to about 200! M, or about 50 to about 150 urn, or about 70 to about 150 after fully cured. When the thickness of the coating layer is in the above-described range, it may exhibit high hardness without problems of curl or cracks.

When the first or second plastic film includes a coating layer on both sides, the coating composition is applied to the other side of the support substrate, that is, the back side. Next, the coating layer is formed by irradiating the coated composition with ultraviolet light to photocuring the same. At this time, in the step of photocuring the coating composition, curing of the previously applied coating composition by performing ultraviolet irradiation on the opposite side of the coating composition The ^' curl ^{' which} can be caused by shrinkage can be offset in the opposite direction to obtain a flat plastic film. Therefore, no additional planarization process is necessary.

The plastic film laminate of the present invention can be produced by bonding the first and second plastic films obtained by the above method by lamination or the like by the above-described adhesive layer.

In the plastic film to be used as a cover of a mobile communication terminal or a tablet PC, it is important to improve the hardness of the plastic film to a level capable of replacing glass. However, it is not easy to implement curl or crack-free films using plastic resin rolls while securing high hardness and impact resistance.

Even if the plastic film laminate according to the present invention is formed to a high thickness so that the overall thickness is 03 mm or more, there is little curl or cracks, and a plastic film having high transparency and layer resistance can be obtained. In addition, without the need to perform several coating and curing processes to increase the thickness, by bonding the two plastic films, process steps and time can be shortened to improve productivity. In addition, the multi-layer coating layer is laminated structure, while exhibiting high transparency and high hardness, the plurality of coating layers can effectively absorb or offset the layer gap from the outside to achieve high layer resistance.

The plastic film laminate of the present invention may have excellent hardness and layer resistance to replace glass. For example, in the plastic film of the present invention, cracks may not occur when 22 g of iron balls are freely dropped 10 times at a height of 60 cm.

In addition, the plastic film locust of the present invention, the pencil hardness at 1 kg load may be 7H or more, or 8H or more, or 9H or more.

In addition, the plastic film laminate of the present invention, after mounting the steel wool (0000) wool steel (0000) in the friction tester may occur less than two scratches when reciprocating 400 times with a load of 500g.

In addition, the plastic film laminate of the present invention may have a light transmittance of about 90.0% or more, or about 91.0% or more, and a haze of about 1.5% or less, or about 1.0% or less, or about 0.8% or less.

In addition, the plastic film laminate of the present invention, the initial color b value (CIE 1976 L * a * b * B *) by the color space may be 1.5 or less. In addition, the difference between the initial color b value and the color b value after 72 hours or more exposure to the UV lamp in the UVB wavelength region may be less than or equal to 5, or less than 0.4.

In addition, the plastic film laminate of the present invention, when exposed at a temperature of 50 ^° C or more and 80% or more at least 70 hours, when placed in a plane, the distance of each corner or one side of the plastic film laminate spaced apart from the plane May have a maximum of about 1.0 mm or less, or about 0.6 mm or less, or about 0.3 mm or less. More specifically, each of the edges or one side of the plastic film laminate spaced apart from the plane when placed in the plane after exposure to 70 to 100 hours at a silver of 50 to 90 ^° C and humidity of 80 to 90% The maximum value may be about 1.0 mm or less, or about 0.6 mm or less, or about 0.3 mm or less.

As described above, the plastic film laminate of the present invention exhibits high hardness, layer resistance, scratch resistance, high transparency, durability, light resistance, high transmittance, and the like, and thus may be usefully used in various fields. For example, the plastic film laminate of the present invention can be utilized in various fields. For example, it can be used for a touch panel of a mobile communication terminal, a smartphone or a tablet PC, and a cover substrate or an element substrate of various displays.

Preparation of Photocurable Elastomers

Preparation Example 1

50 g of polyrotaxane plyme A1000, Advanced Soft Material INC] grafted with caprolactone was added to the reactor, and then Karenz-AOI [2-acryloylethyl isocyanate, Showadenko] 4.53 g, Dibutyltin dilaurate [DBTDL] , Merck Co.] Cyclodextrin with 20 mg, 110 g of hydroquinone monomethylene ether and 315 g of methyl ethyl ketone was added and reacted at 70 ^° C. for 5 hours to form a cyclodextrin bound to a polylactone compound having an acrylate compound introduced at the end thereof. Polyrotasein obtained as a type compound was obtained.

The weight average molecular weight of the obtained polyrotasein was 600,000 g / mol, and elongation measured by ASTM D638 was 20%. Preparation of Adhesive Layer Composition

Preparation Example 2

Acrylic copolymer in which 2-ethyl hexyl acrylate, methyl acrylate and acrylic acid are copolymerized in a weight ratio of 65:25:10 (weight average molecular weight: 1.8 million, molecular weight) Distribution: 5) 0.3 weight part of coronate L which is an isocyanate hardening | curing agent was mixed with 100 weight part, and the contact bonding layer composition was produced. Preparation Example 3

2-ethyl hexyl acrylate and hydroxy butyl acrylate copolymerized in a weight ratio of 98: 2 (weight average molecular weight: 800,000, molecular weight distribution: 4) 0.3 part by weight of coronate L, an isocyanate curing agent, was mixed to 100 parts by weight to prepare an adhesive layer composition. Preparation Example 4

100 parts by weight of an acrylic copolymer having a 2-ethyl hexyl acrylate and an acrylic acid copolymerized at a weight ratio of 90:10 (weight average molecular weight: 1.4 million, molecular weight distribution: 3.8) An adhesive layer composition was prepared by mixing dipentaerythr with 30 parts by weight of nucleated acrylate (DPHA), 1.5 parts by weight of a photoinitiator (trade name: Irgacure 184), and 1 part by weight of coronate L, which is an isocyanate curing agent. Example 1

6 g of trimethylolpropane triacrylate (TMPTA), 4 g of polyrotasein of Preparation Example 1, 0.2 g of photoinitiator (trade name: Darocur TPO), 0.1 g of banjotriazole-based yellowing inhibitor (trade name: Tinuvin 400), fluorine-based interface 0.05 g of the active agent (trade name: FC4430) and 1 g of methyl ethyl ketone were mixed to prepare a first coating composition.

The Crab 1 coating composition was applied on a 15 cm x 20 cm, 188 thick PET support substrate. Next, photocuring was performed by irradiating ultraviolet rays with a wavelength of 280-350 nm using a black light fluorescent lamp to form a coating layer having a thickness of 100 μιη on one side. 1 plastic film was prepared.

Particle size 20-30 nm Nano silica dispersed about 40% by weight ⁰ /. Silica ᅳ dipentaerythroxy nucleoacrylate (DPHA) complex 9 g (3.6 g silica, DPHA 5.4 g), polyrotase of Preparation Example 1 1 g of phosphorus, 0.2 g of photoinitiator (trade name: Darocur TPO), 0.1 g of benzotriazole-based yellowing inhibitor (trade name: Tinuvin 400), 0.05 g of fluorine-based surfactant (trade name: FC4430), and 1 g of methyl ethyl ketone were mixed. The coating composition was prepared. The second coating composition was applied on another PET support substrate 15 cm × 20 cm, thickness 188 μπι. Next, photocuring was performed by irradiating ultraviolet rays with a wavelength of 280-350 nm using a black light fluorescent lamp to prepare a second plastic film having a coating layer having a thickness of 100 mm 3 on one side.

The adhesive layer composition of Preparation Example 2 was applied to a thickness of 50 and laminated between the PET support substrates of the first and second plastic films, followed by thermal curing at a temperature of 60 ^° C., thereby preparing a plastic film laminate. Example 2

6 g of trimethyl propane triacrylate (TMPTA), 4 g of urethane acrylate polymer (trade name: UA200PA, Shinnakamura Chemical, weight average molecular weight 2,600 g / mol, elongation at 170% by ASTM D638), photoinitiator (trade name: Darocur TPO) 0.2 g, benzotriazole yellowing inhibitor (trade name: Tinuvin 400) 0.1 g, fluorine-based surfactant (trade name: FC4430) 0.05 g, methyl ethyl ketone lg was mixed to prepare a first coating composition.

9 g of silica-dipentaeryri (DPHA) composites (3.6 g of silica, 5.4 g of silica) dispersed in about 40% by weight of nano silica having a particle diameter of 20-30 nm, urethane acrylate polymer (UA200PA) 1 g, 0.2 g of photoinitiator (trade name: Darocur TPO), 0.1 g of benzotriazole-based yellowing inhibitor (trade name: Tinuvin 400), 0.05 g of fluorine-based surfactant (trade name: FC4430), and 1 g of methyl ethyl ketone were mixed. Was prepared. The first coating composition was applied on a PET support substrate of 15 cm × 20 cm, thickness 188. Next, photocuring was carried out by irradiating ultraviolet rays with a wavelength of 280-350 nm using a blow light fluorescent lamp to form a first coating layer having a thickness of 100 Hz. A second coating composition was applied to the back side of the support substrate. Next, photocuring was performed by irradiating ultraviolet rays with a wavelength of 280-350 nm using a black light fluorescent lamp. It was carried out to form a crab 2 coating layer having a thickness of 100 to prepare a plastic film having a first and a second coating layer on each side.

The adhesive layer composition of Preparation Example 2 was applied between two plastic films to a thickness of 50, and laminated, and then thermoset at a temperature of 60 ^° C. to prepare a plastic film laminate. Example 3

6 g of trimethylolpropane triacrylate (TMPTA), 4 g of urethane acrylate polymer (trade name: UA340P, Shinnakamura Chemical, weight average molecular weight 13,000 g / mol, elongation 150% according to ASTM D638), photoinitiator (brand name: Darocur TPO) 0.2 g, benzotriazole yellowing inhibitor (trade name: Timivin 400) 0.1 g, fluorine-based surfactant (trade name: FC4430) 0.05 g, methyl ethyl ketone lg was mixed to prepare a first coating composition.

The particle diameter is 20-30nm nano silica is about 40 wt ^_0/0 dispersed silica-hex the dipentaerythritol EPO Li acrylate (DPHA) complex 9 g (silica 3.6 g, DPHA 5.4 g), urethane acrylate-based polymer (UA340P ) 1 g, photoinitiator (trade name: Darocur TPO) 0.2 g, benzotriazole yellowing inhibitor (trade name: Timivin 400) 0.1 g, fluorine-based surfactant (trade name: FC4430) 0.05 g, 1 g methyl ethyl ketone The coating composition was prepared. The first coating composition was applied on a PET support substrate 15 cm × 20 cm, thickness 188 / m. Next, ultraviolet rays having a wavelength of 280-350 nm were irradiated with a black light fluorescent lamp to perform photocuring to form a first coating layer having a thickness of 100. A second coating composition was applied to the back side of the support substrate. Next, photocuring was performed by irradiating ultraviolet rays with a wavelength of 280-350 nm using a black light fluorescent lamp to form a second coating layer having a thickness of 100 to prepare a plastic film having first and second coating layers formed on both surfaces, respectively. .

Preparation example between two plastic films. The adhesive layer composition of 2 was applied so as to have a thickness of 50 and laminated, and then prepared into a plastic film laminate by thermosetting at a temperature of 60 ^° C. Comparative Example 1

In the same manner as in Example 2, the first and second coating layer formed plastic A film was prepared. -Next, the adhesive layer composition of Preparation Example 3 was applied between two plastic films to have a thickness of 50, and laminated, and then prepared into a plastic film laminate by thermal curing ^{at a} temperature of 60 ^° C. Comparative Example 2

In the same manner as in Example 2, a plastic film on which the first and second coating layers were formed was prepared.

Next, after applying and laminating the adhesive layer composition of Preparation Example 4 to a thickness of 50 between the two plastic film, the photocuring by UV irradiation of 200mJ / cm ² and thermal curing at a temperature of 60 ^° C. It was made of a plastic film laminate. The lamination structure and total thickness of the plastic film laminates of Examples 1 to 3 and Comparative Examples 1 and 2 are shown in Table 1 below.

TABLE 1

Total storage thickness of laminated structure adhesive layer

Modulus of elasticity (G ') * (unit: i) Example 1 First coating layer-PET substrate-69 kPa 626

Adhesive Layer (Manufacturing Example 2) -PET Substrate-Second

Coating layer

Example 2 First Coating Layer—PET Substrate—Secondary 69 kPa 826

Coating Layer-Adhesive Layer (Manufacturing Example 2) -First

Coating Layer-PET Substrate-Second Coating Layer

Example 3 First Coating Layer—PET Substrate—Secondary 69 kPa 826

Coating Layer-Adhesive Layer (Manufacturing Example 2)-Article 1.

Coating Layer-PET Substrate-Second Coating Layer

Comparative Example 1 First Coating Layer-PET Substrate-Second 20 kPa 826

Coating layer-window layer (production example 3)-1st

Coating Layer-PET Substrate-Second Coating Layer Comparative Example 2 First Coating Layer-PET Substrate-Second 800 kPa 826 Coating Layer-Window Layer (Preparation Example 4)-First

Coating Layer-PET Substrate-Second Coating Layer

The storage modulus (G ′) of the adhesive layer was measured using a dynamic viscoelasticity measuring instrument (ARES-RDA, TA instruments Inc.). The measurement conditions were measured at room temperature (25 ^° C), a frequency of 1 rad / s, using a plate of 8mm stainless steel disk type, the thickness of the adhesive layer was 1mm.

Experimental Example

1) pencil hardness

Using a pencil hardness tester, the top layer (second coating layer) of each film laminate was reciprocated three times at a load of 1.0 kg according to the measurement standard JIS K5400, and then the hardness without grooves was confirmed.

2) scratch resistance

After the steel batter (# 0000) was attached to the friction tester, the number of grooves was evaluated after reciprocating 400 times at 0.5 kg of dripping with respect to the uppermost layer (second coating layer) of each film laminate. O for 2 or less homes, Δ for 3 or more and 5 or less homes, and X for 5 or more homes. 3) light resistance

The difference in color b values before and after 72 hours exposure to UV lamps in the UVB wavelength range was measured.

4) Transmittance and Haze

Transmittance and haze were measured using a spectrophotometer (device name: COH-400).

5) Moisture Resistance Curl Characteristics Each plastic film laminate was cut into 10 cm x 10 cm, stored in a chamber at a temperature of 85 ^° C and a humidity of 72% for 72 hours, and placed on a flat surface where one side of each corner was less than 1 mm away from the flat surface. OK, evaluated as X when exceeding 1 mm.

6) Cylindrical bend test

^. Each plastic film laminate is wound around a 3 cm diameter cylindrical mantel with the first coating layer on the outside of the film laminate, and it is determined whether or not cracks have occurred. Evaluated as.

7) Layer resistance

When 22 g of iron ball was repeatedly dropped freely 10 times on the second coating layer of each film laminate at a height of 60 cm, the impact resistance was judged by the presence or absence of cracks, and the crack was not generated. Was evaluated by X.

8) Appearance Evaluation

The surface state of the film was visually observed to observe whether there were any grooves such as bubble generation, foreign matter, cracks, and adhesion state. The physical property measurement results are shown in Table 2 below.

TABLE 2

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Pencil Hardness 8H 9H 9H 9H 9H

Scratch Resistance O O 0 0 0

Light Resistance 0.24 0.28 0.18 0.20 0.22

Transmittance 91.3 91.0 92.8 92.5 92.0

Haze 0.5 0.7 0.4 0.3 0.4

Flexural Test 0K OK 0K 0 0K

Heat-resistant curl property 0K OK 0K OK X

Shock Resistance 0K 0K OK OK X Appearance Good Good Good Bubble Generation

Defects As shown in Table 2, the plastic film laminates of Examples 1 to 3 of the present invention exhibited good properties in all of their physical properties. However, in Comparative Example 1 in which the storage elastic modulus of the adhesive layer was low, bubbles were generated in the adhesive layer, and in Comparative Example 2 in which the storage elastic modulus was too high, the adhesive force was reduced, so that the first and second plastic films were not properly bonded, and thus the impact resistance and curling were not achieved. Properties and the like appeared poor.

Claims

【Patent Claims】

【Claim 1】

A first plastic film including at least one coating layer; and a second plastic film including at least one coating layer, wherein the first and second plastic films are bonded to each other by an adhesive layer.

【Claim 2】

The plastic film laminate according to claim 1, wherein the adhesive layer has a storage modulus (G') of 40 to 700 kPa.

[Claim 3]

The method of claim 1, wherein the first and second plastic films each independently, identically or differently, include a support substrate and a coating layer formed on one or both sides of the support substrate, wherein the coating layer is a photocurable crosslinked copolymer. A plastic film laminate comprising a.

【Claim 4】

The plastic film laminate according to claim 3, wherein the coating layers included in the first and second plastic films further include independently the same or different inorganic particles dispersed in the photocurable crosslinked copolymer.

【Claim 5】

The method of claim 3, wherein the photocurable crosslinked copolymer consists of a 3 to 6 functional acrylate monomer, a 1 to 2 functional acrylate monomer, a 1 to 6 functional acrylate monomer, and a photocurable elastic polymer. A plastic film laminate in which one or more binders selected from the group are crosslinked and polymerized with each other.

【Claim 6】

The plastic film laminate according to claim 5, wherein the photocurable elastomer has an elongation of 15 to 200% as measured by ASTM D638.

【Claim 7】

The plastic film laminate according to claim 5, wherein the photocurable elastic polymer includes at least one selected from the group consisting of polycaprolactone, urethane acrylate polymer, and polyrotacene.

【Claim 8】

According to claim 7, wherein the polyrotacene is a cyclic compound in which a lactone-based compound to which a (meth)acrylate-based compound is introduced is bonded to the terminal; a linear molecule penetrating the cyclic compound; and a blocking group disposed at both ends of the linear molecule to prevent the cyclic compound from leaving.

【Claim 9】

The method of claim 5, wherein the monomer to bifunctional acrylate monomer is hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), nucleic acid diol diacrylate (HDDA), tripropylene glycol diacrylate. A plastic film laminate comprising at least one member selected from the group consisting of diacrylate (TPGDA) and ethylene glycol diacrylate (EGDA).

【Claim 10】

The method of claim 5, wherein the 3 to 6 functional acrylate monomers are trimethylolpropane triacrylate (TMPTA), trimethyl propane triacrylate (TMPEOTA), and glycerin propoxylated triacrylate (GPTA). A plastic film laminate containing at least one member selected from the group consisting of pentaerythry tetraacrylate (PETA), and dipentaerythry hexaacrylate (DPHA).

【Claim 11】

The method of claim 3, wherein the support substrate is polyethylene terephthalate (PET) or ethylene vinyl. Acetate (ethylene vinyl acetate, EVA), cyclic olefin polymer COP, cyclic olefin copolymer (COC), polyacrylate (PAC), polycarbonate (PC) , polyethylene (PE), polymethylmethacrylate (PMMA), polyetheretherketon (PEEK), polyethylenenaphthalate (PEN), polyetherimide (PEI), polyimide ( A plastic film laminate containing at least one member selected from the group consisting of polyimide (PI), triacetylcellulose (TAC), MMA (methyl methacrylate), and fluorine-based resin.

[Claim 12]

The plastic film laminate according to claim 3, wherein the thickness of each coating layer is independently the same or different and is 50 to 300 卿.

【Claim 13】

The plastic film laminate according to claim 1, wherein the total thickness is 0.3 to 1.5 mm.

【Claim 14】

The plastic film laminate according to claim 1, wherein no cracks occur when a 22 g steel bead is repeatedly freely dropped from a height of 60 cm 10 times.

【Claim 15】

The plastic film laminate according to claim 1, which exhibits a pencil hardness of 7H or more under a load of 1 kg.

【Claim 16】

The plastic film laminate according to claim 1, wherein no more than 2 scratches occur when the surface is rubbed back and forth 400 times with steel wool #0000 under a load of 500 g.

【Claim 17】

The plastic film laminate according to claim 1, which exhibits a light transmittance of 90% or more, a haze of 1.5 or less, and a b* value of 1.5 or less.

【Claim 18】

The plastic film laminate according to claim 1, wherein the change in b* value of the plastic film is 0.5 or less when exposed to UV B wavelength light for 72 hours:

【Claim 19】

The method of claim 1, wherein when the plastic film is placed on a plane after being exposed to a temperature of 50 ^° C or higher and a humidity of 80% or higher for more than 70 hours, the maximum distance that each edge or one side of the plastic film is separated from the plane is Plastic film laminates below LO mm. 【Claim 20】

The method of claim 1, wherein a plastic resin film, an adhesive film, a release film, a conductive film, a conductive layer, a coating layer, a cured resin layer, a non-conductive film, a metal mesh layer and a patterned film are formed on the first or second plastic film. A plastic film laminate further comprising one or more layers selected from the group consisting of metal layers.