KR101335268B1 - A optical transparent composite film for the use of display laminated with a protective film for processing and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an optical transparent composite film for the use of display laminated with a protective process film, a manufacturing method using the same, and a flexible display product thereof. The optical transparent composite film for the use of display laminated with a protective process film comprises: a polymer substrate containing a thermoplastic transparent base resin; an inorganic gas barrier layer formed on at least one surface of the polymer substrate; and an inorganic-organic hybrid overcoating layer which is formed on the upper surface of the inorganic gas barrier layer and contains a (meth)acrylate monomer, an epoxy group, a (meth)acrylate oligomer with 500-10,000 of weight-average molecular weight, an initiator, silica particles, curable coating fluid with a dispersion medium, a metal alkoxide, a curing accelerator, an inorganic acid, and a curable product of a curable sol solution mixed with the sol solution and solvents. The adhesiveness between the protective process film and the monolayer of the polymer substrate is more than 1gf/inch, and the adhesiveness between the protective process film and the composite layer of the polymer substrate and gas barrier is less than 12gf/inch.

Description

A transparent optical film for the use of display laminated with a protective film for processing and manufacturing method

The present invention relates to an optical transparent composite film for a protective film laminated display for a process, a method for manufacturing the same, and a flexible display product including the same, and for a protective film laminated display for a process having excellent gas barrier properties as well as an improved process yield. The present invention relates to an optical transparent composite film, a method of manufacturing the same, and a flexible display product including the same.

In the modern industry, the display industry is faced with a serious crisis due to overload of supply along with the global economic downturn. Innovative technology or products are absolutely necessary to overcome this.

Flexible display is a key technology industry that can realize low power, low cost, ultra light weight and large area, and is easy to carry and can easily access information anytime and anywhere. Flexible display is used as a roll-to-roll production method, and it is an industry that can emerge as the core of the display market with the commercialization of mass production technology centering on small household devices such as mobile. .

In the case of flexible substrates, many companies and research institutes have already been studied as an interesting topic. Transparency is good, but it is easily damaged by impact due to its lack of impact resistance, and there is a limit to thinning. In addition, the impact, weight, and thickness described above are replaced to replace conventional glass, which has a large weight per unit volume and is difficult for application as a flexible substrate. As well as solving the problems related to the light, thin, flexible, easy to be applied to the flexible substrate, for example, excellent optical properties such as polycarbonate (polycarbonate, PC), polyimide (PI), polyether sulfone thermoplastic polymers such as polyethersulfone (PES), polyarylate (PAR), polyethylene naphthalate, poly (ethylene terephthalate, PET), cycloolefin copolymer Acrylic resins, epoxy resins and unsaturated polyesters. Has been used is a transparent film produced by using the polymer curing the resin.

In order for the film made of these polymers to serve as a substrate used in flexible display products, it has excellent optical properties such as excellent moisture barrier property and oxygen barrier property which directly affect the lifetime of the display, and can serve as a display faithfully. Characteristics are required. However, in practice, since the polymer transparent film is very poor in moisture and oxygen blocking ability, experiments are actively underway to achieve the above properties by coating a functional coating layer in multiple layers.

Currently, it uses a multilayer coating method including an inorganic gas barrier layer to increase moisture and oxygen barrier properties, and an organic-inorganic hybrid coating layer that can further increase barrier properties and provide excellent surface hardness. In order to solve the above problems by using a method such as lowering the surface roughness of the film to stably coat the inorganic gas barrier layer or adding an undercoat layer to minimize the resistance at the interface between the layers, the adhesion between the coating layers is improved. It's going on.

Currently, in order to consider the needs of consumers who want thinner and lighter products and to produce flexible display products that bend freely without breaking unbreakable displays, an optical transparent composite film for a very thin display is needed.

However, when the roll-to-roll process is actually performed using a very thin thin polymer film, it is very susceptible to exposure to extreme conditions such as heat and UV generated during the lamination of the coating film, which is very easy to cause breakage. When the process was given by giving a tension of about 100 to 600 N to proceed, waving and wrinkles are generated due to tension, so that the uniformity of physical properties and fabric damage in the deposition process are prevented. When the tension is 300N or more, breakage of the film occurs.

In order to use the thin polymer transparent film as a substrate of the flexible display in this problem, it is necessary to develop a new technology that can increase the yield in the roll-to-roll process and maintain excellent gas barrier properties and optical properties.

Another problem to be solved by the present invention is to provide an optical transparent composite film for thin process protective film laminated display having excellent physical properties that can be used in a flexible display product by maintaining excellent gas barrier properties and optical properties through the above process. .

The problem to be solved by the present invention is to solve the above problems by attaching a process protective film on the back surface of the coating surface during the roll-to-roll coating process and a method of manufacturing an optical transparent composite film for a process protective film laminated display having a high process yield To provide.

Another problem to be solved by the present invention is to provide a flexible display product using the optical transparent composite film for the protective film laminated display for the process.

In order to solve this problem, according to an aspect of the present invention,

A polymer substrate comprising a thermoplastic transparent base resin;

An inorganic gas barrier layer formed on at least one surface of the polymer substrate; And

It is formed on the upper surface of the inorganic gas barrier layer, the curable coating solution and (metal) alkoxy having a (meth) acrylate monomer, an epoxy group and a (meth) acrylate oligomer, an initiator, silica particles and a dispersion medium having a weight average molecular weight of 500 ~ 10,000 For example, an organic-inorganic hybrid overcoating layer comprising a hardening product of a curable sol solution mixed with a sol solution containing a curing accelerator, an organic acid, and a solvent; And

Including a process protective film laminated on the other surface of the polymer substrate,

Adhesion between the protective film for the process and the polymer substrate is 1 gf / inch or more,

There is provided an optical transparent composite film for a process protective film lamination display, wherein the adhesion between the process protective film and the composite layer of the polymer substrate-inorganic gas barrier layer is 12 gf / inch or less:

According to another aspect of the present invention,

Preparing a polymer substrate comprising a thermoplastic transparent base resin;

Laminating a process protective film on one surface of the polymer substrate;

Forming an inorganic gas barrier layer on the other surface of the polymer substrate; And

A (meth) acrylate monomer, an (meth) acrylate oligomer having an epoxy group and a weight average molecular weight of 500 to 10,000 and an initiator are dissolved in a dispersion medium, and a curable coating solution, a metal alkoxide, a curing accelerator, an inorganic acid, and water in which silica particles are dispersed. Applying a curable sol solution prepared by mixing a sol solution dissolved in a solvent to an upper surface of the inorganic gas barrier layer, and curing the applied curable sol solution to form an organic-inorganic hybrid overcoating layer. There is provided a method of preparing an optical transparent composite film for a protective film-laminated display.

According to another aspect of the present invention, there is provided a flexible display product using the optical transparent composite film for the protective film laminated display for the process.

According to an embodiment of the present invention, the process protective film is attached to the back surface of the coating during the coating process film damage due to heat and UV generated during the process, under the tension conditions of 100 to 600 N level to proceed the process Process yield can be greatly improved by preventing film damage and fracture, such as webbing and wrinkling.

In addition, by adopting such a process method, it is possible to maintain an excellent gas barrier property and optical properties to produce a thin transparent protective film for a process protective film laminated display having excellent physical properties that can be used in flexible display products.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate preferred embodiments of the invention and, together with the description of the invention given below, serve to further the understanding of the technical idea of the invention, And should not be construed as limiting.
1 is a cross-sectional view of an optical transparent composite film for a process protective film lamination display according to an embodiment of the present invention.
FIG. 2 is a cross-sectional view of a polymer substrate having a protective film attached to an upper surface thereof, in order to manufacture an optical transparent composite film for a process protective film laminated display according to an embodiment of the present invention.
3 is a cross-sectional view of the result of laminating the process protective film on the lower surface of the polymer substrate of FIG.
FIG. 4 is a cross-sectional view of the result of removing the protective film of FIG. 3 and forming an inorganic gas barrier layer. FIG.
5 is a cross-sectional view of a result of forming an organic-inorganic hybrid overcoating layer on an upper surface of the inorganic gas barrier layer of FIG. 4.
6 is a cross-sectional view of an optical transparent composite film for a process protective film lamination display according to an embodiment of the present invention.
FIG. 7 is a schematic diagram of a roll-to-roll sputtering dual mode apparatus having six coating zones and a plasma treatment zone for forming an optical transparent composite film for a process protective film lamination display according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It should be interpreted in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined.

Therefore, the embodiments described in the present specification and the configurations shown in the drawings are only the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention. Therefore, It is to be understood that equivalents and modifications are possible.

Process protective film laminated display optical transparent composite film according to an aspect of the present invention by attaching a process protective film on the back surface of the coating during the coating process due to heat and UV damage during the process, to proceed with the process The present invention proposes a method of greatly improving the process yield by preventing film damage and fracture such as wave and wrinkles under tension conditions of about 100 to 600 N. Hereinafter, the present invention will be described in detail.

Process protective film laminated display optical transparent composite film according to an aspect of the present invention,

A polymer substrate comprising a thermoplastic transparent base resin;

An inorganic gas barrier layer formed on at least one surface of the polymer substrate;

It is formed on the upper surface of the inorganic gas barrier layer, the curable coating solution and (metal) alkoxy having a (meth) acrylate monomer, an epoxy group and a (meth) acrylate oligomer, an initiator, silica particles and a dispersion medium having a weight average molecular weight of 500 ~ 10,000 For example, an organic-inorganic hybrid overcoating layer comprising a hardening product of a curable sol solution mixed with a sol solution containing a curing accelerator, an organic acid, and a solvent; And

Including a process protective film laminated on the other surface of the polymer substrate,

Adhesion between the protective film for the process and the polymer substrate is 1 gf / inch or more,

The adhesion between the process protective film and the composite layer of the polymer substrate-inorganic gas barrier layer is 12 gf / inch or less.

Referring to Figure 1, the optical protective composite film 100 for a process protective film lamination display according to an embodiment of the present invention is a polymer substrate (10); An inorganic gas barrier layer 20 formed on at least one surface of the polymer substrate; An organic-inorganic hybrid overcoating layer 30 formed on an upper surface of the inorganic gas barrier layer; And a process protective film 40 laminated on the other surface of the polymer substrate.

The polymer substrate includes a thermoplastic transparent base resin, wherein the thermoplastic transparent base resin includes polyethersulfone, polycarbonate, polyimide, polyarylate, polyethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate glycol, polycyclo Hexylenedimethylene terephthalate glycol, cycloolefin copolymer and the like can be used, but are not limited thereto.

The thickness of the polymer substrate is not particularly limited as long as it satisfies mechanical strength and flexibility at the same time, and may be, for example, 10 to 500 μm, preferably 20 to 200 μm.

In general, such polymer substrates may have various forms of foreign substances on the surface thereof, and thus, many defects may occur when the inorganic layer is formed, thereby deteriorating gas barrier properties. Therefore, to solve the above problems by using a method such as lowering the surface roughness of the polymer film to stably coat the inorganic gas barrier layer or adding an undercoat layer to minimize the resistance at the interface between the layers to improve the adhesion between the coating layers, or Invention is in progress. However, in order to implement such an undercoating layer, a wet process must be performed at least once, and thus, the efficiency of the process may be poor, resulting in economic disadvantages. Therefore, the present invention has a process of eliminating the undercoating process and performing a plasma treatment in a one-pot process prior to the deposition process of the inorganic gas barrier layer to remove foreign substances on the surface and improve surface smoothness. Such plasma treatment not only improves adhesion but also brings unexpected effects such as improvement of gas barrier properties such as moisture barrier property and oxygen barrier property.

As described above, in the optical transparent composite film according to an aspect of the present invention, one surface of the polymer substrate is plasma treated to include a plasma surface treatment layer formed on one surface of the polymer substrate. In plasma surface treatment, the degree of vacuum in the chamber preferably proceeds from 0.1 to 500 mtorr, more preferably from 0.5 to 100 mtorr, even more preferably from 1 to 10 mtorr. Further, the power of the plasma is 0.1 to 5 W / cm ² , preferably 0.3 to 3 W / cm ² , more preferably 0.5 to 1 W / cm ² , and the line speed is 0.1 to 5 M /. Proceed to min speed.

When the degree of vacuum, plasma power and linear velocity described above are deviated, the gas barrier effect and the adhesion with the inorganic barrier layer are not sufficiently obtained, and more specifically, the surface of the substrate during the process when the vacuum or plasma power is too high or the linear velocity is too slow. The roughness of may rather increase. In addition, if the degree of vacuum or plasma power is too low or the line speed is too fast, the surface foreign matter may not be properly removed and the modification may not be perfect. However, it can deform | transform and determine according to the kind and state of a base material within the said range.

In addition, the reaction gas such as O ₂ , Ar, N ₂ , and H ₂ is supplied during the plasma treatment, and the reaction gas does not limit the plasma to generate plasma.

After the plasma treatment, at least 80% of the foreign matter present on the surface, preferably at least 90%, even more preferably at least 95%, should be 10 nm or less, preferably 5 nm or less, more preferably 2 nm or less. In addition, the surface roughness, that is, the Ra value should be 0.3 nm or less, preferably 0.1 nm or less. The smaller the surface roughness is, the more advantageous for the present invention. As such, it is important to control the plasma processing conditions in order to produce a small surface roughness, and the plasma processing conditions mean specific processing conditions, not extreme conditions. When the range of the surface roughness is satisfied, the gas barrier effect and the adhesion with the inorganic barrier layer according to the present invention can be satisfied. In this case, the foreign matter refers to organic dust (organic dust) and the like present in the plasma surface treatment layer, it may be caused by sticking to the film surface in the film manufacturing process or protective film lamination and removal process. The surface roughness and the size of the foreign matter present on the surface were measured using a VEECO Dimension 3100 Atomic Force Microscope (AFM).

The protective film for the process is formed on one surface of the polymer substrate. In order to manufacture an optically transparent composite film for a display, a tension is added to the polymer substrate in a process of forming an inorganic gas barrier layer and an organic-inorganic hybrid overcoating layer on one surface of the polymer substrate, particularly in a roll-to-roll process. . In this case, due to the added tension (for example, about 100 to 600 N), the polymer substrate may cause wave and wrinkles, and thus may result in poor uniformity of physical properties and fabric damage in the deposition process for forming the inorganic gas barrier layer. , Or when a large tension is applied, the film may break and the coating process itself may be impossible.

Thus, the protective film for the process is laminated with a polymer substrate that may be weak due to the tension added during the process, thereby enhancing the physical properties such as tensile strength of the polymer substrate, it is possible to solve the process problems.

The process protective film is easily peeled off when applied to a display or the like without being peeled off from the polymer substrate during the process, and the adhesive layer is not required to be transferred to the polymer substrate. Control of adhesion is very important.

Therefore, the adhesive force between the process protective film and the polymer substrate is 1 gf / inch or more, preferably 2 gf / inch or more, more preferably 3 to 4 gf / inch. In addition, after the inorganic gas barrier layer is formed on the other surface of the polymer substrate, the adhesive force between the composite layer of the polymer substrate-inorganic gas barrier layer and the protective film for the process is 12 gf / inch or less, preferably 9gf / inch or less , More preferably 4 to 8 gf / inch.

As such, when only the protective film for the process is attached to one surface of the polymer substrate, the protective film for the process is attached to the polymer substrate and then the inorganic gas barrier layer is formed, rather than the adhesion between the two. The adhesion between the polymer substrate and the composite layer of the inorganic gas barrier layer is generally increased. It is subjected to a deposition coating process by a physical or chemical method to form an inorganic gas barrier layer on the polymer substrate, and this process also affects between the adhesive layer of the process protective film and the polymer substrate so that both of them are more firmly adhered. It is understood as a result. According to an embodiment of the present invention, in order to prevent post-process process defects and adhesive layer transfer problems, the adhesive force between the composite layer of the polymer substrate-inorganic gas barrier layer and the process protective film is 12 gf / inch or less. Adjusted.

The optical protective composite film for a protective film laminated display for a process according to an embodiment of the present invention is prevented in post-process defects and adhesive layer transfer problems, and maintains excellent optical and gas barrier properties even after a process using a thin film. can do.

The process protective film is composed of an adhesive layer and a base material. The substrate may be applied without limitation as long as it is a film of a material that is laminated with a polymer substrate to impart physical properties such as tensile strength so that the coating process is performed efficiently. Non-limiting examples include polyethylene terephthalate, polypropylene, polyethylene, polyester Polymer films such as these.

In addition, the protective film for the process may be laminated with a polymer substrate by having an adhesive layer, and then peeled off. The adhesive layer may be formed by curing a mixture of a polymer resin, an initiator, a crosslinking agent, and the like by UV irradiation. Examples of such polymer resins include acrylic resins, rubber resins, silicone resins, and the like, of which acrylic resins are excellent in transparency, durability, heat resistance, and the like. Such an acrylic resin book is not specifically limited, It can obtain by superposing | polymerizing various acrylic monomers or methacryl-type monomers according to a use. In addition, the crosslinking agent may further include a crosslinking agent such as an isocyanate compound, an aziridine compound, an epoxy compound, and the like.

It is preferable that the thickness of the said protective film for processes is 20-100 micrometers, for example, it is more preferable that it is 30-80 micrometers, and it is especially preferable that it is 40-60 micrometers.

In addition, the inorganic gas barrier layer may include oxides, nitrides, carbides, oxynitrides, oxide carbides, oxides, nitrides, carbides, Nitriding carbides, or oxynitride carbides. Specifically, the inorganic gas barrier layer may include silicon oxide, silicon nitride, aluminum oxide, or ITO (indium tin oxide).

The inorganic gas barrier layer may be, for example, a thickness of 20 to 500 nm, or 30 to 100 nm, and when the thickness of the inorganic gas barrier layer satisfies this range, a uniform film may be formed and dispersed. This makes it easy to exhibit excellent gas barrier properties, the effect of reducing the interlayer stress by the coating layer is sufficiently expressed, and problems such as cracking and peeling can be prevented.

Subsequently, the organic-inorganic hybrid overcoating layer is formed by UV curing or thermosetting the curable sol solution in which the curable solution and the sol solution are mixed.

The curable sol solution includes a (meth) acrylate monomer, an epoxy group, a (meth) acrylate oligomer having a weight average molecular weight of 500 to 10,000, and an initiator in a dispersion medium, and a curable coating solution in which silica particles are dispersed.

The (meth) acrylate monomer functions to control the viscosity and the curing density of the curable coating liquid and improve the adhesion to the inorganic gas barrier layer. The (meth) acrylate monomers may be monofunctional or polyfunctional monomers. It may also exist in ethoxylated or propoxylated form. Examples of the (meth) acrylate monomer include 2 (2-ethoxyethoxy) ethyl acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, caprolactone acrylate, dicyclopentadienyl methacryl Butanediol diacrylate, 1,4-butanediol dimethacrylate, diethylene glycol diacrylate, ethoxylated bisphenol A di (meth) acrylate, diethyleneglycol diacrylate, Acrylate, ethoxylated bisphenol A dimethacrylate, ethylene glycol dimethacrylate, ethoxylated trimethylol propane triacrylate, pentaerythritol triacrylate, propoxylated glyceryl triacrylate, propoxylated Trimethylolpropane triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tris (2- Hydroxyethyl) isocyanurate triacrylate, or the like, or a mixture of two or more thereof.

The (meth) acrylate oligomer having an epoxy group and a weight average molecular weight of 500 to 10,000 is an oligomer having a (meth) acrylate group and an epoxy group, and the organic-inorganic hybrid overcoat layer is well adhered to the plastic transparent film and the inorganic gas barrier layer . Particularly, it contributes to enhancement of adhesion with a plastic transparent film. Examples thereof include bisphenol-A epoxy acrylate oligomer, flame retardant epoxy acrylate oligomer, novolac epoxy acrylate oligomer, bisphenol-F epoxy acrylate oligomer, glycidyl amine Type epoxy acrylate oligomer, rubber modified epoxy acrylate oligomer, or the like, or a mixture of two or more of them may be used.

The initiator may be any chemical compound capable of initiating the polymerization of (meth) acrylate functional groups by actinic radiation. Examples of suitable photoinitiators include 1-hydroxy-cyclohexyl-phenyl-ketone, benzophenone, 2-hydroxy-2-methyl- 2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-hydroxy- Diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide, mixtures thereof, and the like. Photolatent base type photoinitiators such as 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone can also be used as photoinitiators.

The dispersion medium used in the curable coating liquid may include at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, cyclohexanol, pentanol, octanol, decanol, Examples of the organic solvent include ether, propylene glycol dimethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, Diethylene glycol dimethyl ether, ethylene glycol ethyl ether, ethylene glycol diethyl ether, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Propylene glycol, butylene The solvent may be selected from the group consisting of glycol, dibutylene glycol, tributylene glycol, tetrahydrofuran, dioxane, acetone, diacetone alcohol, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, ethyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, 1-methoxy-2-propanol, ethyl 3-ethoxypropionate, 2-propoxyethanol, ethylene glycol ethyl ether acetate or Mixtures thereof, and the like.

The silica particles dispersed in the curable coating liquid preferably have an average particle size of about 100 nm or less, and more preferably about 5 to 50 nm.

The silica particles may be added to the coating solution in the form of a dry powder or in a colloidal dispersion in a suitable liquid, or other form. Silica particles include those modified as such or by introducing appropriate functional groups on the surface in order to increase the miscibility of the particles to the curable coating solution.

In addition, the curable coating liquid may further include a silicon alkoxide having a (meth) acrylate group. In the present specification, (meth) acrylate means acrylate or methacrylate.

Examples of the silicon alkoxide having the (meth) acrylate group include (3-acryloxypropyl) dimethylmethoxysilane, (3-acryloxypropyl) methyldimethoxysilane, (3-acryloxypropyl) trimethoxysilane, (Methacryloxymethyl) dimethylethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, (3- Methacryloxypropyl) triethoxysilane, (3-methacryloxypropyl) trimethoxysilane, etc. can be used individually or in mixture of 2 or more types, respectively.

The relative amount of each of the components constituting the curable coating liquid for forming the organic-inorganic hybrid overcoating layer can be adjusted according to the properties of the film for the substrate, the (meth) acrylate monomer, epoxy group contained in the curable coating liquid The weight ratio of the (meth) acrylate oligomer and silica particles having a weight average molecular weight of 500 to 10,000 and 1 to 40: 1 to 40: 1 to 25, preferably 10 to 30: 10 to 30: 1 to 10, or more Preferably it is 15-25: 15-25: 1-1.

Thereafter, a sol solution in which a metal alkoxide, a curing accelerator, an inorganic acid, and water is dissolved in a solvent is mixed with the curable coating solution.

As the metal alkoxide contained in the sol solution, it is preferable to use any one selected from metal alkoxides represented by the following formulas (1) to (3) or a mixture of two or more thereof.

≪ Formula 1 >

R ¹ _x M ¹ (OR ² ) _4-x

(2)

R ¹ _y M ² (OR ² ) _3-y

<Formula 3>

_{^{R 1 z Nb (OR 2)}} 5-z

In the above Chemical Formulas 1 to 3, R ¹ is a carbon number of 1 to 4 alkyl group, a vinyl group, an allyl group, (meth) acryloxy group, any one selected from the group consisting of epoxy deugi and amino groups, R ² has a carbon number of 1 a 1-4 alkyl group, M ¹ is a metal selected from the group consisting of Si, Ti, Zr, Ge and Sn, M ² is a metal selected from the group consisting of Al, in and Sb, x is 0, 1, 2, or 3, y is 0, 1 or 2, and z is 0, 1, 2, 3 or 4.

Examples of such metal alkoxides include aluminum acrylate, aluminum ethoxide, aluminum isopropoxide, aluminum methacrylate, antimony III n-butoxide, antimony III ethoxide, antimony III methoxide, germanium n-butoxide, Niobium V ethoxide, tin II ethoxide, tin II methoxide, diethoxyethane, diethoxyethane, diethoxyethane, diethoxyethane, ethoxyethyl ether, n-butyl diacrylate tin di-n-butyl dimethacrylate tin, titanium n-butoxide, titanium ethoxide, titanium isobutoxide, titanium isopropoxide, titanium methacrylate triisopropoxide , Titanium methacryloxyethylacetoacetate triisopropoxide, titanium n-propoxide zirconium n-butoxide, zirconium t-butoxide, zirconium dimethacrylate dibutoxide, Nium ethoxide, zirconium isopropoxide, zirconium methacrylate, zirconium methacryloxyethyl acetoacetate tri-n-butoxide, zirconyl dimethacrylate, methyltrimethoxysilane, methyl triethoxysilane, tetra Ethoxysilane, tetramethoxysilane, etc. can be illustrated, These can be used individually or in mixture of 2 or more types, respectively.

Meanwhile, the curing accelerator included in the sol solution enables condensation reaction even at a relatively low temperature, thereby contributing to roll-to-roll application. An organic acid may be used as the curing accelerator, and specifically, an anhydride, a carboxylic acid, a mixture thereof, or the like may be used. Suitable examples of anhydrides include acetic anhydride, acrylic acid anhydride, cyclic anhydride, hexahydrophthalic anhydride, methacrylic anhydride, propionic anhydride, and mixtures thereof. Possible carboxylic acid components include acetic acid, acrylic acid, formic acid, fumaric acid, itaconic acid, maleic acid, methacrylic acid, propionic acid, methylenesuccinic acid, mixtures thereof and the like. These may be used alone or in combination of two or more.

The inorganic acid may be any inorganic acid capable of catalyzing a sol-gel hydrolysis reaction. Suitable inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, mixtures thereof, and the like.

Examples of the solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, cyclohexanol, pentanol, octanol, decanol, di-n-butyl ether, ethylene glycol dimethyl ether, Diethylene glycol dimethyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol dibutyl ether, ethylene Examples of the organic solvent include methyl ethyl ketone, methyl ethyl ketone, methyl ethyl ketone, glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, ethylene glycol ethyl ether, ethylene glycol diethyl ether, ethylene glycol, diethylene glycol, Diethylene glycol, triethylene glycol, Butylacetate, t-butyl acetate, propylene glycol, propylene glycol, butylene glycol, butylene glycol, tetrahydrofuran, dioxane, acetone, diacetone alcohol, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, ethyl acetate, Propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, 1-methoxy-2-propanol, ethyl 3-ethoxypropionate, 2-propoxyethanol and ethylene glycol ethyl ether acetate. Or a mixture of two or more of them may be used.

The relative amount of each of the components constituting the curable sol solution for forming the organic-inorganic hybrid overcoat layer described above can be appropriately adjusted according to the properties of the desired film and the thickness of the hybrid overcoat layer is 0.1 to 10 ㎛ desirable.

According to an embodiment of the present invention, the process protective film laminated display optical transparent composite film may further include a protective film on the upper surface of the organic-inorganic hybrid overcoat layer.

The protective film is a film attached to prevent the upper surface of the composite film from being damaged during storage or transport of the optically transparent composite film for display, and if the adhesive film adheres well to the overcoating layer and has physical properties that are not damaged by normal external magnetic poles. It can be used without limitation. For example, films of polyethylene, polypropylene, and the like can be used. The thickness of the protective film may be 20 to 100 ㎛.

According to another aspect of the present invention, a method for manufacturing an optical transparent composite film for protective film lamination display for processing,

Preparing a polymer substrate comprising a thermoplastic transparent base resin;

Laminating a process protective film on one surface of the polymer substrate;

Forming an inorganic gas barrier layer on the other surface of the polymer substrate; And

A (meth) acrylate monomer, an (meth) acrylate oligomer having an epoxy group and a weight average molecular weight of 500 to 10,000 and an initiator are dissolved in a dispersion medium, and a curable coating solution, a metal alkoxide, a curing accelerator, an inorganic acid, and water in which silica particles are dispersed. Applying a curable sol solution prepared by mixing a sol solution dissolved in a solvent to an upper surface of the inorganic gas barrier layer, and curing the applied curable sol solution to form an organic-inorganic hybrid overcoating layer. Process protective film Includes a method for producing an optical transparent composite film for laminated display.

As described above, in the roll-to-roll process of a polymer film having a thickness of 50 μm or less, when the process is performed with a tension of about 100 to 600 N, wavering and wrinkles are generated due to tension, and thus physical properties are uniform in the deposition process. Defects and fabric damage occurs, and if the tension is 300N or more breakage of the film occurs, making the process impossible. Thus, in the manufacturing method according to an embodiment of the present invention, the problem can be solved by using a protective film for the process.

With reference to Figures 2 to 6, it will be described a method for manufacturing an optical transparent composite film for a protective film laminated display for a process according to an embodiment of the present invention.

First, a polymer substrate containing a thermoplastic transparent base resin is prepared. In this case, the details of the thermoplastic transparent base resin are as described above. The polymer substrate may be used alone, or may be used in a state in which a protective film is attached to an upper surface of the polymer substrate as shown in FIG. 2. In addition, for the roll-to-roll process, the polymer substrate having the protective film attached to the polymer substrate alone or the upper surface may be prepared in a roll type.

Next, the protective film for the process is laminated on one surface of the polymer substrate. Thereafter, during the process of coating the inorganic gas barrier layer and the organic-inorganic hybrid overcoating layer, a process protective film is attached to one surface of the polymer substrate in order to prevent problems such as weakening or breaking of the polymer substrate. . In the case of the polymer substrate alone, the process protective film may be laminated on one surface of both surfaces, and when the protective film 250 is attached to one surface of the polymer substrate 210 as shown in FIG. The protective film 240 for the process may be laminated on the other surface.

At this time, in the result obtained by laminating the process protective film on one surface of the polymer substrate, the adhesive force between the process protective film and the polymer substrate is 1 gf / inch or more, preferably 2 gf / inch or more, more preferably Is 3 to 4 gf / inch.

In addition, the yield strength of the polymer substrate when the process protective film is laminated is preferably 65 MPa or more, more preferably 70 MPa or more. As a result, the process proceeds stably without breaking and defects at a tension of 300 N or more to yield. Can increase.

After the process protective film lamination process, no bubbles may be generated on the adhesion surface between the process protective film and the polymer substrate so that bubbles acting as process outgassing do not occur in the vacuum deposition process. However, since it is impossible to completely remove these bubbles during the lamination process, it is necessary to limit the size and number of bubbles to prevent the bubbles present in the process from acting as outgassing and causing problems.

As a result, the number of bubbles in the adhesion surface between the process protective film laminated on the polymer substrate and the polymer substrate after laminating the process protective film is 2,000 pieces / m 2 or less, preferably 1,500 pieces / m 2 or less, more preferably Preferably it is 1,000 pieces / m <2> or less, More preferably, it is 500-100 pieces / m <2>, and bubble size is 5 mm or less in width, 500 micrometers or less in height, Preferably 4 mm or less in width, 400 micrometers or less in height, More preferably, width 3 It should be less than 300 mm in height and less than the height, and satisfies the adhesive force range, thereby reducing the number and size of bubbles.

In addition, in the case of the roll-to-roll process, the polymer film has a strong blocking property between the surfaces, and thus, when there is no protective film, the blocking property causes bubbles during the process and bubbles are generated during process outgasing and film. It may cause deformation. Therefore, when the process protective film is selected and laminated with a smaller friction coefficient than the polymer film, the slip property is improved and the roll-to-roll process is facilitated later.

Subsequently, an inorganic gas barrier layer is formed on the other surface of the polymer substrate. Referring to FIG. 4, the inorganic gas barrier layer 320 is formed on the other surface of the polymer substrate 310 on which the process protection film 340 is not laminated.

The inorganic gas barrier layer is an oxide, nitride, carbide, oxynitride or oxide containing at least one metal selected from the group consisting of Si, Al, In, Sn, Zn, Ti, Cu, Ce and Ta as described above. It is formed by vapor coating by physical or chemical methods using carbides, nitrides, or oxynitrides.

Even in this case, when the protective film is not attached to one surface of the polymer substrate, an inorganic gas barrier layer may be directly formed on the surface thereof. If the protective film is attached to one surface of the polymer substrate, the protective film may be removed. An inorganic gas barrier layer is formed. In the case where this step is performed in a roll-to-roll process, the inorganic gas barrier layer may be continuously formed by removing the protective film on one surface of the polymer substrate.

In the result obtained by forming the inorganic gas barrier layer on the other surface of the polymer substrate, the adhesion between the process protective film and the composite layer of the polymer substrate-inorganic gas barrier layer is 12 gf / inch or less, preferably 9 gf / inch Or less, more preferably 4 to 8 gf / inch.

Next, a (meth) acrylate oligomer having an (meth) acrylate monomer, an epoxy group and a weight average molecular weight of 500 to 10,000 and an initiator are dissolved in a dispersion medium, and a curable coating solution, a metal alkoxide, a curing accelerator, and an inorganic acid, in which silica particles are dispersed. And a curable sol solution prepared by mixing a sol solution in which water is dissolved in a solvent, is applied to an upper surface of the inorganic gas barrier layer, and the cured sol solution is cured to form an organic-inorganic hybrid overcoating layer. Referring to FIG. 5, a protective film 440 for a process is laminated on one surface of the polymer substrate 410, and an inorganic gas barrier layer 420 is formed on the other surface of the polymer substrate 410, and the inorganic gas barrier is formed. An optical transparent composite film 500 for a protective film lamination display for a process in which an organic-inorganic hybrid overcoating layer 430 is formed on an upper surface of the layer 420 is illustrated.

The method of forming the organic-inorganic hybrid overcoating layer on the inorganic gas barrier layer is not particularly limited and may be a bar coating method, a spin coating method, a dip coating method, a spray coating method, or the like.

At this time, the coating composition is subjected to UV curing or thermosetting to form an organic-inorganic hybrid coating layer. In the above step, UV curing is not particularly limited as long as it can achieve a radical reaction by a UV light source, but mercury or metal halide lamps can be used alone or in combination. UV curing, for example, can be performed for 1 second to several minutes, such as 1 second to 5 minutes, or 1 minute or less with an energy of 160 m to 1600 mJ / cm ² . On the other hand, the thermosetting may be carried out, for example, at a temperature of 100 to 200 ° C. for 1 minute to several hours, such as 1 minute to 5 hours, or 1 hour or less, or 2 to 10 minutes.

Optical transparent composite film for process protective film lamination display according to an embodiment of the present invention oxygen transmittance of 1 cc / ㎡ / day / atm or less, light transmittance of 90% or more, water vapor transmission rate of 0.1 g / ㎡ / day or less And the adhesion characteristics may be 5B or more.

In addition, the method may further include forming a protective film on an upper surface of the organic-inorganic hybrid overcoat layer. The protective film is a film attached to prevent the upper surface of the composite film from being damaged during the storage or transport of the optically transparent composite film for display manufactured through the above-described steps, and adheres well to the overcoating layer, and to a conventional external stimulus. As long as the material does not break, it can be used without limitation. For example, films of polyethylene, polypropylene, and the like can be used.

Therefore, referring to FIG. 6, the inorganic gas barrier layer formed on the other surface of the polymer substrate 510, the process protection film 540 formed on one surface thereof, and the polymer substrate 510 in the manufacturing method according to the exemplary embodiment of the present invention. 520 and the organic-inorganic hybrid overcoating layer 530, the protective film 550 for the protective film laminated display including a protective film 550 formed on the upper surface of the organic-inorganic hybrid overcoating layer 530 This is provided.

According to another aspect of the present invention, there is provided a flexible display product using an optical transparent composite film for a process protective film laminated display.

When used in the flexible display product, the process protection film may be removed from the process protection film laminated optical optical composite film.

Such display products may include small touch display products such as smartphones or tablet PCs, or large display products such as LCDs or PDPs, or outdoor advertisements (PID, DID).

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to the following examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the following embodiments. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art.

Example 1

50 μm thick PET (polyethylene terephthalate) transparent film (Model: SH34) prepared by SKC was used as the polymer substrate. Before the vacuum deposition process, a 50 μm-thick process protective film of PET (polyethylene terephthalate) made of SUN-A was laminated on one surface of the polymer substrate. When the protective film for the process is used, since the surface of the polymer film PET film is non-polar, a protective film having an adhesive force of 2 gf / inch or more with the PET film, which is a polymer substrate, should be used. It should be low that no bubbles will be generated as process outgassing in the vacuum deposition process. The adhesion characteristics of the process protection film on the polymer substrate showed a difference before and after the deposition process.

The yield strength before laminating the process protective film, that is, after laminating the process protective film on one surface of the polymer substrate itself and the polymer substrate, was 64.5 MPa and 74.2 MPa, respectively, and stabilized after attaching the process protective film. Fairness was shown.

In addition, the adhesion between the process protective film laminated on the polymer substrate and the polymer substrate after laminating the process protective film had a bubble number of 824 pieces / m 2 and an average bubble size of 390 μm in width 2.4 mm in height. .

In order to impart gas barrier properties to the polymer substrate on which the process protective film is laminated, as shown in FIG. 7, six coating zones 742, 743, 744, 745, 746, and 747 are roll-to-coated. Using a roll sputtering dual mode device, a silicon target is mounted in the first coating zone and the second coating zone, and argon and nitrogen gas are injected at a ratio of Ar: N2 = 150: 60, respectively, so that power of 8.8 W / cm ² is obtained. , An inorganic gas barrier layer made of a silicon nitride film was deposited on the upper surface of the polymer substrate at a rate of 1 M / min. The thickness of the silicon nitride film was observed by SEM to confirm that it is 30 nm.

The vacuum deposition revolving, that is, the adhesion between the process protective film and the polymer substrate was 3 gf / inch, after the inorganic gas barrier layer formed on the other surface of the polymer substrate, the composite layer of the polymer substrate-inorganic gas barrier layer and The adhesive force between the process protective film was 8 gf / inch.

Thereafter, a curable sol solution was formed to form an organic-inorganic hybrid overcoating layer. First, 238.1 g of ethanol, tetraethyl orthosilicate (TEOS), 120.7 g, 3.2 g of 36 wt% hydrochloric acid, and 41.1 g of water were stirred at room temperature at 200 rpm for 1 hour. Then, 562.5 g of ethanol was added to form a primary mixture.

0.55 g of hexahydrophthalic anhydride (HHPA), 1.4 g of water and 32 g of ethyl alcohol were stirred at 250 rpm for 1 hour at room temperature, and then added to the primary mixture for 4 hours at about 200 rpm at room temperature. After stirring, a sol solution was prepared by filtration through a 0.2 μm filter.

31 g of a 30 wt% colloidal silica solution based on isopropyl alcohol as a solvent (Nissan Chemical Industries, Catalog no. IPA-ST) was prepared by ultrasonication at room temperature for 60 minutes.

And 52.7 g of ethoxylated trimethylolpropanetriacrylate (Sartomer, catalog number SR-454), 59.8 g of bisphenol-A epoxy acrylate oligomer (Sartomer, catalog number CN120), photoinitiator 1-hydroxy-cyclohexyl- 2.84 g of phenyl-ketone (Ciba, catalog number Irgacure 184), and a latent heat base 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1 1.17 g of propanone (Ciba, Cat. No. 907) was mixed and stirred at about 200 rpm for 5 minutes. After that, 110 g of ethyl acetate and 305 g of 1-methoxy-2-propanol were added, and the mixture was stirred at room temperature for 30 minutes at 250 rpm. The mixture thus formed, the prepared silica solution, and 438 g of isopropanol were mixed again and stirred at 250 rpm for 1 hour at room temperature to prepare a UV-curable composition.

The sol solution was added to the curable coating solution while stirring at 200 rpm, stirred for 1 hour, and filtered through a 1 μm filter to prepare a curable sol solution for forming a hybrid overcoating layer.

Subsequently, the above-mentioned curable sol solution was coated on the inorganic gas barrier layer and dried for 100 seconds at 30 ° C., followed by UV curing by energy of 1,000 mJ / cm 2. The thickness of the organic-inorganic hybrid overcoating layer formed was 2 μm.

Subsequently, in order to protect the surface of the organic-inorganic hybrid overcoating layer, PE (poly ethylene) protective film manufactured by Yu Sang Co., Ltd. was laminated on the upper surface of the organic-inorganic hybrid overcoating layer. Referring to FIG. 6, the process protective film laminated display optical transparent composite film 600 manufactured as described above may include an inorganic gas barrier layer 520 and an organic-inorganic hybrid overcoating layer on the polymer substrate 510. 530 is sequentially stacked, the protective film 540 for the process is laminated on the other surface of the polymer substrate, in order to protect the coating layer, the protective film 550 on the upper surface of the organic-inorganic hybrid overcoat layer 530 Is formed.

Example 2

Before depositing the inorganic gas barrier layer, using a roll-to-roll sputtering dual mode apparatus as shown in FIG. 7, the surface of the polymer substrate was subjected to 60 sccm (Standard Cubic Centimeter per) in the plasma treatment zone 741. Minute (0 ℃, 1 atm)) while maintaining the vacuum at 2 mtorr while applying 0.5 W / cm2 of power to the electrode to generate a plasma to react at a rate of 2.7 M / min to treat the surface of the polymer substrate An optically transparent composite film for a protective film lamination display for a process was manufactured in the same manner as in Example 1, except that the method further comprises the step of.

Comparative Example 1

An optical transparent composite film for a display was manufactured in the same manner as in Example 1, except that the protective film for the process was not laminated on one surface of the polymer substrate and the organic-inorganic hybrid overcoating layer was not formed on the upper surface of the inorganic gas barrier layer.

Comparative Example 2

An optical transparent composite film for a display was manufactured in the same manner as in Example 1, except that the protective film for the process was not laminated on one surface of the polymer substrate.

Table 1 summarizes the yield of the optical transparent composite film for display of Example 1, Comparative Example 1 and Comparative Example 2 prepared by the above-described method.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 yield(%) > 90 > 90 0 0

The yield refers to the ratio of the actual coating area to the total area of the film put into production. Therefore, the yield can be obtained by the following formula.

Yield = (production area / input area) x 100

In addition, the oxygen transmission rate, water vapor transmission rate, light transmittance, haze, banding properties, etc. of the optical protective composite film for protective film lamination display of Examples 1 and 2 according to the following evaluation method were measured and the results are shown in Table 2. . In Comparative Examples 1 and 2, since the process protective film was not laminated, coating could not be stably performed, and thus the following evaluation could not be performed.

1) Water vapor transmission rate: Using Mocon PERMATRAN-W3 / 31 equipment, it was measured for 48 hours at 37.8 ℃ / RH 100%.

2) Oxygen permeability: measured under 35 ° C / RH0% using a Mocon OX-TRAN 2/20 instrument.

3) Light transmittance: Minolta 3600D equipment was measured according to ASTM1003.

4) Haze: Nippon Denshoku's NDH-5000 equipment was measured according to ASTM1003.

5) Scratch resistance: Haze was measured by reciprocating 100 times with a 300g load using steelwool # 0000.

6) Adhesiveness: According to ASTMD3359-02, X-cut coating surface to make 100 squares, and then adhesiveness was evaluated according to the degree of fall when peeling off vertically after adhering the tape (5B: 0%, 4B: Less than 5%, 3B: 5-15%, 2B: 15-35%, 1B: 35-65%, 0B: 65% or more).

Water vapor permeability
(g / m ² / day) Oxygen transmission rate
(cc / m ² /
day / atm) Light transmittance
(550 nm,%) Hayes
(%) Scratch resistance
(%) Adhesion Example 1 0.068 0.47 > 90 <0.3 &Lt; 0.1 5B Example 2 0.007 0.12 > 90 <0.3 &Lt; 0.1 5B

100, 500, 600: Optically Transparent Composite Film for Process Protective Film Laminated Display
10, 110, 210, 310, 410, 510: polymer substrate
20, 320, 420, 520: inorganic gas barrier layer
30, 430, 530: organic-inorganic hybrid overcoating layer
40, 240, 340, 440, 540: Process Protection Film
150: 250: 550: protective film
740: coating drum
741: plasma treatment zone 742: first coating zone
743: second coating zone 744: third coating zone
745: fourth coating zone 746: fifth coating zone
747: sixth coating zone 748: guide roll
749: Unwinder 750: Rewinder

Claims (17)

A polymeric substrate comprising a thermoplastic transparent base resin;
An inorganic gas barrier layer formed on at least one surface of the polymer substrate;
It is formed on the upper surface of the inorganic gas barrier layer, the curable coating solution and (metal) alkoxy having a (meth) acrylate monomer, an epoxy group and a (meth) acrylate oligomer, an initiator, silica particles and a dispersion medium having a weight average molecular weight of 500 ~ 10,000 For example, an organic-inorganic hybrid overcoating layer comprising a hardening product of a curable sol solution mixed with a sol solution containing a curing accelerator, an organic acid, and a solvent; And
Including a process protective film laminated on the other surface of the polymer substrate,
Adhesion between the protective film for the process and the polymer substrate is 1 gf / inch or more,
The optical protective composite film for protective film lamination display for a process, characterized in that the adhesion between the protective film for the process and the composite layer of the polymer substrate-inorganic gas barrier layer is 12 gf / inch or less. The method of claim 1,
Process protective film laminated on the polymer substrate and the adhesion surface between the polymer substrate has a number of bubbles of 2,000 pieces / ㎡ or less, and a process size, characterized in that the bubble size of 5 mm or less in width and 500 ㎛ or less in height Optically transparent composite film for film lamination display. The method of claim 1,
The thermoplastic transparent base resin is a group consisting of polyether sulfone, polycarbonate, polyimide, polyarylate, polyethylene terephthalate, polyethylene naphthalate polyethylene terephthalate glycol, polycyclohexylenedimethylene terephthalate glycol, and cycloolefin copolymer An optical transparent composite film for a process protective film lamination display, characterized in that any one or a mixture of two or more selected from them. The method of claim 1,
The inorganic gas barrier layer may be formed of at least one metal selected from the group consisting of Si, Al, In, Sn, Zn, Ti, Cu, Ce and Ta, oxides, nitrides, carbides, oxynitrides, oxidized carbides and nitrides Or an optical transparent composite film for protective film lamination display for process comprising an oxynitride carbide. The method of claim 1,
The inorganic gas barrier layer has a thickness of 20 to 500 nm, the protective film laminated display optical transparent composite film for a process. The method of claim 1,
Process protection, characterized in that the weight ratio of the (meth) acrylate monomer, epoxy group having a weight average molecular weight of 500 ~ 10,000 and (meth) acrylate oligomer and silica particles is 1-40: 1-40: 1-25. Optically transparent composite film for film lamination display. The method of claim 1,
The metal alkoxide is any one selected from the metal alkoxides represented by the following formula (1) to (3) or a mixture of two or more thereof.
&Lt; Formula 1 >
R ¹ _x M ¹ (OR ² ) _4-x
(2)
R ¹ _y M ² (OR ² ) _3-y
(3)
_{^{R 1 z Nb (OR 2)}} 5 -z
In the above Chemical Formulas 1 to 3, R ¹ is a carbon number of 1 to 4 alkyl group, a vinyl group, an allyl group, (meth) acryloxy group, any one selected from the group consisting of epoxy deugi and amino groups, R ² has a carbon number of 1 a 1-4 alkyl group, M ¹ is a metal selected from the group consisting of Si, Ti, Zr, Ge and Sn, M ² is a metal selected from the group consisting of Al, in and Sb, x is 0, 1, 2, or 3, y is 0, 1 or 2, and z is 0, 1, 2, 3 or 4. The method of claim 1,
The curing accelerator is obtained from acetic anhydride, acrylic anhydride, cyclic anhydride, hexahydrophthalic anhydride, methacrylic anhydride, propionic anhydride, acetic acid, acrylic acid, formic acid, fumaric acid, itaconic acid, maleic acid, methacrylic acid, propionic acid and methylenesuccinic acid. An optical transparent composite film for a process protective film laminated display, characterized in that any one or a mixture of two or more of them selected. The method of claim 1,
The organic-inorganic hybrid overcoat layer has a thickness of 0.1 to 10 ㎛ in the process protective film laminated optical optical transparent composite film for display. The method of claim 1,
The protective film laminated display optical transparent composite film for the process characterized in that it further comprises a protective film on the upper surface of the organic-inorganic hybrid overcoat layer. The method of claim 1,
And a plasma surface treatment layer on which the surface of the polymer substrate is modified by plasma treatment between the polymer substrate and the inorganic gas barrier layer. Preparing a polymer substrate comprising a thermoplastic transparent base resin;
Laminating a process protective film on one surface of the polymer substrate;
Forming an inorganic gas barrier layer on the other surface of the polymer substrate; And
A (meth) acrylate monomer, an (meth) acrylate oligomer having an epoxy group and a weight average molecular weight of 500 to 10,000 and an initiator are dissolved in a dispersion medium, and a curable coating solution, a metal alkoxide, a curing accelerator, an inorganic acid, and water in which silica particles are dispersed. Applying a curable sol solution prepared by mixing a sol solution dissolved in a solvent to an upper surface of the inorganic gas barrier layer, and curing the applied curable sol solution to form an organic-inorganic hybrid overcoating layer. Process protective film A method for producing an optical transparent composite film for laminated display. The method of claim 12,
In the result obtained by laminating the process protective film on one surface of the polymer substrate, the adhesive force between the process protective film and the polymer substrate is 1 gf / inch or more,
In the result obtained in the step of forming an inorganic gas barrier layer on the other surface of the polymer substrate, the process protection, characterized in that the adhesion between the process protective film and the composite layer of the polymer substrate-inorganic gas barrier layer is 12 gf / inch or less Method for producing an optical transparent composite film for film lamination display. The method of claim 12,
The yield strength of the film obtained in the step of laminating the process protective film on one surface of the polymer substrate is 65 MPa or more method for producing an optical transparent composite film for a process protective film laminated display. The method of claim 12,
Curing the curable sol solution applied to the upper surface of the inorganic gas barrier layer to form an organic-inorganic hybrid overcoating layer is an optical transparent composite for protective film lamination display for the process, characterized in that carried out by UV curing or thermal curing Method for producing a film. The method of claim 12,
The method of manufacturing an optical transparent composite film for a protective film lamination display for the process further comprising the step of forming a protective film on the upper surface of the organic-inorganic hybrid overcoat layer. A flexible display product using an optical transparent composite film for protective film lamination display according to any one of claims 1 to 11.

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