KR102133772B1 - Resin composition and film manufactured from the same - Google Patents

Abstract

The present invention is polymerized by sol-gel reaction of a mixed solution containing a first monomer and a second monomer, and the first monomer and the second monomer are composed of trialkoxy silane, dialkoxy silane, monoalkoxy silane, and combinations thereof. It provides a resin composition comprising one selected from the group. The resin composition may provide a film having relatively high hardness characteristics such as tempered glass and having a high softness property, thereby freely deforming the shape.

Description

Resin composition and film manufactured using the same{Resin composition and film manufactured from the same}

The present invention relates to a resin composition and a film prepared using the same, and more particularly, to a resin composition polymerized by sol-gel reaction of a mixed solution containing a first monomer and a second monomer and a film produced using the same .

In general, optical functional products such as optical screens, LED front panels, or windows of electronic products have been mainly used for providing transparency and hardness. However, glass has a problem that it is difficult to reduce weight and has no flexibility, and a defective rate is high during product processing. To overcome this, thermosetting or thermoplastic polymers having properties such as high light transmittance, burst resistance, or high refractive index have replaced glass.

Thermosetting or thermoplastic polymers have excellent transparency and impact resistance, but lack scratch resistance and chemical resistance compared to glass materials, and use technology to coat them with excellent physical strength and transparent materials to improve them.

As a coating agent, there are a thermosetting or photocuring type, and can be divided into an organic coating agent and an inorganic coating agent. Melamine, acrylic and urethane are used as the organic coating agent. On the other hand, the inorganic coating agent mainly consists of silicone.

In the case of a thermosetting coating agent, silicone-based materials are mainly used. In the case of photocuring, since heat is not directly applied, it is possible to coat a substrate that is difficult to heat-cure at high temperatures such as thermoplastics, wood, and paper.

The thermosetting hard coating using polysiloxane is a silicone coating and is widely applied in industry. The silicone-based hard coating solution has a possibility to form a high-hardness film on the plastic surface to prevent surface damage due to the occurrence of scratches, and at the same time improve weatherability, chemical resistance, solvent resistance, etc., thereby making the application field of plastics wider. have.

Currently, in the display field, development of a next-generation display capable of deforming or folding a display such as a foldable or a rollable is progressing. In the case of tempered glass used in existing displays, it has high hardness characteristics but cannot be modified in shape, so it is necessary to research and develop materials for cover windows suitable for next-generation displays. Accordingly, there is an increasing need for a film-type cover window having strong hardness characteristics and at the same time relatively free of deformation of shape.

Silica (SiO ₂ ) is found in sand or quartz, and is also distributed in the cell walls of diatoms. A major component of glass or concrete, it is a mineral that occupies most of the earth's crust.

In the case of the conventional hard coating technology using silica particles, it is possible to realize high surface hardness, but it is difficult to apply for coating purposes of substrates requiring flexibility due to cracks generated during bending.

Korean Registered Patent No. 10-1302720 provides a coating composition for forming a scratch-resistant silica protective film for coating a metal surface composed of two sizes of silica nanoparticles and a manufacturing method thereof, but is prepared using the coating composition The old film may be difficult to apply to the flexible material due to its inflexibility and cracking when bending.

Korean Registered Patent No. 10-1302720

One technical problem to be achieved by the present invention is to provide a resin composition having both high hardness and flexibility.

Another technical problem to be achieved by the present invention is to provide a film manufactured using the resin composition.

Another technical problem to be achieved by the present invention is to provide a cover window provided with the film.

Another technical problem to be achieved by the present invention is to provide an image display device equipped with the film.

The technical problem to be achieved by the present invention is not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by a person having ordinary knowledge in the technical field to which the present invention belongs from the following description. There will be.

In order to achieve the above technical problem, an embodiment of the present invention is polymerized by performing a sol-gel reaction of a mixed solution containing a first monomer and a second monomer, and the first monomer and the second monomer are trialkoxy silane, di Provided is a resin composition comprising one selected from the group consisting of alkoxy silanes, monoalkoxy silanes, and combinations thereof.

The first monomer may include one selected from the group consisting of ether groups, ester groups, C ₃ to C ₁₀ alkyl groups, glycidyloxy groups, and combinations thereof.

The first monomer is (3-glycidyloxypropyl)trimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, (3-(2,3-epoxypropoxy)-propyl)-trimethoxy Silanes and combinations thereof.

The second monomer may include one selected from the group consisting of aromatic groups, C ₄ to C ₁₀ cycloalkyl groups, and combinations thereof.

The second monomer may include one selected from the group consisting of phenyltrimethoxysilane, 1-naphthyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and combinations thereof. Can.

The first monomer may be a soft monomer, and the second monomer may be a hard monomer.

The molar ratio of the first monomer and the second monomer may be 5:1 to 1:5.

The first monomer may be provided in 0.1% to 60% by weight in the mixed solution.

The second monomer may be provided in 0.1% to 60% by weight in the mixed solution.

The mixed solution may further include a catalyst.

The catalyst may include an ion exchange resin.

The catalyst may include one selected from the group consisting of alkylammonium salts, halide salts, and combinations thereof.

The catalyst may be provided in 3% to 7% by weight relative to the total weight of the first monomer and the second monomer.

The resin composition may further include one selected from the group consisting of surfactants, anti-yellowing agents, diluents, anti-foaming agents, dispersants, thickeners, wetting agents, leveling agents, and combinations thereof.

The resin composition may be a composition for hard coating.

One embodiment of the present invention provides a film prepared using the resin composition.

One embodiment of the present invention provides a cover window provided with the film.

One embodiment of the present invention provides an image display device provided with the film.

In the present invention, a resin composition for a film in which the mixed solution containing the first monomer and the second monomer is polymerized by sol-gel reaction, having hardness characteristics such as tempered glass, and at the same time having high-intrinsic characteristics and relatively free form deformation It can provide a film produced using this.

1 is a schematic cross-sectional view of a substrate coated with a resin composition according to an embodiment of the present invention.
Figure 2 is a hardness and modulus evaluation graph of the film according to an embodiment of the present invention.
3 is a load-displacement evaluation graph of a film according to an embodiment of the present invention.
Figure 4 is a pencil hardness evaluation graph of the film according to an embodiment of the present invention.
5 is a graph of bending stiffness evaluation of a film according to an embodiment of the present invention.
6 is a graph of hardness and modulus evaluation of a film according to another embodiment of the present invention.
7 is a pencil strength evaluation graph of a film according to another embodiment of the present invention.
8 is a graph of evaluation of bending stiffness of a film according to another embodiment of the present invention.
9 is a residual depth evaluation graph of a film according to another embodiment of the present invention.
10 is a graph of bending evaluation of a film according to another embodiment of the present invention.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be implemented in various different forms, and thus is not limited to the embodiments described herein. In addition, in order to clearly describe the present invention in the drawings, parts irrelevant to the description are omitted, and like reference numerals are assigned to similar parts throughout the specification.

Throughout the specification, when a part is said to be "connected (connected, contacted, coupled)" to another part, it is not only "directly connected", but also "indirectly connected" with another member in between. "It includes the case where it is. Also, when a part “includes” a certain component, this means that other components may be further provided instead of excluding other components, unless specifically stated otherwise.

The terms used herein are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “include” or “have” are intended to indicate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, and that one or more other features are present. It should be understood that the existence or addition possibilities of fields or numbers, steps, operations, components, parts or combinations thereof are not excluded in advance.

One aspect of the present invention is polymerized by sol-gel reaction of a mixed solution containing a first monomer and a second monomer, and the first monomer and the second monomer are trialkoxy silane, dialkoxy silane, monoalkoxy silane, and these Provided is a resin composition comprising one selected from the group consisting of combinations.

In this specification, “silane” refers to a molecule consisting of one central silicon atom and H or a substituent. In this case, the substituent is a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom having 2 to 20 alkenyl groups, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. It may be a group, a substituted or unsubstituted hetero aryl group having 2 to 30 carbon atoms, a substituted or unsubstituted silyl group, a hydroxyl group, or a combination thereof.

For example, alkoxy silanes can react with hydroxy groups (OH) to form strong chemical bonds within the polymer.

In one embodiment of the present invention, the first monomer may be a soft monomer, and the second monomer may be a hard monomer.

When the sol-gel reaction is performed with the soft monomer as a single monomer, a flexible nanosol may be formed. The soft monomer may form a copolymer upon sol-gel reaction with other types of monomers, and may impart flexibility to the copolymer.

When the sol-gel reaction of the hard monomer is a single monomer, a hard nanosol may be formed. The hard monomer may form a copolymer upon sol-gel reaction with other types of monomers, and may give hardness to the copolymer.

The flexibility of the polymer is influenced by the type of the polymer chain, and since the carbon-carbon bond can rotate freely, it can impart some degree of flexibility. Carbon-oxygen bonds are more flexible because they are free to bend and rotate than carbon-carbon bonds. When the polymer includes a rotatable flexible bond such as carbon-carbon or carbon-oxygen, the chain can be easily bent or rotated to exhibit flexibility, as compared to the case of including an amide or aromatic structure.

For example, the soft monomer may include a bond that is easily bent and rotated.

In one embodiment of the present invention, the first monomer may include one selected from the group consisting of ether groups, ester groups, C ₃ to C ₁₀ alkyl groups, glycidyloxy groups, and combinations thereof.

For example, the first monomer is (3-glycidyloxypropyl)trimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, (3-(2,3-epoxypropoxy)-propyl) -May include one selected from the group consisting of trimethoxysilane and combinations thereof, but is not limited thereto.

For example, the hard monomer may include a bond that is not easy to bend and rotate.

In one embodiment of the present invention, the second monomer may include one selected from the group consisting of aromatic groups, C ₄ to C ₁₀ cycloalkyl groups, and combinations thereof.

For example, the second monomer is selected from the group consisting of phenyltrimethoxysilane, 1-naphthyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and combinations thereof. It may include one, but is not limited thereto.

The molar ratio of the first monomer and the second monomer may be 5:1 to 1:5, such as 4:1 to 1:4, such as 3:1 to 1:3. When the molar ratio is more than 1:5, the flexibility of the film produced using the resin composition is insufficient, and thus cracking may occur when bending. If it is less than 5:1, the hardness of the film is insufficient to protect the substrate sufficiently. Problems may arise.

The first monomer may be provided in 0.1% to 60% by weight in the synthetic solution.

When the first monomer is provided in an amount of less than 0.1% by weight, the flexibility of the film manufactured using the resin composition may be insufficient, resulting in a problem of cracking when bending. When provided in excess of 60% by weight, the hardness of the produced film is A problem may be deteriorated.

The second monomer may be provided in 0.1% to 60% by weight in the mixed solution.

When the second monomer is provided in an amount of less than 0.1% by weight based on the weight of the resin composition, the hardness of the film prepared using the resin composition is insufficient to sufficiently protect the substrate, and the film produced when provided in excess of 60% by weight A problem that a softening property of the deterioration may occur.

In one embodiment of the present invention, a catalyst may be included in the synthesis of the resin composition.

The catalyst may include an ion exchange resin.

For example, the catalyst may include one selected from the group consisting of alkylammonium salts, halide salts, and combinations thereof.

For a specific example, the catalyst is CT-175, CT-275, available from the company Flurolite, IRA-400, IRA-402, IRA-904, IRA available from the company Rohm & Haas. -910 IRA-966, M-500, M-504, M-600, M-500-A, M-500, K-2641, SBR available from Dow, available from Bayer SBR-P, SAR, MSA-1, MSA02, SAlO, SA12, SA 2OA, PA-302, PA-312, PA-412, or PA-308 available from Mitsubishi.

For example, the catalyst may include hexadecyltrimethylammonium chloride, tetra-n-butylammonium chloride, benzyl trimethyl ammonium chloride or benzyl trimethyl ammonium bromide.

The catalyst may be provided in 3% to 7% by weight relative to the total weight of the first monomer and the second monomer.

When the catalyst is provided in an amount of less than 3% by weight, a problem that the sol-gel reaction does not sufficiently occur may occur, and when it is provided in an amount of more than 7% by weight, the reaction rate may not increase any more than the injected catalyst.

In one embodiment of the present invention, the resin composition is a method in which monomers make a polymer through a sol-gel reaction to obtain a resin composition having high particle uniformity, and a liquid reactant that is easy to mold into a thin film form. Can be obtained.

The sol-gel reaction can economically manufacture the resin composition through a hydrolysis reaction and a polycondensation reaction in a solution.

In one embodiment of the present invention, the resin composition may further include one selected from the group consisting of surfactants, anti-yellowing agents, diluents, antifoaming agents, dispersants, thickeners, wetting agents, leveling agents, antistatic agents, and combinations thereof. In addition, it may further include one selected from the group consisting of antioxidants, ultraviolet absorbers, light stabilizers, thermal polymer inhibitors, lubricants, antifouling agents and combinations thereof.

For example, the resin composition may further include an ultraviolet absorber to form a film having an ultraviolet ray blocking effect, thereby improving the reliability of the display device by blocking ultraviolet rays transmitted to the display module.

The resin composition according to an embodiment of the present invention may further improve an antistatic property of a film by further including an antistatic agent, thereby improving a function of preventing contamination due to adsorption of dust and the like.

For example, the antistatic agent may include an anionic surfactant-based antistatic agent.

The resin composition according to an embodiment of the present invention may further include a leveling agent to improve the coating property of the resin composition to improve the smoothness of the film produced using the resin composition.

For example, the leveling agent may include one selected from the group consisting of silicone leveling agents, fluorine leveling agents, acrylic leveling agents, and combinations thereof.

In one embodiment of the present invention, the diluent may be used to control the concentration and viscosity of the resin composition or the thickness of the resulting film.

For example, the diluent may include one selected from the group consisting of methanol, ethanol, propanol, isopropanol, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, toluene, benzene, xylene and combinations thereof. have. At this time, the diluent may be appropriately selected depending on the coating method or the thickness of the desired film.

In one embodiment of the present invention, the resin composition may be used for coating. For example, the resin composition may be used for hard coating applications.

One aspect of the present invention provides a film prepared using a resin composition according to an embodiment of the present invention.

Referring to Figure 1, the film 200 may be formed on a substrate 100, it may be formed by a method of coating the resin composition on the substrate 100 by a known method.

For example, the known methods may include, but are not limited to, spin coating, bar coating, spray coating, inkjet coating, dipping, flow coating, roll coating or screen printing. .

One aspect of the present invention may provide a cover window provided with the film.

One aspect of the present invention can provide an image display device provided with the film.

In one embodiment of the present invention, the image display device may have a cover window attached to a display surface for protection of a display module such as a liquid crystal panel or a light emitting diode panel. The cover window must be firmly attached to the display module through an adhesive layer.

For example, by applying an adhesive to the cover window and temporarily curing, the display module and the cover window are adhered so as to face each other, and placed again to cure, so that the display module and the cover window are attached by the adhesive layer. Can.

The display module may include a display panel and a functional member. For example, the display panel includes an organic electroluminescence display panel, a liquid crystal display panel, an electronic ink display panel, and an electrowetting display panel. Or it may include an electrophoretic display panel.

The display module may include a flexible material.

The functional member may include, but is not limited to, one selected from the group consisting of a protective film, an input sensing unit, an optical member, and combinations thereof.

For example, the optical member may include a polarizer, a light compensation layer, or a phase retarder.

For example, the input sensing unit may be a touch sensing unit, the type of which is not limited, and may be a capacitive type or electromagnetic induction type touch sensing unit.

The resin composition according to an embodiment of the present invention may include a hybrid core nano sol. The resin composition may include a rigid-flex network.

The ductile network may simultaneously impart stiffness and ductility to a film produced using the resin composition.

Currently, in the display field, development of a next-generation display capable of bending or folding in a form such as a foldable display or a rollable display is actively being developed.

In the case of tempered glass used in a conventional display, it has a high hardness characteristic, but cannot be applied to a next-generation display because deformation of the shape is impossible. In addition, the inorganic particles used in the sol-gel process also have the advantage of having high hardness properties, but may have problems in that they are not suitable for use in a foldable display due to inflexibility.

The resin composition according to an embodiment of the present invention can simultaneously implement hard hardness characteristics and high-softness characteristics such as glass.

The film prepared using the composition may have the same hardness characteristics as glass, and at the same time, the shape may be easily deformed.

For example, the resin composition and the film may be applied to next-generation displays such as flexible displays.

Hereinafter, a resin composition according to an embodiment of the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, the examples shown below are only examples to help understanding of the present invention, and the scope of the present invention is not limited thereto.

Example

Comparative Example 1.

The (3-glycidyloxypropyl) trimethoxysilane (GPTMS) and H ₂ O were charged into a spherical flask such that the molar ratio was 1:1.5. At this time, the GPTMS was set to 100 g.

5 g of Amberlite IRA-400 was added to the spherical flask and a sol-gel reaction was performed at 80° C. for 24 hours to produce a reactant.

The reaction product was purified to prepare a resin composition from which reaction by-products and unreacted monomers were removed.

Comparative Example 2.

The 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS) and H ₂ O were charged into a spherical flask such that the molar ratio was 1:1.5. At this time, the ECTMS was set to 100 g.

5 g of Amberlite IRA-400 was added to the spherical flask and a sol-gel reaction was performed at 80° C. for 24 hours to produce a reactant.

The reaction product was purified to prepare a resin composition from which reaction by-products and unreacted monomers were removed.

Comparative Example 3.

The resin composition obtained in Comparative Example 1 and Comparative Example 2 was blended at a ratio of 1:1 to prepare a resin composition.

Example 1.

The molar ratio of (3-glycidyloxypropyl)trimethoxysilane (GPTMS), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS) and H ₂ O is 1.5:0.5:3. It was put into a spherical flask. At this time, the combined weight of the GPTMS and ECTMS was set to 100 g.

5 g of Amberlite IRA-400 was added to the spherical flask and a sol-gel reaction was performed at 80° C. for 24 hours to produce a reactant.

The reaction product was purified to prepare a resin composition from which reaction by-products and unreacted monomers were removed.

Example 2.

Of the production method described in Example 1, 3-glycidyloxypropyl)trimethoxysilane (GPTMS), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS) and H ₂ O A resin composition was prepared in the same manner as described in Example 1, except that the molar ratio was 1.2:0.8:3, which was introduced into a spherical flask.

Example 3.

Of the production method described in Example 1, 3-glycidyloxypropyl)trimethoxysilane (GPTMS), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS) and H ₂ O A resin composition was prepared in the same manner as described in Example 1 above, except that the molar ratio was 1:1:3 to a spherical flask.

Example 4.

Of the production method described in Example 1, 3-glycidyloxypropyl)trimethoxysilane (GPTMS), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS) and H ₂ O A resin composition was prepared in the same manner as in Example 1, except that the molar ratio was 0.8:1.2:3, which was then added to a spherical flask.

Example 5.

Of the production method described in Example 1, 3-glycidyloxypropyl)trimethoxysilane (GPTMS), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS) and H ₂ O A resin composition was prepared in the same manner as described in Example 1, except that the molar ratio was 0.5:1.5:3, and the flask was charged.

Table 1 below is a table recording the compositions of the resin compositions according to Comparative Examples 1 to 3 and Examples 1 to 5.

Example Monomer 1:
GPTMS
(Molar ratio) Monomer 2:
ECTMS
(Molar ratio) H ₂ O
(Molar ratio to monomer 1 + monomer 2) catalyst
(weight%) Comparative Example 1 One 0 1.5 5 Comparative Example 2 0 One 1.5 5 Comparative Example 3 One One 1.5 5 Example 1 1.5 0.5 1.5 5 Example 2 1.2 0.8 1.5 5 Example 3 One One 1.5 5 Example 4 0.8 1.2 1.5 5 Example 5 0.5 1.5 1.5 5

Example 6.

After preparing a polyethylene terephthalate (PET) substrate, and bar coating the resin compositions obtained in Comparative Examples 1 to 3 and Example 3 on the PET substrate, 1 at 40°C to 80°C. Drying for minutes to 10 minutes completely removed the solvent in the resin composition. The coated resin composition was cured to prepare a film. At this time, the thickness of each film was 50 μm, and the thickness of the PET substrate was 100 μm.

Example 7.

After preparing a polyethylene terephthalate (PET) substrate, and bar coating the resin compositions obtained in Comparative Examples 1 and 2 and Examples 1 to 5 on the PET substrate, at 40°C to 80°C Drying for 1 to 10 minutes completely removed the solvent in the resin composition. The coated resin composition was cured to prepare a film. At this time, the thickness of each film was 50 μm, and the thickness of the PET substrate was 100 μm.

Experimental Example 1. Hardness and modulus evaluation.

The hardness and modulus of each of the films obtained in Example 6 were evaluated and the results are shown in FIG. 2.

In the nanoindentation measurement mode of an atomic force microscope (XE-7 from Park systems), nanoindentation evaluation was performed using a Berkovich type diamond cantilever (TD26818), and loading and unloading at a rate of 10 μN/sec. Loading proceeded.

2, it was confirmed that the film prepared using the resin composition obtained in Example 3 exhibits the highest hardness and modulus.

Experimental Example 2. Road-displacement evaluation

The load-displacement evaluation of the film obtained in Example 6 was performed and the results are shown in FIG. 3.

Through the nanoindentation evaluation, the rod values according to the indentation depth were plotted.

Referring to Figure 3, it was confirmed that the film prepared using the resin composition obtained in Example 3 exhibits the lowest indentation depth.

Experimental Example 3. Pencil hardness evaluation

The pencil hardness of the film obtained in Example 6 was evaluated and the results are shown in FIG. 4.

The pencil hardness tester was moved 10 mm at a speed of 60 mm per minute using a 750 g and 1000 g weight on the pencil hardness tester, and then it was confirmed whether or not scratches were generated on the film surface. The pencil hardness that did not occur was derived from the pencil hardness value of the film.

Referring to Figure 4, the film prepared using the resin composition obtained in Example 3 showed a pencil strength of 9H in both 1000g and 750g conditions, it was confirmed that it shows a higher pencil strength compared to Comparative Examples 1 to 3.

Experimental Example 4. Evaluation of bending stiffness

Evaluation of the bending stiffness of the film obtained in Example 6 was performed, and the results are shown in FIG. 5.

The bending stiffness was measured through a three-point indentation test of the UTM from Test one equipment. At this time, the film was cut to a length of 100 mm and a width of 40 mm, and the bending test measurement was set to a distance of 50 mm and pressed at a speed of 15 mm per minute. Proceeded.

5, it was confirmed that the film prepared using the resin composition obtained in Example 3 exhibits a bending stiffness of 1.5 kgf/mm ² .

Experimental Example 5. Hardness and modulus evaluation

The hardness and modulus of the film obtained in Example 7 were evaluated, and the results are shown in FIG. 6.

In the nanoindentation measurement mode of an atomic force microscope (XE-7 from Park systems), nanoindentation evaluation was performed using a Berkovich type diamond cantilever (TD26818), and loading and unloading at a rate of 10 μN/sec. Loading proceeded.

Referring to Figure 6, it was confirmed that the film prepared using the resin composition obtained in Example 4 exhibits the highest hardness and modulus.

Experimental Example 6. Pencil hardness rating

The pencil strength of the film obtained in Example 7 was evaluated and the results are shown in FIG. 7.

The pencil hardness tester was moved 10 mm at a speed of 60 mm per minute using a 750 g and 1000 g weight on the pencil hardness tester, and then it was confirmed whether or not scratches were generated on the film surface. The pencil hardness that did not occur was derived from the pencil hardness value of the film.

Referring to Figure 7, it was confirmed that the film prepared using the resin composition obtained in Example 4 exhibits pencil strength of 9H under both 1000g and 750g conditions.

Experimental Example 7. Evaluation of bending stiffness

Evaluation of the bending stiffness of the film obtained in Example 7 was performed, and the results are shown in FIG. 8.

The bending stiffness was measured through a three-point indentation test of the UTM from Test one equipment. At this time, the film was cut to a length of 100 mm and a width of 40 mm, and the bending test measurement was set to a distance of 50 mm and pressed at a speed of 15 mm per minute. Proceeded.

Referring to Figure 8, it was confirmed that the film prepared using the resin composition obtained in Example 4 exhibits a bending stiffness of 1.9 kgf/mm ² .

Experimental Example 8. Residual Depth Evaluation

Evaluation of the residual depth of the film obtained in Example 7 was performed and the results are shown in FIG. 9.

In the load-displacement evaluation, the difference in the indentation depth value when the load value at loading and unloading becomes 0 μN was calculated to calculate the residual depth value.

9, it was confirmed that the film produced using the resin composition obtained in Example 4 exhibits a residual depth of 11 nm.

Experimental Example 9. Flexural evaluation

The warpage evaluation of the film, prepared using the resin composition obtained in Example 4, obtained in Example 7, was performed and the results are shown in FIG. 10.

The film was cut in the form of 10 mm horizontal × 100 mm vertical, and repeated bending evaluation was conducted at a predetermined bending radius. 100,000 bending cycles were repeated at each bending radius, and when a sample having been evaluated for bending was placed on the floor, the distance from the bottom of the sample peak was measured.

Referring to Figure 10, the film produced using the resin composition obtained in Example 4 shows a bending of 16 mm in the bending radius of 1R, 10 mm in the bending radius of 2R, 3 mm bending in the bending radius of 3R, At a bending radius of 4R or more, no bending phenomenon was observed even after bending evaluation.

The above description of the present invention is for illustration only, and those skilled in the art to which the present invention pertains can understand that the present invention can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present invention is indicated by the following claims, and all modifications or variations derived from the meaning and scope of the claims and their equivalent concepts should be interpreted to be included in the scope of the present invention.

Claims (18)

A mixed solution comprising a first monomer that is a soft monomer and a second monomer that is a hard monomer includes a polymerized nano sol by sol-gel reaction, and a flexible network structure capable of simultaneously imparting stiffness and ductility to a film produced Characterized by including,
The first monomer is characterized in that it comprises one selected from the group consisting of trialkoxy silane, dialkoxy silane, monoalkoxy silane and combinations thereof,
The first monomer is characterized in that it comprises one selected from the group consisting of ether groups, ester groups, C ₃ to C ₁₀ alkyl groups, glycidyloxy groups, and combinations thereof,
The second monomer includes one selected from the group consisting of trialkoxy silane, dialkoxy silane, monoalkoxy silane, and combinations thereof,
The second monomer is an aromatic group, a C ₄ to C ₁₀ cycloalkyl group, and a resin composition comprising one selected from the group consisting of combinations thereof. delete According to claim 1,
The first monomer is (3-glycidyloxypropyl)trimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, (3-(2,3-epoxypropoxy)-propyl)-trimethoxy A resin composition comprising one selected from the group consisting of silanes and combinations thereof. delete According to claim 1,
The second monomer comprises one selected from the group consisting of phenyltrimethoxysilane, 1-naphthyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and combinations thereof. Resin composition, characterized in that. delete According to claim 1,
The resin composition, characterized in that the molar ratio of the first monomer and the second monomer is 5:1 to 1:5. According to claim 1,
The first monomer is a resin composition, characterized in that provided in 0.1% to 60% by weight of the mixed solution. According to claim 1,
The second monomer is a resin composition, characterized in that provided in 0.1 to 60% by weight of the mixed solution. According to claim 1,
The mixed solution is a resin composition further comprising a catalyst. The method of claim 10,
The catalyst is a resin composition comprising an ion exchange resin. The method of claim 10,
The catalyst is a resin composition comprising one selected from the group consisting of alkyl ammonium salts, halide salts and combinations thereof. The method of claim 10,
The catalyst is a resin composition, characterized in that provided in 3% to 7% by weight relative to the total weight of the first monomer and the second monomer. According to claim 1,
The resin composition further comprises one selected from the group consisting of surfactants, anti-yellowing agents, diluents, anti-foaming agents, dispersants, thickeners, wetting agents, leveling agents, and combinations thereof. According to claim 1,
The resin composition is a resin composition, characterized in that the composition for hard coating. A film prepared using the resin composition of claim 1. A cover window provided with the film of claim 16. An image display device provided with the film of claim 16.

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