KR20160089748A - Polymer coating composition - Google Patents

Abstract

The present invention relates to a polymer coating composition which includes: a polyimide resin including an imide repeating unit which contains at least one type of functional groups selected from the group composed of a fluorine-based functional group and a ether functional group; a monomer or an oligomer including at least one type of functional groups selected from the group composed of a (meth)acrylate group, a vinyl group, an epoxy group, and a urethane (meth)acrylate group; a photoinitiator; and an inorganic particle on which a reactive functional group is substituted on the surface.

Description

[0001] POLYMER COATING COMPOSITION [0002]

The present invention relates to a polymer coating composition, and more particularly, to a polymer coating composition capable of providing a single-layer polymer film exhibiting high hardness and having performance and physical properties equal to or higher than that of a multilayer film even by a single layer, .

With the recent development of mobile devices such as smart phones and tablet PCs, thinner and slimmer display substrates have been required. Glass or tempered glass is generally used as a material having excellent mechanical properties on a display window or a front plate of such a mobile device. However, the glass causes the weight of the mobile device to be heavy due to its own weight, and has a problem of breakage due to an external impact.

Plastic resins are being studied as a substitute for glass. Plastic resin films are lightweight and less susceptible to breakage, making them suitable for trends toward lighter mobile devices. In particular, a film is proposed in which a hard coating layer is coated on a resin substrate to achieve a film having properties of hardness and abrasion resistance.

However, in the previously known hard coating film, if the thickness is increased to secure a surface hardness enough to replace the glass, the hardening layer shrinks due to the hardening of the hard coating layer, It is difficult to ensure appropriate physical properties or the application field is limited.

Further, when the thickness of the hard coating film is made thinner in accordance with the recent thinness and slimness of the substrate for display, the scratch resistance and strength of the hard coating film are not sufficiently maintained, and it is difficult to secure the proper physical properties in the same way Limited.

Accordingly, there is a need to develop a method for manufacturing a plastic film or plastic substrate which can have improved physical properties such as strength and hardness even in a thin thickness by a more economical and efficient method.

The present invention is to provide a polymer coating composition capable of providing a single-layer polymer film exhibiting high hardness and having performance and physical properties equal to or higher than that of a multilayer film even with a single layer even through a more economical and simple manufacturing process.

In the present specification, a polyimide resin comprising an imide repeating unit containing at least one or more functional groups selected from the group consisting of a fluorine-based functional group and an ether functional group; A monomer or oligomer containing at least one functional group selected from the group consisting of a (meth) acrylate group, a vinyl group, an epoxy group and a urethane (meth) acrylate group; Photoinitiators; And inorganic particles having a reactive functional group substituted on the surface thereof.

Hereinafter, the polymer coating composition according to a specific embodiment of the present invention will be described in more detail.

As used herein, the term 'single-layer polymer film' refers to a single-layer film produced from a coating solution or raw material having a predetermined composition. The single-layer polymer film is distinguished from a multi-layer laminate film formed by laminating a plurality of films having different compositions or structures. However, the 'single-layer polymer film' is only a material for specifying the above-described single-layer film, and the scope of the present invention is not limited by these descriptions, And methods using the same are included in the scope of the present invention.

In addition, in the present specification, (meth) acrylate means to include both acrylate and methacrylate.

According to one embodiment of the invention, a polyimide resin comprising an imide repeating unit containing at least one or more functional groups selected from the group consisting of a fluorine-based functional group and an ether functional group; A monomer or oligomer containing at least one functional group selected from the group consisting of a (meth) acrylate group, a vinyl group, an epoxy group and a urethane (meth) acrylate group; Photoinitiators; And an inorganic particle having a reactive functional group substituted on the surface thereof.

The inventors of the present invention conducted a study on a method for manufacturing a plastic film or a plastic substrate which can have improved physical properties such as strength and hardness even in a thin thickness by a more economical and efficient method, The use of a polymer coating composition comprising a polyimide resin containing a specific functional group and a monomer or oligomer having the specific functional group and an inorganic particle having a reactive functional group substituted on the surface thereof is used to provide an improved physical properties such as high hardness and strength It is possible to provide a polymer film having a high hardness with a performance and physical properties equal to or higher than that of a multilayer film by using only a single layer. .

Polyimide resins are generally known to have low compatibility or reactivity with monomers, oligomers, or (co) polymers synthesized therefrom, including (meth) acrylate groups and the like, which are selected from the group consisting of the fluorine-based functional groups and the ether functional groups A polyimide resin containing an imide repeating unit containing at least one or more functional groups may be more easily mixed with the above-mentioned monomers, oligomers or (co) polymers synthesized therefrom owing to their chemical structural characteristics .

The imide repeating unit containing at least one or more functional groups selected from the group consisting of a fluorine-based functional group and an ether functional group contained in the polyimide resin has a relatively high dipole moment, and thus the (meth) acrylate group, vinyl (Meth) acrylate group, and a urethane (meth) acrylate group having at least one functional group.

As described above, the polyimide resin containing the specific imide repeating unit is preferably a monomer containing at least one functional group selected from the group consisting of (meth) acrylate group, vinyl group, urethane (meth) acrylate group and epoxy, The oligomer and the reactive functional group can have high compatibility with the surface-substituted inorganic particles, so that the phenomenon that the components are partially united or the composition is uneven in the polymer coating composition of the embodiment can be minimized, May be available.

As described later, a single-layer polymer film can be provided through a method of manufacturing a polymer film including a step of light-treating and heat-treating the polymer coating composition of the embodiment. As the polymer coating composition is subjected to light treatment and heat treatment, inorganic particles in which the polyimide resin, the specific monomer or oligomer, and the reactive functional group are substituted on the surface form a substrate of a single-layer polymer film. A part formed from the mid resin and a part formed from the specific monomer or oligomer and the inorganic particles substituted on the surface with the reactive functional group are distinguished.

Specifically, the single-layer polymer film may include a polyimide resin; (Meth) acrylate-based polymer resin or a vinyl-based polymer resin; And inorganic particles whose reactive functional groups have been substituted on the surface and which have an area ranging from one surface to 10% of the total thickness, or from one surface to 40% of the total thickness, or from one surface to 60% The (meth) acrylate polymer resin or the vinyl polymer resin may be present in a larger amount than the polyimide resin.

The (meth) acrylate-based polymer resin or the vinyl-based polymer resin is formed from a monomer or oligomer containing at least one functional group selected from the group consisting of the (meth) acrylate group, the vinyl group, and the urethane (meth) .

In the single-layered polymer film, as a feature that a part formed from the polyimide resin and a part formed from the specific monomer or oligomer and the inorganic particles whose surface is substituted with the reactive functional group are distinguished, the polyimide resin And the characteristics according to the (meth) acrylate-based polymer resin or the vinyl-based polymer resin can be all expressed.

In addition, the single-layered polymer film has a performance and physical properties equal to or higher than that of the multilayer film at the same thickness and can exhibit high hardness. For example, the single-layered polymer film may be formed by coating a polyimide resin film with a (meth) It can have improved performance and physical properties at the same thickness as the multilayer film.

As described above, the polyimide resin may include an imide repeating unit containing at least one functional group selected from the group consisting of a fluorine-based functional group and an ether functional group.

Specifically, the imide repeating unit may include a repeating unit represented by the following formula (1).

[Chemical Formula 1]

Wherein n is an integer of 1 to 300, Y is a tetravalent functional group containing an aromatic functional group having 6 to 40 carbon atoms, a tetravalent functional group containing an aliphatic functional group having 1 to 40 carbon atoms or an alicyclic group having 4 to 40 carbon atoms X is a divalent functional group containing an aromatic functional group having 6 to 40 carbon atoms, a divalent functional group containing an aliphatic functional group having 1 to 40 carbon atoms or an alicyclic functional group having 4 to 40 carbon atoms , At least one of X and Y contains at least one functional group selected from the group consisting of fluorine, perfluoroalkyl and oxa functional groups having 1 to 10 carbon atoms.

In formula (1), Y may be a quaternary functional group selected from the group consisting of the following formulas (11) to (14).

(11)

In Formula 11, Y ₁ is a direct bond, -O- or -C (CF ₃ ) ₂ -.

[Chemical Formula 12]

In Formula 12, Y ₂ and Y ₃ may be the same or different and are each a direct bond, -O- or -C (CF ₃ ) ₂ -.

[Chemical Formula 13]

In the above formula (13), Y ₄ , Y ₅ And Y ₆ may be the same or different and are each a direct bond, -O- or -C (CF ₃ ) ₂ -.

[Chemical Formula 14]

In the above Formulas 11 to 14, * denotes a bonding point.

In Formula (1), X may be one kind of divalent functional group selected from the group consisting of the following Formulas (21) to (22).

[Chemical Formula 21]

In the formula (21), R ₁ is perfluoroalkyl having 1 to 10 carbon atoms, n is an integer of 1 to 4 as the number of R ₁ substituted on the benzene ring,

[Chemical Formula 22]

In Formula 22, L ₁ is a direct bond, -O- or -C (CF ₃ ) ₂ -, R ₁ and R ₂ are perfluoroalkyl having 1 to 10 carbon atoms, m and p are R ₁ and R ₁ is an integer from 0 to 4 as the number of substitutions on the benzene ring, and L ₁ is a direct bond one when m and p is an integer of 1 to 4, q is an integer from 1 to 5, wherein the formula 21 To 22, * denotes a bonding point.

For example, the polyimide resin may include one or more repeating units selected from the group consisting of the following formulas (31) to (36).

(31)

(32)

(33)

(34)

(35)

(36)

In the above Formulas 31 to 36, x and y are each an integer of 1 to 100.

On the other hand, the polyimide resin may have a weight average molecular weight of 3,000 to 600,000. If the weight average molecular weight of the polyimide resin is too small, the polymer film finally produced may not have sufficient mechanical properties and self-healing ability. In addition, if the weight average molecular weight of the polyimide resin is too large, the composition may become homogeneous in the polymer coating composition and the homogeneity of the shape and physical properties of the finally produced polymer film of the hard coating layer may be lowered.

As described above, the monomer or oligomer containing at least one functional group selected from the group consisting of the (meth) acrylate group, the vinyl group, and the urethane (meth) acrylate group is subjected to a light treatment and a heat treatment (Meth) acrylate-based polymer resin or a vinyl-based polymer resin.

The monomer or oligomer containing at least one functional group selected from the group consisting of the (meth) acrylate group, the vinyl group and the urethane (meth) acrylate group has a high surface hardness and a high transparency And a low yellow index.

Examples of the monomer having a (meth) acrylate group include dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylene propyl tri (Meth) acrylate, ethylhexyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, Acrylate, polycaprolactone modified (meth) acrylate, hydroxyalkyl (meth) acrylate, or a mixture of two or more thereof.

Specific examples of the oligomer having a (meth) acrylate group include urethane-modified acrylate oligomers, epoxy acrylate oligomers and ether acrylate oligomers each containing 2 to 10 (meth) acrylate groups. The weight average molecular weight of such an oligomer may be from 1,000 to 10,000.

Specific examples of the vinyl group-containing monomer include divinylbenzene, styrene, and parirromethylstyrene.

Specific examples of the monomer containing the urethane (meth) acrylate group include (meth) acrylates such as (meth) acrylate, polycaprolactone modified (meth) acrylate and hydroxyalkyl (meth) acrylate and polyisocyanate And urethane acrylate obtained by the reaction.

(Meth) acrylate group, a vinyl group, an epoxy group, and a urethane (meth) acrylate group in the polymer coating composition in consideration of the physical properties and shape of the finally produced polymer film The content of the monomers or oligomers containing the above functional groups can be determined. For example, the polymer coating composition may contain a monomer or oligomer 10 (a) containing at least one functional group selected from the group consisting of the (meth) acrylate group, the vinyl group, and the urethane (meth) acrylate group relative to 100 parts by weight of the polyimide resin To 70 parts by weight.

The polymer coating composition includes inorganic particles whose surface is substituted with the reactive functional group, and inorganic particles whose surface is substituted with the reactive functional group may act to improve surface hardness.

The reactive functional group substituted on the surface of the inorganic particles may be one functional group selected from the group consisting of a (meth) acrylate group, a vinyl group, a siloxane group, an epoxy group and a urethane group.

The inorganic fine particles may include nanoscale inorganic fine particles, for example, nanometer-sized particles having a particle diameter of about 25 nm or less, or about 1 nm to about 25 nm, or about 2 nm to 10 nm. When the size of the inorganic fine particle exceeds 25 nm, the refractive index of the film produced from the polymer coating composition may be shifted and haze may be generated. Specific examples of the inorganic fine particles include silica fine particles, aluminum oxide particles, titanium oxide particles, zinc oxide particles, and mixtures of two or more thereof.

The content of the inorganic particles in which the reactive functional group contained in the polymer coating composition is substituted on the surface can be determined in consideration of the physical properties and shape of the polymer film to be finally produced. For example, the polymer coating composition may include the polyimide resin 100 And 5 to 50 parts by weight of the inorganic particles having the reactive functional groups substituted on the surface thereof.

The polymer coating composition may include a photoinitiator. As the photoinitiator, compounds known to be commonly used in the art may be used without limitation. For example, benzophenone-based compounds, acetophenone-based compounds, An imidazole-based compound, a triazine-based compound, an oxime-based compound, or a mixture thereof. Specific examples of such photoinitiators include benzophenone, benzoyl methyl benzoate, acetophenone, 2,4-diethyl thioxanthone, 2- 2-chloro thioxanthone, ethyl anthraquinone, 1-Hydroxy-cyclohexyl-phenyl-ketone (commercially available from Irgacure 184 of Ciba) or 2 Hydroxy-2-methyl-1-phenyl-propan-1-one.

Meanwhile, the polymer coating composition may further include an organic solvent.

The organic solvent may be used in coating compositions without limitation as long as it is known in the art. For example, ketone-based organic solvents such as methyl isobutyl ketone, methyl ethyl ketone, and dimethyl ketone; An alcohol organic solvent such as isopropyl alcohol, isobutyl alcohol or normal butyl alcohol; An acetate organic solvent such as ethyl acetate or normal butyl acetate; N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N, N-dimethylacetamide (NMP), and the like can be used as the organic solvent such as ethyl cellusolve or butyl cellusolve. N, N-dimethylacetamide (DEAc), N, N-dimethylmethoxyacetamide, dimethylsulfoxide, pyridine, But are not limited to, dimethyl sulfone, hexamethylphosphoramide, tetramethylurea, N-methylcaprolactam, tetrahydrofuran, m-dioxane, (Ethylene glycol) methacrylate (PEGMA), gamma-butyrolactone (GBL (meth) acrylate) ) Or Ekamide (Equamide M100, Idemitsu Kosan Co., Ltd.), but the organic solvent is not limited to the above-mentioned examples.

The amount of the organic solvent to be used may be adjusted in consideration of the physical properties of the polymer coating composition, the coating method, or specific physical properties of the final product. For example, the organic solvent may be used in an amount of 5 to 1,000 parts by weight based on 100 parts by weight of the polyimide resin. have. Such an organic solvent may be removed by 95% or more through the above-described light treatment and subsequent drying process after the heat treatment.

Specific uses of the polymer coating composition include production of a hard coating film, production of a cover window film, and production of a touch-integrated cover window film.

Meanwhile, a single-layer polymer film can be provided through the steps of light-treating and heat-treating the above-described polymer coating composition.

As described above, a single-layer polymer film can be provided through a method of manufacturing a polymer film including a step of light-treating and heat-treating the polymer coating composition of the embodiment. As the polymer coating composition is subjected to light treatment and heat treatment, inorganic particles in which the polyimide resin, the specific monomer or oligomer, and the reactive functional group are substituted on the surface form a substrate of a single-layer polymer film. A part formed from the mid resin and a part formed from the specific monomer or oligomer and the inorganic particles substituted on the surface with the reactive functional group are distinguished.

Specifically, the single-layer polymer film may include a polyimide resin; (Meth) acrylate-based polymer resin or a vinyl-based polymer resin; And an inorganic particle having a reactive functional group substituted on its surface, and a region from one surface to 10% of the total thickness or an area from one surface to 40% of the total thickness, or an area from one surface to 60% The (meth) acrylate-based polymer resin or the vinyl-based polymer resin may exist more than the polyimide resin.

That is, by using the polymer coating composition of the embodiment, it is possible to provide a polymer film having improved physical properties such as high hardness and strength through a more economical and simple manufacturing process. Specifically, even if only a single layer is used, And a single-layer polymer film having physical properties and exhibiting high hardness.

The light treatment may be performed by irradiating the polymer coating composition with a predetermined ultraviolet ray or a visible ray, for example, ultraviolet ray or visible ray having a wavelength of 200 to 400 nm. Specifically, the method for producing the polymer film may include irradiating the polymer coating composition with ultraviolet light in an amount of 10 to 20,000 mJ / cm 2, or 50 to 4,000 mJ / cm 2. In addition, the exposure time of the light treatment is not particularly limited, and can be appropriately changed depending on the wavelength of the exposure apparatus, the irradiation light used, or the exposure dose. The photocurable monomer is reacted through the light treatment to diffuse into the film to form a layer of reactive materials on the upper layer of the film.

The heat treatment may be performed at a temperature of 40 ° C to 250 ° C. The method and time of the heat treatment are not limited to a wide range. The heat treatment may be performed using a known heat source in the temperature range described above, and the heat treatment time may be appropriately changed according to the heat treatment temperature and the characteristics of the heat source. Through the heat treatment, the intermolecular packing density of the polyimide is increased to improve the mechanical properties of the substrate to improve the overall hardness.

The method for producing a polymer film may further include a preheating step of heat-treating the polymer coating composition at a temperature of 25 ° C to 80 ° C before the light treatment. The efficiency of the photoreaction can be increased by reducing the residual solvent through the preheating treatment.

The method and time of the preheat treatment are not limited to a specific one. The heat treatment can be performed using a known heat source in the temperature range described above, and the heat treatment time can be appropriately changed according to the heat treatment temperature and the characteristics of the heat source.

In the production process of the polymer film, a method and an apparatus known to be commonly used in the production of a polymer film can be used except for the above-mentioned contents.

For example, in the production of the polymer film, the polymer coating composition may be applied onto the substrate before the light treatment. Thus, a film having a constant thickness can be produced by coating on a predetermined substrate. The method of applying the polymer coating composition is not limited to a wide range. For example, a spin coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a micro gravure coating method, A coating method, a slot die coating method, or a lip coating method.

On the other hand, in the step of light-treating the polymer coating composition, one side of the polymer coating composition coated on the substrate and having a shape of a sheet or a film is exposed, and at the same time or at another time, As shown in FIG.

When the polymer coating composition coated on the substrate is simultaneously or sequentially light-treated on both surfaces, the (meth) acrylate-based polymer resin or the vinyl-based polymer resin is uniformly dispersed in the single-layer polymer surface A predetermined layer can be formed on both surfaces of the substrate. Thus, the (meth) acrylate-based polymer resin or the vinyl-based polymer resin or the (meth) acrylate-based polymer resin in the region from the both surfaces of the single-layered polymer film to 10% of the total thickness or from 40% to 60% There may be more polymer resin than the polyimide resin.

On the other hand, a single-layer polymer film prepared by light-treating and heat-treating the polymer coating composition includes a polyimide resin; (Meth) acrylate-based polymer resin or a vinyl-based polymer resin; (Meth) acrylate-based polymer resin or vinyl-based polymer resin in an area from one surface of the single-layer polymer film to 10% of the total thickness, Than the polyimide resin.

As described above, as the polymer coating composition of the embodiment is subjected to light treatment and heat treatment, the inorganic particles in which the polyimide resin, the specific monomer or oligomer, and the reactive functional group are substituted on the surface form a substrate of a single layer polymer film In the above-described substrate, a part formed from the polyimide resin and a part formed from the specific monomer or oligomer and the inorganic particles whose surface is substituted with the reactive functional group are distinguished.

The monolayer polymer film is characterized in that the content or distribution of the polyimide resin and the (meth) acrylate polymer resin or the vinyl polymer resin varies depending on the region inside the layer. Particularly, (Meth) acrylate-based polymer resin or vinyl-based polymer resin is more distributed on the other surface of the polyamide resin than on the other surface.

The single-layer polymer film may have high performance and physical properties at the same thickness as the multi-layer film and have a performance and physical properties equal to or higher than that of the multi-layer film. For example, a multi-layer film formed by coating a (meth) acrylate- And can have improved performance and physical properties at the same thickness.

In the case of a multilayer film produced by laminating two or more different polymer films or sequentially coating two or more kinds of polymer coating compositions, there is an interface separating into different components or different layers, and a force exceeding a certain level is applied Although the peeling phenomenon may occur at such an interface, the single-layer polymer film has a feature that there is no interface where such peeling can occur.

Specifically, the single-layer polymer film may include a polyimide resin; (Meth) acrylate-based polymer resin or a vinyl-based polymer resin; And an inorganic particle having a reactive functional group substituted on the surface, wherein in the region from one surface to 10% of the total thickness, or in the region from the one surface to 40% of the total thickness, the (meth) acrylate-based polymer A resin or a vinyl polymer resin may be present in a larger amount than the polyimide resin.

In the single-layered polymer film, as a feature that a part formed from the polyimide resin and a part formed from the specific monomer or oligomer and the inorganic particles whose surface is substituted with the reactive functional group are distinguished, the polyimide resin And the characteristics according to the (meth) acrylate-based polymer resin or the vinyl-based polymer resin can be all expressed.

In addition, the single-layered polymer film has a performance and physical properties equal to or higher than that of the multilayer film at the same thickness and can exhibit high hardness. For example, the single-layered polymer film may be formed by coating a polyimide resin film with a (meth) It can have improved performance and physical properties at the same thickness as the multilayer film.

More specifically, in the region from one surface of the single-layer polymer film to 10% of the total thickness, or in a range of 40% to 60% of the total thickness from the one surface, Polyimide resin: The weight ratio of the (meth) acrylate-based polymer resin or the vinyl-based polymer resin may be 0: 100 to 40: 60.

On the other hand, the (meth) acrylate-based polymer resin or the vinyl-based polymer resin and the inorganic particles whose surface is substituted with the reactive functional group may form a crosslink. Accordingly, the inorganic particles in which the reactive functional groups are substituted on the surface may be distributed in a region where the (meth) acrylate-based polymer resin or the vinyl-based polymer resin is mainly distributed in the single-layer polymer film.

Specifically, in a region where the (meth) acrylate-based polymer resin or the vinyl-based polymer resin is present in a larger amount than the polyimide resin, the reactive functional group is contained in an amount of 30 wt% or more, 50 wt% Or more, or 70 wt% or more.

Meanwhile, as described above with respect to the method for producing the single-layered polymer film, in the step of light-treating the polymer coating composition, one side of the polymer coating composition coated on the substrate and having the shape of the sheet or the film is exposed And exposing another surface opposite to the one surface at the same time or at a time interval.

When the polymer coating composition coated on the substrate is simultaneously or sequentially light-treated on both surfaces, the (meth) acrylate-based polymer resin or the vinyl-based polymer resin is dispersed in the film, A predetermined layer can be formed on both surfaces of the substrate. Thus, the (meth) acrylate-based polymer resin or the vinyl-based polymer resin or the (meth) acrylate-based polymer resin in the region from the both surfaces of the single-layered polymer film to 10% of the total thickness or from 40% to 60% There may be more polymer resin than the polyimide resin.

The monolayer polymer film is characterized in that a polyimide resin containing an imide repeating unit containing at least one or more functional groups selected from the group consisting of the fluorine-based functional group and the ether functional group is added to the (meth) acrylate group, the vinyl group, A urethane (meth) acrylate group and a urethane (meth) acrylate group; And an inorganic particle having a reactive functional group substituted on its surface.

The imide repeating unit containing at least one or more functional groups selected from the group consisting of a fluorine-based functional group and an ether functional group contained in the polyimide resin has a relatively high dipole moment, and thus the (meth) acrylate group, vinyl (Meth) acrylate group, and a urethane (meth) acrylate group having at least one functional group.

As described above, the polyimide resin containing the specific imide repeating unit is preferably a monomer or oligomer containing at least one functional group selected from the group consisting of the (meth) acrylate group, the vinyl group, and the urethane (meth) The reactive functional group can have high compatibility with the inorganic particles substituted on the surface, so that the phenomenon that the components are partially united or the composition is uneven in the polymer coating composition of the embodiment can be minimized, .

The single-layer polymer film may have a pencil hardness of 2H or more, 4H or more, or 6H or more under a load of 0.75kg on one surface where the polyimide resin is more present.

The single-layer polymer film may have a thickness of 1 탆 to 500 탆, or 10 탆 to 200 탆.

According to the present invention, it is possible to provide a polymer film having improved physical properties such as high hardness and strength even through an economical and simple manufacturing process. Specifically, it is possible to provide a polymer film having a high hardness A single-layer polymer film can be provided.

Fig. 1 is a cross-sectional photograph of a polymer film produced in Example 1. Fig.
Figure 2 shows a single layer polymer film made using the photocurable thermosetting coating composition of Example 1.
Fig. 3 shows a polymer film produced using the coating composition of Comparative Example 1. Fig.
Fig. 4 shows a polymer film produced using the coating composition of Comparative Example 2. Fig.
Fig. 5 shows a polymer film produced using the coating composition of Comparative Example 3. Fig.

Embodiments of the invention are described in more detail in the following examples. It should be noted, however, that the following examples are intended to illustrate but not limit the scope of the present invention.

[ Manufacturing example : Production of polyimide resin]

Production Example 1

1 mol of 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFMB) was dissolved in 80 g of diethylformamide (DEF), and 4,4 '- (hexafluoroisopropylidene) A solution containing polyamic acid was prepared by adding 1 mol of diethyl phthalic anhydride (4,4 '- (Hexafluoroisopropylidene) diphthalic anhydride, (6FDA) and 50 g of diethylformamide (DEF) at 50 ° C for 24 hours.

40 g of toluene was added to the above-prepared solution, and water was removed through a dean-stark distillation apparatus, followed by reflux at 160 ° C for 12 hours. After removing water from the Dean-Stark distillation apparatus, the solution was cooled to room temperature to obtain a polyimide resin solution.

Production Example 2

1 mol of 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFMB) was dissolved in 80 g of diethylformamide (DEF), and 2,3,3 ', 4'-biphenyltetracarboxyl (2, 3, 3 ', 4'-BIPHENYL TETRACARBOXYLIC DIANHYDRIDE) was added to 50 g of diethylformamide (DEF) and polymerized at 50 ° C for 24 hours to prepare a solution containing polyamic acid.

40 g of toluene was added to the above-prepared solution, and water was removed through a dean-stark distillation apparatus, followed by reflux at 160 ° C for 12 hours. After removing water from the Dean-Stark distillation apparatus, the solution was cooled to room temperature to obtain a polyimide resin solution.

Production Example 3

1 mol of 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFMB) was dissolved in 80 g of diethylformamide (DEF), 0.8 mol of 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride, 3 ', 4,4'-Biphenyltetracarboxylic dianhydride was added to 50 g of diethylformamide (DEF) and polymerization was carried out at 50 ° C. for 24 hours to prepare a solution containing polyamic acid.

40 g of toluene was added to the above-prepared solution, and water was removed through a dean-stark distillation apparatus, followed by reflux at 160 ° C for 12 hours. After removing water from the Dean-Stark distillation apparatus, the solution was cooled to room temperature to obtain a polyimide resin solution.

Production Example 4

1 mol of 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFMB) was dissolved in 80 g of diethylformamide (DEF), and 0.8 mol of 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride And 0.2 mol of 4,4'-oxydiphthalic anhydride (ODPA) were added to 50 g of diethylformamide (DEF) and polymerized at 50 ° C for 24 hours to prepare a solution containing polyamic acid.

40 g of toluene was added to the above-prepared solution, and water was removed through a dean-stark distillation apparatus, followed by reflux at 160 ° C for 12 hours. After removing water from the Dean-Stark distillation apparatus, the solution was cooled to room temperature to obtain a polyimide resin solution.

Production Example 5

1 mol of 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFMB) was dissolved in 80 g of diethylformamide (DEF) and 2,3,3 ', 4'-BIPHENYL TETRACARBOXYLIC DIANHYDRIDE -BPDA) and 0.2 mol of 4,4'-oxydiphthalic anhydride (ODPA) were added, and the mixture was polymerized at 50 ° C for 24 hours in 50 g of DEF to prepare a solution containing polyamic acid.

40 g of toluene was added to the above-prepared solution, and water was removed through a dean-stark distillation apparatus, followed by reflux at 160 ° C for 12 hours. After removing water from the Dean-Stark distillation apparatus, the solution was cooled to room temperature to obtain a polyimide resin solution.

The weight average molecular weights of the polyimide resins prepared in the above Production Examples are shown in Table 1 below.

Weight average molecular weight Production Example 1 34,000 Production Example 2 45,000 Production Example 3 29,000 Production Example 4 33,000 Production Example 5 38,000

[ Example : Polymer coating composition and Single layer  Preparation of polymer film]

Example 1

(One) Photocurable  Preparation of thermosetting coating composition

30 g of 1,6-hexanediol diacrylate, 50 g of dipentaerythritol hexaacrylate, 20 g of silica particles (particle diameter: 15 nm) having an acrylate group bonded to its surface and 10 g of a photopolymerization initiator And 30 g of the polyimide resin prepared in Preparation Example 1 were mixed with a diethylformamide (DEF) solution (solid content: 70% by weight) prepared by mixing the above components to prepare a photocurable thermosetting coating composition.

(2) Production of coating film

The photocurable thermosetting coating composition obtained above was coated on a glass substrate (thickness 50 탆) by spin coating. Then, the coating was dried at 70 캜 for 10 minutes, and cured by irradiating ultraviolet rays of 740 mW / cm 2 for 5 seconds in a nitrogen atmosphere.

The cured product was heat-treated at a temperature rising rate of 3 ° C / min in a nitrogen atmosphere oven at a temperature of 0 ° C (30min), 150 ° C (30min) and 250 ° C (60min) A single-layer polymer film having a thickness of 25 mu m was prepared.

Example 2

(One) Photocurable  Preparation of thermosetting coating composition

A photocurable thermosetting coating composition was prepared in the same manner as in Example 1, except that 30 g of the polyimide resin prepared in Preparation Example 2 was used.

(2) Production of coating film

A single-layer polymer film having a thickness of 25 탆 was prepared in the same manner as in Example 1, except that the photocurable thermosetting coating composition obtained above was used.

Example 3

(One) Photocurable  Preparation of thermosetting coating composition

A photocurable thermosetting coating composition was prepared in the same manner as in Example 1, except that 30 g of the polyimide resin prepared in Preparation Example 3 was used.

(2) Production of coating film

A single-layer polymer film having a thickness of 25 탆 was prepared in the same manner as in Example 1, except that the photocurable thermosetting coating composition obtained above was used.

Example 4

(One) Photocurable  Preparation of thermosetting coating composition

A photocurable thermosetting coating composition was prepared in the same manner as in Example 1, except that 30 g of the polyimide resin prepared in Preparation Example 4 was used.

(2) Production of coating film

A single-layer polymer film having a thickness of 25 탆 was prepared in the same manner as in Example 1, except that the photocurable thermosetting coating composition obtained above was used.

Example 5

(One) Photocurable  Preparation of thermosetting coating composition

A photocurable thermosetting coating composition was prepared in the same manner as in Example 1, except that 30 g of the polyimide resin prepared in Preparation Example 5 was used.

(2) Production of coating film

A single-layer polymer film having a thickness of 25 탆 was prepared in the same manner as in Example 1, except that the photocurable thermosetting coating composition obtained above was used.

[ Comparative Example : Preparation of polymer coating composition and coating film]

Comparative Example 1

(One) Photocurable  Preparation of thermosetting coating composition

30 g of 1,6-hexanediol diacrylate, 50 g of dipentaerythritol hexaacrylate, 20 g of silica particles (particle diameter: 15 nm) having an acrylate group bonded to its surface and 10 g of a photopolymerization initiator And 30 g of a polyimide resin consisting of the repeating units represented by the following general formula (1) were mixed with a diethylformamide (DEF) solution (solid content: 70% by weight) prepared by mixing the above components to prepare a photocurable thermosetting coating composition.

[Formula 1]

(2) Production of coating film

The photocurable thermosetting coating composition obtained above was coated on a glass substrate (thickness 50 탆) by spin coating. Then, the coating was dried at 70 캜 for 10 minutes, and cured by irradiating ultraviolet rays of 740 mW / cm 2 for 5 seconds in a nitrogen atmosphere.

The cured product was heat-treated at a temperature rising rate of 3 ° C / min in a nitrogen atmosphere oven at a temperature of 0 ° C (30min), 150 ° C (30min) and 250 ° C (60min) A coating film having a thickness of 25 mu m was prepared.

Comparative Example 2

A photocurable thermosetting coating composition and a coating film were prepared in the same manner as in Comparative Example 1, except that a polyimide resin consisting of the repeating units of the following general formula (2) was used.

[Formula 2]

Comparative Example 3

A photocurable thermosetting coating composition and a coating film were prepared in the same manner as in Comparative Example 1, except that a polyimide resin composed of the repeating units represented by the following Formula 3 was used.

[Formula 3]

< Experimental Example : Evaluation of Physical Properties of Polymer Film>

[ Experimental Example ]

The physical properties of the single-layer polymer films of the above examples were evaluated as follows.

1. Evaluation of optical characteristics

The haze was measured using a haze meter (NIPPON DENSHOKU) and the transmittance was measured using UV-vis spectroscopy (Agilent 8453).

2. Hardness measurement

The surface hardness of each of the single-layer polymer films of the examples and the comparative examples was measured based on the pencil hardness at a load of 0.75 kg.

Experimental Example 1 Haze Result
[unit %] EXPERIMENTAL EXAMPLE 1 Transmission results
[unit %]
Average transmittance at 380 to 760 nm Experimental Example 2 Hardness Result
Example 1 0.3 91 3H Example 2 0.2 91 2H Example 3 0.3 91 2H Example 4 0.2 91 3H Example 5 0.3 91 3H

As shown in Table 2, it was confirmed that the single-layered polymer films prepared from the resin compositions of Examples 1 to 5 had surface hardness of 2H to 3H. This is because the photo-curing monomer reacts with the photo-curing monomer to diffuse into the film to form a layer of reactive materials on the upper layer of the film, and a surface having a high hardness is formed through the heat treatment process.

As a result of observing the cross section of the sample using the microtome equipment under the same conditions, it can be confirmed that the cross section is roughly formed in the surface layer of about 2 to 3 탆 of the sample of Example 1. This is because the surface layer of the film and the inside It seems that the cross-sectional shape of the layer is different.

On the other hand, as shown in Table 2 and FIG. 2, the single-layered polymer films of Examples have low haze characteristics and high light transmittance, while polyesters having no fluorine-based functional groups or etheric functional groups as shown in FIGS. Comparative Example 1 prepared from a resin composition comprising a mid resin and a (meth) acrylate monomer showed that the coating film of the nanny 3 exhibited high haze characteristics and cloudiness was observed.

Claims (13)

A polyimide resin comprising an imide repeating unit containing at least one or more functional groups selected from the group consisting of a fluorine-based functional group and an ether functional group;
A monomer or oligomer containing at least one functional group selected from the group consisting of a (meth) acrylate group, a vinyl group, an epoxy group and a urethane (meth) acrylate group;
Photoinitiators; And
Wherein the reactive functional group comprises inorganic particles substituted on the surface.
The method according to claim 1,
The polymer coating composition has photo-curable and thermosetting properties.
The method according to claim 1,
Wherein the imide repeating unit comprises a repeating unit of the following formula:
[Chemical Formula 1]

In Formula 1,
Wherein n is an integer of 1 to 300,
Y is a tetravalent functional group containing an aromatic functional group having 6 to 40 carbon atoms, a tetravalent functional group containing an aliphatic functional group having 1 to 40 carbon atoms or an alicyclic functional group having 4 to 40 carbon atoms,
X is a divalent functional group containing an aromatic functional group having 6 to 40 carbon atoms, a divalent functional group containing an aliphatic functional group having 1 to 40 carbon atoms or an alicyclic functional group having 4 to 40 carbon atoms,
At least one of X and Y contains at least one functional group selected from the group consisting of fluorine, perfluoroalkyl and oxa functional groups having 1 to 10 carbon atoms.
The method of claim 3,
Wherein Y is one tetravalent group selected from the group consisting of the following formulas (11) to (14):
(11)

In Formula 11, Y ₁ is a direct bond, -O- or -C (CF ₃ ) ₂ -
[Chemical Formula 12]

In Formula 12, Y ₂ and Y ₃ may be the same or different and are each a direct bond, -O- or -C (CF ₃ ) ₂ -
[Chemical Formula 13]

In the above formula (13), Y ₄ , Y ₅ And Y ₆ may be the same or different and are each a direct bond, -O- or -C (CF ₃ ) ₂ -
[Chemical Formula 14]

In the above Formulas 11 to 14, * denotes a bonding point.
The method of claim 3,
Wherein X is at least one divalent functional group selected from the group consisting of the following formulas (21) to (22):
[Chemical Formula 21]

In Formula 21,
R ₁ is perfluoroalkyl having 1 to 10 carbon atoms, n is an integer of 1 to 4 as the number of R ₁ substituted on the benzene ring,
[Chemical Formula 22]

In Formula 22, L ₁ is a direct bond, -O- or -C (CF ₃ ) ₂ -
R ₁ and R ₂ are perfluoroalkyl having 1 to 10 carbon atoms, m and p are numbers in which R ₁ and R ₁ are substituted on the benzene ring and are an integer of 0 to 4,
L ₁ is a direct bond, and m and p are integers of 1 to 4,
q is an integer of 1 to 5,
In the above Formulas 21 to 22, * denotes a bonding point.
The method according to claim 1,
Wherein the polyimide resin has a weight average molecular weight of from 3,000 to 600,000.
The method according to claim 1,
Wherein the reactive functional group substituted on the surface of the inorganic particle is a functional group selected from the group consisting of a (meth) acrylate group, a vinyl group, a siloxane group, an epoxy group and a urethane group.
The method according to claim 1,
Wherein the inorganic particles comprise at least one inorganic material selected from the group consisting of silica, aluminum oxide, titanium oxide and zinc oxide.
The method according to claim 1,
Wherein the inorganic particles have a diameter of 25 nm or less.
The method according to claim 1,
And 10 to 70 parts by weight of a monomer or oligomer containing at least one functional group selected from the group consisting of (meth) acrylate group, vinyl group, and urethane (meth) acrylate group with respect to 100 parts by weight of the polyimide resin. Composition.
The method according to claim 1,
And 5 to 50 parts by weight of inorganic particles having the reactive functional groups substituted on the surface thereof with respect to 100 parts by weight of the polyimide resin.
The method according to claim 1,
Further comprising an organic solvent.
The method according to claim 1,
The polymer coating composition is used in the production of a hardcoat film or a cover window film.

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