KR102451413B1 - Method for Fabricating anti-abrasion LCD protective film coated with a hybrid coating liquid of organic and inorganic substance - Google Patents

Abstract

Provided is a method for manufacturing an abrasion-resistant liquid crystal protective film coated with a coating solution in which a nano-ceramic material is dispersed.
The present invention comprises the steps of preparing a binder by adding inorganic oxides of aluminum oxide, silicon dioxide, titania, zirconium oxide, nano fillers, and photocatalysts to an organic synthetic material of oligomers and monomers; It includes the steps of applying the binder to the surface of the base film and forming the coating layer 20 by irradiating UV with a light amount of 400 to 600 mj/cm 2 to the base film to which the binder is applied.

Description

Method for Fabricating anti-abrasion LCD protective film coated with a hybrid coating liquid of organic and inorganic substance

The present invention relates to a method and a liquid crystal protective film for manufacturing a wear-resistant liquid crystal protective film coated with a UV-curable coating solution in which nano ceramic materials are dispersed, and more particularly, to an inorganic material using a coating solution sol-gel process. This dispersed UV-curing polymer-ceramic resin is pre-treated, dried, and specially cured during the manufacturing process to optimally cure the UV resin. Additives of aluminum oxide, silicon dioxide, titania, zirconium oxide, nanofiller, and photocatalyst to the organic compound of oligomers and monomers to maintain hardness to form one binder, and then the binder is mixed with liquid crystal It relates to a method of manufacturing a wear-resistant liquid crystal protective film coated with a nano-ceramic material dispersion coating solution, which is coated on the surface of the protective film and then coated by irradiating UV with a light amount of 400 to 600 mj/cm 2 .

In general, a terminal such as a mobile phone, which is a representative example of a mobile device, has a transparent case to protect the display unit.

In the case of such a transparent case, an acrylic transparent plastic is used to protect the LCD window inside.

In addition, in PDA or mobile PC, etc., in order to protect the touch screen, the material on which the hard coating is applied is attached to the base material of the transparent material.

Here, the acrylic material mainly used in mobile phones is difficult to reduce in thickness, and the price or process is complicated. Various treatments are carried out in the post-process to protect them.

On the other hand, in the case of a hard coating treated on an existing PET material, a surface treatment such as modified acrylic or urethane is performed to increase the hardness of the surface, but in this case, the color of the film is changed to yellow depending on the surface treatment agent There is a problem. .

And, as a protective adhesive film, the film which has a hard-coat layer is used for the prevention of generation|occurrence|production and damage of a flaw on the surface, For example, the protective adhesive film etc. which implement|achieved high surface hardness by a specific layer structure are disclosed.

Here, the protective adhesive film has a high surface strength, but when the surface hardness is increased, cracks may easily occur in the hard coating portion, and cracks or breakage may occur during punching processing.

In addition, even in the case of a screen panel in which such scratches are difficult to occur, there is a problem in that the protective film is deteriorated with time due to long-term use or the protective film is damaged due to pressurization under excessive pressure.

(Patent Document 1) KR10-2015-0015906 A

In Patent Document 1, in the liquid crystal protective film for display protection for protecting the display of a smart device, a base layer formed of an acrylic plate to which a fluorescent dye is added, a hard coating layer laminated on the upper side of the base layer, and a hard coating layer containing ceramic particles; , a PET (Polyethylene Terephthalate) layer that is laminated on the lower side of the base layer and relieves the impact applied from the upper side of the base layer, and is laminated between the base layer and the PET layer, and the UV that laminates the base layer and the PET layer to each other (Ultraviolet) A liquid crystal protection film laminated on the lower side of the adhesive layer and the PET layer, and comprising an adhesive layer that adheres to the display of a smart device and silicone is disclosed.

However, even in such a conventional liquid crystal protective film, scratches are generated in the hard coating layer, and there is a problem in that cracks or breakage occurs during the punching process.

Therefore, the present invention is to solve the above-described problems, and the purpose is to laminate it through a glass plate or the like through an adhesive layer, and even when a thin panel is formed, scratches are difficult to occur, and cracks in the hard coating layer during processing An object of the present invention is to provide a method for manufacturing an abrasion-resistant liquid crystal protective film coated with a coating solution dispersed with a nano-ceramic material that is difficult to produce and has both adhesiveness and peelability.

The technical problems to be achieved in the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those of ordinary skill in the art to which the present invention belongs from the description below. will be able

As a specific means for achieving the above object, the present invention provides inorganic oxides of aluminum oxide, silicon dioxide, titania, and zirconium oxide, nano fillers, and photocatalyst additives to organic synthetic materials of oligomers and monomers. to prepare one binder; A coating solution in which a nano-ceramic material is dispersed is applied, comprising the steps of applying the binder to the surface of the base film and forming the coating layer 20 by irradiating UV with an amount of 400 to 600 mj/cm 2 to the base film to which the binder is applied Provided is a method for manufacturing an abrasion-resistant liquid crystal protective film.

Preferably, the binder is prepared by mixing an inorganic oxide and an organic synthetic material in a weight ratio selected from among 20:80, 30:70, 50:50, and 80:20% by weight, respectively, and then the additives of the nanofiller and the photocatalyst are added. It can be manufactured and manufactured.

Preferably, the monomer may be at least one selected from the group consisting of a hydroxyl group-containing polyfunctional (meth)acrylate and a fluorine-modified polyfunctional (meth)acrylate.

Preferably, the base film is a silicone adhesive, an organic-inorganic hybrid coating layer, a silicone adhesive, and a protective layer on the PET film to form a finished product of a film capable of protecting the liquid crystal.

Preferably, the organic synthetic material may be prepared by mixing the bifunctional Urethane Acrylate oligomer, the polyfunctional TMPTA and DPHA in a 4:3:3 wt% ratio.

Preferably, the coating layer of the composite binder of the organic synthetic fiber material and the inorganic oxide coated on the surface of the base film is a 5H high hardness abrasion-resistant organic/inorganic hybrid coating film with a transparent flexibility with a thickness of about 5-8 μm by UV curing and hot air drying treatment. can be formed.

According to the present invention as described above, there are the following effects.

(1) Since the coating layer of the liquid crystal protective film has the above-described configuration, it is difficult to generate scratches on the surface, and during processing, cracks are not easily generated in the hard coating layer, but also adhesiveness and peelability can be improved.

(2) In use, the visibility of the image display part due to the occurrence of scratches or peeling can be maintained properly, and there is an effect that parts can be easily separated during repair or recycling.

(3) In addition, the coating layer of the present invention has scratch resistance, antistatic properties, and ultra-high hardness properties of 5H or more, and the material has flexibility to avoid adverse effects on optical properties, thereby increasing product reliability. effect is obtained.

1 is a cross-sectional view schematically showing a coating layer coated with a coating solution in which a nano-ceramic material is dispersed in a liquid crystal protective film according to a preferred embodiment of the present invention.
2 is an enlarged cross-sectional view of a liquid crystal protective film according to a preferred embodiment of the present invention.

Hereinafter, with reference to the accompanying drawings, a preferred embodiment in which a person of ordinary skill in the art to which the present invention pertains can easily practice the present invention will be described in detail. However, in the detailed description of the structural principle of the preferred embodiment of the present invention, if it is determined that a detailed description of a related well-known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, the same reference numerals are used throughout the drawings for parts having similar functions and functions.

In addition, throughout the specification, when it is said that a part is 'connected' with another part, it is not only 'directly connected' but also 'indirectly connected' with another element interposed therebetween. include In addition, 'including' a certain component does not exclude other components unless otherwise stated, but means that other components may be further included.

As shown in FIGS. 1 and 2, the liquid crystal protective film 100 according to a preferred embodiment of the present invention is a UV-curing polymer-ceramic in which a nano-ceramic material is dispersed using a coating solution sol-gel process. Through pre-treatment, drying and special curing of the resin (Polymer-Ceramic Resin) during the manufacturing process, it is possible to maintain an ultra-high hardness of 5H or higher with excellent flexibility using the advantages of organic and inorganic materials through optimal curing of the UV resin.

Here, in the present invention, additives of aluminum oxide, silicon dioxide, titania, zirconium oxide, nano filler, and photocatalyst are added to an organic synthetic material of oligomers and monomers to form one binder, and then the binder is described After being coated on the surface of the film 10, the abrasion-resistant liquid crystal protective film 1 coated with the nano-ceramic material dispersion coating solution coated by irradiating UV with a light amount of 400 to 600 mj/cm 2 can be obtained.

Here, the base film 10 of the liquid crystal protective film 1 according to a preferred embodiment of the present invention is a coating layer 20 composed of a composite binder 40 of an organic synthetic material and an inorganic oxide 30 coated on the surface thereof. Including, this coating layer can form a high hardness, abrasion-resistant organic-inorganic composite coating film having a transparent flexibility of about 5-8㎛ thickness by UV curing and hot air drying (120 ℃ / 3 minutes) treatment.

Here, the binder may be prepared by mixing the inorganic oxide and the organic synthetic material in a weight ratio selected from among 20:80, 30:70, 50:50, and 80:20% by weight, respectively, and then adding a photocatalyst. .

Here, the monomer may be at least one selected from the group consisting of a hydroxyl group-containing polyfunctional (meth)acrylate and a fluorine-modified polyfunctional (meth)acrylate.

And, when including the monomer, the UV curable resin in the coating layer 20 is included in 32-56 wt%, the monomer is included in 10-35 wt%, and inorganic nanoparticles are included in 30-50 wt% and the additive of the photoinitiator may be included in an amount of 0.1-5% by weight.

Meanwhile, as the photoinitiator, a known photocatalyst that is conventionally used may be used.

For example, a compound of 1-hydroxycyclohexyl benzophenone (benzophenone-based) may be used, but is not limited thereto.

The photocatalyst may be included in an amount of 0.1-1.0 wt% based on the solid content of the coating layer including the ultraviolet curable resin, the inorganic nanoparticles surface-treated with (meth)acrylate, and the photocatalyst.

Within the above range, pencil hardness and scratch resistance properties are satisfied without hardening.

Here, it may be preferably included in an amount of 0.1-0.5 wt%.

On the other hand, the organic synthetic material can be prepared by mixing a bifunctional urethane acrylate oligomer, a polyfunctional trimethylolpropane triacrylate (TMPTA) and dipentaerythritol hexacrylate (DPHA) in a 4:3:3 wt% ratio.

In addition, a mixture of aluminum oxide, silicon dioxide, titania, and zirconium oxide may be used as the inorganic oxide.

Here, as the surface treatment agent of the inorganic oxide, a nano-filler may be selected.

In addition, the inorganic oxide was prepared by mixing tetraethyl orthosilicate (TEOS) and 3-methacryloxypropyltrimethoxysilane (MPTMS), a silane coupling agent, in a molar ratio of 1:2 or 2:1 by a sol-gel reaction.

Meanwhile, chemical changes of inorganic oxides and organic synthetic materials were analyzed by FT-IR and Si-NMR, and thermal analysis and surface shape of the coating layer were analyzed by TGA/DSC, SEM, and AFM.

Here, as the content of the inorganic oxide and the amount of the silane coupling agent increased, the molecular level miscibility was improved, and the pencil hardness and abrasion resistance were also improved.

The abrasion-resistant liquid crystal protective film using the organic-inorganic hybrid coating agent of the present invention can be formed as a base film by selecting any one of a cellulose ester-based resin, a polycarbonate-based resin, and a polyarylate-based resin.

And, in the present invention, the organic-inorganic hybrid coating layers 20 and 52 on the base film 10 of the liquid crystal protective film 1 can be formed.

Here, the thickness of the base film 10 may be 50 ~ 125㎛, it is preferable to form the thickness of the coating layer 20 to 5 ~ 8㎛.

On the other hand, the base film 10 of the liquid crystal protective film according to a preferred embodiment of the present invention is a silicone adhesive (18-30 μm) 51 on a PET film (25-75 μm) 50 as shown in FIG. 2 , An organic-inorganic hybrid coating layer (5-8㎛) (52), a silicone adhesive (3-10㎛) (53), a protective (25-75㎛) (54) can be formed in stages to protect the liquid crystal. It is a configuration that can make an organic-inorganic hybrid coating layer.

As described above, in the present invention, additives of aluminum oxide, silicon dioxide, titania, zirconium oxide, nanofiller, and photocatalyst are added to an organic synthetic material of oligomers and monomers to form one binder 40 , and then After the binder is applied to the surface of the base film 10, UV light of 400 to 600 mj/cm 2 is irradiated to obtain an organic-inorganic hybrid coating layer.

Therefore, the organic-inorganic hybrid coating layer of the present invention has the above-described configuration, and thus it is difficult to generate scratches on the surface, cracks hardly occur in the coating layer during processing, and has adhesiveness and peelability.

In addition, in use, the visibility of the image display unit due to the occurrence of scratches or peeling can be preferably maintained, and there is an effect that parts can be easily separated during repair or recycling.

In addition, the coating layer of the present invention has a scratch resistance, antistatic property, and an ultra-high hardness of 5H or higher, and the material is flexible to avoid adversely affecting the optical properties.

The above description of the present invention is for illustration, and those of ordinary skill in the art to which the present invention pertains can understand that it 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 likewise components described as distributed may be implemented in a combined form.

1: LCD protective film
10: base film
20: coating layer
30: inorganic oxide
40: binder
50: PET film
51: silicone adhesive
52: coating layer
53: silicone adhesive
54: protective film

Claims (7)

preparing a binder by adding an inorganic oxide 30 of aluminum oxide, silicon dioxide, titania, and zirconium oxide, a nanofiller, and a photocatalyst to an organic synthetic material;
applying the binder to the surface of the base film; and
Forming an organic-inorganic hybrid coating layer by irradiating the base film coated with the binder with UV of 400 to 600 mj/cm 2 light,
The organic synthetic material is prepared by mixing a bifunctional urethane acrylate oligomer, a polyfunctional trimethylolpropane triacrylate (TMPTA), and a dipentaerythritol hexacrylate (DPHA),
The nanofiller is a surface treatment agent for inorganic oxide mixed with Tetraethyl orthosilicate (TEOS) and MPTMS (3-methacryloxypropyltrimethoxysilane) as a sily coupling agent,

The inorganic oxide and the organic synthetic material are mixed in a weight ratio selected from any one of 50:50 and 80:20% by weight,
The base film has a silicone adhesive formed on the PET film,
The organic-inorganic hybrid coating layer includes an inorganic oxide surface-treated with the nano-filler,
The organic-inorganic hybrid coating layer has a thickness of 5-8㎛, has transparent flexibility, and has a high hardness of pencil hardness of 5H A method of manufacturing a wear-resistant liquid crystal protective film coated with a coating solution dispersed with nano-ceramic materials.
delete delete According to claim 1,
The PET film of the base film has a thickness of 25-75 μm, the silicone adhesive has a thickness of 18-30 μm, the organic-inorganic hybrid coating layer has a thickness of 5-8 μm, and the silicone adhesive has a thickness of 3-10 μm, The protective is a method of manufacturing a wear-resistant liquid crystal protective film coated with a coating solution in which the nano-ceramic material is dispersed, characterized in that the thickness is 25 ~ 75㎛.
According to claim 1,
The organic synthetic material is prepared by mixing a bifunctional urethane acrylate oligomer, polyfunctional TMPTA, and DPHA in a 4:3:3 wt% ratio. A method of manufacturing an abrasion-resistant liquid crystal protective film.
delete A base film with a thickness of 25 to 75 μm, a silicone adhesive with a thickness of 18 to 30 μm, an organic-inorganic hybrid coating layer with a thickness of 5 to 8 μm, a silicone adhesive with a thickness of 3 to 10 μm ?? Protectives with a thickness of 25~75㎛ are stacked one after another,
The base film is a PET film,
The organic-inorganic hybrid coating layer is formed by the method of claim 1, claim 4 or claim 5,
The organic-inorganic hybrid coating layer is a liquid crystal protective film, characterized in that it has a transparent flexibility and a pencil strength of 5H.

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