KR100553314B1 - Composites containing fluorinated core-shell particles for Front Display Panel, and Manufacturing method thereof - Google Patents

Abstract

The present invention relates to a fluorine-based composite material for a flat panel display panel containing a core-cell-type fluorine-based polymer particles and a method for manufacturing the same, and more particularly, to form a core by siloxane bond of an inorganic particle and an azo chloride compound, The core-cell-type fluorine-based polymer particles in which a cell is formed by polymerizing a specific fluorine-based polymer compound on the surface thereof are prepared, and the core-cell-type fluorine-based polymer particles and the transparent polymer compound are prepared by dispersion polymerization in a predetermined content range. The present invention relates to a fluorine-based composite material for a flat panel display panel (FDP) having various functions such as water repellency and oil repellency, hard coating, antireflection, contamination and fingerprint prevention, and a method of manufacturing the same.

Inorganic particles, core-cell type fluorine-based polymer particles, flat panel display panel (FDP), fluorine-based composite materials

Description

Fluorine-based composite material for flat panel display panel containing core-cell type fluorine-based polymer particles and manufacturing method thereof {Composites containing fluorinated core-shell particles for Front Display Panel, and Manufacturing method}

1 illustrates a process of forming a layer of a flat panel display panel using a fluorine-based composite material prepared according to the present invention.

The present invention relates to a fluorine-based composite material for a flat panel display panel containing a core-cell-type fluorine-based polymer particles and a method for manufacturing the same, and more particularly, to form a core by siloxane bond of an inorganic particle and an azo chloride compound, The core-cell-type fluorine-based polymer particles in which a cell is formed by polymerizing a specific fluorine-based polymer compound on the surface thereof are prepared, and the core-cell-type fluorine-based polymer particles and the transparent polymer compound are prepared by dispersion polymerization in a predetermined content range. The present invention relates to a fluorine-based composite material for a flat panel display panel (FDP) having various functions such as water repellency and oil repellency, hard coating, antireflection, contamination and fingerprint prevention, and a method of manufacturing the same.

In general, perfluorine-containing compounds have functionality such as water and oil repellency, chemical resistance, lubricity, mold release property and antifouling property due to very low surface energy. With this functionality, the compound is used in the manufacture of everyday life products such as oil repellents in the paper industry, functional repellent cosmetics in the cosmetics industry, and water and oil repellents in the textile and leather industries. In addition, the range of application is very wide such as corrosion prevention of metal materials, automotive exterior coating and precision release technology in polymer processing.

On the other hand, the structure of a display device such as a liquid crystal display device that is rapidly increasing in recent years is composed of the following several functional layers. First, the hard coating layer for protecting and flattening the liquid crystal on the surface of the display panel, the antireflection layer for dispersing the surface reflection light and suppressing the specular reflection of external light to prevent contamination and removal from fingerprints or foreign matters It consists of layers with various functions such as contamination and anti-fingerprint layers, and an anti-fog layer that improves visibility by preventing blur from the display panel.

Looking at the structure of the optical film used in the flat panel display panel (FDP) used in computers, televisions, mobile phones, etc. of the display devices, first, the liquid crystal or polarizing layer, the hard coating layer for protecting and flattening the liquid crystal, and the clear image quality It consists of an antireflection layer to provide, and an antifouling layer to prevent surface contamination. However, in the state of the art, the antireflection layer has a multi-layered structure of inorganic fine particles having a very high hydrophilic property, so that it is easily contaminated during use and is not easy to remove contaminants. If removed, there is a problem that causes damage to the display surface. In addition, the current manufacturing process of the hard coating layer, anti-reflection layer, anti-fog layer and contamination and fingerprint layer of the liquid crystal display consists of a layer of each different material and a complicated process for this has a problem that takes a lot of time and expense .

Accordingly, the present inventors have made efforts to solve the problems of the complexity and antifouling function of the display device process, as a result, to form a core by the siloxane bond of inorganic particles and azo chloride silane compound, a specific fluorine-based Core-cell-type fluorine-based polymer particles, in which polymer compounds are polymerized to form cells, and the core-cell-type fluorine-based polymer particles and transparent polymer compounds are dispersed and polymerized in a predetermined amount, so that excellent reflection and low reflection due to the surface irregularities of the inorganic particles The present invention has been completed by knowing that the fluorine-based polymer compound having a reflective effect and a low surface energy and a low refractive index has functions of water repellency, oil repellency, water repellency, and antifouling property.

Accordingly, an object of the present invention is to provide a core-cell type fluorine-based polymer particle having both diffuse reflection, low reflection effect, and water / oil repellency, water repellency, and antifouling properties.                         

In addition, the present invention is a fluorine-based composite material for a flat panel display panel having various functions such as hard coating, antireflection, contamination and fingerprint prevention in a series of single processes for polymerizing core-cell type fluorine-based polymer particles and a transparent polymer compound, and the preparation thereof. The purpose is to provide a method.

The present invention is characterized by core-cell type fluorine-based polymer particles in which an inorganic particle in which an azo chloride compound is fixed forms a core, and a fluorine-based polymer compound selected from the compounds represented by the following Formulas 1a to 1d forms a cell. .

[Formula 1a]

XC _n F _2n CH ₂ OCOCR ₁ = CH ₂

[Formula 1b]

XC _n F _2n SO ₂ NR ₂ (CH ₂ ) _m OCOCR ₁ = CH ₂

[Formula 1c]

XC _n F _2n CH ₂ CH (OH) (CH ₂ ) _m OCOCR ₁ = CH ₂

[Formula 1d]

XC _n F _2n (CH ₂ ) _m OCOCR ₁ = CH ₂

In Formulas 1a to 1d, R ₁ is H or —CH ₃ , R ₂ is a C ₁ to C ₁₀ alkyl group, X is H, F or Cl, m is an integer of 2 to 6, n is 3 to Is an integer of 21.

In addition, the present invention has another feature of the fluorine-based composite material for a flat panel display panel and the manufacturing method thereof comprising 10 to 50% by weight of the core-cell-type fluorine-based polymer particles and 50 to 90% by weight of the transparent polymer compound.

Hereinafter, the present invention will be described in more detail.

In the present invention, a core is formed by siloxane bond of an inorganic particle and an azo chloride compound, and a core-cell fluorine polymer is formed by polymerizing a fluorine polymer compound selected from the compounds represented by Formulas 1a to 1d on the surface of the core to form a cell. The particles and the transparent polymer compound form a composite material by dispersion polymerization, and during dispersion polymerization, a layer is formed by using the surface migration property of the perfluorine group containing the core-cell type fluorine-based polymer particles. The present invention relates to a novel fluorine-based composite material having various functions such as hard coating, fingerprint, antireflection, and contamination required for water and oil repellency, antifouling property, and flat panel display panel by performing a series of single processes as described above.

The present invention relates to a core-cell type fluorine-based polymer particle composed of inorganic particles to which the azo chloride compound is fixed, and a fluorine-based polymer compound selected from the compounds represented by Formulas 1a to 1d, and a transparent polymer compound. As a feature of the configuration, the conventional fluorine-based composite material of the present invention is capable of performing several functions simultaneously in a single process, whereas the manufacturing process of the optical film of the conventional flat panel display panel is composed of several different functional layers.

Looking at the manufacturing method of the core-cell-type fluorine-based polymer particles of the present invention in more detail as follows.

First, the inorganic particles and the azo-based silane compound are siloxane bonds in a weight ratio of 60/40 to 90/10 to form a core. The inorganic particles have an average particle size of 7 nm to 3 μm, and may be used, for example, one or two or more selected from silica, alumina, titanium oxide, zinc oxide, cerium oxide, copper oxide, nickel oxide, and zirconium oxide. have. These inorganic particles form irregularities on the surface of the composite material to be produced to have excellent effects of diffuse reflection, low reflection, and mechanical properties, and are chemically very stable by siloxane bonds with the azo chloride compound. There is a characteristic. When the average particle size of the inorganic particles is less than 7 nm, the particles are not dispersed and agglomerate with each other, and when the average particle size exceeds 3 μm, sedimentation occurs easily, resulting in poor storage stability and workability. The azo chloride compound is a known one, for example one or two selected from azo monosilane (AMS), azo disilane (ADS) and azo trisilane (ATS). The above can be used. When the azo-based silane chloride compound is less than the above range does not adhere to the inorganic particles, there is a problem in forming a core-cell type. If the azo-based silane chloride compound exceeds the range, the reaction does not proceed any more, so only an additional cost is generated.

Next, the core-cell-type fluorine-based polymer particles are formed by radically polymerizing the core formed above and the fluorine-based polymer compound selected from 1 to 4 compounds represented by Chemical Formula 1 at 50-90 ° C. at a 10/90 to 50/50 weight ratio. Manufacture.

The fluorine-based polymer compound is represented by Chemical Formulas 1a to 1d, and XC _n F _2n CH ₂ OCOCR ₁ = CH ₂ , XC _n F _2n SO ₂ NR ₂ (CH ₂ ) _m OCOCR ₁ = CH ₂ , XC _n F _2n CH ₂ CH (OH) (CH ₂ ) _m OCOCR ₁ = CH ₂ and XC _n F _2n (CH ₂ ) _m OCOCR ₁ = CH ₂ may be selected. The fluorine-based polymer compound containing the perfluorine group has low surface energy and low refractive index, and thus exhibits water repellency, oil repellency, water repellency, and antifouling properties, and in particular, forms a layer by using the surface shiftability of the perfluorinated alkyl group included in the polymer. It is possible to manufacture a composite material used in a flat panel display panel in a single process. If the amount of the inorganic particles and the fluorine-based polymer compound to which the azo chloride compound is fixed is outside the above range, there is a problem that the fluorine-based polymer compound is not sufficiently polymerized on the surface of the inorganic particles to which the azo-chloride silane compound is fixed. The reaction is carried out by a known radical polymerization, if the reaction temperature is less than 50 ℃ takes a lot of reaction time, if it exceeds 90 ℃ problems occur difficult to control the reaction.

Next, the core-cell type fluorine-based polymer particles and the transparent polymer formed by the radical polymerization are added to a mixture of a fluorine-based organic solvent and a hydrocarbon-based organic solvent for dispersion polymerization. The transparent polymer may use one or two or more selected from acrylate or methacrylate monomers, low density polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, and polymethylpentene, and the acrylate or methacryl As a monomer type, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, ethyl hexyl (meth) acrylate, octyl (meth) acrylate Lauryl (meth) acrylate, octadecyl (meth) acrylate, glycidyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, Cyclohexyl (meth) acrylate, 2-hydroxy (meth) acrylate, 2-hydroxypropyl (meth) acrylate, It can be. The core-cell-type fluorine-based polymer particles and the transparent polymer are used in a mixture of 10/90 to 50/50 weight ratio, and when the amount of the core-cell-type fluorine-based polymer particles is less than 10 weight ratio, the effect of internal scattering is small, and the contact angle and the surface free energy are used. The surface characteristics of the back light deteriorate, and when the weight ratio exceeds 50, optical properties such as transmittance and haze deteriorate. The solvent in which the core-cell type fluorine-based polymer particles and the transparent polymer are dissolved may be used by mixing a fluorine-based organic solvent and a hydrocarbon-based organic solvent, and the fluorine-based organic solvent may be 1,2,2, -trichloro-1,1,2- One or two selected from trifluoroethane, trifluoroethanol and trifluoromethoxytoluene may be used, and the hydrocarbon-based organic solvent is used for general polymerization, for example, ethanol, isopropanol, methyl ethyl ketone, tetra Hydrofuran and chloroform may be selected, and more preferably chloroform. Preferably, the fluorine-based organic solvent and the organic solvent are mixed and used in a 70/30 to 30/70 weight ratio, and when the ratio of the mixed solvent is out of the range, transparent polymer precipitates or dispersion stability of core-shell fluorine-based polymer particles. This falling problem occurs.

Next, the core-cell type fluorine-based polymer particles and the transparent polymer, which have been dispersed and polymerized above, are solvent cast at a temperature of 10 to 40 ° C. for 1 to 24 hours, followed by annealing at 100 to 160 ° C. to form a fluorine-based composite material. Manufacture.

The fluorine-based composite material prepared according to the present invention has various functions such as hard coating, antireflection, contamination and fingerprint prevention at the same time in a series of single processes, and thus is suitable for flat panel display panels.

Hereinafter, the present invention will be described in more detail with reference to the following Examples, but the present invention is not limited thereto.

Synthesis Example 1

In a 250 ml tubular Schrank glass reactor, 3 g of silica particles with an average particle size of 12 nm, 50 g of dried toluene and 1 g of triethylamine (TEA) were charged. 1 g of azo chloride silane initiator 4,4-azobis- (4-cyanopentanoic acid- (3-chlorodimethylsilyl) propyl ester is dissolved in 10 mL of dried toluene, and then charged into the reactor and sealed. After removing the gas inside the silica particles, the self-assembled initiator attachment reaction is carried out at room temperature for 1 day, after which the siloxane bond is formed by chemical immobilization on the surface of the silica particles and taken out of the reactor. Wash with toluene, methanol and acetone to remove salts formed after reaction with the initiator.

The dried porous silica support was dried at room temperature, and then placed in a 250 mL tubular Schrank glass reactor, 50 g of C ₈ F ₁₇ C ₂ H ₄ OCOCH = CH ₂ was added, and the reaction was performed for 3 hours in a 60 ° C thermostat. Proceeded. The free polymer remaining after the reaction is washed by Soxhlet extraction using 1,1,2-trichloro-1,2,2-trifluoroethane (R-113).

Synthesis Example 2

In the same manner as in Synthesis Example 1, the reaction was performed using silica particles having an average particle size of 1 μm to synthesize fluorine-based polymer particles.

Example 1

250 ml of R-113 and 100 g of chloroform were added to a glass reactor. 0.3 g of PFA / Silica composite (prepared in Synthesis Example 1) and 0.3 g of polymethyl methacrylate (PMMA) were respectively added. And dispersed. 2 ml of the above dispersed solution was solvent cast on a slide glass at room temperature for 24 hours, and the prepared film was annealed at 120 ° C. for 24 hours. The physical properties of the fluorine-based composite material prepared by the reaction are measured and shown in Table 1 below.

Example 2

The reaction was carried out in the same manner as in Example 1, using 0.6 g of polymethyl methacrylate. The physical properties of the fluorine-based composite material prepared by the reaction are measured and shown in Table 1 below.

Example 3

The reaction was carried out in the same manner as in Example 1, using 0.9 g of polymethyl methacrylate. The physical properties of the fluorine-based composite material prepared by the reaction are measured and shown in Table 1 below.

Example 4

In the same manner as in Example 1, the reaction was performed using 0.04 g of PFA / Silica complex. The physical properties of the fluorine-based composite material prepared by the reaction are measured and shown in Table 1 below.

Example 5

In the same manner as in Example 1, the reaction was performed using 0.1 g of the PFA / Silica complex. The physical properties of the fluorine-based composite material prepared by the reaction are measured and shown in Table 1 below.

Example 6

The reaction was carried out in the same manner as in Example 1, but using 0.1 g of PFA / Silica composite of Synthesis Example 2 and 0.3 g of polymethylmethacrylate. The physical properties of the fluorine-based composite material prepared by the reaction are measured and shown in Table 1 below.

Comparative Example 1

In the same manner as in Example 1, but after the solvent cast, the reaction was carried out without heating and cooling (annealing). The physical properties of the composite material prepared by the reaction are measured and shown in Table 1 below.

Comparative Example 2

0.15 g of the PFA / Silica complex was dissolved in 100 g of R-113, 2 ml of the solvent was cast in a slide glass at room temperature for 24 hours, and then 0.15 g of polymethyl methacrylate (PMMA) was dissolved in 100 g of chloroform. 2 ml of the PFA / Silica composite was cast on a film cast for 24 hours at room temperature, and then the film was annealed at 120 ° C. for 24 hours. The physical properties of the composite material prepared by the reaction was measured and shown in Table 1 below.

Comparative Example 3

The reaction was carried out in the same manner as in Comparative Example 2, using 0.30 g of polymethyl methacrylate (PMMA). The physical properties of the composite material prepared by the reaction was measured and shown in Table 1 below.

Comparative Example 4

In the same manner as in Comparative Example 2, but the reaction was carried out using 0.45 g of polymethyl methacrylate (PMMA). The physical properties of the composite material prepared by the reaction was measured and shown in Table 1 below.

Comparative Example 5

0.30 g of polymethyl methacrylate (PMMA) was dissolved in 100 g of chloroform, and 2 ml of the solvent was cast at room temperature for 24 hours, followed by annealing at 120 DEG C for 24 hours. The physical properties of the composite material prepared by the reaction was measured and shown in Table 1 below.

division Permeability (%) Haze (%) Contact angle (°) Surface free energy (dyn / cm) Fingerprint odor Distilled water Diiodo methane Example 1 93.0 5.5 104.9 74.1 20.6 0 Example 2 92.3 18.8 114.3 88.9 13.2 △ Example 3 92.5 14.7 113.4 90.6 12.5 △ Example 4 92.9 5.6 112.6 89.5 13.0 0 Example 5 92.2 8.4 112.0 90.3 12.7 0 Example 6 92.9 5.5 114.9 90.1 12.7 0 Comparative Example 1 91.6 12.6 99.8 67.4 24.4 △ Comparative Example 2 91.1 47.6 112.1 74.7 20.6 △ Comparative Example 3 90.0 41.5 109.6 72.7 21.5 △ Comparative Example 4 90.5 29.2 96.7 46.7 28.2 △ Comparative Example 5 93.0 1.11  79.2 38.7 41.4  ×

[Measurement of physical properties]

1.Haze and transmittance measurement

Haze and total light transmittance were measured using BYK-Gardner HB-4725. The measurements were then directed to the detector direction and taken at three different points to take an average value. As one of the methods of evaluating the transparency of a film, high transmittance | permeability and low haze show favorable transparency.

2. Contact angle measurement

The contact angle was measured using a Goniometer (Rame-Hart 100-series) equipped with an illuminator using two types of contact liquids such as water and diiodomethane at 25 ± 1 ° C. The measurements were made at five different points with droplets of 2 mm in diameter, and the average was recorded.

3. Surface free energy

Surface free energy is apparent by using contact angles obtained using water (H ₂ O) and diiodomethane (CH ₂ I ₂ ) and geometric mean approximations of Equation 1 below. The energy was calculated.

4. Measurement of contamination and fingerprint prevention

The index finger was used for 5 seconds to leave the fingerprint on the surface of the film to evaluate the ease of wiping the fingerprint with a dry cloth. If the fingerprint is easily wiped, it is easy to wipe well, and it is difficult to wipe, but if no trace remains, it is marked as △.

As shown in Table 1, the composite materials of Examples 1 to 6 according to the present invention was found to be superior to the transmittance, haze, anti-fingerprint, water repellency and oil repellency than Comparative Examples 1 to 5. Although there exist some items which show the numerical value better than an Example among the physical property data of Comparative Examples 1-5, it was confirmed that all the physical properties do not improve at the same time.

As described above, the fluorine-based composite material prepared according to the present invention is water repellent by a fluorine compound having the characteristics of low refractive index and diffuse reflection effect, low reflection effect, low surface energy characteristics with fine concavo-convex structure on the surface by inorganic particles It is economically advantageous to manufacture a fluorine-based composite material having a variety of functions that are widely used in flat panel display panels of displays such as mobile communication devices or monitors at the same time as having properties such as oil repellency, water repellency, and antifouling properties.

Claims (10)

delete delete delete delete 10 to 50% by weight of the core-cell fluorine-based polymer particles in which the inorganic particles to which the azo chloride silane compound is fixed form a core, and the fluorine-based polymer compound selected from the compounds represented by the following Chemical Formulas 1a to 1d forms a cell; A fluorine-based composite material, characterized in that it comprises 50 to 90% by weight of the transparent polymer compound. [Formula 1a] XC _n F _2n CH ₂ OCOCR ₁ = CH ₂ [Formula 1b] XC _n F _2n SO ₂ NR ₂ (CH ₂ ) _m OCOCR ₁ = CH ₂ [Formula 1c] XC _n F _2n CH ₂ CH (OH) (CH ₂ ) _m OCOCR ₁ = CH ₂ [Formula 1d] XC _n F _2n (CH ₂ ) _m OCOCR ₁ = CH ₂ In Formulas 1a to 1d, R ₁ is H or —CH ₃ , R ₂ is a C ₁ to C ₁₀ alkyl group, X is H, F or Cl, m is an integer of 2 to 6, n is 3 to Is an integer of 21. The method of claim 5, wherein the inorganic particles are one or two or more selected from silica, alumina, titanium oxide, zinc oxide, cerium oxide, copper oxide, nickel oxide, and zirconium oxide, and the average particle size is 7 nm to 3 µm. Fluorine-based composite material, characterized in that. 6. The fluorine-based compound according to claim 5, wherein the transparent polymer compound is at least one selected from acrylate or methacrylate monomers, low density polyethylene, polypropylene, polyethylene terephthalate, polycarbonate and polymethylpentene. Composite materials. Reacting an inorganic particle having an average particle size of 7 nm to 3 μm with an azo chloride compound to form a core forming a siloxane bond; Preparing a core-cell type fluorine-based polymer particle by radically polymerizing the formed core with a fluorine-based polymer compound selected from the compounds represented by Formulas 1a to 1d at a temperature of 50 to 90 ° C .; Dispersing and polymerizing the core-cell type fluorine-based polymer particle and the transparent polymer compound; And Solvent casting the polymer polymer at a temperature of 10 to 40 ℃, for 1 to 24 hours, and annealing at 100 to 160 ℃ temperature Method for producing a fluorine-based composite material, characterized in that comprises: [Formula 1a] XC _n F _2n CH ₂ OCOCR ₁ = CH ₂ [Formula 1b] XC _n F _2n SO ₂ NR ₂ (CH ₂ ) _m OCOCR ₁ = CH ₂ [Formula 1c] XC _n F _2n CH ₂ CH (OH) (CH ₂ ) _m OCOCR ₁ = CH ₂ [Formula 1d] XC _n F _2n (CH ₂ ) _m OCOCR ₁ = CH ₂ In Formulas 1a to 1d, R ₁ is H or —CH ₃ , R ₂ is a C ₁ to C ₁₀ alkyl group, X is H, F or Cl, m is an integer of 2 to 6, n is 3 to Is an integer of 21. The method of manufacturing a fluorine-based composite material according to claim 8, wherein a solvent in which the fluorine-based organic solvent and the hydrocarbon-based organic solvent are mixed in a weight ratio of 70/30 to 30/70 is used in the dispersion polymerization. The fluorine-based composite material according to claim 5, wherein the azo chloride compound is at least one selected from azo monosilane (AMS), azo disilane (ADS) and azo trisilane (ATS).

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