KR20090096020A - Organic-inorganic hybrid resin composition, manufacturing method thereof and manufacturing method of optical film using the same - Google Patents

Abstract

An organic and inorganic hybrid resin composition, its preparation method, and an organic and inorganic hybrid resin are provided to lower a coefficient of thermal expansion and to improve optical characteristic without the deterioration of the transparency of a film. An organic and inorganic hybrid resin composition comprises 5-90 wt% of a silica sol whose surface is modified with an epoxy functional group or an amine functional group; 10-90 wt% of a polycarbonate-based or epoxy-based polymer system; and a solvent. The silica sol is prepared by reacting a silane compound represented by the formula I, or a mixture of the silane compound represented by the formula I and a silane compound represented by the formula II, wherein at least one of R1, R2, R3 and R4 is an organic substituent having an epoxy group or an amine group, and the rest are independently OH or a C1-10 alkoxy group; and at least one of R5, R6, R7 and R8 is OH or a C1-10 alkoxy group, and the rest are independently a C1~10 alkyl group, a C6~20 arylene group, a C1~10 alkyl C6~20 arylene group or a C6~20 aryl C1~10 alkylene group.

Description

ORGANIC-INORGANIC HYBRID RESIN COMPOSITION, MANUFACTURING METHOD THEREOF AND MANUFACTURING METHOD OF OPTICAL FILM USING THE SAME}

The present invention relates to an organic-inorganic hybrid resin composition that can be used as a plastic substrate material, a method for manufacturing the same, and a method for manufacturing an optical film for a plastic substrate using the same. More specifically, the inorganic filler is uniformly dispersed in the polymer matrix and the coefficient of thermal expansion It is related with the organic-inorganic hybrid resin composition which is low and excellent translucent, the manufacturing method, and the optical film for plastic substrates using the same.

Plastic substrate material is a key material for next-generation displays and organic solar cell substrates such as plastic flat panel displays and flexible displays, and is expected to generate demand in the future.

However, since plastic substrate materials are more vulnerable to thermal properties, chemical resistance, gas barrier properties, and flatness than glass substrates, high light transmittance, dimensional stability, low thermal expansion coefficient and durability ( In particular, improvements in physical properties such as bendable reliability), rigidity and chemical resistance, thermal properties, and gas barrier properties are required.

In order to satisfy such various characteristics, recently, a plastic substrate using an inorganic barrier layer, an undercoat layer, and an overcoat layer on both sides of a bare optical film, a transparent optical film. Is being developed.

Among these, the bare film is a core substrate material that determines the optical properties such as thermal processing temperature of the substrate material, coefficient of thermal expansion (CTE), optical properties such as transparency and birefringence, and mechanical strength. polyethersulphone (PES), polyethylene terephthalate (PET), polyimide (PI), polyarylate (PAR), polyethylene naphthalate (PEN), polycarbonate (PC), etc. The same polymer film is used.

Until recently, technology development of substrate materials has been focused on improving the glass transition temperature of the bare film material, which determines the gas barrier properties of the barrier layer and the substrate process temperature.

However, in the case of the barrier properties, it has been reported that the level of the barrier properties has recently been improved to the level that satisfies the requirements of the organic light emitting diode (OLED).

In the case of process temperature, amorphous silicon-TFT process temperature is generally around 350 ° C, but currently the process temperature of plastic LCD has been reported to decrease to 150 ° C. Recently, Samsung Electronics developed a 5-inch and 7-inch TFT-LCD module based on a plastic substrate using a 130 ° C process, and expects the process temperature to drop below 100 ° C.

However, even if the gas barrier property is secured and the substrate process temperature is lower than the glass transition temperature of the plastic, not all problems for implementing the flexible substrate are solved.

Current TFT processes have been developed for borosilicate glass with a coefficient of thermal expansion of 4 ppm / ° C, but very high thermal expansion coefficients for isotropic transparent films. Therefore, in the case of a substrate material having a high coefficient of thermal expansion, a misalignment is generated between pixels due to temperature change during the process, and thus, a TFT-array is required. Dimensional stability is not secured.

In addition, in the plastic substrate having a multi-layered thin film structure having different physical properties, the thermal expansion coefficient difference between the interlayer materials (polymer and inorganic material) is large, so that thermal stress occurs at the interface during heating / cooling, causing cracking and Peeling takes place. This is difficult to maintain the gas barrier characteristics of the substrate after processing, serious degradation of the durability and reliability of the substrate. The problem caused by such a high coefficient of thermal expansion is the biggest obstacle to the application of the flexible display, which is a technical problem that needs to be taken in advance for practical use of the plastic substrate in the future.

The present inventors have solved the above problems and proposed a method of mixing an inorganic filler having a low thermal expansion coefficient with a polymer composition forming a bare film in order to reduce the thermal expansion coefficient of a plastic substrate.

As such, when the bare film is manufactured using the mixture of the polymer and the inorganic filler, an effect of reducing the thermal expansion coefficient of the plastic substrate may be obtained. However, in the case of the conventional inorganic filler, the size of the primary particles (nm) primary particles (primary particles), but the primary particles (primary particles) are actually agglomerate, it is difficult to produce particles below the submicron meter (polymer) Since compatibility with the matrix is limited, there is a problem that the inorganic fillers are not uniformly dispersed in the polymer matrix and are aggregated together. Thus, when an inorganic filler aggregates, the problem that the optical characteristic of a film falls is produced.

Therefore, in order to obtain excellent thermal properties without losing optical properties, in particular transparency, of the film, it is required that the added inorganic filler be uniformly dispersed in the polymer matrix.

Accordingly, the present inventors provide an organic-inorganic hybrid resin in which silica is uniformly dispersed in the polymer matrix by mixing a silica sol surface-modified with an epoxy functional group or an amine functional group with a polymer system to form a matrix of a substrate. The object of this invention is to be able to manufacture the optical film for plastic substrates which is excellent in an optical characteristic.

In order to achieve the above object, the present invention is 5 to 90% by weight silica sol surface-modified with an epoxy functional group or an amine functional group; 10 to 90 weight percent of a polycarbonate-based or epoxy-based polymer system; And it provides an organic-inorganic hybrid resin composition comprising a residual solvent.

In addition, the present invention is a step of forming a silica sol by dissolving a silane compound of formula (I) or a mixture of a silane compound represented by formula (I) and a silane compound represented by formula (II) in a solvent and then reacting under an acid or base catalyst ; Preparing a polymer solution by dissolving a polycarbonate-based or epoxy-based polymer system in a solvent; It provides a method for producing an organic-inorganic hybrid resin composition comprising the step of preparing a mixed solution by mixing the silica sol and the polymer solution.

[Formula I]

Wherein R, R _1, R _2, R ₃ and R ₄ at least one is an organic substituent with an epoxy group or an amine, and the other is a hydroxy group and C ₁ are each independently _is selected from the group consisting of _10-alkoxy groups.

[Formula II]

Wherein R, R _5, R _6, R ₇ and R _8, at least one of a hydroxy group or C _{1 -10} alkoxy group, the remains are each independently C _{1 ~ 10} alkyl, C _{6 ~ 20} arylene, alkyl arylene, and Aryl alkylene.

In addition, the present invention comprises the steps of coating the organic-inorganic hybrid resin composition prepared by the above method on a substrate to produce a film; Drying the film; It provides a method for producing an optical film for a plastic substrate comprising the step of concurrently performing the thermal curing of the dried film and the silica sol condensation polymerization.

The present invention has the effect of reducing the coefficient of thermal expansion by adding the inorganic filler silica to the polymer matrix.

In addition, the present invention by dissolving and mixing the sol silica and the polymer system to form a matrix of the substrate in a solvent, so that the silica particles can be uniformly dispersed in the polymer matrix, and as a result has a low thermal expansion coefficient and light transmission It was made possible to manufacture this excellent optical film for plastic substrates.

In addition, the present invention has the effect of improving the interfacial adhesion with the matrix by imparting an epoxy functional group on the silica surface and allowing the functional group to react with the polymer matrix. In addition, by providing the same functional group on the silica surface and the polymer matrix, the effect of improving the compatibility of the silica and the polymer matrix.

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

In the present invention, the inorganic fillers added in order to reduce the coefficient of thermal expansion of the polymer resin in the conventional invention are prevented from agglomerating or incompatibility with the polymer to prevent phase separation, and the inorganic filler can be uniformly dispersed in the polymer matrix. To this end, a silica sol solution is prepared by dissolving sol silica in a solvent, and mixed with a polymer solution to form a matrix to prepare an organic-inorganic hybrid resin composition, whereby an organic-inorganic hybrid in which silica is uniformly dispersed in a polymer matrix. It provides a resin composition. When manufacturing an optical film using such an organic-inorganic hybrid resin composition of this invention, the optical film with a low thermal expansion coefficient and excellent light transmittance can be obtained.

In addition, the present invention is characterized by providing an epoxy functional group or an amine functional group on the surface of the silica, so that these functional groups react with the epoxy functional group contained in the polymer, thereby improving the interfacial adhesion between the polymer matrix and the inorganic filler. .

Organic weapons hybrid  Resin composition

Such organic-inorganic hybrid resin composition of the present invention is 5 to 90% by weight silica sol surface-modified with an epoxy functional group or an amine functional group; It comprises 10 to 90% by weight of polycarbonate or epoxy polymer system and the balance of the solvent.

The silica sol is added to reduce the coefficient of thermal expansion of the transparent polymer resin, and reacts silane compounds having an epoxy functional group or an amine functional group, or a mixture of a silane compound having an epoxy functional group or an amine functional group and another silane compound. Can be prepared by reacting them.

More specifically, the silica sol may be prepared by reacting the silane compounds at a reaction temperature of room temperature to 60 ° C. for 2 to 48 hours under an acid or base catalyst.

It is preferable that the silane compound which has the said epoxy functional group or amine functional group is a compound represented by following formula (I).

[Formula I]

The above formula, R _1, R _2, R ₃ and R ₄ at least one is an organic substituent with an epoxy group or an amine group, the others are each independently selected from the group consisting of a hydroxy group or C _{1 -10} alkoxy.

Examples of the silane compound represented by Chemical Formula I include compounds represented by the following Chemical Formula III.

[Formula III]

In this formula, n is an integer of 1 to 10.

On the other hand, examples of the other silane compound, ie, a silane compound having no epoxy functional group or amine functional group, include compounds represented by the following general formula (II).

[Formula II]

Wherein R, R _5, R _6, R ₇ and R ₈ are at least one of a hydroxy group or C _{1 -10} alkoxy group, and the other is independently a C _{1 ~ 10} alkyl, C _{6 ~ 20} arylene, C _{1 ~ 10} each alkyl, C _{6 ~ 20} arylene and C _{6 ~} C ₂₀ aryl group is selected from the group consisting of alkylene _{of 1 to 10.}

Specific examples of the silane compound represented by Formula II include a silane compound represented by Formula IV below.

[Formula IV]

The content of the silica sol prepared from the above silane compound is preferably about 5 to 90% by weight. If the content of the silica sol is less than 5% by weight, the effect of improving thermal expansion properties is not sufficient, and if the content of the sol is 90% by weight or more, it is not easy to manufacture a flexible film.

Meanwhile, the polymer system is preferably a polycarbonate polymer system or an epoxy polymer system.

First, as the polycarbonate-based polymer system, polycarbonate may be used alone, or a polycarbonate and a monomer or oligomer having an epoxy functional group or an amine functional group may be mixed and used.

In addition, the polycarbonate may be a general polycarbonate, or may be a polycarbonate having an epoxy work container.

The polycarbonate preferably includes one or more repeating units represented by the following Formulas V to VII as a main chain.

[Formula V]

[Formula VI]

On the other hand, as a monomer having an epoxy functional group that can be mixed with polycarbonate, trimethylol propane triglycidyl ether, bis (3,4-epoxycyclohexylmethyl) adipate, trimethylolethane triglycidyl ether, diglycid Dyl 1,2-cyclohexanedicarboxylate, 1,2,7,8-diepoxyoctane, N, N -diglycidyl-4-glycidyloxyaniline, 1,4-butanediol diglycidyl Ether, tris (2,3-epoxypropyl) isocyanurate, 1,4-cyclohexanedimethanol diglycidyl ether, and the like.

In addition, as the monomer having an amine functional group that can be mixed with the polycarbonate, an aliphatic amine, an aromatic amine or an amine compound including two or more primary amine groups can be used.

Specific examples of the aliphatic amine compound include, but are not limited to, diethylene triamine (DETA), diethylene tetraamine, triethylene tetramine (TETA), and methane diamine. diamine, MDA), N-aminoethyl piperazine (AEP), m-xylene diamine, isophorone diamine (IPDI), bis (4-amino 3-methylcyclo Hexyl) methane (bis (4-amino 3-methylcyclohexyl) methane, Larominc 260), N, N'-diethylethylenediamine (N, N-diethylenediamine, N, N-DEDA), tetraethylenepentaamine, TEPA ), Hexamethylenediamine, and the like, and these may be used alone or in combination.

Specific examples of the aromatic amine include, but are not limited to, m-phenylene diamine, 4,4'-dimethylaniline (diamino diphenyl metone) (4,4'-dimethylanilnine (diamino diphenyl) methone), DAM or DDM), diamino diphenyl sulfone (DDS), 9-diphenyl-1,4-phenylenediamine, 1,3-phenyl Rendiamine (1,3-phenylenediamine), diaminodiphenylmethane (diaminoeiphenylemthane) and the like, and these may be used alone or in combination.

On the other hand, in the case of mixing a polycarbonate containing a monomer containing an epoxy functional group or an amine functional group, the epoxy functional group or amine functional groups of the monomer to form a matrix to form a semi-IPN (interpenetrating network) structure with the polycarbonate during the curing reaction Therefore, it is more effective in lowering the coefficient of thermal expansion of polycarbonate.

In addition, by controlling the content of the monomer, it is possible to easily control the degree of curing, flexibility, solvent resistance, glass transition temperature and compatibility with the modified inorganic filler of the film finally formed.

On the other hand, when using a polycarbonate having an epoxy functional group as a polycarbonate, the epoxy functional group of the polycarbonate reacts with the epoxy functional group or the amine functional group of the monomer or silica sol during the curing reaction to form an IPN (interpenetrating network) structure to form a matrix. As a result, the coefficient of thermal expansion can be reduced more efficiently, and the degree of curing, flexibility, solvent resistance, glass transition temperature, and modified inorganic filler of the film finally formed by controlling the content of epoxy functional groups. There is an advantage that can easily control the compatibility with.

Next, as the epoxy-based polymer system, bisphenol A represented by the following formula (VII) or epoxy monomer represented by the following formula (VIII) may be used alone, or a mixture thereof may be used.

[Formula VII]

[Formula VIII]

The polycarbonate-based polymer system or the epoxy-based polymer system as described above is preferably in the content of about 10 to 90% by weight. If the content of the polymer system is less than 10% by weight, the film is brittle and easily broken in use, and if the content of the polymer system exceeds 90% by weight, the CTE control may not be sufficient.

On the other hand, the organic-inorganic hybrid resin composition of the present invention may further comprise an amine curing agent in addition to the above components. In the case of using a polycarbonate having no functional group alone as a polymer system, an amine curing agent is not used. However, when there is an epoxy functional group, an amine curing agent is added.

The amine curing agent is for crosslinking the polymer system with silica, and in the present invention, the amine curing agent is selected from the same compounds as the monomer having the amine functional group, i.e., an amine compound comprising an aliphatic amine, an aromatic amine or two or more primary amine groups. Can be used.

Specific examples of the aliphatic amine compound include, but are not limited to, diethylene triamine (DETA), diethylene tetraamine, triethylene tetramine (TETA), and methane diamine. diamine, MDA), N-aminoethyl piperazine (AEP), m-xylene diamine, isophorone diamine (IPDI), bis (4-amino 3-methylcyclo Hexyl) methane (bis (4-amino 3-methylcyclohexyl) methane, Larominc 260), N, N'-diethylethylenediamine (N, N-diethylenediamine, N, N-DEDA), tetraethylenepentaamine, TEPA ), Hexamethylenediamine, and the like, and these may be used alone or in combination.

Specific examples of the aromatic amine include, but are not limited to, m-phenylene diamine, 4,4'-dimethylaniline (diamino diphenyl metone) (4,4'-dimethylanilnine (diamino diphenyl) methone), DAM or DDM), diamino diphenyl sulfone (DDS), 9-diphenyl-1,4-phenylenediamine, 1,3-phenyl Rendiamine (1,3-phenylenediamine), diaminodiphenylmethane (diaminoeiphenylemthane) and the like, and these may be used alone or in combination.

On the other hand, since the degree of curing of the polymer system can be adjusted by reaction with the epoxy group according to the content of the amine curing agent, it is possible to adjust the content of the amine curing agent based on the epoxy group of the polycarbonate backbone according to the desired degree of curing. In particular, in the equivalent reaction of the amine curing agent and the polycarbonate main chain, one amine group per two epoxy groups is a quantitative concentration, and in the equivalent reaction, the molar ratio of epoxy group / amine group [NH ₂ ] is 2/1. Concentration ratios can be used. Therefore, in the present invention, the content of the amine curing agent is preferably 1.0 to 2.5 so that the molar ratio of the epoxy group [epoxy group] / amine group [NH ₂ ] to 0.5 to 3.0 based on the epoxy group of the polycarbonate main chain. It is preferable to use it so that it may be adjusted.

On the other hand, the organic-inorganic hybrid composition of the present invention is used by dissolving the silica sol, polymer system in a solvent. Since the silica sol and the polymer system of the present invention show excellent solubility in most organic solvents except aliphatic hydrocarbons and alcohols, any solvent capable of mixing the above components may be used. For example, organic solvents, such as tetrahydrofuran, chloroform, and methylene chloride, can be used.

Organic weapons hybrid  Method of Preparation of the Composition

Next, look at the production method of the organic-inorganic hybrid composition of the present invention.

The method for preparing the organic-inorganic hybrid composition of the present invention comprises (1) a silica sol forming step (2) a polymer solution preparing step (3) a mixing step.

On the other hand, if the polymer system includes an epoxy functional group (3) after the step (3) further comprises a curing agent addition step.

Hereinafter, the organic-inorganic hybrid composition of the present invention looks at each step in detail.

(1) silica sol forming step

A silane compound having an epoxy functional group or an amine functional group or a mixture of a silane compound having an epoxy functional group or an amine functional group and another silane compound is dissolved in a solvent and then reacted under an acid or base catalyst to form a silica sol.

At this time, the reaction temperature is preferably between room temperature and 60 ℃, the reaction time is preferably from 2 hours to about 48 hours.

When using a mixture of silane compounds, the mixing ratio of the silane compound having an epoxy functional group or an amine functional group to another silane compound is determined by the physical properties including the degree of crosslinking of the final film to be produced (strength, flexibility, solvent resistance, etc.), the filler and the matrix polymer. Determined in consideration of compatibility. Therefore, the ratio of the silane compound having an epoxy functional group or an amine functional group to another silane compound is not particularly limited, and in some cases, a silane compound having an epoxy functional group or an amine functional group and another silane compound may be used alone.

Meanwhile, the silane compound having an epoxy functional group or an amine functional group used in the present invention is a compound represented by the above formula (I), and the other silane compound is preferably a compound represented by the above formula (II). More preferably, as the silane compound having an epoxy functional group or an amine functional group, a compound selected from the compounds represented by Formula III may be used, and as the other silane compound, a compound represented by Formula IV may be used.

The acid catalyst may be hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, formic acid, acetic acid, propionic acid, butanoic acid, pentanic acid, hexanoic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, oxalic acid, Malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, maleic acid, oleic acid, methylmalonic acid, adipic acid, p-aminobenzoic acid, p-toluenesulfonic acid, or the like may be used alone or as a mixture thereof. , Organic amines, alkylammonium hydroxides and the like can be used alone or in combination.

Meanwhile, as the solvent, any organic solvent having sufficient solubility in the silane compounds may be used, and preferably tetrahydrofuran, chloroform, methylene chloride, or the like may be used.

(2) preparing the polymer solution

Apart from the step (1), the polymer system is dissolved in a solvent to prepare a polymer solution.

This is to maximize the miscibility with the silica sol formed in step (1), the polymer system may be a polycarbonate-based polymer system or an epoxy-based polymer system as described above.

In this case, specific contents of the polycarbonate polymer system and the epoxy-based polymer system are as described above.

That is, as the polycarbonate-based polymer system, a polycarbonate including at least one repeating unit represented by the above formulas (V) and (VI) in the main chain may be used alone or by mixing a monomer having an epoxy group or an amine functional group. As the carbonate, a general polycarbonate or a polycarbonate having an epoxy functional group can be used.

Meanwhile, as the polymer system of the present invention, an epoxy-based polymer system may be used in addition to the polycarbonate polymer system. In this case, specific contents of the epoxy-based polymer system are also the same as those described above. That is, bisphenol A represented by the formula (VII) or the epoxy monomer represented by the formula (VIII) may be used alone or a mixture thereof may be used as the epoxy polymer system.

As the solvent, organic solvents such as tetrahydrofuran, chloroform and methylene chloride can be used as in step (1).

(3) mixing step

The homogeneous mixture is prepared by mixing the silica sol formed in step (1) and the polycarbonate solution prepared in step (2).

At this time, the silica sol and the polycarbonate solution is preferably mixed in a weight ratio of 5: 95 to 95: 5. When the amount of the silica sol is less than 5%, there is insufficient control the CTE of the polymer, when the content of silica sol is 95% or more Multiplexers bill mobility (flexibility) of the film may be insufficient.

The mixing is preferably carried out for at least 1 hour with vigorous stirring at room temperature so that a homogeneous mixture can be produced.

(4) adding the amine curing agent

When the silica sol and the polymer solution are uniformly mixed, an amine curing agent is added to the mixture. As mentioned above, the amine curing agent is for initiating the crosslinking reaction of the epoxy functional group in the polymer system with the epoxy functional group or the amine functional group of the silica sol.

As such an amine curing agent, an amine compound including an aliphatic amine, an aromatic amine or two or more primary amine groups may be used, and the amine curing agent may be added so that one amine functional group is added per two epoxy functional groups. However, the content of the amine curing agent may be adjusted to control the degree of curing.

Specific examples and contents of the amine curing agent that can be used in the present invention are the same as those described above.

 An amine curing agent is added, followed by vigorous stirring and mixing to prepare an organic-inorganic hybrid composition in which the polycarbonate polymer, the silica sol, and the amine curing agent are uniformly mixed.

Since the organic-inorganic hybrid composition of the present invention prepared by the above process uses silica in a sol state, the silica particles do not aggregate with each other and are evenly dispersed in the polymer resin solution.

Hereinafter, the present invention will be described in more detail with reference to specific examples.

Method for manufacturing optical film for plastic substrate

The organic-inorganic hybrid resin solution of the present invention prepared by the above method is coated on a substrate such as a release film, Teflon film and molded in the form of a film, and then dried, and thermally cured and condensation polymerization of silica sol proceeds. Let's do it.

At this time, the drying step is a one-step drying for 1 hour to 48 hours at room temperature, it is preferable to further dry for 1 hour to 24 hours at room temperature ~ 150 ℃, nitrogen atmosphere, the thermosetting and silica sol The polycondensation reaction of is preferably performed for 1 hour to 48 hours at a temperature of 10 to 200 ℃ in atmospheric pressure or vacuum atmosphere.

According to the method for manufacturing an optical film for plastic substrate of the present invention as described above, the sol silica is dispersed in a polymer system, and then molded into a film, heat cured, and grown through a sol-gel reaction of additional silica. Since the prepared silica particles are made, the silica particles do not aggregate with each other, as in the case of using a manufactured silica powder, and as a result, the optical properties of the film can be maintained excellent.

In addition, since the silica particles having a low coefficient of thermal expansion are evenly dispersed in a crosslinked form with the polymer matrix, the effect of reducing the coefficient of thermal expansion is also superior to the conventional method.

Hereinafter, the present invention will be described in more detail with reference to specific examples.

Example  1.Sol Synthesis with Epoxy Group

Triethoxy {3- (oxirane-2-yl-methoxy) -propyl) silane (3 g) and trimethoxyphenylsilane (0.71 g) were dissolved in 10 ml of tetrahydrofuran, followed by 0.2 M HCl. After adding ml and isopropyl alcohol at 3.3 times the molar ratio of silane, the mixture was stirred at room temperature for 12 hours and further stirred at 60 ° C for 1 hour. This silica sol was completely removed solvent from the rotary evaporator.

Example  2. The epoxy group at the end Poly (bisphenol A) and  Sol mixture manufacturers

Epoxy resin DGEBA (diglycidyl ether of bisphenol A, 3.71 g) is dissolved in tetrahydrofuran to prepare a 15 wt% solution. In the solution, the silica sol prepared in Example 1 is mixed at a weight ratio of 1: 1. The mixture is vigorously stirred for 1 hour, then isophorone diamine (0.69 g) is added and then vigorously stirred for 1 hour at room temperature. The mixture was prepared at a room temperature to enable the solvent-casting (viscosity) to the viscosity (solvent-casting) and then poured onto a release film to prepare a film.

Example  3. Epoxy / Silica hybrid  Film manufacturing

The film prepared in Example 2 was dried at room temperature for 12 hours, and then further dried at 40 ° C. for 5 hours. The dried film was reacted for 4 hours at a temperature of 140 ° C. under a nitrogen atmosphere, and then heated to 170 ° C. under vacuum, and then further reacted for 12 hours to prepare an optical film for a plastic substrate.

Experimental Example

The thermal expansion coefficient of the optical film prepared by Example 3 was 50 ppm / ℃, the transmittance is 90%.

Claims (30)

5 to 90 weight percent of a silica sol surface modified with an epoxy functional group or an amine functional group; 10 to 90 weight percent of a polycarbonate-based or epoxy-based polymer system; And an organic-inorganic hybrid resin composition comprising a solvent. The method of claim 1, The silica sol is a silane compound of formula (I); or An organic-inorganic hybrid resin composition, which is prepared by reacting a mixture of a silane compound represented by the following formula (I) and a silane compound represented by the following formula (II). [Formula I]

Wherein R, R _1, R _2, R ₃ and R ₄ at least one is an organic substituent with an epoxy group or an amine, and the other is hydroxy group or C _{1 -10} alkoxy giim independently. [Formula II]

Wherein R, R _5, R _6, R ₇ and R ₈ are at least one of a hydroxy group or C _{1 -10} alkoxy, the remains are each independently C _{1 ~ 10} alkyl, C _{6 ~ 20} arylene, C _{1 ~ 10} alkyl C _{6 ~ 20} arylene and C _{6 ~ 20} aryl C _{1 ~ 10} selected from the group consisting of an alkylene group. The method of claim 2, The reaction of the silane compound is an organic-inorganic hybrid resin composition, characterized in that for 2 hours to 48 hours at an reaction temperature of 60 ℃ at room temperature, under an acid or base catalyst. The method of claim 2, The silane compound represented by the formula (I) is an organic-inorganic hybrid resin composition, characterized in that selected from the group consisting of the compounds shown in formula (III). [Formula III]

Wherein n is an integer from 1 to 10. The method of claim 2, The silane compound represented by the formula (II) is an organic-inorganic hybrid resin composition, characterized in that the silane compound represented by the formula (IV). [Formula IV]

The method of claim 1, The polycarbonate polymer system is an organic-inorganic hybrid resin, characterized in that comprising a polycarbonate containing at least one repeating unit represented by the formula (V) and VI in the main chain. [Formula V]

[Formula VI]

The method of claim 6, The polycarbonate polymer system is an organic-inorganic hybrid resin further comprises a monomer or oligomer having an epoxy functional group or an amine functional group. The method of claim 7, wherein Monomers having the epoxy functional groups include trimethylol propane triglycidyl ether, bis (3,4-epoxycyclohexylmethyl) adipate, trimethylolethane triglycidyl ether, diglycidyl 1,2-cyclohexanedicarboxyl Late, 1,2,7,8-diepoxyoctane, N, N -diglycidyl-4-glycidyloxyaniline, 1,4-butanediol diglycidyl ether, tris (2,3-epoxypropyl An organic-inorganic hybrid resin, characterized in that at least one selected from the group consisting of isocyanurate and 1,4-cyclohexanedimethanol diglycidyl ether. The method of claim 7, wherein The monomer having an amine functional group is diethylene triamine (DETA), diethylene tetraamine, triethylene tetramine (TETA), methane diamine (MDA), N-amino N-aminoethyl piperazine (AEP), m-xylene diamine, isophorone diamine (IPDI), bis (4-amino 3-methylcyclohexyl) methane (bis (4- amino 3-methylcyclohexyl) methane, Larominc 260), N, N'-diethylethylenediamine (N, N-diethylenediamine, N, N-DEDA), tetraethylenepentaamine (TEPA) and hexamethylenediamine At least one aliphatic amine selected from the group consisting of; or m-phenylene diamine, 4,4'-dimethylaniline (diamino diphenyl methone) (4,4'-dimethylanilnine (diamino diphenyl methone), DAM or DDM), diamino diphenylsulfone ( diamino diphenyl sulfone, DDS), 9-diphenyl-1,4-phenylenediamine, 1,3-phenylenediamine, and diaminodiphenyl Organic-inorganic hybrid resin composition, characterized in that at least one aromatic amine selected from the group consisting of methane (diaminoeiphenylemthane). The method of claim 1, The polycarbonate polymer system includes at least one repeating unit represented by the following formulas (V) and (VI) in the main chain, and an organic-inorganic hybrid resin, characterized in that made of a polycarbonate having an epoxy functional group. [Formula V]

[Formula VI]

The method of claim 1, The epoxy-based polymer system is an organic-inorganic hybrid resin, characterized in that it comprises one or more selected from the group consisting of bisphenol A represented by the formula (VII) and epoxy monomer represented by the formula (VIII). [Formula VII]

[Formula VIII]

The method of claim 1, The organic-inorganic hybrid resin composition further comprises an amine curing agent, The amine curing agent is an organic-inorganic hybrid resin composition, characterized in that the molar ratio of the epoxy group [epoxy group] / amine group [NH ₂ ] is 0.5 to 3.0 based on the epoxy group of the polymer system. The method of claim 12, The amine curing agent is diethylene triamine (DETA), diethylene tetraamine (triethylene tetraamine), triethylene tetramine (TETA), methane diamine (MDA), N-aminoethyl pyre Lysine (N-aminoethyl piperazine (AEP), m-xylene diamine, isophorone diamine (IPDI), bis (4-amino 3-methylcyclohexyl) methane (bis (4-amino 3 -methylcyclohexyl) methane, Larominc 260), N, N'-diethylethylenediamine (N, N-diethylenediamine, N, N-DEDA), tetraethylenepentaamine (TEPA) and hexamethylenediamine At least one aliphatic amine selected from the group; or m-phenylene diamine, 4,4'-dimethylaniline (diamino diphenyl methone) (4,4'-dimethylanilnine (diamino diphenyl methone), DAM or DDM), diamino diphenylsulfone ( diamino diphenyl sulfone, DDS), 9-diphenyl-1,4-phenylenediamine, 1,3-phenylenediamine, and diaminodiphenyl Organic-inorganic hybrid resin composition, characterized in that at least one aromatic amine selected from the group consisting of methane (diaminoeiphenylemthane). Dissolving a silane compound of formula (I) or a mixture of a silane compound represented by formula (I) and a silane compound represented by formula (II) in a solvent and then reacting under an acid or base catalyst to form a silica sol; Preparing a polymer solution by dissolving a polycarbonate-based or epoxy-based polymer system in a solvent; And Method for producing an organic-inorganic hybrid resin composition comprising the step of mixing the silica sol and a polycarbonate solution to prepare a mixed solution. [Formula I]

Wherein R, R _1, R _2, R ₃ and R ₄ at least one is an organic substituent with an epoxy group or an amine group, the remains are each independently a hydroxy group or a C _{1 - 10} alkoxy giim. [Formula II]

Wherein R, R _5, R _6, R ₇ and R ₈ are at least one of a hydroxy group or C _{1 -10} alkoxy, the remains are each independently C _{1 ~ 10} alkyl, C _{6 ~ 20} arylene, C _{1 ~ 10} alkyl C _{6 ~ 20} arylene and C _{6 ~ 20} aryl C _{1 ~ 10} selected from the group consisting of an alkylene group. The method of claim 14, Method for producing an organic-inorganic hybrid resin composition characterized in that it further comprises the step of adding an amine curing agent to the mixed solution after the mixed solution manufacturing step. The method of claim 14, The silica sol forming step is a method for producing an organic-inorganic hybrid resin composition, characterized in that made for 2 hours to 48 hours at a temperature of room temperature to 60 ℃. The method of claim 14, The acid catalyst is hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, formic acid, acetic acid, propionic acid, butanoic acid, pentanic acid, hexanoic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, oxalic acid, malonic acid, At least one member selected from the group consisting of sulfonic acid, phthalic acid, fumaric acid, citric acid, maleic acid, oleic acid, methylmalonic acid, adipic acid, p-aminobenzoic acid and p-toluenesulfonic acid, The base catalyst is a method for producing an organic-inorganic hybrid resin composition, characterized in that at least one selected from the group consisting of ammonia, organic amines and alkylammonium hydroxides. The method of claim 14, The solvent is tetrahydrofuran (tetrahydrofurane), chloroform (chloroform) or methylene chloride (methylene chloride) characterized in that the organic-inorganic hybrid resin composition manufacturing method. The method of claim 14, The polycarbonate polymer system is a method for producing an organic-inorganic hybrid resin composition comprising a polycarbonate comprising at least one repeating unit represented by the formula (V) and VI in the main chain. [Formula V]

[Formula VI]

The method of claim 19, The polycarbonate polymer system is an organic-inorganic hybrid resin further comprises a monomer or oligomer having an epoxy functional group or an amine functional group. The method of claim 20, Monomers having the epoxy functional groups include trimethylol propane triglycidyl ether, bis (3,4-epoxycyclohexylmethyl) adipate, trimethylolethane triglycidyl ether, diglycidyl 1,2-cyclohexanedicarboxyl Late, 1,2,7,8-diepoxyoctane, N, N -diglycidyl-4-glycidyloxyaniline, 1,4-butanediol diglycidyl ether, tris (2,3-epoxypropyl An organic-inorganic hybrid resin, characterized in that at least one selected from the group consisting of isocyanurate and 1,4-cyclohexanedimethanol diglycidyl ether. The method of claim 20, The monomer having an amine functional group is diethylene triamine (DETA), diethylene tetraamine, triethylene tetramine (TETA), methane diamine (MDA), N-amino N-aminoethyl piperazine (AEP), m-xylene diamine, isophorone diamine (IPDI), bis (4-amino 3-methylcyclohexyl) methane (bis (4- amino 3-methylcyclohexyl) methane, Larominc 260), N, N'-diethylethylenediamine (N, N-diethylenediamine, N, N-DEDA), tetraethylenepentaamine (TEPA) and hexamethylenediamine At least one aliphatic amine selected from the group consisting of; or m-phenylene diamine, 4,4'-dimethylaniline (diamino diphenyl methone) (4,4'-dimethylanilnine (diamino diphenyl methone), DAM or DDM), diamino diphenylsulfone ( diamino diphenyl sulfone, DDS), 9-diphenyl-1,4-phenylenediamine, 1,3-phenylenediamine, and diaminodiphenyl Method for producing an organic-inorganic hybrid resin composition, characterized in that at least one aromatic amine selected from the group consisting of methane (diaminoeiphenylemthane). The method of claim 14, The polycarbonate polymer system comprises at least one repeating unit represented by the following formulas (V) and (VI) in the main chain, the organic-inorganic hybrid resin composition manufacturing method, characterized in that made of a polycarbonate polymer having an epoxy functional group. [Formula V]

[Formula VI]

The method of claim 14, The epoxy-based polymer system comprises at least one compound selected from the group consisting of bisphenol A represented by the general formula (VII) and epoxy polymer represented by the general formula (VIII). [Formula VII]

[Formula VIII]

The method of claim 14, The silica sol and the polymer system is a method of producing an organic-inorganic hybrid resin composition, characterized in that mixed in a weight ratio of 5: 95 to 95: 5. The method of claim 15, The amine curing agent is diethylene triamine (DETA), diethylene tetraamine (diethylene tetraamine), triethylene tetramine (TETA), methane diamine (MDA), N-aminoethyl pyrerizine (N-aminoethyl piperazine (AEP), m-xylene diamine, isophorone diamine (IPDI), bis (4-amino 3-methylcyclohexyl) methane (bis (4-amino 3- methylcyclohexyl) methane, Larominc 260), N, N'-diethylethylenediamine (N, N-diethylenediamine, N, N-DEDA), tetraethylenepentaamine (TEPA) and hexamethylenediamine At least one aliphatic amine selected from; or m-phenylene diamine, 4,4'-dimethylaniline (diamino diphenyl methone) (4,4'-dimethylanilnine (diamino diphenyl methone), DAM or DDM), diamino diphenylsulfone ( diamino diphenyl sulfone, DDS), 9-diphenyl-1,4-phenylenediamine, 1,3-phenylenediamine, and diaminodiphenyl Method for producing an organic-inorganic hybrid resin composition, characterized in that at least one aromatic amine selected from the group consisting of methane (diaminoeiphenylemthane). The method of claim 15, The amine curing agent is a method for producing an organic-inorganic hybrid resin composition, characterized in that the molar ratio of the epoxy group [epoxy group] / amine group [NH ₂ ] is 0.5 to 3.0 based on the epoxy group of the polymer system. A method of manufacturing a film by coating an organic-inorganic hybrid resin composition prepared by the method of any one of claims 14 to 27 on a substrate; Drying the film; And Condensation polymerization of the dried film and thermal curing of the dried film at the same time comprising the step of condensation polymerization. The method of claim 28, The drying step is dried for 1 hour to 48 hours at room temperature, at room temperature ~ 150 ℃, nitrogen, the optical film manufacturing method for a plastic substrate, characterized in that for 1 hour to 24 hours under a nitrogen atmosphere. The method of claim 28, The thermal curing and condensation polymerization step is an optical film manufacturing method for a plastic substrate, characterized in that for 1 hour to 48 hours at a temperature of 10 to 200 ℃ in atmospheric pressure or vacuum atmosphere.