KR101073069B1 - A method for preparing a polycarbonate resin having a low coefficient of thermal expansion - Google Patents

Abstract

The present invention provides a semi-interpenetrating network (semi-IPN system) comprising preparing a raw material mixture comprising a polycarbonate, a bisphenol compound having an epoxy end, and an amine curing agent, and reacting the raw material mixture. It relates to a method for producing a polycarbonate resin having, a polycarbonate resin produced therefrom, and an optical film comprising the same.

Optical film, plastic substrate, low coefficient of thermal expansion, polycarbonate

Description

A method for producing a polycarbonate resin having a low coefficient of thermal expansion {A METHOD FOR PREPARING A POLYCARBONATE RESIN HAVING A LOW COEFFICIENT OF THERMAL EXPANSION}

The present invention relates to a method for producing a polycarbonate resin having a low coefficient of thermal expansion and suitable for a display substrate and an optical film, and an optical film produced using the same.

Plastic substrate material is a key material for the implementation of plastic flat panel displays (replacement of existing FPD glass substrates) or next-generation displays (conformable display / flexible displays, e-paper). .

When comparing the physical properties of plastic substrates for flexible displays with conventional glass substrates, weight, deformability, nonbreakability, design, and roll-to are the key characteristics of flexible displays. Plastic material is excellent in terms of roll processability. However, in order to use the plastic optical film for the substrate, it is required to improve the physical properties in terms of weak thermal properties, chemical resistance, and gas barrier properties of the plastic substrate compared to the glass.

In order to use the optical film as a substrate material for a display, various properties such as thermal stability, chemical resistance, excellent optical properties, surface flatness, and mechanical properties are required in combination.

In general, an undercoat layer, an inorganic barrier layer and an overcoat layer are applied to both surfaces of a transparent optical film that is a bare film in order to satisfy such various characteristics.

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 or birefringence, and mechanical strength. , PC), polyethersulphone (PES), polyester (Polyethlene Terephthalate (PET), polyimide (Polyimide, PI), polyarylate (Polyarylate, PAR), polyethylene naphthalate (PEN) Most commonly used polymer. The glass substrate and the conventional polymer plastic substrate are as shown in Table 1 below when the physical properties are compared.

Properties Glass PC PES PET PEN Manufacturing method Fusion Solvent casting Extrusion Extrution & biaxially drawing Extrution & biaxially drawing Density (g / cm ³ ) 2.77 1.2 2.2 5.3 6.1 Glass transition temperature (캜) 690 215 223 78 121 Heat shrink Almost none <0.01
@ 180 ℃ <0.8
@ 180 ℃ MD 1.0
TD 0.5
@ 150 ℃ MD 0.5
TD 0.1
@ 150 ℃ Thermal expansion coefficient (ppm / ℃) 8 70 60 80 20 Light transmittance (%) 91 90 89 89 88 Refractive index 1.54 1.61 1.65 1.66 1.70

* Source: MacDonald W. A., J. Materials Chem. 14 (4) (2004)

Until recently, technical development of substrate materials has been focused on improving glass transition temperature of bare film materials that determine gas barrier properties and substrate process temperatures of barrier layers.

However, the barrier properties have been reported to have recently been improved to a level that satisfies the requirements of the organic light emitting diode (OLED), and the requirements for heat resistance of the substrate material have been gradually relaxed.

In the case of process temperature, amorphous silicon-TFT process temperature is generally 350 ℃, but the process temperature of plastic LCD is reported to decrease to 150 ℃, and it is expected that the process temperature will be lowered below 100 ℃. have.

However, even if the gas barrier property is secured and the substrate process temperature is lower than the glass transition temperature of the plastic, the flexible display may not be implemented using all the plastic substrates.

Indeed, current TFT processes have been developed for borosilicate glass with a Coefficient of Thermal Expansion (CTE) of 4 ppm / ° C, but very high CTE for isotropic transparent films (eg 70 ppm for PC). / ° C.). Therefore, in the case of the substrate material having a high CTE, the dimensional stability is secured for the implementation of the TFT-array, which requires the micrometer precision due to the misalignment between pixels due to the temperature change during the process. I can't.

In addition, in a plastic substrate having a multi-layered thin film structure having different physical properties, the thermal expansion rate difference between the interlayer materials (polymer and inorganic material) is large, so that thermal stress occurs at the interface during heating / cooling. .

As a result, crack generation and interfacial peeling occur, which makes it difficult to maintain a gas barrier characteristic of the substrate after the process, thereby seriously reducing durability and reliability of the substrate. The problem caused by low CTE is the biggest obstacle to the application of flexible displays, and it is a technical task to be preempted for the practical use of plastic substrates in the future.

However, polymer materials for substrates with low CTE have not been developed so far enough to meet the demands of set-makers worldwide.

An object of the present invention is to provide a method for producing a polycarbonate resin having a semi-IPN system so as to improve the thermal expansion coefficient of the polymer without inhibiting the optical properties of the polycarbonate.

In addition, the present invention is to provide a method that can further include a silica particle bonded to an organic functional group to participate in the epoxy curing reaction, to facilitate the dispersion of the silica particles and to more effectively reduce the CTE.

Another object of the present invention is to provide a polycarbonate resin having an anti-penetration network (semi-IPN system) prepared by the above method and an optical film comprising the same.

The present invention includes preparing a raw material mixture comprising a polycarbonate, a bisphenol compound having an epoxy terminal, and an amine curing agent, and reacting the raw material mixture, and including a semi-IPN system. It provides a method for producing a polycarbonate resin having.

In addition, the present invention provides a polycarbonate resin having an anti-penetration network (semi-IPN system) prepared according to the manufacturing method and an optical film comprising the same.

Hereinafter, the present invention will be described in detail.

Polycarbonate (PC) is the most widely used material for plastic substrates along with polyether sulfone (PES) from Sumitomo Bakelite. PC substrate materials have been recently developed by Teijin, Japan.

In recent years, since the general PC is a substrate material for display, the heat resistance is poor and the process progresses. Therefore, the glass transition temperature is higher than 60 ° C. and the thermal strain at 180 ° C. is higher than 0.05%. And a substrate PC having a small retardation of less than 1 nm. Deijin's PCs have been applied to mobile phones (monochrome STN-LCDs) since 1999, and are currently producing 500,000 to 600,000 units per month.

The present invention seeks to limit the polycarbonate backbone motion (or fluidity) in order to reduce the high coefficient of thermal expansion, which is the biggest disadvantage of polycarbonate as a substrate material. In order to achieve this, (1) a polycarbonate resin is mixed with a bisphenol-based epoxy compound which is very compatible with the resin and capable of being thermally cured, and then a curing agent is added to perform a thermosetting reaction through the epoxy group in the blend. Proceeded. As a result of the thermal curing reaction, a polymer system having a semi-IPN system (Semi-IPN system, Semi Interpenetrating Polymer Network System) is formed, and the crosslinking system formed at this time restricts the movement of the polycarbonate. It also provides a method of effectively controlling the thermal expansion characteristics of the resin.

In spite of its excellent optical properties, transparent polycarbonate optical films are used for other optical films, including substrates for flexible displays, due to poor dimensional stability due to high coefficient of thermal expansion (CTE). Is limited in applications. Accordingly, the present invention is to provide a method for producing a polycarbonate resin that can control the coefficient of thermal expansion relatively easily, without impairing the optical properties of the polycarbonate, and to provide an optical film comprising the same.

Another advantage of this approach of adding thermosetting epoxy groups is the addition of additional inorganic particles to ensure better CTE properties. When inorganic particles having an organic reactive group are added to the polycarbonate / epoxy system proposed in the present invention, the inorganic particles may participate in an epoxy curing reaction, thereby more effectively reducing the CTE of the polymer system.

In particular, in the past, in order to limit the mobility of the polycarbonate to the main chain (mobility) as described above, a low-molecular weight polycarbonate including a variety of additional reactive functional groups were separately synthesized, and then thermoset reaction was carried out in the present invention. Bisphenol-based cargoes having epoxy ends such as general polycarbonate and DGEBA can be used as they are, and thus, a semi-IPN is used for efficient polycarbonate resin with limited main chain movement without any additional synthesis process. It can be prepared by.

In the present invention, the semi-IPN system (Semi-IPN system, Semi Interpenetrating Polymer Network System) refers to a state in which the cross-linked network polymer and the polymer of the star structure are mingle to each other at the molecular level. Such semi-infiltrating structure (semi-IPN) may enter a broad interpenetrating polymer network (IPN), and the IPN is a polymer having two or more kinds of polymer meshes having a cross-linked network structure in which a polymer is in a state of being bitten together or in a state of the polymer. Say. In particular, the ideal IPN is a structure in which the network structure is uniformly distributed with each other (CIPN: Completely IPN), but in practice, it is difficult to commercialize the polymers, and thus, it is easy to become a phase separated structure (PSIPN: Phase Separated IPN). The IPN structure includes PIPN (Partial IPN), QIPN (Quasi IPN), and the like according to a specific structure state, and includes SIPN (Sequential IPN), SIN (Simultaneous IPN), and LIPN (Latex IPN).

In general, IPN is used for the development of composite materials and functional materials, and is a combination of rubbery polymers and glassy polymers. Ion exchange resins are also produced. In addition, applications in various fields such as soundproofing, dustproof material, silicone polymer having a high loss elastic modulus value over a wide temperature range, and medical materials having excellent biocompatibility, have been attempted. IPN) polycarbonate resin is curable bisphenol-based epoxy having excellent compatibility with polycarbonate, wherein the added epoxy compound (1) limits the mobility between the polycarbonate main chain, (2) inorganic particles added to the polycarbonate Through chemical reaction with, it can be very useful in terms of effectively controlling the thermal expansion characteristics of the polycarbonate, and has an excellent advantage in that it does not require a separate polycarbonate reforming process to achieve this.

The polycarbonate resin according to the present invention can further improve the coefficient of thermal expansion of the polymer by additionally adding an inorganic filler, in this case, the interfacial adhesion between the inorganic filler and the polymer is a very important factor, and for this purpose, Effective organic functional groups can be imparted to form.

In the present invention, the polycarbonate may have a weight average molecular weight of 400 to 50,000, and preferably 1,000 to 30,000, so that the polycarbonate may have a more favorable effect of securing excellent light transmittance and low CTE.

In addition, the main chain of the polycarbonate preferably includes at least one of repeating units represented by the following Chemical Formulas 1 and 2, but is not necessarily limited thereto.

[Formula 1]

[Formula 2]

Bisphenol-based compound having an epoxy terminal used in the production method of the present invention is very compatible with polycarbonate to prepare a homogeneous mixture, and has a thermosetting property, it is very effective when mixing two material systems Semi-IPN systems can be prepared.

In the present invention, the bisphenol compound having an epoxy terminal preferably includes a repeating unit represented by the following Chemical Formula 3, but is not necessarily limited thereto.

 (3)

In addition, as the bisphenol-based compound having an epoxy end, bisphenol A diglycidyl ether (DGEBA, Di-Glycidyl Ether of Bisphenol A) and bisphenol F diglycidyl ether (DGEBF, Di-Glycidyl Ether of Bisphenol F) One or more selected from the group consisting of may be used, and diglycidyl ether of bisphenol A (DGEBA) is more preferable in view of compatibility with polycarbonate.

The bisphenol-based compound having the epoxy terminal can be reacted with 5 to 95 parts by weight, preferably 10 to 90 parts by weight with respect to 100 parts by weight of the polycarbonate. The content of the epoxy terminal is 5 parts by weight or more can obtain the effect of limiting the main chain movement of the polycarbonate, in order not to reach an excessively high degree of curing is preferably 95 parts by weight or less.

In order to effectively limit the mobility of the polycarbonate through the formation of a semi-IPN system, the compatibility between the polycarbonate and the epoxy compound should be good and uniformly mixed. That is, the compatibility between the two constituent compounds should be very good. The reason for the good compatibility of the two compounds is (1) because both compounds are based on bisphenol A, and thus the chemical energy density value This is similar to (2) hydrogen bonding between the carbonyl group of polycarbonate and the hydroxyl group of epoxy of bisphenol-based compound, and (3) when blending the two compounds, a copolymer such as the following scheme is formed, which can act as a compatibilizer. Because

As shown in Scheme 1, when a polycarbonate and a bisphenol-based compound (DGEBA) having an epoxy terminal are mixed, a trans-esterification and an addition reaction proceed to form a copolymer of the polycarbonate and an epoxy compound. Is formed, and the copolymer thus formed can further improve compatibility between the two compounds.

Scheme 1

In the present invention, as the amine curing agent, an aliphatic amine or an aromatic amine may be used, and an amine compound including two or more primary amine groups may be used. The amine curing agent is diethylene tetraamine (Diethylene tetraamine), diethylene triamine (DETA), triethylene tetraamine (Triethylene Tetramine, TETA), methane diamine (MDA), N-aminoethyl pyrazine (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'-Diethylenediamine (N, N'-DEDA), Tetraethylenepentaamine (TEPA), and Hexamethylenediamine M-phenylene diamine or 4,4'-dimethylaniline (diamino diphenyl metone) (4,4'-Dimethylaniline (Diamino) diphenyl methone), DAM or DDM), diamino diphenyl sulfone (DDS), 9-dipe 1 selected from the group consisting of -1,4-phenylenediamine, 9-phenyl-1,4-phenylenediamine, 1,3-phenylenediamine, and diaminoeiphenylmethane. It is possible to use more than one aromatic amine.

The amine curing agent may adjust the degree of curing of the polycarbonate resin prepared by reaction with an epoxy group, and the content of the amine curing agent based on the concentration of the epoxy group of the epoxy compound (eg DGEBA) according to the desired degree of curing degree I can regulate it. In particular, in the equivalent reaction of the amine curing agent and the epoxy group, one amine group per two epoxy groups is a quantitative concentration, and in the equivalent reaction, a molar ratio of epoxy group / amine group [NH ₂ ] is 2/1. Can be used. Therefore, the content of the amine curing agent in the present invention 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 epoxy compound. It is preferable to use it so that it can be adjusted.

In addition, in the present invention, since silica particles have a lower CTE value than organic polymers, the silica particles have a lower CTE value, and a role of reducing the CTE of the polymer by increasing the amorphous intermolecular force as the crosslinked structure is formed. In order to perform the reaction, the organic functional groups may further include silica particles bonded thereto.

The silica particles to which the organic functional group is bonded may be used having an average particle diameter of 5 to 900 nm, preferably 10 to 500 nm. The silica particles have a lower CTE than the polycarbonate resin, and when the polymer is added, the average particle diameter is at least 5 nm or more to obtain the effect of improving the CTE, and in order to secure transparency of the polycarbonate composite, it is 900 nm or less. desirable.

In addition, the silica particles combined with the organic functional group may be reacted with 1 to 100 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the polycarbonate. When the content of the silica particles is 1 part by weight or more to obtain the effect of improving the CTE, in order to secure the transparency of the polycarbonate composite is preferably 100 parts by weight or less.

In the present invention, the silica particles to which the organic functional groups are bonded may be prepared by reacting the silica particles having hydroxy termini with the silane compound represented by the following Chemical Formula 4 or Chemical Formula 5.

[Formula 4]

[Chemical Formula 5]

Where

At least one of R ¹ , R ² , and R ³ is hydroxy, alkoxy having 1 to 10 carbon atoms, and the rest are each independently alkyl having 1 to 10 carbon atoms, and arylene having 6 to 20 carbon atoms, alkyl arylene, or Selected from the group consisting of arylalkylene,

R ⁴ is selected from the group consisting of alkyl having 1 to 10 carbon atoms, and arylene, alkylarylene, or arylalkylene having 6 to 20 carbon atoms,

At least one of R ⁵ , R ⁶ , and R ⁷ is hydroxy, alkoxy having 1 to 10 carbon atoms, and the rest are each independently alkyl having 1 to 10 carbon atoms, and arylene having 6 to 20 carbon atoms, alkyl arylene, or Selected from the group consisting of arylalkylene,

R ⁸ is selected from the group consisting of alkyl having 1 to 10 carbon atoms, and arylene, alkyl arylene, or arylalkylene having 6 to 20 carbon atoms.

In one example of the present invention, silica particles having an hydroxy end and a silane compound represented by Chemical Formula 4 may be reacted to produce silica particles bonded with an amine group, as shown in Scheme 2 below.

Scheme 2

In addition, as another example of the present invention, silica particles having hydroxy-terminated and the silane compound represented by Chemical Formula 5 may be reacted to prepare silica-bonded silica particles as shown in Scheme 3 below.

Scheme 3

In the present invention, the raw material mixture may further include a solvent in order to dissolve and mix the polycarbonate and silica particles well. The solvent is preferably an organic solvent such as THF, chloroform, dichloromethane, and most organic solvents except aliphatic hydrocarbons and alcohols have excellent solubility, and any solvent capable of mixing the above components may be used. .

At this time, the content of the solvent can be adjusted to an appropriate range according to the coating property, preferably it can be used so that the solid content is 5 to 90% by weight, when the solvent content of the raw material mixture is too much viscosity is too low to coat well Some solvent may be removed prior to coating to adjust the viscosity to a degree suitable for coating.

In the present invention, the raw material mixture may be reacted at a temperature of 50 to 250 ℃, preferably at a temperature of 70 to 200 ℃. The raw material mixture is carried out at 50 ℃ or more, and actively proceeds in the vicinity of 200 ℃, it is possible to obtain the effect of shortening the reaction time.

In addition, the present invention may further include the step of (solvent-casting) coating the raw material mixture on a substrate such as a release film, Teflon film, such as to produce an optical film comprising the polycarbonate resin It can be processed into various other forms using molds, etc.

The present invention provides a polycarbonate resin prepared according to the above method and having a semi-interpenetrating network (semi-IPN system) comprising a repeating unit derived from a polycarbonate, a bisphenol compound having an epoxy end, and an amine curing agent. do.

On the other hand, the present invention provides an optical film containing the polycarbonate resin.

In particular, the optical film produced according to the invention is characterized in that the thermal expansion coefficient of 60 ppm / ℃ or less, preferably 10 to 50 ppm / ℃.

The optical film may be prepared by applying a reaction product of a polycarbonate resin prepared according to the method of the present invention in the form of a film, and then drying and curing the same.

At this time, in the production method, the type of catalyst and solvent used, the content of each component is in accordance with the contents described above, the drying of the film is carried out at room temperature (25 ℃) to 100 ℃ temperature, the curing It is preferable to carry out at the temperature of normal temperature (25 degreeC)-250 degreeC from a uniformity of formation of a film.

However, the manufacturing method described only a preferred example of optical film production, the manufacturing method of the optical film of the present invention is not necessarily limited to the above method.

The present invention can prepare a polycarbonate having a semi-IPN system by reacting a polycarbonate, a bisphenol-based compound having an epoxy end, and an amine curing agent to prepare an optical film having a significantly reduced thermal expansion rate. have.

Preferred examples are provided to aid the understanding of the present invention, but the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the following examples.

First, the polycarbonate resin prepared according to the production method of the present invention was measured the coefficient of thermal expansion and permeability through the following evaluation method.

(1) Thermal expansion coefficient (CTE) measurement

Instrument: thermal mechanical analyzer (TMA)

-Measurement section and heating rate: normal temperature ~ 200 ℃, 10 ℃ / min

Sample: film form

 (2) light transmittance measurement

Instrument: UV-VIS spectrometer

Sample: film form

Example  1. Solution Mixing Method solution blending ) PC Of DGEBA semi - IPN  Produce

Before blending two samples of the polycarbonate and bisphenol compound having an epoxy end, the polycarbonate (PC, Aldrich, molecular weight 25,000) and DGEBA (aldrich, molecular weight 386) were dried in a vacuum oven at 130 ° C. for about 24 hours.

30 g of PC was dissolved in 160 g of CH ₂ Cl ₂ in a 500 cc round flask, and 10 g of epoxy was added thereto, followed by stirring at room temperature (magnetic stirrer) to mix sufficiently. After 1 hour, the temperature of the mixed solution was increased to about 50 ° C., and the mixed solvent CH ₂ Cl ₂ was removed by distillation. When almost all of the mixed solvent was removed, the temperature of the reaction vessel was raised to 90 ° C. to remove the amount of the residual solvent to the maximum. The solid amine hardener (diaminodiphenyl methane, DDM) was heated to 100 ° C., dissolved in advance, and mixed with the above solution. The mixed solution is cast on a release film, and the cast film is heated at 90 ° C. for 1 hour, then raised to 160 ° C. for 4 hours to perform crosslinking reaction, and semi-IPN A transparent optical film containing)) polycarbonate resin was prepared.

As described above, the samples were prepared and measured for physical properties. The glass transition temperature (DSC) was 155 ° C, the transmittance (at 550nm, UV-VIS spectrometer) was 85%, and the CTE was 60 ppm / ° C.

Example  2. Melt mixing method melt blending )through PC Of DGEBA semi - IPN  Produce

Prior to blending two samples of polycarbonate and bisphenol-based compound having epoxy ends, polycarbonate (PC, Aldrich, molecular weight 25,000) and DGEBA (aldrich, molecular weight 386) were dried in a vacuum oven at 130 ° C. for about 24 hours. 30 g of PC pellets and 10 g of DGEBA are mixed at 180 ° C. until a clear solution is obtained. The temperature is reduced to 90 ° C. and then premelted DDM (diaminodiphenyl methane, Tm = 92 ° C.). ) Was added. DDM was dissolved at about 100 ° C. and an amount of about 35 parts by weight based on epoxy was used. The mixture thus prepared was poured into a mold and then degassed in a vacuum oven at 80 ° C. for about 30 minutes to perform a curing reaction. The curing reaction was performed at 90 ° C. for 1 hour, followed by a post-cure process at 160 ° C. for 4 hours, and transparent containing semi-IPN polycarbonate resin. An optical film was prepared.

As described above, the samples were prepared and measured for physical properties. The glass transition temperature (DSC) was 155 ° C, the transmittance (at 550nm, UV-VIS spectrometer) was 85%, and the CTE was 57 ppm / ° C.

Example  3 Solution Mixing Method solution blending )through ( PC Of DGEBA semi - IPN ) / Nano silica composite fabrication

A transparent optical film comprising a semi-IPN polycarbonate resin in the same manner as in Example 1, except that nano silica particles surface-treated with 2 g of epoxy silane were additionally added simultaneously with DGEBA. Was prepared.

As described above, the samples were prepared and measured for physical properties. The glass transition temperature (DSC) was 155 ° C, the transmittance (at 550nm, UV-VIS spectrometer) was 85%, and the CTE was 50 ppm / ° C.

Example  4 Melt Mixing Method melt blending )through ( PC Of DGEBA semi - IPN ) / Nano silica composite fabrication

A transparent optical film including a semi-IPN polycarbonate resin was prepared in the same manner as in Example 2, except that nano silica particles surface-treated with 2 g of epoxy silane were additionally added simultaneously with DGEBA. Prepared.

As described above, the samples were prepared and measured for physical properties. The glass transition temperature (DSC) was 155 ° C, the transmittance (at 550nm, UV-VIS spectrometer) was 84%, and the CTE was 48 ppm / ° C.

Comparative Example 1 . Solution mixing method solution blending ) PC  Produce

In a 500 cc round flask, 30 g of polycarbonate (Aldrich, molecular weight 25,000) was dissolved in 160 g of CH ₂ Cl ₂ , stirred at room temperature, and the resulting solution was cast on a release film and cast. ) Was dried sufficiently to prepare a polycarbonate film.

As described above, the samples were prepared and measured for physical properties. The glass transition temperature (DSC) was 155 ° C, the transmittance (at 550nm, UV-VIS spectrometer) was 87%, and the CTE was 70 ppm / ° C.

From the above measurement results, the polycarbonate resin according to Examples 1 to 4 of the present invention forms a semi-reciprocal penetrating structure, and the curing reaction proceeds after the curable compound penetrates into the polymer, whereby the conventional poly according to Comparative Example 1 Compared to the carbonate resin, the coefficient of thermal expansion of the finally produced film can be significantly lowered, and at the same time, it can be seen that there is no loss in the light transmittance due to the decrease in the coefficient of thermal expansion.

The polycarbonate resin of the semi-IPN system manufactured according to the present invention secures excellent light transmittance and low thermal expansion coefficient so as to manufacture a plastic substrate or display optical film having higher performance. It is a useful technique that can contribute.

Claims (19)

A polycarbonate having a main chain including at least one of the repeating units represented by the following Chemical Formulas 1 to 2, a bisphenol compound having an epoxy terminal containing the repeating unit represented by the following Chemical Formula 3, an amine curing agent, and an organic functional group Preparing a raw material mixture comprising silica particles; And Reacting the raw material mixture Including, The bisphenol-based compound is included in 5 to 95 parts by weight based on 100 parts by weight of the polycarbonate, the amine curing agent is a molar ratio of epoxy group / amine group [NH ₂ ] 0.5 to based on the epoxy group of the bisphenol compound 3.0, wherein the silica particles are contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the polycarbonate, and a method for producing a polycarbonate resin having a semi-IPN system. [Formula 1]

[Formula 2]

(3)

The method of claim 1, The polycarbonate is a method of producing a polycarbonate resin having a semi-interpenetrating network (semi-IPN system) having a weight average molecular weight of 400 to 50,000. The method of claim 1, The bisphenol-based compound having the epoxy terminal is a method for producing a polycarbonate resin having a semi-penetrating network (semi-IPN system) to react 10 to 90 parts by weight with respect to 100 parts by weight of the polycarbonate. delete The method of claim 1, The bisphenol-based compound having an epoxy terminal is a semi-IPN system of at least one selected from the group consisting of bisphenol A diglycidyl ether (DGEBA) and bisphenol F diglycidyl ether (DGEBF). The manufacturing method of polycarbonate resin which has. The method of claim 1, The bisphenol-based compound having an epoxy terminal is a method for producing a polycarbonate resin having a semi-penetrating network (semi-IPN system) to react 10 to 33 parts by weight with respect to 100 parts by weight of the polycarbonate. The method of claim 1, The amine curing agent is diethylene triamine (DETA), diethylene tetraamine, diethylene tetraamine (Triethylene Tetramine, TETA), methane diamine (MDA), N-aminoethyl pyrazine (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'-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'-Dimethylaniline (Diamino diphenyl methone), DAM or DDM), diamino diphenylsulfone ( Diamino diphenyl sulfone (DDS), 9-diphenyl-1,4-phenylenediamine, 1,3-phenylenediamine, and diaminodi A method for producing a polycarbonate resin having a semi-IPN system, which is at least one aromatic amine selected from the group consisting of phenylmethane (Diaminodiphenyl-methane). The method of claim 1, The amine curing agent is a poly having a semi-IPN system to react so that the molar ratio of epoxy group / amine group [NH ₂ ] to 1.0 to 2.5 based on the epoxy group of the epoxy compound Method for producing a carbonate resin. The method of claim 1, The average particle diameter of the silica particles bonded to the organic functional group is a method of producing a polycarbonate resin having a semi-penetration network (semi-IPN system) of 5 to 900 nm. The method of claim 1, The average particle diameter of the silica particles bonded to the organic functional group is a method of producing a polycarbonate resin having a semi-penetration network (semi-IPN system) of 10 to 500 nm. The method of claim 1, The silica particles having the organic functional groups bonded thereto are prepared by reacting a silica particle having a hydroxy terminus with a silane compound represented by the following Formula 4, or by reacting a silane compound represented by the following Formula 5. Method for producing a polycarbonate resin having a (semi-IPN system). [Formula 4]

[Chemical Formula 5]

Where At least one of R ¹ , R ² , and R ³ is hydroxy, alkoxy having 1 to 10 carbon atoms, and the rest are each independently alkyl having 1 to 10 carbon atoms, and arylene having 6 to 20 carbon atoms, alkyl arylene, or Selected from the group consisting of arylalkylene, R ⁴ is selected from the group consisting of alkyl having 1 to 10 carbon atoms, and arylene, alkylarylene, or arylalkylene having 6 to 20 carbon atoms, At least one of R ⁵ , R ⁶ , and R ⁷ is hydroxy, alkoxy having 1 to 10 carbon atoms, and the rest are each independently alkyl having 1 to 10 carbon atoms, and arylene having 6 to 20 carbon atoms, alkyl arylene, or Selected from the group consisting of arylalkylene, R ⁸ is selected from the group consisting of alkyl having 1 to 10 carbon atoms, and arylene, alkyl arylene, or arylalkylene having 6 to 20 carbon atoms. The method of claim 1, The silica particles bonded to the organic functional group is a method for producing a polycarbonate resin having a semi-interpenetrating network (semi-IPN system) is reacted at 1 to 6.6 parts by weight based on 100 parts by weight of the polycarbonate. The method of claim 1, The raw material mixture is a method for producing a polycarbonate resin having a semi-penetrating network (semi-IPN system) to react at a temperature of 150 to 250 ℃. Claims 1 to 3 or 5 to 13 of the method according to any one of the claims comprising a polycarbonate, a bisphenol-based compound having an epoxy end, and a repeating unit derived from an amine curing agent Polycarbonate resin having a penetrating network (semi-IPN system). An optical film comprising a polycarbonate resin having a semi-IPN system according to claim 14. The method of claim 15, The optical film has a thermal expansion coefficient of 60 ppm / ℃ or less. The method of claim 15, The optical film has a thermal expansion coefficient of 10 to 50 ppm / ℃. The method of claim 15, The optical film is an optical film for display substrate material having a light transmittance of 84% or more. The method of claim 15, The optical film is an optical film for display substrate material having a light transmittance of 84% to 90%.