KR20210121647A - Curable resine composition and transparent film prepared by using the same - Google Patents

Abstract

The present invention relates to a curable resin composition and a transparent film prepared by using the same. The curable resin composition comprises a binder resin comprising repeating units represented by specific chemical formula structures, an epoxy compound, an antioxidant, and a solvent, wherein a phosphorus-based antioxidant and a phenol-based antioxidant are used as the antioxidant, thereby exhibiting high heat resistance and excellent mechanical properties and manufacturing a transparent film capable of being applicable to a high functional display or semiconductor element.

Description

Curable resin composition and a transparent film manufactured using the same

The present invention relates to a curable resin composition and a transparent film prepared using the same, and more particularly, to a curable resin composition for forming a protective film applied to a touch sensor, and a transparent film prepared using the same.

The touch screen panel is an input device that allows a user's command to be input by selecting instructions displayed on a screen, such as an image display device, with a human hand or an object, and includes a film touch sensor. The touch screen panel is provided on the front face of the image display device and converts a contact position in direct contact with a person's hand or an object into an electrical signal. Accordingly, the instruction content selected at the contact position is accepted as an input signal.

Since such a touch screen panel can replace a separate input device connected to an image display device and operated, such as a keyboard and a mouse, the range of its use is gradually expanding.

In general, a touch screen panel is attached to the outer surface of a flat panel display device, such as a liquid crystal display device and an organic light emitting display device, and is often commercialized. Accordingly, the touch screen panel is required to have high transparency and thin thickness.

Recently, a flexible flat panel display device is being developed, and in this case, a touch screen panel attached to the flexible flat panel display device is also required to have flexible characteristics. Accordingly, even in the case of a film touch sensor provided in a touch screen panel, a protective layer having flexible characteristics is applied.

However, when the protective layer is formed using the alicyclic olefin resin disclosed in Korean Patent Application Laid-Open No. 10-2007-0011281, a resin composition containing inorganic fine particles and a solvent, etc., it provides characteristics such as flexibility and chemical resistance. there are difficulties with

In addition, when a conventional curable resin composition used in a display or semiconductor device process is used, outgas and yellowing phenomena occur, resulting in problems such as increased resistance during electrode formation.

Therefore, there is a need for a curable resin composition that has flexible properties and does not cause deterioration of electrode properties in a subsequent process.

Korean Patent Publication No. 10-2007-0011281

An object of the present invention is to provide a curable resin composition and a transparent film that exhibit high heat resistance and excellent mechanical properties, and can produce a transparent film applicable to a high-functional display or semiconductor device.

The present invention includes (A) a binder resin comprising a structural unit represented by Formula 1 and a structural unit represented by Formula 2, (B) an epoxy compound, (C) an antioxidant, and (D) a solvent, The antioxidant provides a curable resin composition comprising a phosphorus-based antioxidant and a phenol-based antioxidant.

[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently hydrogen or a substituted or unsubstituted C ₁ to C ₂₅ hydrocarbon group, and n is an integer of 1 to 10.

[Formula 2]

In Formula 2, m is an integer from 1 to 10.

In addition, the present invention provides a transparent film prepared by using the curable resin composition.

The curable resin composition according to the present invention may exhibit high heat resistance and excellent mechanical properties.

In addition, the transparent film manufactured using the curable resin composition of the present invention has excellent dimensional stability between processes of display devices or semiconductor devices, and reduces the amount of outgas generated between processes to form electrodes during device processes It is possible to prevent a problem in which the resistance increases at the time of operation, thereby reducing the defect rate of the device. Furthermore, by controlling the yellowing phenomenon occurring in the cured film, that is, the transparent film itself, it is possible to improve the device characteristics of a high-functional display or semiconductor.

As described above, since the transparent film of the present invention has excellent properties, it can be usefully applied as a substrate in a semiconductor device or a flexible display device, and a protective film applied to a film touch sensor, a solar cell, an organic light emitting diode, etc. can also be used.

The present invention includes a binder resin, an epoxy compound, an antioxidant and a solvent including repeating units represented by a specific chemical structure, and includes a phosphorus-based antioxidant and a phenol-based antioxidant as the antioxidant, thereby providing high heat resistance and excellent mechanical properties Disclosed are a curable resin composition capable of producing a transparent film that exhibits characteristics and is applicable to a high-functional display or semiconductor device, and a transparent film manufactured using the same.

The transparent film of the present invention having the above characteristics, by having the above-described characteristics, can be usefully applied to a protective film applied to a film touch sensor, a substrate in a semiconductor device or a flexible display device, a solar cell, an organic light emitting diode, etc. .

Hereinafter, components of the curable resin composition according to embodiments of the present invention will be described in detail. However, this is only an example, and the present invention is not limited thereto.

<Curable resin composition>

The curable resin composition of the present invention comprises (A) a binder resin; (B) an epoxy compound, and (C) an antioxidant, and may further include (C) a solvent for dissolving the components.

(A) binder resin

In one embodiment, the curable resin composition of the present invention includes a copolymerized binder resin including a lactone-based monomer and a methacrylic monomer. The binder resin may be polymerized by further including additional monomers as necessary.

The lactone-based monomer includes a heterocyclic ring structure containing -COO- in the molecule, wherein the ring structure is any of a 4-membered ring structure, a 5-membered ring structure, a 6-membered ring structure, a 7-membered ring structure, an 8-membered ring structure, etc. Also, it may preferably have a 6-membered ring structure.

For example, the binder resin may include a unit structure represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently hydrogen or a substituted or unsubstituted C ₁ to C ₂₅ hydrocarbon group, and n is an integer of 1 to 10.

Examples of the hydrocarbon group include a saturated or unsaturated linear, branched or cyclic aliphatic hydrocarbon group and an aromatic hydrocarbon group. _{Examples of the aliphatic hydrocarbon group include a C 1} to C ₂₅ alkyl group such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group; _{C 2} to C ₂₅ alkenyl group such as ethenyl group and propenyl group; and a C ₃ to C ₂₅ cycloalkyl group such as a cyclopentyl group and a cyclohexyl group. _{Examples of the aromatic hydrocarbon group include a C 6} to C ₂₅ aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group; _{and a C 7} to C ₂₅ aralkyl group such as a benzyl group and a phenylethyl group. In the hydrocarbon group exemplified above, at least one -CH ₂ - may be substituted with an oxygen atom, and at least one hydrogen of the hydrocarbon group is at least one selected from a hydroxyl group, a carboxyl group, an ether group, and an ester group. may be substituted by a group.

The binder resin according to the present invention may exhibit excellent transparency and rigidity retention characteristics by including the structural unit of Chemical Formula 1 above.

In one embodiment of the present invention, the binder resin is copolymerized including a methacrylic monomer, and may include a unit structure represented by the following formula (2).

[Formula 2]

In Formula 2, m is an integer of 1 to 10.

The binder resin of the present invention may further improve the mechanical strength or chemical resistance of the cured film, that is, the transparent film, by including the unit structure represented by Chemical Formula 2 above.

Accordingly, the transparent film made of the curable resin composition according to the present invention exhibits a relatively high glass transition temperature (Tg) of 145 ° C. to 250 ° C., thereby providing an excellent effect of dimensional stability between high temperature processes of 150 to 3000 ° C. have.

In addition, the binder resin of the present invention may include an additional repeating unit structure in addition to Chemical Formulas 1 and 2 above. For example, it may further include additional structures such as maleimide structure, glutarimide structure, etc.) and cyclic anhydride structure (eg, maleic anhydride structure, glutaric anhydride structure, etc.).

In the present invention, only one type of the additional structure exemplified above may be included in the main chain, or two or more types may be included in the main chain. Preferably, at least one selected from a maleimide structure, a maleic anhydride structure, a glutalimide structure, and a glutaric anhydride structure may be included among the materials exemplified above.

The curable resin composition according to an embodiment of the present invention may have better mechanical properties and heat resistance when using the binder resin further including the additional structure, and may exhibit desired optical properties.

In addition, the binder resin included in the curable resin composition of the present invention may be included in an amount of 30 to 90 parts by weight, preferably 40 to 70 parts by weight, based on 100 parts by weight of the total solid content in the composition. When the binder resin is included in the above content range in the curable resin composition of the present invention, it can have high transparency, heat resistance and chemical resistance.

(B) Epoxy compound

The curable resin composition according to an embodiment of the present invention includes an epoxy compound.

Specific examples of the epoxy compound include biphenyl-based epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, cresol novolac epoxy resin, phenol novolac epoxy resin, tetrafunctional epoxy resin, triphenol methane-type epoxy resin, alkyl Modified triphenol methane type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, dicyclopentadiene modified phenol type epoxy resin, etc. are mentioned.

Commercial products of the epoxy compound that can be used in the curable resin composition of the present invention include, but are not limited to, HP7200 (DIC Corporation).

The curable resin composition of the present invention may include at least one compound selected from the group consisting of the epoxy compounds exemplified above.

According to an embodiment of the present invention, the mechanical properties and chemical resistance of the curable resin composition can be improved by mixing and using the above-described binder resin and the epoxy compound.

In addition, the epoxy compound included in the curable resin composition of the present invention may be included in an amount of 40 to 70 parts by weight based on 100 parts by weight of the total solid content in the composition. When the epoxy compound is included in the above content range in the curable resin composition of the present invention, there is an advantage that can provide more improved mechanical properties.

(C) antioxidants

In one embodiment, the antioxidant includes a phosphorus-based antioxidant and a phenol-based antioxidant.

The curable resin composition of the present invention can provide improved thermal resistance including phosphorus-based antioxidants and phenol-based antioxidants, thereby reducing the amount of outgas generated between processes, thereby reducing the defect rate between device processes It is possible to not only reduce the yellowing phenomenon, but also control the yellowing phenomenon.

The phosphorus-based antioxidant is not particularly limited as long as it is a substance containing a phosphorus-based functional group. Specifically, the phosphorus-based antioxidant of the present invention is isodecyl diphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, 3,9-bis (2,6-di-tert-butyl-4) -Methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, diisodecylpentaerythritol diphosphite, bis(2,4-di-t-butyl Phenyl) pentaerythritol diphosphite, 2,2'-methylenebis (4,6-di-t-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, 6- [3- (3- t-Butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1,3,2]dioxaphosphepine, tri Phenylphosphite, phenyldiisodecylphosphite, 4,4'-butylidene-bis(3-methyl-6-t-butylphenylditridecyl)phosphite, octadecylphosphite, tris(nonylphenyl)phosphite Phite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2,4- Di-t-butylphenyl)phosphite, cyclic neopentanetetraylbis(2,4-di-t-butylphenyl)phosphite, clickneopentanetetraylbis(2,6-di-t-butylphenyl) Phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite, tetrakis(2,4-di-t-butylphenyl)[1,1-biphenyl]-4, 4'diylbisphosphonite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester, phosphonic acid, etc. are mentioned.

According to one embodiment, the phosphorus-based antioxidant is preferably isodecyl diphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, etc. in terms of heat resistance and heat resistance discoloration prevention.

Commercially available products of the phosphorus antioxidant include ADK AO-60 (manufactured by ADEKA) and ADK AO-60 (manufactured by ADEKA).

The phenolic antioxidant is not particularly limited as long as it is a material containing a phenolic functional group. Specifically, the phenolic antioxidant of the present invention is 3,9-bis[2-3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]- 2,4,8,10-Traoxaspiro[5.5]undecane, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,3 ,5,-trimethyl-2,4,6,-tris(3'5'-di-t-butyl-4-hydroxybenzyl)benzene, triethyleneglycol-bis[3-(3-t-butyl-5) -methyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-t-butyl-3-methylphenol), tris- (3,5-di-t-butyl-4-hydr Roxybenzyl)-isocyanurate, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurate, 1,6-hexanediol-bis[ 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydro hydroxyphenyl) propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6 -tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2,4-bis[(octylthio)methyl]-O-cresol, 1,6-hexanediol-bis-[3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2 ,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), 1,1,3-tris( 2-methyl-4-hydroxy-5-t-butylphenyl)butane, and 1,3,5-tris(4-hydroxybenzyl)benzene and tetrakis[methylene-3-(3,5′-di- t-butyl-4'-hydroxyphenyl propionate)]methane, etc. are mentioned.

According to one embodiment, among the phenolic antioxidants, in terms of heat resistance and heat resistance discoloration prevention, 9-bis[2-3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]- 1,1-dimethylethyl]-2,4,8,10-traoxaspiro[5.5]undecane, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like.

Commercially available products of the phenolic antioxidant include ADK STAB-135A (manufactured by ADEKA), ADK STAB-2112 (manufactured by ADEKA), and the like.

In the present invention, the phosphorus-based antioxidant may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total solid content of the curable resin composition. In addition, the phenol-based antioxidant may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total solid content of the curable resin composition.

When the phosphorus-based antioxidant and the phenol-based antioxidant are included in each of the above content ranges in the curable resin composition of the present invention, it is possible to reduce the outgas generation rate between processes, and it exhibits improved heat-resistant discoloration prevention properties to control so that yellowing does not occur. There are advantageous advantages.

(D) solvent

The curable resin composition according to the present invention may include a solvent commonly used in the art.

The solvent is used to dissolve the above-mentioned components and to obtain excellent coating properties and a transparent thin film, and an appropriate solvent used in the art may be adopted in consideration of compatibility with the solid component.

Examples of the solvent used in the present invention include alcohols such as methanol, ethanol, methyl ethyl carbitol and diethylene glycol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; propylene glycol dialkyl acetates such as propylene glycol methyl ethyl acetate; propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone, and 4-hydroxy 4-methyl 2-pentanone; or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxyethyl propionate, 2-hydroxy 2-methylpropionate, 2-hydroxy 2-methylpropionate ethyl, methyl hydroxyacetate, ethyl hydroxyacetate, Butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-methyl hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxyl -Methyl butanoate, methyl methoxy acetate, ethyl methoxy acetate, propyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxy acetate , ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, butoxy ethyl acetate, propyl butoxy acetate, butyl butoxy acetate, 2-methoxy methyl propionate, 2-methoxy ethyl propionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxyflopionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate , 2-Butoxypropionate ethyl, 2-butoxypropionate propyl, 2-butoxypropionate butyl, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-methoxypropionate propyl, 3-ethoxypropionate methyl , 3-ethyl ethoxypropionate, 3-ethoxypropionate propyl, 3-ethoxypropionate butyl, 3-propoxypropionate methyl, 3-propoxypropionate ethyl, 3-propoxypropionate propyl, 3-propoxypropionate butyl, esters such as 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate, each of which may be used alone or in combination of two or more. .

Considering the film-forming coating process, the solvent preferably includes propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate.

The solvent may be added so that the entire composition may have an appropriate viscosity, and thus the content thereof is not particularly limited. Other components in the composition for forming a protective layer are added so as to have the above-mentioned content based on 100 parts by weight of the total composition, and occupy the remaining content (residual amount) of the composition.

In the present invention, "residual amount" means the remaining amount such that the weight of the total composition further including the essential components and other additional components of the present invention becomes 100 weight, and due to the meaning of the "residual amount", the composition of the present invention is added It is not limited to the thing which does not contain an ingredient.

For example, based on 100 parts by weight of the total curable resin composition, 20 to 80 parts by weight may be included, but this is only an example and is not limited thereto.

<Transparent film>

The present invention provides a transparent film prepared by using the above-described curable resin composition.

As an example, the transparent film of the present invention may be used as a protective film for the touch sensor film.

The film touch sensor is a separation layer; a protective layer disposed on the separation layer; an electrode pattern layer disposed on the protective layer; and an insulating layer disposed on the electrode pattern layer.

In the present invention, the film touch sensor is manufactured by separating the manufactured laminate from the carrier substrate, and the manufacturing process is performed on the carrier substrate, and the separation layer is a layer formed for separation from the carrier substrate. This separation layer is not removed after separation from the carrier substrate, but covers the electrode pattern layer to protect the electrode pattern layer.

On the other hand, the protective layer serves to cover the electrode pattern layer like the separation layer to prevent contamination of the electrode pattern layer and breakage of the electrode pattern layer upon separation from the carrier substrate.

The transparent film of the present invention may be used as the protective layer.

The transparent film according to the present invention can provide excellent transmittance, flexibility, and chemical resistance, as well as suppress the occurrence of cracks during peeling of the film touch sensor, and provide excellent etch resistance.

In addition, since the transparent film according to the present invention exhibits a high glass transition temperature (Tg) and thus has excellent dimensional stability between high-temperature processes, it is possible to suppress thermal damage such as wrinkles that may occur during the film touch sensor manufacturing process.

Since the transparent film of the present invention has excellent properties, it can be usefully applied not only as a protective film applied to a film touch sensor, but also as a substrate in a solar cell, an organic light emitting diode, a semiconductor device, or a flexible display device.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are for explaining the present invention in more detail, and the scope of the present invention is not limited by the following examples. The scope of the present invention is indicated in the claims, and furthermore, it embraces all modifications within the meaning and scope equivalent to those recorded in the claims. In addition, in the following examples and comparative examples, "%" and "part" indicating the content are by weight unless otherwise specified.

Synthesis example

Synthesis Example 1: Monomer Synthesis Example (Synthesis of Ether Dimer Composition)

In a reactor equipped with a stirring device, a temperature sensor, and a cooling tube, 450.0 parts of α-hydroxymethyl methyl acrylate (RHMA-M) and 13.5 parts of 1,4-diazabicyclo[2,2,2]octane (DABCO) were added It heated up to 90 degreeC, injecting|pouring 0.9 parts of parts and p-methoxyphenol (MEHQ), and stirring. After internal temperature reached 85 degreeC, it was made to react for 9 hours, maintaining 90±5 degreeC in the inside of a reactor in a normal pressure state. After confirming that the reaction solution temperature had reached 40 °C or lower, 355.0 parts of methanol (MeOH) was added to dilute (condition: atmospheric pressure, 35±5 °C). This MeOH dilution solution was dropped into different reactors containing 1485.0 parts of water, and the RHMA ether dimer was crystallized (conditions: atmospheric pressure, 30°C or less). Thereafter, the obtained slurry containing the RHMA ether dimer was filtered using a pressure filter (conditions: normal pressure to 0.1 MPa, 15° C. or less), and then this filter cake was washed with water (conditions: normal pressure to 0.1 MPa, room temperature) . In washing, washing was repeated 3 times using 380.0 parts of water per one time. To the thus obtained RHMA ether dimer cake, 184.0 parts of propylene glycol monomethyl ether acetate (PGMEA) was added and dissolved (conditions: atmospheric pressure, 60°C). This was separated into an oil layer and an aqueous layer containing RHMA ether dimer, and the aqueous layer was removed (conditions: atmospheric pressure, 60°C). The oil layer was 412.5 parts, and the removed water layer was 141.9 parts. To an oil layer (solution containing RHMA ether dimer and PGMEA), PGMEA (5200.0 parts), MEHQ 0.049 parts, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4H-TEMPO ) 0.006 parts to obtain 932.5 parts of a composition (ether dimer composition).

A resin solution of Synthesis Example 2 was prepared using the ether dimer composition, that is, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate (MD) ether dimer composition.

Synthesis Example 2: Synthesis of binder resin of A-1

A separable flask equipped with a cooling tube was prepared as a reaction tank, and on the other hand, as a monomer dropping tank, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate of Synthesis Example 1 (hereinafter referred to as "MD") 20 parts by mass of methacrylic acid (hereinafter referred to as "MAA") and 20 parts by mass of methacrylic acid (hereinafter referred to as "MAA") are prepared by mixing well with stirring, and 3.5 mass of n-dodecanthiol (hereinafter referred to as "n-DM") as a chain transfer agent dropping tank Part and 32 parts by mass of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") were prepared by mixing well with stirring. 128 parts by mass of PGMEA was poured into the reactor, substituted with nitrogen, and heated in an oil bath while stirring to raise the temperature of the reactor to 90°C. After the temperature of the reaction tank was stabilized at 90 degreeC, dripping was started from the monomer dripping tank and the chain transfer agent dripping tank. Dropping was performed over 135 minutes, respectively, maintaining temperature at 90 degreeC. After completion of dripping, the temperature was started 60 minutes later, the reaction tank was 110 degreeC, and 110 degreeC was hold|maintained for 3 hours. Once the internal temperature was cooled to room temperature, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen/nitrogen = 5/95 (v/v) mixed gas was started. Then, 96 parts of PGMEA was added, and binder resin A-1 was obtained.

Examples and Comparative Examples: Preparation of Curable Resin Compositions

After mixing the binder resin described in Synthesis Example 2 and the epoxy compound (HP-7200; DIC Corporation) 1:1 with a solvent so that the total solid content is 20% by weight, an antioxidant is added in the amount shown in Table 1 below. to prepare a curable resin composition.

item Phenolic antioxidants Phosphite-based antioxidants Kinds Content (parts by weight) Kinds Content (parts by weight) Example 1 A 0.1 C 0.1 Example 2 A 0.1 C One Example 3 A 0.1 C 10 Example 4 A One C 0.1 Example 5 A One C One Example 6 A One C 10 Example 7 A 10 C 0.1 Example 8 A 10 C One Example 9 A 10 C 10 Example 10 B 0.1 C 0.1 Example 11 B 0.1 C One Example 12 B 0.1 C 10 Example 13 B One C 0.1 Example 14 B One C One Example 15 B One C 10 Example 16 B 10 C 0.1 Example 17 B 10 C One Example 18 B 10 C 10 Example 19 A 0.1 D 0.1 Example 20 A 0.1 D One Example 21 A 0.1 D 10 Example 22 A One D 0.1 Example 23 A One D One Example 24 A One D 10 Example 25 A 10 D 0.1 Example 26 A 10 D One Example 27 A 10 D 10 Example 28 B 0.1 D 0.1 Example 29 B 0.1 D One Example 30 B 0.1 D 10 Example 31 B One D 0.1 Example 32 B One D One Example 33 B One D 10 Example 34 B 10 D 0.1 Example 35 B 10 D One Example 36 B 10 D 10 Example 37 A 15 C 15 Example 38 B 15 C 15 Example 39 A 15 D 15 Example 40 B 15 D 15 Example 41 A 0.05 C One Example 42 A One C 0.05 Example 43 B 0.05 C One Example 44 B One C 0.05 Example 45 A 0.05 D One Example 46 A One D 0.05 Example 47 B 0.05 D One Example 48 B One D 0.05 Comparative Example 1 A One - - Comparative Example 2 - - C One Comparative Example 3 B One - - Comparative Example 4 - - D One

A: AO-60 (manufactured by ADEKA)

B: AO-80 (made by ADEKA)

C: STAB-135A (made by ADEKA)

D: STAB-2112 (made by ADEKA)

Substrate manufacturing

Each of the curable resin compositions of Examples and Comparative Examples was coated on a glass substrate to have a film thickness of 3 μm using the spin coater (Mikasa), and then heated to form a cured film. The formed cured film volatilizes the residual solvent through the postbake process. The thus-prepared transparent film was tested by the following physical property measurement method and conditions.

Experimental example

1. Yellowing gradient

The substrate coated with the curable resin composition of Examples and Comparative Examples was further heated at 230 degrees for 1 hour to measure transmittance change. The transmittance of light at a wavelength of 400 nm of the attached substrate was measured using a spectrophotometer (manufactured by Hitachi, Ltd., U3210). The results are shown in Table 2 below.

2. Pyrolysis temperature

The thermal decomposition temperature (ie, thermal decomposition initiation temperature) of the specimen was measured using Q600TGA (thermogravimetric analysis) of TA Instruments under the condition of a temperature increase rate of 10 °C/min from room temperature to 500 °C. An evaluation table was prepared based on the temperature decreasing by 1% from the total weight of the curable resin composition. The results are shown in Table 2 below.

<Evaluation criteria>

○: 1% reduction in total weight in the range from 300℃ to 310℃

△: 1% reduction in total weight in the section exceeding 290℃ and below 300℃

X: 1% reduction in total weight in the section above 280℃ and below 290℃

3. Outgas Analysis

Using Frontier-Lab EGA/PY-3030D equipment, prepare a coated sample substrate in a size of 10x30 mm and load the sample. After loading, the gas collected for 30 minutes in a temperature range of 230 ℃ was analyzed, the material was analyzed through the results obtained according to the retention time, and the total amount of emitted gas was evaluated. Thereafter, the reduction rate compared to the reference sample to which no antioxidant was added was evaluated, and the results are shown in Table 2 below.

< Outgas evaluation criteria>

○: More than 20 ~ 40% or less decrease

△: more than 5 ~ 20% or less decrease

X : Less than 1 ~ 5% or less

item yellowing gradient Thermal decomposition temperature (℃) outgas Example 1 ○ ○ ○ Example 2 ○ ○ ○ Example 3 ○ ○ ○ Example 4 ○ ○ ○ Example 5 ○ ○ ○ Example 6 ○ ○ ○ Example 7 ○ ○ ○ Example 8 ○ ○ ○ Example 9 ○ ○ ○ Example 10 ○ ○ ○ Example 11 ○ ○ ○ Example 12 ○ ○ ○ Example 13 ○ ○ ○ Example 14 ○ ○ ○ Example 15 ○ ○ ○ Example 16 ○ ○ ○ Example 17 ○ ○ ○ Example 18 ○ ○ ○ Example 19 ○ ○ ○ Example 20 ○ ○ ○ Example 21 ○ ○ ○ Example 22 ○ ○ ○ Example 23 ○ ○ ○ Example 24 ○ ○ ○ Example 25 ○ ○ ○ Example 26 ○ ○ ○ Example 27 ○ ○ ○ Example 28 ○ ○ ○ Example 29 ○ ○ ○ Example 30 ○ ○ ○ Example 31 ○ ○ ○ Example 32 ○ ○ ○ Example 33 ○ ○ ○ Example 34 ○ ○ ○ Example 35 ○ ○ ○ Example 36 ○ ○ ○ Example 37 ○ ○ △ Example 38 ○ ○ △ Example 39 ○ ○ △ Example 40 ○ ○ △ Example 41 △ ○ ○ Example 42 ○ ○ △ Example 43 △ ○ ○ Example 44 ○ ○ △ Example 45 △ ○ ○ Example 46 ○ ○ △ Example 47 △ ○ ○ Example 48 ○ ○ △ Comparative Example 1 X X X Comparative Example 2 △ △ △ Comparative Example 3 X X X Comparative Example 4 △ △ △

Referring to Table 2, when the curable resin composition according to the embodiment of the present invention was used for manufacturing the transparent film, it was confirmed that high heat resistance and excellent mechanical properties were exhibited. Specifically, when a transparent film is manufactured using the curable resin composition according to the embodiments of the present invention, there is little yellowing due to heat treatment and excellent stability due to high thermal decomposition temperature, and the amount of outgas generated by additional heat treatment Little is known.

On the other hand, when the curable resin composition according to the comparative example was used, yellowing occurred or the outgas reduction rate was not good, or the thermal decomposition temperature was low and the stability was deteriorated, resulting in significantly lowered results compared to the example.

Claims (8)

(A) a binder resin comprising a structural unit represented by Formula 1 and a structural unit represented by Formula 2, (B) an epoxy compound, (C) an antioxidant, and (C) a solvent,
The antioxidant comprises a phosphorus-based antioxidant and a phenol-based antioxidant, the curable resin composition.
[Formula 1]

(In Formula 1, R ₁ and R ₂ are each independently hydrogen, or a substituted or unsubstituted C ₁ to C ₂₅ hydrocarbon group, and n is an integer of 1 to 10. )
[Formula 2]

(In Formula 2, m is an integer from 1 to 10.) The curable resin composition of claim 1, wherein the phosphorus-based antioxidant is included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total solid content of the curable resin composition. The curable resin composition of claim 1, wherein the phenol-based antioxidant is included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total solid content of the curable resin composition. The curable resin composition of claim 1, wherein the phosphorus-based antioxidant comprises at least one selected from isodecyl diphenyl phosphite and tris(2,4-di-t-butylphenyl)phosphite. The method according to claim 1, wherein the phenolic antioxidant is 9-bis[2-3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2; At least one selected from 4,8,10-traoxaspiro[5.5]undecane and pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] A curable resin composition comprising a. The method according to claim 1, wherein the epoxy compound is a biphenyl-based epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a cresol novolac epoxy resin, a phenol novolac epoxy resin, a tetrafunctional epoxy resin, a triphenol methane type epoxy resin, A curable resin composition comprising at least one selected from the group consisting of an alkyl-modified triphenol methane-type epoxy resin, a naphthalene-type epoxy resin, a dicyclopentadiene-type epoxy resin, and a dicyclopentadiene-modified phenol-type epoxy resin. The method according to claim 1, When manufacturing the cured film, the thermal decomposition initiation temperature of the cured film will exceed 300 ℃, the curable resin composition. A transparent film made of the curable resin composition of any one of claims 1 to 7.