KR100625038B1 - Novel polymers and thin film compositions containing them - Google Patents

Abstract

The present invention provides a novel copolymer represented by the following Chemical Formula 1, and a thin film composition comprising a curing catalyst and a solvent added thereto, wherein the thin film composition comprising the polymer of the present invention is a curing catalyst (acid). By adding a generator or a radical initiator) or an auxiliary curing agent, it becomes a thermosetting or photocurable flattening film (Overcoat), and can produce a flattening film having excellent transparency, flatness and hardness required in manufacturing a color filter.

In the above formula, X is derived from an olefin monomer having a functional group selected from an olefin or a hydroxyl group, a carboxylic acid group, an ether group, a nitrile group and an ester, and R ₁ and R ₃ are different from each other and are a hydrogen atom or a methyl group. , R ₂ and R ₄ are different from each other hydrogen, glycidyl methyl group, hydroxyalkyl group or alkyl group having 1 to 33 carbon atoms, Y is a functional group selected from ketones, esters, hydroxy, ether, halogen, nitrile and alkoxy Derived from olefin compounds or styrene derivatives or acrylonitrile monomers, with or without repeating units l, m, n, o where l is 0 <l / (l + m + n + o) <0.7 , m is 0.1 <m / (l + m + n + o) <0.7, n is 0≤n / (l + m + n + o) <0.5 and 0≤o / (l + m + n + o) The condition of <0.5 is satisfied.

Description

Novel acrylate polymer and thin film composition comprising it             

1 and 2 are ¹ H-NMR data and GPC data for the polymer represented by Formula 2,

3 and 4 are ¹ H-NMR data and GPC data for the polymer represented by Formula 3,

5 and 6 are ¹ H-NMR data and GPC data for the polymer represented by Formula 4,

7 and 8 are ¹ H-NMR data and GPC data for the polymer represented by Formula 5,

9 and 10 are ¹ H-NMR data and GPC data for the polymer represented by Chemical Formula 6;

The present invention relates to a novel polymer in which a polymer is cured by a crosslinking reaction by heat or light and a thin film composition containing the same. More specifically, the crosslinking reaction is progressed by radicals or strong acids generated by light or heat, and thus the hardness is high. A novel polymer capable of forming a thin film and a thin film composition such as a TFT-LCD comprising the same.

Recently, with the rapid development of the LCD industry, interest in thin films is increasing.

The use of thin film technology is diversified from ultrafine semiconductor processes to general household appliances and furniture. For example, the semiconductor manufacturing process uses anti-reflective coatings to prevent light reflections, external coatings to improve surface properties in household appliances and furniture, and LCD processes use thin film compositions to protect internal planarization and top of color filters. have.

Techniques for manufacturing thin films can be broadly classified into two types. The first method is to cure using a radical initiator. In this case, the polymer mainly used is a polymer having an unreacted acrylic functional group at its terminal. Unreacted acrylic functional groups are polymerized by radicals and heat, and the thin film is converted into a harder film. Another method of thin film production is to use a polymer containing an epoxy functional group. In this case, crosslinking reaction is advanced using the crosslinking agent or cation catalyst of an amine component.

The technique of preparing a thin film by using a radical initiator has the inconvenience of blocking oxygen in the air, while the technique of manufacturing a thin film by cations or amines does not need to block oxygen.

Thin film compositions include polymers, curing catalysts (acid generators or radical initiators), auxiliary curing agents, surfactants and some additives, and solvents for dissolving them. In the case of polymers in general, acrylate polymers or urethane polymers are generally used. However, in the case of these polymers, since the glass transition temperature of the polymer itself is low, it is difficult to prepare a thin film having high hardness. In addition, it is difficult to uniformly coat the thin film because of its poor solubility in general organic solvents.

In order to compensate for the disadvantage of the hardness of the acrylate polymer, a monomer such as isobornyl acrylate (isobornyl acrylate) in which a lot of hydrocarbon functional groups have been introduced has been introduced. However, even if such functional groups are introduced, there are still difficulties in ensuring solubility in solvents and uniformity of coatings.

Therefore, the inventors of the present invention, while searching for a method to compensate for the shortcomings of the acrylate polymer used in the thin film composition, introduced the olefin compound such as norbonene into the main chain of the polymer, the low glass transition of the acrylate It is possible to improve the temperature, solubility in solvents, uniformity when forming a thin film, and to introduce a functional group into the side chain portion of the acrylate monomer, and to include a functional group that can be cured by a strong acid or radical. Developed.

An object of the present invention is to provide a novel polymer useful as a thin film composition having a high glass transition temperature and high solubility in a solvent.

In addition, an object of the present invention is to provide a thin film composition having improved permeability and flatness by containing such a novel polymer.

The novel polymer of the present invention for achieving the above object is characterized by that represented by the following formula (1).

Formula 1

In the above formula, X is derived from an olefin monomer having a functional group selected from an olefin or a hydroxyl group, a carboxylic acid group, an ether group, a nitrile group and an ester, and R ₁ and R ₃ are different from each other and are a hydrogen atom or a methyl group. , R ₂ and R ₄ are different from each other hydrogen, glycidylmethyl, hydroxyalkyl or alkyl group having 1 to 33 carbon atoms, Y is a functional group selected from ketones, esters, hydroxy, ethers, halogens, nitriles and alkoxy Derived from olefin compounds or styrene derivatives or acrylonitrile monomers, with or without repeating units l, m, n, o where l is 0 <l / (l + m + n + o) <0.7 , m is 0.1 <m / (l + m + n + o) <0.7, n is 0≤n / (l + m + n + o) <0.5 and 0≤o / (l + m + n + o) The condition of <0.5 is satisfied.

In addition, the thin film composition according to the present invention is characterized in that it comprises a copolymer represented by the formula (1), an acid generator and a solvent.

The present invention consists of an acrylate polymer containing an olefin functional group in the polymer backbone and a thin film composition containing the same.

<Polymer>

The novel polymer represented by the formula (1) obtained according to the present invention comprises a monomer (and an acrylic or methacrylic monomer having a functional group selected from hydroxyalkyl group, hydroxy group, glycidyl group or alkyl group) in the main chain. The side chain is characterized by including a functional group capable of curing, such as a hydroxyl group or an epoxy group. In some cases, the polymer may be synthesized by adding a styrene derivative or an olefin derivative including an acrylonitrile or a hydroxyl group as a monomer in order to improve flatness, hardness, adhesion, and the like.

In addition, the polymer generally contains a functional group that can be cured by a strong acid or radical, but may not be included in some cases.

Polymers have different physical and chemical performances depending on the type and content of monomers in the polymer. In general, when the polymer is hydrophilic, the adhesive strength increases, but the hardness of the thin film is deteriorated. In addition, if the hydrophilicity or hydrophobicity is too high, solubility in organic solvents is poor.

The copolymer represented by Formula 1 may be a block copolymer, a random copolymer or a graft copolymer.

Polymerization of the polymer represented by the formula (1) can be carried out by conventional methods, but radical polymerization is preferred.

Radical polymerization initiators are common such as azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), lauryl peroxide, azobisisocapronitrile, azobisisovaleronitrile, and tert-butyl hydroperoxide. There is no particular limitation as long as it is used as a radical polymerization initiator. The polymerization reaction can be carried out by bulk polymerization, solution polymerization, suspension polymerization, block-suspension polymerization, emulsion polymerization, etc.The polymerization solvent is benzene, toluene, xylene, halogenated benzene, diethyl ether, tetrahydrofuran, ester 1 type or more can be selected and used out of the said, ether, lactone, ketone, and amide.

Polymerization temperature can be suitably selected and used according to the kind of catalyst.

The molecular weight distribution of the polymer can be appropriately adjusted by changing the amount of use of the polymerization initiator and the reaction time.

It is preferable to remove the unreacted monomers and by-products remaining in the reaction mixture after the polymerization is completed by precipitation with a solvent.

On the other hand, it can be divided into several methods of input of raw materials during the polymerization reaction. Put all the raw materials into the reactor at once and proceed with the reaction, slow dropping of the acrylate monomer which is faster than olefin, and dropping the initiator and acrylate, and finally, all raw materials with solvent The method of dripping into a reactor gradually is mentioned. In general, a method of slowly dropping an acrylate monomer or an initiator and an acrylate monomer may include a large number of olefin monomers in the main chain. In order to include a large number of olefin monomers in the main chain, in addition to this method, a method in which an olefin is used in excess of the acrylate monomer is possible, but in this case, there is a problem of removing unreacted olefin monomer after the reaction is completed.

Generally, olefins and acrylates are known to have not undergone polymerization. In the case of norbornene derivatives and tertiary olefins, polymerization occurs with acrylate monomers. However, these olefins also hardly copolymerize with methacrylate and proceed with methacrylate homopolymerization. The methacrylate also undergoes a polymerization reaction when triple polymerization of acrylates and these olefins proceeds.

Preferably, the repeating unit of the polymer represented by Formula 1 satisfies (l + m) / (l + m + n + o)> 0.5. These olefin and acrylate polymerizations are significantly lower in molecular weight than in acrylate homopolymerization. However, as a polymer for general thin films, it shows a molecular weight in a very suitable state.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") by gel permeation chromatography (GPC) of the polymer represented by Chemical Formula 1 is 2,000 to 1,000,000, considering the applicability, hardness, etc. as a thin film, 3,000-50,000 Is preferably. The molecular weight distribution of the polymer is preferably 1.0 to 5.0, particularly preferably 1.0 to 3.0.

<Thin Film Composition>

The compound represented by the formula (1) can be used as a thin film composition , the thin film composition is 0.1 to 20 parts by weight of the acid generator based on 10 to 20% by weight of the compound represented by the formula (1), 100 parts by weight of the total solid component To 30 parts by weight, and 250 to 400 parts by weight of solvent based on 100 parts by weight of the total composition excluding the solvent, and 35 to 50 parts by weight of additives based on 100 parts by weight of the polymer represented by Formula 1 as necessary.
Looking at the components of the thin film composition is as follows.
Compound represented by formula (1)
The compound represented by Formula 1 may be used as a thin film composition.

Curing catalyst (acid generator or radical initiator)

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Acid generators generate acids by heat or light, depending on the properties of the compound. Compounds that generate acid by heat or light include onium-based iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, secondary-alkyl-toluenesulfonates and amido Drew.
As the radical initiator, the following may be used, which are generally commonly used Igacure series manufactured by Shiva, Switzerland, and may be represented, for example, under the trade names Igacure 184, Igacure 500, Igacure 369, and Igacure 907. Specific structural formulas of these compounds are as follows.

In particular, secondary-alkyl-toluenesulfonate is an acid generator that can be used easily because of its storage stability and synthesis method. Here, the secondary-alkyl moiety is a general expression of the polymer type, the type including the functional group, and the like. For example, a cyclohexyl group or a cyclopentyl group generates an acid at about 150 ° C., while a substituent such as norbornene generates an acid at around 110 ° C. In the case of tert-alkyl-toluenesulfonate, the storage stability is inferior, whereas in the case of primary-alkyl-toluenesulfonate, thermal stability is excellent and acid is generated at a very high temperature.

The acid generator or radical initiator may be used in an amount of 0.1 parts by weight to 30 parts by weight, preferably 0.3 parts by weight to 10 parts by weight, based on 100 parts by weight of the total solid component. Said acid generator or initiator may be used individually or in mixture of 2 or more types. If the content of the acid generator or radical initiator is less than 0.1 part by weight based on 100 parts by weight of the total solid component of the thin film composition, there is a disadvantage in that the curing speed is slow or sufficient curing does not occur. There is a problem that the coating properties deteriorate or the side reactions progress a lot, so transparency is not good.

In some cases, the crosslinking reaction may proceed with strong heat without using a catalyst. However, it is generally advantageous to use a catalyst in terms of hardness.

additive

In the polymer represented by Formula 1 according to the present invention, if there is a functional group capable of undergoing a curing reaction in itself, it is not necessary to add a separate polymer or a curing material, but in some cases, the hardness of the thin film may be adjusted or the adhesive force may be adjusted. Subsidiary materials can be added as a means for increasing.

In particular, these subsidiary materials may use polymers or monomers of polyols in which two or more glycidyl groups are substituted in order to increase the degree of curing, and polyols or phenol derivatives without substituents.
As another additive, a surfactant may be used to increase the uniformity of the thin film or increase the miscibility of the solution.

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menstruum

In order to obtain a uniform and flat coating film, the thin film composition of the present invention is used by dissolving in a solvent having a suitable evaporation rate and viscosity. Solvents having these properties include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , Propylene glycol monopropyl ether acetate, methyl isopropyl ketone, cyclohexanone, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-heptanone, ethyl carbitol, ethyl lactate, gamma-butyro Lactone and the like, and in some cases, these alone or two or more kinds of mixed solvents are used. The amount of the solvent is adjusted to uniformly form the thin film using an appropriate amount depending on the physical properties of the solvent, that is, volatility, viscosity, and the like.

The present invention will be specifically described as the following Synthesis Examples and Examples. However, the present invention is not limited to these synthesis examples and examples.

Synthesis of Polymer

Synthesis Example 1 Synthesis of Polymer Represented by Chemical Formula 2

After dissolving 97 g of norbornene and 7 g of AIBN in 400 g of ethyl acetate, the reactor was heated to 65 ° C. 44 g of methyl acrylate and 60 g of hydroxyethyl acrylate were slowly added dropwise to the reactor over 4 hours. After dropping, the mixture was stirred at the same temperature for 12 hours and then cooled to room temperature. The cooled reactant is added dropwise into excess hexane solution to give a white precipitate. This precipitate was dried in vacuo to give 118 g of the polymer of formula (2).

¹ H-NMR data and GPC data for the obtained polymer are shown in FIGS. 1 and 2.

Synthesis Example 2 Synthesis of Polymer Represented by Chemical Formula 3

After dissolving 350 g of norbornene and 14 g of AIBN in 1408 g of ethyl acetate, the reactor was heated to 65 ° C. 176 g of methyl acrylate, 151 g of hydroxyethyl acrylate and 27 g of acrylic acid were slowly added dropwise to the reactor over 4 hours. After dropping, the mixture was stirred at the same temperature for 12 hours and then cooled to room temperature. The cooled reactant is added dropwise into excess hexane solution to give a white precipitate. This precipitate was dried in vacuo to give 404 g of the polymer of formula (3).

¹ H-NMR data and GPC data for the obtained polymer are shown in FIGS. 3 and 4.

Synthesis Example 3 Synthesis of Polymer Represented by Chemical Formula 4

After dissolving 80 g of norbornene and 9 g of AIBN in 360 g of ethyl acetate, the reactor was heated to 65 ° C. 40 g of methyl acrylate, 50 g of hydroxyethyl acrylate and 10 g of glycidyl methacrylate were slowly added dropwise to the reactor over 4 hours. After dropping, the mixture was stirred at the same temperature for 12 hours and then cooled to room temperature. The cooled reactant is added dropwise into excess hexane solution to give a white precipitate. This precipitate was dried in vacuo to yield 106 g of a polymer of formula (4).

¹ H-NMR data and GPC data for the obtained polymer are shown in FIGS. 5 and 6.

Synthesis Example 4 Synthesis of Polymer Represented by Chemical Formula 5

 After dissolving 50 g of 3-methyl-3-butenol and 7.5 g of AIBN in 300 g of ethyl acetate, the reactor was heated to 70 ° C. 60 g of methyl acrylate, 15 g of hydroxyethyl acrylate and 25 g of glycidyl methacrylate were slowly added dropwise to the reactor over 4 hours. After dropping, the mixture was stirred at the same temperature for 4 hours and then cooled to room temperature. The cooled reactant is added dropwise into excess hexane solution to give a white precipitate. This precipitate was dried in vacuo to yield 105 g of the polymer of formula (5).

¹ H-NMR data and GPC data for the obtained polymer are shown in FIGS. 7 and 8.

Synthesis Example 5 Synthesis of Polymer Represented by Chemical Formula 6

After dissolving 30 g of norbornene and 7.5 g of AIBN in 300 g of ethyl acetate, the reactor was heated to 70 ° C. 45 g of isobonyl acrylate, 30 g of hydroxyethyl acrylate and 45 g of glycidyl methacrylate were slowly added dropwise to the reactor over 4 hours. After dropping, the mixture was stirred at the same temperature for 4 hours and then cooled to room temperature. The cooled reactant is added dropwise into excess hexane solution to give a white precipitate. This precipitate was dried in vacuo to give 114 g of polymer of formula (6).

¹ H-NMR data and GPC data for the obtained polymer are shown in FIGS. 9 and 10.

<Manufacturing and performance test of thin film composition>

Example 1

15 g of the polymer of Chemical Formula 2 obtained in Synthesis Example 1 and 7 g of an acrylate monomer having 3 to 6 functional groups, Aldrich's Dipentaerythritol penta- / hexa-acrylate 7 g, a photoinitiator Igacure907 0.5 g of Siva, Switzerland, propylene glycol mono A thin film composition was prepared by dissolving in 77 g of methyl ether acetate (hereinafter referred to as PGMEA) and filtering with a 0.2 µm membrane filter.

The obtained composition was spun onto the color filter substrate completed until the R.G.B (Red, Green, Blue) coating step at 700 rpm for 10 seconds and heated at 100 ° C. for 120 seconds to form a thin film. The thin film-formed R.G.B color filter substrate was cured with ultraviolet light emitted from a 350W mercury lamp to form a planarization film.

The flattening film formed by curing is formed to a thickness of 2.9-3.2㎛ including R.G.B, and has a flatness of 95% or more and a pencil hardness of 4H as a result of hardness measurement.

In addition, in order to measure the transmittance in the visible light region to form a thin film by rotating the coating for 10 seconds at 700rpm on a transparent glass for LCD for 10 seconds and then heated at 100 ℃. The thin film-formed LCD glass was cured with ultraviolet light emitted from a 350W mercury lamp to form a flattening film. The flattening film formed by curing was formed to a thickness of 1 ~ 1.5㎛ and showed a transmittance of 95% or more.

At this time, the hardness was measured by the Pencil Tester method, the transmittance was measured by UV Spectrophotometer, the flatness was measured by SEM (Scanning Electron Microscope).

Example 2

Instead of the polymer of Formula 2 obtained in Synthesis Example 1 was carried out in the same manner as in Example 1 using the polymer of Formula 3 obtained in Synthesis Example 2 as a result of the flattening film formed by curing the thickness of 2.9 ~ 3.2 ㎛ including RGB It was formed as, had a pencil hardness of 4H when measured in the same manner as in Example 1, showed a flatness of 95% or more and a transmittance of 95% or more.

Example 3

16 g of the polymer of Formula 4 obtained in Synthesis Example 3 and 5 g of iodide salt as an acid generator were dissolved in 82 g of solvent PGMEA, and then filtered through a 0.2 μm membrane filter to prepare a thin film composition.

The obtained composition was spun onto the color filter substrate completed until the R.G.B (Red, Green, Blue) coating step at 700 rpm for 10 seconds and heated at 100 ° C. for 120 seconds to form a thin film. The R.G.B color filter substrate on which the thin film was formed was cured at 220 ° C. for 40 minutes to form a flattening film.

The flattening film formed by curing was formed to a thickness of 2.5 to 3.2 μm including R.G.B, and had a pencil hardness of 4H as measured in the same manner as in Example 1, and showed flatness of 90% or more.

In addition, in order to measure the transmittance in the visible light region to form a thin film by rotating the coating for 10 seconds at 700rpm on a transparent glass for LCD for 10 seconds and then heated at 100 ℃. The thin film-formed LCD glass was cured at 220 ° C. for 40 minutes to form a flattening film.

The flattening film formed by curing was formed to a thickness of 0.9 ~ 1.5㎛ and showed a transmittance of 95% or more when measured in the same manner as in Example 1.

Example 4

 Instead of the polymer of Formula 4 obtained in Synthesis Example 3 was carried out in the same manner as in Example 3 using the polymer of Formula 5 obtained in Synthesis Example 4 as a result of the cured planarization film formed of 2.5 ~ 3.2㎛ including RGB Formed to a thickness, and measured in the same manner as in Example 1 had a pencil hardness of 4H, showed a flatness of 90% or more and transmittance of 95% or more.

Example 5

Instead of the polymer of Formula 4 obtained in Synthesis Example 3 was carried out in the same manner as in Example 3 using the polymer of Formula 6 obtained in Synthesis Example 5 as a result of the cured flattening film is 2.5 ~ 3.2㎛ thickness including RGB It was formed as, the measurement method in the same manner as in Example 1 had a pencil hardness of 4H, showed flatness of more than 85% and transmittance of more than 95%.

Example 6

In Examples 4, 5 and 6, 7g of Aldrich's 1,1,1-Tris (4-hydroxyphenyl) ethane was added as a monomer having a phenol group as a co-curing agent, respectively, and dissolved and filtered through a 0.2 μm membrane filter. Was prepared in the same manner as in Example 3. As a result, the flattening film formed by curing was formed to a thickness of 2.8 to 3.5 μm including RGB, and had a pencil hardness of 4H when measured in the same manner as in Example 1, and was visible The light transmittance showed more than 95% transmittance and more than 90% flatness.

Example 7

In Example 6, a polyphenolstyrene of Nippon Soda Co., Ltd., a polymer having a phenol group instead of a monomer having a phenol group, was used as an auxiliary curing agent. It was formed as, and has a pencil hardness of 4H when measured in the same manner as in Example 1, showed a transmittance of 95% or more and a flatness of 90% or more in the visible light region.

Example 8

The polymer of Formula 4 obtained in Synthesis Example 3 and the polymer of Formula 5 obtained in Synthesis Example 4 were mixed at a ratio of 4: 5 to 1: 1, and 5 g of iodide salt as an acid generator was dissolved in 82 g of solvent PGMEA, followed by 0.2 The thin film composition was prepared by filtration with a 탆 membrane filter. The thin film composition was performed in the same manner as in Example 3, and as a result, the flattening film formed by curing was formed to a thickness of 3.0 to 4.0 탆 including RGB, in the same manner as in Example 1. When measured, it had a pencil hardness of 4H, and showed a transmittance of 95% or more and a flatness of 94% or more in the visible region.

Example 9

The polymer of Formula 4 obtained in Synthesis Example 3 and the polymer of Formula 6 obtained in Synthesis Example 5 were mixed at a ratio of 2: 3 to 1: 1, and 5 g of iodide salt as an acid generator was dissolved in 82 g of solvent PGMEA, followed by 0.2 The thin film composition was prepared by filtration with a 탆 membrane filter. The thin film composition was performed in the same manner as in Example 3, and the cured flattening layer was formed to a thickness of 3.0 to 4.0 탆 including RGB, in the same manner as in Example 1. It had a pencil hardness of 4H when measured, and exhibited 95% or more transmittance and 90% or more flatness in the visible light region.

Example 10

The polymer of Formula 5 obtained in Synthesis Example 4 and the polymer of Formula 6 obtained in Synthesis Example 5 were mixed at a ratio of 2: 1 to 1: 1, and 5 g of iodide salt was dissolved in 82 g of solvent PGMEA as an acid generator, followed by 0.2 μm. A thin film composition was prepared by filtration with a membrane filter. The thin film composition was performed in the same manner as in Example 3. As a result, the flattening film formed by curing was formed to a thickness of 3.0 to 3.2 μm including RGB, and measured in the same manner as in Example 1. It had a pencil hardness of 4H, and showed over 95% transmittance and over 95% flatness in the visible region.

Example 11

18 g of the polymer of Chemical Formula 4 obtained in Synthesis Example 3 was dissolved in 81 g of a solvent PGMEA, filtered through a 0.2 μm membrane filter to prepare a thin film composition, and the same process as in Example 3 was performed. It is formed to a thickness of 2.5 ~ 3.2㎛, and has a pencil hardness of HB ~ 3H when measured in the same manner as in Example 1, showed a flatness of 70% or more and transmittance of 95% or more.

Example 12

Instead of the polymer of Chemical Formula 4 obtained in Synthesis Example 3, the polymer of Chemical Formula 5 obtained in Synthesis Example 4 was carried out in the same manner as in Example 11, and the resultant cured flattening film was formed at a thickness of 2.3 to 3.2 μm including RGB. It was formed, and measured in the same manner as in Example 1 had a pencil hardness of HB ~ 3H, and showed a transmittance of 95% or more and a flatness of 70% or more in the visible light region.

Example 13

Instead of the polymer of Chemical Formula 4 obtained in Synthesis Example 3, the polymer of Chemical Formula 6 obtained in Synthesis Example 5 was carried out in the same manner as in Example 11, and as a result, the planarized film formed by curing had a thickness of 2.3 to 3.2 μm including RGB. When formed in the same manner as in Example 1 had a pencil hardness of HB ~ 3H, and showed a transmittance of 95% or more and a flatness of 70% or more in the visible region.

Example 14

In each of the polymers of Examples 11, 12, and 13, 7 g of Aldrich's 1,1,1-Tris (4-hydroxyphenyl) ethane was added as a monomer having a phenol group as an auxiliary curing agent, respectively, and dissolved and filtered through a 0.2 μm membrane filter. The thin film composition was prepared in the same manner as in Example 3, and the cured flattening film was formed to have a thickness of 2.8 to 3.5 μm, including RGB, and measured at 4H in pencil hardness. In the visible region, the transmittance was 95% or more and 90% or more.

Example 15

In Example 14, a polyphenolstyrene of Nippon Soda Co., Ltd., a polymer having a phenol group instead of a monomer having a phenol group, was used as the auxiliary curing agent, in the same manner as in Example 14, and the resultant cured flattening film was 2.3 to 3.2 μm including RGB. Formed to a thickness and measured in the same manner as in Example 1 had a pencil hardness of 4H, in the visible region showed more than 95% transmittance and 80% or more flatness.

Example 16

The polymer of Formula 4 obtained in Synthesis Example 3 and the polymer of Formula 5 obtained in Synthesis Example 4 were mixed at a ratio of 1: 1, dissolved in 81 g of solvent PGMEA, and filtered through a 0.2 μm membrane filter to prepare a thin film composition. The flattening film formed by hardening as a result of step 3 was formed to have a thickness of 2.3 to 3.2 μm including RGB, and had a pencil hardness of HB to 3H as measured in the same manner as in Example 1, and in the visible region 95 More than% transmittance and more than 70% flatness.

Example 17

The polymer of Chemical Formula 4 obtained in Synthesis Example 3 and Chemical Formula 6 obtained in Synthesis Example 5 were mixed at a ratio of 1: 1, dissolved in 81 g of solvent PGMEA, and then filtered through a 0.2 μm membrane filter to prepare a thin film composition. As a result, the flattening film formed by curing was formed to have a thickness of 2.3 to 3.2 μm including RGB, and had a pencil hardness of HB to 3H as measured in the same manner as in Example 1, and was 95% in the visible region. The above transmittance and flatness of 70% or more were shown.

Example 18

The polymer of Formula 4 obtained in Synthesis Example 4 and the polymer of Formula 6 obtained in Synthesis Example 5 were mixed at a ratio of 1: 1, dissolved in 81 g of solvent PGMEA, and filtered using a 0.2 μm membrane filter to prepare a thin film composition. The flattening film formed by hardening as a result of step 3 was formed to have a thickness of 2.3 to 3.2 μm including RGB, and had a pencil hardness of HB to 3H as measured in the same manner as in Example 1, and in the visible region 95 More than% transmittance and more than 70% flatness.

As described in detail above, the thin film composition including the polymer of the present invention becomes a thermosetting or photo-curable flattening film (overcoat) by adding a curing catalyst (acid generator or radical initiator) or an auxiliary curing agent, thereby producing a color filter. A flattening film having excellent transparency, flatness, and hardness required at the time can be manufactured.

Claims (7)

The polymer represented by the following formula (1). Formula 1

In the above formula, X is derived from an olefin monomer having a functional group selected from an olefin or a hydroxyl group, a carboxylic acid group, an ether group, a nitrile group and an ester, R ₁ and R ₃ are different from each other and are a hydrogen atom or a methyl group, R ₂ and R ₄ are different from each other and are a hydrogen atom, a glycidylmethyl group, a hydroxyalkyl group or an alkyl group having 1 to 33 carbon atoms, Y is derived from an olefin compound or a styrene derivative, or an acrylonitrile monomer, with or without a functional group selected from ketones, esters, hydroxy, ethers, halogens, nitriles and alkoxy, Repeating units l, m, n, o are 0 <l / (l + m + n + o) <0.7, m is 0.1 <m / (l + m + n + o) <0.7, n is 0 The following conditions are satisfied:? N / (l + m + n + o) <0.5 and 0? O / (l + m + n + o) <0.5. The polymer according to claim 1, wherein (l + m) / (l + m + n + o)> 0.5 is satisfied. A thin film composition comprising at least one polymer represented by the following general formula (1), a curing catalyst and a solvent. Formula 1

In the above formula, X is derived from an olefin monomer having a functional group selected from an olefin or a hydroxyl group, a carboxylic acid group, an ether group, a nitrile group and an ester, R ₁ and R ₃ are different from each other and are a hydrogen atom or a methyl group, R ₂ and R ₄ are different from each other and are a hydrogen atom, a glycidylmethyl group, a hydroxyalkyl group or an alkyl group having 1 to 33 carbon atoms, Y is derived from an olefin compound or a styrene derivative, or an acrylonitrile monomer, with or without a functional group selected from ketones, esters, hydroxy, ethers, halogens, nitriles and alkoxy, Repeating units l, m, n, o are 0 <l / (l + m + n + o) <0.7, m is 0.1 <m / (l + m + n + o) <0.7, n is 0 The following conditions are satisfied:? N / (l + m + n + o) <0.5 and 0? O / (l + m + n + o) <0.5. 4. The thin film composition according to claim 3, wherein the curing catalyst is an acid generator or a radical initiator. The thin film composition according to claim 4, wherein the acid generator is at least one selected from sulfonium salts and secondary-alkyl toluenesulfonates. The thin film composition according to claim 3 or 4, wherein the curing catalyst is included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the total solid component. (Twice correction) The thin film composition of Claim 3 or 4 which further contains a phenol derivative as an additive.

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