KR100777965B1 - Thermosetting One-Solution type Composition for Protective Film of Color Filter and Color Filter by using the Same - Google Patents

Abstract

The present invention relates to a protective film composition for a thermosetting one-component color filter, and more particularly to a copolymer of (meth) acrylate having an epoxy ring structure in the side chain and a (meth) acrylate having a terminal hydroxyl group, and (meth) acrylic acid, A protective film composition for a thermosetting one-component color filter containing an organic solvent, a color filter comprising a protective film manufactured using the same, and a liquid crystal display device including the color filter.

The protective film composition for thermosetting one-component color filters of the present invention can provide an effect of excellent flatness, adhesion, transmittance, film strength, and heat resistance and improved storage stability compared to the conventional protective film composition for thermosetting color filters.

Thermosetting, One Component, Color Filter, Protective Film, Liquid Crystal Display

Description

Thermosetting One-Solution type Composition for Protective Film of Color Filter and Color Filter by using the Same}

The present invention relates to a protective film composition for a thermosetting one-component color filter, and more particularly to a copolymer of (meth) acrylate having an epoxy ring structure in the side chain and a (meth) acrylate having a terminal hydroxyl group, and (meth) acrylic acid, A protective film composition for a thermosetting one-component color filter containing an organic solvent, a color filter including a protective film prepared using the same, and a liquid crystal display device including the color filter.

In general, a protective film is provided on the surface of the color filter for a liquid crystal display device for the purpose of flattening and protecting the flatness. This surface protective film should exhibit optical transparency and sufficient film strength, and should also have sufficient heat resistance to withstand the process of forming a transparent conductive film on the protective film.

Meanwhile, recently developed protective films for vertically oriented liquid crystal displays require acid resistance to withstand etching in addition to transparency, film strength, and heat resistance, and also require alkali resistance to withstand resist stripping processes.

Background Art A protective film forming material and a forming method of a color filter have been widely known. That is, Japanese Unexamined Patent Application Publication No. 1-134306 discloses glycidyl methacrylate as a main component, and Japanese Patent Application Laid-Open No. 62-163016 discloses a polyimide as a main component, and Japanese Patent Application Laid-Open No. 63-131103 No. discloses having a mixture of melamine resin and epoxy resin as a main component.

In addition, high reliability technologies such as adhesive strength, heat resistance, chemical resistance, water resistance, and the like are known as protective film compositions for color filters using epoxy resins. That is, Japanese Patent Laid-Open No. 08-050289 discloses a curable resin composition using a phenol-based curing agent for a glycidyl methacrylate polymer. In addition, Japanese Patent Application Laid-Open No. 08-201617 discloses a resin composition for a transparent film composed of an epoxy resin, a curing agent, and an organic solvent, wherein a reactant of a styrene maleic anhydride copolymer polymer and amines is used as the curing agent.

In general, epoxy resins have a fast reaction with a curing agent, and thus are often used in a so-called two-component type in which a main body and a curing agent are mixed at the time of use, and it is known that one-component solution is difficult. That is, the two-part type has a problem in that handling is complicated and not suitable for use in industrial production.

However, in the above-mentioned conventional known technologies, transparency, film strength, heat resistance, acid resistance, and alkali resistance are all satisfied, and at the same time, there is no case where even one liquidation of the epoxy resin is possible. Japanese Patent Laid-Open No. 2001-091732 discloses a technique for protecting storage stability by protecting a polyfunctional carboxylic acid compound with vinyl ether or the like. However, such protective vaporization is cumbersome and inevitably affects the price. In addition, since the use of the vinyl ether compound is harmful to the human body, it is questionable whether it can be used industrially.

SUMMARY OF THE INVENTION An object of the present invention is to provide a protective film composition for thermosetting one-component color filters which has good adhesion strength, transparency, film strength, heat resistance, acid resistance, and alkali resistance, and which can be stored for a long time.

Another object of the present invention to provide a color filter comprising a protective film excellent in flatness, adhesion and film strength prepared using the composition.

Still another object of the present invention is to provide a liquid crystal display device including the color filter.

One aspect of the present invention for achieving the above object comprises a copolymer of (meth) acrylate having an epoxy ring structure in the side chain and a (meth) acrylate having a terminal hydroxyl group and (meth) acrylic acid and an organic solvent A protective film composition for thermosetting one-component color filters.

Another aspect of the present invention for achieving the above object relates to a color filter comprising a protective film prepared using the composition.

Another aspect of the present invention for achieving the above object relates to a liquid crystal display device including the color filter.

The protective film composition for a thermosetting one-component color filter according to the present invention comprises: (i) a self-curing copolymer comprising one of the following Formulas 1a and 1b and a repeating unit of Formulas 2 and 3; (ii) an organic solvent; And (iii) bisphenol A type epoxy, bisphenol F type epoxy, phenol novolak type epoxy, cresol novolak type epoxy, epoxy resins including substituted epoxy, poly (meth) acrylate, nylon, polyester, polyimide And at least one polymer selected from polymers including silicone polymers.

[Formula 1-a]

[Formula 1-b]

(In said formula, R <_1> , R <_2> represents a hydrogen atom or a methyl group each independently, a and b represent 10 mol%-90 mol%, respectively, and p represents the integer of 1-10.)

[Formula 2]

(In the formula, each R ₃ independently represents a hydrogen atom or a methyl group, c is 5 mol%-45 mol% are shown, q shows the integer of 1-10. )

[Formula 3]

(In said formula, R <_4> represents a hydrogen atom or a methyl group each independently, and d represents 5 mol%-45 mol%.)

The weight average molecular weight of the self-curable copolymer is characterized in that 3,000 to 1,000,000.

The self-curable copolymer includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate (Meth) acrylate, N-methyl acrylamide, N-ethyl acrylamide, N-isopropyl acrylamide, N-methol acrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-iso which are said Propyl methacrylamide, N-methinol methacrylamide, N, N-dimethyl acrylamide, N, N-diethyl acrylamide, N, N-dimethyl methacrylamide, N, N-diethyl methacrylamide Acrylamide, styrene, α-methylstyrene, styrene containing hydroxy styrene, N-vinyl birrolidone, N-vinyl formamide, N-vinylamide and N-vinylimidazole. 1 or more types It characterized in that it further comprises a structural unit of.

The organic solvent is ethylene glycol, ethylene glycol containing diethylene glycol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, glycol ether containing diethylene glycol dimethyl ether, ethylene glycol Glycol ether acetates including monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycols, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, Propylene monobutyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethers containing dipropylene glycol diethyl ether, propylene glycol monomethyl ether ace , Propylene glycol ether acetates containing dipropylene glycol monoethyl ether acetate, N-methylpyrrolidone, dimethyl formamide, amides containing dimethylacetamide, methyl ethyl ketone (MEK), methyl isobutyl ketone ( MIBK), ketones containing cyclohexanone, toluene, xylene, petroleum containing solvent naphtha, ethyl acetate, butyl acetate, esters containing ethyl lactate, and mixtures thereof. It features.

According to the present invention, there is provided a color filter comprising a protective film made of a protective film composition for thermosetting one-component color filters.

According to the present invention, there is provided a liquid crystal display including the color filter.

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

The copolymer used in the protective film composition for a thermosetting one-component color filter of the present invention is thermally crosslinked by a thermal crosslinking reaction between one of Chemical Formulas 1a and 1b and the structural units of Chemical Formulas 2 and 3. The repeating unit copolymer represented by Formula 1, Formula 2, Formula 3, and Formula 4 may be in any form such as random copolymer, alternating copolymer, block copolymer, graft copolymer, and the like.

[Formula 1-a]

[Formula 1-b]

(In said formula, R <_1> , R <_2> represents a hydrogen atom or a methyl group each independently, a and b represent 10 mol%-90 mol%, respectively, and p represents the integer of 1-10.)

[Formula 2]

(In the formula, each R ₃ independently represents a hydrogen atom or a methyl group, c is 5 mol%-45 mol% are shown, q shows the integer of 1-10. )

[Formula 3]

(In said formula, R <_4> represents a hydrogen atom or a methyl group each independently, and d represents 5 mol%-45 mol%.)

According to the present invention, the self-curable copolymer is further provided with a protective film composition for thermosetting one-component color filters, further comprising a structural unit represented by the following formula (4).

[Formula 4]

(In the above formula, each R ₅ independently represents a hydrogen atom or a methyl group, e represents 10 mol% to 30 mol%, and R x is one species selected from compounds represented by the following formula (5).)

[Formula 5]

(In the formula, t represents an integer of 4 to 12, and R ₆ represents a hydrogen atom or a methyl group.)

By further comprising a structural unit represented by the formula (4) when the copolymer is prepared, transparency and organic solvent solubility can be improved.

On the other hand, the component ratio e of the structural unit represented by the formula (4) is preferably in the range of 10 mol% to 30 mol% in a range that does not impair adhesion strength, transparency, film strength, heat resistance, acid resistance, alkali resistance and long-term storage possibility. Do.

On the other hand, the molecular weight of the self-curable copolymer is not particularly limited, but the weight average molecular weight is preferably 3,000 to 1,000,000. The reason is that if the molecular weight is too low, sufficient curability cannot be obtained. If the molecular weight is too high, solvent solubility may be lowered or the applicability may be lowered.

Although the organic solvent which is an essential component of the protective film composition for thermosetting one-component color filters of the present invention is not particularly limited, it is preferable that the copolymer can be dissolved. Examples of organic solvents that can be used include ethylene glycols such as ethylene glycol and diethylene glycol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, glycol ethers such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether, and ethylene. Glycol ether acetates such as glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycols such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Propylene glycol ethers such as monopropyl ether, propylene monobutyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether, and propylene glycol monomethyl ether Propylene glycol ether acetates such as acetate and dipropylene glycol monoethyl ether acetate, amides such as N-methylpyrrolidone, dimethylformamide and dimethylacetamide, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK) And ketones such as cyclohexanone, petroleum such as toluene, xylene, and solvent naphtha, esters such as ethyl acetate, butyl acetate, and ethyl lactate, and mixtures thereof.

On the other hand, the self-curable copolymer can be synthesized without particular limitation using a conventionally known method, using a radical polymerization initiator in an organic solvent, such as an organic solvent constituting the protective film composition for thermosetting one-component color filter of the present invention. It is preferable to synthesize.

That is, the organic solvent used for the copolymerization of the self-curable copolymer is not particularly limited, but preferably, an organic solvent such as an organic solvent used as an essential component of the protective film composition for thermosetting one-component color filters of the present invention described above is used. do. On the other hand, the amount of the organic solvent used for the polymerization is preferably adjusted so that the concentration of the self-curable copolymer in the solution of the organic solvent and the self-curable copolymer is 5 to 50% by weight. More preferably, it is 10-30 weight%. When the concentration of the self-curable copolymer in the solution is less than 5% by weight, the polymerization rate is slow, the monomer remaining unreacted is a problem, and when it exceeds 50% by weight, the viscosity is too high to handle and difficult to react. There are also problems such as difficulty in controlling.

As the polymerization initiator used for the polymerization of the self-curable copolymer, known ones such as thermal polymerization initiators, photopolymerization initiators, and redox initiators can be used, but in terms of ease of handling, reaction rate and molecular weight control can be facilitated. It is preferable to use radical polymerization initiators, such as a peroxide system and an azo system.

Examples of peroxide-based polymerization initiators usable in the present invention include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) 3,3, 5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (tert -Hexyl peroxy) cyclohexane, 1,1-bis (tert-butylperoxy) cyclododecane, isobutyl peroxide, lauroyl peroxide, succinic peroxide, 3,5,5-trimethylhexanoyl peroxide, Benzoyl peroxide octanoyl peroxide, stearoyl peroxide, diisopropyl peroxy dicarbonate, dinormal propyl peroxy dicarbonate, di-2-ethylhexyl peroxy dicarbonate, di-2-ethoxyethyl peroxy dicarbonate, di- 2-methoxybutyl peroxydicarbonate, bis- (4-tert -Butylcyclohexyl) peroxydicarbonate, (α, α-bis-neodecanoylperoxy) diisopropylbenze, peroxy neodecanoic acid cumyl ester, peroxy neodecanoic acid octyl ester, peroxy neodecanoic acid hexyl ester , Peroxy neodecanoic acid-tert-butyl ester, peroxy pivalinic acid-tert-hexyl ester, peroxy pivalinic acid-tert-butyl ester, 2, 5- dimethyl-2,5-bis (2-ethylhexanoyl fur Oxy) hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, peroxy-2-ethylhexanoic acid-tert-hexyl ester, peroxy-2-ethylhexanoic acid-tert- Butyl ester, peroxy-2-ethylhexanoic acid-tert-butyl ester, peroxy-3-methylpropionic acid-tert-butyl ester, peroxylauric acid-tert-butyl ester, tert-butylperoxy-3,5 , 5-trimethylhexanoate, tert-hexylperoxyisopropylmonocarbonate, tert-butylperoxyisopropylcarbonate, 2,5-dimethyl-2,5-bis (benzoyl Oxy) there may be mentioned hexane, and ethyl -tert- butyl ester, and -tert- acid hexyl ester, and acid -tert- butyl ester and the like. In addition, a reducing agent may be added to the peroxide-based polymerization initiator described above and used as an oxidation-reduction initiator.

Examples of azo polymerization initiators usable in the present invention include 1,1-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2-methyl-butyronitrile), and 2,2'- Azobisbutyronitrile, 2,2'-azobis (2,4-dimethyl-valeronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2, 2'-azobis (2-amijino-propane) hydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] hydrochloride, 2,2'-azo Bis [2- (2-imidazolin-2-yl) propane] hydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane], 2,2 '-Azobis2-methyl-N- (1,1-bis (2-hydroxymethyl) -2-hydroxyethyl] propionamide, 2,2'-azobis [2-methyl-N- (2- Hydroxyethyl) propionamide], 2,2'-azobis (2-methyl-propionamide) dihydrate, 4,4'-azobis (4-cyano-acetic acid), 2,2'-azobis (2-hydroxymethylpropionitrile), 2,2'-azobis (2-methylpropionic acid) dimethyl ester ( Methyl-2,2'-azobis (2-methylpropionate)) (produced by Wako Industry Co., Ltd.: and the like V-601), 2-cyano-profile azo formamide.

In addition to the above-described peroxide polymerization initiator and azo polymerization initiator, in order to achieve a preferable molecular weight range in the polymerization step of the self-curable copolymer, known molecular weight regulators such as a chain transfer agent, a chain stopper and a polymerization accelerator may be added. . Examples thereof include mercaptopropionic acid, mercaptopropionic acid ester, thioglycol, thioglycerine, dodecyl mercaptan, α-methylstyrene dimer and the like.

On the other hand, it is also possible to add another solvent in addition to the organic solvent used for the said polymerization for the purpose of the solubility assistance of a component, leveling property, drying rate control, etc. after superposition | polymerization.

In addition, the synthesized copolymer can be extracted as a solid for the purpose of purification, preservation, solvent change, etc., and it is also possible to construct a protective film composition for thermosetting one-component color filters using this. Although there is no restriction in the extraction method, spray drying, film drying, dropping into a poor solvent, reprecipitation, etc. are mentioned.

Moreover, in order to improve the etching resistance, alkali resistance, etc. of the protective film composition for thermosetting one-component color filters of this invention, or to adjust fluidity | liquidity, another polymer other than the said self-hardening copolymer can be added further. Although there is no restriction | limiting in particular in the polymer to add, Epoxy resins, such as a bisphenol-A epoxy, a bisphenol F-type epoxy, a phenol novolak-type epoxy, a cresol novolak-type epoxy, a substituted epoxy, poly (meth) acrylate, nylon, Polyester, polyimide, silicone polymer, etc. are mentioned. It is preferable that the quantity of the polymer added is 50 weight part or less with respect to 100 weight part of said self-curable copolymers.

In addition, an amine compound, phosphorus compound, boron compound, antimony compound, carboxylic acid compound, euphonic acid compound and the like can be added to the protective film composition for thermosetting one-component color filter of the present invention as a catalyst for thermosetting reaction. The addition amount of the thermosetting reaction catalyst is preferably 10 parts by weight or less based on 100 parts by weight of the self-curable polymer from the viewpoint of storage stability.

On the other hand, in the protective film composition for thermosetting one-component color filters of the present invention, conventionally known ones such as antioxidants, infrared stabilizers, plasticizers, leveling agents, coupling agents, fillers and the like can be blended as necessary.

Meanwhile, in order to manufacture the protective film for color filters, the protective film composition for thermosetting one-component color filters of the present invention may be screen printed, curtain coated, blade coated, spin coated, spray coated, dip coated, or flow coated. ), Roll coating (slit coating), slit coating (slit coating) and the like on the substrate. The thickness of a coating film is the range of 0.5-5 micrometers after drying, Preferably it is the range of 0.7-2.5 micrometers. If the film thickness is too thin, less than 0.5 μm, sufficient planarization performance cannot be obtained for the step, and if the film thickness is too thick, more than 5 μm, not only will lower the transmittance, but also take time to dry and cure, and decrease productivity. Done.

The substrate on which the protective film composition for thermosetting one-component color filters of the present invention is applied is volatilized by a dry-heat curing process, and cured by a crosslinking reaction to form a firm film. The drying step and the thermosetting step may be performed simultaneously or separately. However, if the heating process is too rapid, foaming or cracking may occur. Therefore, the drying step and the thermosetting step are preferably performed separately.

Although the apparatus used for a drying process is not specifically limited, Any thing, such as a warm air dryer, a far-infrared dryer, a hotplate, can be used. The drying temperature is preferably in the range of 50 to 150 ° C., and the drying time varies depending on the dryer capacity, air volume, temperature and film thickness, but is preferably in the range of 1 to 10 minutes.

Although the apparatus used for a thermosetting process is not specifically limited, Any thing, such as a warm air oven, a far infrared oven, and a hotplate, can be used. The heat treatment temperature is preferably in the range of 150 to 250 ° C., but when the heat treatment temperature is less than 150 ° C., there is a problem that the curing reaction does not proceed sufficiently. When the heat treatment temperature exceeds 250 ° C., the depolymerization reaction or the carbonization reaction of the polymer compound is performed. This happens and there is a problem that the performance of the obtained membrane is lowered.

On the other hand, the color filter including the protective film manufactured by the above method can be used in the liquid crystal display device.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the following Examples are provided for the purpose of description and are not intended to limit the present invention.

Example 1

300 g of propylene glycol monomethyl ether acetate was added to a 500 ml flask equipped with a reflux condenser and a stirrer, and then the reaction temperature was raised to 80 ° C while stirring. The reaction temperature was maintained at 80 ° C., and 24 g of methacrylic acid, 24 g of 2-hydroxyethyl methacrylate, 52 g of methacrylic acid glycidyl and dimethyl-2,2′-azobis (2- A mixture of 8 g of methyl propionate) was added dropwise for 1 to 1.5 hours. After all of the mixture was added dropwise, the reaction temperature was maintained at 80 ° C and reacted for 4 to 5 hours while stirring to obtain a transparent polymer solution (A). The solution was measured by Gel Permeation Chromatography (hereinafter referred to as "GPC") method, and the polystyrene reduced weight average molecular weight was 30,000.

To 40 g of the obtained polymer solution (A), 3.5 g of an epoxy resin (EP-152 made by JER), 1.4 g of a silane coupling agent (S-510 made by Chisso), 0.12 g of a surfactant (F-475 made by DIC), and propylene glycol monomethyl 30 g of ether acetate was added, sufficiently stirred and dissolved, followed by filtration to obtain a protective film composition (E) for a desired thermosetting one-component color filter.

The above-mentioned protective film composition (E) for thermosetting one-component color filter was applied to a glass substrate (Corning Company No. 1737, plate thickness 0.7 mm) and a dummy color filter having an RGB pattern using a spin coater. After drying for 3 minutes in a 80 degreeC dryer, it hardened again at the temperature of 230 degreeC for 50 minutes, and obtained the transparent protective film and color filter of 1.5 micrometers in thickness.

Example 2

300 g of propylene glycol monomethyl ether acetate was charged into a 500 ml flask equipped with a reflux condenser and a stirrer, and then the reaction temperature was raised to 80 ° C while stirring. The reaction temperature was maintained at 80 ° C, and 20 g of methacrylic acid, 10 g of 2-hydroxyethyl methacrylate, 32 g of methacrylic acid glycidyl, 38 g of dicyclopentanyl methacrylate and dimethyl-2, were stirred in the flask. A mixture of 8 g of 2'-azobis (2-methylpropionate) was added dropwise for 1 to 1.5 hours. After all of the mixture was added dropwise, the reaction temperature was maintained at 80 ° C. and reacted for 4 to 5 hours while stirring to obtain a transparent polymer solution (B). As a result of measuring this solution by GPC method, the polystyrene reduced weight average molecular weight was 32,000.

Except having used 40g of said polymer solutions (B) instead of a polymer solution (A), it carried out by the same method as Example 1, and obtained the protective film composition (F) for thermosetting one-component color filters.

A transparent protective film having a thickness of 1.5 μm and a color filter were prepared in the same manner as in Example 1, except that the protective film composition for thermosetting one-component color filters (F) was used instead of the protective film composition for thermosetting one-component color filters (E). Got it.

Example 3

300 g of propylene glycol monomethyl ether acetate was charged into a 500 ml flask equipped with a reflux condenser and a stirrer, and then the reaction temperature was raised to 80 ° C while stirring. The reaction temperature was maintained at 80 ° C., and 20 g of methacrylic acid, 10 g of 2-hydroxyethyl methacrylate, 32 g of methacrylic acid glycidyl, 38 g of styrene and dimethyl-2,2′-azobis were stirred in the flask with stirring. A mixture of 8 g of (2-methylpropionate) was added dropwise for 1 to 1.5 hours. After dropping all the mixtures, the reaction temperature was maintained at 80 ° C. and reacted for 4 to 5 hours while stirring to obtain a transparent polymer solution (C). As a result of measuring this solution by GPC method, the polystyrene reduced weight average molecular weight was 23,000.

Except for using the polymer solution (C) 40g instead of the polymer solution (A), the same procedure as in Example 1 was carried out to obtain a protective film composition (G) for a thermosetting one-component color filter.

A transparent protective film having a thickness of 1.5 μm and a color filter were prepared in the same manner as in Example 1, except that the protective film composition for thermosetting one-component color filters (G) manufactured instead of the protective film composition for thermosetting one-component color filters (E) was used. Got it.

Comparative Example 1

300 g of propylene glycol monomethyl ether acetate was charged into a 500 ml flask equipped with a reflux condenser and a stirrer, and then the reaction temperature was raised to 80 ° C while stirring. The reaction temperature was maintained at 80 ° C, and 60 g of methacrylic acid, 25 g of dicyclopentanyl methacrylate, 15 g of styrene, and 8.5 g of dimethyl-2,2'-azobis (2-methylpropionate) were added to the flask while stirring. Was added dropwise for 1 to 1.5 hours. After all of the mixture was added dropwise, the reaction temperature was maintained at 80 ° C and reacted for 3 hours with stirring to obtain a transparent polymer solution (D). As a result of measuring this solution by GPC method, the polystyrene reduced weight average molecular weight was 27,000.

To 40 g of the polymer solution (D), 3.5 g of an epoxy resin (EP-152 made by JER), 1.4 g of a silane coupling agent (S-510 made by Chisso), 3.1 g of trimellitic anhydride (manufactured by Aldrich), an interface 0.12 g of an activator (F-475 made by DIC) and 31 g of propylene glycol monomethyl ether acetate were added, followed by sufficient stirring and dissolution, followed by filtration to obtain a protective film composition (H) for a desired thermosetting one-component color filter.

A transparent protective film and a color filter having a thickness of 1.5 μm were obtained by the same method as Example 1 except that the protective film composition for thermosetting one-component color filters (H) was used instead of the protective film composition (H) for thermosetting one-component color filters.

<Property Evaluation>

The glass substrates and color filters obtained through Examples 1 to 3 and Comparative Example 1 were evaluated by the method described below, and the flatness, adhesion, and film strength were evaluated, and the storage stability of the obtained thermosetting composition was evaluated, and the results were as follows. It is shown in Table 1.

 ① Flatness evaluation

For the evaluation of the flatness, the difference (difference between pixels) between the heights of the red and green pixels of the dummy color filter was determined. Thereafter, the difference between the heights of the central portions of the red pixels and the green pixels of the color filters coated with the protective films of Examples 1 to 3 and Comparative Example 1 was determined. According to the following formula (1), the ratio R of the inter-pixel step d ₁ before the protective film application and the inter-pixel step d ₂ after the protective film application is obtained, and the protective film composition prepared according to the present invention is The flatness was evaluated in 5 steps of 1-5.

R = d ₂ / d ₁ . … (1)

When R> 0.4 obtained in the above formula, 1, 0.4 ≦ R ≦ 0.3, 2, 0.3 <R ≦ 0.2, 4, 0.2 <R ≦ 0.1, and 5 when R <0.1. 1 indicates low planarization performance, and 5 indicates high planarization performance.

② Adhesion and chemical resistance test

100 cross-cuts were placed on the color filter protective film obtained in Examples 1 to 3 and Comparative Example 1 in the shape of a checkerboard, and a peeling test (crosscut test) was performed using a cellophane tape. After that, the peeling state of the checkerboard scale was visually evaluated to test the adhesion.

Furthermore, the obtained color filter protective film was immersed in 40 degreeC N-methyl- 2-pyrrolidone (NMP), 10% potassium hydroxide aqueous solution, and etchant solution (product name CYANTEK CORPORATION LCE-12K) for 30 minutes, The adhesion test was carried out in the same manner as described above, and the chemical resistance of each solution was evaluated by marking failure as 100 (after deposition) / 100 (before deposition) according to the peeling state of the scale.

③ film strength evaluation

The transparent protective film prepared in Examples 1 to 3 and Comparative Example 1 was scraped with six pencils (1H to 6H) manufactured by Stadler, and the strength of the film was evaluated from 1H to 6H according to the degree of damage to the substrate. .

④ Storage stability evaluation

The viscosity of the thermosetting compositions obtained in Examples 1 to 3 and Comparative Example 1 was measured for the first time, and each of them was placed in a 10 ml vial and stored in a 40 ° C. incubator, and then measured every 3 days. After 12 days, a total of five viscosity measurement results indicated that the numbers of the intervals where the viscosity increase exceeded 10% by numbers 0, 3, 6, 9 and 12, respectively. However, 3 or less was marked as defective.

division Flatness Adhesion Chemical resistance Strength Storage stability Example 1 4 100/100 Passed (acid, base, organic) 5H 6 Example 2 4 100/100 Passed (acid, base, organic) 5H 9 Example 3 3 100/100 Passed (acid, base, organic) 5H 9 Comparative Example 1 2 100/100 Failed (base) 4H 3 (bad)

As can be seen in Table 1, it can be seen that the flatness, adhesion, and film strength of the protective film for color filters manufactured by the protective film composition for thermosetting one-component color filter of the present invention. On the other hand, the storage stability of the prepared composition can be seen that it lasts for a long time compared with the conventional protective film composition for thermosetting color filters.

The protective film composition for thermosetting one-component color filter of the present invention can be stored for a long time as compared to the conventional thermosetting color filter composition, and the flatness, adhesion, and film strength of the color filter protective film manufactured using the same are also excellent.

Claims (7)

(i) one of the following Formulas 1a and 1b, and Formula 2, Formula 3, Formula 4 ', and methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate , (Butyl) (meth) acrylate, (meth) acrylate containing benzyl (meth) acrylate, N-methyl acrylamide, N-ethyl acrylamide, N-isopropyl acrylamide, N-methol acrylamide, N -Methyl methacrylamide, N-ethyl methacrylamide, N-isopropyl methacrylamide, N-methinol methacrylamide, N, N- dimethyl acrylamide, N, N- diethyl acrylamide, N, N- Dimethyl methacrylamide, acrylamides containing N, N-diethylmethacrylamide, styrenes including styrene, α-methylstyrene, hydroxystyrene, N-vinyl birrolidone, N-vinylformamide, N-vinylamide and N-vinyl A self-curing copolymer comprising at least one repeating unit selected from the group consisting of midazoles; (ii) an organic solvent; And (iii) epoxy resins containing bisphenol A epoxy, bisphenol F epoxy, phenol novolac epoxy, cresol novolac epoxy, substituted epoxy, poly (meth) acrylate, nylon, polyester, polyimide And at least one polymer selected from polymers including silicone polymers. [Formula 1-a]

[Formula 1-b]

(In said formula, R <_1> , R <_2> represents a hydrogen atom or a methyl group each independently, a and b represent 10 mol%-90 mol%, respectively, and p represents the integer of 1-10.) [Formula 2]

(In said formula, R <_3> represents a hydrogen atom or a methyl group each independently, c shows 5 mol%-45 mol%, q shows the integer of 1-10.) [Formula 3]

(In said formula, R <_4> represents a hydrogen atom or a methyl group each independently, and d represents 5 mol%-45 mol%.) [Formula 4]

(In the above formula, each R ₅ independently represents a hydrogen atom or a methyl group, e represents 10 mol% to 30 mol%, and R x is one species selected from compounds represented by the following formula (5).) [Formula 5]

(In the formula, t represents an integer of 4 to 12, and R ₆ represents a hydrogen atom or a methyl group.) delete The protective film composition of claim 1, wherein the self-curable copolymer has a weight average molecular weight of 3,000 to 1,000,000. delete The organic solvent of claim 1, wherein the organic solvent includes ethylene glycol, ethylene glycol containing diethylene glycol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether. Glycol ethers, glycol ethers including ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol monopropyl ether, propylene monobutyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethers containing dipropylene glycol diethyl ether, propylene glycol mono Methyl ether acetate, propylene glycol ether acetates containing dipropylene glycol monoethyl ether acetate, amides containing N-methylpyrrolidone, dimethylformamide, dimethylacetamide, methyl ethyl ketone (MEK), methyl isobutyl Ketones (MIBK), ketones containing cyclohexanone, toluene, xylene, petroleum containing solvent naphtha, ethyl acetate, butyl acetate, esters containing ethyl lactate, and mixtures thereof The protective film composition for thermosetting one-component color filters characterized by the above. A color filter comprising a protective film made of the protective film composition for thermosetting one-component color filters according to any one of claims 1, 3, and 5. A liquid crystal display device comprising the color filter of claim 6.