KR20120055220A - Thermally curable resin composition for overcoat - Google Patents

Abstract

PURPOSE: An overcoat resin composition is provided to improve preserving stability remarkably, and to provide an overcoat film having improved adhesion to a substrate. CONSTITUTION: An overcoat resin composition comprises: a copolymer of an acid-generating ethylenically unsaturated monomer, an epoxy group-containing ethylenically unsaturated monomer, and a reactive silyl group-containing polymerizable monomer; and a reactant of hydroxy-containing epoxy resin and alkoxy silane. The acid-generating ethylenically unsaturated monomer comprises a latent acid group which is an acetal group or a tertiary t-butyl. The acid-generating ethylenically unsaturated monomer is one or more selected from 2-tetrahydropyranyl methacrylate, 2-tetrahydropyranyl acrylate, or tertiary t-butyl.

Description

Thermosetting overcoat resin composition {THERMALLY CURABLE RESIN COMPOSITION FOR OVERCOAT}

The present invention is not only excellent in a variety of chemical resistance, such as heat resistance, acid resistance, alkali resistance, but also excellent in the coating property on the substrate, the thermosetting overcoat resin composition capable of forming a cured film excellent in the re-coating property for subsequent processes, and It relates to the cured film formed using and the liquid crystal display element containing this film.

A color liquid crystal display device is treated with a solvent, an acid or an alkali solution, or the like during its manufacturing process, or the surface of the device is locally treated at high temperature when forming a transparent electrode layer by sputtering.

In some cases, even when the transparent electrode layer is etched to a desired shape, the device is also exposed to an acid, an alkaline solution, or the like under intense conditions. In order to prevent the pixel from being damaged by heat or chemicals by this process, a protective film made of a thin film resistant to the above process is formed.

A display element such as an in-plane switching (IPS) mode liquid crystal display device must have no thickness variation in order to make the liquid crystal layer to be filled uniformly, and maintenance of the cell gap is important, so a protective film having excellent planarization property is required.

The protective film should be excellent in adhesiveness, transparency, heat resistance and light resistance to the substrate on which the protective film is formed and the layer formed on the protective film, and should not cause deterioration such as coloring or discoloration over a long period of time, and various chemicals. For example, those having resistance to acids, alkalis, organic solvents, and the like are required. As a material for forming a protective film having such characteristics, two kinds of photocurable and thermosetting resins are known depending on the film formation method.

The protective film formation process using the photocurable resin composition is generally as follows. First, the photocurable resin composition to be processed into a protective film is applied to the surface of the substrate by a suitable method, for example, spin coating, and then exposed to light and developed through prebake, and then a film is formed by postbake. .

On the other hand, since the thermosetting resin composition does not require an exposure and development process during the film formation process using the photocurable type, there is an advantage in that the equipment investment cost required for the exposure and development equipment and the space of the clean room are saved. However, thermosetting resin compositions typically comprise an epoxy resin and a carboxylic acid or carboxylic anhydride, due to the continuous reaction of the epoxy resin with the curing agent, carboxylic acid or carboxylic acid anhydride. Poor storage stability of the composition, there is a problem that the composition is cured rapidly due to carboxylic anhydride.

Therefore, it was common to use a thermosetting resin composition mixed with an epoxy resin and a hardening | curing agent just before use.

Recently, a one-component thermosetting resin composition has been proposed in which the reactivity of the curing agent is weakened to alleviate the problem of storage stability, but has not been sufficiently satisfactory in terms of storage stability. That is, even when the problem of storage stability is alleviated, the reaction between the curing agent such as an acid or an acid anhydride and the epoxy group occurs continuously as long as each component remains, so that curing occurs before actual postbake and thermal curing. There existed a problem that the storage safety of a resin composition falls.

The present invention has been made to solve the problems of the prior art as described above, the present invention is a thermosetting overcoat resin composition which can provide an overcoat film with improved storage stability and improved adhesion to the substrate at the same time, thereby formed An object of the present invention is to provide an overcoat film and a liquid crystal display device comprising the overcoat film.

In order to solve the above problems, the present invention is a copolymer of an acid-generating ethylenically unsaturated monomer, an epoxy group-containing ethylenically unsaturated monomer, a reactive silyl group-containing polymerizable monomer; And a reactant of a hydroxyl group-containing epoxy resin with an alkoxy silane.

At this time, the acid-generating ethylenically unsaturated monomer is characterized in that it comprises a latent acid group to decompose at 150 ~ 250 ℃ to generate an acid.

In addition, the latent acid group is characterized in that the acetal group or tertiary butyl group. In addition, the acid-generating ethylenically unsaturated monomer is characterized in that at least one selected from 2-tetrahydropyranyl methacrylate, 2-tetrahydropyranyl acrylate, tertiary butyl (meth) acrylate.

In addition, the epoxy group-containing ethylenically unsaturated monomer is an aliphatic epoxy group-containing unsaturated monomer; Aliphatic cyclic epoxy group-containing unsaturated monomers; And at least one selected from the group consisting of aromatic epoxy-containing unsaturated monomers.

In addition, the epoxy group-containing ethylenically unsaturated monomer is allyl glycidyl ether, glycidyl 5-norbornene-2-methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene, 1 , 2-epoxy-9-decene, 3,4-glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, glycidyl α-n-propyl (meth) acrylate, glycidyl Dill α-n-butyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 4,5-epoxypentyl (meth) acrylate, 5,6-epoxyheptyl (meth) acrylate, 6, It is characterized by at least one member selected from the group consisting of 7-epoxyheptyl α-ethyl acrylate, methyl glycidyl (meth) acrylate, and the compound represented by the following formula (1).

Formula 1

Formula 2

Formula 3

In Formulas 1 to 3, R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 3 is alkylene having 1 to 6 carbon atoms.

The reactive silyl group-containing polymerizable monomer may be vinyl trimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, methylvinyldimethoxysilane, or β- (meth) acryl Oxyethyltrimethoxysilane, β- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth ) Acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, and γ- (meth) acryloxypropyldimethylethoxysilane It is characterized by one or more selected from the group.

In addition, the copolymer is characterized in that it comprises 5 to 50% by weight of acid-generating ethylenically unsaturated monomer, 10 to 90% by weight of epoxy group-containing ethylenically unsaturated monomer, and 5 to 60% by weight of reactive silyl group-containing polymerizable monomer. .

In addition, the copolymer may further comprise aliphatic or aromatic (meth) acrylates; Caprolactone modified (meth) acrylates; Acrylates having a hydroxyl group; Vinyl aromatic monomers; It characterized in that it comprises one or more selected from the group consisting of conjugated diene monomer.

In addition, the weight average molecular weight of the copolymer is characterized in that 2,000 to 100,000.

Further, the hydroxyl group-containing epoxy resins include bisphenol type epoxy resins, novolac type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, linear aliphatic epoxy resins, alicyclic epoxy resins, and biphenyl type epoxy resins. It is characterized in that at least one member selected from the group consisting of.

In addition, the alkoxy silane is tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, Methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, vinyl tree Methoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxy From the group consisting of silane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, and partial condensates thereof 1 chosen Characterized in that at least.

The thermosetting overcoat resin composition may further include at least one additive selected from the group consisting of a polyfunctional monomer having an ethylenically unsaturated bond, an adhesion aid, a surfactant, and a thermal polymerization inhibitor.

On the other hand, the present invention provides an overcoat film prepared from the thermosetting overcoat resin composition.

Moreover, this invention provides the color filter for liquid crystal display elements containing the overcoat film manufactured from the said thermosetting overcoat resin composition.

Moreover, this invention provides the liquid crystal display element provided with the said color filter.

The thermosetting overcoat resin composition according to the present invention can exhibit excellent storage safety by using a latent curable monomer that causes curing of an epoxy group due to an acid generated by pyrolysis upon postbake of 150 ° C. or higher. Excellent adhesiveness can be exhibited by using an ethylenically unsaturated monomer containing a reactive silyl group together with a curable monomer.

The thermosetting overcoat resin composition according to the present invention comprises a copolymer of an acid-generating ethylenically unsaturated monomer, an epoxy group-containing ethylenically unsaturated monomer, and a reactive silyl group-containing polymerizable monomer; And a reactant of a hydroxyl group-containing epoxy resin with an alkoxy silane.

In addition, the present invention is characterized by providing an overcoat film made from the thermosetting overcoat resin composition.

Moreover, this invention is characterized by providing the color filter for liquid crystal display elements containing the overcoat film manufactured from the said thermosetting overcoat resin composition.

Moreover, this invention is characterized by providing the liquid crystal display element provided with the said color filter.

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

The thermosetting overcoat resin composition according to the present invention uses a copolymer of an acid-generating ethylenically unsaturated monomer, an epoxy group-containing ethylenically unsaturated monomer, and a reactive silyl group-containing polymerizable monomer as a binder resin, wherein a hydroxyl group-containing epoxy resin and an alkoxy silane are used. And reactants as essential components.

In the copolymer constituting the binder resin, the acid-generating ethylenically unsaturated monomer preferably includes a latent acid group that decomposes at 150 to 250 ° C. to generate an acid.

Here, the "potential acid group" refers to a functional group that generates an acid when reaching a specific temperature as described above, and may be an acetal group or a tertiary butyl group in the present invention.

Specific examples of the acid-generating ethylenically unsaturated monomer containing the latent acid group include one selected from 2-tetrahydropyranyl methacrylate, 2-tetrahydropyranyl acrylate and tertiary butyl (meth) acrylate. Above all, among these, tertiary butyl (meth) acrylate is particularly preferable.

The acid-generating ethylenically unsaturated monomer is preferably 5 to 50% by weight, particularly 10 to 40% by weight, and less than 5% by weight of the copolymer constituting the binder resin, the desired curing may not occur sufficiently, 50% by weight When exceeded, the shrinkage of the film thickness formed during the main firing is severe compared to the film thickness after preliminary firing, so that it is difficult to maintain flatness and the adhesive strength is also lowered.

On the other hand, the epoxy group-containing ethylenically unsaturated monomer in the copolymer constituting the binder resin is not particularly limited as long as it is a compound having both an ethylenically unsaturated bond and an epoxy group capable of radical polymerization in a molecule.

However, in order to be used as a color filter protective film for LCD, transparency must be excellent, and therefore an uncolored compound is preferable.

Specific examples of the epoxy group-containing ethylenically unsaturated monomer include aliphatic epoxy group-containing unsaturated monomers; Aliphatic cyclic epoxy group-containing unsaturated monomers; And it may be one or more selected from the group consisting of an aromatic epoxy-containing unsaturated monomer, more specifically, for example, non-limiting examples of the aliphatic epoxy group-containing unsaturated monomer, allyl glycidyl ether, glycidyl 5-norbornene 2-methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, 3,4-glycidyl (meth) acrylate, glyc Cydyl α-ethyl (meth) acrylate, glycidyl α-n-propyl (meth) acrylate, glycidyl α-n-butyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate , A group consisting of 4,5-epoxypentyl (meth) acrylate, 5,6-epoxyheptyl (meth) acrylate, 6,7-epoxyheptyl α-ethylacrylate, and methylglycidyl (meth) acrylate Is selected from,

The aliphatic cyclic epoxy-containing unsaturated monomer may be a compound represented by the following Chemical Formulas 1 to 3.

Formula 1

Formula 2

Formula 3

In Formulas 1 to 3, R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 3 is alkylene having 1 to 6 carbon atoms.

The alkyl group of R2 may be one of straight and branched chain, and specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group and n-pentyl group. It is selected from the group consisting of.

 In addition, the alkylene group of the R3 may be one of linear and branched chain, specific examples thereof include methylene group, ethylene group, propylene group, isopropylene group, n-butylene group, iso-butylene group, sec- At least one selected from the group consisting of a butylene group and an n-pentylene group.

Among the epoxy group-containing ethylenically unsaturated monomers, glycidyl (meth) acrylate or 3,4-epoxycyclohexyl (meth) acrylate is most preferred.

The epoxy group-containing ethylenically unsaturated monomer is preferably in the range of 10 to 90% by weight, in particular 20 to 70% by weight, of the copolymer constituting the binder resin, when less than 10% by weight, the desired strength of the overcoat film is not formed sufficiently, It is easy to produce defects in chemical resistance and heat resistance, and when it exceeds 90% by weight, there is a tendency that the curing content is insufficient due to a relatively insufficient monomer content.

On the other hand, the reactive silyl group-containing polymerizable monomer in the copolymer constituting the binder resin may be satisfied as long as it is an ethylenically unsaturated compound containing at least one reactive silicone in a molecule.

Specific examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, methylvinyldimethoxysilane, β- (meta) acryloxyethyltrimethoxysilane , (beta)-(meth) acryloxyethyl triethoxysilane, (gamma)-(meth) acryloxypropyl trimethoxysilane, (gamma)-(meth) acryloxypropyl triethoxysilane, (gamma)-(meth) acryloxypropyl methyl dimethyl Oxysilane, (gamma)-(meth) acryloxypropyl dimethyl methoxysilane, (gamma)-(meth) acryloxypropyl methyl diethoxysilane, (gamma)-(meth) acryloxypropyl dimethyl ethoxysilane, etc. are mentioned.

Among them, (meth) acryloxyalkyltrialkoxysilane is preferable, and γ- (meth) acryloxypropyltrimethoxysilane is particularly preferred because the reactive silyl group has high reactivity and good stability.

As a commercial item used suitably as a silicone type (meth) acrylate monomer, KBM-503, KBM-5103, etc. by ShinEtsu Chemical Co., Ltd. are mentioned.

The reactive silyl group-containing polymerizable monomer is preferably in the range of 5 to 60% by weight, particularly 10 to 50% by weight, and less than 5% by weight of the copolymer constituting the binder resin. When it exceeds%, there exists a possibility that the mechanical strength of the formed cured film may fall.

The copolymer constituting the binder resin of the present invention may be aliphatic or aromatic (meth) acrylate, if necessary, in addition to the above monomers; Caprolactone modified (meth) acrylates; Acrylates having a hydroxyl group; Vinyl aromatic monomers; It may include one or more selected from the group consisting of conjugated diene monomer.

Examples of the aliphatic or aromatic (meth) acrylates include benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n May be any one selected from the group consisting of -butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate,

The caprolactone modified (meth) acrylate is TONE M-100, TONE M-101, TONE M-201 (above DOW Chemical) and FM-1, FM-2, FM-3 (above Daicel UCB) It is selectable from the back,

Examples of the acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, and the like.

Vinyl aromatic monomers include styrene, 4-methoxystyrene, 4-methylstyrene and the like.

In addition, the conjugated diene monomers include 1,3-butadiene or isoprene, but are not limited thereto.

The selectively included monomers can be used in various ways to appropriately control the physical properties of the overcoat film obtained from the thermosetting resin composition, for example, mechanical strength, adhesion, flatness, and the like, and the content of the monomers in the binder resin of the present invention. It may be included in 1 to 50% by weight.

From the above components, the binder resin according to the present invention may be prepared by any one of various polymerization methods known in the art, such as solution polymerization, emulsion polymerization, random copolymers, block copolymers, and the like. Any can be used. In addition, the molecular weight of the copolymer prepared according to such a method is not particularly limited as long as it can implement a flat film, it can be appropriately selected depending on the thickness of the film to be formed, the equipment to be applied, conditions and purposes for forming the film.

As for the weight average molecular weight (Mw) of the said copolymer, the range of about 2,000-100,000 polystyrene conversion is suitable normally, and the range of 3,000-50,000 is especially preferable. When the molecular weight is less than 2,000, the film forming performance of the thermosetting resin composition tends to be lowered, and when the molecular weight is more than 100,000, the copolymer is not easy to be handled and flatness is lowered.

Moreover, the thermosetting overcoat resin composition of this invention contains the reaction material of a hydroxyl-containing epoxy resin and an alkoxy silane.

Examples of the hydroxyl group-containing epoxy resins include bisphenol type epoxy resins, novolac type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, linear aliphatic epoxy resins and alicyclic epoxy resins, and Any one selected from the group consisting of phenyl type epoxy resins is preferred. Among these, bisphenol type epoxy resin or novolak type epoxy resin can be used more preferably.

In particular, the bisphenol-type epoxy resin obtained by using bisphenol A, bisphenol S, bisphenol F, or these hydrogenated additives as bisphenol among the said bisphenol-type epoxy resins is the most general use, and may be more preferable.

In addition, the bisphenol-type epoxy resin has a hydroxyl group that can react with the alkoxy silane. The hydroxyl group does not need to have all the molecules constituting the bisphenol type epoxy resin, and can be satisfied as long as it has a hydroxyl group as the whole bisphenol type epoxy resin.

The said novolak-type epoxy resin can be obtained by making a phenol novolak resin and a cresol novolak resin react with haloepoxide, for example.

The glycidyl ester type epoxy resin can be obtained by, for example, reacting epichlorohydrin with other basic acids such as phthal. The glycidyl amine epoxy resin can be obtained by, for example, reacting polyamines such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin.

The linear aliphatic epoxy resin and alicyclic epoxy resin can be obtained, for example, by treating olefins with peracid such as peracetic acid.

The said biphenyl type epoxy resin can be obtained, for example by making biphenols and epichlorohydrin react.

Specific examples of the alkoxysilane include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane and tetrabutoxysilane; Methyltrimethoxysilane, Methyltriethoxysilane, Methyltripropoxysilane, Methyltributoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxy Silane, isopropyltrimethoxysilane, isopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxy Trialkoxysilanes such as cyclohexylethyltriethoxysilane; Or partial condensates thereof, and among these, partial condensates of tetramethoxysilane or alkyltrimethoxysilane may be preferable.

The reaction between the hydroxyl group-containing epoxy resin and the alkoxysilane is obtained by a dealcohol condensation reaction. For example, it is carried out by putting in each said component, and dealcohol condensation reaction, distilling off the alcohol produced | generated by heating. The reaction temperature is preferably 50 to 130 ° C, more preferably 70 to 110 ° C, and the total reaction time is preferably 1 to 15 hours. In addition, in the above-mentioned dealcohol condensation reaction, it is possible to use a conventionally known catalyst for promoting the reaction or even in the presence of a solvent.

The thermosetting resin composition according to the present invention is a multi-pipe having a solvent and ethylenically unsaturated bonds in addition to the binder resin, the reactant group containing the hydroxyl group-containing epoxy resin and the alkoxy silane, depending on the film forming performance, adhesion to the substrate, chemical stability and other uses. It may include one or more selected from the group consisting of a functional monomer, an adhesion aid, a surfactant, and a thermal polymerization inhibitor.

The solvent is not particularly limited as long as it can dissolve the components uniformly and at the same time is chemically stable and is not reactive with the components of the composition. Examples of the solvent include alkyl ketones such as methyl ethyl ketone and cyclohexanone; Ethers such as tetrahydrofuran; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and ethylene glycol butyl ether acetate; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol propyl ether acetate; Ethylene glycols such as butyl cellosolve, 2-methoxyethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol diethyl ether; Esters such as ethyl acetate, ethyl lactate, ethyl 3-ethoxypropionate; Or mixtures thereof.

As a polyfunctional monomer which has the said ethylenically unsaturated bond, the compound of 2-6 unsaturated functional groups is preferable. This is because the strength and chemical resistance of the cured film can be improved by crosslinking each functional group connected to the central point with another polyfunctional monomer to form a net structure. Non-limiting examples of the polyfunctional monomer having an ethylenically unsaturated bond include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentylglycol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra Polyfunctional (meth) acrylates, such as (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate, etc. are mentioned, The compound chosen here is single or 2 types It can mix and use the above. In particular, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are preferable.

The use ratio of the polyfunctional monomer which has the said ethylenically unsaturated bond is 1-200 weight part with respect to 100 weight part of copolymers which are binder resins of this invention, Especially 5-100 weight part is preferable. Since the multifunctional monomer, which is a crosslinkable compound, is lower molecular weight than the binder resin of the present invention, it is effective in improving planarity, and in particular, when used in the above composition range, the coating film is excellent in its ability to form and there is no problem in that the formed coating film becomes sticky.

The adhesion aid is a compound that serves to enhance adhesion to the substrate, and is not particularly limited as long as the above object is satisfied. As the adhesion aid, a silane compound can be used. Non-limiting examples of silane compounds include methacryloxypropyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl trimethoxysilane, γ- Mercaptopropyl trimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, or a mixture thereof. It is preferable to use the said adhesion | attachment adjuvant within 30 weight part, especially 20 weight part with respect to 100 weight part of heat binder resins of this invention. When the said adhesion aid is used in the said ratio, it is excellent in coating property and storage stability.

Other additives include components generally used in coating liquids, such as surfactants and thermal polymerization inhibitors. As surfactant, a fluorine-type or silicone type surfactant can be used. In addition, examples of the thermal polymerization inhibitor include hydroquinone, 4-methoxyphenol, quinone, pyrocatechol, t-butyl catechol, phenothiazine, and the like. The other additive is preferably used within 2 parts by weight based on 100 parts by weight of the binder resin. When the surfactant is used in such a composition, it is possible to prevent the problem of excessive foaming.

The solid content of the thermosetting resin composition may be appropriately selected depending on the method of forming the film and the purpose thereof, preferably 1 to 60% by weight, more preferably 5 to 40% by weight from the viewpoint of coating properties.

The thermosetting resin composition according to the present invention may form a cured film according to conventional methods known in the art.

Hereinafter, as an example of the cured film forming method, the thermosetting resin composition solution is applied on a substrate by an appropriate method, and then prebake is performed to remove the solvent and to form a coating film. By carrying out, a cured film is formed.

The coating method is not particularly limited, but a spray method, a roll coating method, a spin coating method, a slit nozzle coating method, or the like can be used, and in general, a spin coating method is widely used. In some cases, some residual solvent may be removed under reduced pressure after precoating after application.

The conditions of prebake and postbake depend on the composition of the composition and the purpose of use. For example, preliminary baking can be performed in the range of 0.5 to 5 minutes at 60-130 degreeC normally. In addition, the main baking (postbake) can be carried out over a 10 minutes to 2 hours in a temperature range of 150 ~ 250 ℃ usually. In addition, each preliminary firing and the main firing can be carried out in one step or a combination thereof. In the present firing step, due to the reaction of the epoxy group and the decomposed acid in the thermosetting resin to form a cured film of the net structure.

The cured film formed according to the method described above is not only excellent in flatness but also high in surface hardness and excellent in various chemical resistances such as heat resistance, acid resistance and alkali resistance, and thus is useful as a color filter protective film material for liquid crystal display devices.

Moreover, this invention provides the liquid crystal display element provided with the color filter containing the said protective film. The liquid crystal display device includes a black matrix and a color filter, and may be manufactured according to conventional methods known in the art.

In the following Examples, the present invention will be described in more detail, but the present invention is not limited to these Examples. The weight part in an example means based on 100 weight part of thermosetting resins.

Example  One

1-1. Thermosetting Overcoat Resin Composition

Phenol novolac epoxy to a copolymer containing 25 parts by weight of tertiary butyl (meth) acrylate, 45 parts by weight of glycidyl methacrylate, and 30 parts by weight of γ- (meth) acryloxypropyltrimethoxysilane. After mixing the reaction product of the resin with tetramethoxysilane, 200 parts by weight of propylene glycol methylether acetate was added, and the flask temperature was raised to 90 ° C, and then 3.0 parts by weight of azobisvaleronitrile (AVN) was added for 15 hours. The temperature was maintained. The reacted resin solution was dropped in an excess of nucleic acid to form a precipitate and dried under vacuum to obtain a binder resin.

1-2. Cured film

The thermosetting resin composition prepared in Example 1-2 was applied on a glass substrate by spin coating and spinless coating, and then dried on a hot plate at 90 ° C. by prebake for 2 minutes and then in a clean oven at 220 ° C. This postbake was carried out for about 30 minutes to form a cured film F1 having a thickness of 2.0 μm.

1-3. Planarization film

Using pigment dispersion type color resists (R, G, B) on a glass substrate, three color filters of red, green, and blue were formed in a stripe shape with a line width of 100 µm, respectively. The height difference of the color filter was measured using a contact surface step measuring device α-step (manufactured by Tencor), and the difference between the highest height and the lowest height was 2.0 µm. The planarization film F2 was formed on the substrate on which the color filter was made by performing the same method as the cured film formation process.

Comparative example  One

The reaction product of a phenol novolak epoxy resin and tetramethoxysilane in the copolymer containing 20 weight part of methacrylic acid, 50 weight part of glycidyl methacrylates, and 15 weight part of (gamma)-(meth) acryloxypropyl trimethoxysilane. After mixing, 200 parts by weight of propylene glycol methylether acetate was added and the same procedure as in Example 1-1 was performed. Thus, 3 parts by weight of azobisvaleronitrile (AVN) was added and gelated in the reactor 3 hours after the start of the polymerization.

Experimental Example  One. Cured film  And Planarization film  evaluation

In order to evaluate the physical property of the cured film formed using the thermosetting resin composition of this invention, the following experiment was performed.

1-1. OC Coating

The thermosetting resin compositions prepared in Examples and Comparative Examples were coated on a glass substrate by spin coating and spinless coating (TOK, TR45 spinless), respectively, and then subjected to VCD and prebake. The coating property was evaluated by observing the curling. At this time, the curling did not occur at all (O), 10mm or more from the edge of the curling is generated as a bad (X) and these results are shown in Table 1 below.

1-2. Surface hardness

Pencil hardness of the cured film (F1) was measured by the method according to ASTM-D3363, and their results are shown in Table 1 below.

1-3. Adhesion

According to the method of ASTM-D3359, 100 checkerboard scales were formed by the cutter knife with respect to the cured film F1 according to the checkerboard scale tape method, and then peeled off with a tape. At this time, the number of checkerboard pattern peeled out of 100 was measured and the adhesive strength was evaluated by the following criteria.

O: The number of peeled checkered patterns is 5 or less

△: 6-49 number of the checkerboard patterns which peeled

X: 50 or more of peeled checkered patterns

1-4. Permeability

The glass substrate on which the cured film F1 was formed was transmitted at 400 nm, respectively, and the results are shown in Table 1 below.

1-5. Acid resistance

The glass substrates on which the flattening film F2 was formed were soaked for 30 minutes in an aqueous solution of 5.0 wt% HCl at 30 ° C. for 30 minutes, and the acid resistance was evaluated by observing the appearance change of the flattening film F2. At this time, there is no change in appearance is good (O), the appearance is peeled off or deteriorated as white (X) is shown as the results in Table 1 below.

1-6. Alkali resistance

The glass substrate on which the flattening film F2 was formed was soaked for 30 minutes in an aqueous solution of 5.0% by weight of NaOH at 30 ° C. for 30 minutes, and the alkali resistance was evaluated by observing the appearance change of the flattening film F2. At this time, there is no change in appearance is good (O), the appearance is peeled off or deteriorated as white (X) is shown as the results in Table 1 below.

1-7. Solvent resistance

The glass substrate on which the flattening film F2 was formed was immersed in an NMP solution at 40 ° C. for 10 minutes, and the change in thickness of the flattening film F2 was observed to evaluate solvent resistance. At this time, the change in the thickness is within 3% of good (O), more than 3% is indicated as poor (X) and these results are shown in Table 1 below.

OC coating Surface hardness Adhesion Permeability Acid resistance Alkali resistance Solvent resistance Example O 4H O > 98% O O O Comparative example X 4H X > 97% X X X

Claims (16)

Copolymers of an acid-generating ethylenically unsaturated monomer, an epoxy group-containing ethylenically unsaturated monomer, and a reactive silyl group-containing polymerizable monomer; And a reactant of a hydroxyl-containing epoxy resin with an alkoxy silane. The method of claim 1,
The acid-generating ethylenically unsaturated monomer is a thermosetting overcoat resin composition, characterized in that it comprises a latent acid group to decompose at 150 ~ 250 ℃ to generate an acid. The method of claim 2,
The latent acid group is an acetal group or a tertiary butyl group (t-butyl) thermosetting overcoat resin composition, characterized in that. The method of claim 2,
The acid-generating ethylenically unsaturated monomer is a thermosetting overcoat resin composition, characterized in that at least one selected from 2-tetrahydropyranyl methacrylate, 2-tetrahydropyranyl acrylate, tertiary butyl (meth) acrylate.
The method of claim 1,
The epoxy group-containing ethylenically unsaturated monomer is an aliphatic epoxy group-containing unsaturated monomer; Aliphatic cyclic epoxy group-containing unsaturated monomers; And at least one member selected from the group consisting of aromatic epoxy-containing unsaturated monomers. 6. The method of claim 5,
The epoxy group-containing ethylenically unsaturated monomers include allyl glycidyl ether, glycidyl 5-norbornene-2-methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene, 1,2 -Epoxy-9-decene, 3,4-glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, glycidyl α-n-propyl (meth) acrylate, glycidyl α -n-butyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 4,5-epoxypentyl (meth) acrylate, 5,6-epoxyheptyl (meth) acrylate, 6,7- A thermosetting overcoat resin composition, characterized in that at least one selected from the group consisting of epoxyheptyl α-ethylacrylate, methylglycidyl (meth) acrylate, and the compound represented by the following formulas (1) to (3).
Formula 1

(2)

(3)

In Formulas 1 to 3, R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 3 is alkylene having 1 to 6 carbon atoms. The method of claim 1,
Examples of the reactive silyl group-containing polymerizable monomer include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, methylvinyldimethoxysilane, and β- (meta) acryloxyethyl Trimethoxysilane, β- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryl From the group consisting of oxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, and γ- (meth) acryloxypropyldimethylethoxysilane Thermosetting overcoat resin composition, characterized in that at least one selected.
The method of claim 1,
The copolymer is a thermosetting overcoat comprising 5 to 50% by weight of an acid-generating ethylenically unsaturated monomer, 10 to 90% by weight of an epoxy group-containing ethylenically unsaturated monomer, and 5 to 60% by weight of a reactive silyl group-containing polymerizable monomer. Resin composition. The method of claim 1,
The copolymer may further comprise aliphatic or aromatic (meth) acrylates; Caprolactone modified (meth) acrylates; Acrylates having a hydroxyl group; Vinyl aromatic monomers; A thermosetting overcoat resin composition comprising at least one member selected from the group consisting of conjugated diene monomers. The method of claim 1,
Thermopolymer overcoat resin composition, characterized in that the weight average molecular weight of the copolymer is 2,000 ~ 100,000. The method of claim 1,
The hydroxyl-containing epoxy resin consists of a bisphenol type epoxy resin, a novolak type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a linear aliphatic epoxy resin, an alicyclic epoxy resin, and a biphenyl type epoxy resin. A thermosetting overcoat resin composition, characterized in that at least one member selected from the group. The method of claim 1,
The alkoxy silane is tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltri Butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, vinyltrimethoxy Silane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, Phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, and partial condensates thereof 1 or more types It is a thermosetting overcoat resin composition characterized by the above-mentioned. The method of claim 1,
The thermosetting overcoat resin composition further comprises at least one additive selected from the group consisting of a polyfunctional monomer having an ethylenically unsaturated bond, an adhesion aid, a surfactant, and a thermal polymerization inhibitor. An overcoat film prepared from the thermosetting overcoat resin composition of claim 1. The color filter for liquid crystal display elements containing the overcoat film | membrane manufactured from the thermosetting overcoat resin composition of Claim 1. A liquid crystal display device comprising the color filter of claim 15.