KR20210052878A - Thermosetting overcoat resin composition, overcoat film, color filter and display device - Google Patents

Abstract

The present invention relates to a thermosetting overcoat resin composition, including: a binder resin including an epoxy group-containing monomer and an oxethane group-containing monomer, wherein the combined content of the epoxy group-containing monomer and the oxethane group-containing monomer is 40 mol% or more based on 100 mol% of the total monomers forming the binder resin; an epoxy curing agent; and a solvent, to an overcoat film, to a color filter, and to a display device. Particularly, the thermosetting overcoat resin composition may further include at least one of an epoxy-based multifunctional monomer, an oxethane-based multifunctional monomer, and an acrylate-based multifunctional monomer, or may further include an acrylate-based multifunctional monomer, wherein the acrylate-based multifunctional monomer is used in an amount of 10 wt% or less based on the total weight of the thermosetting overcoat resin composition.

Description

Thermosetting overcoat resin composition, overcoat film, color filter, and display device {THERMOSETTING OVERCOAT RESIN COMPOSITION, OVERCOAT FILM, COLOR FILTER AND DISPLAY DEVICE}

The present specification relates to a thermosetting overcoat resin composition, an overcoat film, a color filter, and a display device.

In recent color liquid crystal display devices, the use of a color resist containing a high-level material content and a photo-alignment film process are spreading and being applied in order to reproduce high color and improve processability.

Due to UV treatment in the polyimide (PI) photo-alignment process and exposure to high temperatures, defects in liquid crystal phases caused by color resist due to high-temperature exposure are occurring, and accordingly, chemical resistance and out gas are generated in the polyimide (PI) process. The importance of these less overcoat materials is increasing.

Korean Patent Publication No. 10-2012-0022616

The present specification provides a thermosetting overcoat resin composition, an overcoat film, a color filter, and a display device having improved chemical resistance.

An exemplary embodiment of the present specification is a monomer containing an epoxy group; And a monomer containing an oxetane group, wherein the sum of the monomer content including the epoxy group and the monomer content including the oxetane group is 40 mol% based on 100 mol% of the total monomers constituting the binder resin. The above binder resin; Epoxy curing agent; And it provides a thermosetting overcoat resin composition comprising a solvent.

An exemplary embodiment of the present specification provides an overcoat film manufactured using the thermosetting overcoat resin composition.

An exemplary embodiment of the present specification provides a color filter including the overcoat layer.

An exemplary embodiment of the present specification provides a display device including the color filter.

The thermosetting overcoat resin composition according to an exemplary embodiment of the present specification has an increased curing property to improve chemical resistance, and has a low out gassing property.

1 is a schematic diagram of an overcoat film.
2 is a diagram showing the results of evaluation of N-methyl-2-pyrrolidone (NMP) elution of overcoat films according to Examples and Comparative Examples.

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

The present specification is a monomer containing an epoxy group; And a monomer containing an oxetane group, wherein the sum of the monomer content including the epoxy group and the monomer content including the oxetane group is 40 mol% based on 100 mol% of the total monomers constituting the binder resin. The above binder resin; Epoxy curing agent; And it provides a thermosetting overcoat resin composition comprising a solvent.

In the case of manufacturing an overcoat film using the overcoat resin composition according to the present specification, the pigment elution characteristics for the PI main solvent NMP (N-Methyl-2-pyrrolidone) in the photo-alignment PI process are improved to improve chemical resistance. have.

In addition, by reducing out gassing by UV irradiation or heat, it is possible to provide an overcoat film with a reduced defect rate.

In the binder resin in the overcoat resin composition according to the present specification, the sum of the monomer content including the epoxy group and the monomer content including the oxetane group is 40 mol based on 100 mol% of the total monomers constituting the binder resin in the binder resin. % Or more, the curing properties of the binder resin are improved.

Specifically, the thermosetting overcoat resin composition according to the present specification increases the curing density of the overcoat film upon curing the thermosetting overcoat resin composition through an increase in the bonding site of the epoxy group and the oxetane group in the thermosetting overcoat resin composition and an increase in the content of the epoxy curing agent. It is possible to improve chemical resistance and out gassing characteristics through

In the case of a conventional overcoat composition, a part of the polyfunctional acrylate-based composition is added for flatness characteristics, or the epoxy content in the binder composition is limited for the aging stability of the composition. In the case of the present invention, stability on the thermosetting overcoat resin composition can be secured by controlling the epoxy group content and the oxetane group content, and the existing flatness characteristics are greatly reduced by adding a low molecular weight alicyclic epoxy monomer instead of a polyfunctional acrylate. It is possible to realize high chemical resistance and low out gassing characteristics without doing so.

In the present specification, when a certain part "includes" a certain component, it means that other components may be further included rather than excluding other components unless specifically stated to the contrary.

In the exemplary embodiment of the present specification, the monomer including the epoxy group may be represented by Formula 1-1 or 1-2 below.

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,

L101 and L102 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted alkylene group; Or a substituted or unsubstituted arylene group,

R1 to R6, R101 and R102 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

T is a substituted or unsubstituted aliphatic hydrocarbon ring,

r101 is an integer of 1 to 3, and when r101 is 2 or more, R101 is the same as or different from each other,

r102 is an integer greater than or equal to 1, and when r102 is greater than or equal to 2, R102 is the same as or different from each other.

In the exemplary embodiment of the present specification, r102 is an integer from 1 to 9, and when r102 is 2 or more, R102 is the same as or different from each other.

In an exemplary embodiment of the present specification, L101 and L102 are methylene groups.

In an exemplary embodiment of the present specification, R1 and R4 are methyl groups.

In an exemplary embodiment of the present specification, R2, R3, R5, R6, R101 and R102 are hydrogen.

In the exemplary embodiment of the present specification, the monomer containing the epoxy group may be represented by any one of the following formulas.

According to an exemplary embodiment of the present specification, the monomers including the epoxy group may be those generally used in the art.

In the exemplary embodiment of the present specification, the monomer containing an oxetane group may be represented by Formula 2 below.

[Formula 2]

In Formula 2,

L103 is a direct bond; A substituted or unsubstituted alkylene group; Or a substituted or unsubstituted arylene group,

R7 to R9 and R103 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

r103 is an integer of 1 to 7, and when r103 is 2 or more, R103 is the same as or different from each other.

In an exemplary embodiment of the present specification, L103 is a methylene group.

In an exemplary embodiment of the present specification, R7 is a methyl group.

In an exemplary embodiment of the present specification, R103 is an ethyl group.

In an exemplary embodiment of the present specification, R8 and R9 are hydrogen.

In the exemplary embodiment of the present specification, the monomer containing an oxetane group may be represented by the following formula, but is not limited thereto.

In an exemplary embodiment of the present specification, the sum of the content of the monomer including the epoxy group and the content of the monomer including the oxetane group is 40 mol% or more and 80 mol% or less based on 100 mol% of the total monomers constituting the binder resin. to be.

Since the sum of the content of the monomer containing the epoxy group and the monomer containing the oxetane group satisfies the above range, there is an effect of improving the chemical resistance of N-methyl-2-pyrrolidone (NMP) after the reaction with the curing agent.

Specifically, when the sum of the monomer content including the epoxy group and the monomer content including the oxetane group is 40 mol% or more, the chemical resistance of the film is increased by increasing the bonding density through bonding with a curing agent, and out of the subsequent thermal process. The effect of reducing gassing can be obtained. When the sum of the content of the monomer including the epoxy group and the content of the monomer including the oxetane group exceeds 80 mol%, the properties of the composition over time at room temperature may be impaired, and thus use may be limited due to an increase in viscosity.

In the exemplary embodiment of the present specification, the content of the monomer including the epoxy group: the content ratio of the monomer including the oxetane group is 1:0.1 to 1:2. Preferably, the content of the monomer containing the epoxy group: the ratio of the content of the monomer containing the oxetane group is 1:0.1 to 1:0.9.

When the content of the monomer containing the epoxy group: the content ratio of the monomer containing the oxetane group satisfies the above range, it is possible to buffer the effect of inhibiting the stability over time of the composition by increasing the overall epoxy content without inhibiting the reactivity of the cured product. In addition, in the case of a monomer containing an oxetane group, it may contribute to excellent storage stability compared to a curing property equivalent to that of a monomer containing an epoxy group.

In an exemplary embodiment of the present specification, the binder resin is a vinyl aromatic monomer; And at least one selected from the group consisting of (meth)acrylate-based monomers.

The vinyl aromatic monomer may be represented by the following formula (3).

[Formula 3]

In Formula 3,

Ar is a substituted or unsubstituted aryl group,

R10 to R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In an exemplary embodiment of the present specification, Ar is a phenyl group.

In an exemplary embodiment of the present specification, R10 to R12 are hydrogen.

In the exemplary embodiment of the present specification, Formula 3 may be represented by the following formula, but is not limited thereto.

The (meth)acrylate-based monomer may be represented by the following formula (4).

[Formula 4]

In Formula 4,

R13 to R5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In an exemplary embodiment of the present specification, R13 to R5 are hydrogen.

In the exemplary embodiment of the present specification, Formula 4 may be represented by the following formula, but is not limited thereto.

As the (meth)acrylate-based monomer, methacrylic acid, (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, Isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-phenoxyethyl (meth)acrylic Group consisting of acrylate, tetrahydrofurpril (meth)acrylate, hydroxyethyl (meth)acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate and butyl α-hydroxymethyl acrylate It may be selected from, but is not limited thereto.

In an exemplary embodiment of the present specification, the binder resin may be represented by the following structure.

In the above structure,

a is the mole fraction, 0 <a <1,

b is the mole fraction, 0 <b <1,

c is the mole fraction, 0 <c <1,

d is the mole fraction, 0 <d <1,

e is the mole fraction, 0 <e <1,

a + b + c + d + e ≤ 1,

는 다른 작용기 또는 모노머에 연결되는 위치이다.

Is a position connected to another functional group or monomer.

The mole fractions of a, b, c, d and e refer to a value obtained by dividing the number of each unit repetition by the total sum of unit repetitions. That is, a is a value obtained by dividing the number of unit repetitions of formula 4 by the total number of units of the copolymer, b is a value obtained by dividing the number of unit repetitions of formula 3 by the total number of units of the copolymer, and c is the number of unit repetitions of formula 1-1 Is the value divided by the total number of units in the copolymer, d is the value obtained by dividing the number of unit repetitions in Formula 1-2 by the total number of units in the copolymer, and e is the value obtained by dividing the number of unit repetitions in Formula 3 by the total number of units in the copolymer. . The mole fraction does not mean the repetition order or the number of repetitions.

According to an exemplary embodiment of the present specification, the binder resin may have a weight average molecular weight of 4,000 g/mol or more and 100,000 g/mol or less.

When the weight average molecular weight of the binder resin is within the above range, properties such as coating properties, flatness, and out gassing may be effective. If the molecular weight is less than 4,000 g/mol, flatness is advantageous, but out gassing or coating property is disadvantageous, and if the molecular weight is more than 100,000 g/mol, the flatness characteristic may be disadvantageous.

The weight average molecular weight is one of average molecular weights whose molecular weight is not uniform and the molecular weight of a certain polymer material is used as a reference, and is a value obtained by averaging the molecular weights of component molecular species of a polymer compound having a molecular weight distribution by weight fraction.

The weight average molecular weight can be measured through Gel Permeation Chromatography (GPC) analysis.

According to an exemplary embodiment of the present specification, the acid value of the binder resin is 10 to 200 KOH mg/g.

When the acid value of the binder resin satisfies the above range, it is effective in curing reaction with the epoxy curing agent and stability over time of the solution.

In the present specification, examples of the substituents are described below, but are not limited thereto.

In the present specification, the term "substitution" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, the position where the substituent can be substituted, When two or more are substituted, two or more substituents may be the same or different from each other.

는 다른 작용기 또는 다른 모노머에 연결되는 위치이다.In this specification,

Is a position linked to another functional group or another monomer.

In the present specification, "monomer" may mean "monomer" or "unit".

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Hydroxy group (-OH); Alkyl group; Alkenyl group; Aryl group; Heteroaryl group; And one or more substituents selected from the group containing a heterocyclic group containing one or more of N, O, or S atoms, or two or more of the above exemplified substituents is substituted with a linked group or does not have any substituents. .

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. According to an exemplary embodiment, the alkyl group has 1 to 30 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-oxy And the like, but are not limited to these.

In the present specification, the alkenyl group may be a straight chain, a branched chain, or a cyclic chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 25. As a specific example, an alkenyl group substituted with an aryl group such as a stylbenyl group or a styrenyl group is preferable, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the number of carbon atoms of the aryl group may be 6 to 20, and may be 6 to 10. The aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, indenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, triphenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

In the present specification, the heteroaryl group includes one or more atoms other than carbon, that is, heteroatoms, and specifically, the heteroatom may include one or more atoms selected from the group consisting of O, N, and S. The number of carbon atoms is not particularly limited, but is preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heteroaryl group include a thiophene group; Furanyl group; Pyrrole phase; Imidazolyl group; Thiazolyl group; Oxazolyl group; Oxadiazolyl group; Pyridyl group; Bipyridyl group; Pyrimidyl group; Triazinyl group; Triazolyl group; Acridil group; Pyridazinyl group; Pyrazinyl group; Quinolinyl group; Quinazolinyl group; Quinoxalinyl group; Phthalazinyl group; Pyridopyrimidyl group; Pyridopyrazinyl group; Pyrazino pyrazinyl group; Isoquinolinyl group; Indole group; Carbazolyl group; Benzoxazolyl group; Benzimidazolyl group; Benzothiazolyl group; Benzocarbazolyl group; Benzothiophene group; Dibenzothiophene group; Benzofuranyl group; Phenanthrolinyl group; Isoxazolyl group; Thiadiazolyl group; Phenothiazinyl group; And a dibenzofuranyl group, but are not limited thereto.

In the present specification, an alkylene group means that the alkyl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the alkyl group described above can be applied.

In the present specification, an alkenylene group means that the alkenyl group has two bonding positions, that is, a divalent group. The description of the alkenyl group described above can be applied except that these are each bivalent group.

In the present specification, an arylene group means that the aryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the aryl group described above may be applied.

In the present specification, the heteroarylene group means that the heteroaryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the aforementioned heteroaryl group may be applied.

In the present specification, the heterocycle includes one or more atoms other than carbon and one or more heteroatoms, and specifically, the heterocycle may include one or more atoms selected from the group consisting of O, N, and S. The heterocycle may be monocyclic or polycyclic, and may be an aromatic, aliphatic, or condensed ring of aromatic and aliphatic, and may be selected from examples of the heteroaryl group except that it is not monovalent.

In an exemplary embodiment of the present specification, the thermosetting overcoat resin composition is an epoxy-based polyfunctional monomer; Oxetane-based polyfunctional monomer; And one or more of (meth)acrylate-based polyfunctional monomers.

As the epoxy-based polyfunctional monomer, those generally used in the art may be used.

In the exemplary embodiment of the present specification, the epoxy-based polyfunctional monomer includes two or more epoxy groups.

The epoxy-based polyfunctional monomer may be selected from, for example, bisphenol A, F type epoxy and hydrogenated bisphenol-A, F type epoxy, phenol novolak type epoxy, and cresol novolak type epoxy resin. It can be used when the number of epoxy functional groups is 2 or more among the alicyclic epoxy having no unsaturated bond in the external structure. In the case of the alicyclic epoxy, Daicel's Celloxide products may be used.

The oxetane-based polyfunctional monomer may be those generally used in the art.

The oxetane-based polyfunctional monomer is, for example, bis[1-ethyl(3-oxetanyl)]methyl ether, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 3- Ethyl-3-(phenoxymethyl)oxetane, di[(3-ethyl-3-oxetanyl)methyl]ether, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl- 3-cyclohexyloxymethyl and the like can be used. For the oxetane-based monomer, Toagosei's Aron Oxetane products may be used.

The (meth)acrylate-based polyfunctional monomer is a monomer that serves to form a photoresist phase by light, and includes a polyfunctional urethane acrylate. There is no limitation on the number of functionalities, and it is preferably 2 or more and 20 or less. Specifically, propylene glycol methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol acrylate, neopentyl glycol diacrylate, 6-hexanediol diacrylate, 1,6-hexanediol acrylate tetra Ethylene glycol methacrylate, bisphenoxy ethyl alcohol diacrylate, trishydroxyethyl isocyanurate trimethacrylate, trimethylpropane trimethacrylate, diphenylpentaerythritol hexaacrylate, pentaerythritol It may be one or a mixture of two or more selected from the group consisting of trimethacrylate, pentaerythritol tetramethacrylate, and dipentaerythritol hexamethacrylate.

In the exemplary embodiment of the present specification, the thermosetting overcoat resin composition further comprises an acrylate-based polyfunctional monomer, and the acrylate-based polyfunctional monomer is contained in an amount of 10% by weight or less based on the total weight of the thermosetting overcoat resin composition. It provides a thermosetting overcoat resin composition.

In the exemplary embodiment of the present specification, the acrylate-based polyfunctional monomer is included in an amount greater than 0 and 10% by weight or less based on the total weight of the thermosetting overcoat resin composition.

Specifically, the acrylate-based polyfunctional monomer is included in an amount of 0.1% by weight or more and 10% by weight or less based on the total weight of the thermosetting overcoat resin composition.

When the acrylate-based polyfunctional monomer satisfies the weight range, there is an effect of having excellent chemical resistance.

In the exemplary embodiment of the present specification, the epoxy curing agent is included in an amount of 8% by weight or more based on the total weight of the thermosetting overcoat resin composition.

The epoxy curing agent is included in an amount of 8% by weight or more and 20% by weight or less based on the total weight of the thermosetting overcoat resin composition.

When the epoxy curing agent satisfies the above content range, there is an effect of improving chemical resistance through improving curability with epoxy.

In one embodiment of the present specification, the epoxy curing agent is an acid anhydride-based epoxy curing agent.

The epoxy curing agent may be those generally used in the art. As an example, the epoxy curing agent may be Trimellitic anhydride (TMA, Samchun pure chemical company), but is not limited thereto.

In one embodiment of the present specification, the thermosetting overcoat resin composition comprises 40 to 90 parts by weight of the binder resin based on 100 parts by weight of the solid content of the thermosetting overcoat resin composition; And 8 to 20 parts by weight of the epoxy curing agent.

The thermosetting overcoat resin composition may include 0.1 to 30 parts by weight of an epoxy-based polyfunctional monomer; And 0.1 to 10 parts by weight of an acrylate-based polyfunctional monomer.

When each component in the thermosetting overcoat resin composition satisfies the above content range, there is an effect of having excellent chemical resistance and low out gassing.

In the present specification, the total weight of the solid content means the sum of the total weight of the components excluding the solvent in the resin composition. The basis of the solid content and the weight percent based on the solid content of each component can be measured by a general analysis means used in the art, such as liquid chromatography or gas chromatography.

The solvent is acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether , Propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1 ,1,2-trichloroethane, 1,1,2-trichloroethene, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, t-butanol, 2 -Ethoxy propanol, 2-methoxy propanol, 3-methoxy butanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate (PGMEA), propene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3 -It may be one or more selected from the group consisting of ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether, but is not limited thereto. .

In one embodiment of the present specification, the thermosetting overcoat resin composition is an adhesive agent; And it further includes at least one selected from the group consisting of surfactants.

According to an exemplary embodiment of the present specification, the content of the adhesion aid or surfactant may be 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the thermosetting overcoat resin composition.

A silane coupling agent is used as the adhesive agent used in the present specification, and specifically, methacryloyloxy propyltrimethoxy silane, methacryloyloxy propyldimethoxy silane, methacryloyloxy propyltriethoxy silane, One or more methacryloyl silane coupling agents such as methacryloyloxy propyldimethoxysilane can be selected and used, and as an alkyl trimethoxy silane, octyltrimethoxy silane, dodecyltrimethoxy silane, and octadecyl One or more types can be selected and used from trimethoxy silane and the like.

The surfactant is a fluorine-based surfactant, specifically F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443 manufactured by DIC (DaiNippon Ink & Chemicals) , F-444, F-445, F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F -482, F-483, F-484, F-486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129 , TF-1126, TF-1130, TF-1116SF, TF-1131, TF1132, TF1027SF, TF-1441, TF-1442, TF-1697, etc. may be used, but are not limited thereto.

An exemplary embodiment of the present specification provides an overcoat film manufactured using the thermosetting overcoat resin composition according to the above.

The overcoat film may be prepared according to a conventional method known in the art.

As an example, the thermosetting overcoat resin composition may be applied and cured on a substrate in an appropriate manner to prepare an overcoat film.

The coating method is not particularly limited, but a spray method, a roll coating method, a spin coating method, or the like may be used, and generally, a spin coating method is widely used. In addition, after forming the coating film, a part of the residual solvent can be removed under reduced pressure in some cases.

As the curing method, a thermal curing method may be used, and as an example, a prebake may be performed and then a post bake may be performed. Specifically, pre-baking may be performed at 80°C to 120°C within a range of 1 minute to 5 minutes, and post-baking may be performed at 150°C to 250°C within a range of 10 minutes to 1 hour.

An exemplary embodiment of the present specification provides a color filter including the overcoat layer.

An exemplary embodiment of the present specification provides a display device including the color filter.

The display device includes a plasma display panel (PDP), a light emitting diode (LED), an organic light emitting diode (OLED), a liquid crystal display (LCD), and a touch screen. It may be any one of a touch screen panel (TSP), a thin film transistor liquid crystal display (LCD-TFT), and a cathode ray tube (CRT).

Hereinafter, examples will be described in detail in order to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present specification to those of ordinary skill in the art.

<Production of binder resin>

In a nitrogen atmosphere, the following monomers 1 to 5 were added to the methyl-3-methoxy propionate (MMP) solvent in a molar ratio (mole%) shown in Table 1 below.

V65 (Wako company, bis azo type initiator) as a thermal initiator was added in an amount of 4.5 parts by weight based on the total amount (100 parts by weight) of the monomers 1 to 5, and after reacting at 60° C. for 16 hours, Butylated Hydroxytoluene (BHT) Was put in.

After reacting for an additional hour in an oxygen atmosphere, it was cooled to room temperature to obtain a binder resin that satisfies the molar ratio conditions of Table 1 below of 20% solid content.

The prepared binder resin is represented by the following structure.

A to e of the above structure means the mole fraction of each repeating unit, which is as described in Table 1 below.

Monomer-1 (a)
(mole %) Monomer-2 (b) (mole %) Monomer-3 (c) (mole %) Monomer-4 (d) (mole %) Monomer-5 (e) (mole %) Binder Resin-1 31 19 30 10 10 Binder Resin-2 36 24 10 20 10 Binder Resin-3 36 24 10 10 20 Binder Resin-4 31 19 30 20 - Binder Resin-5 35 35 10 10 10 Binder Resin-6 31 29 20 10 - Binder Resin-7 36 34 10 20 -

<Production of thermosetting overcoat resin composition>

Example 1.

85 parts by weight of the prepared binder resin-1 based on 100 parts by weight of the solid content of the thermosetting overcoat resin composition, 12 parts by weight of Trimellitic anhydride (TMA, Samchun pure chemical company) as an epoxy curing agent, and a Silane coupling agent (KBM-403) as an adhesive agent. , Shinetsu Company) 2.9 parts by weight and 0.1 parts by weight of a fluorine-based surfactant (TF-1697, DIC Company), and then propylene glycol monomethyl ether acetate (PGMEA) and diethylene glycol methyl as a solvent. A thermosetting overcoat resin composition 1 was prepared by adding ethyl ether (Diethylene Glycol Methyl Ethyl Ether, MEDG). The thermosetting overcoat resin composition 1 had a solid content of 13% by weight of the thermosetting overcoat resin composition and 87% by weight of the solvent based on the total weight of the thermosetting overcoat resin composition.

Example 2.

In Example 1, a thermosetting overcoat resin composition 2 was obtained with the same composition except that binder resin-2 was applied instead of binder resin-1.

Example 3.

In Example 1, a thermosetting overcoat resin composition 3 was obtained with the same composition except that binder resin-3 was applied instead of binder resin-1.

Example 4.

In Example 1, 85% by weight of the binder resin-1 was reduced to 65% by weight, and instead, 20% by weight of an epoxy-based MM-1 (Celloxide-2021P, Daicel) was added to obtain a thermosetting overcoat resin composition 4.

Example 5.

In Example 1, 85% by weight of the binder resin-1 was reduced to 65% by weight, and instead, 20% by weight of an epoxy-based MM-2 (EHPE-3150, Daicel) was added to obtain a thermosetting overcoat resin composition 5.

Example 6.

In Example 1, 85% by weight of the binder resin-1 was reduced to 65% by weight, and instead, 20% by weight of oxetane-based MM (OXT-221, Toagosei Corporation) was added to obtain a thermosetting overcoat resin composition 6.

Example 7.

In Example 1, 85% by weight of the binder resin-1 was reduced to 75% by weight, and instead, 10% by weight of an acrylate-based MM (GPO-303, Japanese Chemicals 1) was added to obtain a thermosetting overcoat resin composition 7.

Comparative Example 1.

In Example 1, a thermosetting overcoat resin composition of Comparative Example 1 was obtained with the same composition except that binder resin-4 was applied instead of binder resin-1.

Comparative Example 2.

In Example 1, a thermosetting overcoat resin composition of Comparative Example 2 was obtained with the same composition except that binder resin-5 was applied instead of binder resin-1.

Comparative Example 3.

In Example 1, a thermosetting overcoat resin composition of Comparative Example 3 was obtained with the same composition except that binder resin-6 was applied instead of binder resin-1.

Comparative Example 4.

In Example 1, a thermosetting overcoat resin composition of Comparative Example 4 was obtained with the same composition except that binder resin-7 was applied instead of binder resin-1.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Binder resin-1 85 - - 65 65 65 75 Binder resin-2 - 85 - - - - - Binder resin-3 - - 85 - - - - Binder resin-4 - - - - - - - Binder resin-5 - - - - - - - Binder resin-6 - - - - - - - Binder resin-7 - - - - - - - Epoxy system
MM-1 - - - 20 - - - Epoxy system MM-2 - - - - 20 - - Oxetane system
MM - - - - - 20 - Acrylate system
MM - - - - - - 10 Epoxy hardener 12 12 12 12 12 12 12 Adhesion aid 2.9 2.9 2.9 2.9 2.9 2.9 2.9 Surfactants 0.1 0.1 0.1 0.1 0.1 0.1 0.1

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Binder resin-1 - - - - Binder resin-2 - - - - Binder resin-3 - - - - Binder resin-4 85 - - - Binder resin-5 - 85 - - Binder resin-6 - - 85 - Binder resin-7 - - - 85 Epoxy system
MM-1 - - - - Epoxy system MM-2 - - - - Oxetane system
MM - - - - Acrylate system
MM - - - - Epoxy hardener 12 12 12 12 Adhesion aid 2.9 2.9 2.9 2.9 Surfactants 0.1 0.1 0.1 0.1

<Formation of overcoat film>

Thermosetting overcoat resins of Examples 1 to 7 and Comparative Examples 1 to 4 After forming a film by coating the composition under the following conditions, the amount of outgas was measured through NMP (N-Methyl-2-pyrrolidone) elution evaluation and Purge & Trap sampler-GC/MS (EQC-0290).

1. OC Spin coating: Thickness 1.5㎛

2. VCD(Vacuum Dry): 65Pa

3. Pre bake(Hot plate): 100℃, 100sec

4. Post bake(Convection oven): 230℃, 20min

<Overcoat film evaluation>

[Evaluation of NMP elution characteristics]

The following NMP (N-Methyl-2-pyrrolidone) elution characteristics of the overcoat films of Examples 1 to 7 and Comparative Examples 1 to 4 prepared above on the color filter veneer coated with DCI Grade Color (RGB) It was evaluated in the same way as.

For the Color (RGB), RGB (Color) PR having a high-tech content that satisfies the Digital Cinema Color Standard (DCI) of LG Chem was used.

After preheating the veneer on a 180°C hot plate, 2 drops of NMP (N-Methyl-2-pyrrolidone) were dropped, covered with a cover glass, and treated for 5 minutes.

After treatment, the veneer was cooled to room temperature, and the cover glass part and the overcoat film in contact with NMP (N-Methyl-2-pyrrolidone) were washed with 5 g of NMP.

The washed solution was measured for Absorbance value using a UV-vis spectrometer.

When the elution characteristic of NMP (N-Methyl-2-pyrrolidone) is 0.1 or less, it indicates excellent.

[Outgas amount evaluation]

An overcoat film using the thermosetting overcoat resin composition of Examples 1 to 7 and Comparative Examples 1 to 4 was prepared on a bare glass veneer, and the amount of outgas was evaluated and described in "OC" in Table 1 below. When the amount of outgas is 1 ppm or less, it indicates excellent performance.

An overcoat film using the thermosetting overcoat resin composition of Examples 1 to 7 and Comparative Examples 1 to 4 was prepared on a color veneer, and the amount of outgas was evaluated, and it is described in "Color+OC" of Table 1 below. When the amount of outgas is 2 ppm or less, it indicates excellent performance.

After preparing an overcoat film using the thermosetting overcoat resin composition of Examples 1 to 7, Comparative Examples 1 to 4 on a color single plate, UV (254 nm) was treated once to evaluate the amount of outgas, and the "Color+OC" in Table 1 below. UV treatment". When the amount of outgas is 2 ppm or less, it indicates excellent performance.

The amount of outgas was analyzed by P&T-GC/MS after putting a 1cm X 5cm sample (3.5g) in a Pat tube.

-Measuring equipment: Purge & Trap sampler-GC/MS (EQC-0290)

-Reagent: Toluene (Burdick & Jackson, HPLC grade, 99.9%), MeOH (J.T. Baker, HPLC grade, 100.0%)

[Storage stability evaluation]

The thermosetting overcoat composition was allowed to stand at room temperature (25° C.) for 2 weeks to observe a change in viscosity over time, which is described as “storage stability” in Tables 4 and 5 below.

If the viscosity change is less than 5%, it indicates excellent storage stability.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 NMP
Elution characteristics
@517nm Absorbance 0.0096 0.0206 0.0098 0.0213 0.0247 0.0163 0.0185 P&T MS
Out gas
(ppm) OC 0.81 0.90 0.87 0.87 0.78 0.80 0.79 Color+OC 1.16 1.29 1.23 1.21 1.18 1.18 1.22 Color+OC UV treatment 1.21 1.40 1.49 1.25 1.31 1.30 1.28 Storage stability (%) <5% <5% <5% <5% <5% <5% <5% Whether or not defects have occurred radish radish radish radish radish radish radish

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 NMP
Elution characteristics
@517nm Absorbance 0.0098 0.5502 0.5240 0.5510 P&T MS
Out gas
(ppm) OC 0.91 2.99 2.86 3.05 Color+OC 1.35 5.98 6.04 6.23 Color+OC UV treatment 1.78 6.07 6.25 6.31 Storage stability (%) <10% <5% <5% <5% Whether or not defects have occurred radish U U U

In the case of the Example, it was confirmed that there was almost no color elution by NMP (N-Methyl-2-pyrrolidone) treatment compared to the Comparative Example, and the amount of Outgas was 1/3 compared to the Comparative Example. In addition, the storage stability of the example was superior to that of the comparative example.

Accordingly, it was confirmed that the thermosetting overcoat resin composition according to the present specification can improve chemical resistance and outgas characteristics, thereby improving flowability foreign matter defects.

In particular, in the case of Comparative Example 1 to which the binder resin-4 containing no oxetane group was applied, it was confirmed that the film properties were excellent, but the storage stability was relatively deteriorated.

Claims (12)

A monomer containing an epoxy group; And a monomer containing an oxetane group, wherein the sum of the content of the monomer containing the epoxy group and the content of the monomer containing the oxetane group is 40 mol% based on 100 mol% of the total monomers constituting the binder resin. The above binder resin;
Epoxy curing agent; And a thermosetting overcoat resin composition containing a solvent. The method according to claim 1, Epoxy-based polyfunctional monomer; Oxetane-based polyfunctional monomer; And one or more of an acrylate-based polyfunctional monomer. The thermosetting overcoat resin composition of claim 1, further comprising an acrylate-based polyfunctional monomer, wherein the acrylate-based polyfunctional monomer is contained in an amount of 10% by weight or less based on the total weight of the thermosetting overcoat resin composition. The thermosetting overcoat resin composition of claim 1, wherein the epoxy curing agent is contained in an amount of 8% by weight or more based on the total weight of the thermosetting overcoat resin composition. The method according to claim 1, wherein the binder resin is a vinyl aromatic monomer; And at least one selected from the group consisting of (meth)acrylate-based monomers. The method according to claim 1, Adhesion aid; And the thermosetting overcoat resin composition further comprises at least one selected from the group consisting of surfactants. The thermosetting overcoat resin composition of claim 1, wherein the epoxy curing agent is an acid anhydride-based epoxy curing agent. The thermosetting overcoat resin composition according to claim 2, wherein the epoxy-based polyfunctional monomer contains two or more epoxy groups. The method according to claim 1, 40 to 90 parts by weight of the binder resin based on 100 parts by weight of the solid content of the thermosetting overcoat resin composition; And 8 to 20 parts by weight of the epoxy curing agent. An overcoat film prepared by using the thermosetting overcoat resin composition according to any one of claims 1 to 9. A color filter comprising the overcoat film according to claim 10. A display device comprising the color filter according to claim 11.

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