Thermosetting resin composition, and cured film and protection layer for photo device using same

Abstract

The present invention relates to: a thermosetting resin composition; and a cured film and a protection film for a photo device, using same. The thermosetting resin composition includes: a binder resin; a compound including a (meth)acryloyl group; a compound including an epoxy group; and a compound including an acrylic reactive functional group and an epoxy reactive functional group.

Description

Thermosetting resin composition and cured film using the same, protective film for optical devices

[0001] The present invention relates to a thermosetting resin composition having excellent shielding properties and compatibility when applied as a protective film for an optical device such as an LCD, a cured film using the same, and a protective film for an optical device.

[0002] Optical devices such as LCDs are subjected to local high-temperature heat treatment on the surface by sputtering during the manufacturing process, such as immersion treatment with organic solvents, acids, or alkaline solutions, or when forming a wiring electrode layer. Therefore, a protective film is sometimes installed on the surface to prevent deterioration during manufacturing.

[0003] The protective film must be able to withstand the above-described treatments while also having excellent adhesion to the substrate or lower layer, high smoothness and surface hardness, excellent transparency, excellent heat and light resistance to prevent discoloration, yellowing, and whitening over a long period of time, and excellent chemical resistance such as solvent resistance, acid resistance, and alkali resistance, as well as water resistance. In addition, when applying such a protective film to a color filter of a color liquid crystal display element, it is desirable that the base substrate be capable of flattening the steps of a general color filter.

[0004] The above protective film is composed of a cured film of a curable resin composition, which can be broadly divided into thermosetting and photocurable (photosensitive) types. When pattern formation of the protective film is required, a photosensitive resin composition is required, but otherwise, a thermosetting resin composition is used. This is because thermosetting resin compositions are more convenient in terms of processability than photosensitive resin compositions, and can increase crosslinking density, resulting in superior mechanical properties and heat resistance.

[0005] Meanwhile, attempts are being made to improve the color reproducibility of LCDs by increasing the thickness of each R, G, and B color filter, or by changing the concentration, mixing ratio, and type of pigment and dye to achieve more realistic colors. However, as the thickness of each R, G, and B increases and the type and size of the pigments change, certain substances generated from each color can migrate to the liquid crystal layer, interfering with operation. To address this issue, excellent shielding properties of the overcoat, used as a protective film and planarizing material over the color filter, are required.

[0006] In addition, since the compatibility between the components is low during curing of the composition, embossing stains may occur, which may cause display defects in liquid crystal display devices. Therefore, excellent compatibility is also required to solve this problem.

[0007] The purpose of the present invention is to provide a thermosetting resin composition that satisfies the characteristics required in the prior art as described above, has excellent shielding properties and compatibility, and is highly suitable as a material for forming a protective film for an optical device, and a cured film using the same, and a protective film for an optical device.

[0008] In order to solve the above problems, the present specification provides a thermosetting resin composition comprising: a binder resin; a compound having a (meth)acryloyl group; a compound having an epoxy group; and a compound having an acrylic reactive functional group and an epoxy reactive functional group.

[0009] The present specification also provides a cured film comprising a cured product of the thermosetting resin composition.

[0010] The present specification also provides a protective film for an optical device including the cured film.

[0011] Hereinafter, a thermosetting resin composition according to a specific embodiment of the invention and a cured film and a protective film for an optical device using the same will be described in more detail.

[0012]

[0013] Unless explicitly stated otherwise in this specification, terminology is used only to describe specific embodiments and is not intended to limit the invention.

[0014] As used herein, the singular forms also include the plural forms unless the context clearly dictates otherwise.

[0015] As used herein, the term “including” means specifying a particular characteristic, region, integer, step, operation, element and / or component, but does not exclude the presence or addition of other particular characteristics, regions, integers, steps, operations, elements, components and / or groups.

[0016] In this specification, (meth)acrylic means both acrylic and methacrylic.

[0017] In this specification, the term "substitution" means that another functional group is bonded instead of a hydrogen atom in a compound, and the position of substitution is not limited as long as it is a position where a hydrogen atom is substituted, i.e., a position where a substituent can be substituted, and when two or more are substituted, the two or more substituents may be the same or different from each other.

[0018] The term "substituted or unsubstituted" as used herein means a group that is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a cyano group; a nitro group; a hydroxy group; a carbonyl group; an ester group; an imide group; an amide group; a primary amino group; a carboxyl group; a sulfonic acid group; a sulfonamide group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthioxy group; an arylthioxy group; an alkylsulfoxy group; an arylsulfoxy group; a silyl group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an aralkyl group; an aralkenyl group; an alkylaryl group; an alkoxysilylalkyl group; an arylphosphine group; or a heterocyclic group containing at least one of N, O, and S atoms, or a heterocyclic group containing at least one of N, O, and S atoms, or a substituted or unsubstituted group in which two or more of the above-mentioned substituents are linked. For example, the "substituent linked with two or more substituents" may be a biphenyl group. That is, the biphenyl group can be an aryl group or can be interpreted as a substituent in which two phenyl groups are connected.

[0019] In this specification, , or means a bond that is connected to another substituent, and a direct bond means that there is no separate atom in the part indicated by L. In this specification, means a bond that connects to another functional group.

[0020] In this specification, aromaticity is a characteristic that satisfies the Huckels Rule, and can be defined as aromaticity when all of the following three conditions are satisfied according to the Huckels Rule.

[0021] 1) There must be 4n+2 electrons that are completely conjugated by empty p-orbitals, unsaturated bonds, and unpaired electrons.

[0022] 2) The 4n+2 electrons must form a planar isomer and form a ring structure.

[0023] 3) All atoms in the ring must be able to participate in conjugation.

[0024] In this specification, the term "aliphatic" refers to a compound that does not contain a ring structure among organic compounds other than the aforementioned aromatic compounds. In addition, in this specification, the term "alicyclic" refers to a compound that contains a ring structure among organic compounds other than the aforementioned aromatic compounds.

[0025] In the present specification, hetero refers to an atom other than carbon, which includes one or more heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S.

[0026] In this specification, a multivalent functional group is a residue in which multiple hydrogen atoms bonded to any compound are removed, and examples thereof include a divalent functional group, a trivalent functional group, and a tetravalent functional group.

[0027] In this specification, a direct bond or single bond means that no atom or group of atoms exists at that position, and is connected by a bond line. Specifically, it means that there is no separate atom in the part indicated by L1 or L2 in the chemical formula.

[0028] In the present specification, an alkyl group is a monovalent functional group derived from an alkane, which may be straight or branched, and the number of carbon atoms in the straight-chain alkyl group is not particularly limited, but is preferably 1 to 20. In addition, the number of carbon atoms in the branched-chain alkyl group is 3 to 20. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptan-4-yl, etc., but are not limited thereto. The alkyl group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.

[0029] In the present specification, a cycloalkyl group is a monovalent functional group derived from cycloalkane, which may be monocyclic or polycyclic, and has, but is not particularly limited to, 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 10 carbon atoms. Specifically, examples thereof include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2,2,1]heptyl, and the like. The cycloalkyl group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.

[0030] In the present specification, the aryl group is a monovalent functional group derived from arene, and is not particularly limited, but preferably has 6 to 20 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. The monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, etc., but is not limited thereto. The aryl group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.

[0031] In the present specification, an alkylene group is a divalent functional group derived from an alkane, and the description of the alkyl group described above may be applied to these groups except that they are divalent functional groups. For example, they may be linear or branched, and may be a methylene group, an ethylene group, a propylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a pentylene group, a hexylene group, etc. The alkylene group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.

[0032] In the present specification, an arylene group is a divalent functional group derived from arene, and the description of the above-mentioned aryl group may be applied to these except that they are divalent functional groups. For example, they may be a phenylene group, a biphenylene group, a terphenylene group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group, an anthracenyl group, etc. The arylene group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.

[0033] In the present specification, a cycloalkylene group is a divalent functional group derived from cycloalkane, and the description of the cycloalkyl group described above may be applied except that it is a divalent functional group. The cycloalkylene group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.

[0034]

[0035] According to one embodiment of the invention, a thermosetting resin composition can be provided, comprising: a binder resin; a compound having a (meth)acryloyl group; a compound having an epoxy group; and a compound having an acrylic reactive functional group and an epoxy reactive functional group.

[0036] The thermosetting resin composition of the above embodiment may include a binder resin. The binder resin of the present invention may be obtained by a conventionally known polymerization method, and may be synthesized by radical polymerization of a monomer containing an unsaturated carboxylic acid compound, an epoxy group-containing unsaturated compound, a styrene-based compound, and an unsaturated imide compound in a solvent in the presence of a polymerization initiator.

[0037] That is, the binder resin may be a copolymer of monomers containing an unsaturated carboxylic acid compound, an epoxy group-containing unsaturated compound, a styrene-based compound, and an unsaturated imide compound. More specifically, the binder resin may be a copolymer of monomers containing an unsaturated carboxylic acid compound, an epoxy group-containing unsaturated compound, a styrene-based compound, and an unsaturated imide compound.

[0038] The above unsaturated carboxylic acid compound may be a monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, or a dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, or itaconic acid; and acrylic acid and methacrylic acid are preferably used in view of copolymerization reactivity, heat resistance, and ease of acquisition.

[0039] The above unsaturated carboxylic acid compound may be included in the binder resin at 7 to 15 wt%, and within the above range, the shielding power of the cured film and the preservation stability of the copolymer are excellent.

[0040] In addition, as the epoxy group-containing unsaturated compound, at least one selected from among glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate, α-n-propyl acrylate, glycidyl α-n-butylacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether can be preferably used in that it increases copolymerization reactivity and the heat resistance and hardness of the resulting protective film.

[0041] The above epoxy group-containing unsaturated compound may be included in the binder resin at 30 to 55 wt%, which is preferable when considering the heat resistance and surface hardness of the resulting cured film or the preservation stability of the copolymer.

[0042] In addition, examples of the styrene-based compounds include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, etc. Among these, the use of styrene may be preferable in terms of copolymerization reactivity and heat resistance.

[0043] The above styrene compound may be included in the binder resin at 28 wt% to 50 wt%, which is preferable when considering the preservation stability of the copolymer and the heat resistance and surface hardness of the cured film.

[0044] In addition, examples of the unsaturated imide compounds include maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, etc. Among these, the use of maleimide may be preferable in terms of copolymerization reactivity and heat resistance.

[0045] The above unsaturated imide compound may be included in the binder resin at 3 wt% to 15 wt%, which can suppress the occurrence of embossing by increasing compatibility with the compound having a (meth)acryloyl group and the compound having an epoxy group in the composition.

[0046] Meanwhile, solvents that can be used in the synthesis of the binder resin include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; and esters such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propene glycol propyl ether acetate, propylene glycol butyl ether acetate, and methyl 3-methoxypropionate. The solvent may be included in the binder resin at 60 wt% to 70 wt%.

[0047] In addition, as a polymerization initiator that can be used in the synthesis of the above binder resin, any polymerization initiator that is generally known as a radical polymerization initiator can be used without limitation. As a radical polymerization initiator, for example, azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile; organic peroxides such as benzoyl peroxide, t-butylperoxypivalerate, and 1,1'-bis(t-butylperoxy)cyclohexane; and hydrogen peroxide can be used. The polymerization initiator can be included in the binder resin in an amount of 1 wt% to 10 wt%, and preferably, it can be advantageous in terms of heat resistance and flattening properties of the cured film to include 1 wt% to 5 wt%.

[0048] The above binder resin may be contained in an amount of 50 wt% to 80 wt% based on 100 wt% of the solid content of the thermosetting resin composition of the above embodiment.

[0049] In addition, the binder resin may have a viscosity change rate of 3% or less, or 2.5% or less, or 2% or less, or 0.1% or more, or 0.1% to 3%, or 0.1% to 2.5%, or 0.1% to 2% according to the following mathematical formula 1.

[0050] [Mathematical Formula 1]

[0051] Viscosity change rate (%) = {(second viscosity - first viscosity) / first viscosity} X 100

[0052] In the above mathematical expression 1, the first viscosity is the viscosity measured immediately after the solution including the binder resin and the solvent is prepared, and the second viscosity is the viscosity measured 24 hours after the solution including the binder resin and the solvent is stored at 45°C. The viscosity was measured twice using a Brookfield viscometer (RVDV-II+P) at 25°C with spindle No. 0 or 1 at 30 rpm (torque range 40-50%), and the average value was determined.

[0053] In the above mathematical formula 1, the solvent may be an alcohol such as methanol or ethanol; an ether such as tetrahydrofuran, diethylene glycol dimethyl ether, or diethylene glycol diethyl ether; an ester such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propene glycol propyl ether acetate, propylene glycol butyl ether acetate, or methyl 3-methoxypropionate. The solvent may be included in a solution including a binder resin and a solvent at 60 wt% to 80 wt%.

[0054] High stability can be secured when the viscosity change rate of the binder resin according to the following mathematical formula 1 satisfies 3% or less, or 2.5% or less, or 2% or less, or 0.1% or more, or 0.1% to 3%, or 0.1% to 2.5%, or 0.1% to 2%.

[0055] On the other hand, if the viscosity change rate of the binder resin according to the following mathematical formula 1 increases excessively, such as exceeding 3%, the stability is low, making it difficult to secure productivity and fairness, and making it difficult to secure reliability during the curing process.

[0056] Meanwhile, the thermosetting resin composition of the above embodiment may include a compound having a (meth)acryloyl group. The compound having the (meth)acryloyl group may be a monofunctional, difunctional, or trifunctional or higher (meth)acrylate, which is preferable in terms of good polymerizability and improved heat resistance and surface hardness of the resulting cured film.

[0057] Specifically, for acrylic monomers, monofunctional, difunctional, or trifunctional or higher (meth)acrylates are preferred due to their good polymerizability, low shrinkage upon curing, and improved adhesion even under high temperature and high humidity conditions. Such monofunctional, difunctional, or trifunctional or higher (meth)acrylates may be used in combination.

[0058] Monofunctional (meth)acrylates of the present invention include 2-hydroxyethyl (meth)acrylate, carbitol (meth)acrylate, isobornyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, etc.

[0059] Examples of the bifunctional (meth)acrylate of the present invention include ethylene glycol (meth)acrylate, 1,6-hexanediol (meth)acrylate, 1,9-nonanediol (meth)acrylate, propylene glycol (meth)acrylate, tetraethylene glycol (meth)acrylate, bisphenoxy ethyl alcohol fluorene diacrylate, and the like.

[0060] In addition, examples of the trifunctional or higher, or trifunctional to hexafunctional (meth)acrylate of the present invention include trihydroxyethyl isocyanurate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

[0061] The compound having the (meth)acryloyl group may be contained in an amount of 5 to 30 wt% based on 100 wt% of the solid content of the thermosetting resin composition of the above embodiment. In addition, the compound having the (meth)acryloyl group may be contained in an amount of 5 to 150 parts by weight, or 10 to 100 parts by weight, based on 100 parts by weight of the binder resin, which may be advantageous in terms of the shielding power and adhesion of the cured film.

[0062] Meanwhile, the thermosetting resin composition of the above embodiment may include a compound having an epoxy group. Any compound having at least one epoxy group in the molecule may be used without limitation, and any monofunctional or bifunctional or more polyfunctional epoxy compound may be used. Thermosetting properties can be secured through the compound having the epoxy group.

[0063] Specific examples of compounds having the above epoxy group include glycidyl acrylate and novolac epoxy resin.

[0064] The compound having the epoxy group may be contained in an amount of 1 to 10 wt% based on 100 wt% of the solid content of the thermosetting resin composition of the above embodiment. In addition, the compound having the epoxy group may be contained in an amount of 0.1 to 30 wt% based on 100 wt% of the binder resin. This is because if the amount exceeds the above range, the proportion of low molecular weight in the composition increases, which is not only disadvantageous in terms of the shielding power and adhesion of the cured film, but also disadvantageous in terms of outgassing.

[0065] Meanwhile, the thermosetting resin composition of the above embodiment may include a compound having an acrylic reactive functional group and an epoxy reactive functional group. In the past, when a thermosetting resin composition of the above embodiment simultaneously contained a compound having a (meth)acryloyl group and a compound having an epoxy group, there was a limitation in that display defects occurred due to embossing caused by differences in reaction because each had a curing system.

[0066] On the other hand, the thermosetting resin composition of the above embodiment includes a compound having an acrylic reactive functional group and an epoxy reactive functional group, thereby increasing compatibility between a compound having a (meth)acryloyl group and a compound having an epoxy group, thereby achieving an effect of suppressing occurrence of embossing stains in a cured film.

[0067] The compound having the above-described acrylic reactive functional group and epoxy reactive functional group may include an acrylic reactive functional group capable of reacting with the (meth)acryloyl group contained in the compound having the above-described (meth)acryloyl group.

[0068] The above acrylic reactive functional group may include at least one functional group selected from the group consisting of a (meth)acryloyl group and a vinyl group. That is, the acrylic reactive functional group may include a (meth)acryloyl group, a vinyl group, or a mixture thereof.

[0069] Additionally, the compound having the acrylic reactive functional group and the epoxy reactive functional group may include an epoxy reactive functional group capable of reacting with the epoxy contained in the compound having the epoxy group described above.

[0070] The epoxy reactive functional group may include at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an epoxy group, and an amine group. That is, the epoxy reactive functional group may include a carboxyl group, a hydroxyl group, an epoxy group, an amine group, or a mixture of two or more thereof.

[0071] The compound having the above-described acrylic reactive functional group and the epoxy reactive functional group may have the acrylic reactive functional group at one end of the molecule and the epoxy reactive functional group at the other end. Accordingly, at one end of the compound having the acrylic reactive functional group and the epoxy reactive functional group, a physical and chemical interaction with the compound having the (meth)acryloyl group described above occurs due to the acrylic reactive functional group, and at the other end, a physical and chemical interaction with the compound having the epoxy group described above occurs due to the epoxy reactive functional group. Accordingly, the compatibility between the compound having the (meth)acryloyl group and the compound having the epoxy group can be improved by the compound having the acrylic reactive functional group and the epoxy reactive functional group.

[0072] Specifically, the compound having the acrylic reactive functional group and the epoxy reactive functional group may include a central functional group; an acrylic reactive functional group bonded to one terminal of the central functional group; and an epoxy reactive functional group bonded to the other terminal of the central functional group. Examples of the central functional group are not particularly limited, and may include all chain and ring structures of aliphatic, alicyclic, heteroaliphatic, heteroalicyclic, or aromatic groups, and may have a divalent, trivalent, or higher polyfunctional group.

[0073] When the central functional group is a divalent functional group, one acrylic reactive functional group bonded to one terminal of the central functional group and one epoxy reactive functional group bonded to the other terminal of the central functional group may be included.

[0074] In addition, when the central functional group is a trivalent or higher functional group, at least one acrylic reactive functional group bonded to one terminal of the central functional group and at least one epoxy reactive functional group bonded to the other terminal of the central functional group may be included. That is, while at least one acrylic reactive functional group and one epoxy reactive functional group are each required, an acrylic reactive functional group and an epoxy reactive functional group may be additionally included at the terminals of the remaining central functional groups.

[0075] More specifically, the compound having the acrylic reactive functional group and the epoxy reactive functional group may include a compound represented by the following chemical formula 1.

[0076] [Chemical Formula 1]

[0077]

[0078] In the above chemical formula 1, R1 is a central functional group, R2 is an acrylic reactive functional group, R3 is an epoxy reactive functional group, L1 and L2 are the same as or different from each other, and are each independently a direct bond or a divalent organic functional group, and n1 and n2 are the same as or different from each other, and are each independently an integer greater than or equal to 1.

[0079] In the above chemical formula 1, R1 may be a polyfunctional group containing an aliphatic, alicyclic, heteroaliphatic, heteroalicyclic, or aromatic structure and having a valence of (n1+n2). Examples of R1 in the above chemical formula 1 are not particularly limited, but include, for example, a cycloalkylene group, an arylene group, an alkylene group, a functional group in which an arylene group is bonded to both ends of an alkylene group, or a functional group represented by the following chemical formula 1-1.

[0080] [Chemical Formula 1-1]

[0081]

[0082] In the above chemical formula 1-1, a is an integer greater than or equal to 1.

[0083] More specific examples of R1 in the above chemical formula 1 include a cyclohexylene group, a benzenediyl group, 2,2-bisphenylpropane, ethylene, etc.

[0084] Meanwhile, in the above chemical formula 1, R2 is an acrylic reactive functional group. The acrylic reactive functional group may include at least one functional group selected from the group consisting of a (meth)acryloyl group and a vinyl group. That is, the acrylic reactive functional group may include a (meth)acryloyl group, a vinyl group, or a mixture thereof.

[0085] In the above chemical formula 1, R3 is an epoxy reactive functional group. The epoxy reactive functional group may include one or more functional groups selected from the group consisting of a carboxyl group, a hydroxyl group, an epoxy group, and an amine group. That is, the epoxy reactive functional group may include a carboxyl group, a hydroxyl group, an epoxy group, an amine group, or a mixture of two or more thereof.

[0086] In the above chemical formula 1, L1 and L2 are the same or different from each other, and each independently represents a direct bond or a divalent functional group having an aliphatic, alicyclic, heteroaliphatic, heteroalicyclic, or aromatic structure.

[0087] The compound having the above-mentioned acrylic reactive functional group and epoxy reactive functional group may include, for more specific examples, at least one compound selected from the group consisting of 2-acryloyloxyethylhexahydrophthalic acid, 2-acryloyloxyethyl 2-hydroxyethyl phthalate, bisphenol A monoglycidyl ether monoacrylate, 2-(dimethylamino)ethyl acrylate, and a compound represented by the following chemical formula 2.

[0088] [Chemical Formula 2]

[0089]

[0090] In the above chemical formula 2, a is an integer greater than or equal to 1.

[0091] The compound having the acrylic reactive functional group and the epoxy reactive functional group may be contained in an amount of 13 wt% to 30 wt%, or 13 wt% to 20 wt%, or 13 wt% to 17 wt%, based on 100 wt% of the solid content of the thermosetting resin composition of the embodiment. If the compound having the acrylic reactive functional group and the epoxy reactive functional group is excessively reduced to less than 13 wt% based on 100 wt% of the solid content of the thermosetting resin composition of the embodiment, it is difficult to achieve a sufficient level of embossing stain removal effect. In addition, if the compound having the acrylic reactive functional group and the epoxy reactive functional group is excessively increased to more than 30 wt% based on 100 wt% of the solid content of the thermosetting resin composition of the embodiment, problems such as a decrease in the shielding power and curability of the cured film may occur.

[0092] In addition, the compound having the acrylic reactive functional group and the epoxy reactive functional group may be contained in an amount of 200 to 500 parts by weight, or 200 to 400 parts by weight, or 250 to 350 parts by weight, based on 100 parts by weight of the compound having the epoxy group. In addition, the compound having the acrylic reactive functional group and the epoxy reactive functional group may be contained in an amount of 50 to 200 parts by weight, based on 100 parts by weight of the compound having a (meth)acryloyl group.

[0093] If the amount of the compound having the acrylic reactive functional group and the epoxy reactive functional group is excessively reduced compared to the compound having the epoxy group or the compound having the (meth)acryloyl group, it is difficult to achieve a sufficient level of embossing stain removal effect. In addition, if the amount of the compound having the acrylic reactive functional group and the epoxy reactive functional group is excessively increased compared to the compound having the epoxy group or the compound having the (meth)acryloyl group, problems such as a decrease in the shielding power and curing property of the cured film may occur.

[0094] In addition, the compound having the acrylic reactive functional group and the epoxy reactive functional group may be contained in an amount of 10 to 50 parts by weight based on 100 parts by weight of the binder resin.

[0095] The thermosetting resin composition of the present invention can be prepared by uniformly mixing the binder resin as described above; a compound having a (meth)acryloyl group; a compound having an epoxy group; and a compound having an acrylic reactive functional group and an epoxy reactive functional group; and each component. Usually, the thermosetting resin composition of the present invention is dissolved in a suitable solvent and used in a solution state. That is, the binder resin; a compound having a (meth)acryloyl group; a compound having an epoxy group; and a compound having an acrylic reactive functional group and an epoxy reactive functional group; and other additives are mixed in a predetermined ratio to prepare the thermosetting resin composition in a solution state.

[0096] The examples of the above additives are not particularly limited, and various additives widely known in the field of thermosetting resin compositions applied to conventional protective films for optical devices can be applied without limitation. However, examples include acid anhydride curing agents, silane coupling agents, and surfactants.

[0097] The above acid anhydride hardener is added for epoxy curing, and is represented by (RCO)2O, where R includes aliphatic, alicyclic, aromatic, and halogen groups, and monocarboxylic acids or dicarboxylic acids that do not contain or contain a carboxylic acid group can be used. A specific example is trimellitic anhydride.

[0098] The above silane coupling agent is used to provide adhesiveness, and examples thereof include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Such silane coupling agent may be used in an amount of 20 parts by weight or less, or 10 parts by weight or less, per 100 parts by weight of the binder resin. If the amount of the silane coupling agent exceeds 20 parts by weight, heat resistance is likely to deteriorate.

[0099] The surfactants mentioned above include surfactants for improving application properties. Surfactants include fluorine and silicone surfactants, such as FC-129, FC-170C, and FC-430 from 3M. These surfactants can be used in an amount of 1 part by weight or less, or 0.1 part by weight or less, per 100 parts by weight of the binder resin. If the amount of surfactant exceeds 5 parts by weight, foaming is likely to occur during application.

[0100] In addition, the thermosetting resin composition of the present invention is dissolved in a suitable solvent and used in a solution state. Examples of the solvent used in the present invention include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; and propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate.

[0101] According to a preferred embodiment of the present invention, among these solvents, propene glycol monomethyl ether acetate can be preferably used in terms of solubility, reactivity with each component, and convenience of film formation.

[0102] The composition solution prepared as above can be used after being filtered using a filter having a pore diameter of 0.05 ㎛ to 5 ㎛.

[0103]

[0104] Meanwhile, as another embodiment of the present invention, a cured film comprising a cured product of the thermosetting resin composition according to the present invention may be provided. The description of the thermosetting resin composition includes all of the contents described above in the above embodiment.

[0105] The cured product of the thermosetting resin composition refers to a result obtained through a curing process of the thermosetting resin composition. The curing process of the thermosetting resin composition is not particularly limited, and various curing processes widely known in the field of thermosetting resin compositions applied to conventional protective films for optical devices can be applied without limitation. However, as an example, the thermosetting resin composition can be applied to a base substrate and cured by treating in an oven at 150°C to 300°C for 10 to 100 minutes. The example of the base substrate is not particularly limited, and examples thereof include a glass substrate or a laminate in which a resist pattern is formed on a glass substrate.

[0106] In addition, the maximum absorbance value at a wavelength of 515 nm to 520 nm for the washing solution obtained by heat-treating the laminate including the cured film at a temperature of 180° C. for 30 minutes while exposing it to a solvent and then washing the upper and lower substrates with the solvent may be 0.09 or less, or 0.08 or less, or 0.07 or less, or 0.06 or less, or 0.01 or more, or 0.01 to 0.09, or 0.01 to 0.08, or 0.01 to 0.07, or 0.01 to 0.06.

[0107] The laminate may include a lower glass substrate, a red resist pattern formed on the lower glass substrate, the cured film formed on the red resist pattern, and an upper glass substrate formed on the cured film, and a solvent may be injected between the cured film and the upper glass substrate. Injection of the solvent between the cured film and the upper glass substrate means a state in which the laminate including the cured film is exposed to the solvent.

[0108] N-methyl-2-pyrrolidone (NMP) can be used as the solvent injected between the cured film and the glass substrate. The amount of N-methyl-2-pyrrolidone (NMP) injected can be 50 μl to 150 μl. To prevent the solvent from leaking from the laminate injected between the cured film and the upper glass substrate, the laminate can be wrapped with heat-resistant tape and sealed tightly.

[0109] In the cleaning solution obtained by washing the above glass substrate with a solvent, N-methyl-2-pyrrolidone (NMP) may be used as the solvent. The amount of N-methyl-2-pyrrolidone (NMP) added may be 1 ml to 10 ml. The absorbance of the cleaning solution obtained by washing both the lower glass substrate in contact with the resist pattern and the upper glass substrate in contact with the cured film may be measured.

[0110] After heat-treating the laminate including the above-mentioned cured film at 180°C for 30 minutes, and then washing the glass substrate with a solvent, the maximum absorbance value at a wavelength of 515 nm to 520 nm for the obtained washing solution satisfies 0.09 or less, or 0.08 or less, or 0.07 or less, or 0.06 or less, or 0.01 or more, or 0.01 to 0.09, or 0.01 to 0.08, or 0.01 to 0.07, or 0.01 to 0.06, thereby securing high shielding power and having excellent shielding characteristics, it can be applied to a color filter for a high-color reproduction model in which the size of the dye or dispersed pigment is small, and excellent panel characteristics can be maintained even under harsh reliability conditions.

[0111] On the other hand, if the maximum absorbance at a wavelength of 515 nm to 520 nm for the washing solution obtained by heat-treating the laminate including the above-mentioned cured film at 180°C for 30 minutes and then washing the glass substrate with a solvent increases excessively, such as exceeding 0.09, the shielding power is low, making it difficult to apply it to a color filter for a high-color reproduction model.

[0112]

[0113] Meanwhile, as another embodiment of the present invention, a protective film for an optical device including a cured film according to the present invention may be provided. The description of the cured film includes all of the contents described above in the other embodiment.

[0114] The protective film for an optical device of another embodiment described above is useful as a color filter protective film, and can be applied to both the IPS method and the TN method, and can be particularly useful in the manufacture of a liquid crystal display device having a structure in which a color filter is formed on a thin film transistor substrate, i.e., an array substrate.

[0115] According to the present invention, when applied as a protective film for an optical device such as an LCD, a thermosetting resin composition having excellent shielding properties and compatibility, a cured film using the same, and a protective film for an optical device can be provided.

[0116] Figure 1 shows the results of measuring the surface embossing of the cured film obtained in Example 1.

[0117] Figure 2 shows the results of measuring the surface embossing of the cured film obtained in Comparative Example 1.

[0118] Figure 3 shows the results of measuring the surface embossing of the cured film obtained in Reference Example 1.

[0119] The invention is described in more detail in the following examples. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited by the following examples.

[0120]

[0121] <Manufacturing Example: Manufacturing of Binder Resin>

[0122] Manufacturing Example 1

[0123] In a reaction vessel equipped with a condenser and a stirrer, 10 parts by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator and 400 parts by weight of methyl 3-methoxypropionate as a solvent were dissolved relative to 100 parts by weight of the total monomer content used for the synthesis of the copolymer. Subsequently, 5 parts by weight of maleimide, 10 parts by weight of methacrylic acid, 55 parts by weight of glycidyl methacrylate, and 30 parts by weight of styrene as monomers were added and stirred under a nitrogen purge. The temperature of the solution was raised to 80°C and maintained at this temperature for 6 hours to obtain a polymer solution including copolymer A-1.

[0124]

[0125] <Examples, Comparative Examples, Reference Examples>

[0126] A thermosetting resin composition was prepared by mixing the copolymer obtained in the above manufacturing example or reference manufacturing example as binder resin [A] and propylene glycol monomethyl ether acetate as a solvent, and then mixing [B] a compound having a (meth)acryloyl group, [C] a compound having an epoxy group, [D] a compound having an acrylic reactive functional group and an epoxy reactive functional group, and [E] other additives while changing the contents as shown in Table 1 below.

[0127] Classification [A][B][C][D][E] Example 1A-155155D-11510 Example 2A-1451510D-12010 Example 3A-155155D-21510 Example 4A-155155D-31510 Example 5A-155155D-41510 Example 6A-155155D-51510 Comparative Example 1A-1551520D-1010 Comparative Example 2A-155035D-1010 Reference Example 1A-1551510D-11010

[0128] In the above Table 1, each content unit is weight% based on 100% solid content. [B] used in the above Table 1 is trimethylolpropane triacrylate (TMPTA).

[0129] [C] used in the above Table 1 is EOCN-104S (Nipponkayaku, 213~223g / eq), a novolac epoxy.

[0130] [D] used in Table 1 above is as follows.

[0131] (D-1) 2-Acryloyloxyethylhexahydrophthalic acid (HOA-HH)

[0132] (D-2) 2-Acryloyloxyethyl 2-hydroxyethyl phthalate

[0133] (D-3) Bisphenol A monoglycidyl ether monoacrylate

[0134] (D-4) 2-(dimethylamino)ethyl acrylate

[0135] (D-5) A compound represented by the following chemical formula 2

[0136] [Chemical Formula 2]

[0137]

[0138] In the above chemical formula 2, a is an integer greater than or equal to 1.

[0139] [E] used in the above Table 1 is an acid anhydride curing agent (7 wt%), a silane coupling agent (2.9 wt%), and a silane surfactant (0.1 wt%).

[0140]

[0141] <Experimental Example>

[0142] (1) Viscosity change rate

[0143] The viscosity change rate was calculated using the following mathematical formula 1. A viscosity change rate of 3% or less can be evaluated as good.

[0144] [Mathematical Formula 1]

[0145] Viscosity change rate (%) = {(second viscosity - first viscosity) / first viscosity} X 100

[0146] In the above mathematical expression 1, the first viscosity is the viscosity measured immediately after the polymer solution of the above manufacturing example was manufactured, and the second viscosity is the viscosity measured 24 hours after the polymer solution of the above manufacturing example was stored at 45°C. The viscosity was measured twice using a Brookfield viscometer (RVDV-II+P) at 25°C, with a No. 0 spindle, at 30 rpm (torque range 40-50%), and the average value was determined.

[0147]

[0148] (2) Shielding power

[0149] The shielding power was evaluated according to the following method. A shielding power of 0.09 or less is considered good.

[0150] 1. A 4x4cm pattern substrate was created using RED Photo Resist on a 5x5cm glass.

[0151] 2. The thermosetting resin composition obtained in the above examples and comparative examples was coated with a thickness of 1 μm on the RED Photo Resist pattern obtained in 1 above, and then cured at 230°C for 25 minutes or more.

[0152] 3. Wrap the upper corner of the laminate obtained in 2 above with heat-resistant tape to a size of about 0.5 cm on all sides.

[0153] 4. Add 100 ㎕ of NMP onto the thermosetting resin cured film of the laminate surrounded by heat-resistant tape and cover with a 6x6 cm cover glass.

[0154] 5. Attach the cover glass and the laminate tightly with heat-resistant tape so that there is no space between them.

[0155] 6. Set the hotplate to 180℃, place the substrate obtained in step 5 on it, and heat treat for 30 minutes.

[0156] 7. After 30 minutes, remove the adhesive tape and wash and collect the upper and lower glass plates using 3 ml of NMP.

[0157] 8. Measure the absorbance of the collected solution using a UV-visible spectrometer. (Compare the peak values ​​between 515 and 520 nm based on the RED standard.)

[0158]

[0159] (3) Embo

[0160] Embossing was evaluated using the following method. If no stains occur on the cured film, regardless of size, the film is considered good. A shielding power of 0.09 or less is considered good.

[0161] 1. The thermosetting resin composition obtained in the above examples and comparative examples is coated on a 5x5cm substrate to a thickness of 4 to 5㎛, and then dried at 100°C for 100 seconds.

[0162] 2. Afterwards, place it in a SUS container with a lid, seal it, and harden it in an oven at 230℃ for 25 minutes.

[0163] 3. Afterwards, observe the surface of the cured film using an optical microscope.

[0164] The above measurement results indicate that if embossing occurs, it is marked as ○, if embossing occurs to a moderate degree, it is marked as △, and if embossing does not occur, it is marked as ×.

[0165] Viscosity change rate (%) Shielding power Embossing Example 120.06×(Figure 1) Example 220.04×Example 320.07×Example 420.06×Example 520.05×Example 620.04×Comparative Example 120.11○(Figure 2) Comparative Example 220.13×Reference Example 120.09△(Figure 3)

[0166] Through the above Table 2, it was confirmed that the thermosetting resin composition of the example had a significantly improved shielding ability compared to Comparative Example 1, which did not include a compound having [D] an acrylic reactive functional group and an epoxy reactive functional group, while not causing embossing. On the other hand, in the case of Comparative Example 2, which did not include a compound having [D] an acrylic reactive functional group and an epoxy reactive functional group, embossing did not occur because it did not include a compound having [B] an acryloyl group, but it was confirmed that the shielding ability was significantly worse than that of the example.

Claims

1. Binder resin; A compound having a (meth)acryloyl group; A compound having an epoxy group; and A thermosetting resin composition comprising a compound having an acrylic reactive functional group and an epoxy reactive functional group.

2. In paragraph 1, A thermosetting resin composition, wherein the acrylic reactive functional group comprises at least one functional group selected from the group consisting of a (meth)acryloyl group and a vinyl group.

3. In paragraph 1, A thermosetting resin composition, wherein the epoxy reactive functional group comprises at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an epoxy group, and an amine group.

4. In paragraph 1, The compound having the above acrylic reactive functional group and epoxy reactive functional group is, A thermosetting resin composition having an acrylic reactive functional group at one terminal of the molecule and an epoxy reactive functional group at the other terminal.

5. In paragraph 1, The compound having the above acrylic reactive functional group and epoxy reactive functional group is, A thermosetting resin composition comprising a compound represented by the following chemical formula 1: [Chemical formula 1] In the above chemical formula 1, R 1 is the central functional group, R 2 is an acrylic reactive functional group, R 3 is an epoxy reactive functional group, L 1 , L 2 are identical or different from each other, and each independently represents a direct bond or a divalent organic functional group, n1 and n2 are equal to or different from each other, and are each independently an integer greater than or equal to 1.

6. In paragraph 5, Above R 1 It contains at least one structure selected from the group consisting of aliphatic, alicyclic, heteroaliphatic, heteroalicyclic, and aromatic, and has a valence of (n 1 +n 2 ) is a multifunctional group, a thermosetting resin composition.

7. In paragraph 1, The compound having the above acrylic reactive functional group and epoxy reactive functional group is, A thermosetting resin composition comprising at least one compound selected from the group consisting of 2-acryloyloxyethylhexahydrophthalic acid, 2-acryloyloxyethyl 2-hydroxyethyl phthalate, bisphenol A monoglycidyl ether monoacrylate, 2-(dimethylamino)ethyl acrylate, and a compound represented by the following chemical formula 2: [Chemical formula 2] In the above chemical formula 2, a is an integer greater than or equal to 1.

8. In paragraph 1, The compound having the above acrylic reactive functional group and epoxy reactive functional group is, A thermosetting resin composition, comprising 13 to 30 wt% of the thermosetting resin composition based on 100 wt% of the solid content of the thermosetting resin composition.

9. In paragraph 1, The compound having the above acrylic reactive functional group and epoxy reactive functional group is, A thermosetting resin composition containing 200 to 500 parts by weight based on 100 parts by weight of a compound having an epoxy group.

10. In paragraph 1, The compound having the above acrylic reactive functional group and epoxy reactive functional group is, A thermosetting resin composition containing 50 to 200 parts by weight of a compound having a (meth)acryloyl group based on 100 parts by weight.

11. In paragraph 1, The compound having the above acrylic reactive functional group and epoxy reactive functional group is, A thermosetting resin composition, containing 10 to 50 parts by weight based on 100 parts by weight of binder resin.

12. In paragraph 1, The above binder resin A thermosetting resin composition characterized by being a copolymer of a monomer containing an unsaturated carboxylic acid compound, an epoxy group-containing unsaturated compound, a styrene compound, and an unsaturated imide compound.

13. In paragraph 12, A thermosetting resin composition, wherein the unsaturated carboxylic acid compound is contained in an amount of 7 to 15 wt% in the binder resin.

14. In paragraph 12, A thermosetting resin composition, wherein the epoxy group-containing unsaturated compound is contained in an amount of 30 to 55 wt% in the binder resin.

15. In paragraph 12, A thermosetting resin composition, wherein the styrene-based compound is contained in an amount of 28 to 50 wt% in the binder resin.

16. In paragraph 12, A thermosetting resin composition, wherein the unsaturated imide compound is contained in an amount of 3 to 15 wt% in the binder resin.

17. In paragraph 1, The above binder resin is a thermosetting resin composition having a viscosity change rate of 3% or less according to the following mathematical formula 1: [Mathematical Formula 1] Viscosity change rate (%) = {(second viscosity - first viscosity) / first viscosity} X 100 In the above mathematical expression 1, the first viscosity is the viscosity measured immediately after the solution including the binder resin and the solvent is prepared, and the second viscosity is the viscosity measured 24 hours after the solution including the binder resin and the solvent is stored at 45°C.

18. A cured film comprising a cured product of the thermosetting resin composition of paragraph 1.

19. In paragraph 18, After heat-treating the laminate including the above-mentioned cured film at a temperature of 180°C for 30 minutes, the glass substrate is washed with a solvent, and the maximum absorbance value at a wavelength of 515 nm to 520 nm for the obtained washing solution is 0.09 or less, The laminate comprises a lower glass substrate, a red resist pattern formed on the lower glass substrate, a cured film of claim 18 formed on the red resist pattern, and an upper glass substrate formed on the cured film, wherein a solvent is injected between the cured film and the upper glass substrate.

20. A protective film for an optical device comprising the cured film of Article 18.

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