TWI282796B - Curing resin composition and its uses - Google Patents

Abstract

There is disclosed a curing resin composition which can form a coating film that is extremely excellent not only in the heat resistance but also in the transparency. The curing resin composition is a curing resin composition which comprises a polymer component (A) and a curing component (B), wherein the curing component (B) includes at least one selected from among compounds (b1) having a radically polymerizable double bond and compounds (b2) having an epoxy group, with the curing resin composition being characterized in that the polymer component (A) is a polymer (a) which is formed by polymerizing a monomer component including a specific ether dimer as an essential component.

Description

1282796 (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a novel curable resin composition and use thereof. [Prior Art] Conventionally, a curable resin composition having excellent heat resistance has been proposed to contain a monomer component containing 2-(hydroxyalkyl) acrylate, to be polymerized, and to contain a lactone ring by cyclization of a lactone. A resin composition containing a polymer and a curing component (for example, refer to Patent Document 1) and a resin composition containing a polymer and a curing component obtained by polymerizing a monomer component containing maleimide (for example, reference) Patent Documents 2, 3) and the like. [Patent Document 1] Japanese Unexamined Patent Application Publication No. Publication No. Publication No. JP-A------- [Disclosure of the Invention] [Problems to be Solved by the Invention] However, the former resin composition containing a polymer derived from 2-(hydroxyalkyl)acrylate has low polymerizability and residual/monomer when the polymer is obtained. There is a tendency to become more and more, and more water and ethanol occur in the cyclization of lactones. These residual monomers or water and ethanol have a good influence on the physical properties of the hardenable and hardened films. Further, when the lactone ring containing a lactone ring polymer is easily opened under a base, for example, when it is used for an alkali-developing type of photoresist material, etc., according to the condition, it is also known as the condition of -4 - 1282796 (2) There is a problem that the hardened portion is missing and the shape of the pattern is deteriorated. Further, the latter contains a resin composition derived from a polymer of maleimide. Since the maleimide-based polymer contains a nitrogen atom, the polymer is colored yellow to yellowish brown, and the transparency of the cured film is Insufficient problem. This problem of transparency is particularly remarkable in the case where the film thickness of the cured film is thick, and is more colored if subjected to heat treatment. Thus, the problem to be solved by the present invention is to provide a curable resin composition which can form a coating film which is excellent in heat resistance and transparency, and a color filter and a display device using the curable resin composition. [Means for Solving the Problems] The present inventors conducted an effort to review the above problems. As a result, it has been found that a resin composition containing a polymer obtained by polymerizing a specific structural compound of an ether dimer of 2-(hydroxyalkyl) acrylate and a curing component can solve the above problems and complete the present invention. That is, the curable resin composition of the present invention is composed of at least one selected from the group consisting of a polymer component (A), a compound having a radical polymerizable double bond (bl), and a compound having an epoxy group (b2). The curable resin composition of the hardening component (B), wherein the polymer component (A) is represented by the following general formula (1): OR1 OR2 (in the formula (1), R1 and R2 each independently represent a hydrogen atom or may have A polymer obtained by polymerizing a compound represented by a monomer component having a carbon number of from 1 to 25, which is a hydroxyl group of from 1 to 25,282 (3) and having a carbon number of (a), which is characterized by the color filter of the present invention. In the color filter formed by providing a cured resin layer on a substrate, the resin composition as the cured resin layer is the curable resin composition of the present invention. In the display device of the present invention, a display device using a color filter formed by providing a hardened resin layer on a substrate is used. The resin composition of the cured resin layer is the curable resin composition of the present invention. [Effects of the Invention] The curable resin composition of the present invention can form a coating film which is excellent in heat resistance and transparency, and is suitable, for example, for use in a photoresist material, various coating agents, paints and the like. Further, according to the present invention, it is possible to provide a color filter having no good quality of pattern defects and development residues. Further, according to the present invention, it is possible to provide a display device which has high brightness and color purity and which does not cause good display quality such as color unevenness. [Best Mode for Carrying Out the Invention] The curable resin composition of the present invention contains the following general formula (1)

OR2 (1) -6 - 1282796 (4) (In the formula (1), R1 and R2 each independently represent a hydrogen atom or a hydroxyl group having 1 to 25 carbon atoms which may have a substituent) (hereinafter also referred to as a compound) The "ether dimer" is a polymer component (A) in which the polymer (a) polymerized as an essential monomer component is an essential component. Thus, the curable resin composition of the present invention can form a cured coating film which is extremely excellent in heat resistance and transparency. It is presumed that the ether dimer is subjected to a cyclization reaction during polymerization, and a tetrahydropyran ring structure is formed in a constituent unit derived from an ether dimer. Hereinafter, the above polymer (a) will be described. In the above general formula (1), the hydroxyl group represented by R1 and R2 and having a carbon number of 1 to 25, which is a substituent, is not particularly limited, and examples thereof include a methyl group and an ethyl group. a linear or branched alkyl group such as n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl or 2-ethylhexyl; An aryl group such as a phenyl group; a cyclohexyl group, a tert-butylcyclohexyl group, a dicyclopentadienyl group, a tricyclodecanyl group, an isobornyl group, an adamantyl group, a 2-methyl-2-alkanyl group or the like a cyclic group, an alkyl group substituted by an alkoxy group such as 1-methoxyethyl or 1-ethoxyethyl; an alkyl group substituted by an aryl group such as a aryl group; and the like. Among them, a primary or secondary carbon substituent which is particularly liberated by a hard acid such as a methyl group, an ethyl group, a cyclohexyl group or a benzyl group and a heat is preferred in terms of heat resistance. Further, R1 and R2 may be the same substituent or may be a different substituent. Specific examples of the ether dimer include, for example, dimethyl-2,2-~[hydroxybis(methylene)]bis-2-propanate, diethyl-2,2-one [hydroxyl double ( Methylene)] bis-2-propionate, di(n-propyl)-7- 1282796 (5) a 2,2 / - [hydroxy bis(methylene)] bis-2-propionate, two (Isopropyl)-2,2 / - [hydroxy bis(methylene)] bis-2-propionate, di(n-butyl)-2,2/-[hydroxybis(methylene)] a 2-propionate, di(isobutyl)-2,-[hydroxybis(methylene)]bis-2-propanate, di(t-butyl)-2,-hydroxyl (sub Methyl)] bis-2-propionate, bis(t-pentyl)-2,2/-[hydroxybis(methylene)]bis-2-propionate, bis(stearyl)-2 , 2> — [hydroxy bis(methylene)] bis-2-propionate, bis(lauryl)-2,2/-[hydroxybis(methylene)]bis-2-propionate, (2-ethylhexyl)-2,2/-[hydroxybis(methylene)]bis-2-propionate, (1-methoxyethyl)- 2,2 / - [hydroxy bis(methylene)] bis- 2 -propionate, bis(1 -ethoxyethyl)-2,2 / -[hydroxy bis ( Methylene)] bis- 2-propionate, dibenzyl-2,2/-[hydroxybis(methylene)]bis-2-propanate, diphenyl-2,2/-[hydroxyl Bis(methylene)] bis-2-propionate, dicyclohexyl-2,2/-[hydroxybis(methylene)]bis-2-propanate, di(t-butylcyclohexyl) a 2,2 / -[hydroxybis(methylene)]bis-2-propionate, bis(dicyclopentadienyl)-2,2^-[hydroxybis(methylene)]bis-2 - propionate, bis(tricyclodecyl)-2,2/-[hydroxybis(methylene)]bis-2-propionate, bis(isobornyl)-2,2/-[hydroxyl double (methylene)] bis-2-propionate, diamantyl-2,2/-[hydroxybis(methylene)]bis-2-propionate, bis(2-methyl-2- Adamantyl)-2,2 / - [hydroxy bis(methylene)] bis-2-propionate. Among them, dimethyl- 2-8-8282796 (6), 2〃-[hydroxybis(methylene)]bis-2-propanate, diethyl-2,2/[hydroxyl double ( Methylene)] bis-2-propionate, dicyclohexyl-2, 2〃-[hydroxybis(methylene)]bis-2-propionate, bis-2,-hydroxyl (sub. Base)] double one 2-propionate is preferred. These ether dimers may be used alone or in combination of two or more. The ratio of the ether dimer in the monomer component when the polymer (a) is obtained is not particularly limited, and is 2 to 60% by weight, preferably 5 to 55% by weight, based on the total monomer component. Good is 5 to 50% by weight. When the amount of the ether dimer is too large, it is difficult to obtain a substance having a low molecular weight during polymerization, or it may be gelled. On the other hand, if the amount is too small, the film properties such as transparency and heat resistance are insufficient. The aforementioned polymer (a) is preferably a polymer having an acid group. In this way, the curable resin composition obtained is a curable resin composition in which an acid group reacts with an epoxy group to form an ester bond, and a cross-linking reaction (hereinafter simply referred to as "acid epoxy hardening") is carried out by using the ester bond, or A composition in which an uncured portion is imaged by an alkaline developing solution. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups may be one type or two or more types. When the polymer (a) is introduced into an acid group, for example, a monomer having an acid group and a monomer capable of imparting an acid group after polymerization (hereinafter also referred to as "a monomer for introducing an acid group") are selected. At least one of them can be polymerized as a monomer component. Further, in the case where a monomer capable of imparting an acid group after polymerization is introduced into an acid group as a monomer component, it is necessary to impart an acid group treatment as described later after the polymerization. -9- 1282796 (7) The monomer having an acid group may, for example, be a monomer having a mercapto group such as (meth)acrylic acid or itaconic acid, or a phenolic hydroxyl group of N-hydroxyphenylmaleimide#. A monomer having a carboxylic anhydride group, such as a monomer, maleic anhydride, and itaconic anhydride, and the like, particularly preferably (meth)acrylic acid. Examples of the monomer which can impart an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, a monomer having an epoxy group such as glycidyl (meth)acrylate, and 2 a monomer having an isocyanic acid group such as an isocyanate (ethyl) acrylate or the like. The monomers for introducing such acid groups may be one type or two or more types. When the monomer component in the case where the polymer (a) is obtained also contains the monomer for introducing an acid group, the content ratio thereof is not particularly limited, and the total monomer component is 5 to 70% by weight, preferably 1 Å. ~6〇% by weight. The polymer (a) is preferably a polymer having a radical polymerizable double bond. The above-mentioned polymer is a compound (b i ) having a radically polymerizable double bond which will be described later, and also serves as a hardening component (B). Into the polymer (a), a radical polymerizable double bond is introduced, for example, a monomer which can impart a radical polymerizable double bond after polymerization (hereinafter also referred to as "a single sheet for introducing a radical polymerizable double bond" After the polymerization is carried out as a monomer component, the treatment for imparting a radical polymerizable double bond as described later may be carried out. The monomer which can impart a radically polymerizable double bond after the polymerization may, for example, be a monomer having a residue such as (meth)acrylic acid or itaconic acid; or the like; maleic acid, itaconic anhydride or the like; Anhydride group-based monomer; (methyl) propylene glycol glycidol vinegar, (meth) propylene acid 3,4-epoxycyclohexyl methacrylate, o. 10 - 1282796 (8) one (or between, or a) A fine base group of glycidol-brewed monomers and the like. These monomers for introducing a radically polymerizable double bond may be used alone or in combination of two or more. When the monomer component obtained when the polymer (a) is obtained also contains the monomer for introducing a radical polymerizable double bond, the content ratio thereof is not particularly limited, and the total monomer component is 5 to 70% by weight. It is preferably from 1 to 60% by weight. The polymer (a) is preferably a polymer having an epoxy group. Thereby, the polymer (a) is a hardening component (B) which is a compound (b2)' having an epoxy group to be described later. When the epoxy group is introduced into the polymer (a), for example, a monomer having an epoxy group (hereinafter also referred to as "a monomer for introducing an epoxy group") is polymerized as a monomer component. can. The monomer having an epoxy group may, for example, be glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, ortho- (or meta-, or p-)ethylene. Glycidyl glycidyl ether and the like. These monomers for introducing an epoxy group may be used alone or in combination of two or more. When the monomer component in the case where the polymer (a) is obtained also contains the monomer for introducing an epoxy group, the content ratio thereof is not particularly limited, and the total monomer component is 5 to 70% by weight, preferably 10 ~60% by weight. The monomer component in the case of obtaining the polymer (a), except for the ether dimer of the essential component, the monomer for introducing the acid group, and the monomer for introducing a radical polymerizable double bond, In addition to the monomer to which the epoxy group is introduced, other copolymerizable monomers may be contained as needed. -11 - 1282796 (9) Examples of the other copolymerizable monomer include, for example, methyl methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (methyl) propylene storage acid. Propyl ester, n-butyl (meth)acrylate, (meth)propene; isobutyl phthalate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (methyl) (meth) acrylate such as cyclohexyl acrylate, (meth) acrylate, etc., isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate An aromatic vinyl compound such as phenethylbenzene, vinyl toluene or α-methylstyrene; Ν-phenylmaleimide, Ν-cyclohexylmaleimide, etc. - substituted for mala Imines; butadiene or substituted butadiene compounds of butadiene, isoprene, etc.; ethylene or propylene, acrylonitrile, etc. ethylene or substituted ethylene compounds; vinyl acetate, etc. Esters and the like. Among them, methyl (meth)acrylate, cyclohexanic acid (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, styrene are also used. It is good in transparency and it is difficult to impair heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more. When the monomer component in the case where the polymer (a) is contained also contains the other monomer which can be copolymerized, the content ratio thereof is not particularly limited, and is preferably 95% by weight or less, and more preferably 85 % by weight or less. The polymer (a) can be easily obtained by polymerizing the above-mentioned monomer component which is at least necessary for the ether dimer. At this time, the method of performing the cyclization reaction of the ether dimer simultaneously with the polymerization and forming the tetrahydropyran ring structure-12-1282796 (10) the polymerization reaction of the above monomer components does not particularly use various previously known polymerization methods. However, in particular, solution polymerization, polymerization temperature and polymerization concentration (polymerization concentration = [single weight / (total weight of monomer component + solvent weight)] > depending on the type and ratio of monomer components used, target polymer, Preferably, the polymerization temperature is 40 to 150. (: The polymerization concentration is preferably 5 to a polymerization temperature of 60 to 130 ° C, and the polymerization concentration is 10 to 40%. When a solvent is used for the polymerization of the monomer component, a solvent for the reaction is used. Specifically, examples thereof include a ketone such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, such as dicrosane, ethylene glycol dimethyl ether or diglyme. Esters such as ester, butyl acetate, propylene glycol monomethyl ether acetate, 3-methyl ester; alcohols such as methanol, ethanol, isopropanol, n-butanol, ether, propylene glycol monomethyl ether; toluene, xylene, Aromatic hydrocarbons; chloroform; dimethyl azulene, etc. These solvents Further, it is also possible to use two or more kinds of the above-mentioned solvents, and it is preferable that the solvent which is formed with respect to the produced polymer (a) and the viscosity of the polymerization liquid is low, depending on the type and ratio used. When the monomer is formed, a part of the ether dimer is not cyclized and the amount of the ether dimer which causes the crosslinking reaction exceeds a certain amount, and the molecular weight and gelation are as appropriate. The crosslinking of the ether dimer is intended to be polymerized. The liquid is more likely to be caused, so that by appropriately selecting the viscosity of the polymerization liquid, the crosslinking reaction of the ether dimer can be suppressed and the polymer restriction can be prevented, and the law can be adopted. The whole c 1 0 〇) of the body composition is the root. Molecular weight and ~50%, more often free radicals such as tetrahydrofuran ether; acetone; acetic acid ethoxybutyl acetate ethylene glycol monomethyl ethylbenzene and other aromatics using only one kind of solvating strong body component of the polymerization reaction , cross-linking, an abnormally high viscosity, a higher solvent, amount and gelation - 13 to 1282796 (11). For example, a polymerization having an acid group is obtained by using a monomer having the aforementioned acid group as a monomer component. When, for example, if two When an ether such as glycol or dimethyl ether or an alcohol such as isopropyl alcohol is used in part or all of the solvent, the polymerization solution can be made to have a low viscosity. Further, the solvent used in the polymerization is selected based on the above criteria, and finally When the polymer (a) having a different solvent solution type from the solvent used in the polymerization is obtained, the above-mentioned standard is selected after polymerization using a mixed solution of the solvent selected in the above-mentioned standard and the solvent required for the final solution to be obtained. The solvent may be distilled off. For example, an alcohol or an ether such as isopropyl alcohol is used as a solvent in the polymerization, and when the polymer (a) is finally selected from an ester solution such as propylene glycol monomethyl ether acetate, For example, after polymerization is carried out using a mixed solvent of propylene glycol monomethyl ether acetate and isopropyl alcohol, isopropyl alcohol is distilled off to prepare a propylene glycol monomethyl ether acetate solution. When the monomer component is polymerized, a polymerization initiator which is usually used may be added as needed. The polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, diisopropylbenzene hydroperoxide, dibutyl butyl peroxide, lauric acid peroxide, benzammonium peroxide, and t-butyl peroxide. Organic peroxides such as oxyisopropyl carbonate, third amyl peroxy-2-ethylhexanoate, and tert-butylperoxy-2-ethylhexanoate; 2, 2 / —Azobis(isobutyronitrile), 1,1/-azobis(cyclohexaneacetonitrile), 2,2/-azobis(2,4-dimethylvaleronitrile), 2,2>- An azo compound such as azobis(dimethyl 2-methylpropionate) or the like. These polymerization initiators may be used alone or in combination of two or more. Further, the amount of the polymerization initiator to be used can be appropriately determined depending on the combination of the monomers to be used, the reaction conditions, the molecular weight of the target polymer, and the like, and is not particularly limited, but is not gelled and has a weight of -14 to 1282796 (12). The polymer having an average molecular weight of from several thousands to several tens of thousands is from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight, based on the total monomer component. When the monomer component is polymerized, a chain shifting agent which is usually used may be added in order to adjust the molecular weight. Examples of the chain shifting agent include mercaptan chain movement such as n-dodecyl mercaptan, mercaptoacetic acid, methyl mercaptoacetate, 3-hydrothiopropionic acid, and methyl 3-hydrothiopropionate. Agent, α-methyl styrene dimer, etc., preferably having a high chain shifting effect, can reduce residual monomers, and is also easy to obtain a positive 12-base thiol, thiol-acetic acid, 3-hydrogenthio group Propionic acid is preferred. When a chain shifting agent is used, the amount of the monomer to be used may be appropriately determined depending on the combination of the monomers to be used, the reaction conditions, the molecular weight of the target polymer, and the like, and is not particularly limited. However, the amount of the weight-average molecular weight is not gelled. In terms of the polymer of from 1,000 to tens of thousands, it is 0.1 to 15% by weight, preferably 0.5 to 10% by weight based on the total monomer component. In the above polymerization reaction, although the cyclization reaction of the ether dimer is considered to proceed simultaneously, the cyclization rate of the ether dimer at this time is not necessarily 1% by mole. When the polymer (a) is obtained, a monomer which imparts the acid group is used as a monomer component, and when an acid group is introduced thereby, it is necessary to carry out a treatment for imparting an acid group after the polymerization. The treatment for imparting an acid group varies depending on the kind of the monomer which can impart an acid group, for example, when a monomer having a hydroxyl group like 2-hydroxyethyl (meth)acrylate is used, for example, succinic anhydride is added, An acid anhydride such as tetrahydrophthalic anhydride or maleic anhydride may be used. When an epoxy group-containing monomer such as glycidyl (meth)acrylate is used, for example, a compound having an amine group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol is added. 1282796 (13) Alternatively, for example, an acid anhydride formed by adding an acid such as (meth)acrylic acid, for example, an acid anhydride such as an acid anhydride, tetrahydrophthalic anhydride or maleic anhydride may be used. When a monomer having an isocyanate group such as ethyl isocyanate (meth) acrylate is added, for example, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added. When the polymer (a) is obtained, a monomer which can impart the radical polymerizable double bond is used as a monomer component, and when a radical polymerizable double bond is introduced, it is necessary to impart a radical polymerization after polymerization. The treatment of sexual double bonds. The treatment for imparting a radically polymerizable double bond varies depending on the type of the monomer which can impart a radically polymerizable double bond, and for example, a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid is used. In the case of adding glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethacrylate (meth)acrylate, ortho- or m-, or p-vinylvinyl glycidyl ether, etc. The compound having an oxy group and a radically polymerizable double bond may have a hydroxyl group such as 2-hydroxyethyl (meth)acrylate when a monomer having a carboxylic anhydride group such as maleic anhydride or itaconic anhydride is used. A compound having a radically polymerizable double bond may be, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, ortho- (or meta-, or p-) When a monomer having an epoxy group such as a carbaryl ether or a glycidyl ether is added, a compound having an acid group and a radical polymerizable double bond such as (meth)acrylic acid may be added. The weight average molecular weight of the polymer (a) is not particularly limited, and is preferably from 2,000 to 200,000, more preferably from 5,000 to 100,000. When the weight average molecular weight exceeds 200,000, it becomes too high viscosity and it is difficult to form a coating film, and the other side 1282796 (14) surface, if it is less than 2 Ο Ο Ο, it is difficult to sufficiently express heat resistance. In the case where the polymer (a) has an acid group, the acid hydrazine is preferably from 30 to 500 mgKOH/g, more preferably from 50 to 400 mgKOH/g. When the acid enthalpy of the polymer (a) is less than 30 mgKOH/g, it is difficult to apply to alkaline development, and when it exceeds 50,000 mgKOH/g, it tends to be too high in viscosity and it is difficult to form a coating film. The curable resin composition of the present invention may contain the polymer component (A) as the polymer (a), and may contain, in addition to the polymer (a), a (meth)acrylic resin or a styrene system. A resin or a butadiene-based resin is generally used for a conventionally known polymer of a curable resin composition. Further, when the polymer other than the polymer (a) is contained, the content of the polymer (a) in the polymer component (A) is preferably 50% by weight or more. The curable resin composition of the present invention contains, as an essential component, a hardening component (B) composed of at least one of a compound (b1) having a radical polymerizable double bond and a compound (b2) having an epoxy group. Thereby, the curable resin composition of the present invention can exhibit good curability. In particular, when the hardening component (B) is a compound (b 1 ) containing a radically polymerizable double bond, the curable resin composition of the present invention is cured by radical polymerization, and the hardening component (B) When the compound (b 2 ) having an epoxy group is contained, the curable resin composition of the present invention is cured by radical polymerization or acid-epoxy curing. The above compound (bi) having a radical polymerizable double bond is an oligomer and a monomer, and examples of the oligomer include, for example, an unsaturated ester, an epoxy acrylate, and an amine -17-1282796 (15) urethane acrylate. , a polyester acrylate, an acrylic polymer having a double bond in a side chain, and the like, and examples of the monomer include styrene, α-methyl styrene, α-chlorostyrene, vinyl toluene, and divinyl benzene. An aromatic vinyl monomer such as diisopropyl phthalate or diallyl phenyl phosphonate; a vinyl ester monomer such as vinyl acetate or vinyl adipate; methyl (meth)acrylate; a (meth) acrylate monomer such as 2-methylol (meth)acrylate or (2-oxy-1,3-dioxadecyl-4-yl)methyl (meth)acrylate; (2) Ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol Di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol Alcohol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, two a polyfunctional (meth) acrylate such as pentaerythritol hexa(meth) acrylate or tris(hydroxyethyl)isocyanurate tris(meth) acrylate; triallyl cyanurate; The epoxy resin is added with an epoxy (meth) acrylate of (meth)acrylic acid or the like. The content ratio of the compound (b 1 ) having a radical polymerizable double bond in the curable resin composition of the present invention is preferably from 5 to 1,000% by weight, more preferably from 5% to 1,000% by weight, based on the polymer component (A). 1〇~600% by weight. Examples of the compound (b2) having the epoxy group include a bisphenol A type epoxy resin (commercial products such as "Epicoat 8 2 8", n Epicoat 1001", "Epicoat 1002", and "Epicoat 1 0 0 4". The above is the oil 1282796 (17). The lesser one is the polymerization initiator (c). In particular, when the radical initiator (c 1 ) is contained as a polymerization initiator, the curable resin composition of the present invention For example, by irradiating light energy such as ultraviolet rays, it is possible to form a photocuring by radical polymerization (this form is regarded as the form (i)). In this case, in particular, the polymer (a) is an acid group-containing polymerization. In the case of the material, the curable resin composition of the present invention can be used as an alkali-developing negative-type photoresist material, and is suitable, for example, for use in the production of color filters and optical waveguides, etc. On the other hand, it contains a thermal radical generating agent ( When the polymerization initiator (c) is used as the polymerization initiator (c), the curable resin composition of the present invention can be thermally cured by radical polymerization by imparting thermal energy (this form is regarded as the form (ii)). Form (i), form (Π), can also be divided The photoradical initiator (c 1 ) and the thermal radical initiator (C2 ) are not used as a polymerization initiator. Further, the hardening component (B) is a compound having a radical polymerizable double bond (b 1 ) When the polymerization initiator (c) is not contained, the curable resin composition of the present invention can be cured by radical polymerization by imparting high-energy radiation energy and thermal energy such as X-rays and electron beams. (This form is regarded as the form (iii)). The photoradical initiator (c 1 ) may, for example, be a benzoin such as benzoin, benzoin methyl ether or benzoin ethyl ether, or an alkyl ether thereof; Anthraquinone, 2,2-dimethoxy-2-phenylethenzene, 1,1,dichloroethenzene, etc.; 2-methylindole, 2-pentylhydrazine , 2 - tert-butyl hydrazine, 1-chloro hydrazine, etc.; 2,4 dimethyl thioxanthone, 2 ' 4 isopropyl thioxanthone, 2-chlorothiophene a thioxanthone such as ketone; a ketal such as acetophenone ketal or benzyl dimethyl ketal; a benzophenone such as benzophenone, etc. -20- 1282796 (18); Methyl-l-[4-(methylthio)phenyl)- 2 - cylinyl-propyl- 1 - fluorene and 2-carbyl 2- dimethylamino- 1 - (tetramorphine benzene) Base) butyl ketone-1; fluorenyl phosphine oxide; xanthone ketone. When the curable resin composition of the present invention contains the radical initiator (c 1 ), the content thereof is preferably 0.1 to 50% by weight based on the total amount of the polymer component (A) and the hardening component (B). More preferably, it is 0.5 to 3 〇 by weight. The thermal radical initiator (c2) may, for example, be cumene hydroperoxide, diisopropylbenzene peroxide, dibutylbutyl peroxide, lauryl peroxide, benzammonium peroxide or t-butyl peroxide. Organic peroxides such as oxyisopropyl carbonate, tert-butylperoxy-2-ethylhexanoate, and third amyl peroxy-2-ethylhexanoate, 2, 2 / - azobis(isobutyronitrile), 1,1/-azobis(cyclohexaneacetonitrile), 2,2/-azobis(2,4~dimethylvaleronitrile), 2,2/ An azo compound such as azobis(dimethyl 2-methylpropionate) or the like. When the curable resin composition of the present invention contains the thermal radical initiator (c2), the content thereof is a total amount of the polymer component (A) and the hardening component (B), preferably 0.1 to 50% by weight. %, more preferably 〇·5~30% by weight. In the curable resin composition of the present invention, when the curing component (B) is a compound (b2) having an epoxy group, it further contains at least a photoacid generator (c3) and a thermal acid generator (c4). One is preferably used as a polymerization initiator (e). In particular, when the photoacid generator (c3) is contained as the polymerization initiator (c), the curable resin composition of the present invention is, for example, a ketone which is irradiated with -21,282,796 (21) hexanone or the like; Esters of ethyl ester, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc.; methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether Alcohols such as alcohols; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform, dimethyl sulfene, and the like. Further, the content of the solvent may be appropriately set depending on the optimum viscosity when the resin composition is used. In addition to the polymer component (A), the curing component (B), the polymerization initiator (C), and the solvent, the curable resin composition of the present invention may contain, for example, a range that does not impair the effects of the present invention. Filling materials such as aluminum hydroxide, talc, clay, molybdenum sulfate, dyes, pigments, defoamers, coupling agents, leveling agents, sensitizers, mold release agents, slip agents, plasticizers, antioxidants, ultraviolet absorption A known additive such as a solvent, a flame retardant, a polymerization inhibitor, a tackifier or a dispersant. The curable resin composition of the present invention can pass the polymer component (A) and the hardening component (B) which are essential components (however, as described above, the polymer (a) serves as a hardening component (B). When the component is changed to only the polymer component (A)), and if necessary, the polymerization initiator (C) and the solvent and other additives are uniformly mixed, the curable resin composition of the present invention can be prepared to be transparent. It is excellent in heat resistance, for example, it can be used for photoresist materials, various coating agents, paints, etc. In particular, when the polymer (a) has an acid group, it is suitable for use as a color filter and an optical waveguide. Such as alkaline development type negative photoresist materials. Moreover, 'Yongkou (a) is a tetrahydrofuran structure in its structure, and also -24- 1282796 (22) has good pigment dispersibility, so it is suitable for use in color filter with colored curable resin. Things. The color filter of the present invention is a color filter in which a cured resin layer is provided on a substrate, and the resin composition as the cured resin layer is the curable resin composition of the present invention. The so-called filter is a micro-pixel having at least three primary colors on the transparent substrate and an optical filter for dividing the black matrix on the transparent substrate, and the three primary colors are generally red (R) and green (G). ), blue (B). The constituent members constituting the color filter are specifically three primary color (RGB) pixels, a resin black matrix, a protective film, and a columnar spacer, and the color filter of the present invention is a member constituting the filter. At least one of them may be formed by hardening the curable resin composition. In the color filter of the present invention, the hardened resin layer as the three primary color (RGB) pixels and the resin black matrix is the polymer having the acid group in the above forms (i) and (iv) The curable resin composition at the time is preferably formed, and the hardened resin layer as the protective film and the columnar spacer is the polymer in the above forms (i), (iii), (iv), (vi) a) It is preferable to form a curable resin composition in the case of a polymer having an acid group. Further, the curable resin composition in the case of forming RGB pixels is a pigment containing three primary colors of red, green, and blue, and the curable resin composition in the case of forming a resin black matrix is a pigment containing black, and a protective film or columnar spacer is formed. The curable resin composition at the time of the case may not contain a pigment. Further, in the case of containing a pigment, it is also preferable to contain a dispersing agent. The color filter of the present invention can be produced, for example, as follows. -25- 1282796 (23) 1 ) The curable resin group containing the pigment is coated, dried, and dried by a transparent substrate net rod, a flow coater, a bar coat, a roll coater, or a spray device such as an alkali-free glass or a transparent plastic. , making a coating film. 120C' is preferably at a temperature of 60 ° C to 10 ° ° C for preferably 30 seconds to 10 minutes, under normal pressure or under vacuum 〇 2) thereafter, the film is patterned according to the desired pattern shape, The above coating film is placed in contact, and the light is irradiated to harden it. Here, it also means that the ultraviolet rays, X-rays, and electron beams are optimal. The ultraviolet source is generally irradiated with high-pressure mercury 3), and the solvent, water, and test are used. Among them, it is preferred that the alkaline aqueous solution is negative for the environment. The alkaline component is preferably a hydroxide bait or the like. The concentration is preferably 0.01 to 5% by weight, and preferably 1 to 1% by weight, if the curable resin composition is too high, the solubility is too high and development is high. A surfactant may also be added to the deterioration solution. First, using the step of hardening the black pigments 1) to 3), the tree is formed on the substrate, and the hardening resin composition is formed, green (G), blue (B), and the composition is repeated. In the glass, preferably, a known coating drying condition of a spinner, a metal mister or the like is at room temperature~, for 10 seconds to 60 minutes, and the method of heating and drying is preferably a mask provided with an opening portion. (In the ί state or non-contact state, the light is not only the visible light, but the ultraviolet light is suitable for use. <Low load and high sensitivity 1. Sodium hydroxide and sodium carbonate are preferred, and 0.05 to 3 parts by weight. If the alkali concentration is lower than the solubility of the above hydrazine, the opposite is true. Further, in the alkaline water-soluble, the resin composition is subjected to a fat black matrix. The step of changing the material into red (R described 1) to 3), -26- 1282796 (24) forms pixels of R, G, and B, and creates RGB pixels. Next, a protective film is formed as needed to protect the RGB pixels formed on the substrate and to improve the smoothness of the surface. Further, when the color filter is a color filter for a liquid crystal display device, it is preferable to form a columnar spacer. The columnar spacer can be produced by applying the curable resin composition to the thickness of the desired spacer to the surface on which the spacer is to be formed, and by the above steps 1) to 3). When a color filter is produced, it is heated (post-baking) after development, and then cured, and it is preferably removed completely when the solvent is left. The temperature at the time of post-baking is preferably 120 to 300 ° C, and more preferably 150 to 250 ° C, and most preferably 180 to 230 ° C. When the post-baking temperature is as described above, the pixels are colored, and the smoothness of the coating film may be impaired by thermal decomposition. On the other hand, if the temperature is low, the progress of hardening is small, and the coating film strength is lowered. The post-baking can be carried out after development in the formation of each of the members, and can also be carried out after forming all the members. In the display device of the present invention, in the display device using the color filter in which the cured resin layer is provided on the substrate, the resin composition as the cured resin layer is the curable resin composition of the present invention. A specific example of the display device of the present invention is preferably a liquid crystal display device. However, the present invention is not limited thereto. For example, an organic EL display device or the like can be used. Hereinafter, the case of the liquid crystal display device will be described. The liquid crystal display device is a color filter substrate in which the color filter and the optional I TO electrode and the alignment film are provided, and an alignment film, an ITO electrode, and a counter substrate of the driving element are provided as needed, and liquid crystal is used. The spacers are kept at a certain interval, and the liquid crystal material is sealed in the interval, and the alignment of the liquid crystal is changed via the electric -27- 1282796 (25) gas signal, so that the light transmittance is variable and the liquid crystal is loaded into the liquid crystal display panel displaying the color. Display device. A well-known method can be used for the action type and the driving method of the liquid crystal, and it is preferable in terms of display quality and response speed in the T F T mode. In the liquid crystal spacer, a columnar spacer of a photosensitive resin or the like can be used, but a columnar spacer formed using the curable resin composition of the present invention is suitable. An operation pattern of each liquid crystal is provided on the color filter substrate and the counter substrate, and has an alignment film that is aligned according to a driving method, and fine protrusions (ribs) as needed, and an alignment film of polyimine is Suitable for use. Further, the rib portion may be a curable resin composition of the present invention in addition to polyimine. Further, on the outer side of the color filter substrate and the counter substrate, it is necessary to arrange an operation pattern of each liquid crystal, a deflection film corresponding to the driving method, and an optical compensation film. [Embodiment] [Embodiment] Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited thereto. In addition, as long as there is no special specification, "parts" are "partial weights" in Table 75, and "%" is not "% by weight". The analysis in each of the synthesis examples and the comparative synthesis examples was carried out as follows. (Weight average molecular weight) The gel permeation chromatography measuring apparatus ("Shodex GPC System 1282796 (26) - 1 1 Η") manufactured by Showa Denko Co., Ltd. was used, and it measured by the polystyrene. (Polymer concentration in the polymer solution) 1 g of the polymer solution was added to 4 g of acetone and the dissolved solution was allowed to dry naturally at normal temperature, and then dried under reduced pressure for 5 hours (160 ° C / 5 mmHg). The inside of the dryer was allowed to cool and the weight was measured. The nonvolatile content of the polymer solution was calculated from the weight reduction amount, and this was regarded as the polymer concentration. (sour acid) In 0.5 to 1 gram of the polymer solution, 80 ml of acetone and 1 ml of water were added and stirred to dissolve them, and a 0.1 mol/liter KOH aqueous solution was used as a titration solution, and an automatic titration device was used. ("COM — 5 5 5" Hirauma Industrial System) was titrated and the acid enthalpy of the solution was measured. The acid enthalpy of the polymer was calculated from the acid enthalpy and polymer concentrations of the solution. (Synthesis Example 1) A separable flask equipped with a cooling tube was prepared as a reaction tank, and on the other hand, 'prepared to prepare dimethyl 2,2/-[hydroxybis(methylene)]bis-2-propionate 40 parts (hereinafter referred to as "MD"), 40 parts of methacrylic acid (hereinafter referred to as "MAA"), 120 parts of methyl methacrylate (hereinafter referred to as r MMA), and t-butylperoxy-2 -ethylhexanoate ("Derbutyl 0" manufactured by Nippon Oil & Fats Co., Ltd.; hereinafter referred to as "Ρ Β Ο") 4 parts, 2 diol monomethyl ether acetate (hereinafter referred to as "PGMEA") 4 parts thoroughly mixed As a monomer dropping tank, and preparing n-dodecyl mercaptan (hereinafter -29-1282796 (33) parts, and reacting as it is at 1 l ° ° C for 9 hours. Thereafter, force p into DMDG 1 2 8 parts and cooled to room temperature' to obtain a polymer solution having a concentration of 30%. The weight average molecular weight of the polymer was 17000' and the acid strontium was 70 mgKOH/g. (Synthesis Example 1 〇) Preparation for separation with a cooling tube The flask was used as a reaction tank, and 467 parts of PGMEA, 40 parts of MD, 80 parts of GMA, 32 parts of ΜΑA, 30 parts of St, 18 parts of MMA, and dimethyl were placed in the reaction tank. Base 2, azobis(2,4-dimethyl pentyl nitrile) ("V-65" manufactured by Wako Pure Chemical Industries, Ltd.; hereinafter referred to as "V-65") 20 parts, and after nitrogen replacement, stir well and mix. Thereafter, the temperature of the reaction vessel was raised to 70 ° C by heating in an oil bath while stirring, and the temperature was maintained at this temperature for 3 hours, and then cooled to room temperature to obtain a polymer solution having a concentration of 30%. The molecular weight was 21,000, and the acidity was 104 mgKOH/g. (Comparative Synthesis Example 1) The reaction was carried out in the same manner as in Synthesis Example 1 except that the MD was changed to N-phenylmaleimide (hereinafter referred to as "PMI"). 30% polymer solution. The weight average molecular weight of the polymer is 13,000, and the acid hydrazine is 2 mg Κ Ο H / g 〇 (Comparative Synthesis Example 2) except that the amount of MD is changed to PMI, and the amount of pbo is changed to 2 parts, n — The amount of DM was changed to 4 parts, and treated with Synthesis Example 2 to obtain a polymer solution having a concentration of -36 to 1282796 (34) 30%. The weight average molecular weight of the polymer was 18,000. (Comparative Synthesis Example 3) Except for MD Change the amount of PMI and PBO to 2 parts, and change the amount of n-D to 4 parts. The polymer solution having a concentration of 30% was obtained by the same treatment as in Synthesis Example 3. The weight average molecular weight of the polymer was 1,800 Å, and the acid cerium was 104 mgKOH/g. (Comparative Synthesis Example 4) In addition to changing MD to α-(hydroxyl) Methyl methacrylate (hereinafter referred to as "ΜΗΜΑ"), the amount of hydrazine was changed to 2 parts, and the amount of n-DM was changed to 4 parts, and treated in the same manner as in Synthesis Example 3 to obtain a polymer solution. However, water and methanol were formed during the cyclization of the lactone, and the concentration of the obtained polymer solution was 25% due to the increase in residual monomers. The polymer had a weight average molecular weight of 17,000 and a acid hydrate of 85 mgKOH / g. (Comparative Synthesis Example 5) The same as in Synthesis Example 3, except that 40 parts of MD was changed to 80 parts of BzMA, the amount of MMA was changed to 88 parts, the amount of PBO was changed to 2 parts, and the amount of η-DM was changed to 4 parts. A polymer solution having a concentration of 30% was obtained. The weight average molecular weight of the polymer is 20,000, and the acid hydrazine is 1 〇 5 mg KOH / g 0 <Example 1 - 1 (Form (i)) > -37- 1282796 (35) 10 parts of the polymer solution obtained in Synthesis Example 1 and dipentaerythritol pentaacrylate (hereinafter referred to as "DPPA") 3 parts 0.09 parts of a photoradical initiator ("Ivugacure 907" manufactured by Ciba Geigy Co., Ltd.; hereinafter referred to as "Irg 907") and 5 parts of PGMEA were uniformly stirred and mixed to obtain a curable resin composition. The obtained curable resin composition was applied to an alkali-free glass using a spin coater to have a thickness of 2 // m after drying, and dried at 80 ° C for 5 minutes on a hot plate, and then an ultrahigh pressure mercury lamp was used. The test piece A was obtained by irradiating ultraviolet rays with an irradiation amount of 200 mJ/cm2, and the photocurability was evaluated by the following method using the test piece A. On the other hand, the test piece A was further heated by a hot plate at 20 ° C for 1 hour to obtain a test piece b, and the obtained test piece B was used to evaluate transparency and heat resistance. The results are shown in Table 1. (Photohardenability) The state of the coating film when the test piece A was immersed in tetrahydrofuran at room temperature for 1 minute was visually observed and judged on the following basis. 〇: The coating film is not peeled off, and the X film is peeled off (transparency) The transmittance (%) in the wavelength of 38 () to 800 nm is measured using a spectrophotometer ("UV-3100" Shimadzu). (Heat resistance) The film thickness of the test piece B was measured using a stylus type surface roughness meter ("Dektak IIA", Japan Vacuum Technology 1282796 (36)). Thereafter, the test piece B was heated at 250 ° C for 1 hour with a hot plate, and after cooling to room temperature, the film thickness was measured again. Thereafter, the film thickness reduction rate (%) due to heating was calculated. · <Example 1 2 (Form (iv)) > 10 parts of the polymer solution obtained in Synthesis Example 2 and a photoacid generator ("SP-170" Asahi Chemical Co., Ltd.; hereinafter referred to as "SP-170") 0.09 parts, trimellitic anhydride 〇·6 parts were uniformly stirred and mixed to obtain a curable resin composition. Using the obtained curable resin composition, it was treated in the same manner as in Example 1-1 to evaluate photocurability, transparency, and heat resistance. The results are shown in Table 1. <Example 1 - 3 (Form (vi)) > 10 parts of the polymer solution obtained in Synthesis Example 3, cresol novolac lacquer type epoxy resin ("EOCN - 103S" manufactured by Nippon Kayaku Co., Ltd., hereinafter referred to as 3 parts of "EOCN-103S"), 0.3 parts of trimellitic anhydride, and 5 parts of PGMEA were uniformly stirred and mixed to obtain a curable resin composition. φ The obtained curable resin composition was coated on an alkali-free glass using a spin coater to a thickness of 2 // m after drying, and dried on a hot plate at 8 (TC for 5 minutes, and then hot plated) The test piece B was obtained by heating at 200 ° C for 1 hour, and the test piece B obtained was treated in the same manner as in Example 1-1 to evaluate the transparency and heat resistance. The results are shown in Table 1. <Comparative Example 1 - 1 (Form (i)) > Compare the polymer solution obtained in Synthesis Example 1 with aliquots, DPP A 3 parts, -39-1282796 (37)

0.09 parts of Irg 907 and 5 parts of PGMEA were uniformly stirred and mixed to obtain a curable resin composition. Using the obtained curable resin composition, the film was treated in the same manner as in Example 1-1 to evaluate photocurability, transparency, and heat resistance. The results are shown in Table 1. &lt;Comparative Example 1 - 2 (Form (iv)) &gt; The polymer solution obtained in Comparative Synthesis Example 2, 1 part by weight, SP - 1 70 0.09 part, and 0.6 parts of trimellitic anhydride were uniformly stirred and mixed to obtain a hardenable tree φ lipid composition. Things. The obtained curable resin composition was treated in the same manner as in Example 1-1 to evaluate photocurability, transparency, and heat resistance. The results are shown in Table 1. &lt;Comparative Example 1 - 3 (Form (W)) &gt; 1 part of the polymer solution obtained in Comparative Synthesis Example 3, 3 parts of EOCN-103S, 0.3 parts of trimellitic anhydride, and 5 parts of PGMEA were uniformly stirred and mixed to obtain curability. Resin composition. φ The obtained curable resin composition was treated in the same manner as in Example 1-3 to evaluate transparency and heat resistance. The results are shown in Table 1. -40- 1282796 (38) Table 1 Example 1-1 Example 1-2 Example 1-3 Comparative Example 1-1 Comparative Example 1-2 Comparative Example 1-3 Photocuring 〇〇一〇〇一___ ·--- Transparency 97% or more 97% or more 97% or more 90% or more 90% or more 90% or more Heat resistance 1% or less 1% or less 1% or less 1°/. 1% or less and 1% or less of the following <Example 2 - 1 to 2 - 2, Comparative Example 2 - 1 to 2 - 2 &gt; The composition ratio shown in Table 2 (the number is expressed in parts by weight) is uniform The mixture was stirred and mixed to obtain a curable resin composition. The obtained curable resin composition was filtered through a filter paper of 1 // m, and then coated on an alkali-free glass plate using a spin coater to have a thickness of 2 // m after drying, and a hot plate at 8 (TC). After drying for 5 minutes, ultraviolet rays were irradiated with an ultrahigh pressure mercury lamp at an irradiation dose of 100 mJ/cm2 through a mask having a line/space portion of 10 // m intervals. Secondly, the unirradiated portion was 0.05% hydroxide. The potassium aqueous solution was dissolved and removed, and washed with pure water for 1 minute to obtain a test piece A, and the pattern was evaluated by the following method using the test piece A. On the other hand, the test piece A was heated at 20 (TC heating 1). In the test piece B, the test piece B was obtained in the following manner, and the transparency and heat resistance of the portion of the cured coating film were evaluated by the following method. The results are shown in Table 2. (Pattern) The test piece A was observed under an optical microscope and judged by the following criteria. 〇: The shape of the ultraviolet ray irradiation part (residual pattern) is good and is not observed -41 - 1282796 (39) The residue is not observed in the shot part X: The ultraviolet ray irradiation part (residual pattern) is defective and peeled off, and is observed in the unirradiated part. Residue (transparency) using spectroscopic The transmittance (%) at a wavelength of 380 to 800 nm is measured by a photometer ("UV-3100"). (Heat resistance) Measured using a stylus type surface roughness meter ("Dektak IIA" manufactured by Nippon Vacuum Technology Co., Ltd.) The film thickness of the test piece B. Then, the test piece B was heated at 25 ° C for 1 hour on a hot plate, and after cooling to room temperature, the film thickness was measured again. Thereafter, the film thickness reduction rate by heating was calculated. (%) ° -42 - 1282796 (41) Table 3 Example 3-1 Example 3-2 Example 3-3 Polymer solution used Synthesis Example 4 Synthesis Example 7 Synthesis Example 8 Kind of colored resin composition RGBKRGBKRGBK Polymer solution 10 10 10 10 10 10 10 10 10 10 10 10 Mixing dipentaerythritol hexaacrylate 3 3 3 3 3 3 3 3 3 3 3 3 3 Red pigment dispersion 20 — — — 20 — — — 20 — — — Green Pigment Dispersion — 17 — — 17 — — — 17 — — Blue Pigment Dispersion — 25 — — — 25 — — — 25 — Carbon Black Dispersion — One Twenty One One — One 20 — One — 20 Irg 907 2 2 2 2 2 2 2 2 2 2 2 2 PGMEA 40 43 35 40 40 43 35 40 40 43 35 40

-44- 1282796 (42)

Table 4 Comparative Example 3-1 Comparative Example 3-2 Polymer solution used Comparative Synthesis Example 3 Comparative Synthesis Example 5 Coloring type, RGBKRGBK composition of the resin composition Polymer solution 10 10 10 10 10 10 10 10 Dipentaerythritol hexaacrylic acid Ester 3 3 3 3 3 3 3 3 Red Pigment Dispersion 20 — — — 20 — — — Green Pigment Dispersion One 17 One — One 17 One — Blue Pigment Dispersion One Percent One 25 One — One 25 — Carbon Black Dispersion— One to one 20 - one to one 20 Irg 907 2 2 2 2 2 2 2 2 PGMEA 40 43 35 40 40 43 35 40

-45- 1282796 (44) The mercury lamp is irradiated with ultraviolet light at an exposure of 300 mj/cm2. Then, the unirradiated portion was dissolved and removed in a 0. 05% potassium hydroxide aqueous solution, and washed with pure water for 1 minute to obtain a test piece C, and the test piece C was used to evaluate the pattern property by the following method. On the other hand, the test piece C was heated at 2 ° C for 1 hour on a hot plate to obtain a test piece D, and the obtained test piece D was used to evaluate the OD 硬化 of the cured coating film portion by the following method. The results are shown in Table 5. (Pattern) The test piece C was observed with an optical microscope and judged on the following basis. 〇: The shape of the ultraviolet ray irradiation part (residual pattern) is good, and the residue is not observed in the unirradiated part. X: The ultraviolet ray irradiation part (residual pattern) is defective and peeled off, and the residue is observed in the unirradiated part (〇D値). Spectrophotometry is used. The 〇D値 in 550 nm was measured. 1282796 (45)

Table 5 Example 3-1 Example 3-2 Example 3-3 RGBKRGBKRGBK pattern; 〇〇〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇〇〇〇 Y Y 26 63 21 27 64 23 27 65 23 / X 0.58 0.31 0.14 0.58 0.31 0.14 0.58 0.31 0.14 y 0.33 0.55 0.16 0.33 0.55 0.16 0.33 0.55 0.16 0D値3.2 3.3 3.4 Example 3 - t 匕 Comparative example 3-2 RGBKRGBK pattern generation 〇X 〇X 〇〇〇X chromaticity Y 24 59 19 / 25 60 18 / X 0.58 0.31 0.14 0.58 0.31 0.14 y 0.33 0.55 0.16 0.33 0.55 0.16 0D値3.0 3.1

-48- 1282796 (46) <Example 4 - 1 to 4-6, Comparative Example 4 - 1 to 4 - 2> The components of the mixing ratio shown in Table 6 (indicated by parts by weight) were uniformly stirred and mixed. A curable resin composition was obtained. The obtained curable resin composition was filtered through a filter paper of 1 V m, and then coated on a non-glass plate using a spin coater to have a thickness of 2 // m after drying, and a hot plate at 80 ° C. Dry for 5 minutes. Thereafter, the ultraviolet ray was irradiated with an ultrahigh pressure mercury lamp at an irradiation dose of 100 mJ/cm2 through a mask having a line/space portion of 1 〇 // m interval. Next, the unirradiated portion was dissolved and removed with a 0.05% aqueous potassium hydroxide solution, and washed with pure water for 1 minute to obtain a test piece A, and the test piece A was used to evaluate the pattern property by the following method. On the other hand, the test piece A was heated at 200 ° C for 1 hour with a hot plate to obtain a test piece B, and the obtained test piece B was used to evaluate the transparency, surface hardness, and drug resistance of the cured coating film portion by the following method. Properties, heat discoloration and heat resistance flatness. The results are shown in Table 6. Further, in Example 4-6, ultraviolet irradiation and patterning were not evaluated, and after drying at 80 ° C for 5 minutes, the test piece B was obtained by heating at 20 ° C for 1 hour on a hot plate, and the obtained sample was obtained. The test piece B was evaluated for transparency, surface hardness, chemical resistance, heat discoloration resistance, and heat resistance flatness of the cured coating film portion by the following method. (Pattern) The test piece B was observed with an optical microscope and judged on the following basis. 〇: The shape of the ultraviolet ray irradiation part (residual pattern) is good and the residue is not observed in the unirradiated part -49- 1282796 (47) x : The ultraviolet ray irradiation part (residual pattern) is defective and peeled off. Transparency) The transmittance (%) at a wavelength of 380 to 800 nm was measured using a spectrophotometer ("UV - 3 1 0 0" Shimadzu system). (Surface hardness) The surface hardness was measured in accordance with the pencil scraping test of JI S K - 5 4 0 〇. (Chemical resistance) The test piece B was immersed in N-methylpyrrolidone at 3 ° C, and dried for 30 minutes at 200 ° C on a hot plate, and then adhered according to the jigging method of JIS K-5400. Test and evaluate with the number of remaining squares / 1 〇〇. (Heat-resistant discoloration property) After the test piece B was heat-treated at 250 ° C for 1 hour on a hot plate, the transmittance (%) at a wavelength of 400 to 800 nm was measured using a spectrophotometer ("UV-3100" manufactured by Shimadzu Corporation). Next, the transmittance before the heat treatment (the transmittance measured by the transparency evaluation) and the transmittance after the heat treatment were measured, and the rate of decrease in the transmittance was calculated according to the following formula and evaluated according to the following criteria. Rate of decrease of penetration rate (%) = [(penetration rate before heat treatment, penetration rate after heat treatment) / penetration rate before heat treatment] xl 00 〇: reduction rate less than 1% -50- 1282796 (48) χ : Reduction rate of 1% or more (heat resistance flatness) After heating the test piece to a hot plate at 250 °C for 1 hour, a stylus type surface roughness meter ("Dektak IIA" manufactured by Nippon Vacuum Technology Co., Ltd.) was used. The surface roughness Ra 値 (A ) of the cured coating film was measured.

-51 - 1282796 (50) &lt;Example 5, Comparative Example 5 &gt; Each of the mixing ratios (the number is expressed by parts by weight) in Table 7 was uniformly stirred and mixed to obtain a curable resin composition. The obtained curable resin composition was applied to a non-alkali glass plate by a spin coater to a thickness of 虔//m after drying, and dried at 80 ° C with a hot plate. 5 minutes. Thereafter, the ultraviolet ray was irradiated with an ultrahigh pressure mercury lamp at an irradiation of 100 mJ/cm2 through a photomask having an opening of 1; Next, the unirradiated portion was dissolved and removed with a % potassium hydroxide aqueous solution, and washed with pure water for 1 minute, and heated on a hot plate at 200 t for 1 hour to form a spacer pattern. Thereafter, the breaking load (gf) of the spacer portion was measured at a load of 0.27 sec and a small compression tester using a flat presser of the apparatus. See Table 7. Ingredients filtration [5 liters after 0.05 minutes, make gf / fruit -53- (51) 1282796 Table 7 Example 5 Comparative Example 5 Polymer solution Synthesis Example 1 Comparative Synthesis Example 5 Polymer solution 10 10 II Pentaerythritol hexaacrylic acid 3 3 ester mixture ratio EOCN-103S - 3 trimellitic anhydride 0.2 0.2 Irg 907 0.09 0.09 PGMEA 5 10 destruction load. "gf" 13 10

&lt;Example 6 &gt;

The color filter and the liquid crystal display device were produced and evaluated as follows. Further, each of the curable resin compositions used for producing the color filter was as shown in Table 8. • 54- 1282796 (52) Table 8 Example 6 Comparative Example 6 Black resin composition Example 3 - 3 Comparative Example 3-2 Red resin composition Example 3-3 Comparative Example 3 - 2 Green resin composition Example 3 -3 Comparative Example 3 - 2 Blue Resin Composition Example 3 - 3 Comparative Example 3 - 2 Resin Composition for Protective Film Example 4 - 3 Comparative Example 4 - 2 Resin Composition for Spacer Example 5 Comparative Example 5 (Production and evaluation of color filter) First, a black curable resin composition was applied by spin coating on a non-alkali glass substrate of 300 mm x 400 mm and a thickness of 1.1 mm to form a coating film. Pre-bake for 5 minutes at 0 °C. Thereafter, an ultrahigh pressure mercury lamp is used as a proximity exposure machine of the light source at a exposure amount of 500 mJ/cm 2 , and a predetermined black matrix is used for positioning exposure, and the image is developed with an alkaline developing solution. After washing with pure water, post-baking was carried out at 23 ° C for 30 minutes to form a black matrix (thickness 1.2/zm). Next, a red hard resin composition was applied by spin coating on a substrate on which a black matrix was formed, and a coating film was formed, and prebaked at 80 ° C for 5 minutes. Thereafter, using an ultra-high pressure mercury lamp as a light source as a light source, the exposure amount of 1 〇〇mJ /cm2 is used for positioning exposure through a designated pixel, and the image is developed with an alkaline developing solution to pure water. After washing, post-baking was performed at 200 ° C for 30 minutes to form a red pixel pattern (thickness 2 · 0 // m ). In the same manner, a green pixel pattern was formed using a green curable resin composition, -55-1282796 (53), and a blue pixel pattern was formed using the blue curable resin composition. Next, a resin composition for a protective film was applied by spin coating on a substrate on which a black matrix and respective color pixels were formed, and a coating film was formed, and prebaked at 80 ° C for 5 minutes. Thereafter, using an ultra-high pressure mercury lamp as a light source as a light source, the exposure amount of 100 m 〗 / cm 2 is used to perform positioning exposure through a mask of a designated protective film, and the image is developed with an alkaline developing solution to obtain pure water. After washing, post-baking was carried out at 200 ° C for 30 minutes to form a protective film (thickness 1.5 // m). Next, a resin composition for a spacer was applied by spin coating on a substrate on which a protective film was formed, and a coating film was formed, and prebaked at 80 ° C for 5 minutes. Thereafter, using an ultra-high pressure mercury lamp as a light source adjacent to the exposure machine at a exposure amount of 100 m]/cm 2 , positioning exposure is performed with a mask through a designated spacer, and imaging is performed with an alkaline developing solution to be pure After washing with water, post-baking at 220 °C for 30 minutes to form a spacer (height 4.8 // m, bottom 12 // m X 12 // m square). When the produced color filter was examined by an optical microscope, there was no pattern defect and development residue, and the smoothness of the surface of the protective film was also good. (Production and Evaluation of Liquid Crystal Display Device) A transparent conductive layer (thickness: 0.1 5 // m) composed of indium tin oxide was formed by sputtering on the color filter produced by the above-described process, and a polyfluorene was further provided. After the imine alignment layer is subjected to alignment treatment (friction), an epoxy resin-based encapsulant is bonded to the TFT alignment substrate, and a TN-type liquid crystal is sealed between the color filter and the TFT alignment substrate by an injection port provided in the sealing portion. Thereafter, the injection port was sealed, and an optical film such as a polarizing plate was attached to prepare a liquid crystal display device of the TN-56-1282796 (54) type. The liquid crystal display device produced has high brightness and color purity, and does not cause color unevenness and the like, and achieves good display quality. &lt;Comparative Example 6&gt; A color filter and a liquid crystal display device were produced in the same manner as in Example 6 except that each of the curable resin compositions used in the production of the color filter was changed to the material shown in Table 8 At the time of evaluation, pattern defects and development residues were observed on the color filter, and the liquid crystal display device was low in brightness and color purity, and also caused color unevenness. [Industrial Applicability] The curable resin composition of the present invention is suitably used for, for example, a photoresist material, various coating agents, paints, and the like.

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Claims (1)

I28279§_ 年月El修(更)正木 I 95. 1.20 Pickup, Patent Application Scope 93 1 0634 Patent Application No. 5 Chinese Patent Application Revision Amendment January 1, 1995, 1st. 1. A curable resin composition characterized by containing a polymer component (A), a compound having a radical polymerizable double bond (bl), and a compound having an epoxy group (b2) a curable resin composition of the hardening component (B) composed of at least one selected, the polymer component (A) being the following general formula (1) (In the formula (1), R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.) The polymer is a polymer obtained by polymerizing the necessary monomer component (a). And satisfying any of the following conditions (i) or (ii), (i) the polymer (a) is a polymer having an acid group or an epoxy group, and the compound (b 1 ) is contained as the hardening component (B) When it is contained in a proportion of 5 to 1,000,000% by weight of the polymer component (A), and when the compound (b2) is contained as the hardening component (B), the ratio of the polymer component (A) is 5 to 5 1 000% by weight; (ii) the polymer (a) is a polymer having an acid group or an epoxy group, and the polymer (a) is a compound (b1) having a radical polymerizable double bond and having a ring At least one selected from the compound (b2) of the oxy group, and 1282796 also serves as the hardening component (B). 2. The curable resin composition of claim 1, wherein the polymer (a) is a polymer having an acid group. 3. The curable resin composition of claim 1, wherein the polymer (a) is also a compound (b1) having a radical polymerizable double bond and a compound (b2) having an epoxy group. At least one selected is also a hardening component (B). 4. The curable resin composition according to claim 1, wherein the hardening component (B) is a compound having a radical polymerizable double bond (bl), and further contains a photo radical initiator (cl) and At least one selected from the thermal radical initiator (c2) is used as a polymerization initiator (C). 5. The curable resin composition according to claim 1, wherein the hardening component (B) is an epoxy group-containing compound (b2), and further contains a photoacid generator (c3) and a thermal acid generator. (c4) at least one selected as a polymerization initiator (C). 6. A color filter characterized in that a color filter provided with a hardened resin layer on a substrate is used as a resin composition of the hardened resin layer as in any one of claims 1 to 5 of the patent application. A curable resin composition. 7. A display device which is characterized in that, in a display device using a color filter in which a hardened resin layer is provided on a substrate, a resin composition as the hardened resin layer is as claimed in claims 1 to 5 of the patent application. A curable resin composition.