KR100685229B1 - Curing Resin Composition and Its Uses - Google Patents

Abstract

(Problem) It provides the curable resin composition which can form the coating film which was extremely excellent also in heat resistance and transparency.

(Solution means) The curable resin composition according to the present invention comprises a curable component comprising at least one selected from a polymer component (A), a compound (b1) having a radical polymerizable double bond and a compound (b2) having an epoxy group. Curable resin composition containing (B), The said polymer component (A) is a polymer (a) formed by superposing | polymerizing the monomer component which makes a specific ether dimer essential. It is characterized by the above-mentioned.

Description

Curing Resin Composition and Its Uses

The present invention relates to a novel curable resin composition and its use.

Conventionally, as a curable resin composition excellent in heat resistance, for example, a resin composition containing a lactone ring-containing polymer and a cured component formed by polymerizing and lactone cyclizing a monomer component containing 2- (hydroxyalkyl) acrylic acid ester (for example, a patent) Reference Document 1), a resin composition containing a polymer obtained by polymerizing a monomer component containing maleimide, and a curing component (for example, see Patent Documents 2 and 3) and the like have been proposed.

(Patent Document 1) Japanese Patent Application Laid-Open No. 2002-303975

(Patent Document 2) Japanese Patent Application Laid-Open No. 4-130128

(Patent Document 3) Japanese Patent Application Laid-Open No. 10-31308

However, in the resin composition containing the former polymer derived from 2- (hydroxyalkyl) acrylic acid ester, the polymerizability at the time of obtaining a polymer tends to be low, and there exists a tendency for many residual monomers, and water and Since alcohol is generated, these residual monomers, water, or alcohol sometimes adversely affect the curability or the physical properties of the cured film. In addition, since the lactone ring of the lactone ring-containing polymer is likely to be ring-opened with alkali, for example, when applied to an application such as an alkali developing resist material, there are also problems that the hardened portion is missing and the pattern shape deteriorates depending on the developing conditions. . In addition, in the resin composition containing the latter maleimide-derived polymer, since the maleimide-based polymer contains an oxygen atom, the polymer is colored yellow to yellowish brown, and there is a problem that transparency of the cured film becomes insufficient. This transparency problem is particularly remarkable when the cured film is thick, and may be further colored by heat treatment.

Therefore, the subject to be solved by this invention is providing the curable resin composition which can form the coating film which was excellent also in heat resistance and transparency, and the color filter and display apparatus using the said curable resin composition.

MEANS TO SOLVE THE PROBLEM This inventor earnestly examined in order to solve the said subject. As a result, a resin composition containing a polymer formed by polymerizing a compound having a specific structure which is an ether dimer of 2- (hydroxyalkyl) acrylic acid ester with a curing component can be found to solve the above problems at one time, and the present invention Completed.

That is, the curable resin composition which concerns on this invention consists of at least 1 sort (s) chosen from the compound (b1) which has a polymer component (A), a radically polymerizable double bond, and the compound (b2) which has an epoxy group. Curable resin composition containing the said polymer component (A) is a polymer (a) formed by superposing | polymerizing the monomer component which makes the compound represented by following General formula (1) essential.

(In formula (1), R <^1> and R <^2> represents a C1-C25 hydrocarbon group which may respectively independently have a hydrogen atom or a substituent.)

The color filter which concerns on this invention is a color filter in which a cured resin layer is formed on a board | substrate WHEREIN: The resin composition used as the said cured resin layer is the curable resin composition of the said invention, It is characterized by the above-mentioned.

The display apparatus which concerns on this invention is a display apparatus using the color filter in which a cured resin layer is formed on a board | substrate WHEREIN: The resin composition used as the said cured resin layer is the curable resin composition of the said invention, It is characterized by the above-mentioned.

Curable resin composition of this invention is a polymer (a) formed by superposing | polymerizing the monomer component which makes the compound represented by following General formula (1) (Hereinafter, it may be called "ether dimer") as an essential component. It contains as a polymer component (A).

(In formula (1), R <^1> and R <^2> represents a C1-C25 hydrocarbon group which may respectively independently have a hydrogen atom or a substituent.)

Thereby, the curable resin composition of this invention becomes able to form the cured coating film which was extremely excellent also in heat resistance and transparency. This is presumably because the ether dimer undergoes cyclization reaction upon polymerization to form a tetrahydropyran ring structure in the structural unit derived from the ether dimer.

Hereinafter, the said polymer (a) is demonstrated.

Although there is no restriction | limiting in particular as a C1-C25 hydrocarbon group which may have a substituent represented by R <^1> and R <^2> in the said General formula (1) which shows the said ether dimer, For example, methyl, ethyl, n-propyl Linear or branched alkyl groups such as isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl and 2-ethylhexyl; Aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; Alkyl group substituted by alkoxy, such as 1-methoxyethyl and 1-ethoxyethyl; Alkyl groups substituted with aryl groups such as benzyl; And the like. Among these, substituents of primary or secondary carbon, which are difficult to be detached by an acid or heat such as methyl, ethyl, cyclohexyl, benzyl and the like, are preferable in terms of heat resistance. In addition, R <^1> and R <^2> may be a substituent of the same kind, and may be another substituent.

Specific examples of the ether dimer include, for example, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate and diethyl-2,2'-[oxybis (methylene)] bis-2- Propenoate, di (n-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis -2-propenoate, di (n-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene) )] Bis-2-propenoate, di (t-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[ Oxybis (methylene)] bis-2-propenoate, di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2' -[Oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxy Ethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, Di (1-ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propeno Ate, diphenyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butylcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis 2-propenoate, di (tricyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (Methylene)] bis-2-propenoate, diamantyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2 , 2 '-[oxybis (methylene)] bis-2-propenoate, and the like. Among them, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate and dicy Chlohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate are preferred. 1 type may be sufficient as these ether dimers, and 2 or more types may be sufficient as them.

Although the ratio of the said ether dimer in the monomer component at the time of obtaining the said polymer (a) is not restrict | limited, It is 2 to 60 weight% of the total monomer components, Preferably it is 5 to 55 weight%, More preferably, 5 It is good that it is -50 weight%. When the amount of the ether dimer is too large, it may be difficult to obtain a low molecular weight one or polymerize easily when polymerizing. On the other hand, when the amount of the ether dimer is too small, the coating film performance such as transparency and heat resistance may be insufficient. .

It is preferable that the said polymer (a) is a polymer which has an acidic radical. The curable resin composition obtained by this is a curable resin composition or crosslinking reaction (hereinafter, abbreviated as "acid-epoxy curing") using an acid group and an epoxy group reacting to generate an ester bond, or an uncured portion is an alkaline developer. It can be set as the composition which can be developed. Although it does not restrict | limit especially as said acid group, For example, a carboxyl group, a phenolic hydroxyl group, a carboxylic anhydride group, etc. are mentioned. 1 type of these acid groups may be sufficient, and 2 or more types may be sufficient as them.

The introduction of an acid group into the polymer (a) is selected from, for example, a monomer having an acid group and a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as "monomer for introducing an acid group"). What is necessary is just to make a species or more superpose | polymerize with a monomer component. Moreover, when introduce | transducing an acidic radical as a monomer component the monomer which can provide an acidic radical after superposition | polymerization, the process for providing an acidic radical, for example, mentioned later after superposition | polymerization is needed.

As a monomer which has the said acid group, For example, the monomer which has carboxyl groups, such as (meth) acrylic acid and itaconic acid, the monomer which has phenolic hydroxyl groups, such as N-hydroxyphenyl maleimide, carboxylic acid, such as maleic anhydride and itaconic anhydride Although the monomer etc. which have an anhydride group etc. are mentioned, (meth) acrylic acid is especially preferable among these. As a monomer which can provide an acidic radical after the said superposition | polymerization, the monomer which has hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, the monomer which has epoxy groups, such as glycidyl (meth) acrylate, and 2-isocyanate ethyl ( The monomer etc. which have isocyanate groups, such as meth) acrylate, etc. are mentioned. 1 type of monomers for introducing these acid groups may be sufficient, and 2 or more types may be sufficient as it.

When the monomer component at the time of obtaining the said polymer (a) also contains the monomer for introduce | transducing the said acidic radical, the content rate is although it does not specifically limit, 5-70 weight% of all the monomer components, Preferably it is 10-60 It is good that it is weight%.

It is preferable that the said polymer (a) is a polymer which has a radically polymerizable double bond. Thereby, the said polymer (a) becomes the compound (b1) which has a radically polymerizable double bond mentioned later, and also serves as a hardening component (B).                     

In the case of introducing a radical polymerizable double bond into the polymer (a), for example, a monomer capable of imparting a radical polymerizable double bond after polymerization (hereinafter, also referred to as "a monomer for introducing a radical polymerizable double bond"). May be performed as a monomer component, followed by treatment for imparting a radical polymerizable double bond as described later.

As a monomer which can provide a radically polymerizable double bond after the said superposition | polymerization, For example, Monomer which has carboxyl groups, such as (meth) acrylic acid and itaconic acid; Monomers having carboxylic acid anhydride groups such as maleic anhydride and itaconic anhydride; Monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether; And the like. 1 type may be sufficient as the monomer for introduce | transducing these radically polymerizable double bonds, and 2 or more types may be sufficient as it.

When the monomer component at the time of obtaining the said polymer (a) also contains the monomer for introduce | transducing the said radically polymerizable double bond, the content rate is although it does not restrict | limit especially, 5-70 weight% of all monomer components, Preferably Is preferably 10 to 60% by weight.

It is preferable that the said polymer (a) is a polymer which has an epoxy group. Thereby, the said polymer (a) becomes the compound (b2) which has an epoxy group mentioned later, and also serves as a hardening component (B).

In order to introduce an epoxy group into the said polymer (a), what is necessary is just to superpose | polymerize the monomer which has an epoxy group (henceforth "the monomer for introduce | transducing an epoxy group") as a monomer component, for example.                     

As a monomer which has the said epoxy group, glycidyl (meth) acrylate, 3, 4- epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, etc. are mentioned, for example. This is listed. 1 type of monomers for introducing these epoxy groups may be sufficient, and 2 or more types may be sufficient as it.

When the monomer component at the time of obtaining the said polymer (a) also contains the monomer for introduce | transducing the said epoxy group, the content rate is not specifically limited, Although it is 5-70 weight% among all monomer components, Preferably it is 10-60 weight It is good to be%.

The monomer component at the time of obtaining the said polymer (a) is necessary in addition to the said ether dimer which is an essential component, the monomer for introduce | transducing the above-mentioned acid group, the monomer for introducing a radically polymerizable double bond, and the monomer for introducing an epoxy group. Depending on the composition, other copolymerizable monomers may be contained.

Examples of the copolymerizable monomers mentioned above include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate and isobutyl (meth) acrylate. T-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) (Meth) acrylic acid esters such as 2-hydroxyethyl acrylate; Aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexyl maleimide; Butadiene or substituted butadiene compounds, such as butadiene and isoprene; Ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride and acrylonitrile; Vinyl esters such as vinyl acetate; And the like. Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and styrene have good transparency and are difficult to impair heat resistance. It is preferable at the point. These other copolymerizable monomers may use only 1 type or may use 2 or more types together.

When the monomer component at the time of obtaining the said polymer (a) also contains the said copolymerizable other monomer, the content rate is not specifically limited, 95 weight% or less is preferable and it is more preferable that it is 85 weight% or less.

The said polymer (a) can be easily obtained by polymerizing the said monomer component which makes at least the said ether dimer essential. At this time, the cyclization reaction of the ether dimer proceeds at the same time as the polymerization to form a tetrahydropyran ring structure.

There is no restriction | limiting in particular as a method of the polymerization reaction of the said monomer component, Although conventionally well-known various polymerization methods can be employ | adopted, it is especially preferable by solution polymerization method. In addition, polymerization temperature and polymerization concentration (polymerization concentration = [total weight of a monomer component / (total weight of a monomer component + solvent weight)] x100) are the kind and ratio of the monomer component to be used, and the target polymer Although it changes with molecular weight, Preferably it is good to set it as the polymerization temperature of 40-150 degreeC, and the polymerization concentration of 5 to 50%, More preferably, you may set it as the polymerization temperature of 60 to 130 degreeC and the polymerization concentration of 10 to 40%.

In the superposition | polymerization of the said monomer component, when using a solvent, what is necessary is just to use the solvent used by normal radical polymerization reaction as a solvent. Specifically, For example, ether, such as tetrahydrofuran, a dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; chloroform; Dimethyl sulfoxide; And the like. These solvent may use only 1 type or may use 2 or more types together.

As said solvent, it is preferable to select especially a solvent according to the kind and ratio of the monomer component to be used so that the dissolving power with respect to the polymer (a) produced | generated is strong, and a viscosity of a polymerization liquid becomes low. In the polymerization of the monomer component containing the ether dimer, a part of the ether dimer may cause crosslinking reaction without cyclization polymerization, and if the amount of the ether dimer crosslinking exceeds a certain amount, abnormal high molecular weight or Causes gelation. Since the crosslinking reaction of the ether dimer is more likely to occur as the viscosity of the polymerization liquid becomes higher, the solvent can be appropriately selected so that the viscosity of the polymerization liquid is lowered, whereby the crosslinking reaction of the ether dimer can be suppressed to prevent high molecular weight or gelation. For example, when obtaining the polymer which has an acidic radical using the monomer which has the said acidic radical as a monomer component, ethers, such as diethylene glycol and dimethyl ether, alcohols, such as isopropyl alcohol, etc. are used for some or all of the said solvent. In this case, the polymerization liquid can be reduced in viscosity. In addition, when selecting the solvent used at the time of superposition | polymerization as said reference | standard, and finally wanting to obtain polymer (a) as a solution of the solvent different from the solvent used at the time of the said superposition | polymerization, After the polymerization is carried out using a mixed solution with a solvent required for the solution to be obtained, the solvent selected according to the above criteria may be removed. For example, when using alcohols and ethers, such as isopropyl alcohol, as a solvent at the time of superposition | polymerization, and finally wanting to obtain polymer (a) as a solution of ester, such as propylene glycol monomethyl ether acetate, propylene glycol mono After the polymerization is carried out using a mixed solvent of methyl ether acetate and isopropyl alcohol, isopropyl alcohol can be removed to form a propylene glycol monomethyl ether acetate solution.

When superposing | polymerizing the said monomer component, you may add the polymerization initiator normally used as needed. Although it does not specifically limit as a polymerization initiator, For example, cumene hydroperoxide, diisopropyl benzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxy isopropyl carbonate, t Organic peroxides such as amylperoxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl2,2 Azo compounds such as' -azobis (2-methylpropionate); And the like. These polymerization initiators may use only 1 type or may use 2 or more types together. The amount of the polymerization initiator may be appropriately set according to the combination of the monomers used, the reaction conditions, the molecular weight of the target polymer, and the like, and is not particularly limited. However, a polymer having a weight average molecular weight of thousands to tens of thousands without gelation may be used. From the point which can be obtained, it is good to set it as 0.1 to 15 weight% with respect to all the monomer components, More preferably, you may be 0.5 to 10 weight%.

When polymerizing the said monomer component, you may add the chain transfer agent normally used as needed for molecular weight adjustment. Examples of the chain transfer agent include n-dodecyl mercaptan, mercaptoacetic acid, mercaptoacetic acid methyl, 3-mercaptopropionic acid, and mercaptan-based chain transfer agent such as 3-mercaptopropionate, and α-methylstyrene dimer. Preferably, however, n-dodecyl mercaptan, mercaptoacetic acid and 3-mercaptopropionic acid, which have a high chain transfer effect, can reduce residual monomer, and are easily available, are preferred. In the case of using a chain transfer agent, the amount used may be appropriately set according to the combination of the monomers used, the reaction conditions, the molecular weight of the target polymer, and the like, but it is not particularly limited. Since a polymer can be obtained, it is preferable to set it as 0.1 to 15 weight% with respect to all the monomer components, More preferably, it is 0.5 to 10 weight%.

In the said polymerization reaction, it is thought that the cyclization reaction of an ether dimer advances simultaneously, but the cyclization rate of an ether dimer at this time does not necessarily need to be 100 mol%.

When obtaining the said polymer (a), when using the monomer which can provide the acidic radical mentioned above as a monomer component, and introducing an acidic radical by this, it is necessary to perform the process for providing an acidic radical after superposition | polymerization. The treatment for imparting an acid group varies depending on the type of monomer capable of imparting an acid group to be used, but, for example, in the case of using a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, for example, Acid anhydrides such as succinic anhydride, tetrahydrophthalic anhydride and maleic anhydride may be added, and when monomers having an epoxy group such as glycidyl (meth) acrylate are used, for example, N-methylamino benzoic acid and N-methyl Acid anhydrides, such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride, for example, to add a compound having an amino group and an amino group such as aminophenol, or to a hydroxyl group generated after addition of an acid such as (meth) acrylic acid May be added, and isocyanates such as 2-isocyanate ethyl (meth) acrylate When using a monomer having a group include, for example, it may be to add a compound having a hydroxyl group and the acid group, such as 2-hydroxybutyric acid.

When obtaining the said polymer (a), when using the monomer which can provide the above-mentioned radically polymerizable double bond as a monomer component, and when introduce | transducing a radically polymerizable double bond by this, a radically polymerizable double bond is made after superposition | polymerization. It is necessary to perform a process for giving. The treatment for imparting a radical polymerizable double bond varies depending on the type of monomer capable of imparting a radical polymerizable double bond to be used. However, when a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid is used, And radically polymerizable double bonds such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether What is necessary is just to add the compound which has the compound which has the thing, and when using the monomer which has carboxylic acid anhydride groups, such as maleic anhydride and an itaconic acid anhydride, hydroxyl groups, such as 2-hydroxyethyl (meth) arcrelate, and a radically polymerizable double bond It is good to add the compound which has the thing, and glycidyl (meth) acrylate, 3, 4- epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbene In the case of using a monomer having an epoxy group such as zylglycidyl ether, a compound having an acid group such as (meth) acrylic acid and a radical polymerizable double bond may be added.

Although the weight average molecular weight of the said polymer (a) is not specifically limited, Preferably it is 2000-200000, More preferably, it is 5000-100000. When the weight average molecular weight exceeds 200000, the viscosity becomes too high and it becomes difficult to form a coating film. On the other hand, when the weight average molecular weight is less than 2000, there is a tendency that it becomes difficult to express sufficient heat resistance.

In the case where the polymer (a) has an acid group, the acid value is preferably 30 to 500 mg KOH / g, more preferably 50 to 400 mg KOH / g. When the acid value of the polymer (a) is less than 30 mg KOH / g, it becomes difficult to apply it to alkali development, and when it exceeds 500 mg KOH / g, it tends to become too high viscosity and it becomes difficult to form a coating film.

The curable resin composition of this invention may make the said polymer (a) essential as a polymer component (A), and it is usual other than the said polymer (a), for example, (meth) acrylic-type resin, styrene resin, butadiene-type resin, etc. It may contain a conventionally well-known polymer used for curable resin composition. Moreover, when it contains polymers other than the said polymer (a), it is preferable to make content of the said polymer (a) in a polymer component (A) into 50 weight% or more.

Curable resin composition of this invention has a hardening component (B) which consists of 1 or more types chosen from the compound (b1) which has a radically polymerizable double bond, and the compound (b2) which has an epoxy group as an essential component. Thereby, curable resin composition of this invention becomes what can express favorable sclerosis | hardenability. Specifically, when the compound (b1) having a radical polymerizable double bond is contained as the curable component (B), the curable resin composition of the present invention is cured by radical polymerization, and the curable component (B In the case of containing a compound (b2) having an epoxy group, the curable resin composition of the present invention is cured by cationic polymerization or acid-epoxy curing.

Examples of the compound (b1) having the radically polymerizable double bond include an oligomer and a monomer, and examples of the oligomer include an unsaturated polyester, an epoxy acrylate, a urethane acrylate, a polyester acrylate, and an acrylic polymer having a double bond in the side chain. And the like, and examples of the monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, divinylbenzene, diallyl phthalate and diallylbenzenephosphonate; Vinyl ester monomers such as vinyl acetate and vinyl adipic acid; (Meth) acrylate type monomers, such as methyl (meth) acrylate, 2-hydroxymethyl (meth) acrylate, and (2-oxo-1,3-dioxolan-4-yl) -methyl (meth) acrylate ; (Di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra ( Polyfunctional (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tri (meth) acrylate of tris (hydroxyethyl) isocyanurate ) Acrylate; Triallyl cyanurate; Epoxy (meth) acrylates such as (meth) acrylic acid added to an epoxy resin; And the like.

The content ratio of the compound (b1) having the radically polymerizable double bond in the curable resin composition of the present invention is preferably 5 to 1000% by weight, more preferably 10 to 10 to the polymer component (A). 600% by weight.

Examples of the compound (b) having the epoxy group include bisphenol-A epoxy resins (such as commercially available products such as "epicoat 828", "epicoat 1001", "epicoat 1002" and "epicoat 1004"). Epoxy products), bisphenol F type epoxy resin (as a commercial item, for example, "Epicoat 807", "EP-4001", "EP-4002", "EP-4004" or more, Yuccacel epoxy product etc.) Volac type epoxy resin (As a commercial item, for example, "EPPN-201" or more, Nippon Kayaku Co .; "EP-152", "EP-154" or more, Yuccacel epoxy product; "DEN-438" or more, Dow Chemical Products; etc.), cresol novolac-type epoxy resins (commercially available products such as "EOCN-102S", "EOCN-1020", "EOCN-104S", Nippon Kayaku etc.), trisphenol methane type epoxy resin ( As a commercial item, "EPPN-501", "EPPN-502", "EPPN-503" or more, the Nippon Kayaku Co., etc., alicyclic epoxy resin (As a commercial item, for example, "Ceroxide 2021P", " three Side EHPE "or more, Daicel Kagaku Kogyo Co., Ltd.), copolymerized epoxy resin (commercially available products such as" CP-15 "," CP-30 "," CP-50M "," CP-20MA "or more, Nippon) Oils and the like), fluorene epoxy resin (commercially available products such as "ESF-300", Nippon Steel Chemical Co., Ltd.), triglycidyl isocyanurate (commercially available products such as "TEPIC" Nissan Chemical Industries, Ltd.) And biphenylglycidyl ethers (such as "YX-4000" Yuccacel epoxy products, etc.) as a commercial item, etc. are mentioned.

The content rate of the compound (b2) which has the said epoxy group in curable resin composition of this invention is 5 to 1000 weight% with respect to the said polymer component (A), More preferably, it is 10 to 600 weight% .

Curable resin composition of this invention WHEREIN: When the said hardening component (B) is a compound (b1) which has a radically polymerizable double bond, it is an optical radical generator (c1) and a thermal radical generator (c2) as a polymerization initiator (C). It is preferable to further contain 1 or more types chosen from. Specifically, in the case of containing an optical radical generator (c1) as the polymerization initiator (C), the curable resin composition of the present invention can be photocured by radical polymerization, for example, by irradiating light energy such as ultraviolet rays. (The form is called form (i)). Under the present circumstances, especially when the said polymer (a) is a polymer which has an acidic radical, the curable resin composition of this invention is used suitably as preparation of a color filter, an optical waveguide, etc. as an alkali developing negative resist material, for example. . On the other hand, when it contains a thermal radical generating agent (c2) as a polymerization initiator (C), the curable resin composition of this invention becomes what can be thermoset by radical polymerization by providing thermal energy (the said aspect is a form (ii)). In the form (i) and the form (ii), you may use both an optical radical generating agent (c1) and a thermal radical generating agent (c2) as a polymerization initiator, respectively. Moreover, when the said hardening component (B) is a compound (b1) which has a radically polymerizable double bond, even when it does not contain the said polymerization initiator (C), curable resin composition of this invention is X-ray, an electron beam, etc. By imparting high energy radiation energy or thermal energy, curing by radical polymerization becomes possible (the form is referred to as form (iii)).

As said optical radical generating agent (c1), For example, benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and its alkyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; Anthraquinones such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; Thioxanthones, such as 2, 4- dimethyl thioxanthone, 2, 4- diisopropyl thioxanthone, and 2-chloro thioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 ; Acyl phosphine oxides, xanthones, etc. are mentioned.

When the curable resin composition of this invention contains the said optical radical generating agent (c1), the content rate becomes like this. Preferably it is 0.1-50 weight% with respect to the total amount of a polymer component (A) and a hardening component (B), More preferably Preferably it is 0.5-30 weight%.

Examples of the photo-radical generator (c2) include cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butylperoxy isopropyl carbonate, organic peroxides such as t-butylperoxy-2-ethylhexanoate and t-amylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2, Azo compounds, such as 2'- azobis (2-methylpropionate); And the like.

When the curable resin composition of this invention contains the said thermal radical generating agent (c2), the content rate becomes like this. Preferably it is 0.1-50 weight% with respect to the total amount of a polymer component (A) and a hardening component (B), More preferably, it is 0.5-30 weight%.

Curable resin composition of this invention WHEREIN: When the said hardening component (B) is a compound (b2) which has an epoxy group, 1 type chosen from a photo-acid generator (c3) and a thermal-acid generator (c4) as a curing initiator (C). It is preferable to further contain the above. Specifically, in the case of containing the photoacid generator (c3) as the polymerization initiator (C), the curable resin composition of the present invention can be photocured by cationic polymerization, for example, by irradiating light energy such as ultraviolet rays. (The form is referred to as form (iv)). Under the present circumstances, especially when the said polymer (a) is a polymer which has an acidic radical, the curable resin composition of this invention is used suitably as an alkali developable negative resist material, for example, manufacture of a color filter, an optical waveguide, etc. On the other hand, when it contains a thermal acid generator (c4) as a polymerization initiator (C), the curable resin composition of this invention becomes what can be thermoset by cationic polymerization by providing thermal energy (the said aspect is a form (v)). In the form (iv) and the form (v), both the photoacid generator (c3) and the thermal acid generator (c4) may be used as the polymerization initiator, respectively. Moreover, when the said hardening component (B) is a compound (b2) which has an epoxy group, even if it does not contain the said polymerization initiator (C), the said polymer (a) is a polymer which has an acidic radical, or is trimellitic acid, tri In the case of further containing a polyfunctional acid group-containing compound such as merit acid anhydride, methyl methacrylate / methacrylic acid copolymer, styrene / maleic anhydride copolymer, or an acid group-containing polymer, the curable resin composition of the present invention is thermal energy By imparting, acid-epoxy curing is possible (the form is referred to as form (vi)).

As said photo-acid generator (c3), for example, diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxy Diaryl iodonium salts, such as phenyl phenyl iodonium trifluoro acetate; Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, Triarylsulfonium salts such as 4-phenylthiophenyldiphenyltrifluoromethanesulfonate and 4-phenylthiophenyldiphenyltrifluoroacetate; And the like.

When curable resin composition of this invention contains the said photo-acid generator (c3), the content rate is 0.1 to 50 weight% with respect to the total amount of a polymer component (A) and a hardening component (B), Preferably it is more preferable. Preferably it is 0.5-30 weight%.

Examples of the thermal acid generator (c4) include onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts, and the like, and sulfonium salts and benzothiazonium salts are particularly preferred. Specific examples of the sulfonium salt and the benzothiazonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate and 4-acetoxyphenylbenzylmethyl Sulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoro Antimonates and the like. These thermal acid generators can also function as photoacid generators.

When the curable resin composition of this invention contains the said thermal acid generator (c4), the content rate is preferably 0.1-50 weight% with respect to the total amount of a polymer component (A) and a hardening component (B), More preferably, Preferably it is 0.5-30 weight%.

The curable resin composition of this invention may contain a solvent as a diluent as needed.

There is no restriction | limiting in particular as said solvent as long as it melt | dissolves each component of the said polymer component (A), hardening component (B), and the polymerization initiator (C) contained as needed uniformly, and does not react with each component. Specifically, For example, ether, such as tetrahydrofuran, a dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; Chloroform, dimethyl sulfoxide; And the like. In addition, what is necessary is just to set content of a solvent suitably according to the optimum viscosity at the time of using a resin composition.

Curable resin composition of this invention is the range which does not impair the effect of this invention other than the said polymer component (A), the said hardening component (B), the said polymerization initiator (C), and the said solvent, for example, aluminum hydroxide, a talc Known additives such as fillers such as clay, barium sulfate, dyes, pigments, antifoaming agents, coupling agents, leveling agents, sensitizers, thinners, lubricants, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, polymerization inhibitors, thickeners, and dispersants. It may contain.

Curable resin composition of this invention is an essential component, when the said polymer component (A) and the said hardening component (B) (however, as mentioned above, the said polymer (a) can also serve as a hardening component (B), it is essential. A component becomes only a polymer component (A)) and the said polymerization initiator (C), the said solvent, and other additives contained as needed can be prepared by mixing uniformly.

Curable resin composition of this invention is excellent in transparency and heat resistance, for example, it can be used for uses, such as a resist material, various coating agents, and a coating material, Especially when a polymer (a) has an acidic radical, a color filter and an optical waveguide It can be used suitably as an alkali developing type negative resist material etc. for producing etc. Moreover, since polymer (a) also has favorable pigment dispersibility by the tetrahydropyran ring structure in the structure, it can be used suitably for the colored curable resin composition for color filters.

As for the color filter of this invention, in the color filter by which a cured resin layer is formed on a board | substrate, the resin composition used as the said cured resin layer is curable resin composition of the said this invention. The color filter is an optical filter having a fine matrix of three or more primary colors and a black matrix that distinguishes it from a pixel on a transparent substrate, which is necessary for colorizing an image. As the three primary colors, red (R), green (G), and blue ( B) is used. As a member which comprises a color filter, although a three primary color (RGB) pixel, a resin black matrix, a protective film, and columnar spacer are specifically, 1 of each member which comprises the said filter is a color filter of this invention. What is necessary is just to form the thing by hardening | curing the said curable resin composition.

In the color filter of this invention, the cured resin layer used as a three-primary color (RGB) pixel and the resin black matrix is curable resin composition in the case where the polymer (a) is a polymer which has an acidic radical in the said forms (i) and (iv). It is preferable to form, and the cured resin layer used as a protective layer and columnar spacer is a polymer in which the polymer (a) has an acidic radical in the said form (i), (iii), (iv), (vi). It is preferable to be formed of curable resin composition in the case. In addition, the curable resin composition at the time of forming an RGB pixel contains the raw material of each of three primary colors of red, green, and blue, and the curable resin composition at the time of forming a resin black matrix contains a black raw material, and a protective film Or curable resin composition in the case of forming columnar spacer does not need to contain a pigment. In addition, when it contains a pigment, it is preferable to contain a dispersing agent.

The color filter of this invention can be produced as follows, for example.

1) The curable resin composition containing the pigment is applied to a known coating device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, and a spray on a transparent substrate such as glass, preferably an alkali free glass, or a transparent plastic. Was applied and dried to prepare a coating film. As drying conditions, the method of heat-drying under the temperature of 10 second-60 minutes, Preferably 30 second-10 minutes, normal pressure or a vacuum at the temperature of room temperature-120 degreeC, Preferably 60 degreeC-100 degreeC is preferable.                     

2) Then, the photomask (patterning film) which provided the opening part according to a desired pattern shape is put in contact or non-contact state on the said coating film, and it irradiates and hardens light. Here, light means not only visible light but also radiation, such as an ultraviolet-ray, an X-ray, an electron beam, but an ultraviolet-ray is the most preferable. As an ultraviolet source, a high pressure mercury lamp is generally used preferably.

3) After light irradiation, image development is performed with a solvent, water, an aqueous alkali solution, and the like. Among them, the aqueous alkali solution is preferable because there is little load on the environment and the development of high sensitivity can be performed. As an alkaline component, potassium hydroxide, sodium hydroxide, sodium carbonate, etc. are preferable. As alkali concentration, 0.01-5 weight% is preferable, 0.05-3 weight% is more preferable, 0.1-1 weight% is the most preferable. When alkali concentration is lower than the said range, there exists a possibility that the solubility of the said curable resin composition may run short, On the contrary, when the alkali concentration is high, a solvent may be too high and developability may fall. Moreover, you may add surfactant to aqueous alkali solution.

First, the following steps 1) to 3) are performed using a curable resin composition containing a black pigment to form a resin black matrix on the substrate.

Next, the pigment of curable resin composition is changed into red (R), green (G), and blue (B) sequentially, and the process of said 1) -3) is repeated, and the pixel of R, G, B is performed. To form an RGB pixel.

Next, a protective film is formed as needed for the purpose of improving the protection and surface smoothness of RGB pixels formed on the substrate.                     

In addition, when the said color filter is a color filter for liquid crystal display devices, it is preferable to form columnar spacers. The columnar spacers can be produced by coating the curable resin composition with a thickness that becomes the height of the desired spacer on the surface on which the spacers are to be formed, and through the steps 1) to 3) above.

When producing a color filter, when developing each member, after image development, it heats (postbaking) hardening further, and when a solvent remains, it is preferable to remove this completely. As temperature at the time of post-baking, 120-300 degreeC is preferable, 150-250 degreeC is more preferable, 180-230 degreeC is the most preferable. If the post-baking temperature is higher than the above, the pixel may be colored or the thermal decomposition may impair the smoothness of the coating film. On the contrary, if the postbaking temperature is low, the progress of curing may be small and the coating film strength may be lowered. Post-baking may be performed after image development in each member formation, and may be performed after all members are formed.

As for the display apparatus of this invention, in the display apparatus using the color filter in which the cured resin layer is formed on the board | substrate, the resin composition used as the said cured resin layer is curable resin composition of the said invention. As a specific example of the display apparatus of this invention, although a liquid crystal display device is enumerated preferably, it is not limited to these, For example, the display apparatus etc. which used organic electroluminescent may be sufficient. Hereinafter, the case of a liquid crystal display device is demonstrated.

The liquid crystal display device is a liquid crystal spacer between the color filter and the color filter substrate on which the ITO electrode and the alignment film are formed, if necessary, and the counter substrate on which the alignment film, the ITO electrode and the driving element are provided, at regular intervals. It is a liquid crystal display device containing a liquid crystal display panel for holding and holding, encapsulating a liquid crystal material within the interval, changing the orientation of the liquid crystal by an electric signal, and varying the transmittance of light. Although a well-known thing can be used as an operation mode and a drive system of a liquid crystal, TFT method is especially preferable at the point of display quality, response speed, etc ..

As said liquid crystal spacer, although a well-known fine particle spacer, columnar spacer using an exposure resin, etc. can be used, the columnar spacer formed using the curable resin composition of this invention is preferable.

The color filter substrate and the counter substrate are provided with an alignment film having an orientation corresponding to an operation mode of each liquid crystal, a driving method, or a fine protrusion (rib) as necessary, but an alignment film of polyimide is preferably used. In addition, in addition to a polyimide, you may use curable resin composition of this invention for rib. Moreover, it is necessary to arrange | position the deflection plate according to the operation mode of each liquid crystal, a drive system, and an optical compensation film on the outer side of a color filter substrate and a counter substrate.

(Example)

Although an Example demonstrates this invention more concretely below, this invention is not limited at all by these. In addition, unless otherwise indicated, "part" shall represent "mass part" and "%" shall represent "weight%."

The analysis in each synthesis example and the comparative synthesis example was performed as follows.

(Weight average molecular weight)

It measured by polystyrene conversion using the gel permeation chromatography measuring apparatus ("Shodex GPC System-21H" Showa Denko).

(Polymer concentration in polymer solution)

The solution obtained by adding 4 g of acetone to 1 g of the polymer solution and dissolving was naturally dried at room temperature, further dried under reduced pressure (160 ° C./5 mmHg) for 5 hours, and then cooled in a desiccator to weigh. And the non volatile matter of the polymer solution was computed from the weight loss amount, and this was made into the polymer concentration.

(Acid value)

80 mL of acetone and 10 mL of water are added to 0.5-1 g of the polymer solution, and the mixture is stirred and dissolved uniformly. An 0.1 mol / L aqueous KOH solution is used as a titration solution ("COM-555", manufactured by Hiranuma Sangyo Co., Ltd.). Titration was carried out to measure the acid value of the solution. And the acid value of the polymer was computed from the acid value of a solution and the polymer concentration.

Synthesis Example 1

A detachable flask equipped with a cooling tube was prepared as a reaction tank, and on the other side, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate (hereinafter referred to as "MD") as a monomer dropping tank. 40 parts, methacrylic acid (hereinafter referred to as "MAA") 40 parts, methyl methacrylate (hereinafter referred to as "MMA") 120 parts, t-butylperoxy-2-ethylhexanoate ( Nippon fat and oil product "perbutyl O": 4 parts of "PBO" below, 40 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") was prepared by stirring well mixing, as a chain transfer agent dropping tank, 8 parts of n-dodecanethiol (henceforth "n-DM") and 32 parts of PGMEA were stirred and mixed well.

395 parts of PGMEA was put into a reaction tank, nitrogen-substituted, and it heated with the oil-bath while stirring, and heated up the temperature of the reaction tank to 90 degreeC. After the temperature of the reaction tank was stabilized at 90 degreeC, the monomer dropping tank and chain | strand were chained. Dropping was started from the transfer agent dropping tank. The dropping was performed for 135 minutes, respectively, maintaining the temperature at 90 degreeC. 60 minutes after completion | finish of dripping, temperature rising was started and the reaction tank was 110 degreeC. After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the detachable flask and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was initiated. Subsequently, 70 parts of glycidyl methacrylate (henceforth "GMA") and 2,2'-methylenebis (4-methyl-6-t-butylphenol) (henceforth "MBMTM") are added to a reaction tank. ) 0.4 parts and 0.8 parts of triethylamine (hereinafter referred to as "TEA") were put in, and reacted as it was at 110 degreeC for 12 hours. Thereafter, 150 parts of PGMEA was added and cooled to room temperature to obtain a polymer solution having a concentration of 30%. The weight average molecular weight of the polymer was 18000, and the acid value was 2 mg KOH / g.

Synthesis Example 2

A detachable flask equipped with a cooling tube was prepared as a reaction tank, and on the other side, a mixture of 40 parts of MD, 80 parts of GMA, 80 parts of MMA, 80 parts of PBO, and 3 parts of PGMEA was well stirred and mixed as a monomer dropping tank. As a moving agent dripping tank, 6 parts of n-DM and 24 parts of PGMEA were stirred and mixed well.

403 parts of PGMEA were put into a reaction tank, nitrogen-substituted, and it heated with the oil bath with stirring, and heated up the temperature of the reaction tank to 90 degreeC. After the temperature of the reaction tank was stabilized at 90 ° C, dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was performed over 135 minutes, respectively, maintaining the temperature at 90 degreeC. 60 minutes after completion | finish of dripping, temperature rising was started and the reaction tank was 110 degreeC. After maintaining 110 degreeC for 3 hours, it cooled to room temperature and obtained the polymer solution which concentration is 30%. The weight average molecular weight of the polymer was 19000.

Synthesis Example 3

A detachable flask equipped with a cooling tube was prepared as a reaction tank, and on the other side, a mixture of 40 parts of MD, 32 parts of MAA, 128 parts of MMA, 3 parts of PBO, and 40 parts of PGMEA was well stirred and mixed as a monomer dropping tank. As a moving agent dripping tank, 6 parts of n-DM and 24 parts of PGMEA were stirred and mixed well.

403 parts of PGMEA were put into a reaction tank, nitrogen-substituted, and it heated with the oil bath with stirring, and heated up the temperature of the reaction tank to 90 degreeC. After the temperature of the reaction tank was stabilized at 90 ° C, dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was performed over 135 minutes, respectively, maintaining the temperature at 90 degreeC. 60 minutes after completion | finish of dripping, temperature rising was started and the reaction tank was 110 degreeC. After maintaining 110 degreeC for 3 hours, it cooled to room temperature and obtained the polymer solution of 30% of concentration. The weight average molecular weight of the polymer was 17000, and the acid value was 104 mg KOH / g.

Synthesis Example 4

A detachable flask equipped with a cooling tube was prepared as a reaction tank, and on the other side, as a monomer dropping tank, 40 parts of MD, 32 parts of MAA, 80 parts of benzyl methacrylate (hereinafter referred to as "BzMA"), 48 parts of MMA, A mixture of 3 parts of PBO and 40 parts of PGMEA was well prepared, and a mixture of 6 parts of n-DM and 24 parts of PGMEA was well prepared as a chain transfer dropper.

403 parts of PGMEA were put into a reaction tank, nitrogen-substituted, and it heated with the oil bath with stirring, and heated up the temperature of the reaction tank to 90 degreeC. After the temperature of the reaction tank was stabilized at 90 ° C, dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was performed over 135 minutes, respectively, maintaining the temperature at 90 degreeC. 60 minutes after completion | finish of dripping, temperature rising was started and the reaction tank was 110 degreeC. After maintaining 110 degreeC for 3 hours, it cooled to room temperature and obtained the polymer solution of 30% of concentration. The weight average molecular weight of the polymer was 17000, and the acid value was 104 mg KOH / g.

Synthesis Example 5

A detachable flask equipped with a cooling tube was prepared as a reaction tank, and on the other side, 40 parts of MD 40 parts, 32 parts of MAA, 60 parts of cyclohexyl methacrylate (hereinafter referred to as "CHMA"), and 68 parts of MMA as monomer dropping tanks. , 3 parts of PBO and 40 parts of PGMEA were prepared by stirring well, and a mixture of 6 parts of n-DM and 24 parts of PGMEA was prepared well by stirring as a chain transfer agent dropping tank.

403 parts of PGMEA were put into a reaction tank, nitrogen-substituted, and it heated with the oil bath with stirring, and heated up the temperature of the reaction tank to 90 degreeC. After the temperature of the reaction tank was stabilized at 90 ° C, dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was performed over 135 minutes, respectively, maintaining the temperature at 90 degreeC. 60 minutes after completion | finish of dripping, temperature rising was started and the reaction tank was 110 degreeC. After maintaining 110 degreeC for 3 hours, it cooled to room temperature and obtained the polymer solution of 30% of concentration. The weight average molecular weight of the polymer was 18000, and the acid value was 104 mg KOH / g.

Synthesis Example 6

A detachable flask equipped with a cooling tube was prepared as a reaction tank. On the other side, a monomer dropping tank was used as a monomer dropping tank, 40 parts MD, 32 parts MAA, 50 parts styrene (hereinafter referred to as "St"), 78 parts MMA, and 3 parts PBO. And stir-mixed 40 parts of PGMEA were prepared well, and the mixture which stir-mixed 6 parts of n-DM and 24 parts of PGMEA was prepared as a chain transfer agent dripping tank.

403 parts of PGMEA were put into a reaction tank, nitrogen-substituted, and it heated with the oil bath with stirring, and heated up the temperature of the reaction tank to 90 degreeC. After the temperature of the reaction tank was stabilized at 90 ° C, dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was performed over 135 minutes, respectively, maintaining the temperature at 90 degreeC. 60 minutes after completion | finish of dripping, temperature rising was started and the reaction tank was 110 degreeC. After maintaining 110 degreeC for 3 hours, it cooled to room temperature and obtained the polymer solution which concentration is 30%. The weight average molecular weight of the polymer was 18000, and the acid value was 104 mg KOH / g.

Synthesis Example 7

A detachable flask equipped with a cooling tube was prepared as a reaction tank, and on the other side, as a monomer dropping tank, MD 40 parts, MAA 60 parts, BzMA 80 parts, MMA 20 parts, PBO 4 parts, diethylene glycol dimethyl ether (hereinafter, 40 parts of well-prepared stirring mixtures were prepared, and 8 parts of n-DM and 32 parts of DMDG mixtures were prepared well as a chain transfer agent dropping tank.

395 parts of DMDGs were put into the reaction tank, nitrogen-substituted, and it heated with the oil bath with stirring, and heated up the temperature of the reaction tank to 90 degreeC. After the temperature of the reaction tank was stabilized at 90 ° C, dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was performed over 135 minutes, respectively, maintaining the temperature at 90 degreeC. 60 minutes after completion | finish of dripping, temperature rising was started and the reaction tank was 110 degreeC. After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the detachable flask and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Subsequently, 56 parts of GMA, 0.4 parts of MBMTB, and 0.8 parts of TEA were put into a reactor, and it was made to react at 110 degreeC for 9 hours as it was. Then, 128 parts of DMDGs were added and it cooled to room temperature, and the polymer solution of 30% of concentration was obtained. The weight average molecular weight of the polymer was 16000, and the acid value was 70 mg KOH / g.

Synthesis Example 8

A detachable flask equipped with a cooling tube was prepared as a reaction tank, and on the other side, as a monomer dropping tank, MD 60 parts, MAA 62 parts, BzMA 78 parts, PBO 3 parts, PGMEA 30 parts, isopropyl alcohol (hereinafter referred to as "IPA"). 30 parts of the mixture was prepared by stirring well, and as a chain transfer agent dropping tank, 4.4 parts of 3-mercaptopropionic acid, 15 parts of PGMEA, and 15 parts of IPA were well stirred and mixed.

189 parts of PGMEA and 189 parts of IPA were put into the reaction tank, and after nitrogen-substituting, it heated in the oil bath with stirring, and heated up until IPA refluxed. After the IPA was refluxed, dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was performed for 135 minutes, respectively, keeping IPA reflux. 60 minutes after completion | finish of dripping, temperature rising was started, IPA was removed, IPA removal was stopped when the reaction tank became 110 degreeC, and IPA was refluxed for 90 minutes. Thereafter, a gas introduction tube was attached to the detachable flask and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Subsequently, 68 parts of GMA, 0.4 parts of MBMTB, and 0.8 parts of TEA were put into a reactor, and the reaction was carried out for 9 hours under IPA reflux as it is. Thereafter, 210 parts of PGMEA was added, and the IPA was removed under reduced pressure, followed by cooling to room temperature to obtain a polymer solution having a concentration of 37%. The weight average molecular weight of the polymer was 13500, and the acid value was 72 mg KOH / g.

Synthesis Example 9

As a reaction tank, a detachable flask equipped with a cooling tube was prepared, and on the other side, a mixed well of MD 40 parts, MAA 60 parts, CHMA 60 parts, MMA 40 parts, PBO 4 parts, and DMDG 40 parts was mixed with a monomer dropping tank. Then, as a chain transfer agent dropping tank, 8 parts of n-DM and DMDG 32 were mixed well and prepared.

395 parts of DMDGs were put into the reaction tank, and after nitrogen reduction, it heated in the oil bath with stirring, and heated up the temperature of the reaction tank to 90 degreeC. After the temperature of the reaction tank was stabilized at 90 ° C, dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was performed over 135 minutes, respectively, maintaining the temperature at 90 degreeC. 60 minutes after completion | finish of dripping, temperature rising was started and the reaction tank was 110 degreeC. After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the detachable flask and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was initiated. Subsequently, 56 parts of GMA, 0.4 part of MBMTB, and 0.8 part of TEA were put therein, and the mixture was reacted at 110 ° C for 9 hours. Then, 128 parts of DMDGs were added and it cooled to room temperature, and the polymer solution of 30% of concentration was obtained. The weight average molecular weight of the polymer was 17000, and the acid value was 70 mg KOH / g.

Synthesis Example 10

A detachable flask equipped with a cooling tube was prepared as a reactor, and 467 parts of PGMEA, 40 parts of MD, 80 parts of GMA, 32 parts of MAA, 30 parts of St, 18 parts of MMA and dimethyl 2,2'-azobis were prepared in the reactor. 20 parts of (2,4-dimethylvaleronitrile) ("V-65" manufactured by Wako Pure Chemical Industries, Ltd .; hereafter referred to as "V-65") were added thereto, nitrogen-substituted, stirred and mixed well, and then stirred with oil. It heated by the bathtub and heated up the temperature of the reaction tank to 70 degreeC. After hold | maintaining this temperature for 3 hours, it cooled to room temperature and obtained the polymer solution whose concentration is 30%. The weight average molecular weight of the polymer was 21000, and the acid value was 104 mg KOH / g.

Comparative Example 1

A polymer solution having a concentration of 30% was obtained in the same manner as in Synthesis Example 1 except that MD was changed to N-phenylmaleimide (hereinafter, referred to as "PMI"). The weight average molecular weight of the polymer was 13000, and the acid value was 2 mg KOH / g.

(Comparative Example 2)

A polymer solution having a concentration of 30% was obtained in the same manner as in Synthesis Example 2, except that MD was changed to PMI, the amount of PBO was changed to 2 parts, and the amount of n-DM was changed to 4 parts. The weight average molecular weight of the polymer was 18000.

(Comparative Example 3)

A polymer solution having a concentration of 30% was obtained in the same manner as in Synthesis Example 3, except that MD was changed to PMI, the amount of PBO was changed to 2 parts, and the amount of n-DM was changed to 4 parts. The weight average molecular weight of the polymer was 18000, and the acid value was 104 mg KOH / g.

(Comparative Example 4)

As in Synthesis Example 3, MD was changed to methyl α- (hydroxymethyl) acrylate (hereinafter referred to as "MHMA"), the amount of PBO was changed to 2 parts, and the amount of n-DM was changed to 4 parts. To obtain a polymer solution. However, since water and methanol generate | occur | produce when lactone cyclization, and there are many residual monomers, the density | concentration of the obtained polymer solution was 25%. The weight average molecular weight of the polymer was 17000, and the acid value was 85 mg KOH / g.

Comparative Example 5

A polymer having a concentration of 30% in the same manner as in Synthesis Example 3 except for changing 40 parts of MD to 80 parts of BzMA, 88 parts of MMA, 2 parts of PBO, and 4 parts of n-DM. A solution was obtained. The weight average molecular weight of the polymer was 20000, and the acid value was 105 mg KOH / g.

Example 1-1 (Shape (i))>

10 parts of the polymer solution obtained in Synthesis Example 1, 3 parts of dipentaerythritol pentaacrylate (hereinafter referred to as "DPPA") and an optical radical generating agent ("Ilgacua 907" from Chiba-Kaiishasha; hereinafter referred to as "Irg") 907 ") and 9 parts of PGMEA were stirred and mixed so that it might become uniform, and the curable resin composition was obtained.

The curable resin composition obtained was applied on an alkali free glass plate using a spin coater so as to have a thickness of 2 μm after drying, and dried at 80 ° C. for 5 minutes with a hot plate, and then used as an ultrahigh pressure mercury lamp to give an irradiation amount of 200 mJ / cm. Ultraviolet rays were irradiated to ² to obtain a test piece A, and photocurability was evaluated using the test piece A by the following method. On the other hand, the said test piece A was heated on the hotplate for further 1 hour at 200 degreeC, the test piece B was obtained, and transparency and heat resistance were evaluated by the following method using the obtained test piece B. The results are shown in Table 1.

(Photocurability) The state of the coating film when immersing test piece A in tetrahydrofuran at room temperature for 1 minute was visually observed, and the following references | standards judged.

O: No peeling on the coating film ×: Peeling was confirmed on the coating film

(Transparency) The transmittance | permeability (%) in wavelength 380-800 nm was measured using the spectrophotometer ("UV-3100" Shimadzu Corporation make).

(Heat resistance) The film thickness of Test Piece B was measured using a stylus type surface roughness meter ("Dektak IIA" manufactured by Nippon Shinkugi Jutsu). Then, the said test piece B was heated at 250 degreeC for 1 hour by the hotplate, cooled to room temperature, and the film thickness was measured again. And the reduction rate (%) of the film thickness by heating was computed.

<Example 1-2 (Form (iv))>

10 parts of the polymer solution obtained in Synthesis Example 2, 0.09 parts of photoacid generator (hereinafter referred to as "SP-170", "SP-170"), and 0.6 parts of trimellitic anhydride were mixed and mixed so as to be uniform. A composition was obtained.

Using the obtained curable resin composition, it carried out similarly to Example 1-1, and evaluated 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, 3 parts of the cresol novolac-type epoxy resin ("EOCN-103S" manufactured by Nippon Kayaku; hereinafter referred to as "EOCN-103S"), 0.3 parts of trimellitic anhydride, and 5 parts of PGMEA It stirred and mixed so that it might become uniform, and the curable resin composition was obtained.

The resulting curable resin composition was applied on an alkali free glass plate using a spin coater to have a thickness of 2 μm, dried at 80 ° C. for 5 minutes with a hot plate, and then heated at 200 ° C. with a hot plate for 1 hour. Test piece B was obtained. Using the obtained test piece B, transparency and heat resistance were evaluated in the same manner as in Example 1-1. The results are shown in Table 1.

Comparative Example 1-1 (Form (i))

Ten parts of the polymer solution obtained in Comparative Synthesis Example 1, 3 parts of DPPA, and Irg 907 were stirred and mixed so as to make 0.009 parts and 5 parts of PGMEA uniform, thereby obtaining a curable resin composition.

Using the obtained curable resin composition, it carried out similarly to Example 1-1, and evaluated photocurability, transparency, and heat resistance. The results are shown in Table 1.

Comparative Example 1-2 (Form (iv))

Ten parts of the polymer solution and SP-170 obtained in Comparative Synthesis Example 2 were stirred and mixed so that 0.09 parts and 0.6 parts of trimellitic anhydride were uniform, thereby obtaining a curable resin composition.

Using the obtained curable resin composition, it carried out similarly to Example 1-1, and evaluated photocurability, transparency, and heat resistance. The results are shown in Table 1.

Comparative Example 1-3 (Form (vi))

Ten parts of the polymer solution and EOCN-103S obtained in Comparative Synthesis Example 3 were stirred and mixed so as to make 3 parts, 0.3 parts of trimellitic anhydride and 5 parts of PGMEA uniform, thereby obtaining a curable resin composition.

Using the obtained curable resin composition, it carried out similarly to Example 1-3, and evaluated transparency and heat resistance. The results are shown in Table 1.                     

Example 1-1 Example 1-2 Example 1-3 Comparative Example 1-1 Comparative Example 1-2 Comparative Example 1-3 Photocurable O O - O O - Transparency 97% or more 97% or more 97% or more over 90 over 90 over 90 Heat resistance Less than 1% Less than 1% Less than 1% Less than 1% Less than 1% Less than 1%

<Examples 2-1 to 2-2, Comparative Examples 2-1 to 2-2>

Each component of the compounding ratio (value shown by weight part) shown in Table 2 was stirred and mixed so that it might become uniform, and the curable resin composition was obtained.

After filtering the obtained curable resin composition using a 1 micrometer filter, it applied on the alkali free glass plate using a spin coater so that the thickness after drying might be set to 2 micrometers, and it dried at 80 degreeC with a hotplate for 5 minutes. Subsequently, ultraviolet rays were irradiated with an ultra-high pressure mercury lamp so that the amount of irradiation was 100 mJ / cm ² through a mask having line-and-space portions at intervals of 10 μm. Subsequently, the unirradiated part was dissolved and removed by 0.05% potassium hydroxide aqueous solution, and it wash | cleaned for 1 minute with pure water, the test piece A was obtained, and patternability was evaluated using the said test piece A by the following method. On the other hand, the said test piece A was heated by hotplate at 200 degreeC for 1 hour, the test piece B was obtained, and transparency and heat resistance of the cured coating-film part were evaluated using the obtained test piece B by the following method. The results are shown in Table 2.

(Pattern) Test piece A was observed with an optical microscope, and the following references | standards were determined.

O: The shape of the ultraviolet irradiation part (residual pattern) is good, and no residue is visible in the unilluminated part.                     

X: An ultraviolet irradiation part (residual pattern) has a defect and a residue is seen in an unilluminated part.

(Transparency) The transmittance | permeability (%) in wavelength 380-800 nm was measured using the spectrophotometer ("UV-3100" Shimadzu Corporation make).

(Heat resistance) The film thickness of Test Piece B was measured using a stylus type surface roughness meter ("Dektak IIA" manufactured by Nippon Shinkugi Jutsu). Then, the said test piece B was heated at 250 degreeC for 1 hour by the hotplate, cooled to room temperature, and the film thickness was measured again. And the reduction rate (%) of the film thickness by heating was computed.

Example 2-1 Example 2-2 Comparative Example 2-1 Comparative Example 2-2 Used Polymer Solution Synthesis Example 3 Synthesis Example 3 Comparative Synthesis Example 4 Comparative Synthesis Example 3    Compounding cost Polymer solution 10 10 12 10 DPPA 3 - 3 - EOCN-103S - 3 - 3 Trimellitic anhydride - 0.3 - 0.3 lrg907 0.09 - 0.09 - SP-170 - 0.09 - 0.09 PGMEA 5 5 3 5  evaluation Pattern O O × O Transparency 97% or more 97% or more 93% or more over 90 Heat resistance Less than 1% Less than 1% 4% Less than 1%

<Examples 3-1 to 3-3, Comparative Examples 3-1 to 3-2>

Each component of the mixing ratios (values are expressed in parts by weight) shown in Tables 3 and 4 is stirred and mixed so as to be uniform, and colored (R), green (G), blue (B), and black (K) colored curable resin compositions Got. Moreover, as a red pigment dispersion liquid, the dispersion liquid of "Pigment Red 254", as a green pigment dispersion liquid, "Pigment Green 36": "Pigment yellow-138" = 6: 4 (weight ratio) dispersion liquid, As a blue pigment dispersion liquid, A dispersion of "Pigment Blue 15: 6" was used, respectively.

Example 3-1 Example 3-2 Example 3-3 Used Polymer Solution Synthesis Example 4 Synthesis Example 7 Synthesis Example 8 Type of colored resin composition R G B K R G B K R G B K     Compounding cost Polymer solution 10 10 10 10 10 10 10 10 10 10 10 10 Dipentaerythritol hexaacrylate 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 - - - 20 - - - 20 - - - 20 lrg907 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

Comparative Example 3-1 Comparative Example 3-2 Used Polymer Solution Comparative Synthesis Example 3 Comparative Synthesis Example 5 Type of colored resin composition R G B K R G B K     Compounding cost Polymer solution 10 10 10 10 10 10 10 10 Dipentaerythritol hexaacrylate 3 3 3 3 3 3 3 3 Red Pigment Dispersion 20 - - - 20 - - - Green Pigment Dispersion - 17 - - - 17 - - Blue Pigment Dispersion - - 25 - - - 25 - Carbon Black Dispersion - - - 20 - - - 20 lrg907 2 2 2 2 2 2 2 2 PGMEA 40 43 35 40 40 43 35 40

After filtering the obtained red, green, blue colored curable resin composition using a 1 micrometer filter, it apply | coated on an alkali free glass substrate so that the thickness after drying may be set to 2 micrometers using a spin coater, and it was carried out by 80 with a hotplate. It dried at 5 degreeC. Subsequently, ultraviolet rays were irradiated with an ultra-high pressure mercury lamp through a mask having line-and-space portions having a 20 μm interval so that the irradiation amount was 100 mJ / cm ² . The unirradiated part was dissolved and removed with 0.05% potassium hydroxide aqueous solution, washed with pure water for 1 minute, and then, test piece A was obtained, and the pattern property was evaluated using the said test piece A by the following method. On the other hand, the said test piece A was heated by hotplate at 200 degreeC for 1 hour, the test piece B was obtained, and the chromaticity of the cured coating-film part was measured using the obtained test piece B by the following method. The results are shown in Table 5.

(Pattern) Test piece A was observed with an optical microscope, and the following references | standards were determined.

O: The shape of the ultraviolet irradiation part (residual pattern) is good, and no residue is visible in the unilluminated part.

X: An ultraviolet irradiation part (residual pattern) has a defect and a residue is seen in an unilluminated part.

Chromaticity The chromaticity (Y side, x value, y value) was measured using the spectrophotometer.

On the other hand, after filtering the obtained black colored curable resin composition using a 1 micrometer filter, it apply | coated on an alkali free glass substrate so that the thickness after drying might be set to 1 micrometer using a spin coater, and it heated at 80 degreeC with a hotplate at 5 degreeC. It was dried for a minute. Subsequently, ultraviolet rays were irradiated with an ultra-high pressure mercury lamp through a mask having line-and-space portions having a 10 μm interval so that the irradiation amount was 300 mJ / cm ² . The unirradiated portion was dissolved and removed with 0.05% aqueous potassium hydroxide solution, washed with pure water for 1 minute, and then Test Specimen C was obtained, and the Test Pattern C was used to evaluate the patternability. On the other hand, the said test piece C was heated by hotplate at 200 degreeC for 1 hour, the test piece D was obtained, and the obtained test piece D was measured for the OD value of the cured coating-film part by the following method. The results are shown in Table 5.

(Pattern) Test piece C was observed with an optical microscope, and the following references | standards were determined.

O: The shape of the ultraviolet irradiation part (residual pattern) is good, and no residue is visible in the unilluminated part.

X: An ultraviolet irradiation part (residual pattern) has a defect and a residue is seen in an unilluminated part.

(OD value) The OD value in 550 nm was measured using the spectrophotometer.                     

Example 3-1 Example 3-2 Example 3-3 R G B K R G B K R G B K Pattern O O O O O O O O O O O O  Chromaticity 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 OD value 3.2 3.3 3.4 Example 3-1 Comparative Example 3-2 R G B K R G B K Pattern O × O × O O O ×  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 OD value 3.0 3.1

<Examples 4-1 to 4-6, Comparative Examples 4-1 to 4-2>

Each component of the compounding ratio (value shown by weight part) shown in Table 6 was stirred and mixed so that it might become uniform, and the curable resin composition was obtained.

After filtering the obtained curable resin composition using a 1 micrometer filter, it applied on the alkali free glass plate using a spin coater so that the thickness after drying might be set to 2 micrometers, and it dried at 80 degreeC with a hotplate for 5 minutes. Subsequently, ultraviolet rays were irradiated with an ultra-high pressure mercury lamp so that the amount of irradiation was 100 mJ / cm ² through a mask having line-and-space portions having a 10 μm interval. The unirradiated portion was dissolved and removed with an aqueous 0.05% potassium hydroxide solution, washed with pure water for 1 minute, and then Test Specimen A was obtained, and Patternability was evaluated using the Test Specimen A in the following manner. 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. Using the obtained test piece B, the transparency, surface hardness, chemical resistance, thermal discoloration resistance, and thermal flatness of the cured coating film portion were as follows. Was evaluated. The results are shown in Table 6.

In addition, about Example 4-6, after irradiating with ultraviolet irradiation and a pattern property, and drying at 80 degreeC for 5 minutes, it heated continuously at 200 degreeC with a hotplate for 1 hour, and obtained the test piece B, The obtained test piece B Using the following method, the transparency, surface hardness, chemical resistance, heat discoloration resistance, and heat flatness of the cured coating film portion were evaluated.

(Pattern) Test piece A was observed with an optical microscope, and the following references | standards were determined.

O: The shape of the ultraviolet irradiation part (residual pattern) is good, and no residue is visible in the unilluminated part.

X: An ultraviolet irradiation part (residual pattern) has a defect and a residue is seen in an unilluminated part.

(Transparency) The transmittance | permeability (%) in wavelength 380-800 nm was measured using the spectrophotometer ("UV-3100" Shimadzu Corporation make).

(Surface Hardness) The surface hardness was measured according to the pencil scratch test of JIS K-5400.

(Drug Resistance) Test piece B was immersed in N-methylpyrrolidone at 30 ° C., dried at 200 ° C. for 30 minutes with a hot plate, and then subjected to the adhesion test according to the JIS K-5400 checker tape method. The number of remaining checkerboard scales was evaluated.

(Heat discoloration resistance) The test piece B was heat-treated at 250 degreeC for 1 hour by the hotplate, and the transmittance | permeability (%) in wavelength 400-800 nm was measured using the spectrophotometer ("UV-3100" Shimadzu Corporation make). . Then, from the transmittance before the heat treatment (transmittance measured in the evaluation of the transparency) and the transmittance measured after the heat treatment, the rate of decrease of the transmittance was calculated by the following formula and evaluated according to the following criteria.

% Reduction in transmittance = [(transmittance before heat treatment-transmittance after heat treatment) / transmittance before heat treatment] x 100

O: reduction rate is less than 1%

×: reduction rate is 1% or more

(Heat-resistance flatness) After heating Test Piece B at 250 ° C. for 1 hour with a hot plate, a Ra value, which is the surface roughness of the cured coating film, was measured using a stylus type surface roughness meter (manufactured by “Dektak IIA” Nippon Shinkugi Jutsu). It was.

Example 4-1 Example 4-2 Example 4-3 Example 4-4 Example 4-5 Example 4-6 Comparative Example 4-1 Comparative Example 4-2 Used Polymer Solution Synthesis Example 5 Synthesis Example 9 Synthesis Example 10 Synthesis Example 6 Synthesis Example 10 Synthesis Example 10 Comparative Synthesis Example 3 Comparative Synthesis Example 5   Compound ratio Polymer solution 10 10 10 10 10 10 10 10 Dipentaerythritol hexaacrylate 3 3 3 - - - 3 - EOCN-103S 3 3 - 3 - - 3 3 Trimellitic anhydride 0.3 - - 0.3 0.3 0.3 0.3 0.3 lrg907 0.09 0.09 0.09 - - - 0.09 - SP-170 - - - 0.09 0.09 - - 0.09 PGMEA 10 10 5 5 - - 10 5   evaluation Pattern O O O O O - O O Transparency 97% or more 97% or more 97% or more 97% or more 97% or more 97% or more over 90 97% or more Surface hardness 3H 3H 3H 3H 3H 3H 3H 2H Chemical resistance 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 Heat discoloration resistance O O O O O O O × Heat resistance 50 40 50 40 60 60 50 200

<Example 5, Comparative Example 5>

Each component of the compounding ratio (value shown by weight part) shown in Table 7 was stirred and mixed so that it might become uniform, and the curable resin composition was obtained.

After filtering the obtained curable resin composition using a 1 micrometer filter, it applied on the alkali free glass plate using a spin coater so that the thickness after drying might be set to 5 micrometers, and it dried at 80 degreeC with a hotplate for 5 minutes. Subsequently, ultraviolet rays were irradiated with an ultrahigh pressure mercury lamp so that the amount of irradiation was 100 mJ / cm ² through a mask having openings of 15 µm square. The unirradiated portion was dissolved and removed with an aqueous 0.05% potassium hydroxide solution, washed with pure water for 1 minute, and then heated to 200 ° C. on a hot plate for 1 hour to form a spacer pattern. Then, using a microcompression tester equipped with a planar indenter, the breaking load (gf) of the spacer portion was measured at a load load of 0.27 gf / sec and room temperature. The results are shown in Table 7.

Example 5 Comparative Example 5 Used Polymer Solution Synthesis Example 10 Comparative Synthesis Example 5    Compounding cost Polymer solution 10 10 Dipentaerythritol hexaacrylate 3 3 EOCN-103S - 3 Trimellitic anhydride 0.2 0.2 lrg907 0.09 0.09 PGMEA 5 10 Breaking load `` gf '' 13 10

Example 6

As described above, a color filter and a liquid crystal display device were produced and evaluated. In addition, each curable resin composition used for color filter preparation is as showing in 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 Filters)                     

First, the black curable resin composition was apply | coated to the alkali free glass substrate of 300 mm x 400 mm and thickness 1.1mm by the spin coater method, the coating film was formed, and the prebaking was performed at 80 degreeC for 5 minutes. Thereafter, using a proximity exposure machine using an ultra-high pressure mercury lamp as a light source, an exposure of 500 mJ / cm ² is performed by alignment exposure through a predetermined black matrix photomask, and development is performed with an alkaline developer. After washing with pure water, post-baking was carried out at 230 ° C. for 30 minutes to form a black matrix (thickness of 1.2 μm).

Next, the red curable resin composition was apply | coated by the spin coater method on the board | substrate with which the black matrix was formed, the coating film was formed, and prebaking was performed at 80 degreeC for 5 minutes. Thereafter, using a proximity exposure machine using an ultra-high pressure mercury lamp as a light source, alignment exposure was performed through a predetermined pixel photomask at an exposure dose of 100 mJ / cm ² , development was performed with an alkaline developer, washed with pure water, and then 200 Post-baking was performed at 30 degreeC for 30 minutes, and the red pixel pattern (thickness 2.0 micrometers) was formed. Similarly, the green pixel pattern was formed using the red curable resin composition, and the blue pixel pattern was formed using the blue curable resin composition.

Subsequently, the protective film resin composition was apply | coated by the spin coater method on the board | substrate with which the black matrix and each color pixel were formed, the coating film was formed, and prebaking was performed at 80 degreeC for 5 minutes. Thereafter, using a proximity exposure machine using an ultra-high pressure mercury lamp as a light source, alignment exposure is performed through a predetermined protective photomask at an exposure dose of 100 mJ / cm ² , development is performed with an alkaline developer, washed with pure water, and then Post-baking was performed at 200 degreeC for 30 minutes, and the protective film (thickness 1.5 micrometers) was formed.

Next, the resin composition for spacers was apply | coated by the spin coater method on the board | substrate with a protective film, the coating film was formed, and the prebaking was performed at 80 degreeC for 5 minutes. Thereafter, using a proximity exposure machine using an ultra-high pressure mercury lamp as a light source, alignment exposure was performed through a predetermined photomask for spacers at an exposure dose of 100 mJ / cm ² , development was performed with an alkaline developer, washed with pure water, and then 200 Post-baking was performed at 30 degreeC for 30 minutes, and the spacer (4.8 micrometers in thickness, 12 micrometers x 12 micrometers of bottom parts) was formed.

When the produced color filter was inspected by the optical microscope, there was no pattern defect or developing residue, and the smoothness of the surface of the protective film was also good.

(Production and Evaluation of Liquid Crystal Display Device)

On the color filter produced as mentioned above, the transparent conductive layer (0.15 micrometer in thickness) which consists of indium tin oxide is formed by the sputtering method, Furthermore, a polyimide orientation layer is formed and orientation treatment (rubbing) After bonding to the TFT-array substrate using an epoxy resin sealant, the TN-type liquid crystal is sealed between the color filter and the TFT array substrate from an injection hole provided in the seal portion, and then the injection hole is sealed. Moreover, the optical filter, such as a polarizing plate, was bonded together and the liquid crystal display device of TN system was produced.

The produced liquid crystal display device had high luminance and color purity, and obtained good display quality without causing color unevenness.                     

Comparative Example 6

A color filter and a liquid crystal display device were produced and evaluated in the same manner as in Example 6 except that each curable resin composition used for color filter production was changed to that shown in Table 8. No defects or developing residues were observed, and the liquid crystal display device had low luminance and color purity, and no color irregularities.

Curable resin composition of this invention can form the coating film which was extremely excellent also in heat resistance and transparency, for example, can be used suitably for the use of resist materials, various coating agents, coating materials, etc. In addition, according to the present invention, it is possible to provide a color filter of good quality without pattern defects or developing residues. Further, according to the present invention, it is possible to provide a display device of high display quality without high luminance and color purity and without causing color unevenness.

Claims (7)

As curable resin composition containing a polymer component (A) and the hardening component (B) which consists of 1 or more types chosen from the compound (b1) which has a radically polymerizable double bond, and the compound (b2) which has an epoxy group, Curable resin composition characterized by the above-mentioned polymer component (A) being polymer (a) which superposes | polymerizes the monomer component which makes the compound represented by following General formula (1) essential.

(In formula (1), R <^1> and R <^2> represents a C1-C25 hydrocarbon group which may respectively independently have a hydrogen atom or a substituent. The said substituent is an alkoxy group or an aryl group.) The curable resin composition according to claim 1, wherein the polymer (a) is a polymer having an acid group. The polymer (a) is at least one selected from a compound (b1) having a radically polymerizable double bond and a compound (b2) having an epoxy group, and also serves as a curing component (B). Curable resin composition. The compound (b1) according to claim 1, wherein the curable component (B) is a compound having a radically polymerizable double bond (b1), and is selected from an optical radical generator (c1) and a thermal radical generator (c2) as a polymerization initiator (C). Curable resin composition further containing 1 or more types. The said cured component (B) is a compound (b2) which has an epoxy group, and contains 1 or more types chosen from a photo-acid generator (c3) and a thermal acid generator (c4) as a polymerization initiator (C). Curable resin composition characterized by the above-mentioned. The color filter in which a cured resin layer is formed on a board | substrate WHEREIN: The resin composition used as the said cured resin layer is curable resin composition in any one of Claims 1-5, The color filter characterized by the above-mentioned. The display device using the color filter in which a cured resin layer is formed on a board | substrate WHEREIN: The resin composition used as the said cured resin layer is curable resin composition in any one of Claims 1-5 characterized by the above-mentioned. Device.