KR20160016619A - Curable resin composition and color filter - Google Patents

Abstract

The present invention provides a curable resin composition which can achieve an additional improvement in developing speed, can stably exhibit a variety of physical properties such as curing properties, solvent resistance after curing, adhesion to a substrate (base material), heat resistance and transparency, has excellent storage stability, and is useful in various uses such as a color filter or the like. In addition, provided are a cured product formed by the curable resin composition, and a color filter using the cured product, and a display device. The curable resin composition comprises (A) a polymer having a ring structure in a main chain, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) a solvent, wherein the polymer (A) is obtained by polymerizing a monomer represented by predetermined structural formula and a monomer mixture containing acrylic acid.

Description

TECHNICAL FIELD [0001] The present invention relates to a curable resin composition and a color filter,

The present invention relates to a curable resin composition and a use thereof (for example, a color filter and the like).

The curable resin composition that can be cured by heat or an active energy ray has been variously examined for various applications such as optical members and electric and electronic devices and the like, and the curable resin composition Has been developed. A color filter is a main component that constitutes a liquid crystal display device, a solid-state image pickup device, and the like, and generally includes a substrate, at least three primary colors (red (R), green (G) (B), and a resin black matrix (BM) for partitioning them, as well as a protective film formed to cover and protect the pixel and the resin black matrix and to planarize their concavities and convexities.

In general, in the case of forming a pixel of a color filter by using a curable resin composition, it is preferable that (1) a coating step of applying the curable resin composition on the entire surface of the substrate, and (2) An exposure step of patterning the resist film through a photomask to cure the exposed part, followed by insolubilization of the cured part; and (3) a step of removing the unexposed part with a developer and then firing (baking) (Baking) process is performed, and the same process as that of the process is repeated in each color. In recent years, in order to increase the productivity, it is required to accelerate the developing speed of (3). Thus, for example, the techniques described in Patent Documents 1 to 3 have been proposed.

Japanese Laid-Open Patent Publication No. 2010-145719 Japanese Laid-Open Patent Publication No. 2010-270208 Japanese Patent Application Laid-Open No. 2010-266740

As described above, Patent Literatures 1 to 3 and the like propose a technique for increasing the developing speed. However, even with these techniques, the development speed tends to be slow.

The present invention has been made in consideration of the above-described circumstances, and it is possible to achieve further improvement of the developing speed and to stably exhibit various physical properties such as curability, solvent resistance after curing, adhesion with the substrate (substrate), heat resistance and transparency And a curable resin composition which is excellent in storage stability and is useful for various applications such as color filters. The present invention also aims to provide a cured product formed from such a curable resin composition, and a color filter and a display device using the cured product.

(A) a polymer having a ring structure in the main chain, (B) a polymerizable compound, (C) a photopolymerization initiator, and (A) is a polymer obtained by polymerizing a monomer mixture comprising a specific monomer as an ether dimer and acrylic acid, and a developing time during alkali development can be shortened by using the polymer (A) as a curable resin composition containing a solvent And it has been found that the productivity can be further improved and the manufacturing cost can be reduced. Generally, when obtaining an alkali-soluble resin used in applications such as color filters, methacrylic acid is often used rather than acrylic acid as an acid group-containing monomer. This is because the use of methacrylic acid improves the heat resistance of the alkali-soluble resin. However, the inventors of the present invention have found that the use of acrylic acid as one component of the monomer giving the polymer (A), as compared with the above conventional technical knowledge, I found that I can remarkably shorten.

Such a curable resin composition is particularly useful for a color filter application and is particularly preferable as a resin composition for forming a pixel for a color filter. Therefore, the cured product, the color filter, and the display device formed from such a curable resin composition can cope sufficiently with demands for high productivity and high performance in recent years, and find out that the cured product, color filter, and display device are very useful in the optical field and the electric and electronic fields , And the present invention has been accomplished on the basis of being able to solve the above problem well.

That is, the present invention provides a curable resin composition comprising (A) a polymer having a cyclic structure in its main chain, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) A curable resin composition obtained by polymerizing a monomer mixture comprising a monomer represented by the following general formula (1) and acrylic acid.

[Chemical Formula 1]

In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group of 1 to 25 carbon atoms which may have a substituent.

In the present invention, as the monomer represented by the general formula (1), it is preferable to use an ether dimer composition comprising the monomer represented by the general formula (1) and water, wherein the content of water is such that the total amount of the ether dimer composition is 100 Is preferably 0.1 to 10% by mass with respect to the mass%.

It is preferable that the monomer mixture further includes a monomer having a cyclic structure.

The polymer (A) preferably has a weight average molecular weight of 5,000 to 50,000 and an acid value of 50 to 200 mgKOH / g.

The present invention is also a cured product obtained by curing the above-mentioned curable resin composition.

The present invention is also a color filter having a cured product on a substrate.

The present invention is also a display device configured using the color filter.

Since the curable resin composition of the present invention has the above-described constitution, it has good developability, can achieve further improvement of the developing speed, and is excellent in curability, solvent resistance after curing, adhesion with substrate (substrate) And the like, and is also excellent in storage stability and useful for various applications such as color filters. Therefore, a color filter and a display device having a cured product (cured film) formed from such a curable resin composition are very useful in the field of optics and the electric and electronic fields.

Hereinafter, the present invention will be described in detail. It is a preferred embodiment of the present invention that two or three or more individual preferred embodiments of the present invention described below are combined. "A to B" indicating the range means "A or more and B or less".

[Curable resin composition]

The curable resin composition (also referred to simply as " resin composition ") of the present invention comprises (A) a polymer having a cyclic structure in its main chain, (B) a polymerizable compound, (C) a photopolymerization initiator, and , And these containing components may be used individually or in combination of two or more. Further, if necessary, one or more other components may be contained.

In the present specification, the polymer having a ring structure in the main chain (A) is also referred to as "polymer (A)" or "component (A) Component (C) ", and the solvent (D) is also referred to as" component (D) ". The term " (meth) acrylic acid " refers to both methacrylic acid and acrylic acid.

The content of the components (A) to (C) is not particularly limited. For example, the component (B) is 20 to 300 parts by mass, the component (C) is 5 to 50 parts by mass, Mass part is preferable. As a result, the curability and transparency become higher. More preferably, 30 to 200 parts by mass of the component (B) and 10 to 50 parts by mass of the component (C) are contained per 100 parts by mass of the component (A). The content of the component (D) is preferably 20 to 5000 parts by mass, for example, with respect to 100 parts by mass of the component (A). More preferably 50 to 2000 parts by mass.

Hereinafter, the components contained in components (A) to (E) will be described in more detail.

(A) a polymer having a cyclic structure in the main chain

The polymer (A) is a polymer obtained by polymerizing a monomer mixture containing an acrylic acid and a monomer represented by the above general formula (1) (also referred to as "ether dimer"). By using an ether dimer, it is presumed that the ether dimer undergoes a cyclization reaction during polymerization to form a tetrahydropyran ring structure (main chain ring structure) in the structural unit of the polymer. The curable resin composition containing such a polymer (A) is excellent in heat resistance, surface hardness and adhesion, and further suppresses time-dependent changes after exposure at high temperatures such as post-bake (heat treatment) A cured product capable of stably expressing physical properties can be provided.

The acid value (AV) of the polymer (A) is preferably 50 to 200 mgKOH / g. As a result, sufficient alkali solubility is exhibited, and a cured product having a better developability (developing speed) can be provided. More preferably 60 to 180 mgKOH / g, further preferably 70 to 160 mgKOH / g, particularly preferably 70 to 150 mgKOH / g.

In the present specification, the acid value of the polymer can be determined by the method described in the following Examples.

The weight average molecular weight (Mw) of the polymer (A) is not particularly limited, but is preferably 5000 to 50000, for example. When it is 5000 or more, more sufficient heat resistance can be exhibited, and when it is 50000 or less, the viscosity of the curable resin composition becomes more appropriate, and the coating film is easily formed, and thus the developability is further improved. More preferably 6,000 to 30,000, and still more preferably 8,000 to 20,000.

In the present specification, the weight average molecular weight can be measured by the method described in the following Examples.

The polymer (A) may be a polymer obtained by polymerizing a monomer mixture containing the ether dimer and acrylic acid (also referred to as a " base polymer ") and may be a polymer obtained by introducing a double bond into the side chain of the base polymer (Also referred to as a polymer having a double bond in the side chain or a side chain double bond-containing polymer). Such side chain double bond-containing polymers are also included in the polymer (A) referred to in the present invention. More preferably, it is a side chain double bond-containing polymer from the viewpoints of photosensitivity, curability, thermal decomposition resistance and the like.

Hereinafter, the raw material components and the polymerization method of the polymer (A) will be further described.

- raw material components (such as monomers) of the polymer (A)

(i) ether dimer

The ether dimer is a compound represented by the above general formula (1). The ether dimer to be used may be one kind or two or more kinds.

In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. The hydrocarbon group having 1 to 25 carbon atoms which may have a substituent is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, A linear or branched alkyl group such as lauryl or 2-ethylhexyl; An aryl group such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl and the like; An alkyl group substituted by alkoxy such as 1-methoxyethyl or 1-ethoxyethyl; And an alkyl group substituted with an aryl group such as benzyl. Of these, particularly preferred are groups having a primary or secondary carbon which is not easily cleaved by an acid or heat, such as methyl, ethyl, cyclohexyl, benzyl and the like, from the viewpoint of heat resistance. The number of carbon atoms in the hydrocarbon group is preferably 1 to 12, more preferably 1 to 8. Also, R < ¹ > and R < ² > may be homogeneous and may have different contributions.

Specific examples of the ether dimer include dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2 '- [oxybis (methylene)] bis- (Isopropyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, di (n-propyl) ] Bis-2-propenoate, di (n-butyl) -2,2 '- [oxybis (Methylene)] bis-2-propenoate, di (t-butyl) -2,2 '- [oxybis Di (stearyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (lauryl) Bis (2-ethylhexyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (1- Methoxyethyl) -2,2 '- [oxybis (methylene)] bis-2-propenoic acid Bis (2-hydroxyethyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, dibenzyl- (Methylene)] bis-2-propenoate, dicyclohexyl-2,2 '- [oxybis (methylene)] bis-2-propenoate Di (dicyclopentadienyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (t-butylcyclohexyl) ] Bis [2-propenoate], di (tricyclodecanyl) -2,2 '- [oxybis (2-methyl-2-adamantyl) bis-2-propenoate, diadamanthyl-2,2 '- [oxybis -2,2 '- [oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2 '- [oxybis (methylene)] bis- (Methylene)] bis-2-propenoate, and / or dibenzyl-2,2 '- [oxybis (methylene)] bis-2- Do.

The content of the ether dimer in the monomer mixture to give the polymer (A) is not particularly limited, but is preferably 2% by mass or more based on 100% by mass of the total amount of the monomer mixture. Thereby, a curable resin composition having superior coating performance such as transparency and heat resistance can be obtained. Further, it is preferably 60 mass% or less. As a result, in the polymerization, a gel having a low molecular weight can be obtained more easily, and the gelation can be sufficiently suppressed. More preferably from 2 to 60% by mass, still more preferably from 5 to 55% by mass, and particularly preferably from 5 to 50% by mass.

Here, the content ratio of the ether dimer in the monomer mixture here means the amount of the ether dimer. That is, even when an ether dimer composition comprising this and an ether as a ether dimer is used as described later, it is preferable to set the amount of the ether dimer in the above preferable range.

In the present invention, as the monomer (ether dimer) represented by the general formula (1), it is preferable to use a composition comprising the monomer represented by the general formula (1) and water (also referred to as an "ether dimer composition" . In this case, the content of water in the ether dimer composition is preferably 0.1 to 10% by mass based on 100% by mass of the total amount of the ether dimer composition. Thereby, the storage stability of the ether dimer is improved, and the storage stability of the obtained polymer (A) and the curable resin composition is also improved. In this range, the storage stability at a high temperature and the storage stability at a low temperature are also improved. The content of water is more preferably from 0.3 to 10 mass%, more preferably from 0.5 to 7 mass%, particularly preferably from 0.7 to 5 mass%, most preferably from 1 mass% to 100 mass%, based on the total amount of the ether dimer composition. To 3% by mass.

The water used in the ether dimer composition is not particularly limited, but pure water is preferred. More preferably, it is ion-exchanged water that has passed through a commonly used ion-exchange resin in consideration of cost.

In the ether dimer composition, the content of the monomer (ether dimer) represented by the general formula (1) is not particularly limited, but it is preferably 10 to 70% by mass based on 100% by mass of the total amount of the ether dimer composition Do. Within this range, the storage stability of the ether dimer is further improved, the content of the main chain ring structure in the polymer (A) becomes more suitable, and the heat resistance and transparency of the curable resin composition are further improved. More preferably from 15 to 40% by mass, and still more preferably from 20 to 30% by mass.

It is preferable that the ether dimer composition further contains a stabilizer and / or a non-aqueous solvent in addition to the monomer represented by the formula (1) and water. As a result, the storage stability is further improved. Each of the components contained in the ether dimer composition may be used alone or in combination of two or more.

The stabilizer is a compound having a function of preventing radical polymerization or oxidation deterioration. For example, a compound usually used as a polymerization inhibitor or an antioxidant can be used, and it is not particularly limited. Specifically, there may be mentioned a phenol compound, an organic acid copper salt, a phenothiazine, a phosphite, a thioether, a hindered amine compound, an ascorbic acid, a thiocyanic acid salt, a thiourea derivative, a nitrite, a sulfite, Hydroxylamine derivatives, N-oxyl compounds, and the like. Among these, a hydroxyl group-containing compound having a cyclic structure is preferable from the viewpoints of coloring and compatibility, and more preferred is a phenol compound. Specific examples include hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, methoquinone, 6-t-butyl-2,4-xylenol, 2,6- Di-t-butyl-4-methoxyphenol, and 2,2'-methylenebis (4-methyl-6-t-butylphenol). N-oxyl compounds are also preferable, and specifically derivatives of 2,2,6,6-tetramethylpiperidine-1-oxyl, among which 4-hydroxy-2,2,6,6-tetramethyl Piperidin-1-oxyl, and the like.

The stabilizer may be used alone or in combination of two or more, but it is particularly preferable to use a combination of a phenolic compound and an N-oxyl compound in order to maximize the storage stability of the ether dimer. The mass ratio of the phenol compound / N-oxyl compound is preferably 15/1 to 5/1. More preferably 10/1 to 7/1, and still more preferably 8/1.

In the ether dimer composition, the content of the stabilizer is not particularly limited, but is preferably 0.001 to 1% by mass based on 100% by mass of the total amount of the ether dimer composition. Within this range, the storage stability is further improved, and the coloration during the storage and the lowering of the polymerizability are more sufficiently suppressed. More preferably from 0.002 to 0.1% by mass, and even more preferably from 0.003 to 0.05% by mass.

The non-aqueous solvent is not limited as long as it is an organic solvent capable of uniformly dissolving the ether dimer, water and stabilizer. Specifically, it is preferably at least one solvent selected from the group consisting of alcohol solvents, ether solvents, ester solvents, ketone solvents, aromatic solvents, amide solvents, nitrile solvents and sulfoxide solvents Do.

Specific examples of these solvents are described below.

(Alcohol-based solvent)

Monohydric alcohols such as methanol, ethanol, isopropanol, n-butanol and s-butanol; Glycols such as ethylene glycol and propylene glycol; And polyhydric alcohols such as glycerin.

(Ether-based solvent)

Cyclic ethers such as tetrahydrofuran and dioxane; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Glycol monoethers such as propylene glycol monobutyl ether and 3-methoxybutanol; A glycol such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether and the like Ethers and the like.

(Ester-based solvent)

Ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether A glycol monoacetate such as acetone, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, Esters of ethers; Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate, and ethyl acetoacetate.

(Ketone-based solvent)

Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

(Aromatic solvent)

Aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene;

(Amide-based solvent)

Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

(Nitrile-based solvent)

Acetonitrile, propionitrile, benzonitrile, etc.

(Sulfoxide type solvent)

Dimethyl sulfoxide and the like.

The kind and amount of the non-aqueous solvent may be appropriately selected depending on the purpose or use of the curable resin composition, the production conditions of the ether dimer composition, and the production conditions of the polymer (A) and the curable resin composition. For example, when the curable resin composition of the present invention is used in resist applications, it is preferable to use the same nonaqueous solvent as the solvent constituting the resist (also referred to as " resist solvent "). In this case, since the resist can be used without removing the nonaqueous solvent when preparing the resist, the process can be simplified. Specific examples of the solvent for resists include esters such as propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethyl lactate; Ketone solvents such as cyclohexanone; And ether solvents such as propylene glycol monomethyl ether, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether, but are not limited thereto. A low boiling point solvent such as methyl acetate, ethyl acetate, acetone, and methyl ethyl ketone, which is easy to remove, is also preferable.

For example, from the viewpoint of lowering the solution viscosity during polymerization and controlling the molecular weight, it is preferable to use an alcohol-based solvent such as methanol, ethanol, isopropanol or propylene glycol monomethyl ether. Among them, when the curable resin composition of the present invention is used for a resist application, an alcohol solvent with a low boiling point such as methanol, ethanol, or isopropanol is more preferable, which is easy to remove.

Therefore, in particular, when the curable resin composition of the present invention is used as a resin composition for an alkali developing negative resist such as a color filter resist, a mixed solvent of the aforementioned resist solvent and alcohol solvent is used as the non-aqueous solvent .

In the ether dimer composition, the content of the non-aqueous solvent is not particularly limited, but is preferably 20 to 90% by mass based on 100% by mass of the total amount of the ether dimer composition. This makes it possible to more uniformly dissolve the ether dimer and water, as well as to make the content of the main chain ring structure in the polymer (A) more suitable, thereby further improving the heat resistance and transparency of the curable resin composition. More preferably 50 to 85% by mass, and still more preferably 55 to 75% by mass.

As a method for producing the ether dimer composition, the ether dimer, water, stabilizer, and non-aqueous solvent are preferably uniformly mixed so as to have the preferable contents described above.

The method for producing the ether dimer (that is, the monomer represented by the general formula (1)) is not particularly limited. However, after the α-hydroxymethylacrylic acid ester is dehydrated and dehydrated with a tertiary amine catalyst, impurities Product or the like) is preferably removed. As a result, a symmetrical ether dimer can be obtained with high yield and high purity. As a method for removing the impurities, known purification methods such as extraction, crystallization, and distillation can be appropriately selected. However, since a high-purity ether dimer can be obtained at a high yield, it is preferable to employ crystallite.

The crystallization means that crystals are precipitated from a liquid phase or the like.

Particularly, from the viewpoint of improving the stability of the ether dimer composition and preventing gelation at the subsequent polymerization, a side reaction product containing a polymerizable unsaturated double bond (crosslinkable compound, ester dimer, 3 Or the like) is 0.001 mass% or less. More preferably, it is removed to below the detection limit. From the viewpoint of preventing discoloration, it is preferable to remove the tertiary amine catalyst to 0.01% by mass or less based on 100% by mass of the total amount of the ether dimer composition. More preferably 0.001% by mass or less, and still more preferably 0.0005% by mass or less.

(ii) acrylic acid

The content of acrylic acid in the monomer mixture is preferably set so that the acid value of the polymer is within the above-mentioned preferable range. For example, it is preferably 7% by mass or more, more preferably 10% by mass or more, and even more preferably 13% by mass or more, based on 100% by mass of the total amount of the monomer mixture. Further, it is preferably 30 mass% or less, more preferably 25 mass% or less, and further preferably 20 mass% or less.

(iii) Other acid group-containing monomers

In the present invention, acrylic acid is essentially used as a monomer having an acid group (referred to as " acid group-containing monomer "), but an acid group-containing monomer other than acrylic acid ("other acid group- The monomer mixture may further contain one or more kinds of other acid group-containing monomers. The acid group may be any functional group capable of neutralization reaction with alkaline water. Specific examples thereof include a carboxyl group, a phenolic hydroxyl group, a carboxylic acid Among them, a carboxyl group and / or a carboxylic acid anhydride group is preferable, and a carboxyl group is preferably a carboxyl group and / or a carboxylic acid anhydride group. Among them, More preferable.

Examples of the other acid group-containing monomer include unsaturated monocarboxylic acids such as methacrylic acid, crotonic acid, cinnamic acid and vinylbenzoic acid; Unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid; Unsaturated monocarboxylic acids such as succinic acid mono (2-acryloyloxyethyl) and succinic acid mono (2-methacryloyloxyethyl), in which an unsaturated group and a carboxyl group are extended in chain; Unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; And a phosphoric acid group-containing unsaturated compound such as Light Ester P-1M (manufactured by Kyowa Chemical Co., Ltd.). Among them, it is preferable to use carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, unsaturated acid anhydrides) from the viewpoints of versatility and availability. More preferably, from the viewpoints of reactivity and alkali solubility, unsaturated monocarboxylic acids are preferably used, and among these, methacrylic acid is particularly preferable.

The amount of the other acid group-containing monomer is not particularly limited as long as the action effect derived from acrylic acid or the ether dimer is sufficiently exhibited. For example, it is preferably 0 to 50 parts by mass relative to 100 parts by mass of acrylic acid. More preferably 0 to 30 parts by mass, still more preferably 0 to 10 parts by mass, particularly preferably 0 to 5 parts by mass.

(iv) a monomer having a cyclic structure

It is preferable that the monomer mixture further comprises a monomer having a cyclic structure. That is, the monomer mixture preferably further comprises a monomer having a cyclic structure. The monomers having a cyclic structure may be used alone or in combination of two or more.

Examples of the monomer having a cyclic structure include N-substituted maleimide-based monomers; (Meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (Meth) acrylate dicyclopentanyl, and other cyclic structure-containing (meth) acrylic acid ester monomers; And aromatic vinyl compounds such as styrene, vinyltoluene, and? -Methylstyrene.

Examples of the N-substituted maleimide-based monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, , N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide, p-methylbenzylmaleimide, p-butylbenzylmaleimide, p-hydroxybenzylmaleimide, o-dichlorobenzylmaleimide, p-dichlorobenzylmaleimide, and the like, and one or more of these may be used. Among them, from the viewpoint of transparency, N-phenylmaleimide and N-benzylmaleimide are preferable, and N-benzylmaleimide is particularly preferable.

Examples of the N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimides such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; substituted phenol-substituted benzylmaleimides such as p-hydroxybenzylmaleimide; halogen-substituted benzylmaleimides such as o-chlorobenzylmaleimide, o-dichlorobenzylmaleimide and p-dichlorobenzylmaleimide.

Of the monomers having the above-mentioned cyclic structure, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, styrene and / or vinyltoluene are preferred because they are excellent in transparency and hardly inhibit heat resistance.

The content of the monomer having a cyclic structure in the monomer mixture is not particularly limited, but is preferably 60% by mass or less based on 100% by mass of the total amount of the monomer mixture. Among them, from the viewpoints of heat resistance and hardness, coloring material dispersibility, development speed, transparency, etc., it is preferably 2 to 60% by mass. More preferably from 2 to 50% by mass, and still more preferably from 3 to 40% by mass.

(v) other monomers

The monomer mixture for obtaining the polymer (A) may also contain other monomers (also referred to as " other monomers ") copolymerizable with the ether dimer and / or acrylic acid, if necessary. The other monomers may be used alone or in combination of two or more.

Examples of the other monomer include a monomer (except the monomer represented by the general formula (1)) which forms a cyclic structure at the time of polymerization. For example, an? - (unsaturated alkoxyalkyl) acrylate-based monomer. Among them, alkyl- (alpha -allyloxymethyl) acrylate-based monomers are preferable. In addition, alkyl- (alpha -methallyloxymethyl) acrylate-based monomers and the like are also preferable.

Examples of the other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (Meth) acrylic acid esters such as t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate; Butadiene or substituted butadiene compounds such as butadiene and isoprene; Ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride and acrylonitrile; And vinyl esters such as vinyl acetate. Of these, methyl (meth) acrylate and / or 2-hydroxyethyl (meth) acrylate are preferable in that they have good transparency and do not hinder heat resistance. These copolymerizable other monomers may be used alone or in combination of two or more.

The content of the other monomer is preferably 0 to 80% by mass based on 100% by mass of the total amount of the monomer mixture when it is used, for example, in a resist for a color filter. More preferably 1 to 80% by mass. When the content is within this range, a resin composition having more excellent heat resistant coloring property and inorganic compound dispersibility can be obtained. More preferably 5 to 75% by mass, and particularly preferably 10 to 70% by mass.

- Polymerization method -

The polymer (A) is obtained by polymerizing the above-mentioned monomer mixture. The method of the polymerization reaction is not particularly limited, and various conventionally known polymerization methods can be employed. Among them, a polymerization method based on a radical polymerization mechanism is preferable because it is industrially advantageous. The polymerization concentration and the polymerization temperature vary depending on the type and ratio of the monomers to be used and the molecular weight of the target polymer, but preferably the polymerization temperature is set to 40 to 150 ° C and the polymerization concentration is set to 20 to 50% , More preferably the polymerization temperature is set to 60 to 130 ° C, and the polymerization concentration is set to 30 to 45%.

When a solvent is used for the polymerization, a solvent used in a conventional radical polymerization reaction may be used as the solvent. Preferably, the solvent contained in the curable resin composition, that is, the compound used as the component (D) is used, thereby facilitating the preparation of the curable resin composition. Specific examples include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and 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 solvents may be used alone or in combination of two or more.

Particularly, when the total content of the acid group-containing monomer relative to the total amount of 100 mass% of the monomer mixture exceeds 30 mass%, in order to prevent precipitation of the polymer, an ester solvent such as propylene glycol monomethyl ether acetate, It is preferable to use a mixed solvent of an alcoholic solvent such as monomethyl ether or isopropanol.

Here, the content of the acid group-containing monomer herein means the amount added for introducing the reactive double bond (polymerizable double bond) into the side chain.

In the polymerization, a commonly used polymerization initiator may be used if necessary.

Examples of the polymerization initiator include, but are not limited to, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate , t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, and the like; Azo compounds such as 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) '-Azobis (2-methylpropionate), and the like. These polymerization initiators may be used alone or in combination of two or more.

The amount of the polymerization initiator to be used is appropriately set according to the combination of the monomers to be used, the reaction conditions, the molecular weight of the desired polymer, and the like, and is not particularly limited. However, it is preferably 0.1 to 15 parts by mass per 100 parts by mass of the total amount of the monomer mixture . As a result, a polymer having a weight average molecular weight within a preferable range (for example, several thousands to several tens of thousands) can be easily obtained without gelation. More preferably 0.5 to 10 parts by mass.

In order to adjust the molecular weight, a chain transfer agent usually used may also be used in the polymerization. Examples of the chain transfer agent include a mercaptan chain transfer agent such as n-dodecyl mercaptan, mercaptopropionic acid, mercaptoacetic acid and methyl mercaptoacetate, and? -Methylstyrene dimer. It is preferably n-dodecyl mercaptan and / or mercaptopropionic acid which has high chain transfer effect, can reduce the residual monomer, and is easily available.

When a chain transfer agent is used, the amount of the chain transfer agent to be used may be suitably set according to the combination of the monomers to be used, the reaction conditions, the molecular weight of the desired polymer, and the like. 15 parts by mass. As a result, a polymer having a weight average molecular weight within a preferable range (for example, several thousands to several tens of thousands) can be easily obtained without gelation. More preferably 0.5 to 10 parts by mass. Particularly, in the present invention, it is preferable that the polymer (A) has a weight average molecular weight of 5,000 to 50,000. In order to obtain such a low molecular weight polymer, the chain transfer agent is used in an amount of 1 to 8 Mass part is particularly preferable.

Here, the polymer (A) preferably contains a polymerizable double bond in the side chain. By having a polymerizable double bond in the side chain, it can be cured by heat or light. Therefore, in addition to improvement in thermal decomposition resistance, sensitivity to light when the photosensitive resin composition is formed is improved, and curing with less light and mechanical strength after curing are also enhanced. As a method for introducing a polymerizable double bond into a side chain, a compound containing a functional group capable of bonding to an acid group and a polymerizable double bond (preferably at least one selected from the group consisting of an epoxy group, an oxazoline group, and a hydroxyl group A compound containing a species and a polymerizable unsaturated double bond) is added. The polymerizable unsaturated double bond is preferably a double bond having a (meth) acryloyl group in view of the reactivity of the resulting polymer.

Examples of the compound containing at least one member selected from the group consisting of an epoxy group, an oxazoline group and a hydroxyl group and a polymerizable unsaturated double bond include (meth) acrylic acid 2-hydroxyethyl, (meth) A compound having a hydroxyl group and a double bond such as hydroxypropyl, allyl alcohol and the like; A compound having a double bond with an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate or allyl glycidyl ether; And compounds having double bonds with oxazoline groups such as vinyl oxazoline and isopropenyl oxazoline. Of these, glycidyl (meth) acrylate and / or glycidyl (meth) acrylate are preferred because they have high reactivity, are easy to control the reaction, are easy to obtain, Or 3,4-epoxycyclohexylmethyl (meth) acrylate is preferable.

The addition amount of the compound having a functional group capable of bonding with the acid group and the polymerizable double bond is preferably 2 to 50 parts by mass based on 100 parts by mass of the total amount of the monomer mixture constituting the base polymer. When the addition amount of the compound is within this range, the curing property of the curable resin composition becomes higher and the strength after curing becomes more sufficient. Besides, the storage stability of the obtained polymer (side chain double bond containing polymer) is further improved, The coloration of the cured product of the resin composition is sufficiently suppressed. More preferably 2 to 45 parts by mass, still more preferably 5 to 40 parts by mass, and particularly preferably 7 to 30 parts by mass.

A method of adding a compound containing a functional group capable of bonding to an acid group and a polymerizable double bond (particularly preferably, glycidyl (meth) acrylate) to a part of the acid group in the base polymer may be a known method And is not particularly limited. For example, the reaction temperature is preferably 60 ° C to 140 ° C. Also, amine compounds such as triethylamine and dimethylbenzylamine; Ammonium salts such as tetraethylammonium chloride; A phosphonium salt such as tetraphenylphosphonium bromide, or an amide compound such as dimethylformamide is preferably used.

The double bond equivalent (molecular weight per 1 mol of the double bond) (g) of the obtained polymer (A) (in this case, the polymer (A) is a polymer having side chain double bonds) Is 300 to 4000 g / mol. When the double bond equivalent is within this range, sensitivity to light is enhanced to further improve developability, coloration upon curing is further inhibited, and storage stability and solubility in solvents are further improved. More preferably 400 to 3000 g / mol, further preferably 500 to 2000 g / mol.

The double bond equivalent is a measure of the amount of the double bond contained in the molecule. When the compound having the same molecular weight is used, the larger the value of the double bond equivalent is, the smaller the amount of the double bond introduced. The double bond equivalent can be calculated from the amount of the compound that introduces the polymer or double bond. It can be measured by various analysis such as titration and elemental analysis, NMR and IR, or differential scanning calorimetry.

(B) a polymerizable compound

The polymerizable compound (B) means a compound having a polymerizable group. Preferably, it is a compound having a polymerizable double bond.

The molecular weight of the compound (B) (converted amount of atomic weight (the number of carbon atoms is 12.01) is preferably 700 or less, more preferably 650 or less, and even more preferably 600 or less. The double bond equivalent is preferably 150 or less, more preferably 140 or less, and further preferably 110 or less. The lower limit of these is not particularly limited and may be any range within which curing is possible.

Among them, a compound having a relatively small molecular weight and a small double bond equivalent is preferable in that it can form excellent pixels. (Meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, Acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tri Tri (meth) acrylates of dipentaerythritol hexa (meth) acrylate, tris (hydroxyethyl) isocyanurate, and the like, such as trimethylolpropane tri (meth) acrylate, dipentaerythritol penta And a functional (meth) acrylate compound. That is, the compound (B) is preferably a polyfunctional (meth) acrylate compound. Among them, it is preferable to use an ethylenic compound having a molecular weight of more than 250 in view of the sensitivity of the obtained curable resin composition. Such compounds include, in particular, pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and / or dipentaerythritol Hexa (meth) acrylate and the like are preferable. When these are used, a composition having a good balance can be obtained, which is preferable.

(C) a photopolymerization initiator

Examples of the photopolymerization initiator (C) include, but are not limited to, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 4- (2- Hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2- 2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, }, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpyrpionyl) benzyl] phenyl} -2-methylpropan-1-one; Benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, 3,3 ', 4,4'-tetra (t- butylperoxycarbonyl) Phenanone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2- propenyloxy) ethyl] benzenethanaminium bromide, Benzyl) trimethylammonium chloride; 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- propanedioxanthone, 2- ( 3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone-9-one methoc chloride; Phenylglyoxylic methyl ester, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. Among them, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- Butanone-1 and the like are preferable.

Specific examples of the product include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (IRGACURE (registered trademark) 907, Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE 369; manufactured by BASF Japan).

(D) Solvent

Examples of the solvent (D) include, but are not limited to, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether and propylene glycol-t-butyl 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, dipropylene glycol monomethyl ether acetate, butyl diglycol acetate and 3-methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; Chloroform; Dimethyl sulfoxide, and the like. Of these, propylene glycol monomethyl ether acetate and / or propylene glycol monomethyl ether are preferable.

(E) Other components

The curable resin composition of the present invention may contain, in addition to the components (A) to (D) described above, a colorant such as a dye and a pigment, an aluminum hydroxide, a talc, Known additives such as fillers (barium sulfate), antifoaming agents, coupling agents, leveling agents, sensitizers, development aids, release agents, lubricants, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, polymerization inhibitors, thickeners, Other component " or " component (E) ").

The amount of the component (E) to be used may be appropriately set depending on the purpose or use, but is preferably 0.01 to 70% by mass, based on 100% by mass of the total solid content of the curable resin composition. More preferably from 0.1 to 60% by mass, and still more preferably from 0.3 to 50% by mass.

The "total solid content" means the total amount of the components forming the cured product (excluding solvents, etc. which volatilize during the formation of the cured product).

As the coloring agent, various organic or inorganic coloring agents may be used alone or in combination. As the organic colorant, organic pigments, dyes, natural pigments and the like can be used.

Specific examples of the organic pigments include yellow pigments such as C.I. Pigment Yellow 1 and 138 described in paragraphs 0103 to 0107 of Japanese Laid-Open Patent Publication No. 2015-42697; Orange pigments such as C. I. Pigment Orange 1; C. I. violet pigments such as Pigment Violet 1; Red pigments such as C.I. Pigment Red 1; Blue pigments such as C. I. Pigment Blue 1; Green pigments such as C.I. Pigment Green 1, 58; Brown pigments such as C. I. Pigment Brown 5; Black pigments such as aniline black, carbon black, lamp black, normal black, black iron, titanium black and C.I. Pigment Black 1; White pigments such as C.I. Pigment White 1, and the like. However, the coloring material of the present invention is not limited to these. The pigments may be used alone, or two or more pigments may be used in combination. "C. Quot; I. " means a color index (published by The Society of Dyers and Colourists, C. I.), and a number means a color index number.

The organic pigment preferably has a color index (C.I.) number as described below.

CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 139, CI Pigment Yellow 138, CI Pigment Yellow 150, CI Pigment Yellow 180 and CI Pigment Yellow 185 Pigment; Red series pigments such as C. I. Pigment Red 1, C. I. Pigment Red 2, C. I. Pigment Red 3, C. I. Pigment Red 254 and C. I. Pigment Red 177; Blue pigments such as C. I. Pigment Blue 15, C. I. Pigment Blue 15: 3, C. I. Pigment Blue 15: 4, C. I. Pigment Blue 15: 6 and the like; Violet based pigments such as C. I. Pigment Violet 23: 19; Pigment Green 7, Pigment Green 36 and other green pigment.

Examples of the dye include organic dyes described in, for example, JP-A-2010-9033, JP-A-2010-211198, JP-A-2009-51896 and JP-A- 2008-50599 Can be used. Among them, preferred are azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

The content ratio of the organic coloring agent (also referred to as a coloring material) (that is, the total ratio of the organic coloring agents) can be appropriately set according to the purpose or use, but a preferable range of the content of the coloring material is 100 mass% By mass to 3% by mass to 70% by mass. More preferably from 5 to 60% by mass, and still more preferably from 10 to 50% by mass. In particular, the content of the pigment is preferably 1 to 500 parts by mass, more preferably 10 to 200 parts by mass, per 100 parts by mass of the component (A).

As the inorganic colorant, an inorganic pigment and / or an extender pigment are preferable. For example, titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, red iron oxide (III), cadmium red, Black, synthetic iron black, and carbon black.

The method for preparing the curable resin composition of the present invention is not particularly limited, and conventionally known mixing methods and purification methods can be employed. It is preferable that the obtained curable resin composition is subjected to filtration treatment with a filter or the like to remove fine dust.

[Use of Curable Resin Composition]

The curable resin composition of the present invention is excellent in various physical properties such as transparency and heat resistance and can be used for, for example, resist materials, various coating agents, paints and the like. Examples of preferable applications include various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, and photoresists used in liquid crystal display devices and solid-state image pickup devices, and electric and electronic devices.

In particular, since the component (A) has an acid group, the curable resin composition of the present invention can be preferably used as an alkali developing negative resist material for producing color filters and optical waveguides. In addition, since it has a tetrahydropyran ring structure in the structure of the component (A), it can exhibit good pigment dispersibility and can be preferably used as a curable resin composition for a color filter. Particularly, in the present invention, by using a polymer having a structural unit derived from acrylic acid and a polymer having a tetrahydropyran ring structure as the component (A), a remarkable improvement in the developing speed can be achieved and therefore, it is very useful for color filter applications. Therefore, a color filter having a cured product obtained by curing the curable resin composition of the present invention on a substrate is not only excellent in various physical properties such as transparency and heat resistance, but also excellent in productivity. Such a color filter is one of the present invention.

As described above, the curable resin composition of the present invention is preferably used as a raw material of a color filter or as a raw material of an optical waveguide. In addition to these, a protective film (a protective film for a color filter, a touch panel type display device Or a dielectric film (an insulating film for a touch panel type display device, or the like).

<Color filter>

The color filter of the present invention is a color filter in which a cured resin layer is formed on a substrate, and the resin composition for imparting the cured resin layer is the curable resin composition of the present invention described above. In the color filter of the present invention, at least one of the members constituting the color filter is formed of the curable resin (resin), the resin black matrix, the protective film, and the columnar spacer. And may be formed by curing the composition.

In the color filter, it is preferable that the cured resin layer to be the three primary color (RGB) pixels, the resin black matrix, the protective film and / or the columnar spacer is formed by the curable resin composition. In the case of forming RGB pixels, the curable resin composition includes pigments of three primary colors of red, green and blue. When the resin black matrix is formed, the curable resin composition contains a black pigment. The curable resin composition in the case of forming a protective film or columnar spacer may not contain a pigment. When a pigment is included, it is preferable to incorporate a dispersing system.

The color filter can be manufactured, for example, as follows.

1) A curable resin composition containing a pigment is coated on a transparent substrate by a known coating method and dried to prepare a coated film.

Examples of the transparent substrate include glass (preferably alkali-free glass) and transparent plastic. Examples of the known coating method include a spin coating method and a spraying method, but the spin coating method is preferable. Regarding drying conditions, the drying temperature is preferably room temperature to 120 ° C, more preferably 60 to 100 ° C. The drying time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 10 minutes. Further, it is preferable to heat-dry at normal pressure or under vacuum.

2) Thereafter, a photomask (patterning film) having openings according to a desired pattern shape is placed on the coating film obtained in the above-mentioned 1) in a contact state or in a noncontact state, and light is irradiated and cured.

The term &quot; light &quot; as used herein means not only visible light but also ultraviolet rays, X-rays, and electron beams. Ultraviolet rays are most preferable. As the ultraviolet ray source, a high-pressure mercury lamp is generally preferably used.

3) After light irradiation of the above 2), development is carried out with a solvent, water, or an aqueous alkali solution. Among these, an alkali aqueous solution is preferable because it can carry out development with a low sensitivity to the environment and a high sensitivity. As the alkali component in the alkali aqueous solution, potassium hydroxide, sodium hydroxide, and / or sodium carbonate are preferable. The concentration of the alkali component is preferably 0.01 to 5% by mass in 100% by mass of the aqueous alkaline solution. When the concentration of the alkali component is within this range, the solubility of the component (A) is further improved and the developability (developing speed) can be further increased. More preferably from 0.05 to 3% by mass, and still more preferably from 0.1 to 1% by mass. To the aqueous alkali solution, a surfactant may be added.

4) The above steps 1) to 3) are carried out using a curable resin composition containing a black pigment to form a resin black matrix on the substrate.

5) Next, the above-mentioned steps 1) to 3) are repeatedly performed by sequentially changing the pigment of the curable resin composition to red (R), green (G) and blue (B) To form RGB pixels.

6) Next, a protective film is formed, if necessary, for the purpose of improving the protection and surface smoothness of the RGB pixels formed on the substrate.

7) When the color filter is a color filter for a liquid crystal display device, it is preferable to further form a columnar spacer. The columnar spacers can be produced by applying the curable resin composition to the surface on which the spacers are to be formed to a thickness corresponding to the height of the desired spacers, and through the steps 1) to 3).

Here, at the time of manufacturing the color filter, it is preferable that the color filter is heated (post-baked) after the development at the time of manufacture of each member, and it is preferable that the solvent is completely removed when the solvent remains. The post-baking temperature is preferably 120 to 300 占 폚. When the temperature is set at this temperature, the decrease of the smoothness of the coating film due to coloring and thermal decomposition of the pixels can be suppressed more sufficiently, and the hardening progresses further and the film strength becomes higher. More preferably 150 to 250 占 폚, and even more preferably 180 to 230 占 폚. Post-baking may be performed after the development in the formation of each member (after the above-mentioned 3) at the time of manufacturing each member, or may be performed after all the members are formed.

<Display device>

The color filter of the present invention can be preferably applied to a display device. In recent years, with the advancement of the technology of display devices and the like, even higher performance is strongly demanded for each member to be used. However, when the color filter of the present invention is used, The display quality of the display device and the reliability of the image quality can be sufficiently enhanced. The display device constructed using the color filter of the present invention is also one of the present invention.

The display device is not particularly limited, and for example, a liquid crystal display device, a solid-state image pickup device, a touch panel type display device, or the like is preferable. The touch panel type display device is preferably a capacitive type display device.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise stated, "part" means "mass part", "%" means "mass%", and "v / v" means volume ratio.

Evaluation of each physical property was carried out as follows.

1, weight average molecular weight

The weight average molecular weight was measured by GPC (gel permeation chromatography) using HLC-8220GPC (manufactured by Tosoh Corporation) and column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation) using polystyrene as a standard substance and tetrahydrofuran as an eluent Respectively.

2, the polymer concentration in the polymer solution

The solution obtained by dissolving 4 g of acetone in 1 g of the polymer solution was naturally dried at room temperature and further dried under reduced pressure (160 ° C / 5 mmHg) for 5 hours, then cooled in a desiccator, Respectively. Then, the nonvolatile content of the polymer solution was calculated from the weight loss amount, and this was regarded as the polymer concentration.

3, acid value

3 g of the resin solution was precisely weighed and dissolved in a mixed solvent of 90 g of acetone and 10 g of water and an automatic titration apparatus (trade name: COM-555, manufactured by Hiranuma Industrial Co., Ltd.) , The acid value of the polymer solution was determined and the acid value per 1 g of the solid content was determined from the acid value of the solution and the solid content of the solution.

4, Developability evaluation

The curable resin composition was coated on a glass substrate having a length of 10 cm by a spin coater and dried in an oven at 90 캜 for 3 minutes. After drying, a 20 m line-and-space pattern photomask was placed at a distance of 100 mu m from the coating film and irradiated with a UV aligner (TME-150RNS, TOPCON) equipped with a 2.0 kW ultrahigh pressure mercury lamp at 100 mJ / Cm &lt; 2 &gt; (365 nm in terms of roughness). After the irradiation with ultraviolet light, 0.05% aqueous potassium hydroxide solution was dispersed in a spin developing machine under the condition of 10 to 60 seconds to dissolve and remove the unexposed portions, and the remaining exposed portions were washed with pure water for 10 seconds. After the development, the formation speed of 20 탆 line and space was checked with a laser microscope (VK-9700, manufactured by Keens) and the developing speed was evaluated in the shortest time for completely removing the unexposed portion.

Monomer Synthesis Example 1 (Synthesis of ether dimer composition)

450.0 parts of methyl? -Hydroxymethyl acrylate (RHMA-M) and 13.5 parts of 1,4-diazabicyclo [2.2.2] octane (DABCO) were added to a reactor equipped with a stirrer, And 0.9 parts of p-methoxyphenol (MEHQ) were charged, and the mixture was heated to 90 DEG C while stirring. After the inner temperature reached 85 캜, the reactor was allowed to react for 9 hours while maintaining 90 캜 and 5 캜 at normal pressure.

After confirming that the reaction liquid temperature became 40 캜 or less, 355.0 parts of methanol (MeOH) was added and diluted (condition: normal pressure, 35 賊 5 캜).

The MeOH diluent was added dropwise to a different reactor containing 1485.0 parts of water and the RHMA ether dimer was crystallized (conditions: normal pressure, 30 DEG C or less). Thereafter, the obtained slurry containing the RHMA ether dimer was filtered using a pressure filter (under the conditions of normal pressure to 0.1 MPa and 15 DEG C or less), and then the filter cake was washed with water (atmospheric pressure to 0.1 MPa, room temperature) . In the cleaning, the cleaning was repeated three times using 380.0 parts of water per one time.

184.0 parts of propylene glycol monomethyl ether acetate (PGMEA) was added and dissolved in the thus obtained RHMA ether dimer cake (condition: normal pressure, 60 DEG C). This was separated into an oil layer containing RHMA ether dimer and an aqueous layer, and the aqueous layer was removed (condition: normal pressure, 60 DEG C). The oil layer was 412.5 parts, and the removed water layer was 141.9 parts.

To the oil layer (a solution containing RHMA ether dimer and PGMEA), PGMEA (5200.0 parts), MEHQ 0.049 parts, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4H- ) Was added to obtain 932.5 parts of a composition (ether dimer composition).

Further, the amount of the crosslinkable compound (ester dimer, trimer) of the side-reaction product was an amount below the detection limit. Each composition was analyzed by gas chromatography, Karl Fischer moisture meter, and spectrophotometer. The analysis results are shown below.

&Lt; Analysis result of ether dimer composition &gt;

Dimethyl-2,2 '- [oxybis (methylene)] bis-2-propenoate (MD): 25.0 mass%

Water: 1.3 mass%

PGMEA: 73.7 mass%

MEHQ: 53 ppm

4H-TEMPO: 6 ppm

In the following Synthesis Examples 1 to 9, the ether dimer composition obtained as described above was used as the MD. The amount of MD used in Synthesis Examples 1 to 9 is the amount of the MD.

Synthesis Example 1 (Synthesis of Resin Solution 1)

20 parts by mass of dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate (hereinafter referred to as &quot; MD &quot;) as a monomer dropping vessel was prepared, while a separable flask equipped with a cooling tube was provided as a reaction tank. , 30 parts by mass of cyclohexyl methacrylate (hereinafter referred to as "CHMA"), 24 parts by mass of methyl methacrylate (hereinafter referred to as "MMA"), 26 parts by mass of acrylic acid (hereinafter referred to as "AA" And 2 parts by mass of butyl peroxy-2-ethylhexanoate (trade name "Perbutyl O", manufactured by Nippon Oil and Fats Co., Ltd., hereinafter referred to as "PBO") were thoroughly stirred and mixed to prepare n-dodecanethiol (Hereinafter referred to as &quot; n-DM &quot;) and 32 parts by mass of propylene glycol monomethyl ether acetate (hereinafter referred to as &quot; PGMEA &quot;).

128 parts by mass of PGMEA was poured into the reaction vessel, purged with nitrogen, and heated in an oil bath with stirring to raise the temperature of the reactor to 90 占 폚. After the temperature of the reaction vessel was stabilized at 90 캜, the dropwise addition was started from the monomer dropping tank and the chain transfer agent dropping tank. The reaction was carried out for 135 minutes while keeping the temperature at 90 캜. After 60 minutes from the completion of the dropwise addition, the temperature was elevated to 110 占 폚 and maintained at 110 占 폚 for 3 hours. Once the internal temperature was cooled to room temperature, a gas introduction tube was attached to the separable flask to start bubbling of an oxygen / nitrogen = 5/95 (v / v) mixed gas. Subsequently, 28 parts of glycidyl methacrylate (hereinafter referred to as "GMA"), 0.10 part of 6-t-butyl-2,4-xylenol, 0.4 part of triethylamine (hereinafter referred to as "TEA" And the mixture was allowed to react at 110 캜 for 12 hours. Thereafter, 96 parts of PGMEA was added and the mixture was cooled to room temperature to obtain a resin solution 1 having a concentration of 33%. The weight average molecular weight and acid value of the component (A) (polymer (A)) in the resin solution 1 are shown in Table 1.

30 parts of the resin solution 1 obtained in Synthesis Example 1 was put in a 50 ml glass screw bottle and sealed and kept in a constant temperature bath at 25 캜 for 12 months. After 12 months, the weight average molecular weight was measured and found to be 16500, and the gel bottle was not observed in the screw bottle, and storage stability was good.

Synthesis Example 2 (Synthesis of Resin Solution 2)

A procedure similar to that for the synthesis of the resin solution 1 was carried out except that benzyl methacrylate (hereinafter referred to as &quot; BzMA &quot;) was used instead of cyclohexyl methacrylate to obtain a resin solution 2 having a concentration of 33%. Table 1 shows the weight average molecular weight and acid value of the component (A) (polymer (A)) in the resin solution 2.

Synthesis Example 3 (Synthesis of Resin Solution 3)

20 parts by mass of MD, 30 parts by mass of CHMA, 32.6 parts by mass of MMA, 17.4 parts by mass of AA and 3 parts by mass of PBO were thoroughly stirred and prepared as a monomer dropping vessel equipped with a cooling tube, , 4.5 parts by mass of n-DM as a chain transfer agent dropping vessel, and 32 parts by mass of PGMEA were well mixed with stirring.

128 parts by mass of PGMEA was poured into the reaction vessel, purged with nitrogen, and heated in an oil bath with stirring to raise the temperature of the reactor to 90 占 폚. After the temperature of the reaction vessel was stabilized at 90 캜, the dropwise addition was started from the monomer dropping tank and the chain transfer agent dropping tank. The reaction was carried out for 135 minutes while keeping the temperature at 90 캜. After 60 minutes from the completion of the dropwise addition, the temperature was elevated to 110 占 폚 and maintained at 110 占 폚 for 3 hours. Once the internal temperature was cooled to room temperature, a gas introduction tube was attached to the separable flask to start bubbling of an oxygen / nitrogen = 5/95 (v / v) mixed gas. Subsequently, 8.3 parts of GMA, 0.10 parts of 6-t-butyl-2,4-xylenol and 0.4 part of TEA were poured into the reaction tank, and the mixture was reacted at 110 ° C for 12 hours. Thereafter, 58 parts of PGMEA was added and the mixture was cooled to room temperature to obtain a resin solution 3 having a concentration of 33%. The weight average molecular weight and acid value of the component (A) (polymer (A)) in the resin solution 3 are shown in Table 1.

Synthesis Example 4 (Synthesis of Resin Solution 4)

20 parts by mass of MD, 30 parts by mass of CHMA, 36.6 parts by mass of MMA, 13.4 parts by mass of AA and 1.5 parts by mass of PBO were thoroughly stirred and prepared as a monomer dropping vessel equipped with a cooling tube, , 2.7 parts by mass of n-DM as a chain transfer agent dropping vessel, and 32 parts by mass of PGMEA were well mixed with stirring.

128 parts by mass of PGMEA was poured into the reaction vessel, purged with nitrogen, and heated in an oil bath with stirring to raise the temperature of the reactor to 90 占 폚. After the temperature of the reaction vessel was stabilized at 90 캜, the dropwise addition was started from the monomer dropping tank and the chain transfer agent dropping tank. The reaction was carried out for 135 minutes while keeping the temperature at 90 캜. After the completion of the dropwise addition, the temperature was elevated to 60 minutes, the reaction tank was kept at 110 占 폚, and the reaction was maintained at 110 占 폚 for 3 hours. Thereafter, 41 parts of PGMEA was added and the mixture was cooled to room temperature to obtain a resin solution 4 having a concentration of 33%. The weight average molecular weight and the acid value of the component (A) (polymer (A)) in the resin solution 4 are shown in Table 1.

Synthesis Example 5 (Synthesis of Resin Solution 5)

20 parts by mass of MD, 30 parts by mass of CHMA, 30.7 parts by mass of MMA, 19.3 parts by mass of AA and 2 parts by mass of PBO were thoroughly stirred and prepared as a monomer dropping vessel equipped with a cooling tube was prepared , 5 parts by mass of n-DM as a chain transfer agent dropping vessel, and 32 parts by mass of PGMEA were well mixed with stirring.

128 parts by mass of PGMEA was poured into the reaction vessel, purged with nitrogen, and heated in an oil bath with stirring to raise the temperature of the reactor to 90 占 폚. After the temperature of the reaction vessel was stabilized at 90 캜, the dropwise addition was started from the monomer dropping tank and the chain transfer agent dropping tank. The reaction was carried out for 135 minutes while keeping the temperature at 90 캜. After the completion of the dropwise addition, the temperature was elevated to 60 minutes, the reaction tank was kept at 110 占 폚, and the reaction was maintained at 110 占 폚 for 3 hours. Thereafter, 45 parts of PGMEA was added and the mixture was cooled to room temperature to obtain a resin solution 5 having a concentration of 33%. The weight average molecular weight and the acid value of the component (A) (polymer (A)) in the resin solution 5 are shown in Table 1.

Synthesis Example 6 (Synthesis of Resin Solution 6)

20 parts by mass of MD, 30 parts by mass of CHMA, 19 parts by mass of MMA, 31 parts by mass of methacrylic acid (hereinafter referred to as &quot; MAA &quot;) and 20 parts by mass of PBO 2 parts by mass were thoroughly stirred and mixed, and 4 parts by mass of n-DM and 32 parts by mass of PGMEA were thoroughly stirred and mixed as a chain transfer agent dropping vessel.

128 parts by mass of PGMEA was poured into the reaction vessel, purged with nitrogen, and heated in an oil bath with stirring to raise the temperature of the reactor to 90 占 폚. After the temperature of the reaction vessel was stabilized at 90 캜, the dropwise addition was started from the monomer dropping tank and the chain transfer agent dropping tank. The reaction was carried out for 135 minutes while keeping the temperature at 90 캜. After 60 minutes from the completion of the dropwise addition, the temperature was elevated to 110 占 폚 and maintained at 110 占 폚 for 3 hours. Once the internal temperature was cooled to room temperature, a gas introduction tube was attached to the separable flask to start bubbling of an oxygen / nitrogen = 5/95 (v / v) mixed gas. Subsequently, 28 parts of GMA, 0.10 parts of 6-t-butyl-2,4-xylenol and 0.4 part of TEA were poured into the reaction tank, and the mixture was immediately reacted at 110 DEG C for 12 hours. Thereafter, 96 parts of PGMEA was added and the mixture was cooled to room temperature to obtain a resin solution 6 having a concentration of 33%. The weight average molecular weight and acid value of the polymer in the resin solution 6 are shown in Table 1.

Synthesis Example 7 (Synthesis of Resin Solution 7)

A resin solution 7 having a concentration of 33% was obtained by carrying out the same operation as in the synthesis of the resin solution 6 except that benzyl methacrylate (hereinafter referred to as &quot; BzMA &quot;) was used instead of cyclohexyl methacrylate. The weight average molecular weight and acid value of the polymer in this resin solution 7 are shown in Table 1.

Synthesis Example 8 (Synthesis of Resin Solution 8)

20 parts by mass of MD, 30 parts by mass of CHMA, 44 parts by mass of MMA, 16 parts by mass of MAA and 1.5 parts by mass of PBO were thoroughly stirred and prepared as a monomer dropping vessel equipped with a cooling tube, , 3 parts by mass of n-DM as a chain transfer agent dropping vessel, and 32 parts by mass of PGMEA were well mixed with stirring.

128 parts by mass of PGMEA was poured into the reaction vessel, purged with nitrogen, and heated in an oil bath with stirring to raise the temperature of the reactor to 90 占 폚. After the temperature of the reaction vessel was stabilized at 90 캜, the dropwise addition was started from the monomer dropping tank and the chain transfer agent dropping tank. The reaction was carried out for 135 minutes while keeping the temperature at 90 캜. After the completion of the dropwise addition, the temperature was elevated to 60 minutes, the reaction tank was kept at 110 占 폚, and the reaction was maintained at 110 占 폚 for 3 hours. After that, 40 parts of PGMEA was added and the mixture was cooled to room temperature to obtain a resin solution 8 having a concentration of 33%. The weight average molecular weight and acid value of the polymer in the resin solution 8 are shown in Table 1.

Synthesis Example 9 (Synthesis of Resin Solution 9)

20 parts by mass of MD, 30 parts by mass of CHMA, 27 parts by mass of MMA, 23 parts by mass of MAA and 2 parts by mass of PBO were thoroughly stirred and prepared as a monomer dropping vessel equipped with a cooling tube, , 5.6 parts by mass of n-DM as a chain transfer agent dropping vessel, and 32 parts by mass of PGMEA were well mixed with stirring.

128 parts by mass of PGMEA was poured into the reaction vessel, purged with nitrogen, and heated in an oil bath with stirring to raise the temperature of the reactor to 90 占 폚. After the temperature of the reaction vessel was stabilized at 90 캜, the dropwise addition was started from the monomer dropping tank and the chain transfer agent dropping tank. The reaction was carried out for 135 minutes while keeping the temperature at 90 캜. After the completion of the dropwise addition, the temperature was elevated to 60 minutes, the reaction tank was kept at 110 占 폚, and the reaction was maintained at 110 占 폚 for 3 hours. Thereafter, 44 parts of PGMEA was added and the mixture was cooled to room temperature to obtain a resin solution 9 having a concentration of 33%. The weight average molecular weight and acid value of the polymer in the resin solution 9 are shown in Table 1.

Synthesis Example 10 (Synthesis of Resin Solution 10)

Separable flask equipped with a cooling tube was provided as a reaction tank. On the other hand, 10 parts by mass of MD, 73 parts by mass of CHMA, 17 parts by mass of MAA and 2 parts by mass of PBO were thoroughly stirred and mixed as a monomer dropping vessel. 14 parts by mass of n-DM and 32 parts by mass of PGMEA were well mixed with stirring.

128 parts by mass of PGMEA was poured into the reaction vessel, purged with nitrogen, and heated in an oil bath with stirring to raise the temperature of the reactor to 90 占 폚. After the temperature of the reaction vessel was stabilized at 90 캜, the dropwise addition was started from the monomer dropping tank and the chain transfer agent dropping tank. The reaction was carried out for 135 minutes while keeping the temperature at 90 캜. After the completion of the dropwise addition, the temperature was elevated to 60 minutes, the reaction tank was kept at 110 占 폚, and the reaction was maintained at 110 占 폚 for 3 hours. Thereafter, 44 parts of PGMEA was added and the mixture was cooled to room temperature to obtain a resin solution 10 having a concentration of 35%. The weight average molecular weight and acid value of the polymer in the resin solution 10 are shown in Table 1.

Production Example 1 (Production of Pigment Dispersion 1)

12.9 parts of propylene glycol monomethyl ether acetate, 0.4 part of Diparron DA-7301 as a dispersing agent, 2.25 parts of CI Pigment Green 58 as a coloring material and 1.5 parts of CI Pigment Yellow 138 were dispersed and dispersed in a paint shaker for 3 hours To obtain a pigment dispersion 1.

Example 1

2.0 parts of Resin Solution 1, 0.70 parts of dipentaerythritol hexaacrylate as a polymerizable compound, 0.35 parts of Irgacure 369 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, 8.5 parts of pigment dispersion 1, , And 6.57 parts of propylene glycol monomethyl ether acetate were mixed to obtain a curable resin composition 1. This curable resin composition 1 was spin-coated on a glass substrate, and the developability evaluation (measurement of development time) was carried out under the above conditions.

Examples 2 to 5 and Comparative Examples 1 to 5

The curable resin compositions 2 to 10 were obtained in the same manner as in Example 1 except that the blend shown in Table 2 was used, and then the development time was measured. The results are shown in Table 2.

Incidentally, the amount of each component in Table 2 is a solid amount.

From the results in Table 2, the following were confirmed.

The curable resin compositions obtained in Examples 1 to 5 include all the components (A) to (D) of the present invention. In particular, all of the resin solutions 1 to 5 used in Examples 1 to 5 include a polymer obtained by polymerizing a monomer mixture containing the monomer represented by the above general formula (1) and acrylic acid as the component (A). On the other hand, all of the resin solutions 6 to 10 used in Comparative Examples 1 to 5 are different from the resin solutions 1 to 5 in that they contain a polymer obtained by using methacrylic acid instead of acrylic acid as the acid group-containing monomer. Particularly, in the resin solution 1 (Example 1) and the resin solution 6 (Comparative Example 1), the polymer containing substantially the same composition except for the kind of the acid group-containing monomer (acrylic acid or methacrylic acid) will be. (Comparative Example 2), Resin Solution 4 (Example 4), Resin Solution 8 (Comparative Example 3), and Resin Solution 5 (Example 5) and Resin Solution 9 (Comparative Example 4) can be said to be the same. Comparing Examples 1, 2, 4, and 5 with Comparative Examples 1, 2, 3, and 4, the cured products were obtained under the same conditions and evaluated for developing performance. In Comparative Examples 1 to 4 In Embodiments 1, 2, 4 and 5, it is clear that the developing speed is greatly shortened. It has also been confirmed that the development time is shortened by decreasing the weight average molecular weight of the resin (polymer) contained in the resin solution to be used and / or increasing the acid value.

Example 5 (resin solution 5: acrylic acid resin) using a resin (polymer) having a molecular weight of 10,000 and an acid value of 150, which tends to have a high developing speed, and Comparative Example 4 (resin solution 9: methacrylic acid resin ), The developing time in Example 5 was 15 seconds, which was much shorter than that in Comparative Example 4 (developing time: 35 seconds).

From the above, the superiority of using acrylic acid as the monomer raw material of the resin can be confirmed.

In addition, it was confirmed that the composition and physical properties adjusted in the above examples exerted advantageous effects within the preferable ranges described in this specification.

Although not shown in the table, all of the cured products obtained in Examples were excellent in various physical properties such as adhesiveness to a substrate, heat resistance, solvent resistance and transparency. All of the curable resin compositions obtained in the examples were also excellent in curability. Further, evaluation of the storage stability (test at 40 占 폚 for 1 month) of each of the curable resin compositions obtained in the examples showed that storage stability was excellent because no precipitate or gel was produced.

The display device member and the display device including the cured product formed by the curable resin composition of the present invention can be preferably used in the optical field and the electric / electronic field.

Claims (7)

A curable resin composition comprising (A) a polymer having a cyclic structure in its main chain, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D)
The polymer (A) is obtained by polymerizing a monomer mixture comprising a monomer represented by the following general formula (1) and acrylic acid.
[Chemical Formula 1]

In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group of 1 to 25 carbon atoms which may have a substituent. The method according to claim 1,
As the monomer represented by the general formula (1), an ether dimer composition comprising the monomer represented by the general formula (1) and water is used,
Wherein the water content is 0.1 to 10% by mass based on 100% by mass of the total amount of the ether dimer composition. 3. The method according to claim 1 or 2,
Wherein the monomer mixture further comprises a monomer having a cyclic structure. 4. The method according to any one of claims 1 to 3,
The polymer (A) has a weight average molecular weight of 5,000 to 50,000 and an acid value of 50 to 200 mgKOH / g. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 4. A color filter having the cured product according to claim 5 on a substrate. A display device comprising the color filter according to claim 6.