TW201610576A - Curable resin composition and color filter - Google Patents

Abstract

This invention aims at providing a curable resin composition that is able to further increase the speed of development, stably performing curability and post-curing solvent resistance, high capability in sealing with substrate (base material), thermal resistance and transparency and other physical properties, moreover, to maintain excellent storage stability and is useful for applications like color filters. In addition, this invention provides a cured product formed by the curable resin composition and a color filter and display device using the cured product. A curable resin composition comprises (A) a polymer having a ring structure in the main chain, (B) polymerizable compound, (C) photopolymerization initiator and (D) solvent. The polymer (A) is obtained by polymerizing a monomer represented by a specific structural formula and a monomer mixture of acrylic acid.

Description

Curable resin composition and color filter

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

The industry has studied various curable resin compositions which can be cured by heat or active energy rays, for example, in various applications such as optical members, motors, and electronic equipment, and has been developed to have excellent curability in various applications. Resin composition. An example of a specific use is a color filter which is a main component such as a liquid crystal display device or a solid-state image sensor, and is usually constituted by a substrate having at least three primary colors (red (R), green (G). ), a blue (B) pixel, a resin black matrix (BM) that separates the pixels, and a protective film that is provided to cover, protect the pixel and the resin black matrix, and flatten the unevenness.

In general, in the case of forming a pixel of a color filter using a curable resin composition, the following steps are performed for one color of a pixel, and the same steps as the above are repeated for each color: (1) a coating step, which is tied to (2) an exposure step of applying a resist film formed on the entire surface of the substrate to the resist film formed by the coating step, and performing pattern exposure through the photomask to cure the exposed portion, thereby insolubilizing the hardened portion And (3) a development and baking (baking) treatment step of removing the unexposed portion by the developer, and then baking (baking) the exposure portion into one Step hardening. In recent years, in order to improve productivity, it is required to speed up the development speed of the above (3). Therefore, for example, the methods described in Patent Documents 1 to 3 have been proposed.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-145719

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-270208

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2010-266740

As described above, a method useful for accelerating the development speed is proposed by Patent Documents 1 to 3 and the like. However, even with these methods, there is a tendency that the development speed is still slow.

The present invention has been made in view of the above circumstances, and an object of the invention is to provide a further improvement in development speed, which can stably exhibit curability, solvent resistance after curing, adhesion to a substrate (substrate), heat resistance, and A curable resin composition which is excellent in various storage properties such as transparency and is excellent in storage stability and is useful for various applications such as color filters. Moreover, an object of the present invention is to provide a cured product formed of such a curable resin composition, and a color filter and a display device using the cured product.

The inventors of the present invention conducted various studies on a curable resin composition useful for various uses such as a color filter, and as a result, found that (A) a polymer having a ring structure in the main chain and (B) a polymerizable property. a compound, (C) a photopolymerization initiator, and (D) a curable resin composition of a solvent, and the polymer (A) is a monomer which contains a specific monomer as an ether dimer and acrylic acid The polymer obtained by polymerizing the mixture can shorten the development time during alkaline development, It can further improve productivity and reduce manufacturing costs. In general, when an alkali-soluble resin used in a color filter or the like is obtained, methacrylic acid is more often used as an acid group-containing monomer than acrylic acid. The reason for this is that the use of methacrylic acid further enhances the heat resistance of the alkali-soluble resin. However, the present inventors have found that, contrary to such prior art knowledge, by using acrylic acid as one of the monomers for providing the polymer (A), it is more remarkable than when methacrylic acid is used. Shorten the development time during alkaline development.

Such a curable resin composition is particularly useful for a color filter application, and a resin composition for forming a pixel for a color filter is preferable. Therefore, it has been found that a cured product, a color filter, and a display device formed of such a curable resin composition can be used in the field of optics, motors, and electronics as long as they can sufficiently meet the demands of high productivity and high performance in recent years. The field is extremely useful, and it is thought that the above problems can be completely solved, and the present invention has been completed.

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

In the formula, 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.

In the present invention, it is preferred to use a composition comprising the monomer and water ether dimer represented by the above formula (1) as the monomer represented by the above formula (1). In this case, the water content is preferably. It is 0.1 to 10% by mass based on 100% by mass of the total of the ether dimer composition.

The above monomer mixture preferably further contains 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.

Moreover, the present invention is also a cured product obtained by hardening the above-mentioned curable resin composition.

Further, the present invention is also a color filter having the above-described cured product on a substrate.

Moreover, the present invention is also a display device which is constructed using the above-described color filter.

Since the curable resin composition of the present invention has the above-described configuration, the developability is good, and the development speed can be further improved, and the curability, the solvent resistance after curing, and the adhesion to the substrate (substrate) can be stably exhibited. It has various physical properties such as properties, heat resistance, and transparency, and is excellent in storage stability, and is useful for various applications such as color filters. Therefore, a color filter and a display device having a cured product (cured film) formed of such a curable resin composition are very useful in the field of optics, motors, and electronics.

The invention will be described in detail below. A preferred embodiment of the present invention is a combination of two or more of the preferred embodiments of the present invention described below. In addition, "A~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 contains (A) a polymer having a ring structure in a main chain, (B) a polymerizable compound, (C) a photopolymerization initiator, and ( D) A solvent, and one or two or more types of these components may be used. Further, one or two or more other components may be further contained as needed.

In the present specification, (A) a polymer having a ring structure in the main chain is also referred to as "polymer (A)" or "(A) component", and (B) a polymerizable compound is also referred to as "compound (B). ") or "(B) component", (C) photopolymerization initiator is also referred to as "(C) component", and (D) solvent is also referred to as "(D) component". Moreover, "(meth)acrylic acid" is a expression expressing both methacrylic acid and acrylic acid.

The content ratio of the components (A) to (C) is not particularly limited. For example, it is preferably 20 to 300 parts by mass based on 100 parts by mass of the component (A), and 5 to 50 parts by mass of the component (C). Share. Thereby, it becomes a harder and transparency. More preferably, the component (B) is 30 to 200 parts by mass, and the component (C) is 10 to 50 parts by mass based on 100 parts by mass of the component (A). Further, the content ratio of the component (D) is, for example, preferably 20 to 5000 parts by mass based on 100 parts by mass of the component (A). More preferably 50 to 2000 parts by mass.

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

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

The polymer (A) is a monomer represented by the above formula (1) (also referred to as "ether dimerization" a polymer obtained by polymerizing a monomer mixture with acrylic acid. It is presumed that by using an ether dimer, the ether dimer undergoes a cyclization reaction at the time of polymerization to form a tetrahydropyran ring structure (main chain ring structure) in a constituent unit of the polymer. The curable resin composition containing such a polymer (A) can provide a cured product which is excellent in heat resistance, surface hardness, adhesion, and high temperature exposure such as post-bake (heat treatment). The subsequent change over time is further suppressed to stably exhibit various physical properties.

The acid value (AV) of the above polymer (A) is preferably from 50 to 200 mgKOH/g. Thereby, sufficient alkali solubility can be exhibited, and a cured product which is more excellent in developability (developing speed) can be provided. More preferably, it is 60 to 180 mgKOH/g, further preferably 70 to 160 mgKOH/g, and 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 above polymer (A) is not particularly limited, and is, for example, preferably from 5,000 to 50,000. When the viscosity is 5,000 or more, the heat resistance can be more sufficiently exhibited. Further, when the viscosity of the curable resin composition is more than 50,000, the coating film can be easily formed, and the developability is further improved. More preferably, it is 6,000 to 30,000, and further 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"), or may be introduced into a double bond as described below. A polymer formed by a side chain of the base polymer (also referred to as a polymer having a double bond in a side chain or a polymer having a side chain double bond). Such a polymer having a side chain double bond is also included in the polymer (A) referred to in the present invention. Better from the viewpoints of photosensitivity or hardenability, heat decomposition resistance, etc. It is a polymer containing a side chain double bond.

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

- the raw material component (monomer, etc.) of the polymer (A) -

(i) ether dimer

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

In the above 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 a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, and a t-butyl group. a linear or branched alkyl group such as a third amyl group, a stearyl group, a lauryl group or a 2-ethylhexyl group; an aryl group such as a phenyl group; a cyclohexyl group, a tert-butylcyclohexyl group, and a dicyclopentadiene group; Alicyclic groups such as trimethylsulfonyl, isodecyl, adamantyl, 2-methyl-2-adamantyl; 1-methoxyethyl, 1-ethoxyethyl, etc. a group-substituted alkyl group; and an aryl group-substituted alkyl group such as a benzyl group. Among these, in terms of heat resistance, a group having a primary or secondary carbon which is not easily desorbed by acid or heat such as a methyl group, an ethyl group, a cyclohexyl group or a benzyl group is particularly preferable. Further, the carbon number of the hydrocarbon group is preferably from 1 to 12, more preferably from 1 to 8. Furthermore, R ¹ and R ^{2 may} be the same group or different bases.

Specific examples of the ether dimer include 2,2'-[oxybis(methylene)]bis-2-carboxylate, 2,2'-[oxy Bis(methylene)]di-2-ethyl acrylate, 2,2'-[oxybis(methylene)]bis-2-propenyl bis(n-propyl) ester, 2,2'-[ Di(isopropylidene) bis(methylene)]bis-2-acrylate, di(n-butyl) 2,2'-[oxybis(methylene)]bis-2-propenoate, 2,2'-[oxybis(methylene)]bis(isobutyl) bis-2-acrylate, 2,2'-[oxybis(methylene)]bis-2-propenoic acid di Tert-butyl)ester, 2,2'-[oxybis(methylene)]bis-2-propenoic acid di(tripentyl)ester, 2,2'-[oxybis(methylene) Bis(stearyl) bis-2-acrylate, bis(lauryl) 2,2'-[oxybis(methylene)]bis-2-acrylate, 2,2'-[oxy double (methylene)] bis(2-ethylhexyl) bis-2-acrylate, bis(1-methoxyethyl) 2,2'-[oxybis(methylene)]bis-2-propenoacrylate Ester, 2,2'-[oxybis(methylene)]bis-2-propenyl bis(1-ethoxyethyl), 2,2'-[oxybis(methylene)] Dibenzyl 2--2-propenoate, 2,2'-[oxybis(methylene)]bis-2-acrylate diphenyl, 2,2 ^' -[oxybis(methylene)]dicyclohexyl bis-2-acrylate, 2,2'-[oxybis(methylene)]bis-2-propenoic acid di(t-butylcyclohexyl) Ester, 2,2'-[oxybis(methylene)]bis-2-cyclopentadienyl bis-2-acrylate, 2,2'-[oxybis(methylene)] double Bis(tricyclodecyl) acrylate, bis(isodecyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, 2,2'-[oxy double (methylene)] bis-adamantyl bis-2-carboxylate, bis(2-methyl-2-adamantyl) 2,2'-[oxybis(methylene)]bis-2-propenoic acid Ester and the like. Among these, dimethyl 2,2'-[oxybis(methylene)]bis-2-acrylate and 2,2'-[oxybis(methylene)]bis-2 are particularly preferred. - diethyl acrylate, 2,2'-[oxybis(methylene)]bis-2-cyclohexyl acrylate, and/or 2,2'-[oxybis(methylene)] double 2-Benzyl acrylate.

The content ratio of the ether dimer in the monomer mixture of the above polymer (A) is not particularly limited, and 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 which is more excellent in coating film properties such as transparency and heat resistance can be obtained. Further, it is preferably 60% by mass or less. Thereby, at the time of polymerization, a low molecular weight can be obtained more easily, and gelation can be sufficiently suppressed. More preferably, it is 2 to 60% by mass, further preferably 5 to 55% by mass, and particularly preferably 5 to 50% by mass.

Further, the content ratio of the ether dimer in the monomer mixture herein means the net content of the ether dimer. That is, even when the ether dimer composition containing an ether dimer and water is used as an ether dimer as described below, it is preferred to set only the amount of the ether dimer therein to the above. The range of good.

In the present invention, as the monomer (ether dimer) represented by the above formula (1), a composition containing a monomer and water represented by the above formula (1) is preferably used (also referred to as a monomer). "Ether dimer composition"). In this case, the content of water in the ether dimer composition is preferably from 0.1 to 10% by mass based on 100% by mass based on the total amount of the ether dimer composition. Thereby, the storage stability of the above ether dimer is improved, and the storage stability of the obtained polymer (A) and the curable resin composition is also improved. Further, within this range, storage stability at high temperatures and storage stability at low temperatures are improved. The content of water is 100% by mass based on the total amount of the ether dimer composition, more preferably 0.3 to 10% by mass, still more preferably 0.5 to 7% by mass, still more preferably 0.7 to 5% by mass, most preferably 1 ~3 mass%.

The water to be used in the ether dimer composition is not particularly limited, and is preferably pure water. If the cost is taken into consideration, it is more preferably ion-exchanged water passing through an ion exchange resin which is usually used.

In the ether dimer composition, the content of the monomer (ether dimer) represented by the above formula (1) is not particularly limited, and is, for example, 100% by mass based on the total amount of the ether dimer composition. It is preferably 10 to 70% by mass. When it is in this range, the storage stability of the ether dimer is further improved, and 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, it is 15 to 40% by mass, and further preferably 20 to 30% by mass.

The ether dimer composition preferably contains a stabilizer and/or a nonaqueous solvent in addition to the monomer represented by the above formula (1) and water. Thereby, the storage stability is further improved. In addition, one or two or more types of each component contained in the ether dimer composition may be used.

The above stabilizer is a compound having a function of preventing radical polymerization or oxidative degradation. For example, a compound which is generally used as a polymerization inhibitor or an antioxidant can be used, and is not particularly limited. Specific examples thereof include a phenol compound, a copper salt of an organic acid, and a phenothiene. Classes, phosphites, thioethers, hindered amine compounds, ascorbic acid, thiocyanates, thiourea derivatives, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, N-oxygen An oxyl compound or the like. Among these, a hydroxyl group-containing compound having a ring structure is preferable in terms of coloring, compatibility, and the like, and a phenol compound is more preferable. Specific examples thereof include hydroquinone, methyl hydroquinone, trimethyl hydroquinone, tert-butyl hydroquinone, p-methoxyphenol, and 6-tert-butyl-2. , 4-xylenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methoxyphenol, 2,2'-methylenebis(4-methyl- 6-tert-butylphenol) and the like. Further, an N-oxyl radical compound is also preferable, and specific examples thereof include derivatives of 2,2,6,6-tetramethylpiperidine-1-oxyl radical, and 4-hydroxy-2 is exemplified. , 2,6,6-tetramethylpiperidine-1-oxyl radical, and the like.

The above stabilizers may be used alone or in combination of two or more. In terms of the storage stability of the ether dimer, the phenol compound and the N-oxyl radical compound are preferably used in combination. The mass ratio of the phenol compound/N-oxyl radical compound is preferably 15/1 to 5/1. More preferably, it is a ratio of 10/1 to 7/1, and further preferably a ratio of 8/1.

In the ether dimer composition, the content of the stabilizer is not particularly limited, and is, for example, 100% by mass based on the total amount of the ether dimer composition, preferably 0.001 to 1% by mass. If it is in this range, storage stability is further improved, and the coloring or the decrease in polymerizability during storage is more sufficiently suppressed. More preferably, it is 0.002 to 0.1% by mass, and further preferably 0.003 to 0.05% by mass.

The above nonaqueous solvent is capable of uniformly dissolving ether dimer, water and stabilizer The organic solvent is not limited. Specifically, it is preferably at least selected from the group consisting of an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, an aromatic solvent, a guanamine solvent, a nitrile solvent, and an anthraquinone solvent. 1 solvent.

Specific examples of the solvents are described below.

(alcohol solvent)

Monools such as methanol, ethanol, isopropanol, n-butanol, and second butanol; glycols such as ethylene glycol and propylene glycol; and polyhydric alcohols such as glycerin.

(ether solvent)

Tetrahydrofuran, two a cyclic ether such as an alkane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, a glycol monoether such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether or 3-methoxybutanol; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, Glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, and propylene glycol diethyl ether.

(ester solvent)

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 acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate And esters of glycol monoethers such as dipropylene glycol monobutyl ether acetate and 3-methoxybutyl acetate; and methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and C Methyl ester, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Propionic acid An alkyl ester such as methyl ester, ethyl 3-ethoxypropionate, methyl acetonitrile acetate or ethyl acetate ethyl acetate.

(ketone solvent)

A ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone.

(aromatic solvent)

An aromatic hydrocarbon such as benzene, toluene, xylene or ethylbenzene.

(amide solvent)

An amide such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone.

(nitrile solvent)

Acetonitrile, propionitrile, benzonitrile, etc.

(Alonite solvent)

Dimethyl adenine and the like.

The type 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, the production conditions of the polymer (A) or the curable resin composition, and the like. For example, when the curable resin composition of the present invention is used for a resist application, it is preferably used as a nonaqueous solvent as a solvent constituting a resist (also referred to as a "solvent solvent"). By. In this case, it is also possible to use a non-aqueous solvent without removing the solvent when preparing the resist, so that the steps can be simplified. Specific examples of the solvent for the resist include ester solvents such as propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethyl lactate; ketone solvents such as cyclohexanone; and propylene glycol alone. An ether solvent such as methyl ether, ethylene glycol dimethyl ether or ethylene glycol diethyl ether is not limited thereto. Further, a low boiling point solvent which is easily removed, such as methyl acetate, ethyl acetate, acetone or methyl ethyl ketone, is also preferred.

Further, for example, it is easy to reduce the viscosity of the solution in the polymerization and to control the molecular weight. From the viewpoint, an alcohol solvent such as methanol, ethanol, isopropanol or propylene glycol monomethyl ether is preferably used. In the case where the curable resin composition of the present invention is used for a resist application, it is more preferably an alcohol solvent having a low boiling point such as methanol, ethanol or isopropyl alcohol which is easily removed.

Therefore, in particular, when the curable resin composition of the present invention is used as a resin composition for an alkaline development type negative resist such as a resist for a color filter, it is preferably used as a nonaqueous solvent. A solvent mixture of the solvent for the resist and an alcohol solvent.

The content of the nonaqueous solvent in the ether dimer composition is not particularly limited, and is, for example, 100% by mass based on the total amount of the ether dimer composition, preferably 20 to 90% by mass. Thereby, the ether dimer and water can be more uniformly dissolved, and 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, it is 50 to 85% by mass, and further preferably 55 to 75% by mass.

As a method of producing the above-described ether dimer composition, it is preferred to uniformly mix the ether dimer, water, stabilizer, and non-aqueous solvent so as to have the above preferable content ratios.

Here, the method for producing the ether dimer (that is, the monomer represented by the above formula (1)) is not particularly limited, and it is preferred to dehydrate the α-hydroxy methacrylate by using a tertiary amine catalyst. A method of removing impurities (catalyst or side reaction product, etc.) after polymerization. Thereby, a symmetric ether dimer can be obtained in high yield and high purity. As a method of removing impurities, a known purification method such as extraction, crystallization, or distillation can be appropriately selected. However, in terms of obtaining a high-purity ether dimer in a high yield, crystallization is preferably employed.

Further, the term "crystallization" means that crystals are precipitated from a liquid phase or the like.

In particular, it improves the stability of the ether dimer composition and prevents subsequent polymerization. From the viewpoint of gelation, it is preferably a side reaction product (crosslinkable compound, ester dimer) containing a polymerizable unsaturated double bond with respect to 100% by mass of the total amount of the ether dimer composition. The trimer or the like is removed until it is 0.001% by mass or less. More preferably removed below the detection limit. Moreover, from the viewpoint of preventing coloring, it is preferred 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, it is removed to 0.001% by mass or less, and further preferably removed to 0.0005% by mass or less.

(ii) Acrylic

The content ratio of acrylic acid in the above monomer mixture is preferably set such that the acid value of the polymer is within the above preferred range. For example, it is preferably 7% by mass or more, more preferably 10% by mass or more, and still more preferably 13% by mass or more based on 100% by mass of the total of the monomer mixture. Moreover, it is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less.

(iii) other acid group-containing monomers

In the present invention, it is necessary to use acrylic acid as a monomer having an acid group (referred to as an "acid group-containing monomer"), but it is also possible to use an acid group-containing monomer other than acrylic acid ("other acid group-containing singles" The body is used as a raw material. That is, the monomer mixture may further contain one or more kinds of other acid group-containing monomers. The acid group may be a functional group which can be neutralized with alkaline water. Specific examples thereof include a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group. In addition, the acid group may have only one of these types, or may have two or more types. Among them, a carboxyl group and/or a carboxylic anhydride group are preferred, and a carboxyl group is more preferred.

Examples of the other acid group-containing monomer include unsaturated monocarboxylic acids such as methacrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid; maleic acid, fumaric acid, and itaconic acid; Unsaturated polycarboxylic acids such as acid, citraconic acid and mesaconic acid; unsaturation of mono(2-propenyloxyethyl) succinate and mono(2-methylpropenyloxyethyl) succinate Unsaturated monocarboxylic acids which are extended by a chain between a base group and a carboxyl group; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; and unsaturated compounds containing a phosphate group such as Light Ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.) . Among these, carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, and unsaturated acid anhydrides) are preferably used from the viewpoint of versatility, availability, and the like. In terms of reactivity, alkali solubility, and the like, it is more preferred to use an unsaturated monocarboxylic acid, and among them, methacrylic acid is particularly preferable.

The amount of the other acid group-containing monomer used is not particularly limited as long as the effect of the action derived from acrylic acid or the above ether dimer can be sufficiently exhibited. For example, it is preferably 0 to 50 parts by mass based on 100 parts by mass of the acrylic acid. More preferably, it is 0 to 30 mass parts, further preferably 0 to 10 parts by mass, and particularly preferably 0 to 5 parts by mass.

(iv) a monomer having a cyclic structure

Further, the above monomer mixture preferably contains a monomer having a cyclic structure. That is, the above monomer mixture preferably further contains a monomer having a cyclic structure. The monomer having a cyclic structure may be used alone or in combination of two or more.

Examples of the monomer having a cyclic structure include an N-substituted maleimide-based monomer; a cyclohexyl (meth)acrylate, a benzyl (meth)acrylate, and a (meth)acrylic acid. Anthracene ester, 1-adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, etc. A (meth) acrylate monomer having a cyclic structure; and an aromatic vinyl compound such as styrene, vinyl toluene or α-methyl styrene.

As the N-substituted maleimide-based monomer, for example, N- Cyclohexyl maleimide, N-phenyl maleimide, N-methyl maleimide, N-ethyl maleimide, N-isopropyl Isobutylene sulfoxide, N-butyl butyl maleimide, N-dodecyl maleimide, N-benzyl maleimide, N-naphthalene Benzene butylide, p-methylbenzyl maleimide, p-butylbenzyl maleimide, p-hydroxybenzyl maleimide, o-chlorobenzyl One or two or more kinds of these may be used, such as cis-butenylenediamine, o-dichlorobenzyl-m-butylene hydrazide, p-dichlorobenzyl-m-butylene hydrazide. Among them, from the viewpoint of transparency, N-phenyl maleimide, N-benzyl maleimide, and especially N-benzyl butadiene hydrazide are preferred. amine.

Examples of the above N-benzylbutylene sulfoxide include benzyl maleimide; p-methylbenzyl maleimide, p-butylbenzyl maleate Alkyl-substituted benzyl maleimide, such as amidoxime; phenolic hydroxy-substituted benzyl-m-butylene hydrazide, such as p-hydroxybenzyl maleimide; and o-chlorobenzyl cis-butane A halogen-substituted benzyl maleimide or the like such as enediethyleneamine, o-dichlorobenzyl maleimide or p-dichlorobenzyl maleimide.

Among the above monomers having a cyclic structure, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, styrene and/or are preferred in terms of good transparency and resistance to heat resistance. Vinyl toluene.

The content ratio 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 of the monomer mixture. Among them, from the viewpoints of heat resistance, hardness, color material dispersibility, development speed, transparency, and the like, it is preferably 2 to 60% by mass. More preferably, it is 2 to 50% by mass, and further preferably 3 to 40% by mass.

(v) other monomers

Further, the monomer mixture for obtaining the above polymer (A) may optionally contain the above Other monomers (also referred to as "other monomers") copolymerized with an ether dimer and/or acrylic acid. One or two or more kinds of other monomers may be used.

Examples of the other monomer include a monomer having a cyclic structure at the time of polymerization (excluding the monomer represented by the above formula (1)). For example, an α-(unsaturated alkoxyalkyl)acrylate monomer can be mentioned. Among them, an (α-allyloxymethyl) acrylate alkyl ester monomer is preferred. Further, an (α-methylallyloxymethyl) acrylate alkyl ester monomer or the like is also preferable.

Examples of the other monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, methyl 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, etc. (methyl Acrylates; 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. Among these, methyl (meth)acrylate and/or 2-hydroxyethyl (meth)acrylate are preferred in terms of good transparency and resistance to heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.

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

- polymerization method -

The above polymer (A) is obtained by polymerizing the above monomer mixture. The method of the polymerization reaction is not particularly limited, and various polymerization methods previously known can be employed. Among them, a polymerization method based on a radical polymerization mechanism is also industrially advantageous, and thus is preferable. Also, the polymerization concentration or polymerization temperature is also based on The type or ratio of the monomer to be used and the molecular weight of the target polymer vary, and it is preferred to set the polymerization temperature to 40 to 150 ° C and the polymerization concentration to 20 to 50% by mass, more preferably The polymerization temperature was set to 60 to 130 ° C, and the polymerization concentration was set to 30 to 45%.

In the case where a solvent is used in the above polymerization, a solvent used in a usual radical polymerization reaction may be used as the solvent. The solvent contained in the curable resin composition, that is, the compound used as the component (D) is preferably used, whereby the preparation of the curable resin composition is facilitated. Specifically, for example, tetrahydrofuran, two Ethers such as alkane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, An ester such as propylene glycol monomethyl ether acetate or 3-methoxybutyl acetate; an alcohol such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether or propylene glycol monomethyl ether; toluene, two An aromatic hydrocarbon such as toluene or ethylbenzene; chloroform; and dimethyl hydrazine. These solvents may be used alone or in combination of two or more.

In particular, when the total content of the acid group-containing monomer relative to 100% by mass of the total amount of the monomer mixture exceeds 30% by mass, in order to prevent precipitation of the polymer, it is preferred to use propylene glycol monomethyl ether acetate or the like. A mixed solvent of an ester solvent and an alcohol solvent such as propylene glycol monomethyl ether or isopropyl alcohol.

In addition, the content of the acid group-containing monomer herein refers to an amount which is consumed in order to introduce a reactive double bond (polymerizable double bond) into a side chain.

In the above polymerization, a polymerization initiator which is usually used may be used as needed.

The polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, diisopropylbenzene hydroperoxide, dibutyl butyl peroxide, lauric acid peroxide, and benzammonium peroxide. Tert-butyl isopropyl carbonate, third amyl peroxy-2-ethylhexanoate, 2-ethyl peroxide Organic peroxides such as tributyl hexanoate; and 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis An azo compound such as (2,4-dimethylvaleronitrile) or 2,2'-azobis(methyl 2-methylpropionate). These polymerization initiators may be used alone or in combination of two or more.

The amount of the polymerization initiator to be used is not particularly limited as long as it is appropriately set depending on the combination of the monomers to be used, the reaction conditions, the molecular weight of the target polymer, and the like, and is 100% by mass based on the total amount of the monomer mixture. The portion is preferably set to 0.1 to 15 parts by mass. Thereby, a polymer having a weight average molecular weight in a preferable range (for example, several thousands to several tens of thousands) can be easily obtained without gelation. More preferably, it is 0.5 to 10 parts by mass.

Further, in the above polymerization, in order to adjust the molecular weight, a chain transfer agent which is usually used may be used as needed. Examples of the chain transfer agent include a thiol-based chain transfer agent such as n-dodecylmercaptan, mercaptopropionic acid, thioglycolic acid, and methyl thioglycolate; and an α-methylstyrene dimer. Preferably, the chain transfer effect is high, the residual monomer can be reduced, and the n-dodecyl mercaptan and/or mercaptopropionic acid can be easily obtained.

In the case of using a chain transfer agent, the amount thereof to be used is not particularly limited as long as it is appropriately set depending on the combination of the monomers to be used, the reaction conditions, the molecular weight of the target polymer, and the like, and is not particularly limited with respect to the monomer mixture. The total amount is 100 parts by mass, preferably 0.1 to 15 parts by mass. Thereby, a polymer having a weight average molecular weight in a preferable range (for example, several thousands to several tens of thousands) can be easily obtained without gelation. More preferably, it is 0.5 to 10 parts by mass. In particular, in the present invention, the weight average molecular weight of the polymer (A) is preferably from 5,000 to 50,000. In order to obtain such a low molecular weight polymer, it is particularly preferable to use a chain of 100 parts by mass relative to the total amount of the monomer mixture. The amount of the transfer agent used is set to 1 to 8 parts by mass.

Here, the polymer (A) preferably contains a polymerizable double bond in the side chain. The polymer (A) can be hardened by heat or light by having a side chain having a polymerizable double bond. Therefore, the thermal decomposition resistance is further improved, and the sensitivity to light when the photosensitive resin composition is formed is improved, so that light hardening can be utilized, and the mechanical strength after hardening is also improved. The method of introducing a polymerizable double bond into a side chain includes a compound containing a functional group capable of bonding with an acid group and a polymerizable double bond (preferably containing a group selected from an epoxy group). A method of adding at least one of a group consisting of an oxazoline group and a hydroxyl group to a compound of a polymerizable unsaturated double bond). As the polymerizable unsaturated double bond, the double bond of the (meth)acryl fluorenyl group is preferably exemplified in terms of the reactivity of the obtained polymer.

Containing the epoxy group selected from the above, Examples of the compound of at least one of the group consisting of an oxazoline group and a hydroxyl group and a polymerizable unsaturated double bond include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. a compound having a hydroxyl group and a double bond such as allyl alcohol; a glycidyl (meth)acrylate, a 3,4-epoxycyclohexylmethyl (meth)acrylate, an allyl epoxidized ether, or the like having an epoxy group Compound with double bond; and vinyl Oxazoline, isopropenyl Oxazoline, etc. A compound such as an oxazoline group and a double bond. Among these, in view of high reactivity and easy control of the reaction, and easy to obtain and not only a radical polymerizable double bond but also a hydroxyl group introduced at the same time, glycidyl (meth)acrylate and / or 3,4-epoxycyclohexylmethyl (meth)acrylate.

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

A method of partially adding a compound having a functional group bonded to an acid group and a polymerizable double bond (particularly, glycidyl (meth)acrylate, etc.) to one of the acid groups in the base polymer is known. The method is not particularly limited. For example, the reaction temperature is preferably from 60 ° C to 140 ° C. Further, it is preferred to use a known catalyst such as an amine compound such as triethylamine or dimethylbenzylamine; an ammonium salt such as tetraethylammonium chloride; a phosphonium salt such as tetraphenylphosphonium bromide; and a dimethyl group. A guanamine compound such as formamide.

As a result of introducing the above double bond, the obtained polymer (A) (in this case, the polymer (A) becomes a polymer having a side chain double bond) has a double bond equivalent (meaning a molecular weight per mole of the double bond) (g)) is preferably from 300 to 4000 g/mol. When the double bond equivalent is in this range, the sensitivity to light is increased and the developability is further improved, and the coloration at the time of curing is further suppressed, and the storage stability or solubility in a solvent is further improved. More preferably, it is 400 to 3000 g/mol, and further preferably 500 to 2000 g/mol.

The double bond equivalent system is a measure of the amount of the double bond contained in the molecule. If the compound is of the same molecular weight, the larger the value of the double bond equivalent, the smaller the amount of introduction of the double bond. The double bond equivalent can be calculated based on the amount of the polymer or the amount of the compound introduced into the double bond. It can also be measured by various analyses such as titration and elemental analysis, NMR, IR, or differential scanning calorimetry.

(B) Polymeric compound

The polymerizable compound (B) means a compound having a polymerizable group. A compound having a polymerizable double bond is preferred.

The molecular weight of the compound (B) (meaning that the atomic weight (the mass of the carbon atom is 12.01)) is preferably 700 or less, more preferably 650 or less, still more preferably 600. the following. Further, the double bond equivalent is preferably 150 or less, more preferably 140 or less, still more preferably 110 or less. The lower limit of these is not particularly limited as long as it is a hardenable range.

Among these, in terms of forming an excellent pixel, a compound having a relatively small molecular weight and a small double bond equivalent is preferable. For example, (2) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (methyl) Acrylate, neopentyl alcohol di(meth) acrylate, neopentyl alcohol tri(meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate Ester, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(methyl) A polyfunctional (meth) acrylate compound such as an acrylate or a tris(meth)acrylate of tris(hydroxyethyl)isocyanurate. That is, the above compound (B) is preferably a polyfunctional (meth) acrylate compound. Among them, in terms of the sensitivity of the curable resin composition obtained, an ethylenic compound having a molecular weight of more than 250 is preferably used. As such a compound, pentaerythritol tetraacrylate, neopentyl alcohol triacrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta (meth) acrylate, And / or dipentaerythritol hexa (meth) acrylate and the like. If these are used, a well-balanced composition can be obtained, which is preferable.

(C) Photopolymerization initiator

The photopolymerization initiator (C) is not particularly limited, and examples thereof include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzoin Methyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-( Methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone, oligomerization {2- Hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone}, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropenyl) Acetophenones such as benzyl]phenyl}-2-methylpropan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin; benzophenone, Methyl o- benzhydrylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra Tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzylidene-N,N-dimethyl-N-[2-(1- 2-benzophenones such as 2-oxo-2-propenyloxyethyl}ammonium bromide, 4-(benzylidenebenzyl)trimethylammonium chloride; 2-isopropyl 9-oxygen sulfur 4-isopropyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-dichloro 9-oxosulfur 1-chloro-4-propoxy 9-oxosulfur , 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-9-oxygen 9-oxosulfurate such as -9-ketone internal race chloride And the like; and methyl phenylglyoxylate, 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzylidene)- Phenylphosphine oxide and the like. Among these, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino group- An α-amino ketone photopolymerization initiator such as 1-(4-morpholinylphenyl)-butanone-1.

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

(D) solvent

The solvent (D) is not particularly limited, and examples thereof include tetrahydrofuran and Ethers such as alkane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol tert-butyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane Ketones such as ketone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol butyl ether acetate, 3-methoxybutyl acetate, etc. Class; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; aromatic hydrocarbons such as toluene, xylene, ethylbenzene; chloroform; Dimethyl adenine and the like. Among these, propylene glycol monomethyl ether acetate and/or propylene glycol monomethyl ether are preferred.

(E) Other ingredients

In addition, the curable resin composition of the present invention may contain, for example, dyes such as dyes and pigments, and aluminum hydroxide and talc, in addition to the components (A) to (D) described above, without impairing the effects of the present invention. , clay, barium sulfate and other fillers; and defoamers, decane coupling agents, leveling agents, sensitizers, development auxiliaries, mold release agents, lubricants, plasticizers, antioxidants, UV absorbers, flame retardant Known additives such as "(E) other ingredients" or "(E) ingredients), such as agents, polymerization inhibitors, tackifiers, and dispersing agents.

The amount of the component (E) to be used may be appropriately set depending on the purpose or use, and is, for example, 100% by mass based on the total amount of the solid content of the curable resin composition, preferably 0.01 to 70% by mass. More preferably, it is 0.1 to 60% by mass, and further preferably 0.3 to 50% by mass. In addition, the "total amount of solid content component" means the total amount of the component which forms a hardened material (except solvent which volatilizes when formation of a hardened material, etc.).

As the coloring agent, one type or two or more types of various organic or inorganic coloring agents can be used. As the organic colorant, an organic pigment, a dye, a natural pigment, or the like can be used.

Specific examples of the organic pigment include, for example, a yellow pigment such as CI Pigment Yellow 1, 138 described in paragraphs 0103 to 0107 of JP-A-2015-42697; an orange pigment such as CI Pigment Orange 1; and a CI Pigment Violet 1st purple pigment; CI pigment red 1 and other red pigment; CI pigment blue 1 and other blue pigment; CI pigment green 1, 58 and other green pigment; CI pigment brown 5 and other brown pigment; aniline black, carbon black, lamp black, bone Black, iron black, titanium black, CI pigment Black pigment such as black 1; and white pigment such as C.I. Pigment White 1. However, the coloring matter of the present invention is not limited to these. Further, the pigments may be used singly or in combination of two or more. "C.I." means the color index (C.I.; The Society of Dyers and Colourists), and the number means the color index value.

As the above organic pigment, it is particularly preferable to use a color index (C.I.) number as described below.

Yellow pigments such as 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, CI, Pigment Yellow 185, etc. CI Pigment Red 1, Red pigments such as CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 254, CI Pigment Red 177; CI Pigment Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, etc. Blue pigment; CI pigment violet 23:19 and other purple pigments; and pigment green 7, pigment green 36 and other green pigments.

For example, the organic dyes described in JP-A-2010-103, pp. Among them, an azo dye, an anthraquinone dye, an anthracycline dye, a quinone imine dye, a quinoline dye, a nitro dye, a carbonyl dye, a methine dye, or the like is preferable.

The content ratio of the above organic coloring agent (also referred to as a coloring matter) (that is, the total ratio of the organic coloring agents) can be appropriately set depending on the purpose or use, and the preferable range of the content ratio of the coloring material is relative to the solid content of the curable resin composition. The total amount of the components is 100% by mass, and is 3 to 70% by mass. More preferably, it is 5 to 60% by mass, and further preferably 10 to 50% by mass. In addition, the content ratio of the pigment is preferably from 1 to 500 parts by mass, more preferably from 10 to 200 parts by mass, per 100 parts by mass of the component (A).

The inorganic colorant is preferably an inorganic pigment and/or an extender pigment. For example, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow dan, zinc yellow, iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, iron blue, chrome oxide green, cobalt green , brown soil, titanium black, synthetic iron black, carbon black and so on.

The preparation method of the curable resin composition of the present invention is not particularly limited, and a conventionally known mixing method or purification method can be employed. Further, the curable resin composition obtained is preferably subjected to a filtration treatment by a filter or the like to remove fine dirt.

[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 example, in resist materials, various coating agents, paints, and the like. For the preferred use, various optical members such as a color filter, an ink, a printing plate, a printed wiring board, a semiconductor element, and a photoresist, which are used in a liquid crystal display device or a solid-state image sensor, a motor, an electronic device, and the like can be given.

In particular, since the (A) component has an acid group, the curable resin composition of the present invention can be preferably used as an alkali-developing type negative resist material for producing a color filter or an optical waveguide. Use. Further, since the structure of the component (A) has a tetrahydropyran ring structure, it can exhibit good pigment dispersibility, and therefore can be preferably used as a curable resin composition for a color filter. In particular, in the present invention, by using a polymer having a structural unit derived from acrylic acid and a tetrahydropyran ring structure as the component (A), a marked improvement in development speed can be achieved, and thus it is extremely useful for color filter applications. . Therefore, it can be said that the color filter having a cured product obtained by curing the curable resin composition of the present invention on the substrate is excellent in various physical properties such as transparency and heat resistance, and is extremely excellent in productivity. Such a color filter is one of the present inventions.

The curable resin composition of the present invention is preferably used as a color filter as described above. In addition to these, the material of the material or the optical waveguide is preferably used as a protective film (a protective film for a color filter, a protective film for a touch panel display device, etc.) or an insulating film (a touch panel) in various display devices. An insulating film for a display device, etc.).

<color filter>

The color filter-based cured resin layer of the present invention is provided on a substrate, and the resin composition of the cured resin layer is the curable resin composition of the present invention. Specifically, the members constituting the color filter include three primary color (RGB) pixels, a resin black matrix, a protective film, and a columnar spacer. The color filter of the present invention is only required to constitute at least one of the members of the color filter. The curable resin composition may be cured and formed.

In the color filter, the cured resin layer which is a three primary color (RGB) pixel, a resin black matrix, a protective film, and/or a columnar spacer is preferably formed of the curable resin composition. Further, in the case where RGB pixels are formed, the curable resin composition contains pigments of three primary colors of red, green, and blue. The curable resin composition in the case of forming a resin black matrix contains a black pigment. The curable resin composition in the case of forming a protective film or a columnar spacer may not contain a pigment. Further, in the case of containing a pigment, it is preferred that the curable resin composition also contains a dispersing agent.

The color filter described above can be produced, for example, in the following manner.

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

Here, examples of the transparent substrate include glass (preferably alkali-free glass) or transparent plastic. Examples of the known coating method include a spin coating method, a spray method, and the like, and a spin coating method is preferred. Regarding the drying conditions, the drying temperature is preferably from room temperature to 120 ° C, more preferably from 60 to 100 ° C. When dry The interval is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 10 minutes. Further, it is preferred to carry out heat drying under normal pressure or under vacuum.

2) Thereafter, a photomask (patterned film) provided with an opening portion corresponding to a desired pattern shape is placed on the coating film obtained in the above 1) in a contact state or a non-contact state, and is irradiated. It hardens by light.

Here, the term "light" means not only visible light but also radiation such as ultraviolet rays, X-rays, and electron beams, and is preferably ultraviolet light. As the ultraviolet source, it is generally preferred to use a high pressure mercury lamp.

3) After the light irradiation of the above 2), development is carried out using a solvent, water, an aqueous alkaline solution or the like. Among these, it is preferred because the alkaline aqueous solution has less load on the environment and can be developed with high sensitivity. The basic component in the alkaline aqueous solution is preferably potassium hydroxide, sodium hydroxide, and/or sodium carbonate. The concentration of the alkaline component is preferably from 0.01 to 5% by mass based on 100% by mass of the aqueous alkaline solution. When the concentration of the alkaline component is within this range, the solubility of the component (A) is further improved, and the developability (developing speed) can be further improved. More preferably, it is 0.05 to 3% by mass, and further preferably 0.1 to 1% by mass. A surfactant may also be added to the alkaline aqueous solution.

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

5) Then, the pigment of the curable resin composition is sequentially changed to red (R), green (G), and blue (B), and the above steps 1) to 3) are repeated to form R, G, and B. Pixels while making RGB pixels.

6) Next, a protective film is formed as needed for the purpose of protecting RGB pixels formed on the substrate or improving surface smoothness.

7) When the color filter is a color filter for a liquid crystal display device, it is preferably Further, a columnar spacer is formed. The columnar spacer can be formed by applying the curable resin composition to the thickness of the desired spacer at the surface on which the spacer should be formed, and passing through the above steps 1) to 3).

Here, in the case of producing a color filter, it is preferred to perform heating (post-baking) after development to further cure each member, and to completely remove the solvent when the solvent remains. The temperature during post-baking is preferably from 120 to 300 °C. When the temperature is set, the coloring of the pixel and the smoothness of the coating film due to thermal decomposition are more sufficiently suppressed, and the curing is further performed to further increase the coating film strength. More preferably, it is 150 to 250 ° C, and further preferably 180 to 230 ° C. The post-baking may be performed after development of each member (the above 3) at the time of production of each member), or after all 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 technologies such as display devices, there has been a strong demand for higher performance for each member to be used. If the color filter of the present invention is used, the display quality or image quality of various display devices can be reliably ensured. Sexually improved to the extent that it can adequately address such needs. Further, as described above, the display device constructed using the color filter of the present invention is also one of the inventions.

The display device is not particularly limited, and is preferably a liquid crystal display device, a solid-state imaging device, a touch panel display device, or the like. As a touch panel type display device, it is particularly preferable to use a capacitive method.

[Examples]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the examples. As long as it is not particularly limited, "parts" means "parts by mass", "%" It means "% by mass", and "v/v" means volume ratio.

The evaluation of each physical property or the like was carried out as follows.

1. Weight average molecular weight

Using polystyrene as a standard material, tetrahydrofuran as a dissolving solution, and using GPC (gel permeation chromatography) method based on HLC-8220GPC (manufactured by Tosoh Corporation) and column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation) The weight average molecular weight was measured.

2. Polymer concentration in polymer solution

A solution obtained by dissolving and 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, and then placed in a desiccator to cool, and the weight was measured. Next, the nonvolatile content of the polymer solution was calculated from the weight loss amount, and this was taken as the polymer concentration.

3, acid value

3 g of the resin solution was accurately weighed and dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and 0.1 eq of KOH aqueous solution was used as a titration solution, and an automatic titration apparatus (manufactured by Hiranuma Sangyo Co., Ltd., trade name: COM-555) was used. The acid value of the polymer solution was measured, 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 applied onto a 10 cm square glass substrate by a spin coater, and dried in an oven at 90 ° C for 3 minutes. After drying, a pattern mask of 20 μm line and gap was placed at a distance of 100 μm from the coating film, and a UV aligner (TME-150RNS, manufactured by TOPCON Co., Ltd.) equipped with a 2.0 kW ultrahigh pressure mercury lamp was used at 100 mJ/ The intensity of cm ² (in terms of 365 nm illuminance) is irradiated with ultraviolet rays. After the ultraviolet ray was irradiated, a 0.05% potassium hydroxide aqueous solution was sprayed on the coating film by a rotary developing machine for 10 to 60 seconds to dissolve and remove the unexposed portion, and the remaining exposed portion was made with pure water. The water was washed in seconds to develop. After development, a 20 μm line and a gap were confirmed by a laser microscope (VK-9700, manufactured by Ens), and the development speed was evaluated in the shortest time to completely remove the unexposed portion.

Monomer synthesis example 1 (synthesis of ether dimer composition)

Adding α-hydroxymethyl methacrylate (RHMA-M) 450.0 parts, 1,4-diazabicyclo[2,2,2] octyl to a reactor equipped with a stirring device, a temperature sensor, and a cooling tube 13.5 parts of alkane (DABCO) and 0.9 parts of p-methoxyphenol (MEHQ) were heated to 90 ° C while stirring. After the internal temperature reached 85 ° C, the reaction was carried out for 9 hours while maintaining the temperature at 90 ± 5 ° C in the reactor under normal pressure.

After confirming that the reaction liquid temperature became 40 ° C or lower, it was diluted with 355.0 parts of methanol (MeOH) (condition: normal pressure, 35 ± 5 ° C).

The MeOH diluted droplets were added to a different reactor containing 1485.0 parts of water to crystallize the RHMA ether dimer (condition: normal pressure, 30 ° C or lower). Thereafter, the obtained slurry containing the RHMA ether dimer was filtered using a pressure filter (condition: normal pressure ~0.1 MPa, 15 ° C or lower), and then the filter cake was washed with water (conditions: Atmospheric pressure ~0.1MPa, normal temperature). For cleaning, use 380.0 parts of water each time and repeat the washing 3 times.

To the filter cake of the RHMA ether dimer thus obtained, 184.0 parts of propylene glycol monomethyl ether acetate (PGMEA) was added and dissolved (condition: normal pressure, 60 ° C). This was separated into an oil layer and an aqueous layer containing a RHMA ether dimer, and the aqueous layer was removed (condition: normal pressure, 60 ° C). The oil layer was 412.5 parts and the removed water layer was 141.9 parts. Add PGMEA (5200.0 parts), MEHQ 0.049 parts, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical (4H) to the oil layer (solution containing RHMA ether dimer and PGMEA) -TEMPO) 0.006 parts to obtain a composition (ether dimer group) Adult) 932.5 parts.

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

<Analysis results of ether dimer composition>

2,2'-[oxybis(methylene)] dimethyl bis-2-acrylate (MD): 25.0% by mass

Water: 1.3% by mass

PGMEA: 73.7 mass%

MEHQ: 53ppm

4H-TEMPO: 6ppm

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 net content of MD.

Synthesis Example 1 (Synthesis of Resin Solution 1)

Prepare a separable flask with a cooling tube as a reaction tank, and on the other hand, prepare to mix and mix dimethyl 2,2'-[oxybis(methylene)]bis-2-acrylate (hereinafter referred to as "MD") 20 parts by mass, 30 parts by mass of cyclohexyl methacrylate (hereinafter referred to as "CHMA"), 24 parts by mass of methyl methacrylate (hereinafter referred to as "MMA"), and acrylic acid (hereinafter referred to as "AA" ") 2 parts by mass of a third butyl peroxy-2-ethylhexanoate (trade name "PERBUTYLO", manufactured by Nippon Oil &Fats; hereinafter referred to as "PBO") as a monomer dropping tank, sufficient preparation A mixture of 3.5 parts by mass of n-dodecylmercaptan (hereinafter referred to as "n-DM") and 32 parts by mass of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") was stirred and mixed as a chain transfer agent dropping tank.

After adding 128 parts by mass of PGMEA to the reaction vessel and replacing it with nitrogen, the mixture was heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 °C. After the temperature of the reaction tank was stabilized at 90 ° C, the dropwise addition was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping system was carried out while maintaining the temperature at 90 ° C for 135 minutes. After 60 minutes from the end of the dropwise addition, the temperature was raised, and the reaction vessel was set to 110 ° C, and maintained at 110 ° C for 3 hours. After the internal temperature was temporarily cooled to room temperature, the gas introduction tube was attached to a separable flask, and foaming of an oxygen/nitrogen=5/95 (v/v) mixed gas was started. Then, 28 parts of glycidyl methacrylate (hereinafter referred to as "GMA"), 0.10 parts of 6-t-butyl-2,4-xylenol, and triethylamine (hereinafter referred to as "g") were added to the reaction vessel. "TEA") 0.4 parts and reacted directly at 110 ° C for 12 hours. Thereafter, 96 parts of PGMEA was added and 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 placed in a 50 ml glass screw bottle and sealed, and stored in a thermostat adjusted to 25 ° C for 12 months. After 12 months, the mass average molecular weight was measured and found to be 16500. Further, no gel was observed in the spiral bottle, and the storage stability was good.

Synthesis Example 2 (Synthesis of Resin Solution 2)

A resin solution 2 having a concentration of 33% was obtained by the same operation as the synthesis of the resin solution 1 except that benzyl methacrylate (hereinafter referred to as "BzMA") was used instead of cyclohexyl methacrylate. The weight average molecular weight and acid value of the component (A) (polymer (A)) in the resin solution 2 are shown in Table 1.

Synthesis Example 3 (Synthesis of Resin Solution 3)

A separable flask equipped with a cooling tube was prepared as a reaction tank, and on the other hand, 20 parts by mass of MD, 30 parts by mass of CHMA, 32.6 parts by mass of MMA, and AA 17.4 were mixed and mixed well. The amount of the PBO and the PBO of 3 parts by mass were used as a monomer dropping tank, and it was prepared to sufficiently stir and mix 4.5 parts by mass of n-DM and 32 parts by mass of PGMEA as a chain transfer agent dropping tank.

After adding 128 parts by mass of PGMEA to the reaction vessel and replacing it with nitrogen, the mixture was heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 °C. After the temperature of the reaction tank was stabilized at 90 ° C, the dropwise addition was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping system was carried out while maintaining the temperature at 90 ° C for 135 minutes. After 60 minutes from the end of the dropwise addition, the temperature was raised, and the reaction vessel was set to 110 ° C, and maintained at 110 ° C for 3 hours. After the internal temperature was temporarily cooled to room temperature, the gas introduction tube was attached to a separable flask, and foaming of an oxygen/nitrogen=5/95 (v/v) mixed gas was started. Then, 8.3 parts of GMA, 0.10 parts of 6-t-butyl-2,4-xylenol, and 0.4 parts of TEA were added to the reaction vessel, and the mixture was directly reacted at 110 ° C for 12 hours. Thereafter, 58 parts of PGMEA was added and 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)

A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, it was prepared to sufficiently mix and mix 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. The dropping was performed in a dropping manner, and it was prepared to sufficiently stir and mix 2.7 parts by mass of n-DM and 32 parts by mass of PGMEA as a chain transfer agent dropping tank.

After adding 128 parts by mass of PGMEA to the reaction vessel and replacing it with nitrogen, the mixture was heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 °C. After the temperature of the reaction tank was stabilized at 90 ° C, the dropwise addition was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping system was carried out while maintaining the temperature at 90 ° C for 135 minutes. After 60 minutes from the end of the dropwise addition, the temperature was raised, and the reaction vessel was set to 110 ° C, and the reaction was maintained at 110 ° C for 3 hours. Then add PGMEA 41 parts and cooled to room temperature to obtain a resin solution 4 having a concentration of 33%. The weight average molecular weight and 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)

A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 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 prepared as a single. The body was dropped, and 5 parts by mass of n-DM and 32 parts by mass of PGMEA were mixed and stirred as a chain transfer agent.

After adding 128 parts by mass of PGMEA to the reaction vessel and replacing it with nitrogen, the mixture was heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 °C. After the temperature of the reaction tank was stabilized at 90 ° C, the dropwise addition was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping system was carried out while maintaining the temperature at 90 ° C for 135 minutes. After 60 minutes from the end of the dropwise addition, the temperature was raised, and the reaction vessel was set to 110 ° C, and the reaction was maintained at 110 ° C for 3 hours. Thereafter, 45 parts of PGMEA was added and cooled to room temperature to obtain a resin solution 5 having a concentration of 33%. The weight average molecular weight and 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)

A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 20 parts by mass of MD, 30 parts by mass of CHMA, 19 parts by mass of MMA, and methacrylic acid (hereinafter referred to as "MAA") 31 were prepared to be sufficiently stirred and mixed. The mass part and the PBO of 2 parts by mass are used as a monomer dropping tank, and it is prepared to sufficiently stir and mix 4 parts by mass of n-DM and 32 parts by mass of PGMEA as a chain transfer agent dropping tank.

After adding 128 parts by mass of PGMEA to the reaction vessel and replacing it with nitrogen, the mixture was heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 °C. After the temperature of the reaction tank was stabilized at 90 ° C, the dropwise addition was started from the monomer dropping tank and the chain transfer agent dropping tank. Drip side while maintaining temperature It was carried out at 90 ° C for 135 minutes on each side. After 60 minutes from the end of the dropwise addition, the temperature was raised, and the reaction vessel was set to 110 ° C, and maintained at 110 ° C for 3 hours. After the internal temperature was temporarily cooled to room temperature, the gas introduction tube was attached to a separable flask, and foaming of an oxygen/nitrogen=5/95 (v/v) mixed gas was started. Then, 28 parts of GMA, 0.10 parts of 6-t-butyl-2,4-xylenol, and 0.4 part of TEA were added to the reaction vessel, and the reaction was allowed to proceed directly at 110 ° C for 12 hours. Thereafter, 96 parts of PGMEA was added and 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 the same operation as the synthesis of the resin solution 6, except that benzyl methacrylate (hereinafter referred to as "BzMA") was used instead of cyclohexyl methacrylate. The weight average molecular weight and acid value of the polymer in the resin solution 7 are shown in Table 1.

Synthesis Example 8 (Synthesis of Resin Solution 8)

A separable flask equipped with a cooling tube was prepared as a reaction tank. On the other hand, it was prepared to sufficiently mix and mix 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. The dropping was performed in a dropping manner, and 3 parts by mass of n-DM and 32 parts by mass of PGMEA were mixed and stirred as a chain transfer agent.

After adding 128 parts by mass of PGMEA to the reaction vessel and replacing it with nitrogen, the mixture was heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 °C. After the temperature of the reaction tank was stabilized at 90 ° C, the dropwise addition was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping system was carried out while maintaining the temperature at 90 ° C for 135 minutes. After 60 minutes from the end of the dropwise addition, the temperature was raised, and the reaction vessel was set to 110 ° C, and the reaction was maintained at 110 ° C for 3 hours. Thereafter, 40 parts of PGMEA was added and cooled to room temperature to obtain a resin solution 8 having a concentration of 33%. Gathering in the resin solution 8 The weight average molecular weight and acid value of the compound are shown in Table 1.

Synthesis Example 9 (Synthesis of Resin Solution 9)

A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, it was prepared to sufficiently mix and mix 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. The body was dropped and the mixture was stirred and mixed with 5.6 parts by mass of n-DM and 32 parts by mass of PGMEA as a chain transfer agent.

After adding 128 parts by mass of PGMEA to the reaction vessel and replacing it with nitrogen, the mixture was heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 °C. After the temperature of the reaction tank was stabilized at 90 ° C, the dropwise addition was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping system was carried out while maintaining the temperature at 90 ° C for 135 minutes. After 60 minutes from the end of the dropwise addition, the temperature was raised, and the reaction vessel was set to 110 ° C, and the reaction was maintained at 110 ° C for 3 hours. Thereafter, 44 parts of PGMEA was added and 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)

A separable flask equipped with a cooling tube is prepared as a reaction tank, and on the other hand, 10 parts by mass of MD, 73 parts by mass of CHMA, 17 parts by mass of MMA, and 2 parts by mass of PBO are prepared as a monomer dropping tank. It is prepared to thoroughly mix and mix 14 parts by mass of n-DM and 32 parts by mass of PGMEA as a chain transfer agent.

After adding 128 parts by mass of PGMEA to the reaction vessel and replacing it with nitrogen, the mixture was heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 °C. After the temperature of the reaction tank was stabilized at 90 ° C, the dropwise addition was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping system was carried out while maintaining the temperature at 90 ° C for 135 minutes. The temperature rises after 60 minutes from the end of the addition. The reaction vessel was set to 110 ° C, and maintained at 110 ° C for 3 hours. Thereafter, 44 parts of PGMEA was added and 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 parts of Disparlon 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 mixed and oscillated in the paint. The dispersion was carried out for 3 hours in the machine, whereby Pigment Dispersion 1 was obtained.

Example 1

2.0 parts of the resin solution, 0.70 parts of dipentaerythritol hexaacrylate as a polymerizable compound, 0.35 parts of Irgacure 369 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator, and 8.5 parts of a pigment dispersion 1. 6.57 parts of propylene glycol monomethyl ether acetate as a solvent are mixed to obtain a curable resin composition 1. The curable resin composition 1 was spin-coated on a glass substrate, and developability evaluation (measurement of development time) was performed 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 composition shown in Table 2 was used, and the development time was measured. The results are shown in Table 2.

Further, the blending amount of each component in Table 2 is the amount of the solid component.

Based on the results of Table 2, the following cases were confirmed.

The curable resin composition obtained in each of Examples 1 to 5 contains all of the components (A) to (D) of the present invention. In particular, any of the resin solutions 1 to 5 used in Examples 1 to 5 contains a polymer obtained by polymerizing a monomer mixture containing a monomer represented by the above formula (1) and acrylic acid as ( A) ingredients. On the other hand, the resin solutions 6 to 10 used in Comparative Examples 1 to 5 were different from the resin solutions 1 to 5 in that each of them contained methacrylic acid instead of acrylic acid as an acid group-containing monomer. The polymer obtained. In particular, the polymer contained in the resin solution 1 (Example 1) and the resin solution 6 (Comparative Example 1) is composed of almost the same composition except for the type of the acid group-containing monomer (acrylic acid or methacrylic acid), and The weight average molecular weight and acid value are also the same. Resin solution 2 (Example 2) and resin solution 7 (Comparative Example 2), resin solution 4 (Example 4) and resin solution 8 (Comparative Example 3), and Resin solution 5 (Example 5) and resin solution 9 (Comparative Example 4), the same can be said. When Examples 1, 2, 4, and 5 were compared with Comparative Examples 1, 2, 3, and 4 under the difference, the cured materials were obtained under the same conditions, and the developability was evaluated. With respect to Comparative Examples 1 to 4, in Examples 1, 2, 4, and 5, it was confirmed that the development speed was greatly shortened. Moreover, it is confirmed that the development time is shortened by reducing the weight average molecular weight and/or increasing the acid value of the resin (polymer) contained in the resin solution to be used.

Here, Example 5 (resin solution 5: acrylic resin) using a resin (polymer) having a molecular weight of 10,000 and an acid value of 150, which has a tendency to develop faster, and Comparative Example 4 (resin solution) When the comparison was made with 9: methacrylic resin, the development time in Example 5 was 15 seconds, which was significantly shortened compared with Comparative Example 4 (development time: 35 seconds).

Based on the above, the advantage of using acrylic acid as a monomer raw material of the resin was confirmed.

Moreover, it was confirmed that the composition and physical properties adjusted in the above embodiment are in the present specification. The advantageous range described in the above shows an advantageous effect.

Further, although not shown in the table, any of the cured products obtained in the examples is excellent in various physical properties such as adhesion to a substrate, heat resistance, solvent resistance, and transparency. Further, any of the curable resin compositions obtained in the examples is excellent in hardenability. Further, each of the curable resin compositions obtained in the examples was evaluated for storage stability (tested at 40 ° C × 1 month), and as a result, neither of them produced a precipitate or a gel. Therefore, it was confirmed that the storage stability was excellent.

[Industrial availability]

The member for a display device and the display device including the cured product formed of the curable resin composition of the present invention can be preferably used in the field of optics, motors, and electronics.

Claims (7)

A curable resin composition comprising (A) a polymer having a ring structure in a main chain, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) a solvent, characterized in that the polymer (A) is obtained by polymerizing a monomer mixture containing a monomer represented by the following formula (1) and acrylic acid. In the 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 curable resin composition of the first aspect of the invention, wherein the monomer dimer composition represented by the formula (1) and water is used as the monomer represented by the formula (1). The content of the water is from 0.1 to 10% by mass based on 100% by mass of the total of the ether dimer composition. The curable resin composition of claim 1 or 2, wherein the monomer mixture further contains a monomer having a cyclic structure. The curable resin composition according to any one of claims 1 to 3, wherein 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 hardening a curable resin composition according to any one of claims 1 to 4. A color filter having a cured product of claim 5 on a substrate. A display device is constructed using a color filter of claim 6 of the patent application.