JP2003215322A - Ionizing radiation-curable resin composition for color filter, color filter and liquid crystal panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photo-curable resin composition free of yellowing and a color tone change due to high temperature and having good various physical properties such as alkali developability and to provide a color filter and a liquid crystal panel using the photo-curable resin composition. <P>SOLUTION: The ionizing radiation-curable resin composition for a color filter comprises components A, B and C. A: an N-substituted maleimide copolymer resin obtained by copolymerizing (a) 10-80 wt.% N-substituted maleimide, (b) 10-80 wt.% aromatic vinyl compound, (c) 1-70 wt.% unsaturated monocarboxylic acid and (d) a desired copolymerizable component and having ≤10 wt.% content of impurities represented by formula (1). B: a photopolymerizable component having three or more ethylenically unsaturated double bonds per molecule C: a photopolymerization initiator. The color filter and the liquid crystal panel are manufactured using the ionizing radiation- curable resin composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ionizing radiation-curable resin composition used for forming a thin film layer or a fine pattern included in a color filter, and a colored layer and a protective layer using the resin composition. The present invention relates to a color filter formed with a thin film layer such as a spacer or a fine pattern, and a liquid crystal panel assembled using the color filter.

[0002]

2. Description of the Related Art In recent years, color liquid crystal display devices have rapidly become popular as flat displays for personal computers and the like. Generally, color liquid crystal display devices (1
01) is the color filter 1 and T as shown in FIG.
The electrode substrate 2 such as an FT substrate is faced with a gap 3 of about 1 to 10 μm, the gap 3 is filled with the liquid crystal compound L, and the periphery thereof is sealed with a sealing material 4. . The color filter 1 includes a black matrix layer 6 formed on a transparent substrate 5 in a predetermined pattern to shield the boundaries between pixels, and a plurality of colors (usually red (R ), Green (G), and blue (B) three primary colors) are arranged in a predetermined order, a protective layer 8, and a transparent electrode film 9 are laminated in this order from the side closer to the transparent substrate. Is taking. Recently, pixels may be formed by using a color hologram instead of the colored layer 7.
An alignment film 10 is provided on the color filter 1 and the inner surface of the electrode substrate 2 facing the color filter 1. Further, in the gap portion 3, pearls 11 having a constant particle diameter are dispersed as spacers in order to maintain the cell gap between the color filter 1 and the electrode substrate 2 constant and uniform.
Then, a color image is obtained by controlling the light transmittance of each of the pixels colored in each color or the liquid crystal layer behind the color hologram.

When the fine-grained pearls 11 shown in FIG. 1 are dispersed as spacers, the pearls are randomly dispersed regardless of whether they are behind the black matrix layer 6 or behind the pixels. To do. When the pearls are arranged in the display area, that is, the pixel portion, the light of the backlight is transmitted through the pearls, and the alignment of the liquid crystal around the pearls is disturbed, so that the quality of the displayed image is significantly deteriorated.
Therefore, as shown in FIG. 2, instead of dispersing the pearls, a columnar spacer having a height corresponding to the cell gap is formed in the region on the inner surface side of the color filter, which overlaps with the position where the black matrix layer 6 is formed. 12
It has come to be formed.

The colored layer 7 and the protective film 8 included in the structure of the color filter have characteristics such as transparency, adhesion, strength, hardness, heat resistance, pattern shape accuracy, and coating flatness. Required. Although the protective film is solidly coated on the colored layer, it is preferable that only the region where the colored layer is formed on the transparent substrate can be selectively covered in consideration of the adhesiveness and hermeticity of the seal portion. . Therefore, although it is not formed in a finer pattern than that of the colored layer, the protective film is required to have the accuracy of the pattern shape similarly to the colored layer. Further, since the columnar spacer 12 is formed behind the black matrix layer, it does not need to be transparent, but other required characteristics are common to the colored layer and the protective film.

The colored layer, the protective film, the thin film layer such as the columnar spacers, or the fine pattern contained in the color filter is exposed to light or light on the surface of the transparent substrate or the surface of any layer provided on the transparent substrate. Coating a coating composition based on a resin composition that can be cured by radiation having a short wavelength, and pattern-expose the formed coating film through a mask as necessary to expose the uncured portion of the unexposed portion. It can be formed by removing by development.

As a photocurable resin composition for a color filter, one using an acrylic resin or an N-substituted maleimide copolymer resin as a binder component is known. Regarding the N-substituted maleimide-based copolymer resin, Japanese Patent Application Laid-Open No. 9-311211 discloses a binder resin containing a copolymer of N-substituted maleimide and a monomer having an acid group as a main component, a dye, a dispersant, and a photopolymerizable resin. It is disclosed that a colored resin layer of a color filter is formed by using a photosensitive coloring composition containing a monomer, a photopolymerization initiator, and a solvent. Further, JP-A-10-300922 discloses a radiation-sensitive composition for a color filter containing a colorant, an alkali-soluble N-substituted maleimide copolymer resin, a polyfunctional monomer, and a photopolymerization initiator. It is disclosed.

Further, in JP-A-4-315101, (a) N-substituted maleimide, (b) aromatic vinyl compound, (c) acrylic acid and / or methacrylic acid, and (d) if necessary. There is disclosed a resin composition for a color filter protective film, which comprises a copolymer resin obtained by copolymerizing another unsaturated monomer and a polyfunctional epoxy resin. However, the resin composition disclosed in JP-A-4-315101 contains an epoxy resin as a curing agent, and an N-substituted maleimide copolymer containing an acid group and an epoxy resin are cured to form a film. It is a thermosetting resin composition. Therefore, no consideration is given to the alkali developability when used as a photocurable resin.

[0008]

The photocurable resin composition for a color filter, which contains an acrylic resin as a binder component, has a drawback that it tends to cause yellowing in the heating step.

Further, according to the research conducted by the present inventors, the copolymerizability between the N-substituted maleimide and the monomer having a carboxylic acid is not so good, so that only two components of the N-substituted maleimide and the carboxylic acid are polymerized. If so, it is difficult to produce a copolymer capable of sufficiently satisfying the performance required for the photocurable resin such as alkali developability and adhesion.

The present invention has been accomplished in view of such circumstances, and a first object thereof is to prevent a change in color tone such as yellowing even when exposed to a high temperature, and to improve alkali developability. Another object of the present invention is to provide a photocurable resin composition for color filters, which has other excellent physical properties.

A second object of the present invention is to provide a color filter and a liquid crystal panel which are excellent in the color tone and transparency of the pixel part, using the photocurable resin composition according to the present invention as described above. Especially.

[0012]

In the present invention, a photocurable resin composition for achieving the first object described above comprises A.
(A) 10 to 80% by weight of N-substituted maleimide, (b)
10 to 80% by weight of an aromatic vinyl compound, 1 to 70% by weight of (c) an unsaturated monocarboxylic acid, and (d) each of the components (a), (b) and (c) as required. A copolymerizable compound, and an N-substituted maleimide copolymer resin having a content of impurities represented by the following formula (1) of 10% by weight or less,

[0013]

[Chemical 2]

(In the formula (1), R ¹ independently represents an alkyl group, a cycloalkyl group, an aryl group, an alkyl-substituted aryl group or a halogen-substituted aryl group, and R ² represents hydrogen or a methyl group, R ^{3 to} R ⁶ are each independently hydrogen, an alkyl group, a cycloalkyl group,
It represents an aryl group, an alkyl-substituted aryl group or a halogen-substituted aryl group. ) B. A photopolymerizable component having three or more ethylenically unsaturated double bonds in one molecule, and C.I. An ionizing radiation curable resin composition for a color filter, which comprises a photopolymerization initiator.

The colored layer of the color filter can be formed by further adding a coloring material such as a pigment or a dye as the component D to the above ionizing radiation curable resin composition.

The ionizing radiation curable resin composition of the present invention is directly applied on the substrate of the color filter, or is applied on any layer or structural portion provided on the substrate to form a coating film, When the coating film is irradiated with ionizing radiation such as ultraviolet rays, active species are generated from the photoinitiator which is the C component, and the trifunctional photopolymerizable component which is the B component undergoes a crosslinking reaction due to the action of the active species, resulting in coating. The coating film hardens. When exposed in a predetermined pattern by a method such as using a photomask at the time of exposure and then developed, since the N-substituted maleimide copolymer resin as the A component has a carboxyl group, a crosslink bond of the B component is formed. The unexposed portion that has not been exposed can be removed by alkali development, and a cured film having a predetermined pattern can be formed.

The N-substituted maleimide copolymer resin as the component A is a copolymer of (a) N-substituted maleimide and (c) unsaturated monocarboxylic acid with (b) an aromatic vinyl compound. It is a binder component having a narrow composition distribution and a stable quality, in which a structural unit derived from an unsaturated monocarboxylic acid is sufficiently incorporated by coexisting with an aromatic vinyl compound.

Therefore, the ionizing radiation-curable resin composition of the present invention is applied onto a substrate of a color filter and exposed to light to obtain excellent physical properties and alkali developability of the N-substituted maleimide copolymer resin as the component A. And the three-dimensional network structure formed by the trifunctional photopolymerizable component, which is the B component, provides various physical properties such as adhesion to the surface of the coated object, film strength, heat resistance, warm pure water resistance, and chemical resistance. An excellent cured film can be formed, and an accurate pattern can be formed when exposing and developing in a predetermined pattern during exposure.

Further, since the ionizing radiation curable resin composition of the present invention contains only a small amount of the impurity of the formula (1) which causes yellowing, it may be colored like the heating for forming the alignment film. It does not yellow even when exposed to the high temperature environment that cannot be avoided in the filter manufacturing process, and has excellent heat resistance stability in terms of transparency and color tone.

Specifically, the ionizing radiation curable resin composition of the present invention is applied onto a glass substrate by spin coating,
After exposure with a dose of 100 mJ / cm ² , 30 at 200 ° C
The coating film formed to a film thickness of 2 μm by heating for 1 minute had a light transmittance of 380 nm of 9 after being heated at 250 ° C. for 1 hour.
It becomes 0% or more.

Furthermore, the coating film made from the ionizing radiation-curable resin composition of the present invention is very hard and has sufficient hardness as well as transparency and heat resistance regarding color tone. Specifically, a coating film having a film thickness of 5 μm formed under the same conditions as described above, that is, an ionizing radiation curable resin composition is applied onto a glass substrate by spin coating, and after exposure with an irradiation dose of 100 mJ / cm ² , Universal hardness (under test load / under test load) was measured when the surface hardness of the coating film formed by heating at 200 ° C. for 30 minutes to a film thickness of 5 μm was 180 ° C. and the Vickers indenter had a maximum load of 20 mN. Surface area of the Vickers indenter) is 200 N / mm ² or more.

By using the ionizing radiation curable resin composition according to the present invention, a thin film layer or a fine pattern included in a color filter can be accurately formed, and a columnar spacer for maintaining a cell gap of a liquid crystal panel. It is also possible to form not only such a film that does not require so much transparency, but also a film of a portion such as a colored layer or a protective layer that has a great demand for transparency and color tone. Therefore, a high quality color filter and a high quality liquid crystal panel using the color filter can be obtained.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION (1) Ionizing radiation curable resin composition for color filter In the present invention, A. (A) N-substituted maleimide 1
0 to 80% by weight, (b) 10 to 8 aromatic vinyl compound
0% by weight, (c) 1 to 70% by weight of unsaturated monocarboxylic acid, and (d) each component (a), if necessary.
A compound copolymerizable with (b) and (c) is copolymerized, and the content of impurities represented by the following formula (1) is 1
0% by weight or less of N-substituted maleimide copolymer resin,

[0024]

[Chemical 3]

(In the formula (1), R ¹ independently represents an alkyl group, a cycloalkyl group, an aryl group, an alkyl-substituted aryl group or a halogen-substituted aryl group, and R ² represents hydrogen or a methyl group, R ^{3 to} R ⁶ are each independently hydrogen, an alkyl group, a cycloalkyl group,
It represents an aryl group, an alkyl-substituted aryl group or a halogen-substituted aryl group. ) B. A photopolymerizable component having three or more ethylenically unsaturated double bonds in one molecule, and C.I. An ionizing radiation-curable resin composition for a color filter, which comprises a photopolymerization initiator, is provided.

The N-substituted maleimide copolymer resin used as the component A is the main binder component of the ionizing radiation-curable resin composition in the present invention, and the total amount of the copolymerization components (monomers) is 100% by weight. Then, (a) N
-Substituted maleimide 10 to 80% by weight, (b) aromatic vinyl compound 10 to 80% by weight, (c) unsaturated monocarboxylic acid 1 to 70% by weight, and optionally (d) each of the above It is a resin obtained by copolymerizing the components (a), (b) and (c) and a compound copolymerizable therewith.

Since the copolymerizability between the N-substituted maleimide and the monomer having a carboxylic acid is not very good, N-
Copolymerization of only two components, a substituted maleimide and a carboxylic acid, makes it difficult to produce a copolymer resin that can sufficiently satisfy the performance required for an ionizing radiation curable resin such as alkali developability, adhesion, and strength. Therefore, even if a copolymer resin having good physical properties can be obtained, it is difficult to stably manufacture and supply products having the same performance repeatedly.

On the other hand, the N-substituted maleimide copolymer resin used in the present invention is a copolymer of N-substituted maleimide and unsaturated monocarboxylic acid together with an aromatic vinyl compound such as styrene as a third copolymerization component. It is a polymerized terpolymer, in which the carboxylic acid is introduced into the N-substituted maleimide-based copolymer at an efficient and uniform copolymerization ratio,
It has excellent physical properties required for ionizing radiation curable resins such as alkali developability, adhesion, strength, hardness and heat resistance.

Further, in the present invention, as the N-substituted maleimide copolymer resin, one having an impurity content represented by the following formula (1) of 10% by weight or less is selectively used. By using the N-substituted maleimide copolymer resin having the content of impurities represented by the formula (1) of 10% by weight or less, an ionizing radiation curable resin composition having sufficient heat resistance stability with respect to transparency and color tone is obtained. To be

[0030]

[Chemical 4]

(In the formula (1), R ¹ independently represents an alkyl group, a cycloalkyl group, an aryl group, an alkyl-substituted aryl group or a halogen-substituted aryl group, and R ² represents hydrogen or a methyl group, R ^{3 to} R ⁶ are each independently hydrogen, an alkyl group, a cycloalkyl group,
It represents an aryl group, an alkyl-substituted aryl group or a halogen-substituted aryl group. The impurity of formula (1) does not form as a by-product when only N-substituted maleimide and unsaturated monocarboxylic acid are copolymerized,
It is a by-product when an aromatic vinyl compound such as styrene is copolymerized with the N-substituted maleimide and the unsaturated monocarboxylic acid. N-substituted maleimide, unsaturated monocarboxylic acid,
Also, when a large amount of the impurity of the formula (1) is contained in the ternary copolymer resin obtained by copolymerizing the aromatic vinyl compound, yellowing easily occurs at high temperature. For example, after forming a protective film on a transparent substrate using a photocurable resin composition containing a N-substituted maleimide copolymer resin containing a large amount of impurities of the formula (1) as a binder, an alignment film is subsequently formed. Then, yellowing of the protective film occurs due to heating in the process of forming the alignment film.

That is, by copolymerizing the aromatic vinyl compound with the N-substituted maleimide and the unsaturated monocarboxylic acid, various physical properties required for the ionizing radiation curable resin such as alkali developability can be improved. However, on the other hand, a new problem arises that heat resistance stability with respect to transparency and color tone is impaired.

On the other hand, in the present invention, the formula (1)
By using the N-substituted maleimide copolymer resin having an impurity content of 10% by weight or less, in addition to various physical properties required for the ionizing radiation curable resin such as alkali developability, transparency and Provided is an ionizing radiation-curable resin which is also excellent in heat resistance stability regarding color tone. This ionizing radiation curable resin has excellent patterning accuracy and various physical properties after curing, and can be suitably used as a material for forming various thin film layers and patterns contained in a color filter. It is possible to form not only a portion such as a spacer that does not require so much transparency, but also a portion that requires transparency such as a protective film or a colored layer.

The first copolymerization component of the N-substituted maleimide copolymer resin as the component A, the N-substituted maleimide (a component), is, for example, phenylmaleimide, benzylmaleimide, naphthylmaleimide, o-chlorophenylmaleimide or the like. Aromatic substituted maleimides; alkyl substituted maleimides such as methylmaleimide, ethylmaleimide, propylmaleimide, isopropylmaleimide, cyclohexylmaleimide and the like can be used. These maleimide-based monomers can be used alone or in combination of two or more. Among these, phenylmaleimide and cyclohexylmaleimide are preferable because they are industrially easily available and the monomer has relatively low toxicity. Further, cyclohexylmaleimide is most preferable from the viewpoint of transparency and thermal stability. When cyclohexylmaleimide is used, it is preferable to use cyclohexylmaleimide in which the content of cyclohexylaminosuccinic anhydride contained as a by-product in cyclohexylmaleimide is reduced to 1% by weight or less.

As the second copolymerization component of the N-substituted maleimide copolymerization resin and the aromatic vinyl compound (component b), for example, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, etc. are used. be able to. These aromatic vinyl monomers can be used alone or in combination of two or more. Among these, styrene is preferable from the viewpoint of industrial availability and polymerizability.

As the third copolymerization component of the N-substituted maleimide copolymerization resin, unsaturated monocarboxylic acid (component c),
A compound having an ethylenic double bond and a carboxyl group can be used, and examples thereof include methacrylic acid and acrylic acid. These unsaturated monocarboxylic acid-based monomers can be used alone or in combination of two or more.

The above-mentioned components (a), (b) and (c) are essential copolymerization components, but in addition to these components, the above essential copolymerization components are also included unless they are contrary to the gist of the present invention. You may use the compound (component (d)) copolymerizable with. Examples of the monomer used as desired include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and 2-ethylhexyl methacrylate; acrylic acid esters such as methyl acrylate and butyl acrylate; acrylonitrile, Vinyl cyanide such as methacrylonitrile; unsaturated dicarboxylic acid anhydride such as maleic anhydride can be used. These desired monomers can be used alone or in combination of two or more.

The N-substituted maleimide copolymer resin as the component A is an essential copolymer component (a), (b), (c).
Although it does not exhibit ionizing radiation curability by itself, it is possible to react a copolymer consisting of these essential copolymerization components with an unsaturated epoxy such as glycidyl methacrylate, or (a)
Together with the essential copolymerization components such as and (b) and (c),
After copolymerization is performed using a compound having a copolymerizable double bond such as the above-mentioned vinyl cyanide compound and a cyano group as the component (d), the cyano group portion is treated with a compound such as (meth) acrylic acid. When a saturated carboxylic acid is reacted, a side chain having a double bond is introduced into the resulting copolymer resin, and the N-substituted maleimide copolymer resin itself acquires ionizing radiation curability (crosslinkability). By using such an N-substituted maleimide copolymer resin having ionizing radiation curability as the component A, the sensitivity of the ionizing radiation curable resin can be improved.

The N-substituted maleimide copolymer resin as the component A has a total amount of the monomer components of 100% by weight,
(A) 10 to 80% by weight of N-substituted maleimide, (b)
10 to 80% by weight of an aromatic vinyl compound, (c) 1 to 70% by weight of an unsaturated monocarboxylic acid, and (d) 0 to 20% by weight of a compound copolymerizable with the essential copolymerization component.
To be synthesized by copolymerization. More preferably,
(A) 15 to 70% by weight, (b) 15 to 70% by weight,
(C) 10 to 60% by weight, (d) 0 to 15% by weight. Particularly preferably, (a) 20 to 55% by weight, (b)
15-55% by weight, (c) 20-55% by weight, (d) 0
10 to 10% by weight.

(C) If the content ratio of the unsaturated monocarboxylic acid is less than the above range, the solubility of the alkaline aqueous solution may decrease, while if it exceeds the above range, the heat resistance and the thermal stability may decrease. There is.

If the content of the (a) N-substituted maleimide is less than the above range, the heat resistance may decrease, while if it exceeds the above range, the aqueous alkali solution solubility may decrease. In addition, the mechanical strength when formed into a film may be reduced.

The N-substituted maleimide copolymer resin is 0.5
% Soluble in alkaline aqueous solution when using 1% KOH aqueous solution
It is preferably 0% by weight or less, more preferably 5% by weight or less, and most preferably 3% by weight or less. The alkali aqueous solution-soluble content of the N-substituted maleimide copolymer resin is specifically 50 ° C. of a film of the N-substituted maleimide copolymer resin having a thickness of 50 μm.
The amount of the alkali-insoluble component was determined by the solubility test in 200 ml of 0.5% KOH aqueous solution in
Can be evaluated.

The content of impurities represented by the above formula (1) contained in the N-substituted maleimide copolymer resin as the component A is preferably 10% by weight or less, more preferably 5% by weight or less, and 2% by weight. % Or less is more preferable, and 1% by weight or less is most preferable. When the content of the impurities represented by the formula (1) exceeds 10% by weight, yellowing easily occurs at high temperature, and the transparency and color tone heat resistance stability of the ionizing radiation curable resin are impaired. In addition, the ability of the ionizing radiation curable resin to dissolve in an aqueous alkali solution may be impaired.

The molecular weight of the N-substituted maleimide copolymer resin is preferably 5,000 to 200,000 in terms of weight average molecular weight, and 5,000, in order to exert alkali-solubility.
0 to 100,000 is more preferable, and 10,000 to
Most preferred is 50,000. If the weight average molecular weight exceeds the above range, the alkali-solubility may decrease,
On the other hand, if it is less than the above range, heat resistance and thermal stability may be deteriorated.

The N-substituted maleimide copolymer resin is
The ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight measured by GPC (gel permeation chromatography) is 4.0.
It is preferably below, more preferably below 3.0, most preferably below 2.5. If the ratio represented by Mw / Mn exceeds 4.0, the thermal stability and the alkali-solubility may decrease.

The N-substituted maleimide copolymer resin is
The acid value is preferably 50 to 300 mgKOH / g, more preferably 150 to 250 mgKOH / g. If the acid value is less than the above range, the alkali-solubility may be reduced, while if it exceeds the above range, the N-substituted maleimide copolymer resin may be brittle.

The N-substituted maleimide copolymer resin is usually added to the ionizing radiation-curable resin composition of the present invention in an amount of 5 to 80% by weight, preferably 10 to 50% by weight.
If the blending ratio of the N-substituted maleimide copolymer resin is less than the above range, the viscosity becomes too low and the coating stability after coating and drying is insufficient, while the blending ratio of the N-substituted maleimide copolymer resin is too small. If it exceeds the above range, the viscosity becomes too high, resulting in a decrease in fluidity and a deterioration in coating property.

As a method for producing the N-substituted maleimide copolymer resin as the component A, known solution polymerization, suspension polymerization, emulsion polymerization and the like can be adopted. In suspension polymerization or emulsion polymerization, a suspending agent or an emulsifier is used. Since it is mixed, it may cause a decrease in transparency. Further, in suspension polymerization or emulsion polymerization, the impurities of the above formula (1) may be generated, the composition distribution may be easily spread, and the alkali-solubility may be decreased.
Further, in suspension polymerization or emulsion polymerization, since the copolymerization components are reacted in a dispersed state in water, when the copolymerization reaction is attempted to proceed while supplying the copolymerization components to the reaction system by the method described below. In addition, the copolymerization component to be supplied later may not be sufficiently mixed in the reaction system, and the alkali solubility and heat resistance stability of the obtained copolymer resin may be reduced.

Therefore, it is preferable to use, as the N-substituted maleimide copolymer resin, one obtained by a solution polymerization method in which a maleimide monomer is used for copolymerization in the presence of a solvent. Furthermore, it is most preferable to use an N-substituted maleimide copolymer resin obtained by a batch solution polymerization method using a maleimide-based monomer.

The polymerization temperature in the copolymerization reaction may be set according to the polymerization initiator used and is not particularly limited, but is preferably 50 to 200 ° C, more preferably 80 to 150 ° C. When the polymerization temperature is lower than the above range, it is necessary to use an initiator having a low decomposition temperature, and equipment for cooling and storing the initiator is required, which is disadvantageous for industrial production. On the other hand, if the polymerization temperature exceeds the above range, the polymerization components start to undergo thermal polymerization before reaching the decomposition temperature of the initiator, which is not preferable.

The solvent used in the above solution polymerization is not particularly limited as long as it does not hinder the solution polymerization reaction and is capable of dissolving both the raw material copolymerization component and the produced N-substituted maleimide copolymerization resin. There is no limitation, for example, methanol,
Aliphatic alcohols having 1 to 3 carbon atoms such as ethanol and glycol; cellosolves such as cellosolve and butyl cellosolve; carbitols such as carbitol and butyl carbitol; cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, etc. , Ethers such as diethylene glycol dimethyl ether; cyclic ethers such as tetrahydrofuran; ketones such as cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone; or polar organic solvents such as dimethyl sulfoxide and dimethylformamide. The solvent used for the non-aqueous dispersion polymerization is not particularly limited as long as it is a liquid in which the raw material copolymerization component is soluble, and the produced N-substituted maleimide copolymerization resin is insoluble, for example, benzene, toluene,
Liquid hydrocarbons such as hexane and cyclohexane, or other non-polar organic solvent can be used. The amount of the solvent used for the solution polymerization or the non-aqueous dispersion polymerization is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, based on the total weight of the polymerization components. If the amount of the solvent is less than the above range, stirring may be insufficient due to thickening at the end of the polymerization, while if it exceeds the above range, the molecular weight of the N-substituted maleimide copolymer resin produced may be too small. There is.

As the polymerization initiator for producing the N-substituted maleimide copolymer resin, peroxides and azo initiators which are known radical polymerization initiators are preferably used. The polymerization initiator is appropriately selected according to the polymerization temperature, and is usually used in a proportion of 0.001 to 1.0% by weight based on the total amount of the copolymerization components.

In order to control the molecular weight of the N-substituted maleimide copolymer resin, a chain transfer agent can be used during the polymerization, and examples thereof include α-methylstyrene and mercaptan chain transfer agents.

In the copolymerization process for producing the N-substituted maleimide copolymer resin, it is preferable to specially devise the method of supplying the copolymerization component to the reaction system. Specifically, (b) an aromatic vinyl compound, (c) a part of unsaturated monocarboxylic acid, and optionally a solvent are placed in a reactor in advance, and an initiator is added to carry out the polymerization reaction. Once started, along with the remaining components (b) and (c), (a) N-
It is most preferable to carry out the polymerization reaction while continuously or intermittently supplying the substituted maleimide to the reaction system, and to continue the reaction for 0.5 hours or more after all the polymerization components have been supplied. The (a) N-substituted maleimide is not placed in the reactor in advance, but only a small amount is allowed. Therefore, almost all of the component (a) is continuously or intermittently supplied to the reaction system after the polymerization reaction is started. Further, it is preferable that the component (a) is not preliminarily mixed with the component (b) and the component (c), but is supplied to the reaction system separately from the component (b) and the component (c).

(A) The N-substituted maleimide is added to the reaction system in advance before the polymerization is started, and the ratio of the amount supplied to the reaction system continuously or intermittently after the initiation of the polymerization reaction is 0 to. It is preferably in the range of 5% by weight / 100 to 95% by weight, more preferably in the range of 0 to 1% by weight / 100 to 99% by weight, but the total amount (100% by weight) is after the initiation of the polymerization reaction. Most preferably, it is supplied.

The amount of the aromatic vinyl compound (b) to be added to the reaction system before the initiation of the polymerization and the amount of the aromatic vinyl compound to be continuously or intermittently supplied to the reaction system after the initiation of the polymerization reaction are from 1 to It can be adjusted in a wide range of 99% by weight / 99 to 1% by weight, but is preferably in the range of 5 to 90% by weight / 95 to 10% by weight, and 30 to 60% by weight / 70 to 40% by weight.
More preferably, it is in the range of wt%.

(C) The unsaturated monocarboxylic acid is added to the reaction system in advance before the initiation of the polymerization and the ratio of the amount supplied to the reaction system continuously or intermittently after the initiation of the polymerization reaction is 1 It can be adjusted in a wide range of from 99 to 99% by weight / 99 to 1% by weight, but the range of 10 to 90% by weight / 90 to 10% by weight is preferable, and 25 to 75% by weight / 75 to 25% by weight More preferably, the range is 30 to 7
The most preferable range is 0% by weight / 70 to 30% by weight.

By adopting such a polymerization method, it is possible to suppress the production of the impurities represented by the formula (1) and suppress the decrease in the aqueous alkaline solution solubility, and further, The maleimide-based monomer remaining in the obtained N-substituted maleimide copolymer resin can be effectively reduced. (A) N-substituted maleimide and (b)
When the whole amount of the aromatic vinyl compound is put in the reaction system in advance and the polymerization is started, the alternating copolymer of the component (a) and the component (b) is preferentially produced at the initial stage of the polymerization, and thereafter,
Subsequently, a polymer having a large amount of structural units derived from the remaining (c) unsaturated carboxylic acid is produced. Therefore, the alternating polymer composed of the components (a) and (b) and the unsaturated carboxylic acid monomer It is a mixture with a maleimide-based copolymer having many derived structural units. As a result, the resulting maleimide-based copolymer has a very broad composition distribution and a poor alkali-solubility, which is not preferable. Furthermore, if (a) N-substituted maleimide and (b) aromatic vinyl compound are put in the reaction system in advance and polymerization is started, impurities of the formula (1) are likely to be by-produced during heating and during polymerization. Become.

After all the (a) N-substituted maleimide has been supplied to the reaction system, the polymerization reaction is continued for 0.5 hour or longer, more preferably 1 hour or longer, whereby the remaining maleimide monomer The amount can be reduced. (A) N-
The substituted maleimide is required to carry out the polymerization reaction under the condition that 90% by weight or more, preferably 95% by weight or more, and more preferably the whole amount of the used maleimide is continuously or intermittently added to the reaction system after the initiation of the polymerization reaction. There is. When the polymerization reaction is started under the condition that the initial charge amount of (a) N-substituted maleimide exceeds 10% by weight of the amount used, an alternating polymer of (a) N-substituted maleimide and (b) aromatic vinyl compound is formed. This is because the amount may increase and the alkali-solubility may decrease.

Further, (a) N-substituted maleimide and (b)
It is preferable that the aromatic vinyl compound is not mixed before being supplied to the reaction system and is separately supplied to the reaction system. (A)
When the component and the component (b) are mixed and supplied, the impurity of the formula (1) is easily formed as a by-product in the mixed liquid.

As the method for removing the volatile matter from the reaction solution after the completion of the polymerization reaction to separate the N-substituted maleimide copolymer resin, the reaction solution is heated under vacuum, or the reaction solution is put into a poor solvent. Although a method of precipitating and filtering can be adopted, the method of pouring into a poor solvent and filtering is not industrially suitable because the equipment is too large. Therefore, a method of volatilizing and removing the solvent and the residual monomer by heating under vacuum is preferable.
Further, it is preferable to provide a facility for recovering the solvent and the residual monomer that have been volatilized and removed. Vacuum heating in a devolatilization tank and desolvation in a twin-screw extruder are preferably used as the heating solvent recovery equipment. In addition, after preliminarily concentrating the reaction solution in the devolatilization tank, the solvent removal can be completed with a twin-screw extruder. Further, after the polymerization, it is possible to use it for various purposes in a solution state without separating the solid content.

The N-substituted maleimide copolymer resin is (a)
The residual volatile content of the copolymerization components other than the N-substituted maleimide or the solvent is preferably 2000 ppm or less, more preferably 1000 ppm or less, and particularly preferably 500 ppm or less. A large amount of residual volatile matter is not preferable because it causes deterioration of thermal stability and causes coloring. Further, it is more preferable to reduce the amount of the (a) N-substituted maleimide remaining in the N-substituted maleimide copolymer resin. Specifically, the residual amount of (a) N-substituted maleimide is preferably 500 ppm or less, more preferably 200 ppm or less, and particularly preferably 100 ppm or less.

The ionizing radiation curable resin composition for color filters of the present invention uses, as the component B, a photopolymerizable component having three or more ethylenically unsaturated double bonds in one molecule. The tri- or higher functional photopolymerizable component used as the component B is a component that causes cross-linking by the action of ionizing radiation in the present invention to cure the ionizing radiation curable resin composition. As such a tri- or higher functional photopolymerizable component,
For example, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols or their dicarboxylic acid modified products can be used. Specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, succinic acid modified pentaerythritol triacrylate, succinic acid modified pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol. Examples thereof include tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, and the like.
Of these, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate are particularly preferably used.

The photopolymerizable component having a functionality of 3 or more, which is the component B, is usually contained in the ionizing radiation-curable resin composition of the present invention.
The amount is 5 to 70% by weight, preferably 10 to 40% by weight. When the amount of the trifunctional or higher photopolymerizable component is less than the above range, the unexposed portion is not easily removed during development. On the other hand, when the amount exceeds the above range, the viscosity becomes too low and the coating stability after coating and drying is poor. Since it is insufficient, it causes inconvenience such as impairing the suitability for exposure and development.

If necessary, a monofunctional or difunctional photocopolymerizable component as a reaction diluent may be added to the ionizing radiation curable resin composition together with a photopolymerizable component having three or more functional groups. . Specific examples of such a photocopolymerizable component include (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. In addition, "(meth) acrylate" means
It means that either acrylate or methacrylate may be used.

A photopolymerization initiator is added as the component C to the ionizing radiation-curable resin composition for color filters of the present invention. As the photopolymerization initiator used as the C component, active species such as radicals, cations and anions are generated by ionizing radiation having a wavelength of 365 nm or less, and the polymerization reaction of the trifunctional or more photopolymerizable component as the B component is performed. Use what you can get started. Further, the photopolymerization initiator preferably has high solubility in the solvent of the ionizing radiation curable resin composition. Examples of such a photoinitiator are compounds that generate free radicals by the energy of ultraviolet rays, and include benzophenone derivatives such as benzoin and benzophenone or derivatives thereof such as esters; xanthone and thioxanthone derivatives; chlorosulfonyl, chloromethyl. Halogen-containing compounds such as polynuclear aromatic compounds, chloromethyl heterocyclic compounds, and chloromethylbenzophenones; triazines; imidazolines; fluorenones; haloalkanes; redox couples of photoreducible dyes and reducing agents; organic sulfur compounds Examples thereof include peroxides. Among these, triazines and imidazolines are preferably used. These initiators can be used alone or in combination of two or more.

The photopolymerization initiator which is the component C is usually contained in the ionizing radiation-curable resin composition of the present invention in an amount of 0.05 to 20.
It is blended in a ratio of wt%, preferably 2 to 15 wt%.
When the blending ratio of the photopolymerization initiator is less than the above range, the curability of the coating film is insufficient. On the other hand, when it exceeds the above range, the unexposed portion is not easily removed during development, or the coating after post-baking is performed. This causes inconvenience such as yellowing of the film.

When it is desired to improve the sensitivity of the ionizing radiation curable resin composition, a sensitizer may be added to the resin composition. The sensitizer used is preferably a styryl compound or a coumarin compound. Specific examples of the styryl compound include 2- (p-dimethylaminostyryl) quinoline, 2- (p-diethylaminostyryl) quinoline, 4- (p-dimethylaminostyryl) quinoline, and the like. As a coumarin compound,
Examples thereof include 7-diethylamino-4-methylcoumarin, 7-ethylamino-4-trifluoromethylcoumarin, and 4,6-diethylamino-7-ethylaminocoumarin.

When the colored layer of the color filter is formed using the ionizing radiation curable resin composition of the present invention, a coloring material such as a pigment or a dye is blended as the D component in the resin composition. As the color material, there is heat resistance that can withstand the heating process of the color filter from among the organic colorant and the inorganic colorant in accordance with the desired color of R, G, B, etc. of the pixel portion,
In addition, fine particles that can be well dispersed can be selected and used.

As the organic colorant, for example, a dye, an organic pigment, a natural pigment or the like can be used. Further, as the inorganic colorant, for example, an inorganic pigment, an extender pigment or the like can be used.

Specific examples of the organic pigment include color index (CI; The Society of Dyers and Colorists).
(Published by the company), compounds classified as Pigment, that is, compounds having the following color index (CI) numbers can be mentioned. CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13 and other yellow pigments; CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3 and other red pigments; and CI Pigment Blue 15, CI pigment blue 15: 3, CI pigment blue 15: 4 and other blue pigments.

Specific examples of the inorganic pigment or extender pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), and cadmium red. , Ultramarine, dark blue, chrome oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like. In the present invention, the coloring materials may be used alone or in combination of two or more.

The colorant is usually contained in the ionizing radiation-curable resin composition of the present invention in an amount of 40 to 75% by weight, preferably 45 to 75% by weight.
It is mixed at a ratio of 70% by weight. When the mixing ratio of the coloring material is less than the above range, the coloring power of each colored layer is insufficient, and it is difficult to display a clear image. On the other hand, when it exceeds the above range, the light transmittance of each colored layer is low. It causes inconvenience such as insufficient.

When the coloring material is blended with the ionizing radiation-curable resin composition, a dispersant may be blended with the ionizing radiation-curable resin composition in order to uniformly and stably disperse the coloring material. . As the dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone, fluorine-based surfactants, etc. can be used. Among the surfactants, the following polymer surfactants (polymer dispersants) are preferable.

That is, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene alkyl such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Polymer surfactants such as phenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid modified polyesters; tertiary amine modified polyurethanes are preferably used.

The ionizing radiation-curable resin composition of the present invention may be blended with a thermosetting resin which reacts with an acid to be cured by heating. An acid-reactive thermosetting resin is mixed with the ionizing radiation curable resin composition of the present invention, the resin composition is applied to the surface of the substrate, and a cured pattern is formed by exposing and developing the resin composition in a desired pattern. After the formation, when the cured pattern is heated to a predetermined temperature, it reacts with the carboxyl groups remaining in the cured pattern to consume the carboxyl groups and improve the alkali resistance, and at the same time, due to the crosslinking reaction of the thermosetting resin. The physical properties of the cured pattern are improved. As a result, the heat resistance, adhesion, hot pure water resistance and chemical resistance (particularly alkali resistance) of the film or pattern formed from the ionizing radiation curable resin composition of the present invention are improved.

The acid-reactive thermosetting resin is preferably an epoxy resin, particularly an epoxy resin having two or more epoxy groups in one molecule. Specifically, bisphenol A
Type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin and the like.

The thermosetting resin is usually added to the ionizing radiation-curable resin composition of the present invention in an amount of 1 to 20% by weight, preferably 3 to 15% by weight. If the blending ratio of the thermosetting resin is less than the above range, sufficient alkali resistance cannot be imparted to the coating film, while if it exceeds the above range,
Inconveniences such as deterioration in storage stability and developability of the photosensitive resin composition occur.

The ionizing radiation-curable resin composition of the present invention may contain various additives other than those mentioned above, if necessary. For example, a silane coupling agent such as vinyl silane, acryl silane, or epoxy silane can be added to the ionizing radiation curable resin composition to improve the adhesiveness with the base material or another adjacent coating layer.

The ionizing radiation curable resin composition of the present invention comprises
In consideration of paintability and coating suitability, it is usually diluted with a solvent. As the solvent, N-substituted maleimide copolymer resin,
It is desired that the compounding components such as the trifunctional photopolymerizable component and the photoinitiator are dissolved, the boiling point is high, and the spin coating property is good. Examples of usable solvents include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol and i-propyl alcohol;
Cellosolve solvents such as methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxy ethoxy ethanol and ethoxy ethoxy ethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate; acetone , Methyl isobutyl ketone, cyclohexanone and other ketone solvents; methoxyethyl acetate,
Cellosolve acetate solvents such as ethoxyethyl acetate and ethyl cellosolve acetate; Carbitol acetate solvents such as methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate; ether solvents such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetrahydrofuran; N, N-dimethylformamide,
Aprotic amide solvents such as N, N-dimethylacetamide and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; benzene, toluene, xylene,
Examples thereof include unsaturated hydrocarbon solvents such as naphthalene; and organic solvents such as saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane. Among these solvents, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether and the like are preferable.

The amount of the solvent used is appropriately adjusted in consideration of the dissolved state of the blended components and the coatability, but usually the solid content concentration is adjusted to about 5% to 50%.

In order to produce the ionizing radiation-curable resin composition of the present invention, the component A is an N-substituted maleimide copolymer resin, the component B is a trifunctional photopolymerizable component, and the component C is a photopolymerization component. An initiator and, if necessary, a colorant which is the D component, and further other compounding ingredients are mixed in an arbitrary order, or are added to a solvent in an arbitrary order, and a paint shaker,
A bead mill, a sand grind mill, a ball mill, an attritor mill, a two-roll mill, a three-roll mill, etc. are used to stir and uniformly dissolve and disperse.

(2) Color Filter According to the Present Invention A method for forming a cured film (including one formed in a predetermined pattern) using the ionizing radiation curable resin composition of the present invention will be described below. First, the ionizing radiation curable resin composition of the present invention is applied to the surface of an object to be coated, and the formed coating film is irradiated with ionizing radiation such as ultraviolet rays or electron beams to be exposed and cured. When the coating film is irradiated with ionizing radiation,
In the coating film, active species are first generated from the photoinitiator (component C) by the action of ionizing radiation, and the crosslink reaction of the trifunctional photopolymerizable component (component B) is initiated by the action of the active species, and The coating film hardens.

At this time, when it is desired to form the coating film in a predetermined pattern such as pixels or columnar spacers, the coating film is exposed through a photomask or the like to be exposed in a predetermined pattern and developed. The coating film can be alkali-developed because the N-substituted maleimide copolymer resin as the component A has a carboxyl group. The N-substituted maleimide copolymer resin does not have photopolymerization reactivity when it is composed of only structural units derived from the copolymerization components (a), (b) and (c), It is an essential binder component for imparting film forming properties, strength, adhesion, transparency, alkali developability and the like. Further, by introducing a side chain having an ionizing radiation-curable functional group such as an ethylenic double bond into the molecule of the N-substituted maleimide copolymer resin, the N-substituted maleimide copolymer resin is a component B. Three
It becomes possible to carry out a crosslinking reaction with a functional photopolymerizable component, and the physical properties such as exposure sensitivity and strength of the film are improved.

The coating film is exposed to light and cured and, if necessary, developed, and then the coating film is further heated and cured to obtain a cured film. When the exposure-cured coating film has an ethylenic double bond of the component B remaining, the crosslinking reaction can be further advanced by the heating step. Further, when the coating film contains a thermosetting resin such as a bifunctional epoxy resin, it reacts with the carboxyl group of the component A remaining in the coating film to consume the carboxyl group. At the same time, cross-linking occurs. As a result, the heat resistance, adhesion, hot pure water resistance and chemical resistance (particularly alkali resistance) of the cured film are improved.

A cured film obtained using the ionizing radiation-curable resin of the present invention is excellent in various physical properties such as adhesion to the surface of an object to be coated, film strength, heat resistance, hot pure water resistance, and chemical resistance, and Accurate pattern formation can be achieved by alkali development. Furthermore, it is excellent in heat resistance stability with respect to transparency and color tone, and in particular, even when exposed to a high temperature environment such as a heating step when forming an alignment film in a color filter manufacturing process, yellowing does not occur, and the transparency is high. It is possible to form a high protective film and a colored layer having a desired color tone.

Specifically, the ionizing radiation curable resin composition of the present invention is applied onto a glass substrate by spin coating,
After exposure with a dose of 100 mJ / cm ² , 30 at 200 ° C
A coating film formed by heating for 2 minutes to a film thickness of 2 μm was 380 n after heating the coating film at 250 ° C. for 1 hour.
The light transmittance of m can be maintained at 90% or more.

Further, the coating film prepared from the ionizing radiation-curable resin composition of the present invention is very hard and has sufficient hardness in addition to transparency and heat resistance regarding color tone. Specifically, the same conditions as above, that is, the ionizing radiation curable resin composition is applied onto a glass substrate by spin coating,
After exposure with a dose of 100 mJ / cm ² , 30 at 200 ° C
When a coating film having a film thickness of 5 μm is formed by heating for a minute, the surface hardness of the coating film is 180 ° C. and the Vickers indenter has a maximum load of 20 mN. Surface area of the Vickers indenter) is 200 N / mm ² or more.

The ionizing radiation curable resin of the present invention is suitable for forming a colored layer of a color filter, a protective layer for covering the colored layer, and a columnar spacer for maintaining a cell gap of a liquid crystal panel. .

The color filter comprises a black matrix formed in a predetermined pattern on a transparent substrate, a colored layer formed in a predetermined pattern on the black matrix, and a protective film formed so as to cover the colored layer. ing. A transparent electrode for driving a liquid crystal may be formed on the protective film as needed. In addition, a columnar spacer may be formed on the transparent electrode plate, the colored layer, or the protective film in accordance with the region where the black matrix layer is formed.

The colored layer is formed by arranging a red pattern, a green pattern, and a blue pattern in a desired form such as a mosaic type, a stripe type, a triangle type, and a four-pixel arrangement type, and a black matrix is provided between the colored patterns and between the colored layers. It is provided in a predetermined area outside the formation area. The colored layer can be formed by various methods, but it is preferably formed by the pigment dispersion method using the ionizing radiation curable resin of the present invention. That is, a coating material is prepared by dispersing a color pigment in the ionizing radiation curable resin of the present invention, applied on one surface side of a transparent substrate, and exposed by irradiating ionizing radiation such as ultraviolet rays through a photomask. After the alkali development, the colored layer can be formed by heating and curing in a clean oven or the like. The colored layer is usually formed to have a thickness of about 1.5 μm.

The black matrix can be formed by any of the dyeing method, the pigment dispersion method, the printing method and the electrodeposition method, or may be formed by chromium vapor deposition or the like.

The protective film can be formed by applying the coating liquid of the ionizing radiation curable resin of the present invention by a method such as spin coater, roll coater, spraying or printing. The protective film is formed to have a thickness of about 2 μm, for example.
When using a spin coater, the rotation speed is 500 to 15
Set within the range of 00 revolutions / minute. The coating film of the ionizing radiation curable resin is exposed by irradiating it with ionizing radiation through a photomask, and after alkali development, it is heated and cured in a clean oven or the like to form a protective film.

The transparent electrode on the protective film is made of indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (Sn).
O), etc., and their alloys, etc., are formed by a general method such as a sputtering method, a vacuum deposition method, a CVD method, etc., and if necessary, by etching using a photoresist or using a jig, It is a pattern. The thickness of the transparent electrode can be about 20 to 500 nm, preferably about 100 to 300 nm.

The columnar spacer on the transparent electrode is also coated with the coating liquid of the ionizing radiation-curable resin of the present invention by a method such as spin coater, roll coater, spraying or printing.
It can be formed by exposing to ionizing radiation through a photomask, alkali development, and then heat curing in a clean oven or the like. The columnar spacer is, for example, 5 μm
It is formed to a high level. The rotation speed of the spin coater is 500 to 1500 rotations / similar to the case of forming the protective film.
It may be set within the range of minutes.

A liquid crystal panel is obtained by forming an alignment film on the inner surface side of the color filter thus manufactured, facing the electrode substrate, filling the gap with liquid crystal and sealing the liquid crystal.

[0097]

(Example 1) (Synthesis of N-substituted maleimide copolymer resin solution 1) 3.7 parts by weight of styrene, 3.7 parts by weight of methacrylic acid, and diethylene glycol dimethyl ether (DMDG) in a polymerization tank.
55 parts by weight and 1.0 part by weight of α-methylstyrene dimer were charged, and the temperature of the polymerization system was raised to 110 ° C., and then t-butylperoxyisopropyl carbonate as an initiator was added.
Polymerization was started by adding 05 parts by weight, and 6.3 parts by weight of styrene and 6.
3 parts by weight, 0.05 parts by weight of t-butylperoxyisopropyl carbonate, 12 parts by weight of N-cyclohexylmaleimide (CHMI) as a dropping system (B) were added to DMDG12.
What was melt | dissolved at 60 degreeC in weight part was continuously supplied over 3 hours, and superposition | polymerization was continued for 2 hours. DM the polymerization solution
After diluted with DG, it was poured into hexane to obtain a maleimide copolymer as a precipitate. The acid value of the obtained maleimide copolymer is 238 mgKOH / g, the polymerization average molecular weight is 28,000 in terms of polystyrene, and the glass transition point is 2.
It was 01 ° C. The obtained polymer was redissolved in DMDG to obtain N-substituted maleimide copolymer resin solution 1 having a solid content of 20%.

(Preparation of Curable Resin Composition 1) The following amounts of each material and the above N-substituted maleimide copolymer resin solution 1 (solid content 2
0%): 69.0 parts by weight-dipentaerythritol pentaacrylate (SR399, Sartomer): 11.0 parts by weight-Orthocresol novolac type epoxy resin (Epicote 180S70, manufactured by Yuka Shell Epoxy Co., Ltd.): 15.
0 parts by weight 2-methyl-1- (4-methylthiophenyl) -2-
Morpholinopropanone-1: 2.1 parts by weight of 2,2'-bis (O-chlorophenyl) -4,5,
4 ′, 5′-Tetraphenyl-1,2′-biimidazole: 1.5 parts by weight / diethylene glycol dimethyl ether: 66.0 parts by weight were stirred and mixed at room temperature to obtain a curable resin composition 1.

(Example 2) (Synthesis of N-substituted maleimide copolymer resin solution 2) 2.8 parts by weight of styrene, 4.6 parts by weight of methacrylic acid, 4.2 parts by weight of styrene in a dropping system, and methacrylic acid were added. The same operation as in the synthesis method of Example 1 was carried out except that the amount was changed to 8.4 parts by weight, and the polymerization solution was diluted with DMDG and then poured into hexane to obtain a maleimide copolymer as a precipitate. .
The acid value of the obtained maleimide copolymer is 285 mgKO.
H / g, polymerization average molecular weight is 2400 in terms of polystyrene
0, the glass transition point was 208 ° C. The obtained polymer was redissolved in DMDG to obtain N-substituted maleimide copolymer resin solution 2 having a solid content of 20%.

(Preparation of Curable Resin Composition 2) A curable resin composition 2 was prepared in the same manner as in Example 1 except that the resin used was N-substituted maleimide copolymer resin solution 2. Got

(Example 3) (Synthesis of N-substituted maleimide copolymer resin solution 3) CHM
The same operation as in the synthesis method of Example 1 was carried out except that N-phenylmaleimide was used instead of I, and the polymerization solution was diluted with DMDG and then poured into hexane to give a maleimide-based copolymerization product as a precipitate. Got united. The acid value of the obtained maleimide copolymer was 234 mgKOH / g, the polymerization average molecular weight was 26000 in terms of polystyrene, and the glass transition point was 206 ° C. The obtained polymer was redissolved in DMDG to obtain N-substituted maleimide copolymer resin solution 3 having a solid content of 20%.

(Preparation of Curable Resin Composition 3) A composition was prepared in the same manner as in Example 1 except that the resin used was changed to N-substituted maleimide copolymer resin solution 3 and curable resin composition 3 was prepared. Got (Example 4) (Synthesis of N-substituted maleimide copolymer resin solution 4) CHM
The same operation as in the synthesis method of Example 1 was carried out except that N-benzylmaleimide was used in place of I, the polymerization solution was diluted with DMDG, and the mixture was poured into hexane to give a maleimide-based copolymerization product as a precipitate. Got united. The acid value of the obtained maleimide copolymer was 239 mgKOH / g, the polymerization average molecular weight was 29000 in terms of polystyrene, and the glass transition point was 189 ° C. The obtained polymer was redissolved in DMDG to obtain N-substituted maleimide copolymer resin solution 4 having a solid content of 20%. (Preparation of curable resin composition 4) A curable resin composition 4 was obtained by preparing a composition in the same manner as in Example 1 except that the resin used was changed to the N-substituted maleimide copolymer resin solution 4. .

(Example 5) (Synthesis of N-Substituted Maleimide Copolymer Resin Solution 5) The polymerization solution obtained in Example 1 was not diluted with DMDG, but a twin-screw extruder with a vent, which was a devolatilizer. And put it under reduced pressure for 20
The solvent was removed at 0 ° C., the maleimide copolymer was extruded, and the obtained strand was pulverized to obtain a maleimide copolymer. The acid value of the obtained maleimide copolymer is 241 m.
gKOH / g, polymerization average molecular weight is 2 in terms of polystyrene
The glass transition point was 3000 and glass was 195 ° C. The obtained polymer was redissolved in DMDG to obtain a solution containing 20% solid content of N.
-Substituted maleimide copolymer resin solution 5 was obtained.

(Preparation of Curable Resin Composition 5) A curable resin composition 5 was prepared in the same manner as in Example 1 except that the resin used was changed to N-substituted maleimide copolymer resin solution 5. Got

(Example 6) (Synthesis of N-substituted maleimide copolymer resin solution 6) 4.6 parts by weight of styrene initially charged and 3.7 parts of methacrylic acid were charged.
Parts by weight, styrene in the dropping system was 8.4 parts by weight, methacrylic acid was 6.3 parts by weight, and CHMI was 9 parts by weight.
After diluted with MDG, it was poured into hexane to obtain a maleimide copolymer as a precipitate. The acid value of the obtained maleimide copolymer was 239 mgKOH / g, the polymerization average molecular weight was 32000 in terms of polystyrene, and the glass transition point was 181 ° C. The obtained polymer was redissolved in DMDG to obtain N-substituted maleimide copolymer resin solution 6 having a solid content of 20%.

(Preparation of Curable Resin Composition 6) A composition was prepared in the same manner as in Example 1 except that the resin used was N-substituted maleimide copolymer resin solution 6, and the curable resin composition 6 was prepared. Got

Comparative Example 1 (Synthesis of Acrylic Copolymer Resin Solution 1) 250 parts by weight of benzyl methacrylate, 350 parts by weight of styrene, 150 parts by weight of acrylic acid, and 200 parts by weight of 2-hydroxyethyl methacrylate were added to azobisisobutyrate. A solution prepared by dissolving 5 parts by weight of ronitrile and 650 parts by weight of 3-methoxybutyl acetate in a polymerization tank containing 1000 parts by weight of 3-methoxybutyl acetate was added dropwise at 100 ° C. for 6 hours.
Polymerization was performed to obtain an acrylic copolymer resin solution 1. The solid content of the obtained resin solution was 20%. The acid value of the acrylic copolymer obtained as a precipitate by pouring the obtained resin solution into hexane was 110 mgKOH / g, the polymerization average molecular weight was 43,000 in terms of polystyrene, and the glass transition point was 92 ° C.

(Preparation of curable resin composition 7) A composition was prepared in the same manner as in Example 1 except that the acrylic copolymer resin solution 1 was used as the resin used to obtain a curable resin composition 7. It was

(Comparative Example 2) (Synthesis of N-substituted maleimide copolymer resin solution 7) 53 parts by weight of DMDG and 1.0 part by weight of α-methylstyrene dimer were charged into a polymerization tank, and the temperature of the polymerization system was raised to 110 ° C. Then, 0.1 part by weight of t-butylperoxyisopropyl carbonate as an initiator was added to start polymerization, and 0.1 part by weight of t-butylperoxyisopropyl carbonate and 5 parts by weight of DMDG were added as a dropping system (A). As a dropping system (B), 10 parts by weight of styrene and 10 parts of methacrylic acid were added.
6 parts by weight, 12 parts by weight of CHMI and 7 parts by weight of DMDG
What was melt | dissolved at 0 degreeC was continuously supplied over 3 hours, and superposition | polymerization was continued for 2 hours. The polymer solution was diluted with DMDG and then poured into hexane to obtain a maleimide copolymer as a precipitate. The acid value of the obtained maleimide copolymer was 235 mgKOH / g, the weight average molecular weight was 36000 in terms of polystyrene, and the glass transition point was 141 ° C. The obtained polymer was redissolved in DMDG to obtain N-substituted maleimide copolymer resin solution 7 having a solid content of 20%.

(Preparation of Curable Resin Composition 8) A composition was prepared in the same manner as in Example 1 except that the resin used was changed to N-substituted maleimide copolymer resin solution 7, and the curable resin composition 8 was prepared. Got

The physical properties of the resulting copolymer are shown in Table 1.

[0112]

[Table 1]

(Example 7) (Formation of black matrix) First, the following amount: Black pigment: 23 parts Polymer dispersant (manufactured by BYK Japan KK)
sperbyk 111): 2 parts by weight Solvent (diethylene glycol dimethyl ether): 7
5 parts by weight of the components were mixed and sufficiently dispersed by a sand mill to prepare a black pigment dispersion liquid.

Next, the following amount -The above black pigment dispersion: 61 parts by weight -Curable resin composition of Example 1: 1:20 parts by weight ・ Diethylene glycol dimethyl ether: 30 parts by weight The components described in (1) above were thoroughly mixed to obtain a light-shielding layer composition.

Then, the above composition for a light-shielding layer was applied onto a glass substrate (AL material manufactured by Asahi Glass Co., Ltd.) having a thickness of 1.1 mm by a spin coater and dried at 100 ° C. for 3 minutes to form a light-shielding film having a thickness of about 1 μm. Layers were formed. The light-shielding layer is exposed to a light-shielding pattern with an ultra-high pressure mercury lamp, developed with a 0.05% potassium hydroxide aqueous solution, and then subjected to heat treatment by leaving the substrate in an atmosphere of 180 ° C. for 30 minutes. A black matrix was formed in the area where the light-shielding portion should be formed.

(Formation of Colored Layer) A red curable resin composition having the following composition was applied by spin coating (coating thickness: 1.5 μm) on the substrate on which the black matrix was formed as described above, and then 70 Dry in an oven at 0 ° C for 30 minutes.

Then, a photomask was arranged at a distance of 100 μm from the coating film of the red curable resin composition, and a 2.0 kW ultrahigh pressure mercury lamp was used by a proximity liner to form only a region corresponding to the formation region of the colored layer. The sample was exposed to ultraviolet rays for 10 seconds. Then, it was immersed in a 0.05 wt% potassium hydroxide aqueous solution (liquid temperature 23 ° C.) for 1 minute for alkali development to remove only the uncured portion of the coating film of the red curable resin composition. Then, the substrate is placed in an atmosphere of 180 ° C. for 3
By leaving it for 0 minutes, heat treatment was performed to form a red relief pattern in the region where the red pixel was to be formed.

Next, using the green curable resin composition having the following composition, in the same process as the formation of the red relief pattern,
A green relief pattern was formed in a region where a green pixel should be formed.

Further, a blue curable resin composition having the following composition was used to form a blue relief pattern in a region where a blue pixel is to be formed, in the same process as that for forming a red relief pattern, and red (R), A colored layer composed of three colors of green (G) and blue (B) was formed.

A. Composition of red curable resin composition C.I. I. Pigment Yellow 139: 2 parts by weight C.I. I. Pigment Red 254: 8 parts by weight, polysulfonic acid type polymer dispersant: 3 parts by weight, curable resin composition of Example 1 1: 5 parts by weight, 3-methoxybutyl acetate: 82 parts by weight b. Composition of green curable resin composition C.I. I. Pigment Green 36: 6 parts by weight C.I. I. Pigment Yellow 138: 4 parts by weight, polysulfonic acid type polymer dispersant: 3 parts by weight, curable resin composition of Example 1 1: 5 parts by weight, 3-methoxybutyl acetate: 82 parts by weight c. Composition of blue curable resin composition C.I. I. Pigment Blue 15: 6: 10 parts by weight, polysulfonic acid type polymer dispersant: 3 parts by weight, curable resin composition of Example 1 1: 5 parts by weight, 3-methoxybutyl acetate: 82 parts by weight (Examples 8) (Formation of protective film) The curable resin composition 1 of Example 1 was applied onto the glass substrate on which the colored layer was formed in Example 7 by spin coating and dried to form a coating film having a dry film thickness of 2 μm. Formed.

100 μm from the coating film of the curable resin composition 1
A photomask was placed at a distance of m, and an ultraviolet ray was irradiated for 10 seconds only by a proximity liner using a 2.0 kW ultra-high pressure mercury lamp on an area corresponding to the area where the colored layer was formed. Next, it was immersed in a 0.05 wt% aqueous solution of potassium hydroxide (liquid temperature: 23 ° C.) for 1 minute for alkali development to remove only the uncured portion of the coating film of the curable resin composition.
Then, the substrate was left in an atmosphere of 200 ° C. for 30 minutes for heat treatment to form a protective film, and a color filter of the present invention was obtained.

(Example 9) (Application of Curable Resin Composition 1) (Formation of Spacer) On the glass substrate on which the colored layer was formed in Example 7, the curable resin composition 1 obtained in Example 1 was applied. Was applied by a spin coating method and dried to form a coating film having a dry film thickness of 5 μm.

100 μm from the coating film of the curable resin composition 1
A photomask was placed at a distance of m, and a 2.0 kW ultra-high pressure mercury lamp was used by a proximity liner to irradiate only the spacer formation region on the black matrix with ultraviolet rays for 10 seconds. Next, it was immersed in a 0.05 wt% aqueous solution of potassium hydroxide (liquid temperature: 23 ° C.) for 1 minute for alkali development to remove only the uncured portion of the coating film of the curable resin composition. Then, the substrate was left in an atmosphere of 200 ° C. for 30 minutes for heat treatment to form a fixed spacer, and a color filter of the present invention was obtained.

(Example 10) The substrate temperature of 2 was applied to the surface of the color filter obtained in Example 9 including the fixed spacers.
A transparent electrode film was formed by using DC and magnetron sputtering method with ITO as a target, using argon and oxygen as discharge gas at 00 ° C. After that, an alignment film made of polyimide was further formed on the transparent electrode film.

Next, the color filter and the TFT
The liquid crystal display device of the present invention, in which a glass substrate on which the above is formed is bonded using an epoxy resin as a sealing material under a pressure of 0.3 kg / cm ² at 150 ° C. to form a cell, and TN liquid crystal is sealed. Was produced.

(Example 11) On the colored layer of the glass substrate on which the colored layer was formed in Example 7, or in Example 8.
A transparent electrode film was formed on the protective film of the color filter having the colored layer and the protective film, at a substrate temperature of 200 ° C., using argon and oxygen as discharge gas, and DC magnetron sputtering with ITO as a target.
Then, an alignment film made of polyimide was further formed on the transparent electrode film to obtain a color filter.

(Evaluation of Heat Resistance) The curable resin composition 1 obtained in Example 1 was applied onto a glass substrate of 10 cm by a spin coater (MIKASA, model 1H-DX2), dried and dried. A coating film having a thickness of 2.2 μm was formed. This coating film was heated on a hot plate at 90 ° C. for 3 minutes. After heating, UV aligner equipped with a 2.0 kW ultra-high pressure mercury lamp (manufactured by Dainippon Screen, type MA
1200), a strength of 100 mJ / cm ² (405
Ultraviolet rays were radiated in terms of nm illuminance conversion).

After the irradiation of ultraviolet rays, the coating film was cleaned in a clean oven (manufactured by Ninpo Institute, SCOV-250 Hy-S).
o) dried at 200 ° C for 30 minutes, film thickness 2.0 μm
A cured film of was obtained. The light transmittance (380 nm) of the cured film thus obtained on the glass substrate was used as a reference for the glass substrate, and an absorptiometer (manufactured by Shimadzu Corporation, UV-310).
0PC).

Then, the measured glass substrate with a cured film was attached to a clean oven (SCOV-2 manufactured by Ninpo Research Institute Co., Ltd.).
50 Hy-So) was heated at 250 ° C. for 1 hour to obtain a heat-test cured film. The transmittance of visible light (380 nm to 780 nm) of the cured film thus obtained on the glass substrate was measured using an optical spectrometer (UV-3100PC, manufactured by Shimadzu Corporation) with the glass substrate as a reference.

The heat resistance of the cured film was evaluated from the change in the light (380 nm) transmittance before and after the heating test. Further, similarly to the above method, coating films of the curable resin compositions 2 to 6 obtained in other examples were formed, and light (3) before and after the heating test was formed.
The heat resistance of the cured film was evaluated from the change in transmittance of 80 nm). Thus, Table 2 shows the evaluation results of the heat resistance of the cured resin compositions 1 to 6.

(Evaluation of Physical Properties of Cured Film) The curable resin composition 1 obtained in Example 1 was applied onto a glass substrate having a size of 10 cm by a spin coater (manufactured by MIKASA, model 1H-DX2) and dried, A coating film having a dry film thickness of 5.4 μm was formed. This coating film was heated on a hot plate at 90 ° C. for 3 minutes. After heating, UV aligner equipped with a 2.0 kW ultra-high pressure mercury lamp (Dainippon Screen, type M
A 1200), a strength of 100 mJ / cm ² (40
Ultraviolet rays were irradiated at a 5 nm illuminance conversion. After irradiation with ultraviolet rays, the coating film was cleaned in a clean oven (manufactured by Ninja Research Institute,
SCOV-250 Hy-So) 30 at 200 ° C
After drying for a minute, a cured film having a thickness of 5.0 μm was obtained.

The hardness of the obtained cured film was measured with an ultra-micro hardness meter (manufactured by Fisher Instruments Co., WIN-H).
CU) and the surface temperature of the cured film is 180 ° C with a heating jig.
Universal hardness (surface area of Vickers indenter under test load / test load) when surface hardness is measured under the condition that the maximum load of Vickers indenter is 20 mN.
It was evaluated by.

Further, similarly to the above-mentioned method, coating films of the curable resin compositions 2 to 6 obtained in other examples were formed, and the hardness of these cured films was measured by a heating jig. When the surface temperature was 180 ° C., the universal hardness (test load / surface area of Vickers indenter under test load) when the surface hardness was measured under the condition that the maximum load of the Vickers indenter was 20 mN was evaluated. Thus, Table 2 shows the evaluation results of the heat resistance of the cured resin compositions 1 to 6.

(Evaluation of developability) The curable resin composition 1 obtained in Example 1 was applied onto a glass substrate of 10 cm by a spin coater (manufactured by MIKASA, model 1H-DX2), dried and dried. A coating film having a thickness of 2.2 μm was formed. This coating film was heated on a hot plate at 90 ° C. for 3 minutes. After heating, a UV mask aligner equipped with a 2.0 kW ultra-high pressure mercury lamp with a photomask placed at a distance of 100 μm from the coating film (manufactured by Dainippon Screen, type MA
1200), a strength of 100 mJ / cm ² (405
Ultraviolet rays were radiated in terms of nm illuminance conversion).

After irradiation with ultraviolet rays, a 0.05 wt% aqueous potassium hydroxide solution was applied to the coating film by a spin developing machine (Applied).
Process Technology, INK, MO
DEL: 915) for 60 seconds, the unexposed area was dissolved and removed, and the remaining exposed area was washed with pure water for 60 seconds for development. After development, the exposed film was cleaned in a clean oven (SCOV-250 Hy-manufactured by Ninja Institute).
So), heating at 200 ° C. for 30 minutes. And
The developability of the obtained film was observed with an optical microscope (Olympus Optical Co., Ltd., MHL100) and a stylus type surface roughness measuring device (Japan Anerva Co., Ltd., Dektak 1600) for observing the shape of the relief pattern. Poor shape was marked with x, good one was marked with o, and very good one was marked with ◎.

Further, by the same method as described above, the curable resin compositions 2 to 6 obtained in other examples and comparative examples were prepared.
The coating film was formed, and the shape of the relief pattern after development was observed. In this way, the developability of each curable resin composition 1 to 6 was evaluated. The results are shown in Table 2.

[0137]

[Table 2]

[0138]

As described above, the ionizing radiation-curable resin composition according to the present invention can be cured by irradiation with ionizing radiation, and after curing, adhesion, film strength,
A film with excellent physical properties such as heat resistance, hot pure water resistance, and chemical resistance. Further, since the coating film of the ionizing radiation curable resin composition according to the present invention can be exposed to a predetermined pattern and then accurately developed with an alkali, precise patterning is possible. Furthermore, since the content of impurities that cause yellowing is low, it does not yellow even when exposed to the high temperature environment that is unavoidable in the color filter manufacturing process, such as heating for forming the alignment film, and it has transparency and color tone. Has excellent heat resistance stability.

By using the ionizing radiation curable resin composition according to the present invention, a thin film layer or a fine pattern included in a color filter can be accurately formed, and a columnar spacer for maintaining a cell gap of a liquid crystal panel. It is also possible to form not only such a film that does not require so much transparency, but also a film of a portion such as a colored layer or a protective layer that has a great demand for transparency and color tone. Therefore, a high quality color filter and a high quality liquid crystal panel using the color filter can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of an example of a liquid crystal panel.

FIG. 2 is a schematic cross-sectional view of another example of a liquid crystal panel.

[Explanation of symbols]

1 ... Color filter 2 ... Electrode substrate 3 ... Gap 4 ... Sealing material 5: Transparent substrate 6 ... Black matrix layer 7 (7R, 7G, 7B) ... Colored layer 8 ... Protective film 9 ... Transparent electrode film 10 ... Alignment film 11 ... Pearl 12 ... Column spacer

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 222/40 C08F 222/40 G02F 1/1335 505 G02F 1/1335 505 G03F 7/004 505 G03F 7/004 505 7 / 037 7/037 (72) Inventor Shunsuke Sega 1-1-1 Ichigaya-Kagacho, Shinjuku-ku, Tokyo Within Dai Nippon Printing Co., Ltd. (72) Kenichi Ueda 5-8 Nishimitabicho, Suita-shi, Osaka (72) Inventor Minoru Yamaguchi 5-8 Nishimitabicho, Suita City, Osaka Prefecture F-Term (Reference) 2H025 AA04 AA11 AB13 AC01 AD01 BC82 BJ00 BJ10 CA00 CB08 CB10 CB25 CB43 CC11 FA17 2H048 BA02 BA48 BB02 2H091 FA02Y FB02 FB11 GA01 LA30 4J011 PA65 PA69 PA70 PC02 PC08 QA03 QA23 QA24 QA34 QA35 RA03 RA04 RA10 SA21 SA31 SA62 SA04 SA04 SA04 SA04 SA04 SA04 SA04 SA02 SA04 SA02 SA04 SA02 SA04 SA02 SA04 SA02 SA04 SA02 SA04 SA02 SA01 SA04 SA02 SA04 SA01 SA04 SA02 SA04 SA02 SA01 BC43P BC49P CA05 DA01 DA25 DA2 9 JA38

Claims (7)

[Claims] 1. A. (A) 10-substituted N-substituted maleimide
80% by weight, (b) 10 to 80% by weight of an aromatic vinyl compound, (c) 1 to 70% by weight of an unsaturated monocarboxylic acid,
And, if necessary, (d) each of the components (a), (b),
An N-substituted maleimide copolymer resin having a content of impurities represented by the following formula (1) of 10% by weight or less, which is obtained by copolymerizing a compound copolymerizable with (c). (In the formula (1), R ¹ independently represents an alkyl group, a cycloalkyl group, an aryl group, an alkyl-substituted aryl group or a halogen-substituted aryl group, R ² represents hydrogen or a methyl group, and R ^{3 to} R ⁶ is independently hydrogen, an alkyl group, a cycloalkyl group, an aryl group,
It represents an alkyl-substituted aryl group or a halogen-substituted aryl group. ) B. A photopolymerizable component having three or more ethylenically unsaturated double bonds in one molecule, and C.I. An ionizing radiation curable resin composition for a color filter, which comprises a photopolymerization initiator. 2. An ionizing radiation curable resin composition is applied onto a glass substrate by spin coating to give 100 mJ / cm ^2.
After exposure with a dose of 2
The ionizing radiation curable resin composition according to claim 1, wherein the coating film formed to have a thickness of μm has a transmittance of light having a wavelength of 380 nm of 90% or more after being heated at 250 ° C. for 1 hour. 3. An ionizing radiation-curable resin composition is applied onto a glass substrate by spin coating to give 100 mJ / cm ^2.
After exposure with the irradiation amount of, the film thickness is 5 by heating at 200 ° C for 30 minutes.
The universal hardness (test load / surface area of Vickers indenter under test load) is 200 N / mm when the surface hardness of the coating film formed to have a surface temperature of 180 ° C and the maximum load of 20 mN is applied to the Vickers indenter. The ionizing radiation curable resin composition according to claim 1 or 2, which is ² or more. 4. A transparent substrate, a colored layer formed on the transparent substrate, and a protective film covering the colored layer, wherein the protective layer is any one of claims 1 to 3. A color filter, which is formed by curing the ionizing radiation curable resin composition described in 1. 5. A transparent substrate, a colored layer formed on the transparent substrate, and a spacer provided at a position overlapping with the non-display portion in order to maintain a gap between the electrode substrate to be opposed, 4. The color filter, wherein the spacer is formed by curing the ionizing radiation curable resin composition according to any one of claims 1 to 3. 6. A transparent substrate and a colored layer formed on the transparent substrate, wherein the colored layer cures the ionizing radiation curable resin composition according to any one of claims 1 to 3. A color filter, which is characterized by being formed by 7. A liquid crystal panel, characterized in that the color filter according to any one of claims 4 to 6 and an electrode substrate are opposed to each other, and a liquid crystal compound is enclosed between the two.